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KRIBHCO SHYAM FERTILIZERS LIMITED, PIPROLA

Krishak Bharati Cooperative Limited (KRIBHCO) is an Indian cooperative society, which manufactures fertilizer, mainly urea. It registered under the Multi-State Cooperative Societies Act in 1985, and was promoted by the Government of India, and some agricultural co-operative societies spread all over the country. Its main plant is located in Surat, Gujarat. Oil & gas findings in Bombay High and South Basin triggered the birth of eight new generation fertilizer plants to fulfill the ever-growing food needs of the country. KRIBHCO was among the first two projects in the first phase. KRIBHCO Shyam Fertilizers Limited manufactures nitrogenous fertilizer viz. urea through our integrated urea and ammonia manufacturing facility at Shahjahanpur in the state of Uttar Pradesh in India. The Fertilizer Plant is the latest Greenfield Urea Plant in Indiacommissioned in November 1995. The Fertilizer Plant is strategically located in North India, right in the middle of a high urea consumption belt and based on Natural Gas as feedstock supplied through the Hazira-Vijaypur-Jagdishpur ("HVJ") gas pipeline. The Fertilizer Plant is located at Village Piprola, on State Highway No. 29 and is about 12 km from the District Headquarters of Shahjahanpur. It has an installed capacity of 864,600 MTPA of urea and 501,600 MTPA of ammonia. We have been operating our Fertilizer Plant at more than 100% capacity utilisation since acquisition. The plant is ISO 9001:2000 and ISO 14001:1996 certified by KPMG Quality Registrar (a business unit of KPMG). The marketing of Urea and surplus ammonia produced by the Company is undertaken by KRIBHCO, one of the promoters Company. The urea is sold under the brand , under a marketing arrangement with KRIBHCO. Kribhco Shyam fertilizers Limited [KSFL] is a joint venture of KRIBHCO and Shyam Fertilizers. Krishak Bharati Co-Operative ltd. (KRIBHCO) holds 85 % stake in the Joint venture and the remaining 15 % lies with the Shyam Fertilizers. KRIBHCO is one of the leading producers of Fertilizer in India. It has established a world class hi-tech plant at Hazira, Gujarat, which has a double unit for urea production. It also has a 25 % stake in the Oman Fertilizer, Oman, United Arab Emirates (UAE). The plant has urea and ammonia manufacturing facility at Shahjahanpur in the state of Uttar Pradesh in India. The fertilizer plant is the latest Greenfield urea plant in Indiacommissioned in November 1995. The fertilizer plant is strategically located in north India, right in the middle of a high urea consumption belt and based on natural gas as feedstock supplied through the Hazira-Vijaypur-Jagdishpur (HVJ) gas pipeline. The fertilizer plant is located at village Piprola, on state highway no. 29 and is about 12 km from the district headquarters of Shahjahanpur. It has an installed capacity of 864,600 MTPA of Urea and 501,600 MTPA of ammonia. They have been operating their fertilizer plant at more than 100% capacity utilisation since acquisition. The plant is ISO 9001:2000 and ISO 14001:1996 certified by KPMG Quality registrar (A business unit of KPMG). The marketing of urea and surplus ammonia is undertaken by KRIBHCO.

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BRIEF DESCRIPTION OF THE PROCESS

Installed Capacity Process Licensor Process Technology Raw Material 1350 MTPD Haldor Topsoe, Denmark NG-Steam Reforming Feed NG Fuel - NG/Naphtha

