Performance of HT & LT Catalyst

Amit Kumar Jha MT (Chemical) # 0247/7161

Contents Catalyst overview Process wise use of HT & LT shift conversion Operation condition of HT & LT Systems employed to CO Conversion Catalyst design Effect of variables on catalyst activity Catalyst poisoning factors Operational caution

Catalyst overview
The first time a catalyst was used in the industry was in 1746 by J. Roebuck in the manufacture of lead chamber sulfuric acid. Catalyst components : I. Promoters : are substances that increase the catalytic activity, even though they are not catalysts by themselves. II. Inhibitors, poisons : Substances that reduce the action of catalysts are called catalyst inhibitors if reversible, and catalyst poisons if irreversible. III. Support : is the material, usually a solid with a high surface area, to which a catalyst is affixed. IV. Catalyst : Substance which increases reaction

Catalysts reduce the amount of energy needed to activate chemical reactions. Catalysts vary in composition, structure and shape - according to the chemical reaction in which they are used. Catalysts are used by chemists to speed up chemical reactions that otherwise would be inconveniently slow.

Process wise use of HT & LT shift conversion

The conversion of carbon monoxide(CO) with steam(H2O) to give hydrogen(H2) and carbon dioxide(CO2) Chemistry involved : CO +H2O CO2 + H2 9.838 Kcal/mole Favorable conditions : High steam Low temperature (i.e. reaction is exothermic) High pressure

Advantages of HT & LT water gas shift conversion catalyst 1. Reduction in steam requirement i.e. low energy requirement 2. Greater yield of H2 3. Reduction in equipment size and cost 4. Lower loop pressure 5. For Urea as final product , higher CO2 production

Operating condition of HT & LT

HT Input Temp. (C) 370 Pr. (Kg/cm2) 29.2 output 427 28.6 LT Input Temp. (C) 210 Pr. (Kg/cm2) 28 output 230 27.3

Gas composition (%): CO2 8.989 16.439 CO 12.184 3 H2 56.063 59.660 Steam/gas ratio : 0.6 0.7

Gas composition (%): CO2 16.439 18.630 CO 3 0.3 H2 59.660 60.718 Steam/gas ratio : 0.4 0.5
Source : Amm-III operating manual

Systems employed to CO Conversion HTS Cooling CO2 removal Heating HTS Cooling CO2 removal HTS Cooling HTS Cooling CO2 removal HTS Cooling LTS Cooling CO2 removal LTS Cooling CO2 removal Selection of process depends on feed stock quality and capacity of plant

Catalyst Design(HT CO Conversion pyrophoric catalyst)

TYPE : CDC-85 SHAPE & SIZE : Solid Cylindrical Tablet 6 mm dia. 6 mm height QUANTITY IN M3 : 52.70 BULK DENSITY KG/LIT : 1.05 0.05 QUANTITY IN MT : 55.34 SPECIFICATION : Fe2O3 -85 to 90%wt. Cr2O3- 8 to 10% wt. EXPECTED LIFE : 5 yrs SUPPLIER : M/S P.D.I.L SINDRI For HTS (330C-530C) should not exit 200C

Catalyst Design (LT CO Conversion pyrophoric catalyst)

TYPE : CD-LT-21A SHAPE & SIZE : CYLINDRICAL TABLETS 6X4 mm QUANTITY IN M3 : 59.40 BULK DENSITY KG/LIT : 1.25 0.05 QUANTITY IN MT : 74.25 SPECIFICATION : CuO - 30% wt. ZnO - 30% wt. Mixed Oxide (Al2O3 ,TiO2,Fe2O3 etc.) - 40% wt. EXPECTED LIFE : Guaranteed -1yr. Expected-3 yrs SUPPLIER : M/S P.D.I.L SINDRI For LTS (200C- 250C) should not exit 50C

Effect of variables on catalyst activity

Temperature- Activity increases with increase in temperature. Pressure- Activity increases with increase in pressure. Pressure does not effect thermodynamic equilibrium. Flow rate- Decreasing the flow rate , for a fixed catalyst volume, results in a closer approach to equilibrium and a conversion of a greater % of the CO in feed.

 Steam/gas ratio- Increasing this ratio results in a lower equilibrium CO and a decrease in contact time. Catalyst size- Activity is affected by the geometric surface areadecreasing the size of the catalyst will result in an increase in reaction rate and pressure drop.

