07 Ammonia Synthesis

2011 Synthesis y Gas Seminar Margarita g Ammonia Synthesis
November 24, 2011
Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011
Page 1
Typical NH3 Process Flowsheet

Steam HC Fe ed Air
H TS
P u rification
P re R efo rm er
P rim ar y Ref or m er
S eco n d ary R efo rm er
C O2
R ef o rm in g
A mm on ia
H T CO S h if t
L T C O Sh ift
C O 2 Rem o val
M ethan atio n
N H 3 Syn th esis Lo o p
Page 2
Overview
Ch i t Process Chemistry P Consequences C Catalysts R Reactor t Technologies T h l i Pre/Post-Operation
Loading Reduction & S/U Discharge+Disposal Effect of key operating parameters: T, P, Inerts, H/N ratio Deactivation: Poisons, , Thermal sintering g Performance Monitoring and Evaluation
Operating Considerations
Common Problems/Troubleshooting
Page 3
NH3 Synthesis Thermodynamics
N2 + 3H2
2NH3 + HEAT
Higher g NH3 Conversion Is Favored By: y

Lower Temperatures Higher Pressure
Not equimolar 4 moles to 2 moles
Page 4
Catalyst Types
Ru/C R /C KAAP converter t Fused Fe catalyst promoted with Ca, Al, K

and other rare earth elements
Magnetite as precursor: Fe3O4 Wustite as precursor: Fe1-x (x=0.03-0.15) 0.03 0.15) 1 xO, (x
Sd-Chemies AmoMax-10
Typical size: 1 1.5-3mm 5 3mm Pre-reduced+Stabilized / Oxides Wustite Based
Since commercialization in 2003, 65 charges of AmoMax-10 have b been installed! i t ll d!

AmoMax-10 1.5-3 mm Granules
Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011 Page 5
Ammonia Synthesis AmoMax-10
AmoMax-10 1.5-3mm Granules:

Provides numerous advantages over traditional magnetite magnetite-based based catalysts: - superior mechanical stability, - higher low-temperature activity, %NH3 - enhanced thermal stability, Stable - higher resistance to poisoning, - lower light-off temperature, - and quicker and easier start-ups. Has demonstrated stable performance with run lengths g >7.5 YOS
Steady dP Matches Production
AmoMax-10 1.5-3 mm Granules

Reactor Technologies TVA Tube Cooled
Advantage
Integrated heat exchange with the catalyst for pseudo isothermal design Relatively e at e y s simple pe
Disadvantages
Inefficient temperature profile Pressure drop of Axial Flow
Page 7
Reactor Technologies TVA Tube Cooled

Temperature / NH3 Profile for a TVA type Tube Cooled Converter
1100
593
1000
Temperature, oF T
538
Temperature, oC
Page 8
900
482
800
427
700 0 5 10 % NH 3 15 20 25
371
Reactor Technologies Four Bed Quench

QUENCH GAS MAIN INLET
Advantage
Multiple Beds with inter-bed cooling No inter-bed heat exchangers
CAT AL YST BEDS
Disadvantages
Pressure drop of Axial Flow
CAT AL YST BASKET PRESSURE VESSEL
HEA T EXCHANGER
OUTLET
Reactor Technologies Four Bed Quench

Four Bed Quench - Typical Profile
530
986
Equilibrium 480
Tempe erature, oC
896
Tempe erature, oF
Page 10
430 Optimum 380
806
716
330 0 5 10 % NH 3 15 20
626
Reactor Technologies 2 Bed Quench/Intercooling

MAIN INLET QUENCH QUENCH
CAT AL YST BEDS
CAT AL YST BASKET PRESSURE VESSEL
HEA T EXCHANGER
COLD BYP ASS
OUTLET
Page 11
Reactor Technologies 2 Bed Quench/Intercooling 2 Bed Quench/Intercooling - Typical Profile

593
1100
1000
538
900
482
800
427
700
371
600 0 5 10 % NH 3
316
15
20
25
Page 12
Reactor Technologies 3 Bed Radial Flow

OUTLET QUENCH GAS
Advantage
Multiple Beds with intercooling via internal heat exchangers Axial-Radial flow can take advantage ad a tage of o smaller s a e catalyst cata yst particles = higher activity, more conversion
HEA T EXCHANGER
CA T AL YST BEDS HEA T EXCHANGER
CA T AL YST BASKET PRESSURE VESSEL
Disadvantages
Increased complexity in design/costs
MAIN
INLET
Page 13
Reactor Technologies 3 Bed Radial Flow

