KRIBHCO SHYAM FERTILISERS LTD AMMONIA PLANT FEEDSTOCKS AND RAW MATERIALS

Nitrogen and hydrogen are the two basic raw materials used in the manufacture of ammonia. Nitrogen is available in abundance, the source being atmosphere. The sources of hydrogen for nitrogenous fertilizer production are natural gas, naphtha, fuel oil, coal and from electrolysis of water.

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SHORT DESCRIPTION ABOUT DIFFERENT FEEDSTOCKS

Natural gas
Natural gas composition varies with location. Higher the concentration of Methane, lower will be the C : H ratio. The natural gas occurs either in association with crude petroleum or as non-associated gas. When it occurs as non-associated gas, it is called free gas and when it occurs in association with crude petroleum, it is called associated gas.

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SHORT DESCRIPTION ABOUT DIFFERENT FEEDSTOCKS

Typical compositions of free gas & associated gas Constituents

Associated Gas (Vol. per cent)

Free gas

CH4 C2H6 C3H8 C4H10 C5H12 O2, N2, CO2 etc.

69.2 13.5 9.3 4.0 1.7 2.3

80.2 8.0 4.4 1.9 0.8 4.7

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SHORT DESCRIPTION ABOUT DIFFERENT FEEDSTOCKS

Naphtha The light distillate fraction of petroleum produced during the refining of crude oil with maximum boiling point in the range of 94 deg 232 deg C is called straight-run naphtha.

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SHORT DESCRIPTION ABOUT DIFFERENT FEEDSTOCKS

Typical analysis of Naphtha Sp Gravity Sulphur Lead Chloride Paraffin Olefin Naphthalene Aromatic C/H ratio (by weight) Boiling point range

0.700-0.715 0.15 % max 1.7 ppm 0.4 ppm 79 % 1% 14 % 6% 5.45-5.42 94 deg 232 deg C

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SHORT DESCRIPTION ABOUT DIFFERENT FEEDSTOCKS

Fuel oil or heavy petroleum fraction

These are heavy residual fractions obtained by primary distillation and cracking of crude oil. The heavy fraction could be fuel oil, high sulphur heavy stock or low sulphur heavy stock.

Lignite
Lignite is inferior coal, containing high water and having low heat value and mechanical strength.

Coal
The estimated coal resources in India are to the tune of 81 billion tones. Two fertilizer plants namely Ramagundam and Talcher are based on coal gasification.

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SHORT DESCRIPTION ABOUT DIFFERENT FEEDSTOCKS

Coke Oven gas

Coke oven gas is produced during coal carbonization in steel plant. This gas contains Hydrogen methane, carbon monoxide etc, which can be used for ammonia manufacturing. The fertilizer plant at Rourkela is based on coke oven gas.

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COMMERCIAL AVAILABLE AMMONIA TECHNOLOGY

Haber suggested that ammonia can be produced by synthesis reaction of H2 & N2 in the ratio 3 to 1 at high pressure and high temperature in presence of iron catalyst. Due to advancement of technology, ammonia production was commercialized and specific energy consumption also reduced. Various commercial ammonia process/ technologies available are

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COMMERCIAL AVAILABLE AMMONIA TECHNOLOGY

Haldor Topsoe Process ICI Process (AMV Process) MW Kellogg Low Energy Process C. F. Braun KTI PARC Process Humphery & Glasgow (MDF &LEAD Process)

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INSTALLED CAPACITY
PROCESS LICENSOR

- 1520 MTPD
- HALDOR TOPSOE, DENMARK

PROCESS TECHNOLOGY - NG STEAM REFORMING RAW MATERIAL - FEED-NG FUEL NG AND/OR NAPHTHA

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NG FEED STOCK SPECIFICATION

Ammonia plant can be fed with one of the feed/fuel gas having the following characteristics at battery limits:

CASE A Rich Gas

CASE B After LPG extraction

CASE C Lean gas

Methane Ethane Propane I-Butane N-Butane I-Pentane N-Pentane Hexane Carbon Dioxide Oxygen Nitrogen Total Sulfur content as H2S Normal Design Pressure Temperature

78.84 7.23 4.59 0.88 1.10 0.26 0.24 0.26 6.49 0.10 0.01 10ppm 50ppm 43 Kg/cm2g 30 C

83.29 7.60 2.10 6.9 0.10 0.01

98.39 1.40 0.10 0.10 0.01

F
Natural gas 98% CH4
387 Deg C 32Kg/Cm2

HP Stea Stack Process air m 10.95% 0.3%CH4 CH4 950 Deg C Primary Reformer 770 Deg CSec. Reformer RG Boiler