Catalyst activity and Life

(Catalyst poisoning factors) Normal operating life for HT catalyst : 3 - 5 years LT catalyst : 1 - 2 years Catalyst de-activators are of two types : 1. Chemical poison which react with it and reduces activity 2. Physical blockage which deposit on catalyst and prevent the reactant from contacting the catalyst

HT catalyst poisoning compound

1. Sulfur compound :- Hydrogen sulfide and COS , due to incomplete desulfurization result in conversion of Iron oxide to Iron sulfide and if fully sulfided the activity could be halved. possible solution:- stabilized desulfurization and pure feed stock 2. Phosphorus compound :- Phosphate may be introduced into process steam and contact to HT catalyst. possible solution:- pure BFW and steam

3. Oxygen :- If oxygen ( i.e. Air ) introduced during shutdown or unusual condition , will react with reduced (Fe3O4 ) catalyst in highly exothermic reaction and if reaction is uncontrolled ,catalyst may sintered and de-activated. possible solution:- keep in pressurized condition during shutdown with the help of N2 , controlled oxidation (if necessary) 4. Carbon compound :- Abnormal operation of PR & ATR can lead to high conc. of hydrocarbon to HT converter. 2CO CO2 + C possible solution:- stabilized reformation section , controlled hydrocarbon slip

LT catalyst poisoning compound

LT catalyst is more sensitive to poison than HT catalyst. 1. Sulfur compound :- Hydrogen sulfide and COS , due to incomplete desulfurization Possible solution:- stabilized desulfurization , pure feed stock , guarded by ZnO catalyst in separate vessel or directly on top of LT catalyst. 2. Cl2 :- As low as 0.1 ppm Cl2 poison LT catalyst possibly carry over by boiler solid , contamination in process air. Possible solution:- pure process air , pure boiler feed water.

3. Oxygen :-will react with reduced copper catalyst to give

copper oxide in highly exothermic reaction and if reaction is uncontrolled ,catalyst may sintered and deactivated. Possible solution:- keep in pressurized condition during shutdown with the help of N2 , controlled oxidation for reuse (if necessary). 4. Steam :- Heating up reduced catalyst with the help of steam should not below condensation point since water deposition weaken the catalyst. Possible solution:- keep steam temp. 10 20 C above condensation point .

de-activation due to Physical blockage

De-activation due to Physical blockage may occur in two ways 1. From fine solid particles as dust in gas stream 2. Form volatilization of solid into gas from high temp. stages which deposit on catalyst. Dust :- can erode catalyst pellet and disintegrate and increase pressure drop. Source :- Upstream catalyst and refractory lining , ATR process air , maloperation of PR to produce carbon or soot Solution :- Vacuuming , pressurization and depressurization by steam through upper vent.

 Silica :- volatilize into steam from high pressure boiler Source :- BFW with silica more than design value , volatilization of silica from PR and ATR catalyst and refractories . Solution :- pure BFW , high purity alumina refractory base of PR and ATR. Nickel :- Not volatilize in normal operation , possible during shutdown when CO content can stand over Ni catalyst at low pressure in the form of Ni(CO)4 which is highly toxic to man. Solution :- All CO containing gas must be purged while its hot not allow to cool down within system

 Potash :- Potash transfer arises from alkalized nickel catalyst used in PR from Kalsinite (KAlSiO4). This compound hydrolyzes to free potash which volatilizes either in form of KOH (high vap. pr.)or K2CO3 (low vap. pr.) at 200 to 800 C Caustic soda :- similar to Caustic potash present in PR & ATR catalyst. Cadmium :- From Sulfur removal catalyst (Zinc oxide and cadmium oxide) during reduction Solution :- A layer of ceramic ball on top of HT catalyst traps nearly almost all deposits.

Operational caution
Scenario 1 :- caution must be taken during shut down , keep HT & LT in pressurized condition in order to not allow air to enter in catalyst bed otherwise excessive heating during oxidation of reduced catalyst by O2 with reduced catalyst may damage catalyst . Scenario 2 :- Reduction of new HT catalyst , must not allow temp. to exceed 500 C, control by dilution with steam. Even to dis-card of used catalyst otherwise vessel may damage. Similarly for new LT catalyst , must not allow temp. to exceed 230 C, control by lowering inlet temp. Even to dis-card of used catalyst otherwise vessel may damage.

 Scenario 3 :- Before putting LT converter inline the following shall be ensured: SCNG available with sulphur content less than 0.5 ppm. SCNG temperature is about 190-200 0C. HT temp. difference should be at least 30 C. Scenario 4 :- Before putting HT converter inline the following shall be ensured: Inlet temp. should be above 200 C at 5 Kg/Cm2 otherwise steam condensation may take place.

 Scenario 5 :- High temp. diff. in Converter . possible reason : exit CO content high from upstream, reduced catalyst performance Indication for catalyst performance reduction : > Pr. Drop increase > Reduction in temp. diff. possible solution : increase Steam to HT , increase inlet temp. Caution : Dont allow increase in temp. beyond 230 C in LT & 500 C in HT otherwise catalyst may sinter. sintering temp. :- sintering temp is general nothing but the temp at which the grains of solid formed from powder start connecting through its boundries and merge so forms a larger grain. its generally between 2/3rd of melting temp of that material.

 Scenario 6 :- ATR trip Action : Bypass LT because LT temp. runaway may possible Reason: CO slip may increase

References :
A-III Operation Manual Ammonia technology A. V. Slack G. R. James Vol 2 Part : I,II

Thank You