Ammonia is manufactured from the famous Habers process. The consultants for the process are The HALDOR TOPSOE A/S, Denmark. The ammonia plant here at Piprola, utilises conventional natural gas steam reformation process of Haldor Topse. The major process steps are hydro desulphurization of natural gas, primary and secondary reforming, high and low temperature shift conversion, CO2 removal by Giammarco Vetrocoke process, methanation, synthesis gas compression followed by ammonia synthesis and separation. The synthesis loop operates at 140 ata and has a purge gas recovery unit (PGRU) built in at the grass root stage itself. The Giammarco Vetrocoke process employs dual (glycine and diethanol amine) activated potassium carbonate solution and there are two regeneration towers to make it a low energy process. The Natural Gas containing hydrocarbons is reacted with steam to produce carbon dioxide, carbon monoxide and hydrogen. Air is injected in to the system to provide source of nitrogen for Ammonia synthesis. The carbon monoxide produced by reaction of hydrocarbons with steam is converted to carbon dioxide, which is removed and recovered by absorption in potassium carbonate solution. The Ammonia is produced by reaction of hydrogen and nitrogen. To achieve zero effluent from the plant, the following inbuilt facilities have been provided: 1) Process condensate stripper to strip off dissolved gases from process condensate with steam. After stripping the condensate is sent to DM plant for further treatment to convert it to the Demineralized Water. 2) Turbine condensate is sent to DM plant for polishing and used as boiler feed water. 3) Boiler blow down is used as cooling tower make up.

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UNIT I

GENERAL CONSIDERATIONS

Properties of Ammonia: IUPAC name - Azane Other names - Hydrogen Nitride, Trihydrogen Nitride, Nitro-Sil
Molecular formula Molar mass Appearance Density NH3 17.031 g/mol Colourless gas with strong pungent odour 0.86 kg/m3 (1.013 bar at boiling point) 0.73 kg/m3 (1.013 bar at 15 C) 681.9 kg/m3 at 33.3 C (liquid) 817 kg/m3 at -80 C (transparent solid) 77.73 C, 195 K, -108 F 33.34 C, 240 K, -28 F 47%(0C) 31%(25C) 28% (50 C) 9.3 (water), 10.5 (DMSO) 4.75 Trigonal Pyramid

Melting point Boiling point Solubility in water

Acidity (pKa) Basicity (pKb) Molecular shape

Climatic & Seismic Conditions at the Site:The plant site has semitropical monsoon climate characterised by a rainy season from June to September and a virtually rainless season from November through April. The air temperature varies throughout the day and the year and the extremes of heat and cold are met. The plant site experiences occasional earthquakes.

1) Atmospheric PressureMaximum, mbar Minimum, mbar : : 998.1 973.3

2) Air TemperatureSummer (Max), C Winter (Min), C : 46 : -1.5

3) RainfallAnnual Rainfall, mm : 1400 58

Max. Rainfall in one hour, mm : Avg. Rainfall recorded in the Month of July, mm : 349

4) Wind-

P age |4 Max. Wind velocity, km/hr. : 162

Project Design Basis:1) Project at a Glance:i) General- Shahjahanpur has been selected as one of the six sites in inland locations where Natural gas
based fertilizer projects are to be established. The HBJ Pipeline System to transport offshore Natural Gas to these projects has been established and is feeding gas to the three fertilizer plants already in operation- Vijaypur, Aonla and Jagdishpur.

ii) Project LocationVillage District Longitude Latitude Elevation : : : : : Piprola Shahjahanpur (Uttar Pradesh) 79 50 E 27 50 N 150 m above MSL

iii) Capacity Of Plants/FacilitiesAmmonia : 1 x 1350 MTPD (First Production in 1995) 1 x 1530 MTPD (Reassessed) 1 x 1800 MTPD (Present Production) 1 x 2012 MTPD (Future Goal after revamp) Steam Generation : 100 (2 + 2) T/h

Captive Power (GTG) : 20 MW (1 + 1) DMW Plant Cooling Water Ammonia Storage DM Water Storage : : : : 450 cum./h 39,000 cum./h 1 x 5000 T/day 2 x 1500 cum./h

2) Climatic Conditions: - For the purpose of design, the following values shall apply:
-Atmospheric Pressure 939 mbar

-Rainfall
Heaviest in an hour Design (max. rate) 58 mm 60 mm

-Wind Speed: For design against wind forces, wind load shall be increased by 30% to cater for the effect on piping systems, platforms, ladders, etc.