3 Bed Radial Flow - Typical Profile
1100
593
1000
538
900
482
800
427
700
371
600 0 5 10 % NH 3
316
15
20
25
Page 14
Reactor Technologies New Generation KAAP
New Generation 4 Bed KAAP System
Description
Reactor consists of 4 beds with indirect cooling between each 1st bed contains AmoMax-10 or magnetite ag et te catalyst cata yst Bottom 3 beds contain Ruthenium promoted higher activity catalyst
A R
Page 15
Reactor Technologies New Generation KAAP

Four Bed KAAP - Typical Profile
1000
538
900
Tem mperature, oF
482 Te emperature, oC
Page 16
800
427
700
371
600 0 5 10 % NH 3
316
15
20
25
Reactor Technologies Casale IAC C Casale l Isothermal I th l Ammonia A i Converter C t (IAC)
Reaction heat is removed by preheating the feed gas in a plate exchanger with radial elements Can be configured as axial or axial-radial flow Cold bypasses allow near isothermal operation, taking advantage of the optimum temperature profile to achieve maximum conversion
Adiabatic design Isothermal design Equilibrium line
Ammonia c conversion
Max reaction rate curve Temperature

Pre-Operation: Loading
To sieve or not to sieve? Dense Loading

Advantages:
Eliminates the need for vibration to ensure adequate loaded densities Better gas flow distribution Minimize bed shrinking Maximize converter volume utilization
If dense loaded, typical AmoMax-10 loaded

densities:
2.9-3.2 Kg/L (oxides) 2.3-2.6 Kg/L (pre-reduced+stablized)
(Check with appropriate catalyst vendor for loaded densities)
Loading usually performed in inert atmosphere Progressive check on loaded densities recommended
Page 18
Pre-Operation: Reduction & S/U
Required to yield active metal Fe phase Reduction procedure crucial for optimum catalytic performance Reduction to be p performed such that there is
Minimum sintering of Fe crystallites minimize exposure of metallic Fe to H2O formed from reduction Maximum dispersion of K (electronic promoter) Start to make NH3 once metallic Fe is formed
Reduction typically performed using syn MUG Key yp points during g reduction:
High gas circulation rate to ensure no back diffusion Low loop pressure to ensure good flow distribution and control NH3 synthesis reaction during reduction (exothermic) Control C l H2O levels: l l <1000 ppmw (prereduced+stablized) <2500 ppmw (oxides) Adhere to recommended heating rates
Page 19
Why Pre-reduced catalyst?

Only 10% oxidized Less water evolved during reduction Lower initiation temperature Once initiated, provides source of heat to reduce load on S/U heater Shortens reduction time Most economic: Top beds pre-reduced pre reduced
Page 20

Reduction Profile for 3-Bed Converter
1000 900 800 700
Te emparature, F
600 500 400 300 200 Bed 3 Inlet 100 0 0 00 00 0:00:00 Bed 3 Outlet Bed 1 Inlet Bed 1 Outlet Bed 2 Inlet Bed 2 Outlet
12 00 00 12:00:00
24 00 00 24:00:00
36 00 00 36:00:00
48 00 00 48:00:00
60 00 00 60:00:00
72 00 00 72:00:00
84 00 00 84:00:00
96 00 00 96:00:00
108 00 00 120:00:00 108:00:00 120 00 00
Hours of Operation
Post-Operation: Discharge & Disposal
Spent catalyst is pyrophoric May be stabilized prior to discharge lengthy During discharge:
process
Have water hoses available for quenching Discharge with a N2 blanket in vessel to prevent oxidation while catalyst is in reactor Have H only l one di discharge h port t open t to prevent t air i d drawn in via chimney effect Monitor bed temperatures for overheating Catalyst remains reduced after water evaporates
Spent catalyst can be handled safely when wet but:

Page 22
Operating Considerations: T, P, Inerts

70
60
P=13800 kPag (2000 psig) Inerts=10% H/N=3:1 P, Equi %NH3
50
Eq quilibrium % %NH3
Optimum T: Set by catalyst activity More active catalyst, lower T for max conversion
40
30
P=13800 kPag (2000 psig) Inerts=5% H/N=3:1 Inerts, Equi %NH3 P=6800kPag (1000 psig) Inerts=10% H/N=3:1 T , Equi %NH3
20
10
0 250
300
350
400
450
500
550
Temperature, oC
Operating Considerations: H/N ratio

19 1.2
18
1.0
17 08 0.8 16
Efficient Operating Window: H2:N2 2.2:1 to 3.0:1
0.6
15
14
0.4
13 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 H 2 :N 2 Ratio

