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AMINE PLANT

TRAINING
SESSION
March 11, 2010

Course Outline

Overview

JV

Sweetening Methods
Process Flow Diagram / Specifications
General Operating and Design Considerations
Equipment
Metallurgy
Cost Considerations
Acid Gas Handling
Amine Workbook
Acid Gas Handling - Membranes

JM

OVERVIEW

Gas Treating Overview


To Flare, Reinjection,
Sulfur Recovery
Acid Gas
(H2S, CO2)
Sweetening
(amine, mol
sieve)

Dry Lean
Gas
Sweet
Gas

Dehydration
(mol sieve,
glycol)

Dry Rich
Gas

Residue Gas
Compression

Spec
Gas
To Pipeline

HC Liquid
Recovery
(DPC, TE)

H2O

Sour, Wet
Gas

Recycle
Gas

LP Separation

HC Liquids

HC Liquid

Production

HC Liquid
Stabilization /
Fractionation

Compression
HP Separation

Sour H2O

To Disposal,
Reinjection, Treatment

NGL /
Stabilized
Condensate

To Pipeline or
Storage

Pipeline Product Specifications


Sales Gas

Water

7 lb / MMSCF (US)
4 lb / MMSCF (Canada / Europe)

HC Dewpoint

15 32 F

H2S

< 4 ppmv ( grain H2S / 100 SCF)

CO2

< 2 mol%

CO2 / N2

< 2mol%

NGL

C3+

< 2 mol% C1/C2

Stabilized Condensate

C5/C6+

RVP 13.5 psia


TVP 13.0 psia

SWEETENING
METHODS

Sweetening - Terminology
H2S

Hydrogen Sulfide

Gas Impurity

COS

Carbonyl Sulfide

Gas Impurity

CS2

Carbon Disulfide

Gas Impurity

CH3SH, C2H5SH

Mercaptans

Gas Impurity

EG

Ethylene Glycol

Dehydration

TEG

Triethylene Glycol

Dehydration

MEA

Monoethanolamine

Sweetening

DEA

Diethanolamine

Sweetening

MDEA

Monodiethanolamine

Sweetening

DGA

Diglycolamine

Sweetening

Sweetening - Methods
Chemical Absorption

Amines

Most widely used

Potassium Carbonate
Physical Absorption

Selexol, Methanol

For high H2S and CO2


concentrations

Solid Bed - Regenerative

Molecular Sieve

Limited to H2S Removal

Non-Regenerative

Iron Sponge (Iron Oxide)

For low conc. (<3000 ppm)


Disposal problems, pyrophoric

Zinc Oxide

Expensive

SulfaTreat
(refined Iron Sponge)

Expensive , Non-hazardous waste


Difficult Handling, Exothermic in Air

NaOH

Product is NaSH

Direct Conversion

Conversion of H2S directly to elemental S

Membranes

Bulk CO2 Removal

Extractive Distillation / Cryogenics

Bulk CO2 Removal

Absorption Processes
Mixed or
Hybrid

Chemical

NaOH

DEA

Flexsorb

MEA

Physical

Water
Rectisol
(Methanol)

DGA

Sulfinol

Activated MDEA
(add DEA)

Selective MDEA
(proprietary additives)

Selexol

Amines
MEA

10 20 wt%

Reacts rapidly with H2S and CO2 (non-selective)


Largest carrying capacity (lowest circulations rate)
Chemically stable (minimum solution degradation)

DEA

25 35 wt%

Similar to MEA
Reacts with COS and CS2
Removes H2S and CO2 (non-selective)

DGA

40 70 wt%

Proprietary designs

MDEA

30 50 wt%

Tertiary Amine
Proprietary designs
Reacts with H2S in presence of CO2 (selective)

Sulfinol D or M (Shell)

Proprietary Mixture of sulfolane, water and either DIPA (D) or MDEA (M)

Flexsorb HP, PS, SE, SE+ (ExxonMobil)

Proprietary mixture of hindered amines

MDEA Selectivity
Selectivity is improved by:

Colder Temperatures
Lower Pressures
Higher Ratios of CO2 to H2S

Selectivity is achieved by:

Kinetic effects due to more rapid absorption of H2S compared to CO2


(i.e. more rapid pickup of H2S). Contact time is limited.
Equilibrium effects due to more favorable equilibrium solubility of H2S
compared to CO2