P age |5 -Ambience: Due to the location within an industrial complex, air may contain particles of sand and urea. The air may accidentally contain ammonia vapour and for this reason, no part in direct contact with the atmosphere must be constructed from copper or copper alloys. -Ambient Temperature: Heating and Ventilation, Winter Summer Cooling Towers, Wet bulb Dry bulb Air Coolers : : : : 29C 36C 40C : min., -1.5C max., 46C

Process Air Compressor & Air Blower :35C

3) Seismic Conditions: - The design is executed in accordance with the guidelines given below: a) For non critical items, the seismic coefficient method under clause 3.4.2.3 of IS 1893 should be
adopted. The actual site at Shahjahanpur is defined as being situated in Zone Four (IV).

b) For critical items like towers, reactors, columns and critical structures i) When specified a detailed dynamic analysis of any particular structure or equipment shall be carried
out.

ii) For typical rotating machinery such as high speed compressors and pumps the foundation-structureequipment system shall be checked for overall stability under maximum credible earthquake conditions.

iii) IS 1893-1975 should not be referred to for determining seismic forces in the above cases. 4) Process Feedstock: - Range of feedstock gas compositions:
1 2 Gas no. Methane 69.24 81.90 Ethane 13.05 15.44 Propane 09.27 00.74 i-Butane 01.66 00.24 n-Butane 02.35 -i-Pentane 00.59 -n-Pentane 00.67 -Hexane --CO2 01.75 -Nitrogen 01.39 01.64 Sulphur as H2S- normal: 10 ppm vol. Pressure at battery limit: 39 kg/cm2g 3 4 94.27 78.84 02.67 07.23 00.86 04.59 00.27 00.88 -01.10 -00.26 -00.24 -00.26 -06.49 01.89 00.01 max: 50 ppm vol. Temperature: 30C 5 83.29 07.69 02.10 -----06.90 00.01 6 98.39 01.40 00.10 ------00.01

5) Utilities: Steam- Steam will be distributed at the following levels:

Normal Mechanical Design

High Pressure Steam (SH)

P age |6 Pressure, kg/cm2g Temperature, C 105 510 130 525

Medium Pressure Steam (SM)

Pressure, kg/cm2g Temperature, C 37 381 44 425

Low Pressure Steam (SL)

Pressure, kg/cm2g Temperature, C 03.50 150/225 06.00 350

Cooling Water- Recirculating cooling water is provided at the following conditions:

Pressure, kg/cm2g Temperature, C Normal range (T) in cooler, C03.50 33.50 10 07.00 70

Max. Allowable P in coolers, kg/cm2g-00.70 Fouling Factor, m2hC/Kcal0.0006

Inert Gas- Nitrogen will be supplied from two sources: i) Nitrogen for purging will be supplied from liquid nitrogen storage. The nitrogen is purchased from outside. ii) Nitrogen for sealing purpose will be supplied from a PSA unit. Instrument AirPressure, kg/cm2g Temperature, C Quality according to ANSI / ISA-S7.3 Minimum pressure for line sizing: 5 kg/cm2g 07.00 ambient 70 10

5) Noise- The noise level should not exceed 90dBA measured 1m from equipment during normal operation.

Production & Consumption Figures: Lean Gas, Design CaseNG for feed and fuel, Nm3/h LHV, Kcal/Nm3 Make-up Water for cooling water, m3/h Make-up DMW, m3/h 8,653 350 173 55,729

P age |7 Electricity, KWh/h 4,100

ProductionAmmonia (as 100% NH3, 3 kg/cm2g, -32.4C), kg/h Carbon-di-oxide (as 100% CO2), Nm3/h HP Steam Export, kg/h MP Steam Export, kg/h Preheat of DMW (export), Gcal/h 62,513 39,667 8,435 18,000 12.214

Lean Gas, Normal CaseNG for feed and fuel, Nm3/h LHV, Kcal/Nm3 Make-up Water for cooling water, m3/h Make-up DMW, m3/h Electricity, KWh/h 50,655 8,653 350 165 4,100

