01 Pretreatment

2011 Synthesis Gas Seminar Margarita y g
Feed Pretreatment
November 24, 2011
Feed Gas Tr eat ment
P bl Problem
components
S lf
HC Feed
Steam
HTS
Sulfur
Chlorides
Olefins
S
S Cl
Cl
Coking
Olefins
Purification Pre Reformer
Primary Reformer
Cl
CO
2
Reforming
S
Cl
H
2
Cl
SynGas Seminar Margarita Nov 2-4,2011 Page 2
HT CO Shift LT CO Shift CO
2
Removal
Methanation
A t i t d C b Ac t i vat ed Car bon
adsor pt i on of H
2
S + or gani c S
H d d lf i ti (HDS) Hydrodesulfurization (HDS)
convert organic S to H
2
S
C t i hl id t HCl Convert organic chlorides to HCl
Chloride Guard remove HCl
Zi O id Ad b H S Zinc Oxide Adsorb H
2
S
ActiSorb
G 1 Sulfur removal
Ac t i vat ed Car bon: C8-6 / C8-
77
ADVANTAGES DI SADVANTAGE
Low Cost Capacity Affected by
Regenerable
Low Temperature
p y y
Heavy Hydrocarbons
Need for Frequent
Low Temperature
Operation
Effective on Virtually
q
Regeneration
Emissions Control
y
all Sulfur Species
during Regeneration
Lead-Lag Reac t or s
Raw Natural Gas Feed
To Regeneration Vent To Regeneration Vent
Regeneration
Steam
Purified Natural Gas
Ac t i vat ed Car bon
A bi Ambient temperature
Steam before initial use
Regenerate upflow with steam to vent (or hot
NG/fuel )
C t l t /NG l it t t fl idi ti Control steam/NG velocity to prevent fluidization
< 0.5 ft/sec (SLV)
Evolution of hydrocarbons and sulfur during Evolution of hydrocarbons and sulfur during
regeneration may need to condense/capture
regeneration steam and hydrocarbons
No oxygen in steam if above 400F (205C)
No oxygen > 200F (95C) without steam
yg ( )
Typical sulfur leakage: < 0.1 ppm
Ac t i vat ed Car bon - Oper at i on
S lf i i d d b 125 F Sulfur capacity is reduced above 125
o
F
Typical operating cycle 7-14 days
Typical feeds: < 5 ppmv RSH
< 5 ppmv H
2
S
T bl i Troublesome contaminants:
Heavy hydrocarbons can reduce capacity
CO2 ( 5 %) d i i ifi l CO2 (>5 %) can reduce capacity significantly
Water vapor can reduce capacity somewhat
Ac t i vat ed Car bon - Oper at i on
C i B R i Capacity Between Regenerations
SCF of Feed per Ft of C8-7
Sulfur Type ppm SCF/ft
1 3 260 000 1-3 260,000
3-5 130,000
H
2
S
1-3 260,000
3-5 130,000
R-SH
COS passes through
Regen Cycle depends on
g y p
bed volume and sulfur concentration
Ac t i vat ed Car bon - Pr obl ems
Reduced capacity between regenerations Reduced capacity between regenerations
Surface Contamination
Incomplete Regeneration Incomplete Regeneration
Heavy Hydrocarbon Buildup
o C5+ can reduce capacity 50% p y
o Insufficient regeneration temperature
Increased Inlet Sulfur
o Adsorbent capacity is fixed
o Cycle length is inversely proportional to S content
5% CO2 can reduce capacity 50% 5% CO2 can reduce capacity 50%
3% H2O can reduce capacity 20-30%
High inlet temperature - > 125F (50C) capacity falls off
g p ( ) p y
A ti t d C b d ti f H S d i S Activated Carbon adsorption of H
2
S and organic S
Hydr odesul f ur i zat i on (HDS)
t i S t H S c onver t or gani c S t o H
2
S
Conver t or gani c c hl or i des t o HCl
Chl id G d HCl Chloride Guard remove HCl
Zinc Oxide Adsorb H
2
S
ActiSorb
G 1 Sulfur removal
Hydr odesul f ur i zat i on
HDMax HDMax
200 200 Series Series

HDMax HDMax
300 300 Series Series HDMax HDMax 300 300 Series Series
CoMo on Alumina
NiMo on Alumina
HDMax
Cat al yst s

