$B~OLu

EPA14150/

276~0

STANDARDS SUPPORT
AND
ENVI

RONME

NTAL

IMPACT

VOLUME
PROPOSED
OF
FOR

.1=

STANDARDS

PE RFO

RMANC

PETROLEUM

SULFUR.

Emissioii

STATEMENT

REFINERY

RECOVERY

Siandards

and Engineering

PT "NTS

Division

Office of Air atld Waste Management

Office of Air Quality Planning a~ld Standards
Research Triangle Park. North Carolina 27'il I
Seplemher

197h

,.,. ~&Pff~~~,~.EPt~::,.,~B~

i. ~-~

This report has been reviewed by the Emission Standards andEngineering

Division,
Office of Air Quality Planning and Standards,
Office of Air and
Waste Management, Environmental Protection
Agency, and approved forpublication.
Mention of company or product names does not constitute
endorsement
by EPA. Copies are available
free of charge to Federal employees, current

contractors

and grantees,

and non-profi.t

organizations--as

supplies

permit--

from the Air Pollution

Technical Information
Center, Environmental Protection
Agency, Research Triangle Park, North Carolina 27711; or may be obtained,
for

a fee,

from the

Road, Springfield,

National

Virginia

Technical

22161.

Infonr~ation

Service,

5285 Port

Royal

Draft

Standards Support and

Environmental Impact Statement

Petroleum Refinery Sulfur Recovery Plants

Type of Action:

Administrative

Prepared

~C

by

:~)B~18~*~,._....~.........~.~.~_.....~~a~l~

Director, Emi
Environmental

Standards and Engineering Division

Protection

ResearchTriangle

Park,

N. C.

27711
Approved

by

p~ ~52~ac~L
--------------------------------------------------------

Assistant

Administrator
and Waste Management
Protection
Agency

401

M Street,

S.W.

Washington,

D. C.

Public

20460

copies may be obtained or reviewed at:

Information

Center

Environmental

Protection

Washington,

D. C.20460

~a~s
(Date)

Office
of Air
Environmental

Additional

Toate)

Agency

(PM-215)
Agency

TABLE

OF CONTENTS

Page
List

of

List

of Figures.

Chapter

Chapter

fables

i.

. ~ ............

....

....

...................

ui

...

viii

SUMMARY

1.1

PROPOSED'STANDARDS

1.2
1.3

ENVIRONMENTAL/ECONOMIC
IMPACT. ...........
INFLATIONARY IMPACT. ................

.................

1.1
14

1.1

2.
2.1
2.2
2.3

INTRODUCTION
AUTHORITYFORTHE STANDARDS.-. ..........
SELECTION OF CATEGORIES OF STATIONARYSOURCES. ...
PROCEDUREFOR DEVELOPMENTOF STANDARDSOF

2.1
2.4

PERFORMANCE. ...................

2.4
2.5
2.6
2.7
2.8

Chapter 3.

Chapter

Chapter

Chapter

Chapter

. 26

CONSIDERATIONOF COSTS ..........

.-.
CONSIDERATIONOF ENVIRONMENTAL
IMPACTS .......
IMPACT ON EXISTING SOURCES .............
REVISION OF STANDARDSOF PERFORMANCE........
REFERENCES ..
; ..................

...

2.10
2.11
2.13
2.14
2.14

SULFURRECOVERY
PLANTSIN PETROLEUM
REFINERIES

3.1
3.2
3.3

PROCESSES AND EMISSIONS.

..............
EXISTING EMISSION CONTROL REGULATIONS.
REFERENCES .......
; .............

4.
4.7
4.2
4.3
4.4

EMISSION CONTROLTECHNOLOGY
ALTERNATIVE EMISSION CONTROLTECHNIOUES. ......
COMMERCIALSTATUS OF TAIL GAS TECHNOLOGY......
P~ERFOR~nANCE
OF EMISSION CONTROLSYSTEMS. ..
.....
REFERENCES .................
: .

4.1
4.19
4.23
4.31

5.
5.1
5.2

MODIFICATION AND RECONSTRUCTION

MODIFICATION OF REFINERY SULFUR PLANTS .......
RECONSTRUCTIONOF REFINERY SULFUR PLANTS ......

5.1
5.6

6.

3.2
3.13
3.15

.......

EMISSIONCONTROL
SYSTEMS

6.1

LOW-TEMPERATURE
CLAUS REACTORSYSTEM ........

6.1

6.2

TAIL GAS SCRUBBING SYSTEM.

6.2

7.

..............

ENVIRONMENTAL
IMPACT

7.1

A~IENT AIR QUALITY

IMPACT.......

7.2
7.3
7.4
7.5
7.6

WATERPOLLUTION IMPACT ...............

SOLID WASTE IMPACT .............
ENERGYIMPACT. .................
OTHER ENVIRONMENTALIMPACTS. ..
REFERENCES .................-

iv

.~ .....

; .........

7.2

7.9
-. ..
7.17
718
7.21
724

Page
Chapter

8.

ECONOMICIMPACT

8.1
8.2
8.3
8.4
8.5

Chapter

INDUSTRY PROFILE.
..................
COST OF ALTERNATIVE EMISSION CONTROL SYSTEMS.
ECONOMIC IMPACT ...............
SOCIO-ECONOMIC AND INFLATIONARY IMPACT. .......
REFERENCES. ...................

9.
9.1
9.2
9.3
9.4
9.5

....
....8.10
..

8.1
8.3
8.34
8.35

RATIONALE FOR ME STANDARDS

SELECTION
SELECTION
REDUCfION
SELECTION
SELECTION
SELECTION

9.6

OF SOURCE FOR CO~ITROL ...........

Or: THE'BEST SYSTEM OF EMISSION
...................
...
OF POLLVTANfS FOR CONTROL .........
OF FORMAT FOR fHE STANDARDS ........
Of EMISSION LIMITS IN THE STANDARDS ...

9.1
9.5
9.12
~. 9.14

SELECTION OF MONITORINGREQUIREMENTSAND
PERFORMANCE TEST METHODS. ..............

APPENDIX A - EVOLUTION OF THE STANDARDS

APPENDIX B -

9.1

INDEX TO ENVIRONMENTAL IMPACT CONSIDERATIONS

APPENDIX C - EMISSION

SOURCE`TESf

DATA

APPENDIX
D - EMISSIONMEASUREMENT
ANDCONTINUOUS
MONITORING

9.17

List

of

Tables

Page
Table

1.1

Environmental
Alternative

and Economic

Impacts

of

Standards

1.3

Table 3.1 Typical Compositionof Gas Streams Entering

and Leaving a Hypothetical
Claus

Plant.

Table 3.2

State Regulations

Table4.1

Listing

Table

for
Claus
Calculated

4.2

........

Gas Treating

Su!f~r
Plants.
.............
Emissions
from a Sulfur

4.20

Emission
Control
..............4.24

Health and Welfare Effects

7.2

Estimated
Plaximum Ambient
Concentrations
..................

fable

7.3

Water Pollution

Table

7.4

of Exposure to H2S,
76

Impact of a Typical. 100,000

...........

Potential
Water Pollution
Impact
Sulfur
Plant NSPS. ................

Table 7.5

Energy Impact of Alternative

Table

Environmental

Table

Domestic

Table

Costs

814

7.72.

Emission Control
: .......

Impact

Delayed Standards.
Dbmestic Refinery
Sulfur

.'7.11
of Refinry

.............

Table 8.1
8.2

of No Standards

...............
Sulfur Plants.

Petroleum

Refineries.

Recovery Plants
for

Su7.fur

.......'.

..

8.4

at Domestic Refineries.

..

8.5

Recovery

Plants

with

Table

8.6

Alternative
Costs for

Table

8.7

Table

8.8

Table

8.9

for

II Emission
Sulfur

Control

Recovery

.Alternative

II Emission

Alternative

Emission

Plant.

(Oxidation).

Plants

Control

Control

8.7

Emission

(Reduction).

System

Costs

........

a 5 Lf/D Sulfur

Plant.

Control

...

8.8

...

8.9

...

8.11

with
for

..

Alternative
Emission Control
System:Costs
a 10 LT/D Sulfur
Plant
..............

Table 8.10 Alternative

for
8.12

System Costs

for

...............

Table 8.11 Large Refiner Model Financial

8.12
8.73

....'8.6

I Emission
Control
..........
Sulfur
Recovery Plants
with

a 100 LT/D Sulfur

Table
Table

.7.22
8.2

.........

Table 8.5

Costs

7.19

or

Incineration
.;.............~.
Costs for Sulfur Recovery Plants with
Alternative

7.3

Air'Pollutant

BBL/DayPetroleum Refinery

Table 8.3

Systems

; ........

fable

Systems.

. 3.14

Units

Recovery

COS and CS3. ..........

7.6

3.6

for Sulfur Recovery Plants...

of Announced Tail

Plant with Various

In~talled.......

Table 7.1

100 LT/D Refinery

...........

8.13

Profile.

Small Refiner
Model Financial
Profile.
Case i:
100 LTJD Sulfur
Plantjl00,000

......

8.14

......
BCD

8.16

R-~~inery

8.17

fable 8.14 Case 2:- 100:LT/DSulfur Plant/50,000 BCD

Refinery

...................

..

8.18

List

of Tables

(continued)
Page

Table

8.15

Table

8.16

Table

8.17

Table

8.18

Table

8.19

Table

8.20

Table

8.2~~

Case 3:
Refinery..
Case 4:
Refinery
Case 5:
Refinery
Case 6:
Refinery
Case 7:
Refinery
Case 8:
Refinery
Case 9:
Refinery

Table 8.2'2

Cdse 10:

Tab'le.8.23

Refinery
Case 11:
Refinery

50 LT/D Sulfur
Plant/50,000
BCD
...........,..,,
..8.19
50 LT/D Sulfur
Plant/30,000
BCD
.......'.,,,.
.......8.20
30 LT/D Sulfur'Plant/30,000
BCD
.....
.......
; ........
8.21
10 LT/D Sulfur
Plant/30,000
BCD
...................
..
8.22
30 LT/D Sulfur
Plant/20,000
BCD
'. ...................,
. 8.23
10 LT/D Sulfur
Plant/20,000
BCD
...............,
....8.24
5 LT/D Sulfur
Plant/20,000
BCD
8.25

5 LT/D Sulfur Plant/15,000

...................
5 LT/D Sulfur
.........

BCD
..

Plant/7500

8.27

Table 8.24 Economic

Impactof Alternative im;srion
Control
Table

8.25

Table 8.26
Tab'e 8.27

Cost

Systems.

Effectiveness

Projected
National
Emissions......

........
vs.

.' .........
Size

of

Sulfur

vii

8.28

Plant.

Growth of Refinery Sulfur Plants

Investment,
Annualized Casts and
.'..............

8.26

BCD

...

....

8.31

8.32
8.31

List

of Figures
Page

Figure 3.1 Typical Packaged Claus Plant (2-Stage).

Figure

3.2

Theoretical

Figure

3.3

Stretord

Claus Sulfur

.......

3.4

Recovery Efficiency

vs. H S/SO2Mole Ratio in Gas Feed. .........

Figure 4.1~ Alternative
Sulfur

Figure 4.2

Figure 4.3
Fi~gure4.4
Figure 4.5
Figure 4.6
Figure 4.7
Fi gure 4.8

3.10

Emission Control Systems for Ref~nery

Plants

4.2

IFP-1 Process ...............-

Sutfreen Process. ...........

Wellman-LordProcess. ...........
I~FP-2Process ..............
Beavon Process. ............
Cleanair Process. .......
SCOTProcess. ...

Figure 4.9 Sulfur

Figure 4.10 Sulfur

3.8

Process

Dioxide Emissions
Dioxide Emissions

SCOTProcess)

....

Figure 4.11 Hydrogen Sulfide

44

; ......

~.

.

IFP-1 Process). ; .....

jWellman-Lord
Process/

:
Em~ss~ons

(BeavonProcess) .....

Figure 4.12 Reduced Sulfur CompoundEmissions (Beavon Process).

vill

46
49
4.71
4.14
..4.16
4.18

4.25
4.27

4.28
4.29

i.
1.1

SU~VIARY

PROPOSED STANDARDS

Standards of performancefor newor modified sulfur recovery

plants within petroleumrefineries are being proposedunder

section ill. of the Clean Air Act. Dependingon the type of emission

control systeminstalled to comply

with these standards,residual
emissions released to the btmospherewill consist of sulfur

dioxide(S02)Drreduced
sulfurcompounds,
i.e. hydrogen
sulfide
(HpS),carbonylsulfide (COS)
andcarbondisulfide(CS2),(see
i;

discussion below). The standards, therefore, limit either the

concentrationof S02, or the concentrationof HgSand the total

concentrationof H2S,COS
andCS2,in the gases-discharged
into
the atmosphere
fromnewor modifiedlrefinerysulfur recoveryplants.

Specifically,emissions
are limitedto either 0.0~ percentbyvolume
of SO2on a dry basis and zero percent~oxygen, or 0.0010 percent by

volumeof H2Sand0.030percentby volumeof reducedsulfur compounds

on a dry basis

and zero percent

The standards

also require

oxygen.

continuous monitoring of the concen-

tration of S0por H2Sand reducedsulfur compounds

in the gases
dischargedinto the atmosphere. This is toensure proper operation
and maintenance
1.2

of the emission

control

systems.

EN~IRONMENTAL/ECONOMIC
TMPACT

Two alternative

emission control

systems were considered to

serve as the basis for standards of performance(i.e. best;system

of emission reduction,

considering

costs)

for refinery

sulfur

recovery plants; the low-temperature extended Claus:'reactlon system

1.1

(alternative

I) and various tail gas scrubbing systems (alternative

The alternative

II).

II systems consist either of oxidation-scrubbinFl

processes

or reduction-scrubbing

prdcesses

first

convert

processes.

emissions

The oxidation-scrubbing

from a refinery

sulfur

plant

to

S02 and then control these emissions with an S02 tail gas scrubbing
system.

The reduction-scrubbing

a refinery

sulfur

processes

convert

emissions

plant to H2S and then controlthese

from

emissions

with an H2Sscrubbing' system. In somecases, the reduction-scrubbing

procesjes

are

also

emissions

released

processes

and the reduction-scrubbing

by incineration
the

atmosphere

followed

followed

consist

surmnarited

alternative

however,

environmental

in Table

I, since

residual

from the oxidatlon-scrubtiing

processes

reductjdn-scrubbing

by incineration,

based

Thus;

which are followed

of 502-. Residual emissions released

from the

standards

an incinerator.

to the atmosphere

The potential
with

with

on

i.

either

There

the level

systems

consist

which

alternative

I or

no impacts

of control

are

not

of H2S, 005 and CS2.

and economic impacts

are

to

associated

alternative

associated

specified

II

are

with

in most state

implementation plans to meet and maintain the NAAQS

for 502
requires

new refinery

emission

control

sulfur

standards,

standards will,

plants.to

install

an alternative

system.

There are no adverse

proposed

recovery

which

environmental
are

based

impacts

on alternative

however, lead to a reduction

by some 55,000 tons per year,

by some'54 million

and a reduction

kw-hr/yr (90,000 barrels

1.2

associated
II.

in national
in national
of fuel oil)

with the
These

502 emissions
energy consumption
i-n 1980.

TABLEi.

Environmental and Economic Impacts of Alternative

Standards

IMPACT

Water

ACTION

Air

Alternative

Alternative

II

(Proposed

Pollution

Solid

Waste

Energy

Noise

+3""

,1XX

,O

Economic

_1XX

Standards)

No Standards

or
Delayed

Standards

Key:

+ Beneficiat Impact

- AdverseImpact

O No Impact

1 Negligible Impact
2 Small Impact

3 Moderate Impact
4 Large Impact .

x~Short-term Impact

xx Long-termImpact

xxx Irreversible

Impact

The economic impact associated

reasonable
however,

on both large
greater

and small refiners.

on small refiners

"economies-of-scale."

their

and that

profitability,

prices

on petroleum

refiner
1.3

the large
products

by only 0.2-1.0

refiners

could reduce

by 1.5-7.5

refiner
by only

is

due to the

the profitability

of a large refiner

of a small refiner

standards

This impact is,

than large

The standards

las measured by return on assets)

percent,

with the proposed

by 0.15-1.5

percent.

To maintain

would have `to increase

0.05-0.3

percent,

and the small

percent.

INFLATIONARY IMPACT

The Agency's
Statement

guidelines

are increased

for developing

operating

costs

an Inflationary

in the fifth

Impact

year of more

than 9100 MMper.year, or increased prices of more than 5 percent.

The increased

operating

costs

In the fifth

year

associated

with the

proposed standards

are only $16 ~Jblper year, and the potential

increase

is

in prices

Inflationary'Impact

less

than

Statement

0.5.percent.

Oonsequentllv;

has not been prepared.

1.4.

an

2.

Standards

INTRODUCTION

of ~erformance

under

section

111 of the

Act are proposed

and promulgated

following

a detailed

of air

control

methods

available

to the

and the impact of their

costs~on

pollution

the information
Petroleum

obtained

refineries.

backgroundand
of these

standards

not be familiar

by interested

Impact

recoverv
detail

and to facilitate
including
aspects

Plants"

Center

(Specif~'
- Petroleum

in

the

analysis
those

who may

of the industry.
Impact Statement

may be obtained.

(PM-215), Environmental

D.C. 20460.
Statement

in

and Environmental

Sulfur`Recovery:

industry

This document summarizes

exnlain

persons,

Support

Information

Agency, Washington,
Environmental

to

with the many technical

Refinery

to the Public

is

of the standards

Copies of the "Standard

Petroleum

purpose

Air

investigation

affected

from such a study of sulfur

Its

basis

the industry.

Clean

"Standard
Refinery

by writing

Protection

Support

and

Sulfur

Recovery

Plants.")
2.1

AUTHORITY

FOR THE

Standards

of performance

developed
as amended
standards

STANDARDS

under section
in 1971).

Section

of performance

welfare."

or contributes

new stationary

sources

are

111 of the Clean Air Act (42 ~.S.C.

111 requires

for

which ". . .may contribute

causes

for

significantly

to the

The Act requires

new stationary

endangerment
that

standards

2.1

the

establishment

sources

to air

of air

1857c-6),
of
pollution

pollution~which

of public

health

of performance

or
for

such

sources

reflect

through

the

".

apPlication

which (takins

into

the Administrator
The standards

best

system

the cost

achievable

of emission

of achieving

has been adequately

to stationary

111 prescribes

sources,

reduction

such reduction)
demonstrated."
the

regulations

construction

are proposed

three

steps

to follow

in establishing

of performance.

The Administrator must identify those categories of

will

sources

ultimately

federal

for

which

standards

be promulgated

of performance

by listing

them in the

Register.

The regulations

applicable

to a category

be proposed by publication

interested

persons

so listed

must

~n the Federal Register

within 120 days of its listing.

3.

limitation

in the Federal Register.

stationary

2.

only

of emission

of which commences after

by publication

i.

Of the

account

apply

Section

degree

determines

or modification

standards

. .the

This proposal provides

an opportunity

for comment.

Within 90 days after

proposal,

promulgate

with any alterations

he deems

bythenselves,do

not guarantee

standards

the Administrator

must

appropriate.

Standards of~performance,
protection

of health

to achieve

any specific

designed

to reflect

or welfare;

best

air

that

quality

demonstrated

account costs3 for the affected

is,
levels.

Rather,

technology

sources.

2,2

they are not designed

they are

(takinq

The overriding

into

purpose

of the collective
suality

body of standards

and to prevent
Previous

legal

is to maintain existing

new pollution

challenges

air

Drobl~ms~fromdeve~oDin~.

to standards

of performance

have

resulted in several court decisionsl,2 of importancein developing

future

standards.

EPA:

In these

(1) made reasoned

of the standards,

information
considered

cases,

decisions

and fully

(2) made available

significant

preparation

cor~ents

developed

becauseunder

this

environmental

effects

impact

under section

sectjon'EPA

of a standard

to provide

a cost-benefit

analysis;

to justify

standards

require

differen~t

that

unless

discriminatory;

a standard

can

by existing

or local

limitations

the

for

political

not

(1) that
necessdry

A~rAct

any counter-productive

costs

what system

it

is not necessary

(3) EPA is notrequired

different

such

achieved

is

in determining

levels

different

and (4)'it

be

parties.

111 of theClean

of control

standards

is sufficient

rather

than

that

may be

for EPA toshow

it

has

been

sources.
of standards

agencies

of performance

from adopting

the ~same sources.

subdivisions

does

not

more stringent

On the

of the Act (42 U.S.C. 1857-D-1) makes clear

other

the basis

parties

statement

(2) in considering

industries

Promulgation

State

were whether

established:

must consider

is "best;"

achieved

to interested

the courtdecisi6ns

of control

that

explained

from interested

of an environmental

for standards

unfairly

issues

on which the stanbards were based, and (3) adequately

Amongother things,

in

the principal

contrary,

that

emission
section

States

may enact more restrictive

2.3

prevent

116

and
standards.

Furthermore, i.n heavily pollQted areas more stringent standards may

be required
order

under section

to attain

prescribed

or maintain

under section

makes clear

that

new source

a State

standards

Although
in terms

national

may not

than~those

standards

expensive.

from storage

vessels'

trations
of storage

tanks

impractical,

short

are normally
where

feasible,

liquids

periods

during

during

make direct

filling

storage)

emission

measurement

a.more practical

111 directs

vessels

approach

the Administrator

a list

of categories

of performance

are'to

be developed.

.if ~the Administratorl

which causes

and fromtime

is to be selected

it may contribute

or contributes

2.4

specifications.

for which standards

A category

determines

thigh

to standards

to publish

of sources

or welfa~e."

during

highly

has_been equipment

to time revise

health

or

and the configuration

OF CATEGORIES OF STATIONARY SOURCES

of public

measurd-

and low concen-

2.2

pollution

physical

of the emissions

forstorage

to air

alterhative

are greatest

of performance

Section

ill.

structured

may be impractical

.The nature

periods

Therefore,

SELECTION

stringent

by EPA under section

In some cases

for petroleum

for longer

section.ll6

For example, emissions of hydrocarbons

and tank filling.

for

less

in

standards

Finally,

or enforce

limits

necessary.

1857c-5)

air qualfty

1857c-4).

adopted

from a new source

exorbitantly

concentrations

adopt

of performance

are sometimes

ment of emissions

ambient

109 (42 U.S.C.

of numerical'emission

approaches

storage

110 of the Act (42 tl.S.C.

significantly

to the endangerment

Considerable

attention

has been given to the development

a methodology for assigning priorities

In brief,

the approach

that

of

to various source categories.

has evolved

is as follows.

Speci fi c

areas of emphasis are identified by consid~rtng the broad

strategy

of the Agency for~implementing

Often,

these

emitted
these

"areas"

are actually

by stationary
Dollutants

sources.

are

then

the Clean Air Act.

pollutants

which are primarily

Source categories

evaluated

and ranked

which emit
taking

into

account such factors as (1) the level of emission control (ff any)
alreadyrequired
control

that

bv State regulations;

might result

source category;
facilities

future

a standard.
a standard

then

time

in a preselected

for the source

required

incremental

category.

to develop

In some cases, it may not be feasible to develop

immediately

This circumstance
development

of performance

made of the

for the

and (4) the estimated

that could be prevented,

bv standards
is

of performance

of

of growth and replacement of existing

for the source categorv;

year,

An estimate

from standards

(3) projections

amount of air pollution

(2) estimated levels

for

a source

category

might occur because

is needed to develop

with a high priority.

aproqram

control

of research

techniques

and

or because

techniques for sampling and measuring emissions may require

refinement.

Selection

of a source category for standards

development leads

to another major hecision,, determination of the tvpes of sources

orfacilities

to which standards

will

2.5

apply.

A source

category

often

has several

~facilities

from some of these

to control.
the

control

facilities

An i nvesti

costs

that
is

that

air

pollution.

ma_v be insignificant

qation

Emissions
or very

of economi cs may show that,

an owner could

better

cause

reasonably

servedby

applying

afford,

standards

air

expensive
wi thi n

pollution

to the most

severe

pollution Droblems. For this reason (or perhaps because there

may be no adequately

demonstrated

fromcertain facilities),
sources

within

Consequentl~,

all

covered

bv standards

facilities

within

For similar

air nollutants

although

a source

source

reasons,

emitted

categorv

of perfon~nance,
that

emissions

standards often do not applyto all

a category.

may not apply~to

system for controlling

standards

by such sources-.

may he selected

not

category

the

all

Dollutants

may be covered

to be
or
by the

standards.
2.3

PROCEDURE FOR DEYELOPMENT OF STANDARDS OF PERFORMANCE

Congress mandated that sources regulated

of the Clean Air Act utilize
control

under section

111

the best system of air pollution

(considerins

costs)

that has been adequately demonstrated

at the time of their

design

and conjtruction.

sought

In so doing,

Congress

to:

i.

Maintain existing air qualitv

2.

Prevent

3.

Ensure

Standards

new air
uniform

Dollution
national

of performance,

problems,
standards

therefore,

and
for

new facilities.

must (1) realistically

reflect best demonstratedcontrol practice; (2) adequatelyconsider

2.F~

the cost

of such control;

(3) be applicable

to existing

that are modiiied as well as new installations;

conditions

for

all

considered

anywhere

The objective
performance

variations
in the

of ooerating

and (4) meet these

conditions

being

country.

of a program for developincl

is to identify

sources

the best

standards

system of emission

of
reduction

wh~ch "has been adequately demonstrated Cconsider~ng costs)."

The legislative
referred

history

to earlier

ofwhat

make.clear

is adequately

are in actual
include

been adequately

assessment

demonstrated

of emission

on results

of tests

has required

that

is not limited

judgment

to systems

the investigation

of control

systems

but for which there

which

that
may

have

is limited

In most. cases, determination of the

limitation

achievable"

of emissions

worldwide

decisions

the Administra~or's

use. Consequently,

operational experience.
"degree

111 and the court

demonstrated

routine

a technical

of section

Is.based

from existing

investigation

sources.

This

and measurement of emissions

from control systems. Other countries with heavily populated,

industrialized
systems

areas

of control

Since

have sometimes developed

thanthose

the best

used

demonstrated

mav not be in widespread

use,

in the

systems

sources

emission

for

limits

United

States.

of emission

reduction

the data base upon which standards

are develoDed may be somewhat limited.

well-controlled

more effective

is an obvious

new sources.

Test data on existing

starting

However,

2.7

since

point
the

in developing
control

of

existing sources general'l~vrepresents retrofit

originally

designed

new sources

to meet an existing

may be able

to meet.more

Other infonation,however,
necessarily

involved

A process
In general,
i.

it

or local

stringent

regulation,

emission

standards.

standards.

for the development

Emissions

State

is also considered and judgment is

in develoning

follows

technology or was

of a standard

the guidelines

from existing

has evolved.

Below.

well-controlled

sources

are

measured.

2.

Data on emissions

consideration

from such sources

for suchfactors

ness of the source

age,'etc.);

tested

are

as:

assessed

with

(a) the rePresentativ~-

(feedstock,

operation,

size;

(b) the age and maintenance of the control

equipment tested

Cand possible

degradation

in the

effic;'encv of control of similar new equipment even

with good maintenance procedures);
uncertainties

for the tyoe of control

considered;
sourceb

3.

and -(d) the degree

wil;l

be able

During development
pilot

to achieve

Drojects,

co?sidered,
technology

e;quinment,
foreign

technology,

especially
appears

contracted

equipment

of uncertainty
similar

of the standards,

and Pri~tot~vpe installations,

of control

(c) the design

level

that

new

of control.

information
guarantees

being

from

by vendors

(but not yet constructed)

and published

literature

for sources where "einerginq"

significant,

2.8

are

4.

Where possible,

standards

are develoned

the use of more than one control

which permit

technique

or licensed

Process.

5.

Where possible,

(or at least

standards

permit)

new Drocesses
systems
6.

developed

to encourage

the use of process

modifications

as a method

of air

Dn!!ution

of control

standards

systems.capable

of controlling

example,

partlculate

are

a scrubber

matter

precipitator

developed

whereas

standards.

The opacity

control

mass standard
installation
than that

standard

on a day-to-day
of a control

In some cases;

however,

Is established

it

tomeet

basis,lbut

Tn these

to limit

2.9

at a level

not requlrethe

as with

cases,

emissions.

emission

the concentration/

is not possible
such

are

and maintenance of the

system more efficient

standards,

of emissions.

may be developed

emissions

by the concentration/mass

concen~ration/mass
sources

matter).

with concentration/mass

system installed

required

and

an electrostatic

for visible

which will require proper operation

emission

gaseous

to oarticulate

standards

in conjunction

"add-on"

to permit

can remove both

is specific

developed

than

more than one pollutant

emissions,

Where appropriate,

rather

or

control.

Where possible;,

(for

7.

are

only

or expensive
standard.

to develop
fugitive
opacity

standards

2.4

CONSIDER~TION

Section

OF COSTS

111 of the Clean Air Act requires

that

costs

considered in developing standards of~erfonance.

an assessment

various

of the

levels

industry.

costs

of control

The first

of estimates
for

impact

in the industry.

level
are

a new plant

a~d product

are

the

The economic
is
with

usually

cbsts

systems,

overall

alternatives

effects

of control

impact

control

costs

that

control

capability.

the economic

upon a new plant

to be addressed
if

Other
costs

is

a certain

aspects

that

upon product

prices

profitability.

of a proposed

both

operating

each

be donstructed

be incurred.

a given

the generation

control

is to determine

would

within

and annual

control

and producer

addressed

the

capital

will

supplies,

of implementing

requires

The fundamental.question

of controlcosts
analyzed

analysis

control

This requires

in new plants

having a different

various

or not

effects

in this

in the analysis

of the

whether

step

demonstrated

system alternative
step

economic

technology

of installed
various

The final

possible

be

standard

in absolute
would

be

terms

upon an industry

and by comparison

incurred

as

result

of

compliance
with typical existing State control regulations. This
incremental

approach

to comnly with

is taken since

State

standard

of performance.

analysis

of the

differential
the

t_vpical

impact

regulations
This
upon the

a new plant

In the
approach
industry

would be required

absence

of a.federal

requires

a detailed

resulting

from the

cost

that exists between a standard of performanceand

State

standard.

2.10

The costs
control

for

costs

control.of

air

considered.

of water

pollutants

wherever

possible.

A thorough

Total

as well

study.of

be made.

placed

it

It

is

the

standards

within

of Federal

an industry

of new plants

as this

to generate

of the additional

adverse

in the absence

to recognize

control

only

for

control

analyzed

the analysis

to know the

canital

the

and price-setting

is essentialto

can be placed

is necessary

are

the profitability

essential

additional

costs

pollutants

of ootential

also

on plants

so that

these

estimate

~re not

environmental

as air

mechanisms of the industry

an accurate

pollutants

economic

impacts

standards

of performance

necessitated

in the proper

perspective.

any constraints
also

by

Furthennore,

on capital

influences

the capital.required
equipment

can

capital.requirements

requirements

factor

so that

availability

the ability
for installation

needed to meet the standards

of performance.

A considerationof the impactof these standards on Inflation

Is of major importance.

to Inflationary
impact
2.5

Any action

pressures

which will

add significantly

is considered major and requires

an inflationary

statement.
CONSIDERATION OF ENVIRONMENTAL IMPACTS

Section 102(2)(c)

of the National Environmental Policy Act (NEPA)

of 1969 (PL 91-19C)) requires'Federal

agencies

to prepare

detailed

environmentalimpactstatements on proposalsfdr legislation or other

major

Federal

actions

human environment.

making prodess
environmental

significantly
The objective

of Federal
aspects

affecting
of NEPA is

agencies

of proposed

a careful
actions.

2?11

the

qual-ity

to build

into

considerationof

of the
the

decision-~

all

As mentioned

earlier,

in a number of legal

of performance

for various

industries,

have held that

environmental

the Federal

impact statements

by the Agency for actions under section

Air Act.

Essentially,

that "...Section

challenges
Courts

11l of the Clean

the Federal Courts of Appeals have determined

equivalent

criteria"...the

construed,

of a NEPAimpact statement"

best system of emission reduction,"

the Adminis'trator

of Appeals

need not be prepared

111 of the Clean Air Act, properly

the functional

to standards

to take into

mental effects

of a proposed

the industry..."

On this

account

basis,

in the sense that the

"...~equire(s)

counter-productive

standard,

as well

therefore,

requires

env~ron-

as economic costs

the Courts

to

"...establash(ed)

a narrowexemptionfrom NEPA
for iPA determinations under section 111."1)2
Tn addition to these judicial
and Environmental
specifically

Coordination

exempts actions

NEPA requirements.

According

affecting

Act (ESECA) of 1974 (PL 93-319)

under the Clean Air Act from

under the Clean Air Act shall

significantly

determinations, tReEnergy Supply

to section

7(c)(l),

"No action

be deemed a major Federal

th~ quality

taken

Bction

of the human environment

within the meaning of the National Environmental Policy Act of 1969."

fhe Agency has concluded,
eni~ironmental

impact

certai n regulatory
to do so by section
statements

will

statements

acti ons.
102(2)(c)

be prepared

however,
could

that

the preparation

have beneficial

of

effects.on

Consequently, while not legally

required

of NEPA,envi'ronmental impact
for various

2.12

regulatory

actions,

including

standards of performance develoPed under section 111 of the

Clean Air Act.

This voluntary

preoaration

of environmental

impact statements, however, in no wav~legally subjects the Agency

to NEPA rerluirements.

To implementthis policy, a separate section is included

in this documentwhich is devoted solely to an analysis of the

potential environmentalimF~ctSassociated with the alternative

standards

considered

and beneficial

increased

imnactsin

solid

are identified

for Proposal
such

and promulgation.

areas

waste disposal

as air

and waterpollution,

and increased

and discussed.

Both adverse

energy

consumption

Appendix B of this document outlines

those sections or chapters whichexaminethese potential environmental

impacts
2.6

in detail.

IMPACT ON EXISTING

Standards

either

SOURCES

of performance

may affect

of two wqys.~ Section

as "any stationary

source,

which is commenced after

existing

sources

111 of the Act defines

the construction

the standards

in

a new source

or modification'of

are proposed."

Consequently,

If an existing source is modified after DroDosalof the standards,

with a subsequent increase

in air Dollution,

standardsf

Amendments to the general

Suboart

performance.

A of 40 CFR Part 60 clarifying

it may be subjectto
provisions

of

the meaning of modification

were promulgated on ~ecember 16, 1975 ~4?fR 58416).

