(lts) low temperature shift catalyst - comprehensive overview
DESCRIPTION
Purpose Chemistry Operating Conditions Catalyst Activity Poisons By-Product Formation Effects of Water Catalyst Requirements VSG-C111/1122 - SeriesTRANSCRIPT
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Low Temperature Shift Catalyst
By:
Gerard B. Hawkins Managing Director, CEO
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Conventional Hydrogen Plant
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Low Temperature Shift
Purpose Chemistry Operating Conditions Catalyst Activity Poisons By-Product Formation Effects of Water Catalyst Requirements VSG-C111/1122 - Series
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LTS - Purpose
Generate H2 from steam - improve plant efficiency
Convert CO to CO2 for easier removal • CO is converted to CO2 in two stages of
shift conversion LTS is the second stage of shift conversion to
generate H2
• Residual CO conversion - critical to operating economics
• Reduce CO levels to typically 0.3 mol% (dry)
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LTS - Chemistry
CO + H2O ⇔ CO2+ H2 ∆H = -41.1 kJ/kgmol
• Reaction catalyzed by Cu for LTS • CO lowered from typically 3% to 0.3% • High conversion is favored by
– Low temperatures – High steam concentration
• Typically accomplished using copper on a zinc-alumina support
Cu
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LTS – Typical Operating Conditions
SOR EOR Temp (°F) 356 - 392 410 - 446 CO (vol%) 3 – 5
Temp (°F) 410 - 518 CO (vol%) 0.2 – 0.3
CO + H2O CO2 + H2
Inlet
Outlet
Inlet temperature ≥ 27°F above dew point
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LTS - Temperature Profile
Top Bed Depth
Bottom
Tem
pera
ture
Ageing
Movement
• Ageing mechanism is gradual poisoning
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LTS - Catalyst Activity
Good, stable catalyst activity • Maximum conversion of CO to CO2 • High kinetic rate at low LTS inlet
temperatures Conversion limited to equilibrium Operational measure of activity:
• temperature gradient through catalyst bed
• higher activity gives steeper gradient
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LTS - Catalyst Activity
Activity is NOT directly related to Cu content or Cu surface area • Cu content must be highly dispersed and
stabilised (hence content is not a good measure)
• Cu crystal phases and structure important to activity (therefore surface area is not a direct measure)
Only real test is in laboratory under faithfully reproduced plant conditions and on operating plants • Initial activity may not have any
relationship with long term activity retention
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LTS – Catalyst Activity
ATE (approach to equilibrium) is usually very close • CO slip not impacted by activity for
most of catalyst life • Does not affect movement of
temperature profile through bed Minimum inlet temperature restricted by
dew point • Not always possible to reduce inlet
temperature to optimal value to take advantage of activity
Not the most important parameter!
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LTS - Temperature Profile
Top Bed Depth
Bottom
Tem
pera
ture
Ageing
Movement
• Ageing mechanism is gradual poisoning Goal: Slow the rate of temperature profile
movement down the bed (poison resistance)
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LTS – Catalyst Poisons
Sulfur • Powerful poison • Trapped by the catalyst as Cu2S and ZnS
Chloride • Severe poison • Reacts with copper and zinc to form
chlorides • CuCl formation provides a mechanism for
loss of activity by sintering
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LTS - Mechanism of Sulfur Poisoning
ZnO
Cu
ZnO
Cu
Zn2+
Cu
ZnO
Cu
Adsorption on Copper Surface Mobility
Surface Sulphide Formation
Bulk Sulphide Formation
SS
ZnS
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LTS - Chloride Poisoning
Chloride reacts with copper to form CuCl (mp = 430oC)
CuCl formation provides a mechanism for loss of activity by sintering
Requires well dispersed and stabilized copper to minimize the effect of chloride
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Chloride Poisoning of LTS Catalysts