0.2
Page 24
Operating Considerations: Deactivation
T Temporary Poisons: P i
Oxygenates: ~100 ppm O2~100 ppm CO2~100 ppm H2O Converted to H2O via methanation H2O reoxidizes idi active ti metallic t lli F Fe surface f Reversible if at low levels and short periods
Permanent Poisons:
Oxygenates at high levels and extended periods: Continuous oxidation+reduction: chemical sintering, reorganization of Fe surface loss of active Fe phase Sulfur: formation of Fe2S3. As low as <0.1wt% <0 1wt% sulfur on catalyst is an issue Chlorides: Formation of volatile potassium chloride loss of electronic promoter Fouling: CO2 + NH3 forms solid ammonium carbamates HC from compressor lube oil carbon deposition
Thermal Sintering from High Temperatures

Page 25
Performance Monitoring & Evaluation
Key Monitoring Points:

Ammonia Production
R Recycle l R Ratio ti MUG + Converter C t inlet i l t fl flow %NH3 at converter outlet
Loop Pressure Total T across converter P across converter Purge
Evaluation
R Recommended d d on a bi bi-annual lb basis i i in conjunction j ti with ith front-end evaluation
Page 26
Troubleshooting: Some common issues

Process Problem
Need to increase purge rate due to inerts build up
Possible Reasons
Loss of catalyst activity Check outlet %NH3 Loss of DT? Loss of catalyst activity Check outlet %NH3 Loss of DT?
If unresolved will lead to.

Inefficient NH3 loss
Possible Actions to Resolve

Check for poisoning: COx, S Cl, S, Cl HC HC. If COx poisoning, could be reversible Check for poisoning: COx, S Cl, S, Cl HC HC. If COx poisoning, could be reversible Close monitoring Shutdown might be required for mechanical work
Need to increase recycle to maintain production
Inefficient Power to drive increasing circulation rate , Cost
Pressure drop increase
Mechanical issues: screen failures, internal hose/manifold issues
Gas channeling in converter Catalyst loss in last bed Non ideal performance Thermal sintering and catalyst deactivation Loss of production
High temperature excursions
Poor heat integration in loop during S/U
Thermal sintering is irreversible Premature change-out might be required
Page 27
Questions?
Page 28

07 Ammonia Synthesis

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2011 Synthesis y Gas Seminar Margarita g Ammonia Synthesis

November 24, 2011

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Typical NH3 Process Flowsheet

S eco n d ary R efo rm er

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

NH3 Synthesis Thermodynamics

Higher g NH3 Conversion Is Favored By: y

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Ru/C R /C KAAP converter t Fused Fe catalyst promoted with Ca, Al, K

Since commercialization in 2003, 65 charges of AmoMax-10 have b been installed! i t ll d!

Ammonia Synthesis AmoMax-10

AmoMax-10 1.5-3mm Granules:

Steady dP Matches Production

AmoMax-10 1.5-3 mm Granules

Reactor Technologies TVA Tube Cooled

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Reactor Technologies TVA Tube Cooled

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Reactor Technologies Four Bed Quench

CAT AL YST BEDS

CAT AL YST BASKET PRESSURE VESSEL

Reactor Technologies Four Bed Quench

430 Optimum 380

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Reactor Technologies 2 Bed Quench/Intercooling

CAT AL YST BEDS

CAT AL YST BASKET PRESSURE VESSEL

COLD BYP ASS

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Reactor Technologies 2 Bed Quench/Intercooling 2 Bed Quench/Intercooling - Typical Profile

Reactor Technologies 3 Bed Radial Flow

CA T AL YST BEDS HEA T EXCHANGER

CA T AL YST BASKET PRESSURE VESSEL

Reactor Technologies 3 Bed Radial Flow

Reactor Technologies New Generation KAAP

New Generation 4 Bed KAAP System

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Reactor Technologies New Generation KAAP

Reactor Technologies Casale IAC C Casale l Isothermal I th l Ammonia A i Converter C t (IAC)

Max reaction rate curve Temperature

To sieve or not to sieve? Dense Loading

If dense loaded, typical AmoMax-10 loaded

Pre-Operation: Reduction & S/U

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Pre-Operation: Reduction & S/U

Why Pre-reduced catalyst?

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Pre-Operation: Reduction & S/U

108 00 00 120:00:00 108:00:00 120 00 00

Post-Operation: Discharge & Disposal

Spent catalyst can be handled safely when wet but:

Operating Considerations: T, P, Inerts

P=13800 kPag (2000 psig) Inerts=10% H/N=3:1 P, Equi %NH3

Operating Considerations: H/N ratio

13 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 H 2 :N 2 Ratio

Operating Considerations: Deactivation

Thermal Sintering from High Temperatures

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011

Performance Monitoring & Evaluation

Key Monitoring Points:

Loop Pressure Total T across converter P across converter Purge

Sd-Chemie Syngas Seminar | Margarita | Nov 2-4, 2011