Second,promulgationof a standard of performancerequires

States

to establish

standards

of performance for existing

in the same industry under section Ill(d)

sources

of the Act; unless.the

standard for new sources limits emissions of a pol'lutant for

whichair quality criteria havebeentar will be) issuedunder

section 108 or one listed as a hazardous pollutant undersection
2,13.

112.

If

a State

does

provisions

not

act,

outlining

proceduref

under section Ill(d)

Subpart
2.7

EPA must

O~ STANDARDS

Congress

was aware

standards

that

into

the cost)..."

that

the

control
but
of
2.8

i.

are proposed
standards
as they

apply
the

revised

of air

pollution

technological
that

the

sources

control

advances.

Administrator

to time.

section

111 are

achievable

Accordingly,
may revise

Although

standards

designed

to require

proposed

system of emission reduction...(taking

the standards

and promulgated

continue

to

reflect

becomeavailable.

to stationary

sources

are reviewed
as necessary
the

best

Such Pevisions
constructed

periodically.

to assure

systems
are

or modified

of emission
not

retroactive.

.after

proposal

standards.

REFERENCES

Portland

(D.C. Cir.
2.

with

by EPA under

of the "...best

Revisions

level

from time

installation
account

the

Act provides

of performance

and promulgated

of existing

General

OF PERFORMANCE

may improve

111 of the

control

standards.

60 on November 17, 1975 (40 FR 58346).

REVISION

section

for

such

were promulgated in the Feder_al Register as

B of 40 CFR Part

by any industry

establish

Cement Association

vs.

Ruckelshaus,

486 F. 2nd 375

1973).

EssexChemical

Corp. vs. Ruckelshaus,

2.74

486 F. 2nd 427 (D.C. Cir.

1973).

3.

SU~FUR RECOVERY PLANTS IN PETROLEUM REFINERIES

Sulfur

emissions

sulfur

content

of the

refinery

from petroleum

of the

crude

and the

refining

oil

being

refinery

fuel

are a function

processed,

the

sources.

of the

complexity

Various

refinery

processes Produce process gas or "fuel" gas which can contain

significant
meet the

amounts of sulfur,
standards

of performance

(39 FR 930R) limiting

combustion
emission

sulfur

in petroleum
codes,

"sweeten"

mainly as hydrogen sulfide.

Promulgated

dioxide

refineries,

and to reduce

in March 1974

emissions

from fuel

or to satisfy

corrosion

or remove hydrogen sulfide

To

state

problems,

gas
or local

refineries

from the fuel

gas before

burning it in process heaters and boilers.

Hydrogen sulfide
with solutions-which
solutions

evolves

with lesser

removal from fuel

gas consists

absorb H2S. Regeneration

a side stream'of

of the scrubbing

concentrated

amounts of carbon dioxide,

of scrubbing

hydrogen sulfide

water vapor and hydrocarbons,

'which is processed in an appropriate recovery facility

Claus

sulfur

plant

Claus sulfur
technology
refineries.

to produce

plants

for sulfur

sulfur.

have long been established

recovery

Claus~ sulfur

elemental

from process

cap`acity

such as a

as effective

gases in petroleum

in U.S. refineries

~totalled

8000longtonsperdayas of April1973.1Sulfurdioxide
emissions
from Claus plants
92 percent

recovery

based on operation
are estimated

at two-thirds

capacity

at 338,000 tons in 1973.

3.1

and

The rapid

rate

them attractive
increases

at which sulfur

plants

candidates for standard development. Forecasted

in domestic petroleum refining

a significant

are being instal`led.makes

growth rate

capacity

in refinerysulfur

Over 1Or)0LT/D or about 13% of existing

indicate

recovery

refinery

that

is forthcoming.

sulfur

plant

capacity was scheduled for completionduring 1974.2

Refinery sulfur plants are currently located in 25 states.3
range from 4 to 375 long tons/day
average

size

plant.

Sizes

(LT/D) with 65 LT/D being an

Sulfurplants

scheduled

for

start-up

in 1974-75

reflect the trendtowardlarger facilities, aveii.aging

11)7LT/D,4
3.1

PROCESSES AND EMISSIONS

As discussed
the regeneration

oreviously,

hydrogen sulfide

gases are released

of amine or other scrubbing solutions

during

which are used

to desulfurize refinery process or fuel 9ases. In addition, someH2Sis

removed from process water by sour water strippers.

include facilities
as part

for steam stripping H2S from saur water streams

of the waste water

is practiced,

the off-gases

to the sulfur

recovery

The Claus

Process

Most refineries

treatment

system.

from the stripper

Where sulfur

are normally routed

plant.

The Claus process has been used almost excl.usively

refineries
the

Claus-

to recoversulfur,
process

recoverv

The basic

are:

(1) H2S+ 1/2 02 ~ H20+ S

(2! H2S+ 3/2 02 ~ SOp+ H20
(3) 2 H2S+ S02c' 35 + 2H20
3.2

exothermic

in petroleum

reactions-for

A tyoical two-stageClaus plant is sho!rninfigure3-1.5

siilfide

gas enters

to sulfur.'

the burner with sufficient

As' much as 50 to 60.percent

Hydrogen

air to convert all H2S

conversion of the hydrogen

sulfide to sulfur takes place in the initial reaction chamberby

Reaction

(1).

Reaction (2) also takes place, forming 502. After cooling,

condensing and removing sulfur,

the 9ases are reheatedby

with a portion

of the gases bypassed

and introduced

into the first

reaction

('Reaction

the effluent

3) occurs.

catalytic

catalytic

converter.

condenser

converter where the Claus

From the first

gas is cooled, sulfur

the gases reheated again.

around the sulfur

mixing

catalytic

converter

condensed and removed, and

The processis

If needed, additional

repeated in thesecond
catalytic

stages may be

added to remove H2S-as sulfur.

Somecarbonyl sulfide (COS)and carbon disulfide

in the reaction

(CS2) are formed

furnace in'the presence of~carbon dioxide and

hydrocarbons:

(4) C02+ H2S = H20+ COS

(5) COS+ H2S = H20+ CS2

(6) CHq+ 2S2 2 CS2~ 2H2S

Depending on the exact nature of the sour-gasfeed

stream and

theaperarinq
conditions
intheups:ream
reaction
furnace
andcatalyst
beds, con~ined005 and CS2levels as high as 5000 ppmvmayexist
in the

tail

gas.

6 Values of~600-1500 ppmvare.more common,however.

3.3

SECONDARY

CONVERTERI

PRIMARY CONVERTER

I-

STEAM

STEAM

CONDENSERS

WASTE HEAT

BURNER

HS GAS
FROM

AkINE
REGENERATOR

TAIL GAS TO
INC INERATOR

i-

-J

CI~

II

I I-I-

ANDSOURWATER

OR TAIL GAS

I-

PROCESSING

I-

STRIPPERAIR

LIQUID SULFUR PRODUCT

~3
-fi

L~--BOILER
FEEDWRTER
STEAM

SULFUR TANK AND SUMP PUMP

Figure3-1. Typicalpackaged
Ctausplant (2 stage).5

The emissions of H2S, SOe, and sulfur vapor from Claus plants
are directly

dependent

Claus Plant.

on theefficiency

For example,

of sulfur

recovery

a 100 LT/D Claus plant operating

in the
at 95 percent

sulfur recovery efficiency would emit 5 L7/D sulfur in the fon~nof H2S,

S02' sulfur vapor, COSand 052 formed in the reaction furnace. Gas
stream.compositions

throughout

a Claus plant

are given in Table 3-1 for

a hypothetical 100 LT/Dplant operatingat 95 percent recoveryefficiency.7

Claus plant

efficiencies

in turn

are dependent

upon the following

variables:8~9,10

Number of catalytic

conversion stages.

(2)

Inlet

feed stream composition.

(3)

Operating temperatures

and catalyst

maintenance.

(4) Maintaining the proper stoichiometri'c ratio of H2S/S02.

(5)

Operating capacitv factor.

For Cleusplants fed with 90 molepercent H2S,the sulfur recovery

is approximately
two' or three
with

Plant.
sulfur

85 percent

stages.

increasing

for one catalytic

The percentage

concentration

For plants'having
recoveries

for

stage

of sulfur

of the

acid

recovery

gas fed

two or three catalytic

various

acid

gas

and 95 percent
also

to the

stages,

concentrations

are

for

increases

Claus

the
approximately

90 percent for a 15~molepercent HpSfeed stream, 93 percent for a

50 mole percent H2S stream, and 95 percent for 90 percent HpS concentration.

Contaminantsin
Hydrocarbons

the feed gas reduce Cfaus sulfur

in Claus feedsto.cks

require

3.5

extra

air

recovery

efficiency.

for combustion.

The

Table

3-1.

TYPICAL COF1POSITIOI~ OF GAS STPEAPlS ENTERING AND LEAVING

~ HYPOTHETICAL100 LT/D REFINERY CLAUS PLANT

(Basis:

sulfur

recovery inClaus

unit of 95 percent)
Claus

Tail

Gas

Claus

Composition (Vol. %)

Intake

Before Incineration

H2S

89.9

0.59

After Incinerationf

SOo

--

0.29

S8 Vapor and mist

--

0.05

COS

--

0.05

CS2

--

0.04

CO

--

0.22

CO2
HC (MW:30)

4.6
0.5

0.86

2.05

H2
H2O

-5.0

i. 60
20.60

20.40

N2

--

75.69

76.54

02

--

--

0.18

Total

Temperature

"F

Pressure

psia

Gas quantity
Relative

Flow

100.00

100.00

104

284

21.3

mole-

SCFM

2028

0.82

100.00

1200

18.5

Atm

3.1

4.45

amount

6,287

*Basedon using 10 percent excess air in the inciherator and CHqas fuel.

9,025

added water'and
the size

inert

gas associated

of the sulfur

plant

with burning h~ydrocarbonsincreases

equipment

and lowers

sulfur

recovery

since

the sulfurgasconcentrations
are decreased.l2Higher-molecular-weiRht
hydrocarbons in the feed also~reduce Claus efficiencies

because of soot

formationon the catalyst.l3 Highfeedstockconcentrationsof C02

adverselyaffect catalyst~ife.l4
Since

the

reactions

in 3 Claus

Plant

recovery is enhanced by removing heat,

are

hence operation

temperature as practicable

in the reactors

vapor on the Claus catalyst

is necessary.

dependent upon catalyst

performance.

Catalyst

life

an plant operation

generally

sulfur

at as low a

without~condensinq
Sulfur

recovery

varies

sulfur

~is also

One vendor has reported

to two percent loss in recovery efficiency

life.'"

exothen~ic,

a one

over~the period of catalyst

from 2 to 5 years

depending

and contaminants in the feedstock discussed

previously.
Deviation

above or below the 2:1 stoichidmetric

ratio

of

HZSand S02for the Claus reaction results in a loss of Claus

efficiency.

Figure

3-2 illustrates

the variation

of recovery

efficiency with H2S/S02concentrationratio in the Claus converters.

Operation
somewhat.

of a Claus plant

below capacity

One vendor has reported

may impair

a two or three

percent

Claus efficiency
loss

in recovery

when
theClausplantwasturneddown
td 20percent
of decign
capacity.l6
Anothervendor

reports

no loss in recovery efficiencywhen

at two-thirds
of capacity.l7

3.7

operating

~ 95

iS
LL
LL

;o

IY
o:
w

.i

os

is

2.0

H2S/S02MOLRAflO
CTAIL GAS)

figure

3-2.

Theoretical

elaus sunur recovery efficiency

3.8

vs. Mole Ratio.

Although the impact of process

represents

in most cases

at the relatively
a one to three
increase

in

The Stretford

a loss

variables

of only one to three

high efficiencies
percent

typical

efficiency

loss

sulfur

emissions.

uncontrolled

as discussed

above

nercent

efficiency,

of Claus operations

represents

a20

(95~),

to 60 percent

Process

TheStretfordpi.ocessl~
Zhown
in Figure3-3is a One-step
process to convert H2S directly
th'e Stretford

process

process

is

the

which has supplanted

to elemental sulfur.

only

commercial

conventional

Claus sulfur

recovery

is installed

in only one U.S. refinery,

in several

refineries

in a refinery.

as part

of the

sulfur

At present
recovery

amine treating

Althoughthe

and

Stretford.

it has found application

tail

gas cleanup.process

for

Claus plants.

Refineiy fuel gas or process gas Is passed into a.countercurrent

column where the hydrogen sulfide in the gas is absorbed.ln the
Stretford

solution.

A summary of the Stretford

reactions

is as follows:

(a) Absorptionof H2S

H2S, Na2C03
;-

(b)

Precipitation

NaHS+ NaHC03

of sulfur

2NaV03+ NaHS+ NaHC03- S~ + Na2V205+ Na2C03+ H20

(c)

Regeneration

of sadium vanadate

Na2Y205
+ ADAf(oxidized)-t

3.9

2NaV03
+ ADA(reduced)

SWEET GAS OUT

SULFUR

AIR TO ATMOSPHERE

FROTH

~-~"~~

FEED TANK

6XTDIZER-T
z
z

v,

1 I

IFI'TER

AIR

FILTRATESOLUTION

v,

E
Y

Ply,

SOURFUEL GAS I ~ I
FROMREFINERY

WATER

I t;
v,

AUTOCLAVE

H2SABSORBER
I

SEPARATOR

~----C/

TANK

PURGE

LIQUID SULFUR
TO STORAGE

STREAM

Figure

3-3.

Stretford

process.

STEAM

;~;~~I;FUR

(d)

Regeneration

of ADA

ADA(reduced) -e 1/2 02 lair)

(e)

Overall

ADA'(oxi di zed)

reaction

H2S+ 1/2 02 ~. SJ + H20

After recirculation through the H2Sabsorber, .the'Stretford solution

is

retained

tation.

in a ho7dingtank
The Stretford

to allow

solution

completion

is then

of su~furprecipi-

regenerated

bv air

and reduced vanadium is restored~by oxygen transfer

Sulfur

formed

in the

solution

is

floa~ted

blowing

from the ADAZ

to the

top

of the

oxidizer

by air where the froths overflow to a settling tank. Sulf;r settles as

a sludge

in the

settling

Some adverse

temperature

tank

side

and trace

and is

reactions

oxidizing

separated

occur

and recovered.

due to increased

gases contained

liquor

in the fuel

gas

(notably oxygen,Sn2and HCN)and result in the huildupof sodium

thiosulfateand.relatedcompounds
in the tirculatingliquorwhich
must

be purged

from the

depends on the partial

gas stream
r-

of thiosulfate

system.

pressure

The rate

of the contaminant

and the pH and tempera'ture

is quite

Purge stream-rates

of thiosulfate

low,rhelawabout

of the liquor.

of feed gas to the Stretford absorber.l9

3.11

gas in the inlet

Formation

1000F.

range from 1.5 to 15 gallons

fAnthraqui none Disul foni c Acid

formation

per 100 moles

The major advantage

of the Stretford

process

is the overall

reduction in emissions,..bothin the desul6rized fuel gas or

process

gas

sulfur

and the

emissions

from the

julfur

recovery

plant.

Outlet

loadings have been designed for less than in ppinv H2S in the

fuel gasor process9a5,20COS

andCSeare notrecovered
bythe
Stretford process.; however, COSand CS2in~fuel.gases or procesj.
gases

are

much lower

Essentially

no sulfur

sulfur

emissions

Emissions
water

are

wastes

than

the

is

emitted

from.the

levels

emitted

from the

Stretford

relatively
and chemical

plants.

tank;

recovery

by process

consumptione

Claus

oxidizer

sulfur

unaffected

from

hence,

portion

variables,

are

nil.

although

high'14, dependent

upon

operation.

The primary disadvantage;of the Stretford process is the lack

of operating

experience

the Stretford

in~the

has~yet

U.S.

In the

to~ demonstrate=good

one U.S.

refinerv

operability,

anplication,

exoeri encing

numerousdesign and operating nroblems.21 Withtime, however,the

design
the

and operational

Stretford

in refinery
Other

problems

Drocess~will.be

will

undoubtedllybe

competitive

with

the

resolvedso
Claus

that

process

applications.

Alternative

Other sulfur

Processes

removal and recovery processes which couldconceivably

replace conventional

amine treating

and Claus sulfur

recovery include

the Fiamnarco-~etrocoke
HpSProcess and the Sulfox Process.22'23 The
Giammarco-Vetrocoke H2S removal process is similar

to the Stretford

process, except that arsenate replaces vanadatein the scrubbing

solution.

The Sulfox

process

uses an aqueous ammonia solution

3.12

to

absorbH2S Elementalsulfur is producedby oxidizing the solution

over

a catalyst.

The Gianrmarco-Vetrocoke
processing

is designed

was only recently

has any operating

discussion
3.2

has been applied

but has not yet been used in refinery

The Sulfox process

recoverybut

process

for refinery

announced.

Since neither

and emissions

gas

sulfur'recovery.

specifically

experiencr~ in refinery

of operation

to natural

applications,

sulfur
process

a detailed

is not included.

EXISTING EMISSION CONTROLREGULATIONSFOR SULFUR RECOVERYPLANTS

Table

3-2 summarizes

for both existing

regulations

current

and new sulfur

for sulfur

state

recovery

Florida

allowable

as 0.004

emissions

a 99.8 percent sulfur

control

plants.

regulations

The most stringent

plant emissions are found in Florida,

County, and ~Philadelphia.

sulfur

emission

regulations

specify

Ib SO2 per

recovery (equivalent

Los Angeles

maximum

Ib sulfur

input,

t~ ~500 ppmv total

or

sulfur

on an undilutedbasis).24 LosAngel'es
Countyrestricts emissions

to 5[10
ppmv
sulfurcalculated
as SOeequivalent,25
whilePhiladelphia
restricts refinerysulfur plants to 5r) ppmv
S02.26
State

codes applicable

to sulfur.recovery

expressed in pounds of sulfur

have sulfur

emission

the same regulation,

input.

regulations

A majority

for sulfur

0.01 Ibs S/lb

plants

S input,

are generally

of s'tates wh~ich

recovery

plants

or~99 percent

have
sulfur

recovery.

The format

of standards

inTable

3-2 shows some states

S02 only, while several have standards for"sulfur

3.13

regulating

emissions."

The

Table

3-2

Stat~ Regulationsfor Sulfur ~Recovery

Plants
RePulation

State

Exis ti no Plants

Alabama

0.16 Ib S/lb S input

Arkansas

le~el

~ew.Plants~
0.08 Ib S/lb

S input.

----

ground

Colorado

-~------

ground level

Connecticut

0.01 Ib S/lb S input

0.01 Ib S/lb S input

Delaware

2000 ppmvSOp

2000 ppmvSQ2

Flori de

0.004 Ib S02/3b S input

0.004 Ib SOZ/lbS input

Louisiana

0.01 Ibs S/lb S input

0.01 Ibs S/lb S input

New Hampshire

0.01 Ibs 5/1b S input

0.01 Ibs S/.lb S input

New3ersey

'15.,000ppmv502

Ohio

0.01 l.b Sjlb S input

only

concentrations

only -----~----

-----------

15,000 ppmv502

ii0.01 Ib S/lb S input

Oklahoma

0.01 Ib S/lb S input

Pennsylvania

(a)

Texas

(a)

Utah

concentrations

(a)

2200
pp.vSOZd(Ref.
28)

-----

(C)

Virginia

0.05 Ib S/lb S input '

0.05 Ib S/lb S input

West Virginia

0-.06 Ib S/lb S input

0.06 Ib S/lb S input

-0.5

(a)

According to A=0.32 E

(b)
(c)

allowable emissions in Ib S02/1b S input.

214 Ibs Sd /hr/1000 scfm effTuent flow rate.
for new sources~with
uncontrol~ed
80~ contro

where E = plant rating

in LT/D~and A =

sulfur

250 ton/year.

(d)

at incinerator

outlet,

calculated

for 50% excess

3.14

air.

emissions

intent of sulfur emissioncodesis not specified,but assumed

to
be S02 re~ulation only, since emissions of H2Sor CS2at these
levels
3.3

1;

would incur

odor problems.

REFERENCES

Genco,~Joseph M. and Tam, Sanuel S., "Characterization

of Sulfur
from Refinery Fuel Gas," EPAContract 68-02-0611, Task 4, June 28,
'1974,

2.

severe

p.

28.

World'Wide HPI Construction

Section

2,

February

1974,

Boxscore, Hydrocarbon Processing,

pp.

3-!0.

3.

Reference

i.

4.

Reference

2.

5.

Reference

i,

6.

Beavon; David K., and Vaell, Raoul P., "The Beavon SuTfur Removal,

page C-l.

Process for Purifying Claus Plant Tail Gas,~presented atthe

Midyear Meeting, API Division of Refining,
7.

Reference

i,

8.

Beers, W.D., "Characterization

EPA Contract

9.

p.

30.

68-02-0242,

of Claus Plant Emi'ssions,"

Task No. 2, April

1973,

p.

9.

Letter,
O.C. Poddy, Vice President,
Ralph M. Parsons Co.
to W.D. Beers, ProcessesResearch
Inc.. March 23, 1972.

1O. Letter,

D.F. Cole, Contract Engineer, J.F. Pritchard

to W.D. Beers,
11.

-37th

May 8-11, 1972, p. 272.

Reference

12. Grekel,
Journal,

8,

Processes
p.

13.

Reference

12.

14.

Reference

1O.

15.

Reference

9.

16.

Reference

9.

17.

Reference

10.

18.

Reference

i,

28,

on.

Inc.,

& Co.

March 23, 1972.

9.

H. et al.,
Oct.

Research

"Why Recover Sulfur

1968,

o; 95.

32-35.

3.15

from H2S?"

Oil andGas

19.

Reference

i,

p.

36.

20. Brochure, "Sulfur Recovery qualifications

and Experience;" J.F.
Pritchard and Company, Kansas City, Mo., Sept. 1973, p. A-4.

21. Letter, L.W.Larsen, Sun Oil Company

to James F.
OAQPS, EPA, dated January
22. Reference

i,

Durham,

ESED,

2, 1975.

pp. 38-40.

23. Conser, R.C., "Here's a NewWay to Clean Process Gases,

01:1 and Gas Journal April i, 1974, pp. 67-70.
24. Duncan, L.J., "Analysis of Final State Implementation Plans Rules and Regulations," EPA Contract 68-02-0248, July 1972,
(APTD-1334) pp. 55-57.
25. "Rules and Regulations,"
Control

District,

County of Los Angeles Air Pollution

Rule 53.2.

26. Section II (B), Air Management Regulation I~II of the Air

Pollution Control Board, City of Philadelphia, adoptedApril 10,

19'70.

27. Reference

24, p. 12..

28. Private communication,Frank 3. Spuhler, TexasAir Control Board

to Charles B. Sedman, Industrial
January

17,

1974.

3.16

Studies Branch, ESED, GAP,

4.
4.1

ALTERNATIVE

EMISSION

EMISSION

Removal of sulfur
by three

general

(1)

CONTROL TECHNOLOGY

CONTROL TECHNIOUES

compounds

from Claus

plant

tail

gas is

possible

schemes:

Extension
sulfur

of the Claus reaction

to increase

overall

recovery;

(2) Conversion of s~;Qur gases to sulfur dioxide (SOZ)

followed by 302 removal technolo;py;

(3) Conversion of sulfur gases to hydrogen sulfide (H2S)

followed

by H2S removal technology.

ODtion C1) is conceptually

in the operating

temperature

simple and requires

of the three-stage

only adjustments

conventional

Claus.

~otion (2) is attractive because the S02 removedcan be recycled

to the Claus plant.

sulfur

An incinerator

which is standard

Plants oxidizes all gaseous sulfur

equipment

for-

comoounds to 302 prior to

scrubbing.

OPtion (3) is attractive

because H2S removal technology is advanced

and H2Scan be recycled to the Claus plant or directly oxidized to

sulfur.

Conversion of all~su.lfur

reducing

gas,

Figure

and a reducing

4-1 shows

and how each utilizes

Claus tail gas.

systems,

control

those

catalyst.

various

options

heat, a

commercially

(1),

(2),

available

control

and (3) to remove sulfur

schemes

from

Although the l~~terature cites many tail gas control

described

technology

commercial

the

species to H2S requires

below were

for Claus sulfur

operation.

4.1

chosen

as representing

plants

and are presently

available

in

CONTROL SYSTEM

(A)(B)hBSORS~ION
ABSORBER
&

OFF-GAS

GENERATION

_ A: WELLMAN-LORD
'B:

IFP-P

RECYCLE
(A')

NCINERATfON

TO

- (B)

S02

(A~(C)(o)(r)
CLAUS

TWO-SfAGE

H,S GAS

r'ROM

CLAUS

REFINERY

SOI,UTION

(B

SULFUR
PLANT

REACTOR
(F)

SUL~UR

C: IFP-1
D: SULF~1EEM

(E)

1(6)

SUL

CONVERSI
p

TAILGAS

TO

(F)
I

STRETfORD
ABSORBEd
OFF-GAS
I

H2S

G) ABSORPTION

SULFUR

PLANT

E: CLEANAIR
F: BEAVON

SULFUR

&
ABSORBER
OFF-GAS
REGENE
RATI O~
'~:
SCOT

H2S RECYCLE
CG)

Figure 4-1. hmissioncontrol systemsfor refinery Clausplants.

Extension

of

the

Claus

Reaction

The conventional

Claus plant,

discussed in Chapter 3.
.efficiency
recovery

Such aunit

of about 95%.
efficiency

can be lowered

develoPed

equilibrium

of additf~nal

for reducing

reaction

by operation

Sulfreen

processes.

IFP-1

To gain further

the

PROCESS

improvement

was

Claus

reaction

Two processes

through

in sulfur

the temperature
of the

sulfur.

emissions

stages,

has a recovery

via the Claus~reaction,

to shift

toward formation

having two or three

extension

at low temperatures.

have been

of the Claus

These are the ITP-1 and

1,2

The basic reaction

involved in the IFP-1 process(figure

is the same one which takes

place

in the reactors

4-2)

of a Claus unit:

Catalyst

2H2S+ S02

35, + 2Fi20

Tail gas which exits a Claus unit at 265-2856Fcan be fed directly

into

the IFP reactor

without

cooling

the gas.

The reactor

is a

packed column with a specially designed "boot" for collecting sulfur.

Metal salts

catalyze

the reaction whichtakes

place in a high boiling

polyglyco~ (PEG)solvent above the melti?g point of sulfur--generally

in the range of 250-2600F,

The metal salts

form a complex with H2S

and SOpin the feed gas, whichin turn reactswithadditiona1 H2Sand S02
to form eler~ntal
coalesces
is

sulfur

and settles

drawn as a molten

and regenerate

the catalyst

into the hoot of the reactor,

product.

4.3

complex.

Sulfur

from which: it

TAIL GAS TO
INCINERATION

SOLV~NT

STEAM
ABSORPTION
TOWER
~i

I!

\I

CATALYST
SOLVENT
RECYCLE

SULFUR
CLAUS PLANT
TAIL GAS BEFORE
INCINERATION

Figure 4-2. Fl~wdiagramfor IFP-1Claustail-gas clean-upprocess..

Thegas leaving the reactor contains about.85OppmH2Sand 420ppm

S02' assuming
a 9n percentconversion.Conversion
efficiencyis
maximiiedat the 2:1 stoichiometric H2S/S02ratio required by the
Claus

reaction.

diminishes;

Above

or

below

hence,~process

this

ratio'the

controls

conversion

must effectively

efficiency

keep the

H2S/S02ratio in:the IFP reactor eeed as near 2:1 as~~ossible. Also,

below 2:1 H2S/S02 ratio

in the gas stream, the solvent tends to

evolve absorbedH2S,nhich also increases ultimate sulfur emissions.

Besides H2S and S02, about 300 ppm sulfur vapor is evolved with
the exit

gas.

This~is

roughly

the equilibrium

concentration

of sulfur

in the vapor phase at 2600Fi. COSand CS2 formed in the Claus plant
are not affected

by the IFP-1; hence, they exit at approximately

the same concentrations

containing

as in the feed gas.

1500-2500 ppm sulfur

incinerated

before

SULFREEN

discharge

PROCESS

The reactor

and some entrained

to the

exhaust

solvent

atmosphere.

3,4

The Sulfreen process (Flgure 4-3) 'reduces the sulfur

in Claus plant

tail

on a catalytic

surface

gas is first
liquid
battery

of reactors

temperatures

gas by further

vapor.

batch

reactor.

Claus

reaction

are carried
in the sulfur
toward

tail

sulfur

gas is then introduced

than those utilized

pUsh the

Claus

to wash out entrained

The tall

content

the Claus reaction

where the Claus reactions

(260-300"2)

Lower temperatures

promoting

in a gas/solid

scrubbed with liquid

and sulfur

is

to a
out at lower'
plant.

completion

due to favorable equilibrium conditions. The catalyst is usually

actlvated.carbon,

though

alumina

is

4.5

also

used.

CONVERTERS

ADSORBING

COOLING AFTER

SULFUR REGENERAT
ION REGENERATION

ABSORBER
OFF-GAS
TO
INCINERATION

SULFUR WASH

CONDENSER
STEAM

SULFUR WASH
NITROGEN TO
REGENERATION CYCLE

, I

Lrqur
SUL

CLAUS PLANT TAIL

GAS BEFORE

INCINERATION

LIQUID
SULFUR
BOILER

FEED WATER
Sd

SULFUR
HOT

GENERATION

FURNACE

GAS

Fi gure 4-3.

Flow diagram for the Sulfreei1 process.

SULFUR

A regenerati on gas, es senti al ly ni trogen , peri odi cal ly desorbs

the sulfur-laden
through

catalyst

the catalyst

beds.

Nitrogen

bed at approximately

is;heated

and cycles

570eF until

all

water and

C02 are driven off.

For the desorption
where sulfur

of sulfur,

vapbrizes,

the temperature

is raised

is swept away with the nitrogen,

to.7500F

and precipitates

in a condenser. The carrier gas is further scrubbed in a sulfur wash

before

returning

to the regeneration

The process

reduces

entrained

cycle.
sulfur,since'the

as an absorbent for liquid`sulfur.

catalyst

acts

However,tail gas passing through

the catalyst bed retains several hundredppmsulfur vapor in equilibrium

with liquid sulfur.
levelsof

H2S and S02 are reduced by 80-85 percdnt to

about 1800 ppmv HZS~and900pprp SOi.

~the levels of H2S and S02 arehighly

dependent upon maintaining

2:1 ratio qf H2S/S02in the Claus tail gas.

by the

Sulfreen

unit may consist'of

and ~ane in desorption

in desorption

the

COSand CS2 are not affected

process.

A Sulireen
absorption

As with the ~FP-1 process,

service

as little
service.

are incinerated

as three reactors,

The gases

before

discharge

from the

two in

reactors

to the atmosphere.

Conversion to S02 Followed by S02 Recovery

Two processes
Claus

sulfur

have been developed

plants

present in the sulfur

of the S02.

through

conversion

plant tail

to reduce emissions
of thesulfur

from

compounds

gas to S02, followed by recovery

These are the Wellman-Lord and IFP-2 processes.

Incineration

of the sulfur plant tail gas effectively converts all the sulfur
4.7

compoundspre;ent to SOpand this is recovered In a conventional

502 scrubbing system.

In both processes the S02 recovered is

recycled to the sulfur

plant for eventual

sulfur

by the

Claus

WELLMAN-LORD

conversion to elemental

reaction.

PROCESS

5,6

The Wellman-Lord process

system to reduce. the stack

Sulfur constituents

(Figure 4-4) uses a wet regenerative

gas sulfur

concentration

in Claus Dlant tail

to less

than 250 ppmv.

gases are oxidized to S02 in

the standard su7fur plant incinerator, then cooled and quenched;

tq
reduce the gas temperature

and remove excess water.

The SOe rich

gas is thencontacted countercurrently with a sodiumsulfite (Na2SO3)

and sodiumbisulfite (NaHS03)

solution whichabsorbs SOpto form
additional
absorbent

bisulfite.
solution

The principal

reaction

between S02and the

is:

SO2+ Na2SOg
+ H20 `J 2NaHSO3
The absorber

at less

off-gas

is

reheated

than 250 ppmv 502 and negligible'

Any S03 produced by the incineration

S0g-rich

the bisulfite
sulfite

and vented

solution

is boiled

to the

atmosphere

amounts of other

is preferentially

sulfur

compounds.

absorbed.

in an evaporator-crystallizer,

wherein

solution decomposesto SO2and H20 vapor and sodium

is precipitated

according

to the reaction:

~~eat

2NaHS03
$ Na2S03'H20+ SOpS
4.8

EVAPORATOR

DISSOLVING

AND STEAM STRIPPING

QUENCH
ANDGAS

TANK

sq, ABSORBERTO STACK

COOLING SECTION

PRODUCT
SO2
RECYCLE 10
CLAUS PLANT

fl

8u

CLAUSPLANT

~AIts~Rs

NaHSO?

SOLUTInN

AFTER

INCINERATION

RECYELE

;o

IQUENCH
WATER)

Na2S03
SLURRY

MAKE-UP

ZY

j.

I
PURGE

u---~

STREAM

Na2SO3 SOLUTION
ACID

WATER PURGE

TO NEUTRALIZATION

Figure 4-4.

i',

NaOH

Flow diagram for the Wellman-LordSOe recovery process.

H2ORECYCLE

Sulfite
solution

crystals

to

the

are separated

and redissolved

for reuse as lean

absorber.

The wet 502 gas flows to a partiaf~condenser where most of the

water

is

condensed

and reused

to dissolve

the

sulfite

crystals.

The enriched S02 stream is then recycled back to the Clausplant

for

conversion

IFP-2

to

PROCESS

elemental

sulfur.

7,8

With the IFP-P process

(Figure

4-5),

Claus plant

tail

gas is

incinerated to convert all sulfur species to 502. The incii~erated'

gas is cooled
absorbed

and

and then fed to an ammonia scrubber,

converted

to

ammonium

sulfite

and

where 502 is

anrrmonium bisulfite

by t~e following reactions:

2NH40H
+S02 $ H20+ (NHq)2S03
NH4"H
+ SD2 ~ NH4HS03
Sulfates
the

and thiosulfates

following

side

are

also

formed

in the

ammonia scrubber

by

reactions:

2NH40H"
S02+ 1/202~ H20+ (NHq)2S04
2NH40H
+ S03 ~ (NHq)2S04
+.HZ0

2NH40H
+ S02+ S -+ H20+ (NH4)2S203
Gas leaving the absorber is reheated and vented to the atmosphere

at less than 250 ppm502 concentration.