ProductionAmmonia (as 100% NH3, 3 kg/cm2g, -32.4C), kg/h Carbon-di-oxide (as 100% CO2), Nm3/h HP Steam Export, kg/h MP Steam Export, kg/h Preheat of DMW (export), Gcal/h 56,415 37,017 9,743 18,000 9.887

Rich Gas, Normal CaseNG for feed and fuel, Nm3/h LHV, Kcal/Nm3 Make-up Water for cooling water, m3/h Make-up DMW, m3/h Electricity, KWh/h 45,269 9,688 350 176 4,100

ProductionAmmonia (as 100% NH3, 3 kg/cm2g, -32.4C), kg/h Carbon-di-oxide (as 100% CO2), Nm3/h HP Steam Export, kg/h MP Steam Export, kg/h Preheat of DMW (export), Gcal/h 39,407 10,568 18,000 9.971 56,414

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UNIT II

DESCRIPTION OF UNITS

A) Desulphurization Section: This section consists of three vessels, one containing the hydrogenation catalyst and the two vessels containing Hydrogen Sulphide (H2S) absorption mass. Over the hydrogenation catalyst, the sulphur containing compounds are converted into H 2S in the presence of H2 and at a temperature of about 390C. Hydrogen Sulphide is absorbed by Zinc Oxide (ZnO) in the absorption vessels. Sulphur content is reduced to below 0.05 ppm. The design of this section is based on the following properties of natural gas- CO2, max. 6.90 mole % and H2S, normal 10 ppm vol./max. 50 ppm vol.

1) Hydrogenation: Natural gas with recycle gas is preheated to 390-400C in the waste heat section of the primary reformer before entering the hydrogenation vessel. Hydrogenation catalyst is the Topse TK-251 (Ni-Mo).

RSH + H2

RH + H2S

(R is a radical of hydrocarbon)

The most advantageous operating temperature is approx. 390C. At lower temperature, the
hydrogenation will not be completed. During normal operation with a sulphur containing gas, the catalyst will be sulphided and contain up to an order of magnitude of 6 wt % sulphur. The sulphur in the catalyst will be in equilibrium with the gas and if the sulphur content of the gas decreases, sulphur will be released from the catalyst. If the catalyst is exposed to more than a few percentage of CO2 in the unsulphided state, Methanation of CO2 will take place. For this reason, the catalyst shall be sulphided.

2) Absorption: After the hydrogenation, the process gas passes through the absorption vessels, where the H 2S is absorbed on ZnO. The absorption mass is the Topse HTZ-3 in the form of cylindrical extrudates, 4 mm by 4 to 8 mm long. The H2S absorption takes place in two vessels operating in series. Normally, only the first vessel will be working, the second acting as guard. When the ZnO in the first vessel has been spent, the operation will continue with the second vessel in service. Downstream of the last vessel, the sulphur content is normally below 0.05 ppm and shall at no time exceed 0.10 ppm by weight. The normal operating temperature will be 300C to 400C, but also at low temperatures, the catalyst will react with H2S according to the following reaction:

ZnO + H2S

ZnS + H2O

At normal operating temperatures, the catalyst will also react with carbonyl sulphides, according to the following reaction:

ZnO + COS

ZnS + CO2

P age |9 To some extent, it will also remove organic sulphur compounds however, these should normally be prehydrogenated. During normal operation, the sulphur content in the feedstock is reduced by contact with zinc oxide catalyst. Fresh catalyst or sulphided zinc oxide reacts neither with hydrogen nor with oxygen at any practicable temperature. Spent zinc oxide is not pyrophoric and needs no special care during unloading. Steaming operations should not be carried out on systems containing zinc oxide. The fresh zinc oxide will hydrate, if exposed to condensing steam and on used zinc oxide the absorbed sulphur will be stripped off at higher temperatures (150-200C).