Catalyst
HDMax
200 HDMax
300
Wt % CoO 4.5 ---
Wt% NiO --- 4.9
Wt% MoO
3
18.5 20.0
Alumina Balance Balance
Operating Temp F 450-800 450-800
C 230 425 230 425
Converts all S species to H
2
S downstream H
2
S trap
C t Cl i t HCl d t HCl t
C 230-425 230-425
Converts Cl species to HCl downstream HCl trap
Hydrogenates olefins
N t ff t d b h h d b
Not affected by heavy hydrocarbons
HDMax
Reac t i ons
R SH H R H H S R-SH + H
2
R-H + H
2
S
RSR + 2 H
2
RH + RH + H
2
S
RS-SR + 3 H
2
RH + RH + 2 H
2
S
COS + H
2
CO + H
2
S
C
4
H
4
S + 4 H
2
C
4
H
10
+ H
2
S
Chlorides R-Cl + H R-H + HCl Chlorides R-Cl + H
2
R-H + HCl
Olefins R
n
H
2n
+ H
2
R
n
H
2n+2
+ Heat
Needed when > 0.5% olefins
T = ~15-18F (8-10C) per 1% molar
Control T with recycle or multi-bed with intercooler
HDMax
- Oper at i on
Temperature
Min-Max = 450-800F (230-425C)
T i l 650 750F (345 400C) Typical range = 650-750F (345-400C)
Limits risk of hydrocarbon cracking
Space Velocity: 1500-6000 /h Space Velocity: 1500 6000 /h
Sulfiding
NG with 2-10 ppmv of sulfur no sulfiding required NG with 2 10 ppmv of sulfur, no sulfiding required
Olefins in the feed must be pre-sulfided
Hydrogen Requirement Hydrogen Requirement
Typical H
2
= 4-7 psia (0.3-0.5 bara)
Olefins H
2
= stoichiometric + 5-10% excess in the effluent
Naphtha H
2
= 15-20%
Sul f i di ng Reac t i ons
S lfidi Sulfiding
CoO + 0.11H
2
+ 0.89H
2
S CoS
0.89
+ H
2
MoO
3
+ 2H
2
S MoS
2
+ 3H
2
O
3NiO + H
2
+ 2H
2
S Ni
3
S
2
+ H
2
O
Desulfiding
CoS
0.89
+ 0.89H
2
Co + 0.89H
2
S
MoS
2
+ 2H
2
Mo + 2H
2
S
2 2 2
Ni
3
S
2
+ 2H
2
2Ni + 2H
2
S
H
2
S t o Sul f i de CoO
1.00E+01
1 00E-01
1.00E+00
0.1 Bar H2 Partial Pressure
1 Bar H2 Partial Pressure
1 00E 03
1.00E-02
1.00E-01
1.00E-04
1.00E-03
1.00E-06
1.00E-05
1.00E-08
1.00E-07
150 200 250 300 350 400 450 500 550
150 200 250 300 350 400 450 500 550
Temperature,
o
C
H
2
S t o Sul f i de Ni O
1.00E+03
1.00E+02
1 00E+00
1.00E+01
1.00E-01
1.00E+00
1.00E-02
1.00E-04
1.00E-03
150 200 250 300 350 400 450 500 550
150 200 250 300 350 400 450 500 550
Temperature,
o
C
H
2
S t o Sul f i de MoO
3
1 00E+01
1.00E+00
1.00E+01
1.00E-02
1.00E-01
1 00E-04
1.00E-03
1.00E-05
1.00E 04
1.00E-07
1.00E-06
150 200 250 300 350 400 450 500 550
150 200 250 300 350 400 450 500 550
Temperature,
o
C
HDS Spec i al Consi der at i on
Cracking Potential Cracking Potential
Carbon laydown and P buildup
If sulfur is low < 2 ppm If sulfur is low - < 2 ppm
Minimize H
2
recycle possibly < 1%
Keep inlet temperature < 700F (370C) Keep inlet temperature < 700F (370C)
No contact with air/O
2
after on line or sulfided No contact with air/O
2
after on line or sulfided
Shutdown
Maintain with inert gas (could be N2, H2, NG)
If Olefins in the feed, purge with inert gas during
shutdown
A i d C b d i f H S d i Activated Carbon adsorption of H
2
S and organic
S
convert organic S to H2S
Convert organic chlorides to HCl Convert organic chlorides to HCl
Chl or i de Guar d r emove HCl
Zinc Oxide Adsorb H S Zinc Oxide Adsorb H
2
S
ActiSorb
G 1 Sulfur removal
Cl Guar d Ac t i Sor b
Cl 2
Alkali 6.5%
LOI 7.0%
Alumina Balance
Density 45 lbs/ft3
0 72 k /L 0.72 kg/L
Ac t i Sor b
Cl 2
Chl id i h LTS Chlorides are a very strong poison to the LTS
Reacts with ZnO: ZnO + 2HCl ZnCl
2
+ H
2
O
Z Cl bli 500F (260C) ZnCl
2
sublimes ~500F (260C)
R i N 2O 2HCl 2N Cl H O Reaction Na2O + 2HCl 2NaCl + H
2
O
Operating Temperature = 70-850F (20-450C)
Vapor Phase or Liquid Phase
Cl pickup = 8-10% wt.
Typically a layer on top of the ActiSorb S 2
2
S and organic
S
Zi nc Ox i de Adsor b H S Zi nc Ox i de Adsor b H
2
S
ActiSorb
G 1 Sulfur removal
Zi nc Ox i de Ac t i Sor b
S 2
Ac t i Sor b
S 2
H S Z O Z S H O H
2
S
(g)
+ ZnO
(s)
ZnS
(s)
+ H
2
O
(v)
An ADSORBENT, not a catalyst
ZnO is consumed by H
2
S containing gas
Not regenerable
Must be replaced when it no longer adsorbs Sulfur
Typical performance 40-60 ppbv (Zn-ZnS equilibrium)
With Pre-Reformer recommend bottom layer of
ActiSorb
305 to achieve < 10 ppb