The S02 rich solution is fed to an S02 regenerator where the

sulfite andbisulfite are thermallydecomposed

to S02,NHQ'
andH20
A saturated

solutidn

containing

anrpnoniumsulfate

is drawn from the bottom of the 502 regeneratorand

and thiosulfate
fed toa

sulfate

reducer.

4.10

,...

ABSORBER OFF-GAS
TO STACK

NH3MAKE-UP

NH3/H20
RECYCLE
SOLVENT MAKE-UP

CLAUSPLANT
TAIL GAS

AMMONIA
SCRUBBER

CATALYTIC
H3S GASFROM REACTOR

AFTER

CLAOS
PLANT
FEED

INCINERATION

SO2

AMMONIACAL
BRINE
EVAPORATOR
ANDI

S
I

I SO2/NH3/H20

REGENERATOR

SULFATE
REDUCER
SO

Figure 4-5.

Flowdiagram

for TFP-2 Claus tail-gas

clean-up

process.

In the sulfate
the side

reducer,

reactions

the sulfates

are thermally

and thiosulfates

formed in

decomposed per the following

reactions:

(NHq)2S04
~ NHqHS04
+ NH3"
(NH4)2S203
3 2NH3f+ S02~+ S + H20t
2NMqHS04
+ S '-t~ 3S02t+ 2NH3"+ 2H201
Gases from the S02 regenerator and sulfate reducer are combined
with an H2S rich stream (normally Claus plant feed gas) and fed to
a catalytic

reactor

where

they

are

contacted

with

a polyethylene

glycolsolvent; TheH2SandS02react in the solution to form

elemental

sulfur.

Sulfur

is withdrawn

in the molten state

and

sent to the Claus plant sulfur pit.

Gases

from

the

reactor

are

cooled

to condense

out water

and NHQ

as NH40H.The NH40H
solution is returned to the ammonia
scrubber.
Any H2Sor SO2which leaves the reactorand
NH40Hsolution
the

ammonia

is notabsorbed by the

is recycled to the incineratqr

and from there to

scrubber.

Conversion to H2S Followed by H2S Recovery

Three

processes

Claus sulfur

plants

have

been

developed

to reduce

through conversion of the sulfur

emissions

from

compounds

present in the sulfur plant tail gas to H2S, followed by H2Srecovery-.

These are the Beavon, Cleanair and SCOTprocesses.
these

processes,

gas' such

as hydrogen

of the sulfur
Beavon

the

sulfur

plant

and pasjed

compounds present

and Clean

air

processes

tail
over

gas

In each of

is mixed with

a reducing

catalyst.

a reducing
Most

are converted to H2S. Both the

then

4.12

use

the

Stretford

process

(discussed

in Chapter 3) to absorb the.H2S and convert it directly

elemental sulfur.

to

In the SCOTprocess the H2S is absorbed in a

conventional H2Sscrubbing system and then wcycled to the Claus

sulfur

plantfor

eventual

BEAVON PROCESS

conversion

to elemental

sulfur.

9,10

The Beavon process

(Figuw

4-6) begins

by converting

sulfur

present in the tail gas ~SOZ,COS,CS2,and elementalsulfur) back

to H2S. This is done by hydrogenationand hydrolysis under moderate
conditions

temoeratureand

Dressure

Claus plant.'

Before the tail

gas enters the packed bed hydrogenatiqn

reactor,

gas is combusted substoichion~~trically

burner

of

fuel

to produce

the

reducing

similar

conditions

to

necessary

those

in

the

in an inline
to convert

sulfur gases to H2S.` The combustion products are mixed with the
tail

~as to provide

made in the

a reducing

fuel-rich

hydrogen already

CO+ H20 ~

atmosphere.

combustion

in the tail

chamber

Extra hydrogen may be

as required

to supplement

gas by the reaction:

H2 + C02

A cobalt-molybdenum

catalyst

promotes

the hydrogenation

and

hydrolysis reactions which reduce S02to~very low values and

(COS+ CS2) to less than lfl0 ppmv. Elemental sulfur is completely
reduced

to

H,S.

Sg + 8H2

The

reactions

are:

8H2S

SO2+ 3H2 3 H2S+ 2H20

COS'+H20 $

CO2+'H2S

CS2+ H20 $ H2S+ COS

4.13

FUEL

GAS

BURNER

AIR

ABSORBER
OFF-GAS
TO INCINERATION
ORSTACK
CLAUS

PLANT

TAIL GAS BEFORE

INCINERATOR

HYDROGENA

LIQUID RETURN

TAIL GAS

STRETFORD SOLUTION
FIXED BED
REACTOR

AfR
.p

I\/I

I
I

I/\I

COOLI

I SULFUR
1 MELTER

ULFUR SCUM

TOWER

FILTER

ST
GASPURIFYINGOXID

OR
CENTRIFUGESULFUR

TOWER ABSORBER
SOUR WATER
TO WAS

TREATMENT)

PURGE
~RERM

Figure 4-6. flow diagramfor the Beavonsulfur removalprocess.

CS2+ 2H2S~ CHqC 4S

4H2+ CS2 ~ 2H2S+ CHq

COS+ 4H2 3 H20+ H2S+ CHq

After hydrogenation., the tail gas is,cooled and water is removed.
The H,S-richtail

gas is fed to the Stretford circuit

for removal of

H2Sto less than i') npm. Final incineration before discharge to the
atmosphere

is optional.

CLEANAlIR PROCESS

The Cleanair

confidential
part

process

processes.

of the Cleanair

Plant.first

11,12

stage

includes

the Stretford

process

and two

Figure 477 is a process diagram.

package includes

to include

a modification

a reducing

An optional

of the ~Claus

and hydrolysis

catalyst.

This causes the conversion of COSand CS2 to H2S according to the

following

reaction:

COS + H O

c H2S+.CO2

CS2+ 2H2O c-t 2H2S+ 002

~Carbon dioxide
of

also is decomposed to CO~to prevent

the recurrence

COS.

Ctaus

vapor,~H2S
water

tail

gas,

with

essentially

all

gaseous

sulfur

and SOe, is quenched to reduce temperature

and entrained

sulfur.

The cooled

gas

is

fed

into

as sulfur

and remove
a reactor

whereH2Sand S02 tin a 2:1 ratio) react, loweringSOpto less than

250 ppmv.
are

Both water

and sulfur'(products

of the Claus reaction)

removed.

Next, the tail

gas is sent to a Stretford

H2S is.removed and oxi.dized to elemental sulfur.

4.15

unit where remaining

Residual SOe,

ABSORBER OFF-GAS

CLAUSPLANT

r ~UENCH
SOLUTION

fAiL GAS BEFORE

--- TO INCINERATION
OR STACK

PACKED

INCENERATI

REACTION

TOWER

RETURNSOLUTION

STRETFORD SOLUTION

RECYCLEREACTANT
SOLUTION

STRETFORDABSORBER
FIXED-BED

CATALYST
REACTOR
f

MAKE-UP
STRET

AIR TO ATMOSPHERE

1,

I I

1 e (

IrLr

'I

ICLARIF
IERJ

ill

REGENERATOR~I11
.

II

IP-~MP
TANK

""

.AIR

SULFUR SCUM ~
FORD PURGE

QUENCH
TOWER

OCLAVE

ACTI

EPARATORSOLUTION

UTI

RETURN
STRETFORD
SOLUTION
AVE
SEPARATOR

AIR

PURGE STREAM

DEPURATOR

L~t

LI9UID SULFURTO STORAGE

Figure4-7. Plowdiagram
for the Cleanal;Claustail-gas treatmentDrocess.

although absorbed by the Stretford

and therefore

increases

chemi-ca~

sol-ution, decomposes the solution

consumption

and liquid

Residual COSand CS2 will pass through unaffected.

may then be sent

to an incinerator

purge

Purified

to oxidize.residual

rate.

gas

sulfur

to

S02 (guaranteed less than 250 ppmv)and COto C02before discharge

to the

atmosphere.
13,14

SHELL CLAUSOFF-GASTREATING(SCOT) PROCESS

Similar to the Beavon process,

first

converts

all

sulfur

compounds

the SCOTprocess (Figure 4-8)

and free

sulfur

in the

tail

gas to H2S Hydrogen,or hydrogenand carbon~mqnoxide

mixtures
are used as the reducing gases while a cobalt/molybdenum-on-alumina
catalystDromotes

the

reactions:

SOp+ 3H2 4 H2S+ 2H20

SS + 8H2 ~ 8H2S

COS
andCS2arereducedin reactionsidentical with those in
the

Beavon

catalytic

as a reducing

agent,

reactor.

Whese.carbon

the following

additional

monoxide

is

reactions

also

present

may occur:

SOp+ 3CO- COS+ 2C02

Sg + 8CO - 8COS

COS
+ Hp0$ CO2+ H2S
CO+ H20f COp+ Hp
CO+ H2SCt COS+ Hp
From the SCOT ~eactor,

the tail

gas containing

less

than 1On ppm

(COS+ CSP)a"d 10 ppmSOpis cooled and excesswater removed. The

H2S (at 20,00~-40,000 ppmv) and some COpare then removed by treating

4.17

Cooling Tower

Packed

Reducing

or

Sour gas to Claus unit

fray

Reactor

Gas
~'

---

Lean amine from regenerator

Fixed-bed

Line Heater

atalvst
Claus

olant

orior

to incinerator

Fuel

tail

Air

reducing
-- -- -

or

water

Trav

Tower

Absorber

gas
:P.

steam

gas
Air
Sour-water
condensate

existing

water

Figure 4-8.

to

sour-

strip~er

FLOWDIAGRAM
FORTHE SHELLCLAUSOFF-GASTREATING
PROCESS

Fat

amine

to regenerator

.~

::

1..

. ..-

-;

:~
r

Ii

.:wjthdi-isbpropanbiamine
soilition_
in a? absorpt~p~col'uin?.l:Th'eH2S-:

:.~jnch
sol:ution
is regene;rate'd
bystrippingH2S
in a conventional
.~'..steam stripping oo!rmmn.
'.Regeherator off-gas, mainly H2Sand s-orbe:

~:::;-j
co,.is Rcycled
asfeedtothefiot:staqe
oftheClaus
unit.:The.absorber
off-9:as,
containing
~essthan
300~~
ppmv'H2S is
incinerated
in;a:standarddiausincinerator.
4.2

. COMMERCIAi'
STATUS ~01~TAIL: GAS TECHNOLOGY-~~

: :

' The Wellman-lord process has demonstrated the:l~ongest trouble-lfree- : -

operation-over
two-years
ona:Claus
plant.15
:Wellman-lbrd.
unitson
Claus plants Bre.in dperation at three~ refineries

wSth:f~ve ~

'- additi.onal
unitssc~eduled
for-start-up
~n1974
andearly
1975.16
~heIFPh2
processij:'being..~nstall
ed in~threeJaDanese
refiner'ies.l!
.:. .

Of units

designed

specifically

'for Claus' tail

gas treating,~the

: Beavon,SCOT,
and'IFP-lun!tshave.beensuccessfullyoperatedinrefinerles.
.Four Beavon'units have 'been running c0ntinuo~sjy`at ~twJo
refineries. since

3ulv 1973.78 Three;oth~r~Beavon

units started up duri?g-.1973,-~wi
th three
morescheduledfor comple;ionin

:Twosnaa~'lscor uni t's

1974.11"~ITwo9

wer~r~e

installedin June 1973,andare-:currentlyit; operation.fpllowing~sdme

modi.fi
cati ons.20 At 1east seven moreSCOT's:were
schedu!edf6r .start-up
In 1974:21

?-

:~: - The IFP-~1 and Sul~reen prodesses

:. ~.::

have been applieb tq natural:

gasplantsin FranceandCanada
for.aboutfiveyears.-22Also,the`
is currently

in, operation

on .jix refinery

sulfur blantsin

;...
IFP-1

.Japan

: andtwoin theU.S.'with::several
molpahnounced.Z3
-. ~:.:::I
. The ClednaiC.ordcess'
was.installed at three U..S.~refineries

ill !973;-but;.a11.are
sti'fi awai~t~ng;tart-up:
$fter processmodificat.ions.24
con trol'
A,detailed
lilst:of:present'
andplanned
Claus
t8i:l:gas

r-..systems
is presented
in fab!~e
4-1.
4;.1''9

: : .. :

OFANNOGNCED.TAIL
GAS.TREATING
:Table4-1. LISTING

.ONITS':iCdlCLAUSSULFUR
PCANTS
AS'OF:3/1/74

.Onstream
.`

Nd.of . Number~Capaci

iYpe
Unit :CompanyiLbeBTiqn_
:I- I.-_pare;:; UnitsClaur
Plant.
LT.
: Beavon.
.. : .UnionDil
Compdny/

July1973:~:.
-1..._2'

.1: ' .WiImington?.:Ca!i fornia

B~eavdn
'
.-Beavon. ...

s~ob~:l
0i1 Company/

IJuly 1973 . 2 -

Torrance, Ca1i forni a ~

.Atjanti.c-Ri.ch
fi eld/

Z/1OP~
'

3/100

- September
1973 i ~1

.1/140

Phi'l ade! phia, Pennsyl vani a

Beavon ~: GettyOil Companyj

November : 1973

.1/30P

Delaware City, Delaware

Beavon

KobeSteel'ColjJapan
'

Oct~ober
1973:-.. 1

Beavon.

Texaco,::Inc:j`

~a~ch 1974 .':-~

1/220

- ~~Lonq
Beach:
~Ca!jfornia
Beavon

Carribbean

Beavbn

Apri111974:
:: 2

: Unknown/
:

: . N~ve;niber
1974

Union bi~ Co'./`'

.S

Rodeo,
Caiiforma

~leanair :...: Atlanti c Richfield Corp; (ARCO)/-

--

3/90

~ -WiImington, Cal~iforni a.

Cleanar.:' .Gulf-Oil_
Co./ ~~.

Phi1adefphi
a,-qe?nsyjvani
a

"` ~'

cledna~i santaFeSpri'ngs.Refinery;
(6ulf
Oil.Co.)/SantaFe
Spri.ngs ; Cal ~forni a :

...~cle`annir

TechmBfhimpbrt,.U.SIS.R. : :: ~: .

:-':We!.lman-Lord
:~Standard

5'a/ : .
bilbiCa~ifoPn

Richmond, California

'1

i.:

.:. ]L- `

:2

iebiua
:
~4..20~

.i.

j :-

:1/290

.:Ja""-~'I:.:la75
~974 .

-1;~::
: : :: .
:

1...-:-'i~29

.T- -

.-:

;: Wellmen-Lo;d
' Kashima
Oilco./ -.~:- ` Kashima, Japan

1/46 .

i'
-:: :I: :

:.;::
;:: : :;
~ : -..

~ :-~.-

.:::--1

:.~Tadie
4-1. (Con~.)LISTING:DF
ANN9UNCEOTAIC
GAS
TREATING
Onstredm

-:ITy'pe.Uni-~.-.
tompany/Location.

Date

No. ~f .'"Numb~r/Capacityof~_''.

-Units : ClausPlant; LT/D.:

: Weli.,,:L,,d
Toa::NenryoiPrlta,
: ;.-; bFrOber
1R74:
:
JaFi~ail
.To~ ~Nenry,l~atjshima,-:
j ~ . __October
1974:
:~ -1 I:j.~: :
We!lman-tord

~J"pan;;:
:~~;

.~Wellmrin-Lord:
Toa

: I\ugu.t
1911
: ; 1: . : ZiZOO;::
:: _
Nen::;;:enryb:Retin.ry/K$.lbtl:,

Wellmd,-L,,d
: Standard
DildfCaiifornial;l
: Septemberl912:_
- 1_
Segundo, Califdrnia
Weilman-iard
Standard
OilbfCaliforni.a/El January.i975
~~Segundo,~Call forni a-

::

Wel.lman-Lord
: Standard Oil of California-

~.. Augu5t'19i4--.

: 2/750

Richmond,,~a~ifornia

.SCOi

- Champlin'
Petroleum

..

June 1973 -

:~. i~-

- Compai7y/Wilmi ngton ,~
Cal i fdrni

SCOT~

: Dbuglas:Oil.
Compar\y/
::.:.:..: ~.~3une`197j.'~..

..

.qaramount~,California

SCOT
:

ShL~11.
.Canada,
-Waterton
. ~`:-:
Gas Treating

Dece~nber.
1974- : 1]:i.'

:.:]1/21001::.

Plant/

A'lberta, Cana.da.

SCOT

.Briti sHPetrol
eum
of Ohioj

October1974

Standard.Oi7

:~- I/jkC

: Marcus
Hopk,
Pennsylvania
:
SCOT

.U. S.- Steel/C14lrtoo,.

:-`Late 397;4~.'~.:

: Pennsylvania

SCOT: :.. : SunOi.ico.lbuncan,Oklahoma. -Lati 1974

SCOT:'

.MarathonOiiCb.J :petrbit ,-Michigan' '

:-Murphy Oil Cp;/.~

:. :

I ~ ~~
: Late 1874

Merauit,'~ i~ouisi~ana

'"

~: ail'H"u'ton;::
: -:: i"" '"" - -:;:-

i:

':: :-

.... .-I~::
fable:4-l.:

(Cont.)

iISTI~G OF ANNOUNCED
TAIL GASTREATING

UNITS FOR CLAUSSULFUR

PLAWSS
ASOF3/1/!4

.::::

;i::-::::

Onstream.

Type
~Unit -: Company/Ldcation

'Da te

_NipponPetrdleumReiining

IFP ~
::

:?apan

:'IIdemitsu
pil/tlimejil
Japan

IFP

.:

IFP

1~971'.'

Japan
Chevron

es- -

ltd'. .:

Staridard

(Chevron Re;earch)/Nevis,
:Atta.',.

.IFP-.

Cbnada

Plant,

LT~

1'/300

.. 1/250 :

i97i.::

j:

I(ybkut;o~
Petrole-m'Industri

Claus

-1

Ij80 .

::~:~
1972'

.;

I :1

I (Mobi
1)/Chial-~Japan
'
.IFP

~N;mber/Capacity

Unl ts

' :~- :

Showa
.0~1:(Shell)jKawasaki
,.:

IFP :'~

' :

No.. of

I~

(Caitex)/Nesishil

Company~

' I

l/i0O.

:j

1s72::
: i :I 1

~ 1/260

.~.'-

; Mitsubishi Oii Company

(Getty)/ ~ .

1972 : .'

1/180

~Mirushimi~,
Japan

IFP

~Mitsubishi
oilCompany
(6etty)l
- . 1972: :1

IFP

I:

Phillips-PetrgleumjBorg~rl..:~
Texas - :`~.

''IFP

..~. MSiushilna, Japan

'~

:1973

1/45~,

i:

i :::

~:'.Ministr~
U.S.S.R.:

IFP j

Ministry
df:IGasjOrembourg
II, .I

1/350

1974 ..

.' 1/800

1/800

U.S.S.R.

ifP ~

- Ministry :of ~s/ qreff~ourgIII,

~U.S.S.R.

~:::
19i4

: 1/800

I:'~:

: Stauffer Chemi~ajl
Company/.~.
Delaware City;.Del.,

IFP

..

U.S.A.~-

~CospClonweal
th:Oi1~Refining/
i Pence, Puerto`Rico,

_;:IFP.j

:. 1973 '. Con'fidential: Gonfidential

;......

1/60

U.S.A.

' Koa:-~i!'
No. l)rularifu,japan~:

:. !FP : ... -1~ :PhjIlips/~lny.;-Texas.

::
-'~]Koa~
Oi1 No. ~
2/Ma
rjf3i'Japafi
:. .
::::Una~nounced/
::. L

1973.

' 19741
~ .._:.
-.'1975j::
:'
.

~.;:. .:.::: ::.1_1.. :~i.]: ; :.I:: :'

1 ': ~ :~/45

~;I'

._

4.3

PERFORMANCE
OF E~ISS~ONCONTROL
SYSTEMS
The Wellman-Lord,

all

guarantee

sulfur

sulfur

recovery

99.9 percent.
emissions

IFP-2,

Beavon,

emissions

including

less

the

The Sulfreen

Claus

SCOT and Cleanair

than200-300

ppmv, for an overall

sulfur

of better

including

Table4-2
emissions

the

Claus

summarizes

as discussed

a 1OT~-1
ong-ton-per-day
are also

inclu(jed

Emission

Source

plant

and IFP-1 are capable

to 1500-3000 ppm, for an overall

recov~ry

sulfur

the

above

than

of reducing

99.0Dercent

sulfur

sulfur

plant.

expected
both

processes

for

Claus sulfur.

concentration
emission

pi ant.

and mass

control

systems

on

Uncont rol led emi s s i ons

for comparison.
Test

Results

Four processes--the

rFP-1,

Wellman-Lord,

SCOT and Beavon--were

testedto determine
emissions
of SOZ.
H2Sandreduced
sulfurcompounds
(H2S,COSand CS2). The data gathered by these tests are presented
in figures

4-9 through 4-12.

The data represented

by black circles

is data gathered by the Agency, while the data represented

circles

is data gathered by refinery

Figure

test

4-9 summarizes

on the IFP-1 process.

by white

personnel or the LA APCD.

the results

obtained

from an emission

This process was not operating

on a

petroleum refinery sulfur recovery plant, but was operating on a large

Claus sulfur plant installed
however, is applicable

to refinery

levels achieved representative

process on a refinery

in a carbon disulfide plant.

sulfur

sulfur

The data,

plants and the emission

of'what: would be achieved by the IFP-1

plant.

of SO2ranged from 2300 to 2600 ppm.

4.23

As shown In Figure 4-9, emissions

Tahle 4-2.

CALCULATED
EMISSIONSFROYSULFURRECC)VER;Y
PROCESSES
IN PETROLEUM
REFINERIES
(Basis: In~ lon~ tons/dav sulfur ~7ant, 9nZ H2S fed)

Overall

Sulfur

Emissions nDmv, (Ib/hr

Removal-

Process

Efficiency

H2S

SOp

2 or 3 Stage Cl~us

95

6000 (200)

3000 (150)

Claus + Incineratora

95

trace

8000-

--

(POO)

Sg vanor

COS

CS2

Total as SOE

500 (120)

500 (30)

400 (30)

14,000 (900)
8000 (900)

--

--

trace --

trace -trace

jn,nnn

Claus .+ IFP-la

:r

trace

--

2~nn (190)

--

--

trace

--

--

2000 (190)

Claus + Sulfreena

99.0

trace

--

2000 (190)

--

--

trace --

trace --

3400 (190)

Claus + SCOT"

99.9

trace

--

200 (14)

--

--

trace --

trace --

200 (14.0)

Claus + Beavon

99.9+

Claus + Cleanair

99.9+

Claus + Wellman-Lord
Claus + IFP-2

--

--

--

--

--

75 (3.0)

75 (5.0)

225 (11)

<10

--

--

--

--

--

75 (3.0)

75

225 (11)

99.9

trace

--

250 (20)

--

--

trace

--

trace

--

250 (20)

99.9

trace

--

250 C2O)

--

--

trace

--

trace

--

250' (20)

Notes

aLevels.shown after

final

incineration

steo.

Figure4-9. SulfurIFP-1
Dioxide
Emis~~ons
Process

4000

Key

$ Rverage
~i EPATest Method
3000

o
p

vl

ru

''E
w

Other Test

O Method

2000

N
o
v,

1000

D1

Facility

Figure

4-10

summarizes

the

results

obtained

from emission

tests on a We'llman-Lord
process and a.SCOTprocess. Test 81
war conducted
personnel

by the

and tests

Agency,

test

82 was conducted

83 and C3 were

The Wellman-Lord

process

the SCOT process

is a reduction-scrubbing

incineration.

is

conducted

by refinery

by the

an oxidation-scrubbing

LA APCD.
process,

process

while

followed

by

Emissions of 302 from the Wellman-Lordprocess ranged

from 10 to 50 ppm and emissions

from the'SCOT

process

averaged

210 ppm.

Figures
emission
by the

4-11 and 4-12 summarize the results

tests
Agency,

and Tests

83,

on the
test

8eavon

Test

82 was conducted

E3 and F3 were

of H2S were undetectable

O to 7 ppm in-the

process.

by the

in four of these tests

fifth.

Emissions

from

B1 was conducted

by refinery

conducted

obtained

of reduced

personnel,
tA APCD.

Emissions

and ranged from

sulfur

compounds

(catculated as 302) generally ranged from 10 to 20 ppmin each

of

these

Vendor

tests.
Guarantees

Vendorsof the higher efficiency tail gas treatment processes

normallyguaranteeemissionsof total sulfur, expressedas S02

equivalent,not to exceed200to 500ppmv.[SOZequivalentis equal

to (SOp
c H25+ COS
c PCS2
+ sulfurvapor)expressed
in gas
concentrati ons only.l

The J.F. Pritchard Company.designedthe

Cleanair tail gas Drocess not to excedd 200 ppmv,250 Dpmv,and 3~n pomv
total sulfur emissions for their first
Union Oil Research

designed

the initial

4. 26

three installations.26~27,28
Beavon units

not to exceed

Figure 4-10.

Sulfur Dioxide Emissilll~s?n ,,

Wellman-Lord
Pro~~ssL~~3U,3'
SCOT Process3L

400 1

Key

Average

Uoo~
I

E
W

200

100

Al

A2

A3

C
Facility

EPA
TestMethod

i.

Other
Test
Method

Figure 4-11. Hydrogen

Sulfide Emissions33,34,35
Reavon

Process

Key
40

$ R*.ngp
C

P30

I EPATest ~ethod

v,
c
o

Other
fest
Method

ex,

v,

L~j

20

v,
cu

10

B1

B2

B3
Facility

Fl

Fl

Figure

4-12.

Reduced
~ulfurCompound
Emissions36,37,38
Reavon

Process

Key

400

$Averaee

V)

EPA Test

O-Other

r
p

Test

Method

r;
o

200
u-

v,

100

ce,
B1

B2

83
Facility

Fl

Method

Fl

210ppmvtotal sulfur emission;.~34

Shell Development
gaveemission
guarantees

installation

of 500 and 400 ppmv hydrogen sulfide~ for their

initial

of the SCOfprocess, though they have cited guarantees

as low as 300 pDmvH2S (before incineration)

in their literature.401"1,42

Davy Power Gas guaranteed 250 ppmvtotal sulfur as S02 on their

first U.S; Claus plant apPlication of the Mellman-Lord

system.43
Other tail gas processes which do not remove COSor CS2 usually
guarantee efficiencies
cannot~be

directly

of H2S and S02 removal. These guarantees

correlated

to a total

sulfur

emission

guarantee

becausethe concentrationsof COSand CS2vary accordingto Claus

feedstock composition and operating
catalytic

converter.

the IFP guarantee

conditions

in the first

An example of vendor emission

at one installation

stage

guarantees

of 9n percentremoval

is

of

H2S+ SOpin Claus tail ~as.44

Neitherof the Yendor

guarantees
s?eciPied
whetherthe concentrations quotedwereona dry or wetbasis or whethertheywereadjusted

to zeroDercent
oxvoen:
Therefore,
thefinallevelsof H2S
endS02
coulddiffer fromthe guaranteed
levelswhentheseconditionsare
taken into

account,

4.30

4.4

i.

REFERENCES

Gendo,Joseph M. andTam, SamuelS., "Characterization of Sulfur

from Refinery
Fuel
1974, pp. 66-68.

2.

'arthee6

et.

al.,

Gas,"

EPA Contract

~IFP Processes

for

68-02-0611,

Recovering

Task

H2S and

4, june

28,

Sfl2from

Claus Unit Tail Gas and for Cleaning 502 from Stack Gas, APCA
Paper

3.
4.

73-304.

Reference
Krill~

i, pp. 84-90.

H. and Storp,

K., "H,S Adsorbed from Tail

Gas," Chemical

Engineering 80~17),pp. 84-85, (July23, 1973)..

5.

Reference

6.

Potter,

1, pp, 52-55.

Brian H., and Earl, Christopher

Recovery

Process,"

presented

7.

Reference

i, pp. 68-71.

8.

Reference

2.

9.

Reference

i,

10.

po.

to the

B., "The Wellman-Lord SOZ

1973 Gas Conditioning

43-49.

Beavon, David D. and Vaell~, Raoul P., "TheBeavon Sulfur

Process for Purifying
Claus Plant Tail Gas," Proceedings,
Division

Conference.

of Refining,

1972,

Volume 52,

pp.

Removal
APT

267-276.

11.

Reference i, pp. 49-50.

12.

Landrum, L.H., Corn, L.H. and Fernald, W.E., "The Cleanair Sulphur
Process,"
presented at the 74th AIChE Meeting, New OrB~eans, March 11-15,
1973.

13.
14.

Reference i, pp. 60-66.

Naber, et.
presente~

al.,

"The Shell Claus Off-Gas Treating

at the 74th AIChE Meeting,

New Orleans,

Process,
March 11-15,

15.

Trip Report - "Visit to Wellman-Lord SO:, Recovery Unit,"

Industrial
Studies Branch, ESED, GAP, N~v. 2, 1973.

16.

Reference l,:p.

17.

Reference i, p. 71.

56.

4.31

1973.

C. Sedman,

18. Trio Report - "Visits to Beavon Sulfur RemovalUnits," C. Sedman,

Industrial

Studihs

Branch,

19.

Reference i, D. 45.

20.

Trip Report
Nov. 2,

- "Visits

ESED, GAP, Nov. 5, 1973.

to SCOT Units,"

C. Sedman, ESED, OAqBS, EPA,

1973.

21.

Reference

1, p. 63.

22.

Reference

i,

23;

Reference

i, pp. 72-73.

pg.

72-87.

24. Conversation,C. Sedman,ESED,OAdPS,

EPA,with Jim Nance,
Los Angeles

County

APCD, Dec.

11,

1974.

25. SourceTest ReeortNo.741SRY-4,

EPAContract
Na.68-02-0232,
Task Order No. ~34,EnvironmentalScience and Engineering,
Gainesville,

26.

Letter,

florida,

H.F. Schaffer,

June 1974.

GuTf Oil Company of Pennsylvania

to

Charles B. Sedman,~ESED, OAQPS,ERA, October 16,1973.

27. Letter, A.A. Muse, Jr., Atlantic Richfield Companyto

Charles B. Sedman, ESED, OAQPS,EPA, November 20, 1973.
28.

Letter,

F.A. eecker,

Gulf Oil Company-U.S. to Charles B. Sedman,

ESED, OAQPS, EPA, November 27, 1973.

29. Source Test Report No. 74-SRY-1,EPAContract No. 68-02-0232,

Task Order No. 34, Environmental Science and Engineering,
Gai nesvi lie , Fla. , March 1974.

30. Letter, ThronRiggs,.Standard

Oil Co.o~ Californiato C. Sedman,
ESED, OAQPS, EPA, dated August 9, 1974.

31. Source Testins Section Report Na. C-1895, Los Angeles County
APCD,February 28, 1973.

32. Source
TestSectionReportNo.C-2104,
LosAngeles
County
APCD,
April 25, 1974.
33. Source Test Report No..74-SRY-2, EPAContract No. 68-02-0232,
Task Order No. 34, Environmental Science and Engineering,
Gainesville,

Fla.,

March 1974.

34. Letter, GeorgeL. Tilley, UnionOil Company

of California, to
C. Sadman,ESED,
OAQPS,
EPA,dated August26, 1974.
4.32

35.

Source Test Section Report Na. C-226, Los Angeles County APCD,
November

6,

1974,

36.

Reference

30.

37.

Reference

31.

38.

Reference32.

39.

Letter,

D.L. Hanley,

B. Sedman,

40.: Private

December

12,

1974.

Union Oil Company of California

ESED, OAqPS, EPA, December

4,

to Charles

1973.

corrsnunication: David Hamilton, Douglas Oil Company,

to Charles

B. Sedman, ESED, OA9PS, EPA, October

16, 1973.

41.

Letter,
R.S. Little,
Champlin Petroleum Company to Charles
Sedman, ESED, OAqPS, ERA, October 24, 1973.

42.

Brochure,

"SCOT Process,"

Ford, Bacon and Davis,

Dallas,

B.
Tecas,

1973.

43. Letter,
Charles

Thron ~Riggs , Standard Oi1 Companyof California

B. Sedman,

ESED, OAQPS, EPA, December

44. Letter,~W.W. Turner, Stauffer

ESED, OAQPS, EPA, dated

June

4.33

12,

to

1973.

Chemical Companyto Don R. Goodwin,

14,

1974.

5.

MODIFICATION AND RECONSTRUCTION

Existing sources which are modified may become subject

to

standards of performanceunder section 111 of the Clean Air Act.

Any physical
results

or operational

in an increase

which a standard
a modified

in the

applies

source,

subject

The full

under

A - General

5.1

MODIFICATION

facility

which

with

of Part

to

to be considered
standards

of modification

.Provisions

facility

of any pollutant

to compliance

discussion

60,

is

of
included

40 CFR.

Of REFINERY SULFUR &I;BNT5

Under the General

to a facility

emissionrate

may cause that

performance.
Subpart

change to an existing

Provisions

resulting
not

of Part 60 40 CFR, physical

from routine

replacement

will

be

an increase

in production

considered

maintenance,
modifications.

taDacity

if this

repair
Also,

changes

or
neither

does not require

capital expenditure,as defined by 560.2(bb); nor theuse of

alternative

raw materials,

to acconnmodate

if the facility

materials,

will

was originally

be considered

designed

modifications.

The H2S gases processed in refinery sulfur plants are

produced throughout a petroleum refinery

in a number of

different process units.

Consequently, almost any change within

a petroleum refinery,such

as a change in the type of crude oil

processed,construc:tion
of newrefiner~yprocessunits, expansion
of existing

process units,

of various Process units,

of an existing

refinery

or even a change in the operation

could potentially

sulfur

plant.

5.1

lead to a modification

Changes such as these

generated
sulfur
are

within

the

could increase

refinery,

recovery

capacity.

overdesigned

tosome

leading

oil

changes

production

extent

production
crude

in refinery

in the

winter

processed.

have excess

changes within
in sulfur

recovery

months

plants,

due to

maximum fuel
to maximum gasoline

or to changes

in the typeS of

~efinery

and can

which require

however,

the refinery

(i.e.,

most

increased

of fluctuations

comnared

capacity

the refinery

recovery

within

operation

As a result,

sulfur

sulfur

in anticipation

in the summer months),

oil

to a need for

Most refinery

in the volume of H2S gasessgenerated

seasonal

the volume of H2S gases

sulfur

readily

plants

accommodate

only moderate

increases

capacity.

