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Solanki Gunjan D.
BE-||| Chemical
Maharaja Sayajirao University, Vadodara
Solanki Gunjan D.
BE-||| Chemical
Sewa Trust belong to this category. An ambitious project 'ICT Initiatives for Farmers and Cooperatives' is launched to promote e-culture in rural India. IFFCO obsessively nurtures its relations with farmers and undertakes a large number of agricultural extension activities for their benefit every year. At IFFCO, the thirst for ever improving the services to farmers and member co-operatives is insatiable, commitment to quality is insurmountable and harnessing of mother earths' bounty to drive hunger away from India in an ecologically sustainable manner is the prime mission. All that IFFCO cherishes in exchange is an everlasting smile on the face of Indian Farmer who form the moving spirit behind this mission. IFFCO, to day, is a leading player in India's fertiliser industry and is making substantial contribution to the efforts of Indian Government to increase foodgrain production in the country.
INDEX
Sr. 1 2 3 4 5 6 7 8 Department/Section Fire and Safety Ammonia Urea Offsites Utility B & MH Process Lab. Duration 5/6/13 6/6/13 to 10/6/13 11/6/13 to 13/6/13 14/6/13 to 17/6/13 18/6/13 to 19/6/13 20/6/13 21/6/13 24/6/13 to 25/6/13
AMMONIA
This single stream plant is based on the Kellog Process with Reliquified Natural Gas as a raw material. The manufacture of Ammonia involves the following 6 basic steps: 1. Desulphurization 2. Primary Reforming 3. Secondary Reforming 4. CO conversion 5. CO2 Absorption And Removal Of CO2 6. Methanation 7. Ammonia Synthesis 8.Refrigeration
1. DESULPHURISATION: Pretreatment of Natural gas feed stock for removal of sulphur, which is a poison for catalysts used in Ammonia plant. This is accomplished in de-sulphuriser. Sulphur compounds present in the natural gas feed are assumed of the reactive type, that is they can be all be removed by hot zinc oxide alone. Provision is made to install a bed of carbon molybadate catalyst in the desulphuriser reactor, should this ever be required to hydrogenate organic sulphur compounds that might be found in natural gas which might not be eliminated by zinc oxide alone. The preheated natural gas enters 102-D from the top and passed through a bed of zinc oxide. All sulphur in the natural gas is absorbed by zinc oxide. natural gas exiting the desulphuriser is expected to contain less than 0.25 ppm sulphur. Other materials detrimental to long zinc oxide are: (1) Gum forming substances such as dienes and oxides of nitrogen. (2) Amine solution (3) Admission of air. (4) Aromatic compounds such as benzene (5) Introduction of alkaline constituents which convert organic sulphur compounds to
unregenerated sulphate of elemental sulphur. The zinc oxide will absorb sulphur compounds with increasing ease in the following order: (1) Hydrogen sulphide (2) Carbonyl sulphide (3) Carbon disulphide. (4) Mercapton sulphur (5) Disulphides (6) Thiophenes
2. REFORMING: Reforming of the desulphurised Natural gas mixture of Hydrogen and Carbon Oxides and addition of air in-between two stages of reforming.