B) Reforming Section: In the reforming section, a gas containing the necessary compounds for preparation of the ammonia synthesis gas is produced by Catalytic Reforming of a mixture of hydrocarbon and steam and addition of air. The steam reforming of hydrocarbons can be described by the following reactions:

CnH2n+2 + 2H2O CH4 + 2H2O CO2 + H2

Cn-1H2n + CO2 + 3H2 - Heat CO2 + 4H2 - Heat CO + H2O - Heat

(1) (2) (3)

Reaction (1) describes a mechanism of reforming the higher hydrocarbons in steps, into lower and lower hydrocarbons finally resulting in Methane (CH4), which is reformed according to (2). The reaction starts at about 500C. Reaction (3) requires a small amount of heat only, whereas the heat required for (1) and (2) will quite dominate the picture. The reactions take place in two steps in the two reformers, the primary reformer, H-1201 and the secondary reformer, R-1203. The necessary heat of reaction in the two reactors is supplied in quite different ways. In the primary reformer, heat is supplied indirectly by firing. In the secondary reformer, heat is supplied as reaction heat by mixing air into the gas. The burning gas provides heat for the rest of reforming. The reforming taking place in the primary reformer is adjusted in such a way that the air supplying the reaction heat in the secondary reformer will give the required H2/N2 ratio of 3 to 1. It is desirable to reduce the methane content of the raw synthesis gas to as low a level as possible to keep the level of inert gases low. The methane content of raw gas is governed by the equilibrium of the reforming reaction (2) and by the approach to this equilibrium obtained in practice. The equilibrium for the reaction (2) is so, that higher temperature, more steam and lower pressure results in lower methane content. On the other hand, by raising the reformer pressure, considerable saving in the power consumption for synthesis gas compressor can be obtained and the equipment can be made smaller. An operating pressure of 30 to 35 kg/cm2g for the reforming section has been found to give a reasonable economic compromise. In order to compensate for the unfavourable equilibrium conditions thereby encountered the relatively high steam to carbon ratio of 3.3 has been chosen. As already mentioned, the heat of reaction is provided in two ways. In the first step, the hydrocarbon/steam mixture preheated to approx. 500C passes downwards through vertical tubes filled with catalyst. The tubes are placed inside a fired heater, the primary reformer, H-1201, where sensible heat and heat of reaction are transferred by radiation from a number of wall burners to the tubes. In order to ensure a complete combustion of the fuel gas, the burners must be operated with an excess of air. A reducing atmosphere should always be avoided, as it may be harmful to the catalyst tube material. 5 % of excess air corresponding to about 0.90 % of oxygen in the flue gas will be suitable. The gas leaving the reformer tubes will be at a temperature of about 800C and the hydrocarbon content, which already here is CH4 only, will be about 11 mole % (dry basis). In the second step, air is mixed into the partly reformed gas and reacts in the upper empty space of the secondary reformer, R-1203. The reaction here is mainly a combustion resulting in temperature rise. From the empty space, the gas passes

P a g e | 10 the catalyst bed in the lower part of the reformer where the reforming reaction is completed with simultaneous cooling of gas. The outlet temperature will be about 990C and the methane concentration 0.30 mole % (dry basis). The outlet gas from the reforming section contains approx. 13 mole % CO and 7.30 mole % Co 2 in the dry gas. In the operation of the primary reformer, carbon may be formed partly outside the catalyst, partly inside the catalyst. Carbon deposits outside the catalyst particles will increase the pressure drop over the catalyst bed and deposits inside the particles will reduce their activity and their mechanical strength. If the catalyst is insufficiently reduced or if it is partly oxidised during the production upsets without subsequent reduction, carbon formation may also take place.

1) Primary Reformer: The primary reformer has a total of 288 reformer tubes installed in two radiant chambers. The reformer is loaded with 11.20 m3 of R-67R-7H catalyst in the form of rings, 16 mm by 11 mm high with 7 axial holes, impregnated with nickel. As already mentioned, all sulphur compounds are very strong poisons to the reforming and LT shift catalysts and maximum 0.10 ppm by weight based on the hydrocarbon flow being acceptable. Sulphur poisoning will result in a reduction of the activity and in severe cases in the

formation of carbon. A serious sulphur poisoning possibly accompanied by carbon formation will require a special regeneration procedure.