Where the increased volume of H2Sgases is more than

that

which

additional
existing

can be readily

plants

accommodated

haveusually

plants.

by existing

been constructed

While some expansion

through operation

this

require

stage

also

probably

to compensate

of the

Claus

In addition,

for

reaction

the

which

alterations

would

than expanding

sulfur

of anoth~r
~hift

accompany

to the existing

plants,

recovery

at higher pressure,

addition

unfavorable

rather

of ex'isting

plants would be possible

would

sulfur

Claus

in the
an inci~ase

furnace

catalyst

equilibrium
in pressure.

and sulfur

condensers

would probably also be necessary to provide increased ~ombustion

capacity

and increased

the expense
recovery

sulfur

and problems

plants,

plus

the

condensation

associated
desire

5.2

capacity.

with expansion
on the

part

As a result,
of existing

of many petroleum

sulPur

refineries

to have excess

sulfur

recovery

capacity

and more than one

sulfur

plant to compensate to some extent for the shut-down of a

sulfur

recovery

construct

plant

additional

existing

due to a malfunction,
sulfur

recovery

has led refineries

plants

rather

than

to

expand

ones.

Although as, discussed

recovery

in Claus plants

in Chapter

3 the efficiency

and hence emissions

of sulfur

from sulfur

plants

are dependenton the compositionof the H2Sgases processed (lower

concentrations
refinereies

decrease efficiency),

such

as those

mentioned

changes within petroleum

earlier

do not

lead

to significant

changes in the composition of the H2Sgases processed by refinery

sulfur

plants.

The amine treating

from the gases generated

by various

recover a gas stream containing

units which remove H2S

refinery

process

units

essentially

80-90 percent H2S regardless

of the

H2Scontent of the original process gas.

Occasionally,

however,

in response

regulations,

petroleum

to local

orstate

air

pollution

cont~rol

required

to control

plants.

These gases usually contain only 30-40 percent H2S and

similar

sour water stripper

concentrations

volume of these

of

ammonia.

In

refiner~4sshave

gases

some

are

in refinery

refineries

the

gases can be about the same as the total

of H2S gases produced by the amine treating

gases

been

mixed with

those

from ~the amine

units.
treating

sulfur

total

volume

If any of these
units,

the

concentration ofH2S in the gases processed by the sulfur plant

is lowered.

In addition,

since

the anrmonia present

5.3

in the sour

water stripper gases results in the formation of ammoniasulfates

in a Claus plant

which can lead to fouling

of the Claus catalyst,

the anunoniahas to be removed by incineration of the sour water

stripper

gases.

This contributes

to even greater

dilution

of the

gases arocessed by the sulfur Dlant because of the fuel and air
required

for

incineration.

Consequently,

stripper

gases

H2S gases produced by the amine treating

unitsin

appreciable
emissions

if sour water

extent

and fed to an existing

from the sulfur

the higher
recovery

sulfur

throughput

efficiency.

modification

plant

arefinery

sulfur

would increase

or not this

recovery

decrease

plant,

would

of both

in sulfur

be termed

would depend on the circumstances

involved.

of the sour water stripDer

into

to introduttion

to any

as a result

and the resulting

Whether

are mixed with the

gases

If prior

the sulfur

plant they were incinerated and vented to the atmosphere, SOp

emissions
general

from the refinery

provisions

as a whole would decrease.

of 40 CFR Part

6~,

in this

situation

Under the
the

sulfur

plant would not be considered as a modified source even though its

emissions

would

If,

however,

incinerated
into

increased.

these`sour

and vented

the sulfur

If the sulfur
gases,

have

recovery
recovery

such as changes

water

stripper

to the atmosphere
plant,
plant

this

required

gases
prior

to their

might be considered
alterations

to the Claus furnace

5.4

had not been

introduction
a modification.

to accommodate these

which requireda

capita~

expenditure
and the

sulfur

standards
plant

to carry out, then this would be considered a modification

recovery

plant

of performance.

required

decision

would -be subject

If,oon

no alteration

as to whether

this

the

to compliance

other

hand,

the

to accommodate

these

gases',

was a modification

would

with

sulfur

recovery

the

hinge

question..."Is

this a change in the method of operation?"

was the sulfur

plant originally

on the

(i.e.,

designed to process these gases?).

If this was concluded to be a change in the method of operation,

the sulfur
subject

recovery

plant

to compliance

The emission

as applicable

with

control

standards

sulfur

plants,

techniques

"add-on"

control

refinery

sulfur

since

techniques

discussed

plant.

sulfur

sulfur

these
which

change the characteristics

operate
the

discussed

in Chapter

~a catalyst

4.

in Chapter

4 are

techniques

are

independently
potential

are to new
essentially

of the

modifications

above ~Jould not.significantly

of the tail gas from the sulfur Plant and

thus would not prevent the use of any'of

discussed

source

plants asthey

control

In addition,

plants

a modified

of performance.

to modified refinery

refinery

of refinery

would be considered

While

change in the first

the

the control techniques

Cleanair

stage

process

catalyst

might

reactor

require

ofa

modified

refinery sulfur plant to reduce formation of COSand CS2, and

the fFP-1 or the Sulfreen
of additional

process

instrumentation

might require

and process

the installation

controls

to ensure

main-

tenance of the proDer H2S/S02ratio in the tail gas from the sulfur
plant,

these

requirements

are

minor

5.5

and could

be readily

accommodated

'

in a modified

re.finery

sulfur

pl~nt.

The Wellman-Lord,

SCOTprocesses,

however, could be installed

refinery

sulfur

plant

emission

control

as well

levels
5.2

techniques,

on modified

refinery

as on a new sulfur

existing

sulfur

plants

both

situations.

in

refinery

as readily

plant.

therefore,

on amodified

Each of these

can be.expected
sulfur

and emissions

Beavon or

plants

to function

as on new

could be reduced

to the same

RECONSTRUCTION OF REFINERY SULFUR PLANTS

Under the

General

Provisions

sources

which are reconstructed

subject

to compliance

of whether

of Part

may.be considered

with standards

emissions

increase

60 40 CFR, existing

as new sources

of performance,

or not.

regardless

An existing

source

will

be

consi;lered reconstructed, however, only if most of the separate

components

of thesource

An incremental
therefore,

is more likelyto

plant

capacity

it would probably

Construction

to an existing

would

not

however,

where

be considered

the

desired

modification
increase

to necessitate

to maintain

in

replacement

sulfur

plant,

the capacity

of the

a new.plant to provide the additional

above.

refinery

catalyst/sulfur

sulfur

plant

reconstruction.

at the same time with a resulting

this

a'potent~a!

components of an existing

of an additional

stage

increased

be considered

be more economical

discussed

sulfur~planti

would be sufficient

plant and construct

capacity.as

a refinery

In t~hose cases

of most of the separate

existing

replaced.

expansionpof

a reconstruction.

sulfur

are

would probably

be considered
5.6

If

condenser

to increase
sulfur

increase

efficiency

capacitv

were

in emissions,

a modlf~cation.

than

As with modified

techniques
sulfur

discussed

plants

be~reduced

refinery

sulfur

plants,

each of the emission

in Chapter 4 are as applicable

as to new.sulfur

to the same levels

plants.'
through

contrql

to reconstructed

Consequently,

emissions

the use of these

control

could

techniqueswhetherthe refinery sulfur.plants were n~ew

or reconstructed.

5.7

6.

Based

on the

alternative

discussion

emission

to serve

6.1

reactor

nresented

control

as the basis

system of emission
Claus

EMISSION CONTROL SYSTEMS

qvstems

emerge

for standards

reduction).

system

and

in the

the

oreceding

as nossible

of nerformance

These systems
tall

gas

chanters,

two

candidates

(i.e.,

the best

are the low temDerature

scrubbing

system.

LOW TEMPERATURE CLAVS REACTOR SYSTEM

As indicated

nreviously,

three-stage

Claus units

efficiency

of about 95%.

mav be added

which generally

to achieve

The low temnerature

comnlex

than.a

overall

sulfur'recovery

reduced

hv about

most sulfur

recovery
achieve

A low temnerature
an imDrovement

Claus catalyst

conventional

efficiency

8n to 85% over

a sulfur

in overall

reaction

recoverv
system

sulfur

recovery.

system ismuch more

sta~eand

to about 99%.
those

are two' or

Claus reactor

reaction

Claus

nlants

it

increases

Emissions

from conventional

are

Claus

nlants.

Like the conventional Claus, the emissions from the ~ow-temperature

system consist
Drier

essentially

to release

of 502. ~ncineration

to the atmosnhere

effectively

of the tail
converts.anv

gases
H2S

remaining, and any COSand CS2formed in the Claus reactors, to SOe.

As with
low-temnerature

the

conventional
Claus

two-

reactor

or three-stage

svsteh

denends

in the

gases

not lead to a significant

orocessed

by a Claus

increase

in emissions

6.1

unit,

onmaintenance

H2S/S02ratio in the gases in the sulfur nlant.

fluctuations

Claus

the
of

the

oroner

Consequently, minor
sulfur

plantthat

from a conventional

would

two- or three-stage
in emissions

unit are likely to result in an appreciable increase

from a low-temnerature

of maintaining

a 99% overall

Claus reactor

sulfur

s~vstem.

removal efficiency,

The problem

therefore,

Is

moredifficult than maintaininga 95%overall sulfur removal

efficienc_v.

Hence, emissions from a low-tem~grature

are likel~v to exhibit

two- or three-stage

considerably
conventional

magnitude

of emi.ssions

6.2

GAS SCRUBBING SYSTEM

TAIL

As discussed

more fluctuation
Claus unit,

Claus reactor

system

than those from a

although the absolute

would be much lower.

in Chapter

4, two different

scrubbing systems may beused to'reduce

types

of tail

gas

emissions from Claus sulfur

plants--reduotion/scrubbing systems or oxidation/scrubbing systems.

Either

type of system increases

99.9 percent,
stage

thereby

Claus sulfur

reducing

plant

syStems the tail

tSonal

emissions

and SCOT processes

gases-from the final

plant

Essentially

recovery

to about

from a.conventional

of the reduction/scrubbing

Claus sulfur

catalyst.

sulfur

ti(ro- or three-

by about 98-99 percent.

The Beavon, Cleanair

are repr~esentative

overall

are reduced

sulfur
through

discussed
systems.

in Chapter

In these

condenser of a conventhe use of a reduction

all the SO2 and about 80-85 percent qf the

COSand CS2is converted to H2S In the Beavonand Cleanair processes

the H2S is then absorbed in a scrubbing solution and converted
directly

to sulfur

via the Stretford

6.2

process (see Chapters 3 and 4).

In the SCOTprocess the H25 is absorbed in a scrubbing solution,

then desorbed and recycled back to ttie Claus sulfur
The Wellman-Lord and`IFP-e
the

oxidatlon/scrubbing

systems.

from an incinerator

ventional

processes

following

Claus sulfur

In.these
the

plant

final

are absorbed

plant.

are representative
systems
sulfur

the

of

tail

condenser

gases

of a on-

in an 502 scrubbing

sy~tem.

The502Is thenregenerated
andIn the We7lman-Lord
processrecvcled
to the~Claus

sulfur

plant.

In the IFP-2 process

the SO2is

with a small bypass gas stream from the HES gases

the sulfur
reactor,

plant

The off-gases

arethen

recycled

Emissions

502.

and then sent

from

Incineration

the

to a low temperature

from the low temperature

to the

processed

Claus

plant

by

Claus catalyst

Claus reactor

incinerator.

oxidation/scrubbing

of the tail

mixed

gases:from

systems

the.Claus

are

essentially

sulfur

plant

prior to en.terin~the Sd2scrubbing

systemeffectivelyconverts
any H2S. COSand CSpto S02. Emissions from the reduction/scrubbing
systems, however, can be either S02 or a mixture or H~SI COSand
CS2, depending on whetherr the tall
~are~incinerated
the

tail

gases

before

from the.final

plant effectively
percent

discharge

gases from the scrubbing system

to the atmosphere.

sulfur

converts allthe

of the COS and CS2 present

therefore,

released

to the

of a Claus

of

sulfur

502 to H2S, but only about 80-85

is converted

and C52 remaining is not absorbed-in

is,

condenser

Reduction

to H2S.

the HZS scrubbing system and

atmosphere

in the

tailgases

and CS2 along with some H2S, unless these gases are first

6.3

The COS

as CO5

incinerated.

Incineration effectively
to S02.

Incineration

atmosphere
part

is

of the

the

Maintaining

provided

nlants

gases before discharge

of the

SCOT process,

but

to the

it

is

not

processes.

overall

sulfur

gas scrubbing

is actually
bY.the

step

or Cleanair

the

by tail

Drovided

of the tail

final

Beavon

converts the~CnS, CS2 and H2Spresent

recovery

systems

efficiency

installed

Claus

reactor

percent

on Claus sulfur

less of a Droblem than mdintaininq

low-temnerature

of 99.9

the lower efficiency

system.

As discussed

above, this sstem.deoends on'maintenance of the H2S/S02ratio in~the

Claus catalyst reactors at 2/1 to achieve the level of overall sulfur

recovery

efficiency

from this

system

of which it
are

sensitive

is canahle.

Consequently,

to fluctuations

that

tend

emissions
to unset

this

ratio.

The tail

gas scrubbing

systems,

however,

do not depend ~on

maintainingthis rqtio~ofH2S/S02.Regardlessof whatthe ratio

of H2S/S02
maybe in the tail gases fromthe sulfur plant, all the HZS
is converted to S02 andabsbrbed in an S02 scrubbing~system, or all

the SOeis converted to H2Sand absorbed inan H2Sscrubbing system.

Neither

type of tail

to fluctuations

gas scrubbing

system,

in the gases processed

operation,

these

systems

sequently,

fluctuations

systems

are

minimal

percent

is achieved

serve

therefore,

by the sulfur

is sensitive
plant

to dampen out fluctuations.

in emissions
and an overall

from these
sulfur

under essentially

6.4

tail

recovery

and in
Con-

gas scrubbing
of about

all normal operating

99.9

conditions.

7.
Refinerrv sulfur
emissions
these

within

ENVIRONMENTAL
IMPACT
plants

are major point

petroleum

emissions

result

refineries,

sources

of sulfur

As discussed

from treatment

of the

gases

dioxide

in Chapter
Droduced

3,

by various

sulfur remeval Drocesses within the refinery.

A typical uncontroiieb

sulfur

recovers about 95X

plant (two- or three-stage

of the sulfur

CTaus plant)

in the incoming gas stream;

dioxide are usually

have

been

in Chapter
identified'

reduction:

6,

is to limit

two alternative

as candidates

various

of sulfur

in the range of 8,000 to 10,000 ppm. The objective

of new source performance standards

As discussed

Thus, emissions

for

low temperature

and a number of tail-gas

these emissions.

emission
the

best

extended

control

system

Claus

systems

of emission

reaction

systems

scrubbing systems. The extendedClaus

reaction systems result in residual emissions of SO2. The tail-gas

scrubbing systems emolov oxidation or reduction-processes 'anb

result in residual emissions of SO2(oxidation) or H2S, COS,and CSE

(reduction).
overall

The reduction

lowest

level

In a~sessin~
of performance
control
could

achieved
serve

of

system generally,

for refinery

sulfur

impact associatedwith
Dlants,

by each alternative
basis

for

standards

against emissions from'uncontrolled

from olants
lations.

controlled.to
Other

facets

leads

to the

emissions.

the environmental

as the

however,

the degree

emission

plants,

of emission

control

needsoo;be

standards

system which

compared

but against

not

only

emissions

meet State Implementation Plan (SIP) ~eguof environmental

7.)

impact;

such

as potential

water pollution,
need

solid waste generation

to be assessed

in the

and energy consumption also

same manner.

As discussed in Chapter 3, most SIP's require new refinery

sulfur~plants

to achieve an overall sulfur recovery of 99 percent.

Thisrequires

a level of emission controlequivalent

control alternative

I.

to emission

A few SIP's, however, require an overall

sulfur recovery of~only~96percent. This level of sulfur recoverv

can be achievedby conventionalthree-stage Claus plants which,

from the point
uncontrolled

of view of this'document,
plants.

Similarly,

are considered

a few local

air

to represent

pollution

control

agencies require an overall sulfur recovery~of 99.9 percent.

is equivalent to emissioncontrol

~alternative II.

of states which.contain no refineries

This

Finally, a number

or oil and gas production facilities

locatedwithin their bordershaveno air pollution regulationslimitin~

emissions from refinery
7.1

Ambient Airquality

sulfur

plants.

Impact

The~healthandwelfareeffects of S02havebeenwell documented!

Thehealthandwelfareeffects of HgSICOS
andCS2,however,
are
not as well documented
as those of SOp. Table7.1 summarizes
the majorhealth andwelfareeffects ~known
to result fromexoosure

to variouslevels of thesepollutants. Ofthe three (H2S,COS,

and CSp),H2SaDPearsto be the most harmful.~It can lead to

death:-.atconcentrationsexceedin~1,500,000~I~/m3
whilecontinuous
exposure to concentrations as low as 15,0~~ ~~/m3 leads .to
7.2

Table

Health and Yelfare LWecb

Pollvtant

1
Hvd~en
Sulllde
nlll.. IPIr11a1s,

"9~9;'"
4

No reoorted

effect

Tarnlrhlnq

of silver

conner after

45

503

CarbonDlrulflde (tS2jL
Plants

HunanHealth

and

Plants

(Untnam)

(un~nom)

(Untnoun)

(Vntnmn)

(Uanam)

(Untn~n)

(Vn~no~)

(Un~nc~m)

(Unkn~nm)

(unmcwn)

(utltMlwn]

~Udnam)

of metallic
2 hn.

as

alfalfa,

adOr threshold

barley

cotton

IL.~M

prsrupt!ono:' loproductiye
proce,sl

15,800

Eve irritation

Yl.rm

aa. Ilmable
oecullttonal

emorure

Is *amn

~a..Illonble
a hr.

(KBIH)

occupational
(ACGIH)

ernorure

15,003

oe
=n

Animals
Wterlals
..

43 hrs.

- InJurY to certain crops

such

lo 61

CarbonvlSulfide (COS

Definite
nercention
of smell

3,51()

Animals Watcr~alr Plants

--.L---L~

`
Discoloration
paints
after

to H2S, t52 and COS

and

Ddor threshold

75

t.l

ofExnosure

1W.r)n)

Olfactorv
fatfpw.ln
2-5 min.
Death In 8-48 bra.

~m,rwn

Danqcro~r after

500,0110

Death after 30 min.

30 min.

In~un

to most Dlants

Slight narcotic effect On

mrvous

1.SYl,lrvl

Ilsndlate
loss of consciousness follo*cd by raold

~=

death

system

after

a leu

boors

503 injury to tobacco

plants after 1M min.:

taratoes after JO min.

nO

Pa

2.MO,M~

No effect noted on laboratory

rabbits

3,200,001

flrious narcotic effect on

lo.rlol,nm

Dan~Krou)alter JOmln.

LS,nM),OM)

lkath

nervous

noter:

I.'~c(CrmEe

2.

system

after

after

30 min.

30 min.

(UnLmnm)

(Untnom)

Death of laboratory rabbits

after

35 min.

symptoms such as conjunctivitis,

For occuPational

Industrial

exposure

Hygienists

sleeolessness,

and pain in the eyes.

the American Conference

of Governmental.

(ACGIH)has set a 4-hour-Der-week exposure

limit of 15,0rlfl tq/m3. The effects of H2Son domestic animals narallel

those

on humans,

while

concentrations.
especially

appreciable

damage to plants

H2S will also cause significant

metallic

and ~inted

surfaces.

may occur

at

lower

damage to materials,

Metals,

such as silver

or copper,

will be tarnishedwhenexDosed
to levels as lowas 4 ~l/m32
ExDeriencewith the use of CS2in the textile and rubber manufacturing

industries,

and to a lesser

degree

from~toxicoloqical

studies,

has shown it to be highly toxic at concentrations approaching 1,0T)n,0OT)rrl/m3.

Workers

exposed

experienced
heart

to lesser

a.variety

disease,

processes

of symptoms,

high

blood

in women (i.e.

pathological
Some of these

changes
effects

concentrations

includinq

pressure,

a number
mental

and changes

disruption

with

as low as 14,000 ~g/m3. The ACGIHlimit

have

coronarv

in normal

composition

been observed

of years

illness,

of the menstrual

in the cellular
have

over

reproductive

cycle

of vaginal

industrial

and
smears).

exposures

for occupational

exposure

to C52,
however,
hasbeen
established
at 67,R57
~q/m3.
It should
be'noted that several countries have established lower occupational

ex~osurelimits, including the USSR

whereit is set at 4553~p/m3.3~4
Comparatively

effects

little

of COS.

information

It appears,

however,

is

available

that

this

relative

to the

compound is less

tox5c than HES or CS2. One study using laboratory

rabbits

indicates

the lethal dosaqeis about~wicethat of CS2.4

To assess

Performance

the

for

environmental

refinery

sulfur

imDact

plants,

7.4

associated

with

standards

of

the maximum impact on ambient

air quality

of emissions from sulfur

The dispersion

model used for estimating

trations

for

Single

Source

averaging

times

Division.

the

Source

year of hourly

stabili

input

by EPA's Meteorology

estimates

Model estimates

for

twomajor

petroleum

model

a 100 LT/B Claus

were

averaging

to the Single

ty-wind-temperature

Chicago,

refining

plant

concen-

from one hour to one year was the

Concentration

the meteorological

is

ranging

maximum ambient air

(CRSTER) Model developed

Assessment

Single

recovery plants was analyzed.

extrapolated

times

less

from

than

one hour.

Source Model`consists

of one

data from Houston and

cities.

with

and

The emission

a stackheight

source

of 5n meters;

which would likely accompanya refinery capacity of about li~T),OClr)

BBL/day.
Tn addition

It was also

to assuming

assumed that

that

fugitive

emissions

are

from a single

emissions

do not exist,

stack,

and adverse

downwash phenomena (which sometimes occur in the lee of stacks or

nearby structures)

do.not

problems

existed,

estimate

the resultant

occur.

a special

If fugitive

dispersion

air quality

emissions

analysis

imPact.

or downwash

would be required~to

It should

be not~d in passing

that such problems can result in ambient concentrations, several times

greater

than

those

predicted

Maximum ambient
to occur

plant.

from

The 24-hour

when there
direction

about

are
at

or near-neutral'

air
0.6

analysis.

concentrations
to 1.6

(see Table 7.2)were

kilometers

and 8-hour maxima will

several,

about

in this

hours

3-7 meters

atmospheric

during
per
stability

7.5

which
second

from the

sulfur

most likely
the wind
and during

condition

is

recovery

occur on days
from a single

whfch

exists.

estimated

a neutral
The one-hour

Table

Estimated

Maximum Ambient

7.2

Air

Pollutant

Concentrations

Stack

Pollutant
Base

Concentration
(Dpm)

2-10 sec.

5 min.

Ambient Air Concentration (rs/m3

15 min.
30 min.
Ihr.
8 hr.

24 hr.

1 yr.

Case

502

9250

860

345

175

15

180

80

25

25

11

<1

Alternative'I

SO2
Alternative
Oxidation

2000
II

SOp

300

--

Redudtion

H3S
CdS

10

100

CSZ

95

aoO LT/day refinery

sulfur

~2

380

25

30

15

540

35

15

10

10

Note:

i.

plant.

Overall sulfur

recovery of 95 percent.

maxima will

occur during

conditions,

accbm~anied

meters
range

per second.
from about

will

the

by light

slightly

wind'speeds

-The downwind distance

0.4to'1.6

unstable

atmosnheric

on the orderof

to the one-hour

1 to 2
maxima will

kilometers.

For averaging times less~than

one hour, the peak concentrations

most likely

winds and unst8ble

conditions.
times

unstable~or

occur under light

The peak

of less

than

contintrations

one hour

will

listed
occur

in Table

atmospheric
7.2

for

approximately'0.5

averaging

kilometers

from

source.

The predicted

concentrations

maximum ground-level

of S02froma

typical

24-hour

and i-year

uncontrolled

ambient air

100 LTlday sulfur

plant are 175 rFl/m3

and 15 ~g/m3,respectively. Theselevels are
well below the corresponding

national

ambient air quality

standards

(NAA9S)
for S02of 365 ~g/m3and 80 tFi/m3,respectively. Basedon
this

analysis,

it

appears'that

emissions

from

uncontrolled

refine~ry

sulfur plants will not by themselves, lead td adverse health or welfare

effects.
sulfur

It

should

recovery

emissions

be kept

plants

from petroleum

themselves arewsually
contain

other

from this

sulfur

major

not

the

only

refineries,

that

source

and that

SOUrCeS: Of SUlfUr
is

apparent

major contribultors

-dloxide
that

to.hiah

emissions

of sulfur
petroleum

located in major industrial

perspective,~it

plants-are

are

in mind,'however,

from

dioxide
refineries

areas whidh normally

emissions.-

uncontrolled

ambient air

Consi dered
refinery

concentrations

of S02, accounting for about 50 percent of the 24-hour and about

20 percent

of the one-year~NAA~S for SO;! in this

7.7

analysis.

It appears

from fable

7.2 that

emission

control

alternative

(low temperature extended Claus reaction) reduces the.maxirmm24-hour

ambient air S02 concentration
one-year ambtent'air
(tail
air

tail

S02 concentration

gas scrubbing),
concentrations

assuming

by a .factor of 7 and the maxina~m

on the other
to essentially

an oxidat!on

tail

by a factor

hand, reduces
zero for all

gas scrubbing

dk 3.
these

practical

Alternative

II

maximum ambiebt
purposes,

system is en~oloyed.

If a reduction

gas scrubbing system is employed, emissions of S02 are eliminated.

Use of a reduction
CS2 which resultj

system, however, leads to emissions of HZS, COSand

in low ambient air concentrations

Specifically,

alternative

of these pollutants.

I reduces the maximum24-hour ambient air

S02 concentr8tion to 25 t~g/m3

and the maximum
one-year ambient air

S02concentrationto 5 Fg/m3~~
If an oxidationsystemis employed,
alternative

II reduces

the maximum 24-~our

and one-year

ambient air

S02 c0"centrations to 4 ~g/m3and <1 FFl/m3,

respectively.

If a reduction
system
is e~l~ed,alternative
II leadstomaximum
2-10 second an~ient air concentrations of H2S, COSand CS2 of

25, 380 and 540.rFl/m3and maximum

one-hour ambient air.concentrations
of i, 7 and'l0- d/m3, respectively.

Althoughthe maximum
2-i0 second

ambient air concentrations qCiH2S,COSand CS2could lead to odor eroblems

or material corrosion problems.if they persisted for longer periods

tone to two hours), the ambient air quality modelingindicates these

concentrations are only ofshort duration.

As shown in Table 7.2,

beyond2-10 seconds the maximum

ambient air concentrations of H2S,.
COSand CS2decrease rapidly and fall well below the threshold limits
for

odor

or material

corrosion

Droblems.

t.8~

Undernormal operation, er;lissions from the reduction emission

control systems are no higher than 10 ppmH25 and 95-100 ppmfor both
005 and CS2 and, as discussed above, the resulting ambient air
concentrations
that

no

of these

adverse

~ollutants

health

or

welfare

and CS2, how~ver,~may increase

high

as 10~0 ppm, if

the

are

sufficiently

not

likely

high

on our present

arise.

approaching

used

reduction

in the

earlier,

in ambient

adverse

most

on alternativeI

air quality.

would

there

Based~on

the

air

levels

as

systems

are

concentrations

health

or welfare

SIP's

require

anoverall

have

little

effects,

based

sulfur

recovery

Consequently,standards

or no impact

subject

to NSPS.

ambient

air

II,

per year.of

502.

on ambient

sulfur

therefore,

of standards

on ambient

presented
plant

the

air

in ChaDter
capaci.tv

beneficial

8,

wilT' be

imPact

in 198~ based an emission

would be to reduce emissions

Water Pollution
Petroleum

imDact

projections

of refinery

Nationwide,

quality

alternative

be a beneficial

growth

bv 1980 some 8100 LTlday

7.2

COS

Only if standards are based onemission control

11 will

quality.

of

However,even at this level these

equivalent to emission control alternative I.

alternative

Emissions

knowledge.

As noted

based

to ensure

considerably,

~to result

to pose

be low enough

effects

catalysts

permitted to deteriorate.3
emissions

will

on

control

by some'55,00r)

tons

Impact

refineries

normally

waste water and can be majbr point

The amount of waste water-discharged

7.9

discharge
sources

large

volumes of

of water pollution.

varies greatly

from refinery

to-refinery,

however,

units'within'

the refinery and the degree of water reuse.

~otentidl

and depends

waterodllutlon

refinery

is

poi lutant

imPact

summarized

with the usebfbest

on both

bfa

in Table

practical

~aischarges,

the

types

of process

The

typical

lrlr),000

As this

table

shows,`even

techndlogy'to

limitwater

7.3.~

central

bbl/day

thi s impact' can be si~gnificant.

Petroleum~ refinery-

Claus sulfur

plants:6y

stream.

comparison

aenerate

an Cxtremely

smal~l waste water

condensation

of water vapor contained in the H2S gases as they

flow from the amine scrubbing

units

This s.tream results

to the.Claus

sulfur

%rom

plant.

:Alth~ough ~thqs sour water -condensate

norinally

contains

1500-2Oa0 ppm

'tl2S and:up~td-'lr)r)r) ppm ammonia,the

volume ofwater-involved

is

usually~less than n.25 liter per minute, and this is easily

handled

in the

refinery~'s

waste

water-'treatment

facilities.

In:.

terms of'the e~amDlepresented above, this is about'0.25 m3/day,

or l-ess than n.Or)2-percentof

the-totdl

discharged~bya

refinery.

moderate

The potential
alternative

di scharged
that

casethis

Table~7.4

various

sys tems .

than

water

polluti.on.impact

emission'control

negligible.
of the

size

waste

waste w`ater:effluent

of

the

s~ystems.outlined

summarizes
water

streams

two

in

Chapter

the characteristic~
discharped

routinely

by each

6 is

and.flow

rates

of these

As t.his table shows, althou~h.-the volume of waste water

by ~same of these emiss i on control
discharged
is~less~than

by the

Claus

50 litersper

7,10

sulfur

.processes

nlant,

minute,

even
which.is

-is l-arger
in.-the
less

worst
than

Table

Water

Pollution

'7,9

Impact

of a Typical

100,000 bbllday Petroleum Refineryl

1

Effluent

flowrate,

m3/day

13,500

Pollutant Load, kg/day

RawWater

BPCT2

COD .

1800

BODg

4500

TOC

1400

350

700

150

TSS
Oil

Phenolics

700

200

1100

150

Ammoni a

450

Sulfides

20

70
1
100
1

Notes:

1.

Development Document for Proposed ~ffluent

Guidelines

Petroleum
Division,
Protection
2.

Best

and

New Source

Performance.Standards

Limitations
for

the

Refining Point Source Category, Effluent Guidelines

Office of Air and Water Pro~rams, Environmental
Agency, December 1973, EPA/44O/1-73/014.

practical

central

technology.

7.11

Table

7.4

Potential
Water
PollutionImpact
of
Refinery Sulfur Plant NSPS'

mo

Amount
DlscharRedWarte
Water
Characteriltfcs

~X

Base Case

co=

7mlTT7b
Claus
SulfurEmission

Control

SourWater
Condenrate n.25llteisWil.

1500-2000

ppm H2S

1000 oomNHJ

Alternatives

AlternativeI

CatalystWash

s28,000Ifters/e years

~X Organic

Solvent

e51Al:~(Wl~~et:l
Salts
Alternative

II

nxldatlon/Scrubhlno Processes

Wellman-Lord

S6UrWaterCondensate

ScrubbingSolution Purge

20 liters/min.

oHs2

15 liters/min.

25%~o~lumSalts
758

IFP-2
Reduction/Scrubbing

SourWater
Condensate
Catalyst Wash

20liters/min.

~28,0001lters/2 years

Water

Same
AsAbove

SameAs Alternative II

Process

Beavon

SburWater
Condensate
ScrubbingSolution Purge

45liters/min..
5 liters/min.

.?

51)ppm
H2S
Trace NH3

21X,
SodlumSalts
98% Water

Cleanalr

SourWaferCondensate
Scrubbing Solution Purge

SCOT

note:

i,

Reference i,

SourWater;Condensate

~45 liters/min.

SameAsAbove

5 liters/min.

SameAs Above

45 liters/min,

SameAsAbove

n.5

percent

of

by a tynical

the

total

emission control
is negligible.

water

is

this

required

to restore

this

contai-ns

about

for the Claus catalyst

water

stream,

waste

water

treatment

1 percent

impact

emission control
than

however,

that

generated

of a sour water

sulfur
salts.
varies

plant,

and, whendischargea,
solvent

and about 20-25 percent

metal salts).

treated

to prevent

streams

of the organic

(alkali

can be easily

additional

As shown in

are required

in the

any adverse

This
refinery

water

from arising.

pollution impact associated with ~aiternative II

svsfems (tail-gas
associated

with

alternative

although slightly
I`systems,

Is

also

purDebes. Generally, the waste water

by the various
condensate,

scrubbing),

tail-gas

similar

scrubbing

to that

and a purge stream containing

The amount and conposition

depending

washing of the

activitv.

glycol),

itself

facilities

negligible for all practical

streams

generate

waste water

by weight

(polyalkyene

The potential'water

greater

not

intermittent

ofwater

alternative

extended Claus reaction)

does

catalyst

of the Claus catalyst

waste

discharged

with

After about two years of operation,

some 28,000 liters

pollution

routinely

associated

alternative

continuously,

Table 7.4,
water

impact

systems (low temperature

streams

are generated.

effluent

refinery.

pollution

Although

waste water

by weight

water

10r),Or)r) bb'l/day

The potential

catalyst

waste

on the particular

processes

generated

either

consist

by the Claus

organic or inorganic

of these

waste water streams

tail-gas

scrubbing

process

used.

The sour water condensate is produced by cooling of the gases pri or

7.13

1.

to the scrubbing

tower,

cases

a build-up

to prevent

and the purge stream

of impurities

is necessary

in most

in the scrubbing

solutions.