PRIMARY REFORMER: The primary reformer consists of 504 tubes suspended in 12 rows of 42 parallel tubes each, in the radiant section. Each row of tubes terminates in a manifold placed within the radiant section of furnace. There are twelve centrally located risers on each of these manifolds. These risers lea the gas flow to a water jacketed transfer line located over the top of primary reformer furnace. As the reforming reaction is endothermic heat is supplied externally to the tubes. The furnace operates with a down firing of natural gas between the rows of tubes to develop a process gas temperature of 818C at the catalyst tube outlet. There are 234 arch burners arranged in 13 rows of 18 burners each. Natural gas, purge and flash gases from ammonia synthesis loop and absorber K.O. drum are used as fuel for the reformer furnace. Inside the catalyst tunes the natural gas-Steam Reforming reaction takes place. the transferline directs the reformed gas into the secondary reformer at the following conditions: Pr. : 33.1 Kg/cm Temp. : 824C REFORMING REACTIONS: The following reactions take place producing a mixture of H2, CO, CO2, CH4 and excess H2O when hydrocarbons undergo steam reforming over nickel catalyst:
CnH2n + 2nH2O = nCO + (2n+1) H2 CH2 + H2O + heat=CO + 3H2 CO + H2O = CO2 + H2 + heat Carbon formation is a serious problem in catalyst tubes when higher hydrocarbons are used as a feed stock. Carbon deposition will hinder reforming and reduce heat transfer so that the tube wall temperature will rise in that zone producing hot bands and hot tubes. Carbon formation also causes disintegration of catalyst resulting in higher pressure drop in reformer tubes, loss of catalyst activity, low steam/ carbon ratio contribute to carbon formation. Precautions should be taken to prevent carbon formation on reforming catalyst for successful performance of reformer operations. SECONDARY REFORMING: Partially reformed gases from the water jacketed transfer line (107-D) are directed to refractory lined and water jacketed secondary reformer (103-D) tangentially. Once it enters the secondary reformer the flow is downward around a centrally located Air inlet pipe of an air burner and passes through a diffuser to enter a mixing zone where the gas and air are mixed before entering a catalyst bed of secondary reform. Preheated air steam mixture from the coil enters the secondary reformer vertically through the centrally located Air burner. Instantaneous mixing and rapid combustion of the air reformed gas take place at the burner tip as per the following equation at a temperature of 1238C. 2H2 + O2 +Air 3.8 N2 = 2H2O + 3.8N2 + heat CH4 + O2 + air3.8 N2 = CO2 + CO + H2O + N2 + heat After combustion the gas mixture flows through a bed of secondary reforming catalyst. The catalyst in the secondary reforming comprises of a layer of high temperature chromia at the op and nickel reforming catalyst at bottom. The shallow layer of chromia has a high fusion temperature and protects the lower layer of nickel catalyst against excessive temperature. A layer of alumina target bricks is laid over the chromia catalyst for protection of catalyst and also proper distribution of gas in the catalyst bed Methane reforming reaction in secondary reformer is as follows: 2CH4 + 3H2O + heat = CO + CO2 + 7H2 The reformed gas leaves the reactor at 996C.
3. CO SHIFT CONVERTER: Conversion of Carbon monoxide to Carbon dioxide. Shift conversion is actually a two-converter system, high and low temperature. The reformed gas flow enters the HT shift converter (104D1) at 371C temperature and about 31.3 Kg/cm pressure and flows through the catalyst bed. The catalyst here is iron chromia catalyst. The following reaction takes place: CO + H2O = CO2 + H2 + heat As indicated by this equation, we are converting most of carbon monoxide to carbon dioxide gaining an additional mole of hydrogen per 1 mole of carbon monoxide. Above reaction is reversible one, with shifting carbon monoxide favored by low temperature. However, the rate of reaction is favored by high temperature. The gas leaves the HT shift converter at 437C temperature and 31 Kg/cm pressure. In passing through the LTS section the 3.3% content of the gas is reduced to appr. 0.3%. the amount of CO converted to CO2 in LTS section is about 30% of that of HTS section the temperature rise will be small with an inlet of 3.3% CO it will be around 27C. The catalyst provided in the LTS section is Copper-zinc which is highly for sulphur and chloride poisoning and high temperature. Hence extreme care is to be exercised while operating with LTS.