PFD
&
SPECIFICATIONS

Process Flow Diagram

Design Parameters
GAS FEED SPECIFICATIONS

Gas Flow Rate


Gas Composition

H2S, COS, CS2


CO2

Contaminants (heavy hydrocarbons, lube oils)

PRODUCT SPECIFICATIONS

H2S, COS, CS2


CO2

ACID GAS HANDLING CONSIDERATIONS


PROCESS HEATING CONSIDERATIONS

Estimation of MDEA
Circulation Rate
0.206 x MM x (H2S + CO2) x MWT
GPM =
ML x WT

GPM

= circulation rate, GPM

MM

= gas flow, MMSCFD

H2S

= mol% H2S to be removed

CO2

= mol% CO2 to be removed

MWT

= molecular weight of MDEA = 119.9

ML

= mol loading, moles acid gas / mol amine

WT

= amine solution, weight percent

Estimation of MDEA
Circulation Rate
0.206 x MM x (H2S + CO2) x MWT
GPM =

0.206 x 44 x (0.012 + (5.0 2.0)) x 119.9


=

ML x WT
=

0.30 x 50

218 GPM

GPM

circulation rate, GPM

MM

gas flow, MMSCFD

H2S

mol% H2S to be removed

CO2

mol% CO2 to be removed (inlet 5% outlet 2%)

3.0%

MWT

molecular weight of MDEA

119.9

ML

mol loading, moles acid gas / mol amine

0.30

WT

amine solution, weight percent

50

44
120 ppm = 0.012%

GENERAL
OPERATING AND
DESIGN
CONSIDERATONS

General Operating Problems

Corrosion

Amines are corrosion inhibitors generally


Acid gases make amine solutions corrosive by lowering pH
Most severe corrosion occurs at high temp (lean/rich exchanger, regenerator
and reboiler)
Stress corrosion cracking prevalent (stress relieving alleviates)
Material selection (SS vs CS)

General Operating Problems

Solution Degradation

Amine solutions will slowly oxidize when exposed to air. Products are
corrosive.
Minimized by gas blanketing amine storage
MEA / DGA react with COS to form insoluble salt (reclaiming to recover amine)
Some degradation products can not be regenerated

General Operating Problems

Foaming

Increases amine losses and can upset entire absorber


Causes:

Suspended solids, Oil lube, charcoal particles from filters


Liquid hydrocarbons
Amine degradation products
Corrosion inhibitors
Too much anti-foam

General Operating Problems

Reclaiming

Batch operation
Distill the water and amine leaving behind entrained solids, dissolved salts and
degradation products that cause foaming and corrosion problems
Operates on 3% or less of the solution circulation rate
Sludge will accumulate below tubes
Not required on DEA and MDEA

General Operating Problems

Filtration

Extremely important
Removes iron sulfide
Filtration to 1 micron level
Full Stream filter used to remove particles to 10-25 micron
Sidestream (20% of circulation rate) activated charcoal filter to 1 micron
Activated carbon filter also removes hydrocarbons, some degradation
products, and reaction products
Full stream filter downstream of charcoal filter

Inhibitors
Foam Inhibitor
Corrosion Inhibitor

General Design Considerations

Inlet Gas Scrubbing

Extremely important
Minimizes foaming, corrosion, and reboiler tube burn-out issues
Removal of liquid hydrocarbons and entrained solids
Removal of upstream corrosion inhibitors and lube oil carryover

General Design Considerations

Amine Losses

Gas Cooler and Scrubber downstream of contactor


Minimizes amine in dehydration unit

Lean/Rich Amine Exchanger

Without a flash drum, LCV should be located downstream of R/L exchanger to


minimize breakout of acid gases to minimize corrosion

General Design Considerations

Amine Regeneration

Most likely spot for troubles and corrosion


Highest temperatures
Acid gases are broken down
Best regeneration occurs at higher pressure but this increases reboiler
temperature / duty
Increased temp leads to excess corrosion and chemical degradation
Temp usually 230 240 F. Max temp 260 F. Pressure typically 25 psia max.
Heating in reboiler: hot oil, direct fired, steam
Direct-fired reboiler difficult to control and minimize hot spots
Direct fired fired up to 100GPM design
Two or more reboiler inlets to improve natural circulation of liquid
Two or more reboiler outlets to reduce stagnant pockets of acid gases

General Design Considerations

Piping Design

Low velocity allows a film on pipe wall to act as a corrosion inhibitor


High velocity causes erosion
Recommendations:

Maintain liquid velocity below 6 ft/s in all piping


Avoid screwed fittings, if practical
Use welded fittings with long radius elbows; avoid tees when possible
Avoid the use of dissimilar metals to avoid bimetallic corrosion

EQUIPMENT

Inlet Coalescer Scrubber

Major cost item due to high pressure


Highly recommended to prevent operational and corrosion problems
Sizing
Gas Flow Rate and Operating Pressure
Typical Sizes:
50 MMSCFD & 700 psig
100 MMSCFD & 700 psig

Options
Separator with mesh pad
Porous Media coalescer
Peco filter separator

48 OD x 84 S/S
72 ID x 120 S/S

Contactor

Major cost item due to high pressure and size


Sizing

Diameter: Gas Flow Rate and Operating Pressure


Height: Amine Circulation Rate
Height: 20 trays typ., 2 - 3 min amine residence time in bottom section
Typical Sizes:

50 MMSCFD & 700 psig

48 ID x 660 S/S

100 MMSCFD & 700 psig

72 ID x 768 S/S

Gas Cooler

Major cost item due to high pressure


Aerial cooler
Gas/gas exchanger used to cross exchange with amine plant inlet if inlet
temperature is low
May not be required depends on contactor outlet temperature
Sizing
Gas Flow Rate and Operating Pressure

Sweet Gas Scrubber / Filter


Coalescer

Major cost item due to high pressure


Recommended to minimize amine losses and contamination of dehydration unit
Sizing
Gas Flow Rate and Operating Pressure
Typical Sizes:

50 MMSCFD & 700 psig

48 OD

100 MMSCFD & 700 psig

72 OD

200 MMSCFD & 700 psig

30 ID x 118 S/S (filter coalescer)

Amine Flash Drum

Intermediate cost item due to medium pressure


Sizing

Amine circulation rate


Sized based on residence time. Typically 5 to 10 mins.
Typical Sizes:

200 GPM

72 ID x 192 S/S

650 GPM

120 ID x 360 S/S

Lean/Rich Exchanger

Intermediate cost item due to medium pressure


Plate and frame exchanger OR S/T exchanger
Sizing
Amine circulation rate

Typical Sizes:

50 GPM

2 MMBTU/HR

200 GPM

7.2 MMBTU/HR

650 GPM

15.5 MMBTU/HR

Amine Regenerator

Also known as Amine Stripper or Amine Still


Low pressure (< 25 psia) - Intermediate cost item due to size and trays
Sizing

Diameter: Amine circulation rate / Acid gas loading


Diameter: typically 6 12 smaller than contactor
Height: Amine Circulation Rate
Height: 20 trays typ., 2 - 3 min amine residence time in bottom section
Typical Sizes:

Top Section

200 GPM

36 ID x 768 S/S

650 GPM

48 ID x 252 S/S

Bottom Section

84 ID x 612 S/S

Regenerator Reflux Condenser

Low pressure (< 25 psia) - Low cost item


Air Cooler
Condensing water from acid gas stream
Sizing

Amine circulation rate / Acid gas loading


Duty:

50 GPM

1 MMBTU/HR

200 GPM

2.6 MMBTU/HR

650 GPM

17.6 MMBTU/HR

Reflux Accumulator

Low pressure (< 25 psia) - Low cost item


Separates condensed water from acid gas stream
Sizing

Amine circulation rate / Acid gas loading


Sizing Basis: 5 - 10 min residence time
Typical Sizes:

200 GPM

24 ID x 84 S/S

650 GPM

48 ID x 120 S/S

Reflux Pump

Low pressure (< 25 psia) - Low cost item


Centrifugal
Recycle water from reflux accumulator to still
Sizing

Amine circulation rate / Acid gas loading


Typical Sizes:

200 GPM

3 - 5 HP

650 GPM

5 HP

Regenerator Reboiler

Low pressure (< 25 psia) - Intermediate cost item


Thermosyphon or BKU Kettle-type Reboiler
Steam, Direct-fired, Electric, Hot Oil
Sizing

Amine circulation rate / Acid gas loading


Estimation: Duty, MMBTU/HR = 1200 x GPM x 60 / 1,000,000
Typical Sizes:

50 GPM

3.6 MMBTU/HR

200 GPM

14.4 MMBTU/HR

650 GPM

46.8 MMBTU/HR

Amine Booster Pump

Low pressure (< 25 psia) - Low cost item


Charges lean amine to high pressure Amine Circulation Pumps
Feed directly from surge section of reboiler / regenerator OR downstream of
lean/rich exchanger
Trade-off: NPSHr vs. lower design temperature
Sizing