As shown in Table 7.4, the amount of sour watercondensate

generated

by these

20 to 45 li:ters

tail

gas scrubbing

acidic.in

nature

oxidation/scrubbing

emission

control

reduction/scrubbing

system.is

used,

`These

refinerl'siwaste

ran9eof

plant.

with -a pH of about. 2 if'an

system is employed.
this

stream

If-;a

is.usuallyonly

containing about 50 ppmH2Sand a trace of amnonia.

streams,-ho~ever;

stream~i~li~harged

is.inthe

per minute for a ln0 LTlday Claus sulfur

This streamis.-usually.

slight'ly.-addic;

processes

can be addedto~thesour

bythe.Claus
watec

sulfur

treatment

Dlant

water.condensate.
for

treatment

inthe

facilities,

For p 100 LT/.day Claus pulfurplant,

the purge st~am from

an oxi:dati on/sc~ubbing emission control.system, such. as the We!!ma~nLord process,~is

in.the

streamconsjsts

range

of 15 liters

essentially.of.a

solution

per minute.

This

of sodium salts

in water and~~pe?eral!~has theL;fol.lowing composition:5

Na2S04

5 percent by weight

NaHS03

5 percentby weight

~Ya2S03'

15percentbyweight

H~O

75 percent by weight

`1

This ftream could tje treated in the refinery waste water

treatment systemGiithoutrli~ffi
culty, or it could'be treated by

7.14

the NICE
orocessdeveloped
by NittetuChemical
Engineering
Ltd.6
The NICEProcess recovers the sodium as~sodium carbonate.(Na2C03)
or soda
sodium

ash,

which

can be used

sulfite/sodium

Davy Power'Gas,

bisulfite

the developer

to Provide

the

necessary

solution

to the

make-up

Wellman-Lord

of the Wellman-Lord process,

process.

is also

developing
a treatmentprocessfor this purgestream.7'tonsequently,
disposal
water

of this

waste

pollution

Unlike
emission

stream

will

not

lead

to

any adverse

impact.

the Wellman-Lord process,

control

'system,

process is essentially
of a third-stage

scrubber.

water

the other

the IFP-2 process,

has no purge stream.

an upgraded alternative

low temperature

Claus

oxidation/scwbbing.

reactor

This

I process and consists

followed

by an ammonia

The only waste water streams discharge(l are the sour water

condensate stream which is commonto`all

and an intermittent
low temperature

waste
Claus

water

catalyst

the tail-~gas scrubbing processes,

stream.resulting
everY

two years

from washing
as mentioned

of the
earlier.

Thus, there is esseetiallv no potential water pollution impact

associated

with

The purge
system,such

use

of

stream

as the

this

stream

IFP-2

Drocess.

from a reduction/scrubbing

Beavon

100 LT/day Claus sulfur

per minute.

the

or Cleanair

process,

emission
installed

control
on a

plant is in the range of 5 liters

As with the purge stream from the Wellman-Ldrdprocess,

consists

essentially

of a solution

of sodium

in water and 9enerally has the followingcomposition:8

7.15

salts

Na2C03

0.5 percent by weight

Na2S2O3

0.5 percent by weight

NaSCN

0.5

percent

by weight

0.5

percent

by weight

Misc.

Sodium Salts

H20

98.n Percent

This stream.could

by weight

also be treated

in-th-~'refinery

wastewater treatment systemwithout difficulty. or treated by thP

NICE process

carbonate

to

could

recover

the

jodium

be used

to provide

as

sodium

the

carbonate.

necessary

The

make-up

sodium

solution

to the Stretford scrubbing unit of the seavon or Cleanair processes.

The potential

water

pollution

the Beavon or Cleanair

impact

processes,

associated

therefore,

with the use of

is negligible.

The SCOTprocess, which is also a reduction/scrubbing emission

control system, does'not generate a purge stwam: Aswi.ththe

IFP-2 process
by this

mentioned

Drocess

is

the

above,
sour

be added to the sour water

Claus sulfur
treatment

plant

two alternative
can be treated

stream

stream

stre~am,

in the refinery's

all

without

Considering

can

by the

waste water
would result

impact.

the waste water

difficulty

generated

which

generated

Thus, use of the SCOT process

emission control

facilities.

condensate

condensate

no water pollution

In conclusion,

treatment

water

for treatment

facilities.

in essentially

the only waste water

streams

generated

by the

systems outlined

in Chapter 6

in the refinery's

waste water

the

small

amount

of waste

waterdischarged
bytheseemission
controlsystems,thepotentia;
water

pollution

negligible,

whether

emission control
refinery's

impact of NSPS for refinery

sulfur

they are based on alternative

plants

will

I or alternative

systems, because of the magnitude of dilution

waste water treatment

7,16

facilities.

be
II

in the

Also, since these waste

water streams

are so small,

of petroleum
7.3

with

refineries
Waste

There

is essentially
plant

II emission

catalysts,

impurities

standards

control

regulations.

itself

waste

based

requires

on ei~~her

periodic

associated

alternative

I or

is

replacement

of the

depending

upon the

of replacement

in the acid gas feed.

or alumina,

impact

rsystems.

the frequency

present

made of bauxite

effluent

no potential.solid

The Claus process

reaction'

quality

Impact

sulfur

alternative

have no.Srr~padt on the abilS'ty

to meet water

Solid

refinerv

they will

Usually

regenerated

the catalyst,

annually

until

a substantial

loss of activityoccurs,normally
in twoto fiveyears.9 Fora InnLT/D
Claus plant,.~eplacement

of the catalyst:would

mately 70 tons of spent catalyst,

(a natural

oxides/hydroxides)

are both non-toxic

system alternhtive

catalyst

replacemei~t

As far

alternative

emission

tail

Alumina (aluminum

aluminum and manganese

materials.

affect

of approxi-

Neither

the rate

emission

or quantity

of

in the Claus plant.

I systems

the oxidation
any.solid

the

mixture of iron,

will

disposal

usually in landfills.

oxide) and bauxite

control

require

control

systems

(low'temperature

themselves,

extended

neither

Claus reaction)

gas scrubbing systems (alternative

waste.

The reduction

do requlre.oeriodic

replacement

tail

gas scrubbing

of the reduction

the

nor

II) generate
systems,

catalysts

how8ver,
about

everytwoyears.l0 Thesecatalystsusuallyhavesignificantsalvage
value, bei no con~oeeed primarf ly~ of colbat t-molyb4enum, and consequently ,
are normally
reduction

returned

to a vendor for renracessing.

tai~f gas scrubbing

systems

waste.

7.17

generate

Hence, even the

essentially

nosolid

7.4

Energy

Impact

Although

not

a significant
petroleum

and fuel

amount
products

oils,

or high

generally

of energy

such

etc.

conversion

recognized,

petroleum

in processing

as petrochemical

The energy
refinery,

crude

oil

feedstocks,

requirements

for

refineries

example,

consume

intovarious
gasolines,

of a typical
usually

moderate

represent

about

10Dercentof the crudeoil throughput.llThus,the energyconsumption

of a nominal
10,000

10r1,000

bbl/day
The-energy

bbl/day

of fuel

oil,

refinery

or some 250,000

requi'rements

smal'l in comparison.

is equivalent

of refinery

to about

kw-hr/hr.

sulfur

plants

are

A 10O LTlday Claus sulfur

plant,

for example,

tyDically consumesless than 1000kw-hr/hrof energy,l2 or

than

0.5

Itself.

percent

of the

energy

Consequently,

emissions

of sulfur

dioxide

or hydrogen

does not significantly

associated

with petroleum

emission

impact

central

within

the

the use of Claus'sulfur

refineries

The energy

consumed

less

refinerv

to control

at petroleum

the energy'requirements

refining.

associated

systems

plants

sulfide

increase

petroleum

quite

with

outlined

each

in Chapter

6f the

alternative

6 is summarized in

Table 7.5. As this table shows,the impactIs negligible in all

cases.

(i.e.
tail

Alternative

I. for example,

has a slight

energy

benefit

overall energv consunption.ls reduced somewhat).due to reduced

gas inci-neration

requirements.

Alternative

TI, on the other

hand, has a slight energy penalty or a moderate energy benefit,

dependingon whether an oxidatian or reduction tail gas scrubbing

emission control

system is emploved and on whether tail

7:18

gas reheat

is required
control
must

to increase

agencies

be above

plume bouyancy.

require

thatgases

a certain

A few local

discharged

minimum temperature

Alternative
control

II has a slight

agencies,

however,

and in most cases

tail

plumedispersion.
either

a Slight

depending

into

to

bouyancy and thus good plume dispersion.'

air

the a~tmosphere

insure

good plume

Under these conditions,

energy penalty.

Most local'

do not have requirements

gas reheat

pollution

is not necessary

air

pollution

of this

nature

to obtain

good

Underthese conditions, Alternative II has

energy penalty

on whether

or a moderate

an oxidation

energy benefit,

system or a reduction

system is

employed. The moderate energy benefit associated with the reductiontail

gas scrubbing

system

arises

because

of reduced

tail

gas incinera~ion

requirements.

As mentionedearlier
refinery
This

sulfur

requires

Consequentl~y,
sulfur

plant

in'thSs

Dlants
a level

to achieve
of emission

if alternative
NSPS, there

will

chapter,

most SIP's

an overall
control

I is selected
be no energy

sulfur

equivalent

require

recoveSy of 99 percent.
to alternative

as the basis
impact

new

1.

for refinery

associated

with

the

standards.

If NSPS are based on alte'rnatvvelI,'

there will be either

a slight energy penaltv or a moderate energy benefit associated

with~the standards in all but those.fewlocalities whichalready

require

this type of emission control

vary from refinery

or a reduction

tail

to refinery

system.

This impact will

depending on whether an oxidation

gas scrubbing system is err~bloyed to comply with

the MPS. As.shown

in Table7.5, useof an oxidationtall gas
7.19

ENERGY IMPACT OF ALTERNATIVE EMIS~InN

Rase Casea'c

Energy Consumptldh
(Gains)

'100 LT/DClaus
:Sulfur Plant

Alternative I

Ib,c

CONTROL SYSTEYS

Ib,e

Alternative II
Tail Gas ~cruhbing

LoW Temperature

Extended ClausReadtion

. ~xidation System
W/OReheat
w~JReheat

Fuel," MMRtu/hr

8.2.

Process

Tncineratidh

8.2;

-8. i':

ReductionSystem_
wlo Reheat ~j/ Reheat

1.77

1.7

- 5.76

5.76

Electricity
k#-hr/hr

. : 140

Steam,EIb/hr
Hiah Pressu~e3

'

: (18';000)

(7,800)

' (7i800)

- i894)

: (1,049)

960_

805

Total,kw-hr/hr

Steam'Credlt5:

Yithout

175

' (18,000)

Low Pressure"
Yith

Steam Cled~t

300

300

: ( 18 ,000j
-

(18,0011)

(4,950)

(4,950)

(950)
'1,120

'-

(38r))

'1,690

370

370

( 18,000)

( 18,000)

(7,500)

(7,500)

(1,300)

..(735)

. 540

Notes

i. mcludes:~ner~y i;onsumptionof Claus sulfur plant.

2. Does not.include steam which could be produced if tail gas incinerat:ors kere- equipped to recover waste heat.
3~
4.

Produced at 550 psig:and 750"5.

Produced at 50 psig and saturated.

5.

Conversions

tokw-hr/hr

as

follows:

Fuel: 10,000 Btu/hr e(iulvalent to 1 ki~-hr~hr:

Steam

Credit:

High -Pre~sure:

Low Pressure:.

6.
7.

Incineration
Fuel usedto

1,000 Ibjhr

of sulfur
planttall
~roduce~reduction

a.

Reference-

12

b.

Reference

5.

c.'

Reference

13.

equivalent

to 90 kw-hr/hr

1.,000.lb/~ir eciuivalent to 30 kw-hr/hr:

gases.
gdjesi

1,110

scrubbing systemwithout

tail

gasreheat

energy~~consumption of a Claus sulfur

Vse of-~ reduction
reheat,

however,

tail

the

th~e overall

plant by about 11 percent.

gas scrubbing

reduces

increases

system without

overall

energy

tail

consumption

gas
by about

50 percent.

Based on the growth projections presented in chapter 8, by 1980

some' 8100 Lf/day of refinery

sulfur

plant canacity wil'l be subject

to NSPS. Standards based on alternative

no impact on national

I will have essentially

energy consumption, since most SIP's already

require the use of this type of emission control system. Standards

based on alternative

II,

however,will

consumption

by some 54 million

of fuel

per year;

oil

capacity
gas

subject

scrubbing

kw-hr/yr,

as'suming half

to compliance

systemswithout

reduce national

or about g0,000 barrels

of the refinery

with NSPS install

tail

gas

energy

sulfur
oxidation

reheatand

hhlf

plant
tail

install

reduction tdil gas scrubbing systems without tail gas reheat.

7.5

Other

Environmental

IrnPacts

Noenvironmen~alimpacts other than those discussed above

are likely
sulfur

to arise

plants,

regardless

system is selected
than those

from standards

resources

of which

as the basis
initially

of performance
alternative

for standards.
required

for refinerv

emission

control

Furthermore,

to construct

either

other
alternative

emission control system (most of which could Probably be salvaged

in one way or another),
irretrievable

As discussed

there do not appear to be any- irreversible

commitment of resources

associ~t~ed with these

above, there is even no overall

increase

in'the

standards.

energy

requirements associated with refinery sulfur plants, since both

7.21

or

Table

7.6

Environmental
impactof No~tandard~or
Delayed

Year

SJ1 furl Plant

1977

Nationwide S~2Emissions (M Tons/vr)

.Car, acit~y

Affectedby Standardsl

1976

3150
'

1978-.

Standards

'

No SIP

2-----~f~3
~Alte rnatlve T'
SI

'130

25 '

25

1425

60

10

10

1815

75

15

15

'

-Alternat'ive 114
2
1

1979

850 -

35

0.5

1980

850

35

0.5

8090

335

60

60

TOTA~

Note

i.

LT/dav.

2.
3.
4.

95% control.
99% control.
99.9X
control.

':- 7:22

emission

control

systems

result

in a net

reduction

in energy

consumption.

Basedon the growthprojections presented in Chapter8, the adverse

environmental
impactof no standardsor delayedstandardson nationwide
S02 emissions
selected

as the

quali'tv

since

currently
as the

is summarized in Table 7.6.

basis

standards,

alternative

required

basis

for

for

there

If alternative

I is

is no adverse

impact

I does not reduce emissions

by most SIP's.

If alternative

standards,..on;tke

other

hand,

on air

beyond levels

II is selected
the

adverse

environmental

impact of delaying standards d~`not setting standards ~s an increase

in nationwide S02 emissions of some5,000 to 25,000 tons per year,

reaching

a total

Since

of about

there

waste disposal

are

adverse

tons

essentially

per

emission

for standards,
impacts'in

these

impact on air quality

year

no adverse

or energy consumption

of the alternative
the basis

55,000

control

impacts

by 1980.

water

associated

solid

with,either

systems which coulaserve

there

is no "tr~de-off"

areas

against

of delaying

pollution,

of potentially

theresulting

standards

as

adverse

or notsetting

standards.

Furthermore, there does not apoear to be any emergingemission

control

technology on the horizon that could achieve greater

reductions
the

emission

sequently,

appears

or result
control
delaying

to present

in lower costs than that represented

alternatives
standards

under
to allow

no "trade-off"

consideration
further

of higher

by

here.

technical

S02 emissions

Con-

developments

in the

near future against lower S02 emissions in the distant future.

7.23

emission

References

i.

"Air Qual3ty Criteria

for Sulfur Oxides," 0.5. Dept. of Health,

Education and Welfare, Public Health Service,

2.

"Preliminary

Air Pollution

U.S. Bent. of Health,

Service,

October

January 1969.

Survey of Hydrolen Sulfide,"

Education

and Welfare,

Public

Health

1969.

3. Peyton, ThomasO., Steels, Robert V. and Mabey,William R.,

"Carbon Dis'ulfide,

Environmental
July.

4.

EPA Contract

Review and

68-01-2940,

Task 23,

1975.

Patty, Frank A., Industrial

2nd Ed.,

5.

Carbonyl Sulfide,,Literature

Assessment,"

Interscience,

Genco, J.M.,

Hygiene and Toxicology, Vol. 2,

New York,

and Tam, S.S.,

1963.

"Characterization

of~Sulfur

Recovery

from Refinery Fuel Gas;c" EPAContract. 68-02-0611, June 1974, D. 54.

6.

Reference

5,

on.

35,

7.

Reference

5,

D. 60.

8.

Reference

5, p. 38.

9.

Letter.
Process

37-38.

Cole, D.F., J.F. Pritchdrd

Research,
Inc. dated June

and Co. to W.D. Beers,

5, 1972.

1O.

Reference

5, on. 52, 57 and 64.

11.

"Impact of Motor Gasoline Lead Additive Regulations

an
Petroleum Refineries
and~Energy Resources - 1974-198(3 Phase i,"
EPA Contract 68-02-1332, Task 4, May 1974, p. V-38.

12.

Beers, W.D.,
EPA Contract

"Characterization
68-02-0242,
Task

of Claus Plant
2, Anril 1973.

Emissions,"

13.' uComparativeAssessmentof Coal BastPrcatron fmtss~~onControl

Systems," EBAContract 68-01-2942,
Task 007, Bopzer~Allen
Applied
Research, October 1975.

7.24

8.

8.1

ECONOMIC IMPACT

INDUSTRY PROFILE

As of April 1975, there were 259 petroleum refineries

in the United

States with a total capacity of 14.8 million barrels per calendar day
(BCD). There refineries ranged in size from 200 BCD
to 445,000 BCD,

withan averagesize of approximately

57,300BCD.1In general.new
refineries

industry

are expected

average.

to be considerably

Information

larger

is available

than the current

on 12 refineries

that have

been projected to be built after January i, 1975. Theserefineries vary

in size from 5,000 BCDto 200,000 BCD, with an average site

of approximately

97.000BCD.2
Not all

plants.
sulfur

petroleum

refineries

At the 259'domestic
recovery plants.

currently

refineries

include

referred'o

There are currently

sulfur

recovery

above, only 81 included

122 sulfur

recovery plants

within the industry, either currently ~nstaileh or due to be installed

in 1975, ranging in size from4 long tons ofsu'lfur.per

day(LTD) to 375

LTD,withan averagesize of 72 Li0.1'2'3 Sulfurrecoveryplants tend

to be found in the larger

refineries.

For example, there are 175 refineries

Table 8-1 illustrates

this

point.

with individual capa~ities less

than 50,000 BCD, amounting to 67 percent of the total

refineries.

These refineries,

however,

account

t~he total

number of 722 sulfur

recovery

plants.

number of 259

foy only 16 percent

Stated

in another

the average size ofa refinery.which Includes asulfurrecovery

of
way,

plant.is

approximately 140,000 BCD. This compares to an average size of approximately

27,000 BCDfor those reff9ieries

without sulfur
8-1

recovery plants.

Table

8-1.

DISTRIBUTION

OF SULFUR RECOVERY PLANTS AT DOMESTIC PETROLEUM REFINERIES

(April

7, 19!5)
Number

Refinery

Size

Number of

Increment (800)

100,001-150,000
150,001-200,000

% of Total

Sulfur

% of Total

Numbe
r

175

67%

19

40

15%

33

20

8%

23

19% -

20

16%

of

Recovery

Refi neri es

0-50,000
~0,001-100i000

1,2,3

Numbe'r

16%

27%

3% -

200, 001-250,000

28'

8-

250,001-300,000

2X

7X

300,001-350,000

1%

5%~

350,001-400,000

400, 001-450,000

2259

''

Plants

~ 7%

1X -

''1X

100%

122

3%
loO%

Table

industry

8;2

summarites

with regard

additional

.detail

the

to sulfur

current

status

recovery

with regardto

of the

plants.

the sulfur

domestic

fable

refining

8-3 provides

recovery plants

that are

currently installed or due to be installed in 1975.

8.2

COST OF ALTERNATIVE.EMISSION

As outlined
systems

that

Alt~rnative
achieves

total

in Chapter

could

serve

suffur

6, there

sulfur

recovery

recovery

more data

sulfur

of 99.0 percent

in the Claus plant feed gases.

sulfur

Since

for refinery

emission

by the IFP-1 and the Sulfreen

by the Beavon, SCOT,'LIellman-Lord,

an overall

are two alternative

as the basis

I, exemplified
an overall

CONTROL SYSTEMS

NSPS.

processes,

measured against

Alternative

Cleanair,

plant

control

the

II, exemplified

and IFP-2 processes,

achieves

of 99.9 percent.

was available,

both

from vendors

as well

as owners,

the IFP-1 and the Wellman-tordand theCeavon processes were taken as

representative

of the two alternative

would have to be comparable

competitive

in the

emission

for the other

marketplace.

Tables

control

systems
8-4i

systems.

Costs

or they would not be

8-5,

8-6,

and 8-7

present

the operating costs for the basic Claus sulfur recovery plant, a Claus
plant with an alternative

I emission control

plant with an oxidatSon alternative

Lord),

and a Claus plant

system

(Beavon).

II emission control

with a reduction

The ptant'with

system (-IFP-1), a Claus

alternative

thecapacity

system (WellmanII emission

of t0.tong

control

tons of surfur

6et day is believed to be representative of a unit required by a typical

small

refinery.

is believed
A plant

to be typical

shown for

with the 100 long ton per day sulfur

of a~unit

with a capac~tyaf

to be too snail

a~

The plant

by a typical

5 long tons of sulfur

to be generally

comparison.

required

utilized

capacity

large

refinery.

per day, while

believed

in typical

refineries,

is also

8-3

~sa~s

~a

II

Ilr

Table

8-2.

SUMMARYOF CURRENT DOMESTIC PETROLEUM REFINERIES

(April

X of
Total

7, 1975)

Total
Capacity

Capacity
Range

(M BCD)~

(MBCD)

.. 95% Recovery

57

22X .

7,211

49%

127

12-445

- 99% Recovery
- 99.9% Recovery

2
22

!x~
84:

184
2,634

1%
18%

92
120

85-99
29-294

- Total

81

' 31%

68%

124

12-445

1 78

69%

32%

27

0.33-406

259

100%6.

1OOX

57

O. 33-445

Refineries

Recovery

without

Recove ry
Total

Sulfur

Refineries

acit
Capac~ty~

Average
Capacity

Number

with

M BCD
(M
BCD)

% of
Total

Number
Refineries

,--

1,3

10,029

Sulfur

4,816 .
14,845

iv:

Table

8-3.

2,3
SUMMARY
OF SULRIRRECOVERY
PLANTS
ATEXISTING
DOMESTIC
REFINERIES

(Apr~l 7, 1975)

Number
of

$ of Total

Total Sulfur

%of Total

Average

SulfurPlants SulfurPlants Capacity

lLTD)SulfurCapacityCapacity
(LTD)
Re~)heries with Sulfur
C~ec~very

t 95XRecovery

94

77f

4,830

572-

51

- 99%Recovery
(fn -99i9%Recovery
- Total -

2
5
122:

' 2%
21%
100%

123
3,591
8,544

1%
43%
100%

62
138
70

4,5,6,7,8,9

Table 8-4.

ANNUAL
COSTS FOR CLAUSSULFURRECOVERY
PLANTSWITH INCINERATION
(June 1975)
Plant

Component

. .

100

1/2

1/2

1/2

928,100

828,100

g28,100

11,200

11,200

11,200

(a)

1,800

3,500

35,300

Direct Labor 8 86.41/hr.

Supv. & Fringes 8 ~0% OL
Electric

Power @ 80.030/Kwh

LTD

10

Manoower.
per Shift .

Fuel @B0.60/MCF

:.:: .

i -.; 2,100

4,100

' 22,700

27,200

83,500

(10,800)

(108,400)

i83,ODDj
83,000

(830,000)
830.000

1g,700)

(739,000)

Mdl.ntenBnce
eis%I~vi

~ Ste~amCredit
:g;.B0150IMLB

'

Sulfur Credit-@ $25/LT.(6)

Sire,

.(5,400)

.:

i(41.500)
41.500

Net OperatingCost

is,doo

(c)
Capita!.:Charges
.@:.17%jInv.

128,700

Total Annual' Cost

;~. .~$~47,~700

Investment(
d)

'JS~j7;ooo

,~~,UuY
153
300
. g!33,600._

:::;

41,300

473'100
-r~u~lvv

~ :-~ B(?65,900)

:':bs~2,ooo : ::82i783,000

ICJotes:

(4)
(b)

350 Operating
Assumes

days per year,

95%lrecovery;`.:-

-:(

ii

;I ;~i::.,i.

(C) Capitalrecoveryfactorfor 15yearsat 10~Interest plus'41%

of Investment
f6r propert~yta~tes,
insurance,

and G&A.

(d) :6/75Chem.Eng.Yndex

I : :I'

:Table
8-5.
:CbSTS
FOR
C;AUS
SULFURRECOVERY
PLANTS
WITH
ALTERNRTIVE
I EMISSION
CONTROL

--

SYSTEM
AND
INCINERATION
4,6,719,10,11,1il
`:

~--(June1.975)...?

: I

.-'.::
...-'~ i I:I - .: .

Claus Piant;Slze, LiD

: -.!:II~onponeht.

: :_~_r~anp~zllclrhnt
@.8~..
4.t-/h~:
Dire~t:Labbr

22,500

~0.03/KWH'8!

Power`(P

MCF
~iSo.60
: :: J-i FU~1
intenance' e:39
.`Inv...(C`la
us ~.`...
ii. -; : Solvent&Catatyst
_:::~:.i:~s;s%
rnv.
;. (IFP-I
:
Condensate@
~O.SO/MGAC
8 $0.50 Mlbs
~.steam
Credit
sulrur
Credit~25/LTdb
1]:
Netpperat~?g
Cost
Capital
Charges
e-1741:
In;.(~)

. 1

:2561:~ ' ~'~$I

B56,~200

:.:::I.;.::I-:Supv;-:P
:iringese'40~qL:er`tr~e
:~~j i~El

:::

10

..~.. ._ :

-;' 22,500
.$4,10b

2:2i 500

4;400

- 2,2q0:~

:: ~.31200. :

1,600~:
1

:; :~:

22,700

.:

900:

1,700

.(5,400)
: ;

61,900
144,0d0
: .
: ~205,900

';: Totsl~Annual:Cost~
:' `.:~Investmen
t: (Ol-au) -

Investment(d)

I""i;otai
.ill__:l.._
.No~te;l

!~~IB00)

-.:.

2$,000::::
174,800
::
,800
.
1.
;
- .819s
902,000- ' :

. :757,000

.(IFP-I )

: 52,300 :i-';:~.]i:.;I:- -

:6?300 ~;~~

200: ;
(108,400)
.]

- :(866,j00)
:866
650,800:- .'I:i :::.:

2,783,aoo

~r 90.000

l~i;,ooa

.1,045,ODD
-: :I~;I.:

$847' 000::

$1,028,00d'~.

-::~3,8281000

::

(")1::
350
bperatlng
days
peryear.

i:~
I (b). -Assumes
recovery,
:~99%
(;C)'.Capltal.recovery
factorForlbyears
at IbX:lnterest~
plus'
48ofinvestment
for-property,
taxes,

insurance,

6/75Chela.

.'-~:
;.. :

-8(15, eoo);

. -

and G&A.

Eng. -Index

.I~-,:-:
- -.-.r.-~

1:

Ta~le8-6. COSTS
FOR
CLAUS
RECOVERY
PLA'NTS
GliiHALfERNATIVE
II'EMISSIO~
SULFUR
CONTROL
SYBTEM
(OXIDATION)
13,14,15
(June 1975)

Component

p~r Shift
:Manpower

.: "

Bo

2,100

Maintenance
'9
31Inv~(Clau~~)
O 5% Inv, (Wellman-Lord)

21,900

StedmCrddit
-O$0.50/MLbs.
ISulfur
Credit
B:bZS/LT
(b)

$158,600 .,

186,200
;

Total:Afinua'l
Cost

:-..-1.

.':93'44.1300

less ~niin.id]r

t6iaus
Wellman-lord)
:

' 730,000

75,600.

4,100

41,300

: 26,100
.;

rj2,odb

70,000

.200

:1,700.

(~,600) .

(96,400)

(87,500);:

(875,000)

9127,800
224,400 . : :-.. :

(8454, 000)

.:.. 768,600

: . $352,200

' ~-871, 000 '

6314,60(3
2,733,000

~:

Assumes
Ibo%
sulfurrecor;ery
withtail gasunit.
::(C)Capital
recovery
factor
for15years
at 10%
interestpl~4~.dfinvestment
forproperey
taxes,
insurance
.(d) .

:. i:

andG&A.

Incinerator.adjustment

from; "Air Poi 1uti'on 'Cont~roa;iechnologyandCdsts:~nSeven :Selecte$

Areas,"ReportNo.EPq-450/3-73-010,
page629.1
.:6/75 Chem. Ens'. Index.

89 ,400

'7,000

.:

~: -

: 449,0bO
:.
..1,788.000
;-' 91,095.00011'1. 51,320,000,: -84,521,000

Total' Investmentle) :

.Noles: ;I.
i. I
(a)::'35db;pera
ti ngdaysperyear

45,000

22,500

(43,700)

- Cagitai:Charges-~~
17X
Invi(c):
-

(4,800)~,

--: :.~:Net Operati ng. Cost

$112,400-- ~

7,600..

. .:3,5~9
100

.:::SoftWa~ter
@Bb.30/m~Gals.:

-45,0001.:-

'`18,300

Chemicals(h 8200jton 50~'NaOH

too .

;.1 $~1;2,4001

. 45,000
.

-.- Ele~tric
eower
9 ~D.Oj/KWH()
:

Investmeht

10
i

. Bi12,400

_Sudv,
8 FringesQ401~DL
.
:e

~-

2 ~

Olr~ct
Labor@
86141/hr

Fuel

Claus;PlantSize,
-LTD

;:Table
8-7.

cos~sFOR
CLAUS
SULFUR
RECOVERY
-PLANTS
WITH
ALTERNATIVE-ii
EiYiSS.ION
-

;i

- .. CONiROL
SYST~M
(REDUCTION)
8,17,18,19
: ~~r.~(clune
!9c75)

CiausPlantSlz~,LTD

_ComPonent

10

Manpower
per Shift

2.

: ~:pirectLapor86.41iHr.
Supv.6 Fringes0:40%
DL
'
Elect;-'icS0wer
bB0.;03/K~JH(")
'-:'Mai:ntena'nce
@3%~Inv.

(ClauB)

9~0'

:26.,100
.:.-

: .

Cataiyst
:&Chemicals

i,

;nnv;l(cl,:
:~ap~tal-Cha~ges
BI17%

~otai
;Annual.dharges

less Incin)(d)

IClaus
-inves.tment.t-

rotal: !?ve~tinent(e)

: (10,7q0')

$419,900
'730,000

$1,456,006 ~

16;300
li 600.:

::

,900
~~
-~

141

-...'247,500
..

141,4001: r~.

100

(43;700~
172,400

'82 ,OdO :1:- :

1,6d0

:i5.~4d0)

SulfurCredit@d35/LT(b
:..I.NetOi~eratingCos~t

- ; ~. ` ~s,sao

44;;700~:`

800

soft.biatereB0.30/MGAL

'~~(482,600)

: 945,400i:

jdo,100-:r

8442.000
~I: ; : 94621800
.
: 2,'733,000:
.-

871,000

811,765.ooo

090--11
1

., Notes:

::

Ta)-j~D]'operat;ng
daysp;eryk8r.

(b) .Assumes.100%
sulf~ recovery
Capi.'tdl recovery,factor for.l5 years dt IbI inte;-~st plus

,, ofInvestment:_fqr:
praper~y
::

::-t~x~e~,
insuranceand
G&A
Pollution Control Technollogy and Costs i~nS'even
.fromI~A;ir
.i~(d) rr;c~nerator
ad]lultment
Selected,AreaS", Report:No.

ce

Eng.Index.

EPA-450/3-73-0101
:p.

`62B~
II;:~

:1

95,000

9,3d~ .I

.36,300

- steamCredit.~:$B.SO/MLBS..

; -

45,000

. 4,700;:'~
400'
21,900

:aii2,40d

45,000

0 5XInv. (Beavon)-

~.

.81~2,400

. - Fuel..e80:60/ycF-

':

:300

1'.
. :1.
:.

: :.:.

! ::

--

. ''"

 I~::
:

I:

_~

: _ ~

'

:1.

...

fables8-8..8-8,and8-10 - sur~ari
-: ...

ze the

economics
of inst~llingan
: .

alternative
I ordltern`a~ti:ve
tI emission
ontrol:sjstem-on
a Cia;s

onLTb.plant,
useofanalternativ~
I
IUlfYi
rec~ pTnt.
F.r::1

system
reduces
theannuai-return-from
82.65,900-to
815,800,.
a lossof
:~:5250,1001per
j,ear..' Useojl an alternative II systemincreases the annual.

'-Sosts
to $314,:604~,8041,:
deeending
on:whether
anoxidation
orred~ion
-:: : ::~process-is
elnpi-oy2ld,
pr a 1bssoq~~580,50d1728,!M3
per.ear.:for_a10
~-~: -- -:

LTOtlaus
plant;'
~si::ofan::arternat)ve
i-~mtssjbn
control
system
increases
-Use
~ear,
:theann.ual_cqits:to
g198,8(50,
a less:of:8~5.20L1Per

of

an

: .alternative
II syrtsnincreas~s
tlie;anluai
coststo~S352,2q0-442,00D',
or

lo,, bf:~18.6P~-308,400
_pery~ar:
Mnal!y,
fo~a 5 LTD
plant,useof
analternative)l!
~stemincrease;
theannual:
coststo 8205,900,
a Ioss:-'
of g58,gOp
per.~y~8ar;wd
tse of an.alternati've.IIsystemincreasesthe

annual
costs.to
8344.000-41,800,
:dr.alossof$197,i60-272,200:
per
:-Lear.:
'8.3

:1 '.:-::':

'ECONOMIC-~MPACr

Impact by Com~any~Size

Two
financialprsfiles:~iqve:
b aeveloped
to evaluate
theeconomic

iopctooe;
thetwoa2ternaiive
emission
control.
systen;s;.:The
.first

:profile.
representslja~
laygd;integrated
oil company
and:
thesecond
represents
a ji?all oil ~cr?pany,l~:The
profi!8 ~~fthe:~grge, integrateil .compdny,
is

-I~.t

:4aS"al"PO?
:an~ana~iysi:of
thepublished
findn2lal]
statements
ofExxon
I.;CsrpOratlon,
`Mobi~~V'7
Corpotion,l
Sye!i:bia
Coinpan),~.PhS'11
ipsPetroleum
- ::.'