Desulphurizer R-1201/1202

360 Deg C 12.96% CO

T 427 Deg C
3.09% CO HT Shift Trim heater CG boiler

Recycle Hydrogen

Steam

Comb. Air Natural gas Purge gas

Boiler feed water

From 2d Stage

Surplus syn gas

BFW Pre heater BFW from E1502 200 Deg C LT T Shift 221 Deg C 0.25% CO BFW BFW Pre heater

Syn gas compressor

M/U gas chiller

Make up syn gas 210 Kg/cm2 & 23 Deg C CO2 TO UREA

26 Kg/Cm2 38 Deg C 74.2% H2 & 24.77% N2 1.03% CH4/Ar Separator Final gas cooler 338 Deg C Methanator 0.1%CO2

17.75% CO2 CO2 Removal

E1311
320 Deg C

SEP Separator L

FPT
Lean and Semi Lean GV Solution

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RAW MATERIAL CONSUMPTION

NG (MSM3/DAY) FEED TO REFORMER FUEL TO REFORMER 1.008 0.273 OR* 0.137 0.068 OR* 0.017 NAPHTHA (MT/DAY) NA NIL OR* 110 NIL OR* 45

FUEL TO SUPER HEATER

(* IN CASE OF MIX-FUEL FIRING)

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ENERGY CONSUMPTION

The Theoretical Specific energy consumption is 4.46 Gcal/te of Ammonia. The actual Specific energy consumption is 7.6 Gcal/te of Ammonia. The difference between these two energies is due to loss of energy from Flue gas of primary reformer and heat loss in cooling tower.

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MAJOR PROCESS STEPS

HYDRO-DESULPHURISATION PRIMARY & SECONDARY REFORMING CO SHIFT CONVERSION

CO2 REMOVAL SYSTEM

METHANATION COMPRESSION AMMONIA SYNTHESIS PROCESS CONDENSATE TREATMENT PURGE GAS RECOVERY

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HYDROGENATION

Natural Gas mainly containing methane (98%) and higher hydrocarbon has 10-50 ppm of sulphur. This sulphur is poisonous to Primary reformer Catalyst and LTS catalyst. In desulphurization process sulphur content is reduced to 0.05 ppm.
Hydrogen is added to Natural gas and sent to Hydrogenator. Here Hydrogen reacts with Sulphur and Hydrogen Sulphide is formed. H2+S

H2S

Type of catalyst TK-251 Volume of catalyst 8.9 M3

(Catalyst Ni & Mo)

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DESULPHURISATION

After hydrogenation the process gas is passed through the absorption vessels where the H2S is absorbed on ZNO ZnO+H2SZnS+H2O

(Catalyst ZnO)

Type of catalyst HTZ-3 of HTAS

Volume of catalyst 13.8 M3

There are two ZNO absorbers in series and one can be isolated in running for replacement of catalyst.

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PRIMARY REFORMER

It is a side fired tubular primary reformer with flue gas heat recovery section. Natural gas is reformed with steam to produce a mixture of hydrogen, carbon monoxide, carbon dioxide and methane.

The reforming reaction is endothermic. The heat required for reforming reaction is supplied by 576 radiant burners.

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PRIMARY REFORMER

The favorable conditions for reformer reaction are low pressure and high temperature. CH4+2H2OCO2+4H2 -- HEAT CO2+H2CO+H2O -- HEAT There are two chambers and each chamber contains 144 tubes. Catalyst volume in Primary reformer is 44 M3 Primary reformer outlet Methane is approx. 11 %.

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SCHEMATIC DIAGRAM OF PRIMARY REFORMER

ID Fan

Stack

FD Fan

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SECONDARY REFORMER

Function of secondary Reformer is to reform the Primary Reformer exit residual methane and to add Nitrogen to the process gas. This is achieved by mixing a stoichiometric quantity of process air to the primary reformer exit gases in Secondary Reformer. The Oxygen present in the air burns with Hydrogen and provides heat for further reforming reaction. Secondary Reformer outlet gas mixture contains hydrogen, nitrogen, carbon monoxide, carbon dioxide and methane (0.3%).

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WASTE HEAT RECOVERY

High temperature process gas exit secondary Reformer at 950 deg C is cooled down in Waste Heat Boiler to 360 deg C and in turn high pressure steam (115 Kg/cm2g) is produced. This Saturated Steam produced is super heated to 510 deg C and utilized as driving force for Syn gas turbine which in turn generate Medium Pressure steam.

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SECONDARY REFORMER AND RG BOILER

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SHIFT CONVERSION

Carbon monoxide is converted to carbon dioxide in two stage shift conversion bringing down the carbon-monoxide content from 12.95% to 0.3 % in the process gas. In the first stage the reaction rate will be higher at High temperature and in the Second stage equilibrium conditions are favorable at low temperature. CO+H2O CO2+H2+HEAT

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SHIFT CONVERSION

High temperature Shift converter Catalyst volume 100 M3 Type of Catalyst SK-201 of HTAS CO Content reduced to 3.09% from 12.96%. Low temperature Shift converter Catalyst volume 116 M3 Type of Catalyst C-18 G/7 of Sud-Cheme CO Content reduced to 0.25% from 3.09%.