4. CO2 ABSORPTION AND REMOVAL OF CARBON DIOXIDE: During the selection of Technology, Monoethanol amine (MEA) solution with sieve tray tower design were selected for CO2 removal section of ammonia plant at IFFCO Kalol. Please refer figure -1. Mononethanol amine solution is highly corrosive and problems of corrosion in CO2 removal section were experienced resulting in frequent shutdown, loss of production and higher energy consumption. To reduce the corrosion rate and for energy saving, UCAR Amine Guard -II system was installed in 1979. With the adoption of UAGII, system, it was possible to reduce the reboiler steam in the CO2 stripper reboiler by 25 t/hr. As a result of this change, frequent failures in the CO2 removal section was eliminated. Reduction in energy consumption was 0.13 Gcal/t of ammonia. This does not include the gain realized by uninterrupted running of the plant. Later while attempting to uprate the plant in 1994 from 910 tpd to 1100 tpd, CO2 removal section was also one of the bottlenecks, due to use of naphtha as part of feed stock. CO2 production was increased by 27 %. UCAR Amine guard II CO2 removal system was major limitation for plant capacity increase to 1100 tpd. Revamp of CO2 removal section was carried out for:-
Increasing CO2 removal capacity To reduce specific energy consumption To reduce corrosion rate To adopt environment friendly and biodegradable chemicals.
Various CO2 removal processes were studied to suit our requirement and it was found that a-MDEA process is the most suitable.
destruction of oxide film. 4. Utilisation of all the existing equipments i.e. not making any changes in the system. 5. Lower energy requirement. 6. Lower MDEA make up requirement. 7. MDEA (Methyl diethanol amine) is environment friendly and biodegradable chemical. 8. MEA solution is a corrosive solution, while MDEA is non-corrosive. Hence MDEA system does not require any corrosion inhibitor. 9. Additional refrigeration system was required for Selexol process.
5. METHANATION: -Final purification of the gas in a methanator to give a pure synthesis gas of H2:N2 in a volumetric ratio of 3:1. Methanation reactions are given below: CO + 3H2 = CH4 + H2O + HEAT CO2 + 4H2 = CH4 + 2H2O + HEAT Both these reactions are highly exothermic, and hence,extreme care is to be taken while operating methanator. The design temperature of the methanator (vessel) is 454C which provides a large
margin of safety in the event carbon oxides in feed gas to methanator are momentarily above normal conditions. The unit is properly protected with high temperature alarms and shut off systems. Methanator vessel, filled with a single bed of nickel catalyst operates at a temp of around 315C inlet. 6. AMMONIA SYNTHESIS: -Compression of pure syn. Gas and synthesis of H2 &N2 in Ammonia converter to form Ammonia. Synthesis gas from the 103-J second case discharge at a pressure of 210 Kg/cm and 119C flows through the shell side of syn. Gas compressor after cooler (156-C) it cools to 40C by cooling water. It is further cooled to 5.6C in tube side of make up gas chiller (140C) by means of refrigerant ammonia from 110-F. In the ammonia converter synthesis reaction takes place at a temperature of 480C. N2 + 3H2 = 2NH3 + HEAT There is also a purge gas system working where argon and methane are inerts. They tend to increase to high values as the process goes on. In order to limit their concentration in synthesis loop to 13.6 vol% a portion of the recycle gas is continuously purged. 7. PROCESS CONDENSATE POLISHING :- Process condensate from raw gas separator, synthesis gas compressor suction drum, and synthesis gas compressor 1st and 2nd stage separators is steam tripped in process condensate stripper to remove bulk of ammonia carbon dioxide and methanol. Stripped gasses along with the steam are vented to atmosphere through primary reformer stack. Condensate collected from bottom of the stripper is polished in mixed bed polisher and is used as make up BFW. Mixed bed polisher contains 1.67 m3 of cation resins and 3.12 m3 of anion resin. Sulfuric acid and caustic soda are used to regenerate this bed once a day. Approximately 45m3 of liquid effluent is generated per regeneration and is sent to DM plant neutralization pit. 8. REFRIGERATION: Separation and purification of Ammonia to get the final Ammonia product. The primary purpose of this system is to condense product ammonia for separating it from the converter feed. Further it is applied (a) to cool make up gas for separation at water (at the interstage of compression), to condense and recover liquid ammonia from purge gas and flash gases, and to cool the product run down to -33C and degassing inerts.