.ihese
C4mpany,~
difiet - ervi'c~ 'ICompanlyl'anb
As hi and~ . Oi 1,:'-Incorporafed,
..:-

::.:

: r

::

t0nlpa"ies~cpnsiiler~
together
should
~adequate~j;
represent:
the'ma30r:

I-integrated
ref~n~sectorof::the
d~estit~il industry;:.
Theresultjnq

-.:-fioancral
profrIa.65'
presented
inTabte
8-11.1
:1:

Table 8-8,

COMPARISON
OF ALTERNATIVE
EMISSIONCONTROL
SYSTEM
COSTSFORA 100 LTDSULFURPLANT

(Cbst Adjusted to June, 1975)

Total Costs
Annual

Operating
Investment

ControlSystem

BaseCase

Emission

Rate

Total Sulfur

Cost

(3)

Invesi~ent

(Lbs/hr)

1$)

932

j,82R,l)nC)(b) (15,800)(b)

LR7

Operating
Cost

Emission

Rate

Total Sulfur
As SO~

(lbs/Fir)

Unit
Cost

($/ton)_

(5)
`'1,045,0r)r) 250,100

. 745

80(c)

II

Oxidation

4,521 O00(b)

Reduction

5,561,0n0b)

19

19

Notes':
(a) Denotes gain,

('b) Includes. costs of base case Claus sulfur recovery plant.

(c)

Annual

S02

As

~2,783,000
(265.900)(a)

Alternative I
Alternative

DifferentialOverPrecedingCase

Incremental costs per Incremental ton of SOe recovered.

.~693,000

1,733,000

330,400

478,600

168

168

468(c)

67alc1 -

Table 8-9. COMPARISION

OFALTERNATIVE
EMISSION
CONTROL
SYSTEM
COSTS
FORA 10 LTDSULFUR
PLANT
~Cpst Adjusted to 3une,1975)
Total Costs
Annual

ControlSystem
Base Case

Investment

(f)

~$ 902,800

II

Oxidation
Reduction

Emission Rate

ODerating

Total Sulfur

($/.vr)

(Lhs/hr)

Cost

$133;600

AlternativeI . l,n28,OnO(a) ~198,600(a)

Alternative

Differential

1,320,000(a) 352,200(4)
1,765,000(a) 4421000(a)

AsS02

Over Precedins Case

Annual

Total Sulfur

(8/yr)

(Lbs/hr)

Investment Cost

($J`

93 .'

126,X00

2
2

292,000
737,000

Ca) Includes costs of base case Claus sulfur recovery plant.

(b) Incremental costs Der incremental ton of S02 recovered.

AsS0p

19

Notes:

Emission Rate

Operating

65,200 '
153,400

243.200

Unit.

Cost

(I/ton)
18

74
17

17

- 210(b)
~b)
3406(b)
2148

Table 8-10.

COMPARISON
OF ALTERNATIVE
EMISSIONCONTROL
SYSTEM
COSTSFORA 5 LTDSULFURPLANT
Total Costs

co~t~S~
Base Case

Alternative
Oxidation

Emission-Rate

Annual

Emission

Rate

ODerating

Total Sulfur

Operating

Total Sulfur

Cost

As SO2

Investment

Cost

As SO2

($)

(8/yr)

(Lbs/hr)

($)

(~yr)

(-Lbs/hr)

%147,500

46.5 '

A47,nnO(a)205,900(")

II

Reduction

Annual

Over Preceding Case

Investment
~$ 757,000

a, Altemative'I

Differential

1,095,000

(a)

1,456,000(a)

9.5

344,800Iaa1
1

419,900

Note:

Includes costs of base case Claus sulfur

recover olant.

(b)

Incremental costs per incremental ton of SOErecovered.

Cost

(Blton)
39

g 9~,i~oo $ 58,400'

37.0

248,000

138,900

8;5

509,000

214,000

8.5

'I~

Unit

375(b)

~3891:1b1
59941
b

Table8-11. LARGE
REFINER--DERIVATION
OFMDDEL
FINANCIAL
PROFILE16
A.

Base

Financial

Data

Total Company.Statistics--Including

Forel'gn Operations:

Exxon

Mobile

Shell

Phi Illps

Cities

$25,990

11,327

5,561

3,635

2,654

Sales

30,618

13,162

6,3!2

3,494

2,234

Total Costs: of Operations

?3,605

10,764

5,739

3,062

2,025

432

209

Assets

.Profit

Before

Taxes-

I 7:i01-3

iTax~S

'4,640`

2,398'

`;: 573':~~

1;;575' '

260

154

Total PetroleumSales

1,958

816

379

163

89

Profile

I
$/Dlrrel

Assets

14.363.

Sales

Total

Cost

16.574

of Opera-

13.519

tions
Profit

Before

Taxes-

Taxes
NetProfit

X; Return

3.055

1.891
~

on Assets

"YearendingSeptember
30.

8.10%

1,P76

2,619

2,473
146 .

- 88

405

:B. `Financial

58

823

in millions~.

Ashland

55

2,373

NOiE:' All quantities

Service

i72

Net Profi t
(Barrels/Year)

1972-1974 Average.

121a

The financial

profile

upon an analysis
Corporation,
United

of the smaller,

of the published

Quaker State

Refining

less

financial

Oil Refining

complex firn

statements

Corporation,

Company, and Edgington~Oil

is based'

of Murphy Oil

APCOOil Corporation,

Com~any.

These firms

con-

sidered together should adequately represent the small refiner jector of

the domestic
in

Table

oil

industry.

The resulting

financial

profile

is presented

8-12.

The economic impact associated

with standards

of performance

results

from the incremental cost imposedon a source to complywith these

standards

above those

or local
State

air

pollution

Implementation

imposed on a source
regulations.
Plans

to comply with existing

As discussed

to meet the national

in Chapter
ambient

air

state

3, most
quality

standards for S02require newplants to achieve an overall sulfur recovery

of 99.0 percent.

A few local

an overall

recovery of 99.9 percent.

sulfur

air

pollution

control

Consequently;

local regulations already require the -installation

emission control

system and standards

alternative

have no economic impact.

will

To assess
emission
standards

system alternative

on the financial

Eleven cases

covering

profile

various

II,

the effect

and sulfur

Cxam~ned, three

representing

small refiner.

These cases are presented

and

are

sun~snarized

in

Table

a~~argerefi?er

8-24.

8-15

most s~ate or

of an alternative

with standards

of a typical

refinery

require

of performance based on this

the economic impact associated

control

regulations

based on

of compliance

refiner
plant

and eight

with

was evaluated.
capacities

were

representing

in Tables ~-13 through 8-23

.Table8-12. SFV\LL
REFINER--DER~YATION
OFMOOEL
FINANCIAL
PROFILE16
A.

Base

Financial

Data

Total Company
Statistics--Including ForeignOperations: 1972-1974
Average
Quaker

Murphy
Assets

'

State

Apco

United

Ed9ington

83.7

; 41.8

165.1

85.6

155,6

72.. 6

'8771.1~

171.1

167.2

592.3

213.7

165.5

506.1

179.6

159.5

86.2

34.1

6.0

9.5 --

43.3

14. 6

2.9

4.7-

5.9

qD Net Profit

42.9

19.5

3.1

4.8

7.1

O~ Total Petrole~rmSales

'51.0

6.7

' 19.4

20.1"

1O.5"

Sales

Total

Cost of Operations

Profit

Before\Taxes,

Taxes

(8arrels/Year)
NOTE:

8.

All

quantities

Financial

in millions.

Profile

$/Barrel
Assets

11.466

Sales

11.348

Total

Cost

Profit

Before

of Operation
fares

Taxes

Net

9.967
1.382
O. 663

Profit

X Return

~0.789
on

Assets

6.27%

agasedon904:of capacity, crude runs not given in Moody's.

13.0

Table8-13. 6ASE
i: InnLTD
SULFUR
PLANTi101).n00
BCD
REFIHERY1

Cost

Flnar;clal
Profile

Base

Case

Alternatl
I

of

Control

ImDact of NSPS

Alternative II
Oxidatlon

Reduction

Assets

14.363

0.029

0.048

0.076

Sales

16.574

O.dr)l

n.noi

o.nni

T; I Cost of nneratlon

1 13.519

n.n07

0.016

Alternative
I-

Alternative

nxidation

0. 021

II

Iternative

Reduction

0.019

0.009

NSPS ImDact on FfnancialProflle

0.047

0.014

Alternative

nxidation

II

Reduction

14.382

14.410

16.574

16.574

13.528

1 13.533

3.055

3.046

3.041

Net profit

1.164

1;161

1.159

%Returnon Assets

8.10

8.07

~---

Profit

Before

Taxes

Price Increase Necessarlv to Halntaln

Return on Assets 1

$/BBL
X
Notes:

i.

2.

-R11 values

In dollars

Larger refiner

model

oer Barrel.

financial profile, Table 8-jl.

3. DerivedfromTable &B;assulnes35()operatingdb~jper year for sulfur planS.

'8.04

0.012
0.07

0.023
0.14

Table
8-14.C~SE
2: 10b
LTD
ZULNR
PLANT/Sn.~nO
BCO
RE~II(Enl

~' ~.~~~ojlbi.~ontrol5~'

'~"

~""

("

.. ...

FlnBncldl

ImDactof NSPS

Alternativ

Rase CaseP

Assets

14.363

0.057

0.095

0.152

Sales

16.574

0.002

0.002

0.032

Cost

AlternativeII
O;idatlon

Alternative
I `

' Reduction

3.ri55

Net Profit

1.164

$ Return on Assets

8.10

---

I ----.

Price Increase

AlternativeII
Oridatlon

Reduction

nxidation

0.038

0.095 :

14.401

i ---

0.0181 0.0251 ---

. ---

Notes:

T;-A~l valuesIn dollars per bdrreii

j. From
Table&8;asslr?sso operdtln9
daysperyearfo~iuj~urpla?t.

II

Reduction
14.458

16.574

113-537113.5(5
. ----

3;037

. L--

3.029

1.157

1.154

8.03

7.98

Necessayv to HaintBln Return on Assets

f/BBL

2. Larger refiner Illodelfinancial prdfile, Table 8-11.

Alternative

Iternatfve
I

;I js~.S74

19.519 0.016 0031 0.0(2

Profit BeforeTa~cs

NSPSImoacton FinancialProfile

"

Profile

Pli .oTnneratlon
O)j

..

0.025

0.045

0.15

0.27

Tlble8-15.CRSE
3: Y)LTD
SULNR
PLIKlln.nO~
BCO
REFIHERYI

Costof Control3

Imoactof NSPS

NSPSImDacton FinancialProfile

Financial

Pyoflle 2 Alternatlv

Base

Case

AlternativeIIOxldation

Assets

14.363

0.024

O.U3~

0.088

Sales

16.574

0.001

0.001

O.OD1

1 13.519 1

0.008

0 011

0. 025 1

qr, I Cost of rmeratlon

~o

Alternative
I

Reduction

AlternativeII
nxidation

0.011

0.003

IternatlYe
I

Reduction

0.064

1 0.017

AlternativeI1
nxidation

Reduction

14.374

14.427

16.574

16.574

1 13.522

13.536

Profit Before Taxes

3.055

3. 052

3.038

Net Profit

1.164

1.163

1.157

~r;beturn

8.10.

8. 09

8. 02

0.004

0.029

on Assets

: Price Increase Necessarv to rcaintaln Return on Assets

$/BBL

0.02
i. All values In dollars per barrel.
2. Larger refiner model financial profile,
a. Interpolated from Tables 88 and 8-9.

fable

Table8-16. CASE
a: 50LTD
SULFUR
PLANT/3n,000
BtDREFINERY1

Cost

of

Control

ImDactof NSPS

NSPSImoact on Financial Profile

F::~~l:l i\lternatlv Alternative

II Alternative Alternative
ii
Ra;eCaseZ

Oxidatian

Reduction

sets

11.466

0.040

0.058

Sales

11.349

n.no2
0.014 1

n.nne
n.nn2
0.030 1 0.042 i.

o~ Costof nnerat~on

( 9967

Profit BeforeTaxes

1.382

Net Profit

0:719

X Returnon Assets

6.27

Oxfdation

0.147

0.018
1 0.016

Price Increase Necessarlv to Yalntaln

Reduction

Notes:

All values in dollars

ner barrel.
Smaller refiner
model financial
Profile,

1.

Internalated

from

Tables.

88

and

8-9.

Table

8-12.

nxidation

Reduction

0.107

11.484

11.573

11.348

0.028' ( ~ ,

11.348
9.983

9995

1.365

1.353

0.710

0.704

6.18

6.08

0.019

0.042

0.17;

0.37

Return on Assets

b/eeL

i.
2.

Itematlve Alternative
II

Table
8-17.CASE
5: )nLTD
SULFUR
PLN(T/3R.rln~
BCD
REFINERYI

Cost of Control

.Imoact of NSPS

NSPSImoact on Financial Profile

Financial

Profile

Alternat~

Ras~ Case

nxldation

11.466

0.026

0.077

0.115

Sales

11.348

n.nnl

n.nnl

n.nr)l

Profit

Net

Before

Taxes

Profit

% Return on Assets

1 9.q67

1. b.011 1

---

---

0.032~ 1

Alternative

Alternative II

l
Reduction

Assets

Cost of nneratlan ~
'U

Alternative I1 -

0.038
-

nxldatlon

Reduction

0.051

0.089

0. 021
I

0.027 I

Ifernatlve
I

Alternative II
nxidation

Reduction

11.517

11555

11.348

11.348

1 9. 988 1 9.994

-~56

1.382

1.360

0.719

0.708

0.704

6.14

6.09

6.27
Price

Notes;

~. All values In dollars

eer barrel.
2. Smaller refiner
model f~naadal
aroflle,
j~ Internolated
from Tables 8-8 and 8-9.

Table

8-12.

Increase

Necessary

to naintain

Return

on Assets

9/8BL

0.028

0.038

ii

0.24

0.34

Table
8-18.CASE
fi: InLTD
SULFVR
PLPbli/30.0nll
BCD
REF(IIERII

Cost

of

Control

Imoact of NSPS

NSPS

Financial

Profile

Alternativ
2

RaseCase
Assets

qa

11.466

ISales

1 11.349

I
n.nl2

Alternative Il

Reduction ~

Oxldatian
0.038

I
0 020

Financial

Profile

Alternative

II

I
nxldatlon

Reduction

0.026

0.067

11.492

11.533

11.348

1 11.348

9.981

9990

Profit Before Taxes

1.382

1.367

r.35E

Net Profit

0.719

0.711

0.706.

X Return on.4ssets

6.27

6. 19

6.12

0.018

0.033

0.16

0.29

NecessaSI

to Yalntain

Return

0. 023

Reduction

9.967

Increase

0.014

nxldation

Cost of naeration

Price

0.029

on

Iternative

Alternative II

1:

0.079

1
ii. 006

Alternative

ImDact

on Assets

8/set
5:

i.

All

2.

Smaller

values

In dollars

j,

From Table

refiner
0-9.

Der

barrel.

model financial

Droflle.

Table` 812.

Table8-19. tASE7: 30 LTDSULFUR

PLANT/2n,T)nl)
BCD.REFINERYl

Castof Control3

Imoact
of NSPS

I NSPS
Imaact
onFinancial
Profile

Financial

Profile
Ras`etase2

Iternative
I
I

Alt~mative III
Oxidation

Assets

1 11.466

Sales

I Costof noeration
1

NetProfit

on.9ssets

b. nnl

9.967 1 0.016

Profit Before Taxes

% Return

11.348

0.039

1.382

6.27

0. 173

n.nrll;

n.nf)

0. 048

I
1

I nxidati6n
-

Table

8-12.

I Reduction

0. 076 :

-' I I
0.0321

Iternatlve
I

Alternative II
I nxidatlon

0. 134

1 11.348 11.348

9999

11349

-;

f I

I o.702 1 0.697

B/BBL

1 -0.042

10.058

Necessayy

to Yalntaln

Return

r)~041

11.600

Increase

Reduction

11.542

0.05P

Notes:

All values In dollars

ner barrel.
Smaller refiner
model financial
nrofite,
Interpolated
from Tables &8 and 8-9.

I
1

Altdmative II
I

I
Price

i.
2.
j~

I Reductilon

0.115

0.719

Alternatlve
1 .. I
I

6.08

~n.~09

6.01

on Assets

0.37

0.51

Table
8-IO.USE
8: InL7D
SULFUR
PWIT/2~,n~n
BCO
REFINERYI
Cost of ControlJ
Financial

Profile

:. ..

aD

r:
P

Rase'Cbse2

sets

11.466

Sales

11.345

Cost of noeratlan
profit

Before

T6xes

Alternat(

9.967

Alternative II

n.rln9

Net Profit

0.il9

I Return on Assets

6.27

.I

nxidati on

NSPSrmoact on Financial Profile

)I

Reduction

0.040

~.101

o.mi

o.a~i

O.rKI1

n.Or)l

0. 030

0. 042

0. 021

0. 033

I ---L

I :---

NecessarY to ~aintaln

--L

All values In dollars Per bairel.

Smaller refiner model financial profile.

3.

From Table

8-9.

fable

8;12..

nxidation

II

Reduction

i11.349
9. 988

---

11.349

( 10.000

7;~i;f

C-1.349

0.708

0.702

6.15

6.07

0. 026

0. 045

0.23

0.40

Return on Assets

S/BBL
es:

Alternative

.5-;

~11R

Prlce Increase

i.
2.

Iternatlve

0.057

~_

1.382

Alternative

Alternative

l)xidation Reduction

0.017

Imoact of NSPS

41

Table 8-21. CASE9: 5 LTDS~LFUR

PLANT/en,nnn
BCDREFINERY

Cast of Control3

Imoact of NSPS

NSPS ImDact an Financial

Financial

Profile 2 Alternatl

Ras~eCase

sets
Sales

~ ICostof nneratlon

'I

AlternativeII
Oxidatlon

Reduction

11.466

0.012

0.046

0.096

11.348

1 9.967

r).nOR
`1 0~027
.

Alternative
i'

I Oxidatlon

Reduction

0.034
,

n.nj7

AlternativeII
0.084

o.019 1 0.029 I

IternatlveC
I

Profile

Alternative IT

nxldation

Reductio~

11.500

11.550

11.348

11.348

I g,986 1 9.996

Profit ReforeTaxes

1.382

1.362

1.~352

Net Profit

0.719

0.709

0.703

X Return

6.27

6.16

6.09

0.026

0.040

on Assets

Price Increase Nece`ssaSv to Yaintaln Return~on7iSs~

B/eeL

0.35

Notes:

i,
2,

All values In dollars wr barrel;

Smaller refinery model financial profile,

j~

from Table

&10.

Table 8,12.

fable 8-22. CASE

In: 5 LTDSULFUR
PLANTTl15,1)T)J
BCDREFINERYl

Financial

Costof ControlJ

ImDactof NSPS

R~:1:e2Rlte*natlv
Alternative
II. Alternative Alternative
II
III
Oxidation

Reduction

Arretr

11.466 n.016 0.062 11.128

Sales

11.348

:. IOxidatlon

NSPSImaacton FinancialProfile

Iternatlve Alternative
II

Reduction

0.046 0.11Z

nxidation

11.512
11.348

P~ I Cost of nnerallon .

Profi t Before Taxes

Net Profit

9.967

r).r)ll ( 0.036
---

1.382

0.050 1~

1 0.025 1 0.039

11.578

71.348

9.992~ ) 10.006
1.356

1.342

0.706

0.698

6.13

6.03

0.031

0.053

0.28

0.47

0.719

X Return on Assets

6.27
Price Increase

Necessary to Yaintaln~iurn~;l~is~;
%/BBL

Notes:

L,

Reduction

i.

All values In dollars wr barrel.

2.

Smaller refiner

j~

From Table

model flnandal

profile,

Table 8-12;

8-10.

t-

i:

Table
8-23.CASE
Ii: 5 LTO
SULNR
PLANT/75nn
BCO
REFII(ERII

Cost of ControlS

tmoact of NSPS

NSPS ImDact on Financial

Profile

F!:~;l~lAlternati Rlternatlve
II AlternativeAlternative
II It;matlve Alternative
I!
Rass CaseS

P)
N

Oxidatlon

Reduction

ssets

11.466

0.033

0.123

n.255

5ales

11.348

o.nni

s.oni

o.noi

0.022

0073

n.~~n

Costof nneration

9..967

Pmf t Before Taxes

1.382

Net profit

0.719

b Return

on Assets -

All values

2.

Smallerrefiner

In dollars

3.

From Table

&10.

nxidation

Reduction

0.090

0.222

0.051

0.078

oer barrel.

model financial

profile.

fable

8-12.

Increase

Necessary

to Yalnta~n

Return

~xfdatlon

Reduction

11.556

11.688

11.348

11.348

10.018

10.045

1.330

1.303

0.692

0.678

5.99

5.80

~/BBL

0.063

0.106

0.55

0.93

6.27
Price

1.

on Assets

Refinery

Sulfur Plant

Caoadty (800)

Profltabll!~ ($ Retlm on Assets)

Caoadt.v _ilTD)

Alternati ve

terna
T~xldatl6n

Price Increaseto HalntainProf~tabill

ve
Reductlan

ternatlve
(3/6BL7 (g)

te matf ve
~xldatlon
Reducflon
(S/BBL)

Large Refiner

sn.am

0. 37

1~6

inn

5r;

Small Refiner

No Impact

~ '1

0, 86

o. 7P

:. 948

0.12 .. 0.99-

(P)

No Impact

0.012

0.07

0.023

0.14

0025

0.15

0. 045

0.27

0.004 6.02 ().D5P0.111

0.019

6.27

30,000

50

1.44

9"

30.~00

so

'~2.07

jr),r)r)n

in

20,000

30

20,000

10

20,000
15,nan

5
5

7,5110

(~/BBL)

9.10

100,000

sn,nnn

($)

NoImgact
1

3.03

' .

2.87

0.17

0. 042

0. 37

0.028 0.24 0.038 0.34

1.28

-2.39

0.018

0. 16

0. 033

0.29

3.03

4.!5

HoImpBct
"~ 0042

0.37

. 058

0.51

1.91

3.19

1.75
2.?3

2.87
3.83

4.45

7.50

0.026' 0.23~ 0.045 0.40

0.026
0.031

0.23
0.28

0.063

0.55 ~ 0.106 0.93

0.040
0.053

0.35
0.47

As shown by the large refiner

on emission contrbl
measured by return
1.48

percent,

system alternative
on assets)

for petroleum products

b3 price

industry.

by 0.02-0.27

integrated

The reduced

that this

refiner

by the

small

cases

an 8.10

growth
refining

prices

purposes negligibbe.

on a small refiner

economies

II decrease

the profitability

by 1.28 to 7.50 percent,

industry

petroleum

are for all practical

dueto

cents per

in product

standards

refiner

percent

increase

of fable'8-24,

system alternative

a ~.27

of the domestic

or the

refiner

control

maintain

To maintain

or about 0.4-4.5

the impact of standards

on a large

refiner

by 0.37 to

impact would retard

sector

profitability,

As might be expected,
than that

increases.

percent,

necessary to maintain profitability,

greater

refiner

a large refiner wouldrhave to increase prices.

It is highly unlikely

among the large

based

II decrease the profitability.(as

of a large integrated

if'unaccompanied

percent return on assets,

barrel.

cases of Table 8-24, standards

of scale.

based

As shown

on emission

of a small

if unaccompanied by price increases.

return'on

assets,

the

small

is

refiner

would

have

To
to

increase prices for petroleum products .by-0.1~' to 0.93 percent, or about

1.8 to 10.6 cents
standards
as that

per barrel.

on the smallest
on the typical

refiner

large

quite small and not likelyto

sector

of the domestic

refiner,
especially

the price
in light

Although

of price

may be from three

refiner,

the magnitude

that

the impact of

to five

times

as severe

of this

impact

is still

retard industry growth amongthe small refiner

petroleum

increases

it appears

refining

industry.

necessary

to maintain

increases

over the past

8-29

As with the large

profitabrlity
three

-to five

are negligible,
years.

The impact analysis

small

size

over~rl
when

of the control

refinery

the

by refinery
investment

operation.

incremental

Table

8-25,

costs

of achieving

Due to economies

and annual

There is,

differences

whichis

size is clouded by the relatively

between

derivedfrom
alternative

of scale,

however.

compared with the

a more pronounced

control

Tables

units

is

8-8 - 8-10,

II utilizing
the cost

cost

five

of controlling

considered.

presents

sizes

effect

the incremental

of control

an incremental

units.
ton of

SOpat the level of alternative II goesfrom$468-678

for~a~100LTD
sulfur

plant

to $3,891-5,994

for a 5 LTD sulfur

plant.

Nation-Wide

Table 8-26 provides

affected facilities

the number and size

distributionof

in the period 1976-1980. itshould

the growth is greaterthan

the projected

ann~al

for

approximately

30 percent

three

reasons.

capacityis
It

First,

not controlled

is assumed that

third`there

will

all

by Claus units

future

be an annual

refinery

be noted that

increase

of refinery

throughput

of t~ecurre~t

so the base is narrow.

capacity.will

replacement

Cfaus plant

refining
Second,

be controlled

of Spercent

and

of the existing

Ctaus plants.
Table 8-27 develops
impact of required
emission

Standards

reductions.

the 7976-1980 forecast

investme'nt

dollars,

the annual

based

on alternative

Standards

based on alternative

to show the~national
cosfs-and
Iwill

the potential
have no impact.

ZI, an the other hand will require

an

i~cremental investment by the domestic petroleum refining industry of some

~110 MMover the five-year
will

increase

the annual

816 MMper year.

by some 57,000

tons

period
operating

of 1975 to 1980.
costs

of'the

In 1980, these

domestic

industry~by

standards
some

In return, the standards will reduce national SOpemissions

per

year.
8-30

Table 8-25.

COSTEFFECTIVENESS
VS. SIZE OF CONTROL
UNIT

Base

Case

(Alternative

-ETiiissidns1

Sulfur Plant
100

(b/Ton
SOZ)

Costs

Controlled

(502'ST/Yr)

4,5

(B/Ton
502)

77,615

(0.20)

706

38,810

1.49

353

736

30

! 23,285

5.80

212

1,257

10

7,760

70

2,777

3,8sd

50 -

c:

Costs

(502.ST/Yr)

II

Emissions
3

Contrblled

Capadty
(LTD)

Alternative

I)

..

25.62
53.07

~ 35

Notes:

i.

99,OX Sulfur

recovery

2. Includes
costof sulfurplantandemlssldn
controlalternativeI
3.

Additional

4.

Cost of oxidation and reduction emission control systems averaged

emissions controlled

5.

Incremental

costs

per

at 99.9% sulfur

recovery

incremiental
ton of SOpcontrolled

573

4,943

Table 8-26.

PROJECTED
GROblTH
OF REFINERY
SULFUR
PLANTS
1976-19801,2,7

Claus

Plant

Size,

LTD

Percent

mat

NC~
Plarits

7.5

15
~ 25
50
100

5-f0

10-20
20-30
30-70
~>70
mTALs

TdtalPlants

11'
4
. 22
1 6r
107

of

TotalCapacity

10
4
21
62
100

2
1
19
83
100

Table8-27. NATIONAL
INVE;TMENT,
ANNUAtIZED
COSTS
AND
E~ISSIONS
(1980)
Cost of Control
Sulfur

Imnact of NSPS

Emissions

Plant

CaDacltv
(LTD) Number Investmentl
- (MM~)

of

Nominal Range Plants

Altn. I

Altn. Ilr

Annual
Costs2
(FPI~/Yr)

Altn.l

-.5-16

0:33

1.85 ~

O.20

0.58

]S

11-20

11

1.87

8. 47

0.83

i 2.38

25

20-30

1.00

3.68

0.38

1.00

gr)

3r)-7r) ~22

9.68

27.94

2.98

. 5.71

67
ln7

70.02
82.90

154.64

196.58

16.76

?TTT2;

27.10
36.77

Notes

i.

Total

2.

Fifth year'annualized

investment

3.

In

4.

Alternative

1975-1980.

costs (1980).

1980.

II oxldation

and reduction

IMMfl

Al=n. -II* Altn; I

7.5

ion TOTAL
,70

~ Investmentl

system casts averaged.

IMIZ/Yr~

Emf
tted3

Altn. TT Altn. I -Rltn.~l'A~tn.

I~/Yrl

I.

Altn. II

NSPS
Impact3

~Lv~

0.38

0. 18

0.02

0. 16

6.6q

1.55

1.29

0.13

1.16

2.68`:... ~

0.62

O.79

0.08

0. 70

.2.73

8.62 '

0.86~

7.76

18.26
-

Annual.
Costs2

84.62

113168

10.34

52.53

T5~i;Z~ .63.40

5.25

. 6.~4

47.28

57.06

8.4

POTENTIAL
SOCIO-ECONOMIC
ANDINFLATIONARY
IMPACT
Since

the

emission

based on either

control

emission control

systems

required

to comply

system alternatives

with

represent

standards

such a

small proportionof the overall equipment

or in;estmentrequired~by
a
petroleum refinery, there should be no more socio-economicimpact assoc~ated'
with

standards

than

unit

to a refinery.

associated

The inflationary

with

the

impact associated

addition

of any.new

with standards

for refinery sulfur plants is negligible.-

processing

of performance

If standards'are~based

on.

emissioncontrol systemalternative I, there is no inflationary impact

at

all.

If

standards

II, the fifth-year

increases

investment

necessary

varies

ar'e based

on- emission

control

system:alternative

annualited cost's are about $16 MM/year, and the'price

~o maintain

the

current

industry'average

from 90.004 to $0.106 per: barrel,

depending

return

on

on the

size of the refinery affected.

`These are well below the Environmental

Protection

for preparationof

Agency's

guidelines

statements.

8-39

inflationary

Impact-

REFERENCES - CHAPTER 8

7.

Oil and Gas Journal,'April

7, 1975, pgs. 100-118.

2. HydrocarbonProcessing, February, 1975, P9s 3-15.

3. Characterization of Sulfur from Refinery Fuel Gas, ~Contract No.
68-02-0611, Task 4), Battelle ColumbusLaboratories, June 28, 1974,
pgs.

4.

22-27.

Department of Labor, Monthly Labor Review, October 1975, p. 96.

5. Ford, BaconandDavis,SulcurRecovery
Plants, 1971,p. 80.
6.

Federal Power Comnission, Typical Electric Bills,

1974 FPCR-83.

7. Beers, W. D., Characterization of Claus Plant Emissiori,~Final

Report from Process Research, Inc., to the United States E.P.A.
Contract
(April

8.

No. 68-02-0242,
1973).

Task No. 2, Report No. EPA-R2-73-1'88

p_ 75.

Letter, Hanley, D. L. Union Oil Companyto Sedman, C. B. E.P.A.,

dated

12-4-73.

9. ComparativeAssessmentof Co~l Gasification Emis~ionControl Systems,

(Contract No. 68-01-2942, Task 007);'~Booz-Allen& Hamiiton, Inc.,

70.

October

1975,

page

A-3.

Letter,

Andrews, J. W., J. F. P. to Genco, J. M., Battelle

dated

12-21-75.

11.

12.

Letter,

Turner, W. W., Stauffer

E.P.A.,

dated

Letter,

Ballard,

E. P. A.,

Chemical Co. to Goodwin, D. R.

6-14-74.

dated

B. F., Phillips

Petroleum Co. to Sedman, C. B.

12-18-74.

13. Trip Report: Sedman,C. B., Standard Oil Company

of California, El
Segundo Refinery,

10-15-73.

14. Hydrocarbon Processing, April 1973, p. 116.

8-35

15. Op. Cit, Boot-Alien & Hamilton, pageA-ll,

16. Moody's Industrial

Manual, 1974 and 1975.

17. Beers,

W. D., op. cit.,

page 94.

18. Beers,

W, D., op. cit.,

page 93.

19

Op. Cit.,

Boot-Alien

12.

& Hamilton,

page A-5,

\;:\

8-36

9.
9.1

SELECTION

Sulfur
function

of the

which

enters

the

refinery

as elemental

in these

catalyst

fuel

oil

crude

portion

oil

sources

and the

the

sulfur

refinerv

i~

Most of the sulfur

is

in petroleum

and elemental

of the

leaves

products

fluid

are

processed

recovered

to the atmosphere

combustion,

regeneration

crude

produced.

or emitted

refineries

A major

petroleum

The major SO2 emission

gas and liquid

of the

in the

products

sulfur,

petroleum

itself.

refinery

for

from

content

petroleum

accounted

FOR THE STANDARDS

FOR CONTROL

emissions

sulfur

of the

the various
not

OF SOURCE

dioxide

complexity

RATIONALE

catalytic
sulfur

as S02
refineries
cracking

recovery.

are
unit

Standards

of performance limiting S02 emissions from gaseous fuel combustion

were promulgated

essentially
it

is

petroleum
P~troleum

above,
emitted

These standards

require the removal of H2Sfrom fuel gas before

burhed,

within

on March 4, 1974 (39 FR 9308).

thus

forcing

increased

elemental

sulfur

recovery

refineries.
refinery

sulfur

are responsible

recovery

for a sizeable

from petroleumrefineries.

plants,

portion
In 1975,

however,

as mentioned

of the total
nationwide

2O2 emissions

refinery

sulfur recovery plant S02 emissions were estimated to be 0.272 x ~~6 ~TT/
vr, or about 1O%of total domestic refinery SO2emissions.
refinery

portion
expected
control.
located

sulfur

recovery

plants

are

(about 1%) of the total

rapid

growth

As of April
in 81 domestic

of these
1975,

for

only

a small

unabated I1.S. SO2 emissions,

facilities.

there

refineries.

responsible

emphasizes

were 122 sulfur

eetween

the

recovery

1976 and 1980,

Although

the

need for
plants
107 new

their

Dlants

are

plants

(about

combined

exoected

to be built.

62X) will

capacities

Well over

have an average

of these

new Dlants

half

of these

new

size

of 100 LTD. The total

will

be about

6,000

LfD

so that by 1980the numberof refinery sulfur recovery~lants will

double.

A very important consideration

refinery

sulfur

in or near

increase

9.2

recovery

plants

is

areas..

As the

size

average

sulfur

content

urban

andthe

increases,

control

SELECTION

in chanter

of nerformance (i.e.

II

systems.

99 nercent

In terms

REDllCTION

emission

control

to serve as the basis for standa'rds

low temperature.Claus

T) and various

only

the

systems

nerformanceof

are

from about
use

bf emission

of

clearly

tail

gas scrubbing

95 Dercent
alternative

reduction,

systems,

to the

the

alternative

Use of an alternative

the overall

an

these

superior

4 and 6;)

system increases

with

refineries

TI).