Chlorided LTS Non-chlorided LTS
Copper clusters normal size Copper clusters sintered
Lost surface area
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Chloride Poisoning of LTS Catalysts
Chlorided LTS
Sintered Copper ball large surface area loss
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Effect of Particle Size on Poisons Resistance
0
20
40
60
80
100
Cumulative Chloride Level
CO conversion (%)
0.3 - 0.6mm
0.6 - 1.0mm
1.18 - 1.4mm
1.4 - 1.7mm
•Poisoning reactions with H2S and HCl are strongly diffusion limited •Poisons resistance and activity can be increased by increasing the pellet geometrical surface area
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LTS - By Product Formation
• Methanol – Effect quality of CO2
– Quality of process condensate • Environmental legislation • Increased treatment costs
– Odor in CO2 vent • Can produce amines • When vented can be a nuisance
– Other oxygenates such as ethanol, ketones
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LTS - By Product Formation
• Methanol Formation CO2 + 3H2 <====> CH3OH + H2O
• MeOH increases with – High Temperatures – High inlet CO levels - increases LTS temperature rise – low S:C ratio – Low space velocity / catalyst bed volume
• MeOH production decreases rapidly in the first few months of LTS catalyst operation
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• Condensate – If catalyst is operated at too low temperature
• Waste Heat Boiler Leaks – Wetting then evaporation reduces strength
significantly – Can cause catastrophic failure due to thermal
shock – Loss of activity due to blocking of active sites – Pressure drop increase
• catalyst break-up • boiler solids fouling catalyst
LTS - Effects Of Water
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LTS - Effects Of Water
• Water will dissolve soluble poisons – wash poisons deep into the bed – Increase affected bed depth – accelerate change-out of the catalyst
Remember
CuCl2 is soluble in water!
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Key Performance Requirements
Poisons Resistance • Self guarding capacity
Selectivity • Minimize by-product formation
(methanol) Activity
• Minimize CO slip • With minimal catalyst volume
Strength • Withstand upsets such as condensation
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VSG-C111/112 Superior Poison Resistance
Low Methanol By-product Options High Activity High Strength
Extended Catalyst Life Short Load Potential to fit T/A Cycles
Maximize Hydrogen Production Address Environmental Concern
Resilient
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Superior Poison Resistance
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Improved Poison Retention using VSG-C111/112 series
High sulfur retention Typical = 1% at top & 0.1% at the bottoms
Impact of chloride poisoning on CO conversion
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Extra Chloride Poisons resistance
Applications confirm expected activity for CO and low methanol.
Additional benefit is the enhanced ability to chloride guard.
• Caesium and potassium have the highest driving force for chloride.
• This is shown by the fact that CsCl and KCl will be formed at very low levels of HCl.
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Equilibrium HCl Concentration
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Chloride Guarding Properties of VSG-C111/112 series
• Very stable chlorides are formed Chloride Mp (oC) Bp (oC) CuCl 430 1490 ZnCl2 283 732 CsCl 645 1290 KCl 770 1500 subl
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Mechanism of Chloride Resistance
ZnO
Cu
Adsorption on Potassium
HCl
CsCl ZnO Cs
Bulk Chloride Formation
K and Cs protect the Cu/ZnO lattice by preferentially reacting with and trapping chloride poison
Cu
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Sulfur Poisoning & Surface Area
Competitors
VSG-C111/112
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2 4 6 8 10 12 14 160
0.2
0.4
0.6
0.8
1
1.2
1.4
Sample Depth (ft)
Poison Level (%)
Cl (%)
S (%)
Poison Profile for VSG-C111, Chinese Hydrogen Plant
Sulfur & Chloride Retention of VSG-C111/112
= 13,000ppm!