Component ppmv Temperature
H
2
S 100
See graph H
2
S 100
See graph
Limited, Short-term Capacity for Organic Sulfurs
RSH / RS-SR' < 10 >600F (315C)
COS < 10 >700F (370C) COS 10 700 F (370 C)
RSR' < 10 >750F (400C)
Thiophenes 0
For temporary, unavoidable circumstances
If feed has organic sulfurs hydrotreat with CoMo or NiMo
Thiophenes 0
If feed has organic sulfurs, hydrotreat with CoMo or NiMo
Ac t i Sor b
S 2 Capac i t y f or
H
2
S H
2
S
Ambient
V
o
l
u
m
eOptimized
(
W
g
t
P
e
r
f
u
r
P
i
c
k
u
p
S
u
l
f
Gas Hourly Space Velocity (V / V / h)
GasHourly Space Velocity (V/V/h)
Sul f ur Adsor pt i on
Fresh ZnO Fresh ZnO
Surface adsorption (gas diffusion)
Solid diffusion
Saturated
Ax i al Pr of i l e of Sul f ur Level
Sat urat ed Sol i d Di ff usi on Gas Di f f usi on Fresh Cat al yst
Sat urat ed Wi t h Sul f ur
T f B d Mi ddl f B d B t t f B d
Top of Bed Mi ddl e of Bed Bot t om of Bed
Ac t i Sor b
S 2 Capac i t y f or
H
2
S H
2
S
Ambient
V
o
l
u
m
eOptimized
(
W
g
t
P
e
r
f
u
r
P
i
c
k
u
p
S
u
l
f
Gas Hourly Space Velocity (V / V / h)
GasHourly Space Velocity (V/V/h)
ZnO Opt i mi zat i on
P f l f Performance results from:
Physical Integrity
ZnO Content active ingredient
Density of finished product
Surface Area better diffusion
Hi gh and Low Sur f ac e Ar ea
5
3
4
Low Surface Area ZnO
2
3
1
0
0 20 40 60 80 100
High Surface Area ZnO
% Bed
ZnO Pr obl ems
P buildup P buildup
Surface contamination
o Solids in the feed o Solids in the feed
o Cracking in the feed heater coil
ZnCl
2
formation ZnCl
2
formation
o Affects structure
o At >500F (>260C) can move downstream; corrosion ( )
CO
2
+ ZnO ZnCO
3
(Zinc Carbonate)
o Forms rapidly 200-500F (95-260C)
o Weakens the physical structure
o Reduces amount of Zn available to form ZnS
o Decomposes at >500F (>260C)
Compar i ng Adsor bent s
ActiSorb S ZnO "C" ZnO "D"
Size 4.8 mm 4 mm 3.2 mm
Shape Pellets Pellets Spheres
Wt% ZnO 90 100 85
Density, lbs/CF 78 68 78