(See chapters

sulfur-nlant

of these

of the crude oilprocessed

6, two alternative

candidates

(alternative

Considering

arerlocated

best system of emission reduction, considerin~

(alternative

alternative

refineries

and number

These systems are the third-stage

reactor~system

control

most

OF THE REST SYSTEM OF EMISSI~N

systems are considered

systems

that

for

of S02 emissions becomes much more critical.

As discussed

costs).

of develoDing standards

the

sulfur
to 99.9

recovery
Dercent,

I emission

alternative

II emission
of a refinery

comnared
control

TI systems

to

s~ystem.

reduce

emissions by 98-99 oercent,' compared to an emission reduction of

onl~y RO-85 percent

achieved

by the alternative

9.2

I systems.

Also,

the alternative
.to

fluctuations

gases

from the

~Iemission

control

whichmight

occur in the comDasition

sulfur

require strict

nlant.

systems

are essentially

The alternative

insensitive

of the tail

I systems,

however,

maintenance of a 2:1 H2S/S02ratio to function properly.

Thus, the alternative II systems are muchless prone to upsets and

are

able

to limit

emissions

to lower

levels

over

a wider

variety

of operating conditions than the alternative Z systems.

Considerin9the

various

both alternatives,

environmental

the alternative

emerge as clearly

II emission

systems result

ambient air
refinerv
substantially

nlant,

require

alternative
based

reduction

a level

of control

control

alternative

essentially

have

systems,

by about

90 percent

nati.onal

SO2 emissions

are

waste

impacts

result

of a

in a

concentrations.

systems.

would

on the alternativeII

there

5 emission-

in the maximum

II systems

of 502 from new or modified refinerv

Considerino

(See chanter 7.)

from the operation

of these

again

however, most State implementation plans (SIP)

I emission

on this

alternative

with

systems

I.

reduction

of 502 arising

the

greater

More imbortantly,
already

coritrol

although the alternative

in a significant

concentrations

sulfur

associated

suDerior to those of alternative

In terms of ambi~nt air quality,

control

impacts

and will

associated

Consequently,

little

or

sulfur

plants.

however, will
lead

no potential
with

either

9.3

on emissions

Standards based

tons

water

alternative

emissions

in the

imPacts

adverse

standards

no impact

to a reduction

environmenta'l

to the

redu'ce'these

by 1900 of some 55,000

possible

essentially

eauivalent

per

in

growth
year.

other

pollution
emission

of

areas,

or solid
control

svstem:.~ \I~~fth
regard to energy consumption, both alternatives
reduce

the

overall

sulfur

plant.

consumntion

Since most SIP's

of alternative
consumption

energy

I emission
can

be

already

control

associated

associated

require

systems,

with

standards

million

~w-hr/yr (.~0,000 barrels

With regard
there

ener~y consumption

appear

commitment

alternative

based

In terms
emission
about

twice

operate
SIP's

control

systems,

impacts,

of

associated

as the alternative
require

Neither

associated

Again,

installation

does

with

2 1/2

either

there

appear

standards.

II systems

and about

impacts,

with

or delaying

I systems.

the

by some 54

or any irreversible

systems.

alternative

as much to install

already

resources

impacts

the

alternative.

envirdnmental

or radiation

economic

on this

be reduced

of potential

for Ret-Qeveloping

of the

in energy

IJ systems. however, the

will

emissioncontrol

to be any incentive

the installation

of fuel oil p'er year) by 1980.

areas

to be no noise

orirretrievable

of these

to oth~r

a refinery

no reduction

If standards are based on the alternative

growth in national

with

the

alternative

generally

times

cost

as much to

however,

of alternative

since

most

I emission

control systems, ther~ewillbe no economicimpactif standards are

based

on this

alternative.

the impatton

a typical

profitability

from about

7.98-8.09
the

percent.

refinerwould

If

large
8.10

have

percent

magnitude

impact,

based

refinery
return

prices

per gallon,
therefore,

9.4

or less

for

on alternative

will

on assets

an 8.10 percent

to increase

cents

are

dntegrated

To maintain

by only 0.03-0.1.2
of this

standards

return
petroleum

reduce

its

to about

on assets,
products

than 0.5 percent.

is negligible'.

II,

The

The impact on a typical

small

refinery

islarger

large. refi nery 'due to the "economies -of-s cal e " .

impact of standards
systems will

based on the.alternative

re~duce the profitability

than that

In this case the

II emission control

of a small

refinery

from about

6.27 percent return on assets to about 5.80-6.18 percent.

maintain

a 6.?7 percent

have to increase

prices

cents per gallon,

twice

its

as severe

magnitude

return

on assets,

s~ petroleum

on the

products

is still

small.refiner

quite

increases

profitability
over

In terms
refining

the

past

of the

industry,

would

large

refiner,

to retard

sector of the domestic refining

the price

are negligible,
three

national

standards

refiner

While this impact is about

as on the

As with the large~refiner,

to maintain

To

by about 0.06'0.25

small and not likely

growth among the small refiner

industry.

the small

or 0.'16-0.94 percent.

on a

certainly

to five

years.

impact

on the

based

inCreases

on' the

necessary

in light

domestic

of price

petroleum

alternative

I emission

control systems will have no impact. Standards based on the

alternative

II systems,

requi red by the~domestic

period

however,

industry

from 1975 to 1980;

industry

will

ess enti ally

emission

control

cos'ts

annual

impact

If standards

systems,

there

are based on the alternative

annuali~ed

the

operating

and increased

national

costs

by some $16 MMper year

inflationary

negl i gi ble.

increase

investment

by some $1-15 MMover the five-year

and the

beincreased

The potential

will

is

of these

in 1980.

standards

and if

II systems, the increased

9.5

is

are based on the alternative

no impact,

product

of the

prices

are

well

standards

fifth-year
below

the

Agency's guidelines of. 81'00MM

per year and 5 percent for signalling
potential

inflationary

Itis

clear,

impact.

therefore,'that

systems -must be selected

considering
sulfur

costs"

p'lants

9.3

must

SELECTION

the

as the

alternative

"best

and that

standards

be based

on the

system of emission
of performance

use of these

above,

sulfurrecovery

of Derformance, therefore,
and modi'fie~~ refinery
alternative

selection-of

processes':
emissions

for refinery

II

control

sulfur

plants.

as the

basis
for

`The objective of standards

Selecting
for

emission

standards,

system alternative

to the

refineries

control

however,

compl~cates

control.

oxidation-scrubbing
.released

in petroleum

is to reduce these emissions from new

oollutants

Emission

reduction,

systems.

~Dlants

are major point sourc~s of SO2 emissions.

the

control

OF POLLUTANTS FOR CONTROL

As discussed

system

II emission

II refers

totwo

and reduction-scrubbi
atmosphere

differ~nt

no. Residual

from `oxidation-scrubbinq

processes consist of S02 Residual emissions released to the''

atmospherefrom reduction-scrubbing

processes,

however, consist

of 502 if the tail gases are incinerated before release to the

atmosphere, or a mixture of reduced sulfur
hydrogen sulfide

(H2S),-carbonyl

sulfide

compounds such as
(COS) and carbon disulfide

(CS2), if the;tail gases are not incinerated (see chapters 4 and 6).
A limit on 502 emissions alone, therefore, while appropriate for
the oxidation-scrubbing~processes,

and those

reduction-scrubbing

processes with'tai~

gas'incineration,

is inappropriate

reduction-scrubbi'ng

processes

tail'gas

without

9.6

for those

incineration.

While e~issions
without

tail

gas incineration

design and operation

will

not

process

of H2S from the reduction-scrubbing

exceed

of the process,

90-100

ppm unless

is permittedto

potential

air

can.vary

on the

emissions of COSand CS2

the

deteriorate.

pollution

widely depending

processes_

reduction

catalyst

Consequently,

problem posed by these

in the

the major

processes

is emissions

of H2S.

Minimizing emissions of H2S from reduction-scrubhing

without

tail

gas

incineration

requires

design

processes

and operation

of the

scrubbing portion of the process~to reduce emissions of H2S to

very low levels

initially.

If standards

of performance

do not limit

emissions of H25, ownersor operators of these processes could

operate

only

the

reduction

the scrubber portion.

portion

of these

The S02 originally

systems

and by-pass

present would merely be

convertedto H2Sand released directly to the atmosphere. A~though

this is possible, it is unlikely because at the ambient air concen-

tration of H2Swhichwouldresult (500-2000

,g/m3,with shorttermpeaks,2-10second,approachii~g
25,000,g/m3)an extremely
severe odor problem would result

(sge chapter 7).

Sources would

tend to control these H2Semissionsto very lowlevels due to

theoffensive odors which would.otherwiseresult.if
not

they were

controlled.

Even in the more likely

situation,

however, where emissions

of H2S were reduced to the range of 200-300 ppm before release

~~tothe atmosphere, ambient air concentrations of H2Sranging from

15 to 60 Fig/m3could arise with short-term peaks as high as500

to 800~g/m3. Sincethe odorthresholdfor H2Sis 45 vg/m3,an

odor air pollution problem could still
9.7

arise.

Althoughemissionsof COS
andCjpare normallyver?llow,
as mentionedabove;' if the reduction catal~st is permitted to
deteriorate, emissions of these compoundsfrom reducti on-scrubbinig

processeswithout tailgas incineration can approach1000ppm.

Underthese conditions, aibient air concentrations of COSand CS2'

ranging from100 to 400,g/m3couldarise, with short-term'peaks

approaching
3500to 5500~g/m3,respectively. Whilee
ambientair
concentrationsof cds and 032 at these levels probablydo not

poseheal.thproblems,
so little healtheffects'datais:available:
on 003and052that this is questionable.iThe~littjedata
available indicate adverse health effectsoccurring only at'

level's greater than 15,d00,g/m3for CSZ,with no data available

for'C0S--see

chapter

7.)

The data do indicate,

however,

that

these short-term peak ambientair concentr'ationsof 032 are at

the odor threshold
~also arise

level for ~CS2,so that transitorv

if the"reduction

Developing standards
from refinery

sulfur

catalyst

is permitted

odors could ~
to deteriorate.

of performance to limit-emissions

recovery

pl.ants,

therefore,

gives

of.S02

rise;to

a rather.unusual

situation.

In some cases,

compliance

with

standards,,

eliminating

SOe emissions,

wouldlead

to`em-issi'ons

while

of reduced~sulfur compounds(i.e.
lead to an odor air

courses ofadtidn
for control

pollution

H2S, COSand CS2), which could

problem.

emerge with regard'to

bit standards

these:

Consequently,~two

selec'iin'the

of performance for refinery

plants:

9.8

alternative

pollutants
sulfur

recovery

i.

Limit emissions of S02 only

2.

Limit emissions of both S02 and reduced sulfur compounds

Limiting emissions of reduced sulfur compounds(i.e. H2S,

COSand CS2)fromreduction-scrubbingemissioncontrol systems

~!ithout tail gas incineration,

however, would makethese pollljtants

"designated pollutants," and all existing reduction-scrubbing emission

control systems withouttail

gas incineration

installed

on refinery

sulfur recoveryplants "designatedfacilities," under section Ill(d)

of the Clean Air Act.

EPA's regulations

(40 CFR 960) would require

document containing
plans

and to solicit
tion

to the

tail

gas

comments on !this

document

incineration

then be required

the

pollutants

and issue

reduction-scrubbing

pollutants
views

installed

to develop

facilities

of interested

parties.

Developing

for states

to develop

document.

Following

it

in final

facilities

refinery

State

there

sulfur

for controlling
with public
These

Those

plans

or disapproval.

tail

sulfur

gas

incineration

recovery

to limit

plants

emissions
9.9

states

without
plants

would

emissions

hearings
would

then

be submitted

If a State's
aplan

plan were

for that

state.

emission

now operating
in some seven

of reduced

of there

to solicit

are about 25 reduction-scrubbing

without

plans

form.

considerachanges

control'systems

the Agency would have to develop

systems

petroleum

guideline

existing

on'refinery

plans

from these

Currently,
control

draft

from these

emission

to the Agency for approval

disapproved,

information

sectionlll(d)

comments, the Agency~would make appropriate

guideline

containing

these

public

of these

the Agency to Issue~a

the necessary

for controlling

implementing

on

states.

sulfurcompounds

from these

facilities,

requiring

the

State

local

and

expenditure

of considerable

of reduced-

reduction-scrubbing

incineration,

could be a significant
resources

underta~ing

at 4he federal,

level.

Emissions

installed

therefore,

sul'fur

emission

compounds

control

ho~~ever, are quite

to comply with State

from

systems

low.

these

existing

without

tail

These systems

or local

air

gas

have been

pollution

regulations

limiting emissions of S02 from ex.istin~ refinery sulfur recovery

nlants.

To ensure

systems

do not

that

lead

the

to local

installation

odor

of

problems,

these

emission

these

regulations

also limit emissions of H2S, COSand CS2, either

indirectly.
limited

~here
directly,

emissions
local

regljlations

of HZS, COS and CS2 that

to.the

atmosphere.

followed,

of reduced

sulfur

specify

can be present

or

compounds are

the maximum concentrations

in the.tail

In each case where this

emissions of H2S are limited

directly

control

gases discharged

approach

has been

to 10 ppm and emissions

of total sulfur (H2S, COSand CS2)are l'imited to either 300 or

500 ppm.

Where emissions
by local

regulations,

emission

control

specifying
pollution

emission control
agencies

these

technology

what'the
control

of reduced

best
agencies

sulfur

compounds are limited

regulations

require

he installed.

emission

that

Tn the process

control'technology

generally

contact

emission

control
9.10

is,

systems

available

of
Ideal

EPA, vendors

syst'ems and other local air pollution

where various

the best

indirectly

air

of various

control

have been installed.

In terms

of emissions

reduction-scrubbing
incineration,
as that

of reduced
emission

this

above,

approach

and all

have been designed

sulfur

control

compounds

systems

has achieved

25 of these

and guaranteed

to limit emissions to lessthan

without

the

systems

from existing
tail

gas

same end result

which

by the vendors

are

now operating

of these

systems

10ppm H2Sand less than 300 or

500ppm
total sulfur(HpS,
COS
andCS2).1
Consequently,

existing

systems

without

tail

gas

sources

of reduced'sulfur

reduction-scrubbi
incineration

are

ng~emission
not

compound emissions.

considered

control
significant

Developing

regulations

to control

facilities,

therefore, Wouldaccomplishno additibnal reduction in

reduced sulfur

emissions of these pollutants.from

State

thdse

compound emissions.

probably the major reason why exi sting reducti on-scrubbj ng

emission control
sources

systems without tail

of reduced -sulfur

gas incineration

compound emissions

these systems have only been installed

metropolitan

areas.

In these areas,

the need for air pollution

is generally

control

agencfes have been in a position

air

pollution

well recognized and the local air'pollution

to develop and enforce

regulations.

Standards of performance for refinery

will require

to date,

in heavily industrialized

control

strong

-is that

are not

the installation

sulfur

of oxidation-scrubblng

plants,

however,

or reduction-

scrubbing emission control

systems on new or modified refinery

recovery

the United States.

plants

throughout

9.11

In saneareas

sulfur

where these systems might be installed,

pollution

control

where these

systems

have already

been installed.

who installed

system without tail

regulation

air

might not be as great as it is in these areas

owners and operators

cdntrol

the need-for stringent

of reduced

a reduction-scrubbing

gas inci'neration

sulfur

In these

areas,

emission

would not face stringent

compounds and they might permit

emissions of H2S to increase to the range of 200 to 300 ppm. At

this point the resulting ambient air concentrations of H2Swould
lead

to noticeable

but

intermittent

earlier.

It Is quite

standards

of performance,

become sources

the standards

possible,

is one of the primary

standards

these
for

taking

gystems.
reducing

problems

emissions

the

of controlling

controlling

account

these

without

the

tail
these

gas

compounds

of these

pollutants.
however,

of performance.

Also,

systems

are

the

is well

demonstrated,

reasonable,

emission

technology

from reduction-

to an adverse

reduction-scrubbing

of emission

and operating

since

compounds

incineration

lead

unless

from arising,

perspective,

emiss~ons

could

plants~could

of installing

sulfur

as discussed

in complying with

the best

costs

from this

emissions

in some cases;

reflect

of reduced

systems

costs

of standards

are.to

Considered

scrubbing

impact

pollution'

odors

sulfur

sulfur

emissions

goals

into

that

limit

ofperformance

reduction;

of reduced

specifically
new air

therefore,

some new refinery

of emissions

Preventing

and transitory

and not
environmental

control

systems

without tail gas incineration can only be includedamongthe best

systems
are

of emission

reduction

if emissions

controlled.

9.12

of reduced

sulfur

compounds

It is also through standards of performance-that the Agency

identifies

the best systems of emission reduction

industrial

sources of air pollution.

limit

emissions

of reduced

sulfur

for various

If the Agency were not to

compounds, therefore,

it would

imply that the Agencydoes not consider controlling these emissions

from reduction-scrubbing
serve

to undercut

processes necessary.

or weaken those

which are now effectively

sulfur

local

controlling

air
these

recovery plants which have installed

emission

control

systems without

A number of good reasons

standards

to cover

tail

exist,

emissions

This view could

pollution

regulations

emissions

from existing

reduction-scrubbing

gas incineration.
therefore,

of reduced

for extending

sulfur

compounds.

the

'However,

a problem may arise if the burden of the state plan submission required
by 40 CFR s60.23

outweighs

its

possible

benefits.

To resolve

this

problem,it is appropriate to consider ~he intent of both standards

of perfoimance

and section

Briefly,

the

the

installation

time

a source

-jection Ill(d)
facilities

welfare,

but
be

as criteria

section

being

of standards
best

systems

constructed

of Performance
of emission

is

to require

control

or modified.

at the

The intent

of

is to reduce emissions of nollutants emitted from

existing

cannot

intent
of the

is

Ill(d).

which

which

pose

a danger

on the

basis

of the

controlled

pollutants,

under

sections

108,

and which

cannot

112 of the Act as hazardous

9.13

to the

public

information
109

and

or

available
110

be controlled

pollutants.

health

of

the

under

Act

Wherean emission'dontrol system installed to complywith a

standard of.perfon~ancemight~.ieed
to the emissionof a pollutant
not origina7jyemitted
is

to limit

by a source,

emissions

does riot lead

of this

to a newair

the logical

new pollutant

pollution~prdblem;

new pdliutantis~~a~~non-cri.te~ia

pojlutant;

course of action

to ensure

that

it

Tn' cases where the

itmust~be

decided

wheth~ror not fo initiat~' the c~iain'oi eve~ts leading'~t~:the

decelopnier;t
of st;ate regulati'onsfor li:mi.tingeihissions:
of~:thi5
pollutant::~rdmexisting sBlrcei already weii csntroi ied for this
poll utant.

Th~'pGll~utantssi;ie~cteh-foi';cdnt:roi`by'these stand~rds~,

therefore,areS02and'rreduceb
'sul7ur'
com~dundj.
A

aeterm~nat~on

of'the.-effdi~:t-invblved~in'deve~6ping:sta;te:'plans
~iil en'a~ble~PA:'
td' determiiie.~wh`ether
'or not tO'~e;velop a guibe:llne document or
initidte

-the -chain -d7.'eventsieading.'to~:t~~e development of std;t~e

plans for controlling

emissions of;reduced.'sulfur 'compoundsfrom'

exi st~i:rig
' redljct`i'6n~sc'.~;j6bi
ng' emis~:i~d;~n
control' syst~ms with`out`
tail

gas inc~i?eratron 3hi`ch'haiie~'been ~nst~aT~~don'j-'efinery su"lfur

plants.

: '"

. ~

: :
1;1.

:E:

9.4. ''SEI1.EijiZON.:OF:
FORMAT
FORTHESTANDARDS
Anumber df~ifferdnt

fbr~~tscou'i~d be selected tollmit

emissions frdm reiiriery s~lfur pl'ants'. Massstandards limiting

I~

~-r

emissionsin:terms of bverall sulfur~:r~covery(i.e.,emissions

per un;t''d-f sulftr; p;roduced;larcon~aine;din 'thE feed to the

9.'14

plant),

or concentration

of emissions
could

standards

in the stack

gases

limiting

the concentration

discharged

into

the atmosphere,

be developed.

While mass standards.may appear more meaningful in the sense

that

they relate

into

the atmosphere,

and the

directly

results

to the quantity

enforcement

more subject

of emissions

of mass standards

to error

than

di scharged

is more costly

enforcement

of concen-

tration standards. Determiningmars emissions, for example,

invariably

requires

developing

a material

balance

of some'fonr~

and this requires process data concerning the operation of

the plant,

whether

flow rates.
necessary

of this

it be input

Gathering

this

chance

for

human

Enforcement

increases

increases

inherent

Concentration

the

within

or production

the testing
costs.

or monitoring

Manipulation

necessary,

the data and increasing

error.

of concentration

standards,

a minimum of data and information,

minimizing

flow rates

the number of calculations

compounding the error

the

data

and consequently

data increases

material

the chances

for error

standards

are also

requires

decreasing

the cos'ts and

in determining

compliance.

somewhat more consistent

of basing

reduction,"

since vendors of emission control equi-pment normally

the perfoimance

concentration

tration

of their

of emissions

fhe primary

standards

of the "best

disadvantage

equipment

systems

with

the concept

guarantee

standards

however,

of emission

in terms of the

discharged.
normally

is that of possible

9.15

associated

circumvention

with concen-

by dilution

of the gasesdischargedto the atmosphere

loweringthe concentration of emissions, but not reducing the total mass emitted.
To ensure that compliancewith concentration standards is not

achievedby dilution, however,section 60.12'of40 CFRPart 60

specificallyprohibitsthe useof dilutionas a meansof complying

with concentration

standards.

Consequently,
enforcement,

considered primarily

concentration

for standards

standards

of performance

lower resource

requirements

mass standards

far

9.5

Of

SELECTION

from the perspective

are

selected

for refinery

sulfur

of concentration

outw~g.gh their
EMISSION

as the

plants.

of

format

.The

standards

over

drawbacks.

LIMITS

IN

THE

STANDARDS

Specific emission limits need to be selected to limit

emissionsof S02fromrefinery sulfur plants whichemployeither

oxidation-scrubbing
emission

limits

emission

control

also

which

without

tail

with

systems
gas

to limit

or reduction-scrubbing

incineration.

Emission

emissions

of H25 and

compounds (H2S, COSand CS2) from refinery

employ

reduction-scrubbing

emission

control

sulfur
systems

~gas incineration.

The data

and information

limits

is summarized

source

tests

to support

in chapter

number of fac.tors

need

selection

4 and consists

by the Agency or local

Since the amount of Mission

emission

tail

need to be selected

reduced sulfur
plants

systems

control

air

to be considered

limits.
9.16

primarily

pollution

data available

of these

control

emission

of emission
agencies.

Is quite limited,

in selecting

the

specific

Considering first the limit for SOe~emissions,the emission

source~test

data

from oxidation-scrubbing

emission

control

systems

shows emissions in the range of 10-50 ppm (tests A1,-A2, A3,

Figure 4-10).

These data,

however, were collected

operating

at less

following

a major equipment

do not
unit

reflect

emi~sion

operating

at

to both vendors
deterioration

than half

full

turnaround.

systems

turnarounds

operate

of this

emission
normal

data,

run

maintenance

for

a period

length

and chemical

According

equipment

lead to lower efficiency.

a year

would
major

replacement

between

emissions

Basing theemission

between

by a

of time.

unavoidable

time,

therefore,

the data

be maintained

about

and duringthis

basis

increase

over

immediately

Consequently,

could

ag~n~g will

much as 100 to 200 ppm.

the

that

capacity

by'as

shorten

capacity

and owners and operators,

these

equipment

design

levels

and chemical

Generally,

its

from a unit

major

ihcrease

limit

solely

on the

significantly

turnarounds
costs

and

oonsiderably.

The emission source test data available from reduction~`scrubhinr1

emission control

systems with tail

gas incineration

of about 200 ppmSn2 (test C, Figure 4-10).

shows emissions

Although thi~ data

is not EPAdata, but is data from a test by a local control agency

(EPA's source testing. at this facility

was invalidated due to

operating problems),.the source testing methodemplovedby this

local agency is consfdered comparable to EPA's.

9.17

This

em'ission

for a typical

level,

however,

reduction-scrubbing

is~considered

higher

than

emission~control.system

normal

with tail

gas incineration.IAccording
to the operatorsat this source,this
particular

facility

is significantly

under-designed

and, in fact,

shortly after this emission test data was gathered, i~ was Ilbebottle-necked" and expanded toimprove its'performance.
In EPA's discussions
with the operators

that

with the vendors

of this

it was "under-designed."

facility,~'they
They also

agreed

indicated,

however, that emissions from.typlca7' reduction-~crubbing emission

control systems with tai~"gas ~ncineratidn'are normally comparable
to those from oxidation~~'scnubbing emission dontrol'systems,
emissions from both systems increase
turnarounds

due to ~navoidab~e

to'about

and that

the iame extent~t;etween

eq~jipment deterioration

andch~mical

aging.

As Ipointed out'in chapters 4 and 7, the reduction-scrubbing

emission

control

s~ystems with

to those without'tail
over

tailgas

~nc~nerar;~on

gas incineration)

oxidation,scrutibing

___~

~as opposeo

have a.number of ddwantages

emissioncontrol

systems.

Operation

of these~jystems involves techniques-withwhic~ most refiners

have had a'great

deal of experience andthus

these systems better,

and generally

ten~to

tend to:favor

refinersunderstana

experience fewer'problems
these systems.

with them

More. i'mpor ta ntl y,': -how`ev

er ,

these reducti on- scrubbi ng..emis s i on contrb~TT

systems with ta i 1 gaS
incineration

produce no wastewater

Both the oxidation-scrubbing

systems without tail

streams

systems

gas incineration

9.18

that

require

disposal.

and the reduction-scrubbing

generate a wastewater stream.

Considel'ing all these factors,

emissions

is set at 250 ppm.

oxidation-scrubbing

emission

scrubbing:emission
In

view

of

the

control
limited

This limit
control

appears

emission

of these

also

that

ensure

installed

emission

these

and well

to both the

s~stems and to the reduction-

data

'gas incineration.

available

and

and the control

to be a reasonable

performance

applies

systems with tail

of both the owners and operators

this

the emission limit for S02

emission
control

alternative

II

the

corr~nents

system vendors,

l.imit consistent

systems.

with the

This limit

emission

control

will

systems

are

operated.

Considering the emission limit for emissions of H2Sand'reduced

sulfur

compounds,

the

available

emission

source

testing

data

from

reduction-scrubbingemissioncontrol systemswithout tail gas

incincratibn

shows that

emissions

of these

pollutants

from these

systemsare quite law. Emissions

of H2S,for example,were
frequently not detectable (tests B1, B2, Fl and Fl, Figure 4-11).
In the one test in which emissio?s of H2Swere detected (test B2),
an ana.lvtical method different
was used and simultaneous

from that employed by the Agency

testing

by the Agency-~detected

no emissions

(test B3) Review ofboth `the Agency's test method and this-o~ther

test methodindicated that this methodwhichdetected H2Semissions

was not as selective

as ~he Agency's

in identifvi~q

~ZS, and was

including some of the COSand CS2 present asH2S.

The

sulfur

emission

source

test

data

available

on emissions

of

compounds (H2S, COSand CS2)'from these emission-control

9.19

reduced

systems

shows that

emissions

of these

pollutants

are in the range

of 10-20ppm(tests B1,Bil, B3,El andFl, Figure4-12). Here

again,

however,

after

major

this

data was collected

equipment

well below~their

turnarounds,

design

from these

or when they

capacity

systems

were

shortly

operating

las low as 1/3 of design

capacity

in one.case).
Discussions

indicated

that

with

the

vendors

unavoidable

equipment

agingleads

to a gradual

Increase

plant

for

indicates

data,

example,

of these

about 200 ppm over a vear's

control

systems

deterioration

in emissions
that

and chemical
with time.

emissions

operation.

also

Thus,

Pilot

increase

by

as discussed

above

for the oxidation-scruhblng systems and the reduction-scrubbing

systems.with

tail

gas

incineration,

basing

the

emission

limits

for reduction-scrubbing emission control systems withou~ tail gas

incineration
shorten

solely

the

the costs

normal

on the

emission

run length

of maintenance

between

and chemical

Considering these factors,

and reduced.sulfur

instal~ationof

local

odor

availab'le

major

replacement

the limit

gas.incineration

would

turnarounds

is

significantly
and increase

considerably.

on emissions of H2S

compounds from reduction

s~stemswfthouttail

respectively.

data

set

scrubbing
at

emission

control

lO ppm and 300 ppm

The 10 ppm limit on H2S emissions will ensure that

these

airpollution

emission

cont~ol

problem.

systems

will

not

The 300 ppmlimit

to the 250.ppm l~mit on S02 emissions in the sensethat

lead

to

is equivalent

both limits

reduce suf fur -emissionsr-be they S02 or H2S, COSand CS2--to the
9.20

samelevel. (The250ppm
~02limit reflectsthe largervolume
of gases discharged to the atmosphere.)
9.6 SELECTION
nF MONITORING,
REOUIREMENTS
ANDPERFORMANCE
TESTMETHODS
The objective
and

easy

control

means

system

for

of monitoring

reduirements

enforcementDersonnel

installed

to comply

to

with

is to provide
ensure

that

standards

a quick

an emission

of performance

is properly oDerated and maintained. For refinerv sulfur recovery

plants,

the most straightforward

and maintenance

is

to monitor

means of ensuring
emissions

released

proper
to

the

operation
atmosphere.

Consequently,where oxldationcscrubbing processes or reductionscrubbing

processes

with tail

gas incineration

are installed

to

comply with the standards, monitoring of S02 emissions is required.

Where reduction-scrubbing

processes

are installed,

of H2S and reduced

monitoring

without

tail

gas incineration

sulfur

compound emissions

is required.

Although monitoring requirements are included for HESand

reduced

sulfur

performance

compound emissions,

specifications

and operators

the Agency has not yet developed

for these

monitors.

of reduction-scrubbing

~ tail gas incineration,

not have to install

emission

these monitors

these

is.included

monitors

to standards

until

in determining
operated

in the regulations

become available,
of performance

will then be required

control

owners

systems without

who are subject to these requirements, will

these

been promulgated in the Federal Register.

monitoring

Consequentl~y,

sources

before

to install

if the emission

the

specifications

have

The requirement for

to ensure

that

when

which became subject

monitors

were

available

monitors to aid enforcement personnel

control

and maintained.
9.21

system is being properly

For determining
Determination
will

of Sulfur

be used where

scrubbing

compliance
Dlo#ide

processes

installed,

Carbon~~

with tail

Sources

Method

Sulfide
will

other
9.7

i.

methods

Details
for

from Stationary

processes

These

Disulfide

are installed.

methods

were

the

Sulfide;

from Stationary
methods

used

to gather

in chapter 4 and Appendix C, which support

as to why these

gathering

gas incineration

of Hydrogen
Emissions

S~ources

or reduction-

gas incineration

18 - Determination

and Carbon

be used.

standards.

Emissions

Method 6 -

processes without tail

the emission data contained

the

the~ standards,

oxidation-scrubbing

Where reduction-scrubbing
are

with

this

data

mhthods

were

ma!, be found

selected

in Appendix~D.

REFERENCES

Telephone conversation, F.L. Porter

(Union Oil), April 28, 1976.

9.22

over

(EPA) with G.L. Tilley

APPENDIX A'
EVOLI~ION

OF STANDARDS

A.1

EVOLUTION OF STANDARDS

Date

8/73-7/74

Surveyed and reviewed

process

emission
control
systems
for
Claus
sulfur
recaver~y
plants.

8/73

Sent letters

to control

reauestina
desian
Beavon, Cleanair,
and

9/73

location

Selected

of

eight

operations
all

and

domestic

eouinment

vendors

data for the Wellman-Lord,

SCOT, and Aquaclaus
orocesses,
well-controlled

refineries

Cl.aus

nlants.

for initial

~lant

insoections.

10/5/73

Contract'ed

for detailed

Claus

aas

tail

.enaineerina

control

systems

study of

klith

Battelle-

Columbus.

10/10-10/19/73

Inspected
Claus
and

10/17/73

sent

10/ 73-2/ 74 '

114

refineries

with well-controlled

pre-surveyed
letters

to

for

regulations

for

sulfur

Cataban,

and Chivoda

for

gas

tail

sulfur

recovery

of
plants.

Thoroughbred

processes

removal.

Test methods for determi ni nq~~gaseous sul fur

compounds in Cfaus tail
PFesurveys-made

2/25-3/13/74

testina,

Contractorsent
additional
letters
to vendors
for design data on the IFP-1, IFP-2, Sulfreen,

gas

H2S, SO2, Sr) investioated

1/11/74

emission

refineries.

~et with Los Angeles APCDfor discussion

their

11/73

eiaht

plants,

of three

e.,

likely

Inspection made of IFP-1 process

sulfur plant.
Emission tests
Beavon,

A.2

completed

and SCOT control

COS

anC61
develope~j.
test

C.S~

sites.

on a C!aus

for Wellman-Lord,
systems.

4/1/74

Inspection made ofsecond

Claus
sulfur
process
sent

5/7/74

plant.
114
to operators.

IFP-1 process on a
letters

onIFP-l

~leetin~ with API's

Committee on Environmental

Affairs
potential

emission

to

discuss
standards.

6/10-6/12/74

Emission test

6/74

Study

test,results

of IFP-l control

entitled

and

system completed.

"Characterization

of Sulfur

Recovery From Refinery Fuel ~as" completed

by Battelle-Columbus
Labs.
Report circulated
to

8/74-

2/.75

API

for

review.

Emission control costs developed; mbnito~rins

and emission test met~bds finalized,
and
dispersion
anal~vses completed.
draft
of EPA Standards
Suoport

Developed first
and Environm~ntal

Impact Document (SrEID).

3/75

Revised SSEID and sent

~roup

4/29/75

5/5-5/6/75

to NAPCTACand ~orkina

members.

Met with

EPA !lorkina

of

and

SSEID

the

r7roup to discuss

recommended

fin~inas

standard.

Met with NAPCTAC

to review the recommended
standard
for
basis forthe

5-7/75

refiner~v
standard

sulfur
plants
and the
outlined
in the SSEID.

Delayed action to resolve potential

aspects
plants.

8-9/75

of standards

Responsibility
ferred

10J75-4/76

for

refinery

for SSEID informally

to Standards

Ill(d:
sulfur

trans-

Development Branch.

SSEIDreviewed, edited and rewritten by

Standards
Development
Branch
with the'general
outline
for

A.3

to conform
a SSEID.