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CARBON DIOXIDE REMOVAL Giammarco Vetrocoke (GV) solution is used to absorb carbon dioxide from the process gas thus reducing carbon dioxide content from 17.72% to 0.05% in gas mixture in CO2 absorber.

GV solution contains

Potassium Carbonate Glycine Di Ethanol Amine

Vanadium penta oxide

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CARBON DIOXIDE REMOVAL

In this Glycine and DEA are used as activator. Vanadium Penta oxide works as corrosion inhibitor. GV solution rich in Carbon dioxide is regenerated in HP & LP regenerators by giving heat & Carbon dioxide is sent to Urea Plant.

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METHANATION

Oxides are harmful for synthesis converter catalyst. 0.25 % Carbon monoxide from LTS outlet and 0.05% Carbon dioxide from CO2 Absorber are converted into methane in this step. CO+3H2 CH4+H2O+HEAT CO2+4H2 CH4+2H2O+HEAT Catalyst Volume 30 M3 Catalyst type PK-5 of HTAS. The exit process gas (Synthesis Gas) contains mainly a mixture of hydrogen and nitrogen in the ratio of 3:1.

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SYNTHESIS GAS COMPRESSION

Synthesis gas is compressed to 210 Kg/cm2g in synthesis gas compressor. This compressor has four stages and one recycle stage. This compressor was supplied by BHEL.

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AMMONIA SYNTHESIS

KRIBHCO SHYAM FERTILISERS LTD AMMONIA PLANT

AMMONIA SYNTHESIS

Conversion of this gas mixture into ammonia takes place in TOPSOE-S200 radial flow converter. Gas inlet temperature is 224 deg C. Converter has two beds with inter-bed heat exchanger. 3H2+N22NH3+HEAT Catalyst volume is 100 M3.

Type of catalyst KM1R/KM1 of HTAS.

Converter outlet gas at 455 deg C is cooled in various heat exchangers and finally separated at 2 deg C in Ammonia Separator.

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REFRIGERATION SYSTEM

Gas mixture containing ammonia is cooled down to separate liquid ammonia from the gases by providing ammonia refrigeration. Separated liquid ammonia is sent to Urea Plant at 2 deg C temperature. In case Urea Plant is not in operation, product Ammonia can be sent to Ammonia Storage at -33 deg C. The operating pressure of chillers

0.05 Kg/cm2g

3.5 Kg/cm2g
6.5 Kg/cm2g

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UTILITIES : STEAM SYSTEM Steam Type SH SM SL Quality Superheated PressureKg/cm2g 110 38 3.5 Temperature C 510 381 260 There are two service boilers and two HRSG boilers in offsite which can generate 100te/hr each at 112Kg/cm2 and 510 DegC. Normally one service boiler and one HRSG boiler are in service. High pressure steam from boiler is distributed to Ammonia plant and Urea plant. In KSFL SH steam pressure is maintained by Offsite. The SH steam is used in running Syn gas turbine and CO2 turbines.

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UTILITIES : ELECTRIC POWER Alternating Current 11000 V 3 phase 3300 V 3 phase 415 V 3 phase 240 V 1 phase Instrumentation and Control 115 V 1 phase

50 Hz 50 Hz 50 Hz 50 Hz 50 Hz

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UTILITIES : COOLING WATER

Inlet temperature to the unit Outlet temperature from the unit Fouling factor for shell side Fouling factor for tube side

34C 44C 0.0006 m2hC/Kcal 0.0006 m2hC/Kcal

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UTILITIES : COOLING WATER

Ammonia cooling tower was designed by Paharpur. There are six cells and each cell is provided with an induced draft fan. There are three cooling water pumps out of which one is motor driven and two are condensing turbine driven. The normal cooling water flow is 20,000 M3/hr and CW header pressure is 3 Kg/cm2g.

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UTILITIES : PURE NITROGEN In KSFL Nitrogen generation plant is not available. So Pure Nitrogen is purchased as per requirement from outside agencies Quality of Nitrogen Nitrogen plus noble gases 99.99 % vol (min.) Carbon dioxide NT Carbon monoxide NT Water NT Oxygen 10 ppm (max.) Pressure 6 Kg/cm2g Temperature 40 C

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PRODUCT SPECIFICATION

Ammonia Quality Ammonia Moisture Oil Temperature Pressure

99.5 wt % max. 0.5 wt % max. 10 ppm max. 12/-33 C 25/5 Kg/cm2g

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PRODUCT SPECIFICATION

Carbon Dioxide: Composition, dry: CO2 H2 N2 Temperature Pressure Water

98.7 % vol 0.8 % vol 0.5 % vol 40 C 0.8Kg/cm2g saturated

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