a clariant group company catalyst seminar 2016 cataly… · a clariant group company catalyst...

A Clariant Group Company

Catalyst Seminar 2016

Shift Catalysts &Case studies

Sunder Parthasarathy30th Sept 2016

A Clariant Group CompanyContentsHigh Temp Shift CatalystShiftMax 120 –the work horseShiftMax 120 HCF‐ New developmentChallenges in High Temp Shift converterLow Temp Shift CatalystShiftMax 210‐ the work horseShiftMax 215 – New developmentShiftMax 220‐ Low Methanol Make LTSMedium Temp Shift catalystShiftMax 300‐ the work horseCase StudyKSFL Case Study

A Clariant Group CompanyShiftMax® 120- Powerful Performance

ShiftMax® 120 proven for –• Long life • High Activity ‐ low CO slip / excellent

low temp activity• Low and stable deltaP• Nil desulfurisation time required• Stable performance in harsh

environment‐ WHB leak‐ we have experience of couple of

catalyst charges having fully washed with boiler feed water and revived back to full activity and run for several months

‐ Refractory carry over from WHB/ Sec Reformer

‐ K carry over, etc.,• Catalyst performance revived after

mishap in many plants and continued to give long life

ShiftMax® 120 6x6 mm Tab


ShiftMax®120 HCF ( Hexavalent Chrome Free)

Why ShiftMax®120 HCF is needed?

• Current HTS catalysts contain certain levels of hexavalent chromium (Cr6+) which is produced

in the manufacturing process

• Cr3+ is needed to increase catalyst stability and longevity

• Cr6+ can lead to start-up concerns unless the catalyst is activated properly as it is extremely

mobile in liquid water / condensate

• During initial reduction, many ammonia plants lack the ability to preheat the HTS catalyst

above the dew point prior to introduction of steam-Can lead to significant concentrations of Cr6+ in the condensate – leads to environmental

problems.

REACH Regulations (annex XIV to EC No 1907/2006) will inhibit the sale of compounds containing Cr6+ beyond a very low ppm threshold in 2017


• SM120 HCF is SM120 further processed insitu to make it Hexa valent Chrome free.

• Gives similar performance as SM120 which is proven in the NH3 / SynGasmarket for more than 30 yrs

• No Hexavalent Chrome - environment friendly catalyst

• No Yellow colour condensate seen during initial steam heating during start-up• No special start-up is required to control the exothermic reaction of hexavalent

chrome to trivalent chrome • Fully complaint with REACH Regulations

ShiftMax®120 HCF


ShiftMax®120 HCF Boiling Water TestTest method

100 catalyst tablets are added into a beaker with 100 ml boiling water and kept there for 5 minutes.

After decantation of the hot water the unbroken tablets are counted.

ResultsNo broken tablets could be found for ShiftMax® 120 as well as for the new ShiftMax® 120 HCFNo yellow water – indicating the absence of hexavalent chromium

The new production process reduces the content of hexavalent chromium to non-detectable levels* in the fresh catalyst. as confirmed by an independent institute.

*according to OECD test #

A Clariant Group CompanyChallenges in High Temp shift Converter

Pressure Drop

• More than 50% of HT shift catalysts are changed out due to pressure drop problems• Pressure drops issues are majorly due to:

• Boiler leaks• Refractory / foreign material carry over- Sec Reformer / WHB refractory damage- Potash leaching from Primary Reformer- Water treatment chemicals/ Silica,etc.,

Sud-Chemie Solution• GRAB Loading• CSK GG Rings

A Clariant Group CompanyAdvantages of GRAB loading & CSK GG Rings

Grab loading is Plant Specific and need to be designed based on the Reactor Conditions. CSK GG rings are recommended to be loaded on top of Shift catalysts replacing the standard alumina balls. Advantages are:

• Improves gas distribution

• Traps foreign material

• Prolongs the Pressure drop growth

• Minimises catalyst deactivation

• Protects to some extent the catalyst from condensation effects


GRAB Loading Reference

Competitor without Grab Loading ShiftMax®120

without Grab Loading

ShiftMax®120 With Grab Loading

GRAB Loading Pattern at PLANT AINLET

INLET

SS Raschig Rings CSK

C12-4 Catalyst

C12-4 Catalyst C12-4 Catalyst

SS Wire Mesh SS Wire Mesh

Alumina Balls of 7.5 M3 Alumina Balls different size

Collector Header Collector Header

Bed I.D = 3880 mm Outlet Bed I.D = 3880 mm Outlet

GRAB Loading Conventional Loading

CSK Rings


Low Temperature Shift Catalyst


ShiftMax®210 proven for –• Long stable life • High Activity ‐ low CO slip / excellent

low temp activity• Stable deltaP• Excellent poison resistance capability• Excellent thermal resistance capability• Catalyst performance revived after

mishap ( condensate flooding) in some plants and continue to give long life

ShiftMax® 210- The Work Horse

ShiftMax® 210 5x3 mm Tab

A Clariant Group CompanyShiftMax®215– New developmentTested at 300oC between the cycles to ensure catalyst stability

SM215 catalyst is made by Smart Manufacturing Process and now available for commercialization having‐• 10% higher activity than SM210• Improved retained crush strength• Higher hydrothermal stability• Better poison resistance


ShiftMax®220-Low Methanol Make LTS catalyst

• Activity‐Low temperature activity : improved CO Conversion at 180 deg.C. ‐Upto 70% conversion due to optimiseddispersion of Cu• Selectivity‐Side reactions like Methanol make are mostly inhibited due to presence of proprietary promoter• Crush Strength‐ SM220 is comparable to SM210

ShiftMax® 220 is our new generation catalyst madeby Smart Manufacturing Process and is having-

Type ShiftMax 210 ShiftMax 220

CuO 47% 47%

ZnO 42% 42%

Al2O3 Balance balancePromoter nil 1%Methanol make, PPM 625 350


ShiftMax® 300 Medium Temperature Shift Catalyst


Features of ShiftMax®300Low Temperature Activity• Formulated with promoters & Highly dispersed copper with Nano crystallite sites• Facilitates reaction at low temperatures such as 185°C• Allows operation at high space velocities and close to equilibrium for sustained periods

Lower Steam to Carbon ratio• Operation at high inlet CO at low S/G 0.31 mol/mol without affecting CO conversion ratio.

Thermal Stability & Robust Domed Structure• Thermal stability at elevated temperatures ~ 325°C due to special calcination procedure. • Robust domed tablet structure offers stable pressure drop

Higher Sulphur Resistance• High copper content with optimized dispersion resulting in higher capability of retaining traces of S• Part of the excess sites of copper used for S absorption does not affect the overall catalyst activity

Easy Start-up• Available in Reduced & Stabilized Version (RS), if required.

A Clariant Group CompanyConclusion

Süd‐Chemie/Clariant has legacy of manufacturing higher performancecatalysts.

ShiftMax®120 HCF is following our ShiftMax®120 in the superiorperformance and also meeting the environmental Challenges.

In Low Temp Shift –1. Established a new catalyst –ShiftMax 215 –which has similar robust

performance as ShiftMax 210 with 10% improved higher activity, Improvedretained crush strength and higher hydrothermal stability.

2. Developed Low methanol Make LTS catalyst Shift Max 220

SCIL have accumulated a wealth of experience in successfully troubleshooting many of the catalyst mishaps especially in Shift catalystsoperation and are always ready to share the same with the end‐users forbetter managing / enhancing the catalyst life.

A Clariant Group CompanyCase StudyWater ingress in Low Temp Shift Reactor

• Location: India (North West India)

• Nameplate capacity: 1520 mtpd

• Type of Catalyst used ShiftMax® 210

SITUATION BACKGROUND

• During December 2015-Ammonia-2 plant was running on normal parameters when the temperature indicator (TI309) inlet of LTS started to gradually decrease

PROBLEM SYNOPSIS

• Initially observed low CO Slip‐‐‐excess water due to leak added to the system.• Increased CO Slip‐ due to leak and increased partial pressure of H2O, the dew point increased resulted into condensation of water on the

catalyst bed thereby reducing activity.• Low Co2 slip in the regeneration section‐ Skewed S/C lead to heat dump in the regeneration section. Which led to enhanced performance of

this section thereby low CO2 slip was observed.• Steam production became low due to decline in BFW temp at RGB inlet.• Condensate flow was progressively increasedAll above led to conclusion that there is leak in exchangers


ACTIONS TAKEN

– Despite the efforts LT temp continued to drop and finally CO slip was coming high.