Performance*:
Wt% S Pickup 26.9 19.6 19.0
S Pickup, lbs/CF 22.5 19.7 14.2
Syst em Desi gn Choi c es 1 Vessel
Medium / High Temperature Single Bed
Cobalt Moly / ZnO Hydrogenation of Sulfur to H
2
S
Ad Advantages
Lowest initial cost system
Handles ALL sulfur species
RAW GAS
and not sensitive to changes
Disadvantages
CoMo
CoMo Thrown Away
Lower Capacity than a 2-bed
system
ZnO
system
Plant must shut down to change-
out
PURIFIED GAS
Syst em Desi gn Choi c es Lead/Lag
Medium / High Temperature Dual Bed
2
S
Advantages
RAWGAS
Advantages
and not sensitive to changes
RAW GAS
g
Increased Sulfur Capacity
50%
Ch O th R
CoMo CoMo
Change On the Run
Disadvantages
CoMo Thrown Away
ZnO ZnO
CoMo Thrown Away
Increased Cost in
vessels/material
PURIFIED GAS
Syst em Desi gn Choi c es: 3-Bed
Medium / High Temperature 3 Bed System
2
S
Advantages Advantages
CoMo life maximized
RAW GAS
CoMo life maximized
Increased Sulfur Capacity
Change On the Run
ZnO ZnO
C M
Disadvantages
Highest Cost in
vessels/material
CoMo
vessels/material
PURIFIED GAS
2
S and organic
S
Zinc Oxide Adsorb H2S Zinc Oxide Adsorb H2S
Ac t i Sor b
G 1 Sul f ur r emoval
Ac t i Sor b
G 1
Hydrodesulfurization Hydrodesulfurization Hydrodesulfurization Hydrodesulfurization
and Sulfur Adsorption and Sulfur Adsorption
In a Single Catalyst In a Single Catalyst In a Single Catalyst In a Single Catalyst
Ac t i Sor b
G 1
Cu 1.5% wt
Mo 3.5% wt
ZnO Balance
Surf Area 30m/g Surf Area 30m /g
Density 75-85 lbs/ft
1 2 1 4 kg/L
Same ZnO lbs/ft as ActiSorb
S 2
S S C it
1.2-1.4 kg/L
Same S Capacity
HDS activity even after S saturation
L ti it f Ol fi h d ti
Low activity for Olefin hydrogenation
Syst em Desi gn Choi c es: 1
Vessel
Single Bed Optimized use of Actisorb G-1
RAW GAS
Option 1 - Lower Cost for
Same Time On-stream (no
RAW GAS
Same Time On stream (no
CoMo required)
Option 2 Up to 30 50% longer
CoMo
G 1
G-1
Option 2 - Up to 30-50% longer
Life with fixed reactor volume
(replace CoMo with G-1)
ZnO G-1
G 1
PURIFIED GAS
Syst em Desi gn Choi c es Lead/Lag
RAW GAS
Dual Bed Optimized use of Actisorb G-1
O ti 1 L C t f Option 1 - Lower Cost for
Same Time On-stream (no
CoMo required)
CoMo CoMo
q )
Option 2 - Up to 30-50% longer
G-1 G-1
ZnO ZnO
(replace CoMo with G-1)
G-
1
G-
1
G-1 G-1
PURIFIED GAS
Syst em Desi gn Choi c es: 3-Bed
3 Bed System Actisorb G-1
Eliminate
RAW GAS
Eliminate
The CoMo Vessel
RAW GAS
ZnO ZnO
(new designs or
replacement)
G-1 G-1
CoMo
PURIFIED GAS PURIFIED GAS
CO
2
and COS
Z O h bl i h COS d CO i h f d ZnO has some trouble with COS and CO
2
in the feed
H
2
S + CO
2
COS + H
2
O
Higher CO
2
means higher COS
Small amount of H
2
O helps COS hydrolysis
COS + H
2
O CO2 + H
2
S
ActiSorb
G 1 can solve the problem

Ac t i Sor b
G 1 and COS
Wi h C M /NiM With CoMo/NiMo
COS + H
2
H
2
S + CO Hydrogenation
COS + H
2
O H
2
S + CO
2
Hydrolysis
Leaving equilibrium COS
In ZnO H
2
S + ZnO ZnS + H
2
O
ActiSorb G 1 has Hydrogenation/Hydrolysis to the
bottom of the bed and continuous H
2
S adsorption
As H
2
S concentration decreases
so does COS equilibrium
With H
2
S concentration ~50 ppb, COS eq = ~0
Feed Pr et r eat ment
A iS b
200/300 i lf d ActiSorb
200/300 to convert organic sulfur and

chloride to H
2
S + HCl
T HCl ith A tiS b
Cl 2 h d f Z O Trap HCl with ActiSorb
Cl 2 ahead of ZnO
Trap H
2
S with ActiSorb
S 2 to 40-60 ppb
Wi h CO /COS A iS b
G 1 li i COS With CO
2
/COS use ActiSorb
G 1 to eliminate COS
For a pre-reformer polish to < 10 ppb S with
A tiS b
305 ActiSorb
305
QUESTI ONS?

01 Pretreatment

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01 Pretreatment

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2011 Synthesis Gas Seminar Margarita y g

200 200 Series Series

305 to achieve < 10 ppb

G 1 can solve the problem

200/300 to convert organic sulfur and

Cl 2 h d f Z O Trap HCl with ActiSorb

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