Sizing: Amine circulation rate


Nominal 50 psi differential
Typical Sizes:

200 GPM

15 HP

650 GPM

50 HP

Lean Amine Cooler

Low operating pressure (50 psig)


High cost item
Cools lean amine from lean/rich exchanger upstream of high pressure Amine
Circulation Pumps
Sizing

Sizing: Amine circulation rate


Typical Sizes:

200 GPM

6.3 MMBTU/HR

650 GPM

28 MMBTU/HR

Amine Particulate Filters and Amine


Charcoal Filter

Low operating pressure (50 psig) - Lower cost item


Sized for full flow or 10-20% slipstream
Filters in series: Particulate Charcoal - Particulate
Sizing

Amine circulation rate


Typical Sizes:

Particulate Filter

Charcoal Filter

200 GPM

18 OD x 56 OAH

42 OD x 49 S/S

650 GPM

36 OD x 60 S/S

84 OD x 264 S/S

Amine Circulation Pump

Also known as Charge Pump


High cost item
High pressure pump sending lean amine to contactor
Multi-stage centrifugal OR positive displacement pump
Sizing

Amine circulation rate and Maximum Contactor Pressure


Typical Sizes:

50 GPM

50 HP

200 GPM

200 HP

650 GPM

500 HP

METALLURGY

METALLURGY

Guidelines per API RP 945: Avoiding Environment Cracking in Amine Plants

Reduce fluid velocity to < 6 ft/sec in rich amine carbon steel piping
Stainless steel in certain locations

Areas of high acid gas loading, flashing vapor

Contactor LCV to Regenerator


Top section of Regenerator
Reflux condenser and piping

Temperatures about 230F

Reboiler tubes

METALLURGY

Guidelines per API RP 945: Avoiding Environment Cracking in Amine Plants

For MDEA: PWHT for all carbon steel equipment, including piping, at operating
temperatures exceeding 180F

Lower section of Regenerator


Reboiler shell
Reboiler inlet / outlet piping

COST
CONSIDERATONS

Equipment Cost Example


200 GPM / 55 MMSCFD
Equipment
Cost
InletFilterCoalescer
Contactor
GasCooler
SweetGasScrubber
FlashDrum
Lean/RichExchanger
Regenerator
RefluxCooler
RefluxAccumulator
RefluxPump(2)
Reboiler
AmineBoosterPump(2)
LeanAmineCooler
AmineCirculationPump(2)
ParticulateFilter(2)
CharcoalFilter
HotOilHeaterPkg

%of
Total

$111,000
$271,000
$
$88,000
$52,000
$10,000
$171,000
$35,000
$18,500
$14,000
$65,000
$23,000
$62,000
$130,000
$20,000
$30,000
$335,000

7.7%
18.9%
0.0%
6.1%
3.6%
0.7%
11.9%
2.4%
1.3%
1.0%
4.5%
1.6%
4.3%
9.1%
1.4%
2.1%
23.3%

$1,435,500

100.0%

LOW SPEC vs HIGH SPEC


EQUIPMENT

LOW SPEC

HIGH SPEC

Inlet Coalescer

Peco Filter Separator

Porous Media Filter/Coalescer

Scrubber with Mesh Pad


Contactor & Stripper

Koch Glitsch Minivalve trays

Koch Glitsch FLEXITRAY T-valve


Trays

Filters

Std Cartridge Filters

3M Cartridge filters / housing


Porous Media filters

Filters

Size for 10-20% Slipstream

Size for full flow

Lean Amine Flow Control

Manual Valve

Flow Control Valve

Reboiler

CS bundle

SS bundle

Reflux Condenser

CS tubes / header

SS tubes / header

Vessels / Shells

No corrosion allowance

1/8 CA

LOW SPEC vs HIGH SPEC


EQUIPMENT

LOW SPEC

Piping & Valves


CS
Contactor LCV to Still Column
Still Column to Condenser
Reflux Vessel to Reflux Pumps to
Still Column
Top 8 tray section of Still Column

HIGH SPEC
SS Contactor LCV to Still Column

ACID GAS
HANDLING

Acid Gas Handling

Incineration

Flare
Incinerator / Thermal Oxidizer with Waste Heat Recovery Unit
Regenerative Thermal Oxidizer