– Data was shared and SCIL done the simulation to find S/G ratio is more at inlet of LTS

– Drying Procedure shared

196

198

200

202

204

206

208

210

212

214

216

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

Prior to Leak

After Trouble shootingCONCLUSION

– Exotherm before and after the incident becomes same.

– Catalyst after incident from past 9 months showing satisfactory performance

LTS catalyst is reliable and robust and has kept the plant performance intact.


Contents

• About KSFL ( Company profile ,plant history, description of plant)• About HTS/LTS Process• Analysis of Problem• Troubleshooting and Solution• Performance comparison• Conclusion

Kribhco Shyam ‐ CASE STUDY


• KSFL is operating its one unit of Ammonia plant and two unit units of Urea plant at

Shahjahanpur, Uttar Pradesh India.

• KSFL Plant is gas based plant and getting gas from HBJ pipeline.

• Ammonia plant was commissioned in November‐1995.

• In current scenario the cost of plant operation is increasing with cost increase of

hydrocarbons.

Plant History


Plant History

• So it was decided to decrease the plant operating cost in terms of energy by

optimization of plant operating parameters and reducing pressure energy loss.

• To achieve the above goal, process gas pipelines, control valve and reactor

pressure drop survey was done.

• Different steps were taken to reduce pressure drop in process gas pipeline and

control valves.


Plant History

• Optimization of catalyst volume loaded in HT & LT shift reactor by short loading .

• With the aim of keeping same CO slip to and reduce pressure drop in the reactor

bed.

• Maximum utilization of catalyst loaded in reactor for its useful life.


Plant History

• Pressure drop reduced from – 0.73 to0.31 Kg/CM2g.

• At the start of run CO slip was 2.37 mole%

• At present CO slip is 2.37 Mole% at 1650 MTPD ammonia production.

• Pressure drop is 0.40 Kg/CM2g


Plant History

• In year 1995, originally HTAS SK‐201 catalyst 101.35 M3 volume was loaded in HT

shift converter.

• Shot loading of catalyst was done in HTS in April‐ 2011 from 101.3 M3 to 75.0 M3

with SM120.

• Ammonia production level before and after catalyst replacement was 1763.2 MT

and 1765.0 MT.

A Clariant Group CompanyHistory of LTS/HTS Charges at KSFL

HTS LTS

Current : SM120 Current : SM210Volume SU Volume SU 75 M3 Apr‐11 96 M3 Oct‐12

Previous : HTAS Previous : SM210Volume SU Volume SU 101.35 M3 Sep‐95 122 M3 Apr‐05


Design Parameters of Shift Reactors

Process Parameters

Design Value

Inlet Temp 370

Outlet Temp 437

Pressure drop 0.3

CO inlet 12.45

CO Outlet 2.95

Inlet S/G 0.51

HTS LTS

Process Parameters

Design Value

Inlet Temp 205

Outlet Temp 221

Pressure drop 0.3

CO inlet 3.0

CO Outlet 0.33

Inlet S/G 0.38

A Clariant Group CompanyKSFL Process Requirements

• Need for Low Pressure Drop Range

• Lower capital cost


Catalyst Performance

Parameters Design Previous Charge (SOR)

Current Charge(SOR)

Plant Load, MTPD 1800 1350 1765

Catalyst Volume, M3 92 101.35 75

Inlet CO, Mole % 12.45 13.2 11.51

Outlet CO, Mole % 2.95 3.08 2.37

Inlet Temp, deg C 370 376 351.7

Outlet Temp, deg C 437 434 420

Inlet S/G 0.51 0.5656

Pressure drop, kg/cm2 0.3 0.52 0.31

HTS


Catalyst Performance ‐ LTS

Parameters Design Previous Charge (SOR)

Current Charge (SOR)

Plant Load, MTPD 1800 1580 1864

Catalyst Volume, M3 70 122 96

Inlet CO, Mole % 3.0 2.53 2.33

Outlet CO, Mole % 0.33 0.17 0.13

Inlet Temp, deg C 205 198 196

Outlet Temp, deg C 221 218 216

Inlet S/G 0.38 0.4

Pressure drop, Kg/cm2 0.3 0.43 0.4


Conclusion

KSFL desired to implement measures to reduce pressure drop across the shift converter sections.

This target of energy saving and reducing capital cost was successfully achieved after internal discussions and recommendation by SCIL by reducing the catalyst volumes of HT Shift and LT Shift reactors.

a clariant group company catalyst seminar 2016 cataly… · a clariant group company catalyst...

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