APPENDIX
INDEX fO

ENVIRONMENTAL

IMPACT

B.1

CONSIDERATIONS

APPENDIX B

INDEX TO ENVIRONMENTAL
IMPACT CONSIDERATIONS

Agency Guidelines

i.

for Preparing

Regulatory Action Environmental

Location Within t'he Standards Support

Impact Statements (39 FR37419)

and EnvironmentalImpact Statement

Backgroundand Description of Proposed Action

Summaryof Proposed Standards

The standards

are summarized in chapter i, section

Statutory

The statutory

basis for the standard is given in

Basis for the Standard

chapter

Facility

Affected

2.

A description
given

~ ,,,,,,,,,.,,.,

of the facility

in chapter

A description
chapter

~ Rvailability
ofContml
Technology
Existing Regulations at State or Local Level

given

of the process

Alternatives

to the

Proposed

No Action or Postponing

Environmental Impacts

affected

of control

is

givenin

technology

regulations

by the standards

on the industry

is included

in chapter

3,

3.

Action

Action

Environmental effects
are

Costs

is

4.

of existing

to be affected
2.

tobe

on the availability

in chapter

A discussion
section

to be affected

3.

3.

Infoimation
is

1.1.

discussed

of not implementing the standards

in chapters

3 and 7.

The costs of not implementing the standards

in chapter

8, section

8.1.

are considered

I:

INDEX
TOENVIRONMENTAL
IMPACT
CONSIDERATIONS
(continued)

Agency
Guidelinesfor Preparing
Regulatory Action Environmental
ImpactStatements(39 FR37419)
Health and WelfareImpact
Alternative

LocationWithinthe StandardsSupport
and EnvironmentalImpact Statement

The
health/welfare impact of not implementing
standards is considered in chapter 7.

I - 99% Control

Environmental

Impacts

The environmental 'mpacts associated with alternative I

emission control systems are considered in chapter 7.

B ,.,,,

The cost

6~ ,,,,,,,,d Welfare
Inpact

The impact

3.

the

impact

of altrrnative

I emission

control

systems

is considered in chapter 8, section 8.2.

of alternative.I

emission

control

systems

on health and welfare is considered in chapter 7.

Environmental Impact of Proposed Action

Air

Pollution

The air pollution impact of the standards is considered

in chapter

7, section

7.1.

WaterPollution

The
impactof the
sidered in chapter

SolidWasteDisposal

solid waste
The
impact
of
the
standard
on
considered in chapter 7, section 7.3.

Energy

standards

7, section

on`water

pollution

is con-

7.2.
disposal

i.s

Theimpactof the standards on energyuse is considered

in chapter

7, section

7.4.

APPENDIX
EMISSION

SOURCE

C.1

C
T:EST

DAfA

EMISSION
C.1

SOURCE

TEST

DATA

INTRODUCTION

This appendix summarizes the emission test data gathered during

the development
information
facility

of standards

for refinery

on each facility
is identified

reference

in this

tested

0.2

appendix

Detailed

is presented

herein.

.Each

to commercial

products

an endorsement

Any

or processes

by the Environmental

Agency.

SUMMARYOF TEST DATA

Four different
sulfur

pl-ants.

by the same coding used in Chapter 4.

by name does not constitute

Protection

sulfur

plant

processes

exhaust

best available

gases were tested

control

of the Clean Air Act.

for removing sulfur

by EPA to determine

technology as required
Pollutants

from Claus

neasured

by EPA Method 18 (~gas chromatograph/flame

the

By section 111

included

total

sulfur

photomettic detection),

SOpby EPAMethod 6, H2Sby EPAMethod 11, carbon monoxideby

EPAMethod 1O, NO, by EPAPlethod 7, hydrocarbons by a flame
i'onirat~on

detector,

Orsat gases by EPAMethod 3, and moisture

by EPA Method 4.
0.3

DESCRIPTION

OF FACILrTIES

Plant A - Plant A consists

of three i'dentical

151) long ton/day

(LS/D)Claus trains, two of which operate with the third on stand-by.

Emissions from each Claus traini's
scrubber.
S02.

controlled

by a Wellman-Lord

Design basis of these We?lman-Lord scrubbers is 250 ppmv

Tests Al and A2 were performed by EPA and refinery

respectively,

during

the period

March 11-13,

1974.

personnel,

In TestAl

sulfur compoundswere.determ~ned by EPAMethod 18 (gas chromatograph/

flame photomet~icdetection) for total sulfur and EPAMethod6 for S02

0.2

Carbon dioxide,

carbon monoxide,

and oxygen were determined

by continuous

methods(non-dispersiveinfrared for COpand COand paramagneticfor 02)

and by the Orsat method.
visible

emissions

Methods

i,

2,

ionization

Nitrogen

oxides were determined

by EPA Method 9, moisture'and

and 4,

and hydrocarbon

flaw

concentrations

by EPA Method 7,

rates

by EPA

by a flame

detector.

In fest AZSOpand.NOx
were determinedby a fuel cell electrochemicalmethod,COS~and
CS2by a gas chromatograph
flame photometric
detector,

CO and 002 by Orsat, 02 6y Orsat and a paramagnetic oxygen

analyzer,

and hydrocarbons

During

Tests

Al and A2 only

due to low refinery

Sulfur

feed rates

6ya hydrogen flamegas

one sulfur

throughputs
during

plant

war operating

Caused 6y the 6PEC oil

the tests

Test A3 was conducted

chroma.tograph.

averaged

embargo.

113 LT/D for three

by the Los Angeles APCD, 3anuary

on all three Claus plants.

Hydrogen sulfide

runs.

10-11,

1973,

was determined by a ZnCO3

impinger
train, and502by Impingers
contafning
a 51 NaOH
solution.
Nitrogen

oxides,

moisture,

hydrocarbons,

and flow rates

in the Source Testing

Sulfur
and 68.8

Plant

feed

LT/D,

basis

three

plants
averaging

B consists
into

of each Beavon tail

during
well

a Beavon tail

with~less than 10 ppmvH2S

0.3

unit

dioxide,

to methods described

APCD.

Test

A3 was 116.6,

below

of two parallel

gas treating

cdrbon

according

Manual of the LosAngeles

respectively,

each of which exhausts

monoxide,

were determined

to the

B -~Plant

carbon

design

76.9,

rates.

l0O LT/D Claus trains,

gas treating

unit.

is 200 ppmv total

Design
sulfur,

Tests

B1 and 82 were

respectively,

during

the

performed
period

compounds were determined

metric detection)
dioxide,

carbon

by EPA and refinery

March 5-7,

1974.

personnel,

In Test

B1 sulfur

by EPA Method 18 ('gas chromatograph/flame

for total
monoxide,

sulfur

and EPAMethod 6 for S02;

and oxygen

were

determined

Carbon'

by continuous

methods (a non-dispersive infrared instrumentfor C02 and CO, and

paramagnetic analyzer for 02) and by the Orsat method. Nitrogen
oxides

were

determined

Method 9, moisture

by EPA Method 7,

and flow

rates

and hydrocarbon concentrations

visible

emissions

by EPA plethods

i,

2,

by a flame ionization

by EPA
and 4,

detector.

In Test 82 mass spectrometry:.was used ~o determine CHq, COS,

S02' H2S, CS2, He, CO!N2,02, Ar, and C02 Gas chromatography
was then used to obtain the CO/N2split.
During Tests
below des~gn levels

B1 and 82 the sulfur

due to the OPEC oil

to each or both Claus tratnCs)Test 83 was conducted

occasions:

plants

embargo.

averaged

24 tests

determine

effect

the

Sampling techniques

overhaul

included

before

24, 1974.
and after

well

feed rate

by the Los Angeles APCDon three

were performed
of

Sulfur

34.2 LT/D for three

3uly 10, August 8, and September

and September

were operating

runs.
'separate

The August 8
overhaul

to

on emissions.

a 5% HC1 solution

In an impinger

to collect arrpnonia,a 3%H2O2solution in an impinger to collect

S02' and~a ZnCO3slurry in an impinger for H2S collection.
samples were made for subsequent determinations
052 by gas chromatograph

with a flame photometrlc

carbon monoxide by non-dispersive

infrared

C.4

Grab

of H2S, COS, and

detectorand

absorption.

photo-

Plant

C - Plant~C

Claus unit
basis

followed

as H2S. An incinerator
to the

of one small

by a SCOT tail

of the SCOT unit

discharge

consists

15LT/D,

two-stage

unit.

Design

gas treating

is 400 ppmv total'sulfur

oxidizes

emissions

calculated

the 40~ppm H2S to 502 before

atmosphere.

Test C3 was conducted

Hydrogen sulfide

by the Los Angeles APCDon February

was determined By a ZnCO3train

at the outlet

14, 1974.

of the

SCOTsystem. At the incinerator stack S02 was determined byan NaOH

train; combustion~ases (CO, C02, and CHq)were analyzed by total

combustion

analysis

using a non-di'spersive

infrared

Instrument

and NO, was determined By hydrogen peroxide/sulfuric

trai ns .
using

Watervapor,

Los Angeles

acid impinger

gas flow and Orsat gases were also

analyzed

APCD methods.

Du~ing Test C3 sulfur

feed averaged

11=1 LT/D.

Plant O - Test D1was conductedJune 10-12, 1974,

by EPA on a large,
an IFP-1 tail

395 LT/D, three-stage

eras process.

acid gases produced

Claus plant~followed

The Claus plant

in a carbon disulfide

recovers
plant.

sulfur

by
from

Emission design

for the TFP-1unit is 90 Percent conversion of (H2S+502) from the

Claus plant.

This corresponds to 1640 ppmvtotal sulfur Cwet) or

2540 ppmv total

In the

first

sulfur
test

(~dry).
total

sulfur

compounds

were

(gas chromatograph/flamephotometrre detection).

determined

by EPA Method

S02 was dete~mSnedby

EPAMethod6, H2S By EQB;Plethod11, NO, by EPAMethod7, moisture

by EPA Method 4, gas flow by EPA Methods 1 and 2, and visible

emissionsby EPAMethod9. CO2,COand 02 weredeterminedby

C.5

18

continuous

methods (non-dispersive

infrared

for C02 and CO, para-

magneticanalyrerfor Og). COpand02 werealso determined

by a gas
chromatograph

with thermal

The second test

conductivity

was,conducted

detection.

using a Meloy Analyzer,

which

oxidizes all sulfur compoundsto 302 and then measures S02 by a

flamephotometric

detector.

a DuPont analyzer,

The third

test

oxidizes

all

which also

was conducted
sulfur

using

compounds to

SOp,but whichthe? measuresS02by UYabsorption.

During these tests,
336

sulfur

feed to the`Claus

unit averaged

LT/D.

Plant

E - Plant

a Beavon tail

E~consSsts

gas treating

of two 96 LT/D Claus

unit.

plants

Test El was conducted

each with

December 12,

~974,bytheLosAngeles
APtD.Analyses
f6r COS.
tSp.HeS,SDp.
H2S04, total
methodology

sulfur,

CO,~and NO, were conducted.

were not spedified,

Details

on test

though ass~med the same as in previous

tests conducted By ios Angeles.County(jests A3 and 83). Noprocess

data

total

were

available.

sulfur,

The Beavon units

were

designed

at 200 ppmv

16 ppmv H2S emission levels.

Plant F -~Plant Fconsists

which removes sulfur
in a petroleum

of a Beavon tail

gas treatingunlt

from four combined Claus pf8nt

refinery.

No design

Los Angeles County conductedtests

or operating

tail

gas streams

da~a are available.

November 6, 1974, for total

sulfur, H2S, and carbon monoxideCtest Fl).

Again, test methods

are~assumed to be LosAngeles APCDmethods as described far

Tests

A3 and

33.

C.6

Table

'FACILITY

Sun~wlary of Results

Test

Number

Al

Run Number

Date
Stack

3/11/74

3/12/74

Average

3/13/74

Effluent:

Flowrate - DNM3/min

197.1

Water vapor - Vol. %

13.0

135.4

209.7

10.6

11.2

180;4

11.6

C02 - Vol. % drya

3.2

5.35

6,3

02 - Vol. %drya~

0.8

2.95 .

1.9

CO - Vol. % drya

0.0

0.0

0.0

002- Vol. %dryb

4.3

5.6

3.8

02 - Vol. %dryb
CO- ppmvdryb

0.9
95

0.2
100

1.5
39

0.9
78

5.9

22.8

7.4

11.7

S02 - ppmvdryc

S02- ppmvdryd

..

38

16

4.6

10

21

COS- ppmvdryd

3.2

1.9

0.9

CS2- ppmv
dryd

2.5

3.4

1.1

H2S- ppmvdryu

<0.1

<0.1

<0.1

TS - ppmv dry d

46.2

24.7

13.1

28

NO,- ppmvdrye
THC- ppmvdryf

17.2
7.5

21.0
4.6

15.7
6.1

Visible

emissions9

9.0
6.2

a0rsat analysis
NDIR/Paramagnetic

"EPA-6

dcC/FpD(EPA-18)
eEpA-7
Total

t~ydrocarbons

as me'thane

by flame

EPA-9
Source:

Reference

C.7

ionization

2.0
2.3

TABLE

FACILITY

Summary of Results
Test

Number

Ail

Run Number

. 1

Date

3/12/74

Stack

2
3/13/74

Effluent:

Flow

rate

Water

DNM'/MIN

vapor

-vol,

C02 - vol. % drya

02 - V01. L~dr~va
CO - vol.

% drya

- 6.6
1.3

6.6
1.3

- 0.3

0.3

SOp- ppmvdryb

1D

COS - ppmvdSvc

'

15

:i3;3

1.5

NO,- ppmvdryb
HC~- ppmvdryd

21.7

25

3.0

electrochemical

'GC/FPD
(EPA-1RJ
Hydrogen

flame

Source:

Reference

23.4
3.0

a0rsat analysis
cell

12.5
0.3

CS2 - ppmvdrye

fuel

Averaae

chromalo~raphy
2

C.8

TABLE
FACILITY

3
A

Summary of Results

Test Number

A3

Run Number

Date

Average

1/11/73

1/11/73

229.37

150.08

127.43

169.05

14.0

10.0

12.0

12.0

16.0

16.0

0.36

0.20

S02 - ppmvdry
H2S- ppmv

31
<.10

38
<.10

COS- ppmv

15

CS2 - ppmv~

13

Stack

1/10/73

2 '

Effluent:

Flow rate,'DNM3/M
Water

vapor

- vol.

002 - vol. % wet

CO - vol.

% dry

'17.0
0.067

0.41

47
1.7

40
0.6

~1

6.0

i.

5.7

NO, -Ib/hr

0.57

0.59

0.46

0.54

HC - Ib/hr

~0.90

0.44

0.21

0.52

Source:

Reference

C.9

TABLE
FACILITY

4
B

Summary of Results
Test

r~umber

B1

Run Nws~er

3/5/74-

3/6/74

3/7/74

DNM3/FT

65.5

71.6

68.8

68.6

Water vapor - vol %

4.2

5.0

3.3

4.2

C02 - vol. % drya

02 - vol. % drya

5.4
0.6

5:5
0.5

6.0
0.3

5.6
0.5

CO - vol.

5.8

5.7

5.9

5.8

Date
Stack

Average

Effluent:

Flow rate,

% drva

C02~- vol. % dryb

02 - vol. 4 dryb
CO- vol. %dryb

0.02
566

0.09
565

0.02
604

0.04
578

S02 - ppmvdrve

3.6

3.8

4.5

4.0

S02- ppmvdrvd

1.5

0.7

0.76

1.0

COS-,ppmvdryd

17

CSZ - ppmv dryd

0.15

H2S- ppmvdr;d
TS - ppmvdryd
NO,- ppmvdry"
THC;ppmv dryf
Visible

emissions

17

15

16

<0.1

<0.1

<0.1

<0.1

19
1.1

17
0

16
0

17
0.4

a0rsat analysis
NDIR/Paramagnet~e
EPA-6

dcC/FpotEPA-18)
eEpA-7

fTotal hydrocarbons
as methaneby flameionization
9EPA-9

.Source: Reference 4
C.10

TABLE
FACILITY

Summary

of

Test Number

Results

B2

Run Number
Date
Stack

3/5/74

3/6/74

3/7/74

5.0

6.0

Averaae

Effluent:

Flow rate,
~later

DNM3/M

vapor

- vol.

H2 - vol. %

5.8

5.6

CO- ppm

479

620

595

565

CHq- ppm

125 -

206

332

221

N2- vo~. %

87.7

02 ' vol. X

H2S- ppmdry
Ar - vol.

86.9

87.2

2.7

1.0

1.0

1.0

1.0

002 -vol. X

63

6.0

6.3

6.2

COS- ppm dry

9.0

S02- ppmdry

1.7

CS2- ppmdry

~0

Source:

Reference

87.0 i

C.11

TABLE 6
FAC ILITY-B

Summary of Results

Test Number

83

dun Number

Date
Stack

1'

7/10/74

8/8/74

Avera?e

9/24/74

9/24/!4

346

335

341

O
68

5
7.0

O
13.0

Effluent:

Flow rate,

DNr?S/M

Water vaporl- vol; ~e

C02 - vol.

4%

CO- ppm
502 - ppmvdryl
COS- ppmvdryl

O
23.0

C5p- ppmvdryl
H25- ppmv
dryl

9.7

Source:

Reference

O
16.0

Note:

i.

Assumemoisture level of 5.6%based on test 52.

C.12

2.4

T)

Table
FACILITY

7
C

Summary of Results
Test

Number

Run Number

Date
Stack

2/14/74
Effluent:

Flow rate -~ ~k~3J~

11.33

H,S - ppr~Ja

<10

H2S- ppmv
a
S02 - ppmv

SOp-Ib/hr

5.5

S03- Ib/hru
NO, - ppmvb

0
14

CO - ppmv b

1500

02-Vol. ~h ~

12.5

COp
~Yol.%b
HC- Vol. %b

aIncinerator
Incinerator
Source:

197

inlet
outlet

Reference

0.13

Table

FACILITY

Summary of Results

Test Number

Run Nlimber

Date

(See be'low)
2

Average

6/10/74

6/11/74

6/12/74

Flowrate - DNMJ/min ~421

431

414

422

37.7

39.0

35.9

1.1

1.1

0.35

0.31

0.31

Stack

Effluent:

Water

vapor

- Vol.

30.9

002- Vol.%drya

1.3

02- Vol.%drya

0.28

CO - Vol.

~].2

% dry

002 - Vol. %dry'

1.5

1.6

7.8

1.6

02 - Vol.%drye

0.1

0.1

0.. 1;

CO - ppmv dry'

3240

2450

3140

2940

S02~ ppmv
dryd

59

42

42

48

420

430

360

400

82

SOp-'ppmvdryer
S02 - ppmvdry:

72

80

132

77

133 ~

H2S- ppmvdry'_
CS2 ppmvdry'

1190
460

1410
180

1950
300

1520
310

-T~ (l) - ppmvdryf

TS ~2) - ppmvdrye

2310
2390

1920
2590

2760

2330
2490

?S j3) - ppnvdry9

2380

2540

2070

2330

COS - ppmv dry'

NO,- ppmv
dryh
Visible

7.8

emissions'

4.0
O

ag,,,t
NDIR

Cparamagnetic
EPA-6

eDupontAnalyzer(includes elemental sulfur)

foC/Fpo(EPA-18)
9~,loy Analyz'er
EeA-7
EPA-9
Source:

Reference

C.14

78
114

4.3
O

Table

FACILITY

Summary of Results

Test

Number

.El

Run Number

Date

12/12/74

Stack

Effluent:

Flowrate, DNM~jmin
Water

vapor'-

Vol.

COS- ppmdryl

CS2- ppmdryl
H2S- ppmdryl

0.5
<1

S02- ppmdryl

<0.4

504 - ppmwet
H2S04-~PPmwet

2
~0.3

TS" - ppm

8+

TSb_ ppm

14

CO - ppm wet

NOx(asNOZ)- ppmwet

250

aTotal of separately measured constituents

bTotalas measured
by sulfur detector(includesmercaptans)
Source:

Reference

Note:

i.

Assumemoisture level of 5.6%based on test B2.

0.15

Table

In

FACILITY

Summary of Results

Test

Number

Fl

Run Number

Date
Stack

11/6/74
Effluent:

Flow rate - DNM31~

311.49

cOS - ppm dry

15.2

CS2- ppmdry H2S- ppmdry

S02 - ppmdry
Total

sulfur

0.1
0
0

- ppm dry

15.4

CO - ppm dry

Source:

Reference

670

1n

C.16

References

i..
:Task

Source

Order

Fla.,

No. 34,

March

2.

Test

Report

Environmental

Thron

ESED, OAQPS, EPA, dated

Source

Task Order

Gai.nesville,

Riggs,

Standard

August

9,

Oil

Co. of California

to C. Sedman,

1974.

Test

No. 34,

Report

No. 74-SRY-2,

Environmental

Science

EPA Contract
and Engineering,

No~ 68-02-0232,
~ainesville,

March 1974.
5.

Letter,

C. Sedman,
6.

7.
April

L. tilley,

27,

testing

Section

1974.

No. C-2082,

Los Angeles

County,

Source Test Report No. 74-SRY-4, EPAContract No. 68-02-0232,

3une

Science

and Engineering,

~ainesville,

1974.

Source Testing

20,

1975.

6,

Report

26,

to

1974.

9.

10.

August

Company of California,

Report No. C-e104, Los Angeles Count~v, APCD,

Task Order No. 34, Environmental

Florida,

Union Oil

1974.

Source Test Section

25,

8.

George

ESED, OAOPS, EPA, dated

Source

APCD, Dec.

Nov.

and Engineering,

28, 1973;

4.

Feb.

No. 68-02-0232,

Source Testing Section Report No. C-1895, Los Anbeles County APCD,

february

Fla;,

Science

EPA Contract

1974.

Letter,

3.

No. 74-SRY-1,

Source Testing

Section

Report No. C-2234, Los Angeles County APCD,

Section

Report No. C-2226, Los Angeles County APC[7,

1974.

C.17

APPENDIX
EMISSION

MEASUREMENT

AND CONTINUOUS

D.1

MONITORING

D.i EMISSION
MEASUREMENT
METHODS
A review

analytical

of

the

coulometry,

chromotography.
for

their

form.a

which

which

ferric

chloride

sequential

variable

the

component

which is measured
method

absorption

did

not

gas emissions.

or components

the

sulfur

compounds'

to form a cadmium

is then reacted

blue,

are

available

sampling

efficiency,

which

with a

this

applications
range

is measured

and analytical
for

to

methyleneblue

of N, N dimethyl-P-phenylene-diamine
methylene

for stack

is

reagents

spectrophotometrically.

of reduced

Automated sampling

collection

in most
this

of stack

of cadmium hydroxide

solution

techniques

deficiencies

compounds:

and gas

concentrations,

The precipitate

to give

photometrical7y.

from

the

suspension

acidic

of sulfur

is then reacted with specific

of a coiorimetric

precipitate.

strongly

air

absorbs

color

involves

in an alkaline

different

In this method a sample is bubbled through a

The solution

sulfide

four

were developed

to measurement

selectively

An example

methods

of'ambient

characteristic

method

that

spectrophotometry,

these

ap~plication

Colorimetry.

desired.

direct

Although

measurement

preclude

solution

revealed

methods could be used for analysis

colorimetry,

cases

literature

and
spectro-

trains

procedure.

using
Inherent

however include

limitations,

and interference

oxidants.

Another colorimetric
impregnated

with

either

method is the use of paper tape samplers

lead

acetate

or cadmium hydroxide.

These

compoundsreact specifically with H2Sto form a colored compound

which can be measured directly

with a densitometer.

0.2

Tape samplers

would not be appiopriate

for all

reduced

su'lfur

compounds unless

they were first reauced quantitatively to HpS. In addition, the

range is limited,
suffers

the method-requires

from light

sensitivity,

precise'humidity

fading,

control

and variability

and

in tape

response.

Coulometry.
a solution

In this method a gas sample is bubbled through

containing

The concentration

an oxidizing

of the

presence

of a titrant

through

the solution

titrant

is consumed

in the gas sample,

solution

to

current

gas sample.

precusor

bromine or iodine

in solution

in solution

response

of responding

The

as an oxidizing

as a reducing

In addition,

frequent

the

method

calibration

suffers

different,

from

to reduce

drift

~are well

established

analytical

D.3

agent,

electric

such as

or a metal

titration

has the

of sulfur

compounds.

ion

high

The

however, and this

of data difficult
maintenance

to acceptable

Spectrop hotometry_. Although infrared

methods

the

agent.

to a wide variety

and reporting

contained

compounds in the

is a free~halogen

to each compound is quite

makes standardization

to break down,

is passed through

For determining emissions coulometric

advantage

current

compounds

concentration.

the'titrant

by the

Consequently, as the

specific

current

titrant

buffered

of an electric

is a measure of the reactive

Normally,

such as silver

with

Bn~elec~ric
the

is

into solution..

by reaction

maintain

required

Passage

the titrant

releasing additional titrant

titrant

in solution

precusor.

causes

or reducing agent (titrant).

in many cases.
and requires

levels.

and mass spectrophotometric

techniques,

most

of these

methods
field

are

considered

too

applications.

analysis

flame

compounds

however

considered

sulfur

recovery

plants

and split

a catalytic

is measured.

reference optical cell.

radiation.

the

routine

for

field

followed

a gds sample is first

into

oxidation

two streams.

by

furnace

The second

stream

where sulfur

passes

mixed

One stream

are oxidized to S02 and then through an opticalcell

absorbance

for

were

and gas chromotography

spectrophotometry

then filtered

through

consuming

detection.

In ultraviolet

passes

at

spectrophotometry

photometric

with air,

and time

Two such methods

of sulfur

ultraviolet

expensive

constituents

where its
through

Since S02 stronglyabsorbs ultraviolet

difference

In absorbance

values

between

the

two

cells is an indirect measureof the non-S02sulfur constituents

in the sample stream. The system is capable of measuring S02
concentrations

in the range of 10 to 2500 ppm.

In gas chromatography/flame
sample is first

injected

a gas chromatograph
through

packing.

amount

column.

carrier

by selective

of each

component

measuring the light

carrier

gas.

a gas

gas flowing

the individual

adsorption/desorption

"band" separated

A flamephotometric

detection,

through

As the' gas sample is transported

Each gas component.

individual
gas.

into an inert

the column by this

are separa'ted

photometric

therefore,

on either
detector

present

leaves

side

is then
in the

on the column
the

column

as an

by a zone of carrier
used

initial

emitted from the excited.S2

0.4

components

to determine
gas sample

the
by

species formed as

the gases leaving the column areburned~in a~~hSldrog_en

flame.
A narrow band-pass

ootical

the photomultiplier

filter

placed

between the flame and

tube provides a high specificity

ratio

(30,000:1) between light emitted from formation of S2 when sulfur

components are burned and light emitted from formation of other
compounds when non-sulfur

components are burned.

The gas shromatography/fl ame photometric detection (GC/FPD)

method was considered

the most promising

the composition of gas streams at sulfur

technique

for monitoring.

recovery plants.

The UV

analyzer described previously was also used to serve as an independent

check on the accuracv of the GC/FPD.. This instrument detects

elemental

sulfur vaporwhichis not detected in the GC/FPD

system.
0.2

MONITORING SYSTEMS AND DEVICES

For determining S02 emissions two ~typesof continuous analyzers

have been used by EPAfor short-term (from a few weeks up to 6 months)
data gathering.

These analyzers

are'described

One is the Dupon 464 Source Monitoring

a complete system including

strip
data

below.
Svs'tem.

sample collection,

The cost

analysis,

and

chart ~recording is in the range of $17,000-19,000.

reduction

can be added

at

additional

companies manufacture analog to di'gital

range of 92,000,$4,0n0

suitable

cost.

converters

of

.Automated

A number

of

in the price

for conversion of the 4-20 milliamp

output of the Model464 to a ppmS02 readout. The DuPont464 svs'tem

is a semicontinuous
and elemental

sulfur.

ultraviolet

analyzer which responds to both S02

Since the response

D.5

to elemental

sulfuris

about

seven-fold that to 502, S02cannot be analyzedbythis method

if appreciable elemental sulfur is present.

The Model 464

has not yet been used as a continuous monitor in sulfur

recovery

plants.

Gas.chromatographylfl-amephotometric detection (GC/FPD)is

another methodfor monitoring S02 emissions. Systemsusing

this

DrinciDle

include

the Bendix Model 8700, Tracor

Model 250HI

These systems Cost about the same as the DuPont464 system discussed
above and are also

semicontinuous

in operation.

one vendor announced a complete iampling,

system for $14~nn~ (Tracor Model 27nH).
reduction

can be added at additional

Recently,

analysis,~and
again,

cost.

ho~ever,

recording

automated data

Integrators

compatible

with GChnalyzers can be programr~edto Drint the concentration of each

sulfur

compound. Cost of these integrators

is in the range of

$3,000-$4,000.

The GC/FPDsystemhas several advantages.

detect

each individual

sensitive,

however,

This presents
is

necessary

capabilities

compound.

and require

a potential
to minimize

Other continuous
avai 7abl e .

sulfur

sample dilutions

of 10~:1 or more.

and frequent calibration

instruments

are corranercially

are summarized accordingto

by Nader et.al.

thev have not been evaluated

are extremely

errors.

monitoring

Many of these

These systems

source of error
such

It can separate and

(EPA-650/2-74-013).
for use on sulfur

D.6

their

Po date, t)owever,
plantg.

For montiroing emissions oftotal

su!fur

systems described Previous~y can be used.

ultraviolet

analyzer-is

and H2S, the two

The DuPont Model 464

caDable of oxidizing

the gas sample and

measuring all sulfur compoundsincluding elemental Pulfur asSOe.

This system,

however,

is not able to monitor

The GC/FPD system

is

capable

H2S emissions.

of monitoring

individual

sulfur

emissions (exceot sulfur vapor). fetal sulfur d'an be detenr~ined

by addingthe individually measuredcomponents

to the estimated
sb!fur

vapor.

pressure

Sulfur

of sulfur

vapor may be calculated

~t the gas stream temperature.

vapor is one of the compounds determined

reported

of reduced

sulfur

requirements

monitors

by GC/FPD, it can be

in the

performance

Since the standards

at zero percent

oxygen,

in the tail

A number of systems
and performance

are available

compounds, compliance

included

EPA promulgates

will

he dela~ved

specifications

specify~that
continuous

are available

specificati'ons

for these

emissions
monitoring

gases discharged

to monitor

emissions

with the monitoring

standards

for these

until

monitors.

must be determined
of the oxygen concen-

to the atmosphere

to monitor

by EPA in 40 FR 46268 on October

0.3

Since H2S

separately.

Although continuous

tration

from the partial

is required.

oxygen concentration

systems

were promulgated

6, 1975.

PERFORMANCE TEST METHODS

EPA Method 18, "Semicontinuous

Emissions

from Stationarv

in determining

refinery

sulfur

comDliante

olants.

Sources,"

Determination
has' been prepared

with new source

performance

This method requires

0.7

of Sulfur
for

use

standards

at

use of the GC/FPD

system discussed
program.

above and utilized

Specifications

technique,

and other

for the dilution

instrumentation

precision, and reliabili~

In lieu
compliance

releasing
applied
fossil

system, calibration

necessary

to insure

for sources

that

incinerate.the

them to the atmosphere.

fuel-fired

accuracy,

are contained in Method1A.

of Method 18, Method 6 may be used~to

to this

dpplicable

during the emission testing

tvDe of source,

effluent

determine
gas before

Although ~ethod 6 has not been

the similarity

steam generators

indicates

here also.

D.8

to emissions

from

the method to be

TECHNICAL REPORT DATA

1. REPORTNO.

.~ ;II ~

I~le~seread Inryucrionsoil fhe reverseb~fo~ecori~pl~iing)

In.
I :llS~ RECIPIENT'SACCESSlOnNO.

EPA-450/2-76-01~6;a
4. TITLE

.REPORTDATE

AND SUBTITLE

Standards Support and Environmental Impact Statement

Volume i:

Petroleum

r 1976

Standards of Performance for

Proposed

Refinery

Sulfur

PERFORMING
ORGANIZATION
CODE

Recoverv Plants

PERFORMING

.AUTHOR(S)

.PERFORMING
ORGAN1ZAflON
NAMEANDADDRESS

ORGANIZATION

REPORT

NO.

110.PROGRAM
ELEMENT
NO.

EPA,Office of Air Quality Planning and Standards,

Emission Standards and Engineering Division,
Triangle Park, N.C. 27711

Research

12.SPONSORING
AGENCY
NAMEANDADDRESS

/GRANT
NO.
I~j~TYPEOF REPORT
ANDPERIOD
COVERED
14. SPONSORING

AGENCY

COD~

15.SUPPLEMENfARY
NoTEsVolume
1 discusses the proposed stpndards' and the resulting
vironmcntal
romulaated,
ib;

Volume 2, to
and economic effects.
between
willdiscuss
any differences

be''puba%sfiqdwhenthe standards are

the ro sed and romul ted standard

ABST)lACT

A national emission standard for sulfur dioxide and reduced sulfur compound

emissionsfrompetroleumrefinery sulfur recoveryplants is being proposedunder

authority of section 111 of the CleanAir Act. Sulfur dioxide is a criteria
pollutant

whose adverse

effects

are well documented.

Reduced sulfur compound

emissions could reach ambient levels sufficient to produce severe odor problems
in the vicinity

of a petroleum

refinery in the absence of the standard.

purpose of the proposed standardis to minimize reduced sulfur

emissions
available

r::

The

and sulfur dioxide

recovery plants to the level attainable with best

from refinery
sulfur
control
technology.

The standard will have the effect of reducing

emissions from a typical refinery sulfur recovery plant by 99.9~0. Environmental
impact and economic impact statements quantifying the impacts of the proposed

standard and alternative control options are included In the document.

KEY WORDS AND DOCUMENT ANALYSIS

DEgtRIPTORS

Ib.~DENTIFIEFISIOPEN
ENOEDTEFIMS
IC COSATIField/G~cup

Air pollution

Air po~lution

control

Petroleum
refineries
Desulfurization

Sulfur

recovery

Emission

plants

standards

sulfur plant tail-gas

treating

is. DISTRIBUTION
STATEMENT
U,llmi ted - Avaii abl e
to the public

free of charge

from:

Public Information Center (PM-215), EPA,

EPA Fo~m 2Pt01

(9)J)

19. SECURltY CLASS (ThLrRrporlj

Unclassi fled

~c~-i~ccAss

(Thlp
page)

Unclassified

"'

PAGES