Sulfur Recovery Plant


Reinjection or Disposal

Compression
Pumping

AMINE
WORKBOOK

ACID GAS
HANDLING
with MEMBRANES

MEMBRANES How They Work

Bulk Removal of CO2 and H2S


These comments apply to Cellulose Acetate based membrane
materials (Cynara and their usual competitors)
Works on DIFFERENCE in Partial Pressures on FEED and PERMEATE sides of the
membranes

Suppose Feed = 500 PSIA and 50% CO2. This = 250 PSIA Partial Pressure of
CO2
Suppose PERMEATE = 50 PSIA. Assuming high CO2%, CO2 partial pressure
on Permeate side may be about 45 PSIA
The difference between 250 PSIA and 45 PSIA of CO2 partial pressure drives
the CO2 across the membranes.

MEMBRANES

Typical CO2 membranes are applied with CO2 in Feed =15% and above
They work better at higher CO2% and higher Pressure in Feed Gas
Typically limited to about 400 PSIA CO2 Partial Pressure in feed
Typically limited to about 750 PSI differential pressure (Feed-Perm)
Typically limited to about 1200 PSI feed pressure. 700 PSI more common
Usually applied in moderate feed temperatures of +30 to +120 Deg F
Lower Feed Partial Pressures result in lower CO2% in Permeate Gas. This can
result in HC loss to permeate gas.
Membranes can be staged to reduce this HC loss, but needs more compression

MEMBRANES

Membranes applied in EOR projects usually have high CO2 Feed content. 35% to
>90% is typical. In this application, it is common to have about 10% CO2 in final
outlet HC gas.
Downstream DPC/NGL plants have Amine systems for the remaining10% CO2 in
their feed.
Common for EOR membrane plants to have permeate gas at 100 PSIA up to over
200 PSIA and to be 96%+ CO2 content. This usually needs compression to some
high reinjection pressure (1500# or more).

MEMBRANES

Membranes applied in pipeline sales gas applications are typically less than 10%
CO2 feed.
Outlet HC gas meet P/L Specs, usually CO2% = 2 to 3%
Note that 10% down to 2% is still a bulk removal.
Permeate Gas is lower CO2 content than EOR; typically 35 to 65% CO2.
Frequently this gas is compressed and permeated again to purify flared permeate
gas and recovers HCs (mostly methane) for lease fuel.
Usually NOT applied to meet an H2S spec.
Usually NOT applied to make a water content spec.

MEMBRANES

Membranes need significant pretreatment to protect membranes for long service life.
With proper pretreatment and operations, membranes can have up to a ten-year
service life but 3 to 6 years is more common service life.
Contaminants which may be harmful are:

Liquid Water (water VAPOR is OK)


Some heavy HCs (benzene family in particular)
Paraffin in solid form
Dirt, scale, etc.

MEMBRANES

OPERATING conditions which may be harmful

Condensing liquid water (can happen on permeate side, too)


Solid sulfur dropout in permeate side (possible if oxygen in feed)
Too Cold with too high feed CO2 partial pressures (softens membrane material)
Too Hot or high feed-to-perm dP (hastens membrane decline in capacity)
Reverse pressure on permeate side (shut down & control issues cause this)
Heavy HCs in feed gas (inadequate P/T)
Note that C5 and lighter condensate is generally not a problem for hollow fiber
form. Spiral-wound form (ex. - Grace) has issues disengaging the condensates.

MEMBRANES

Typical Pretreatment Applied:

Inlet Filter/Sep
Dehydrate to insure no liquid water and to allow carbon steel materials (dry
desiccant dehydration is common in large plants)
Dew Point to reduce C5+ to about 25-35 Deg F at feed pressure
Reheat to about 70 to 100 Deg F

MEMBRANES

WHERE DOES ENERFLEX FIT INTO THESE PROJECTS?

COMPRESSION on inlet gas, permeate products, inter-stage of membranes,


final HC products. (i.e. for K-M at SACROC, Whiting, etc.) Membranes almost
always need compression.
PRETREATMENT equipment. We can package all of it. (Typically an
engineering firm designs this. Cameron/NATCO/Cynara tries to furnish this
themselves. Other membrane companies will claim less pretreatment needed
than for Cynara with dubious results! When pretreatment is for other than
Cynara membranes we would have a better chance at packaging the P/T.)
DOWNSTREAM processing for NGL/DPC, Amines, dry Dehys, cold gas plants

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