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Relative Impact of Activity and Poison
Base (VSG-C111) +20%act +20%poison
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Low By-product Formation (Methanol)
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Plant Performance Optimized alkali promoters to achieve
high activity for shift conversion while reducing methanol synthesis
--------VSG-C111 ---------VSG-C112 Plant Data
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Laboratory Testing
Product Methanol Activity VSG-C112 0.18 Comp A low MeOH 0.26 Comp B low MeOH 0.33
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High Activity
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Activity Comparison (Laboratory)
Minimize CO slip
0.20
0.22
0.24
0.26
0.28
0.30
0.32
0.34
0 2 4 6 8 10
Time on-line (years)
CO
slip
Com petitor A
KATALCO 83-3XCom petitor C
---------- Competitor A ---------- VSG-C112 ---------- Competitor C
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Case Study: Longer Life (1700 stpd China Ammonia Plant)
Previous competitive charge achieved only 3-yr life before high CO slip (> 0.3 mol%) when 4-yr was expected
Replaced with VSG-C112 and operating 5+ yrs with less than 0.25 mol%
$$$ Saved ~ $170,000 +
Avoided Unscheduled S/D +
12-month Extension on T/A
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High Strength
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Relative Strengths of Fresh and Reduced Catalyst
VSG-C112 series formulated to have high strength after reduction
VSG-C112 Competitor A Competitor B
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Horizontal Crush Strength after Reduction and Condensing Steam
Conditions Compares relative strength of VSG-C112
and competitive low methanol products
VSG-C112
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Conclusions
VSG-C112 excels over all products with • More than adequate activity • Poisons resistance at least equal to a
‘famous and soon to be obsolete’ guard material with claimed ‘unrivalled poisons resistance’
• The lowest by-product Methanol in the industry
So for long life, low CO slip, Low Methanol VSG-C112 is the winner
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Catalyst Characteristics
VSG-C111 Copper oxide/Zinc Oxide/Alumina VSG-C112 As above, promoted by alkali metals
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Lab Based Test Program
Ability of the Topsoe LSK Guard to withstand chloride poisoning relative to VSG-C112
Determined in the laboratory using an accelerated poisoning test.
In the test a guard layer of the catalyst sample is placed above a main bed of VSG-C111 catalyst and the CO conversion is measured using LTS gas containing very low levels (50 ppb in this case) of HCl.
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Chloride resistance test rig LTS Feed gas
(60% H 2 , 21% N 2 , 16% CO 2 , 3% CO) with
50 ppb Chloride poison addition
Analysis of CO conversion
Standard bed
Test bed LSK
Analysis of CO conversion
Standard bed VSG-C111
Test bed VSG-C112
VSG-C111
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Chloride poison test results % Conv vs Wt Cl addition (gms)
Run No PR133 - 50 ppb HCl addition
010
2030
405060
7080
90100
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004 0.0045
Wt Cl addition (gms)
% C
onve
rsio
n
PR133B - U4676 Topsoe LSK PR133C - H1106K Std 83-3XVSG-C111
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Chloride poison test results TOPSOE LK-823 and LK-821-2
1ppm HCl additionCharged as guard beds (0.2mls) above main beds Std 83-3 (0.4mls)
Main Bed SV ~ 127000
0
20
40
60
80
100
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Wt Cl addition (gm)
% c
onve
rsio
n
PR59 - 83-3X PR59 - LK-823 PR59 - LK-821-2 PR59 - 83-3KVSG-C111
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Overall comparisons Activity/selectivity on volume comparison
Catalyst Relative Activity(v/v)
Relative Methanol Make(v/v)
LSK 0.52 0.44
LK 821-2 1.20 0.88
VSG-C111 1.18 0.20
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Competitive Summary
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Laboratory Poisoning Data
Analysis of CO conversion
Standard bed
Test bed Cat B
Analysis of CO conversion
Standard bed
Test bed Cat C
LTS Feed gas (60% H2, 21%N2, 16% CO2, 3% CO)
with Chloride poison addition
Analysis of CO conversion
Standard bed VSG-C111
Test bed Cat A
Analysis of CO conversion
Standard bed
Test bed Cat D
VSG-C111 VSG-C111 VSG-C111
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How do We Compare? Product Relative Poisons
Absorption * VSG-C111 1.0 VSG-C112 2.13
Comp A Guard ** 2.1 Comp A std 1.0
Comp A low MeOH 1.28 Comp B std ?
Comp B low MeOH 0.70 * Chloride pickup relative to VSG-C!!! measured by CO slip vs time and chloride analysis on spent material
** Guard with almost no sulfur capacity and very low activity
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