2) Secondary Reformer: -

P a g e | 11 In the secondary reformer, 39.0 m3 of Topse RKS-2-7H catalyst in the form of ceramic rings, 20 mm by 18 mm high, is loaded. In the secondary reformer, the partial combustion of process gas will give high temperature at the top of the catalyst bed. The reforming reactions of methane will lower the temperature during passage of the gas mixture through the catalyst bed and at the exit of the reformer the temperature will be about 990C. The reaction mixture will contact the catalyst at about 1100C to 1200C.

C) Gas Purification Section: The gas leaving the reforming section may have the following composition expressed in percent by volume (dry basis): H2 CO CO2 N2 Ar CH4 56.58 12.95 07.35 22.55 00.27 00.30

Furthermore, the gas contains so much water vapour that the steam to dry gas ratio is about 0.53. Of the above compounds, Ar has not yet been mentioned. Ar is an inert gas introduced with the process air which always contains 0.94 % Ar. The purpose of the gas purification section is to prepare a synthesis gas containing H 2 and N2 in the ratio of 3 to 1 and besides this only containing inert gases such as CH4 and Ar in as low a concentration as possible. Carbon monoxide is converted in the two shift converters, R-1204 and R-1205, according to the following reaction:

CO + H2O

CO2 + H2 + Heat

The reacted gas will contain only about 0.36 mole % CO (dry basis). The reacted part of the CO increases the H2 yield with simultaneous formation of CO2 which is more easily removable. After cooling the gas and condensation of most of the water content, the CO2 is removed in the CO2 removal unit leaving less than 0.10 mole % CO2 in the gas. Even the small amounts of CO and CO2 left are severe poisons to the ammonia synthesis catalyst and should therefore be removed down to a concentration of a few ppm. This is done in the Methanator, R-1311, where the reverse of the reforming reaction will take place:

CO + 3H2 CO2 + 4H2

CH4 +

H 2O + Heat

CH4 + 2H2O + Heat

Thus resulting in formation of methane at the expense of hydrogen. In the ammonia synthesis loop, the inerts will be built up to a level depending on how much gas is purged from the loop. In order to obtain a high production of ammonia, the inert level should be kept low and the purge is therefore increased for high inert content in the feed gas.

1) Shift Conversion: The shift reaction taking place in the converters, R-1204 and R-1205

CO + H2O

CO2 + H2 + Heat

will proceed only in contact with a catalyst. The equilibrium is favoured by low temperature and more water, while the reaction rate will be higher at higher temperature. More water may give an apparently

P a g e | 12 lower reaction rate due to the larger total volume resulting in a shorter contact time. This means, for each catalyst, there will be an optimum temperature, depending on the activity and the quantity, which will give optimum conversion. As the reaction results in temperature rise, the outlet gas will be at an unfavourable equilibrium if removal of heat has not taken place before the conversion is finished. Thus the conversion is performed in two steps. The first step takes place in the HT shift converter, R1204, where a copper promoted iron/chroma based catalyst is installed. The main part of the reaction takes place here, causing a temperature rise of 64C. The outlet temperature is approx. 444C (EOR), which is fully acceptable for the HTS catalyst being more rugged than the LTS catalyst used in the second step of the shift conversion. The LT shift catalyst consists of specially prepared copper, zinc and aluminium oxides having a much higher activity, which means that it can be used at the lower temperature of 200C to 240C. The catalyst is less rugged and loses its activity if the temperatures are higher than 270C. Here the CO content is further reduced to 0.36 mole % (dry basis).

i) HT Shift Converter: The HT shift converter, R-1204, contains 92 m3 of the Topse SK-201 in two beds. SK-201 is a promoted iron oxide catalyst and in the fresh catalyst, the iron oxide is at its highest oxidised level and is thus, not affected by air, steam, CO2 or inerts at elevated temperature. As recrystallization may occur, however, the catalyst should not be heated beyond 400C. Methane is not considered an inert to the catalyst, although methane is not supposed to react below 300C. It will act as a reducing agent and once the reduction has started, the catalyst will probably be spoilt by carbon deposits. Nor must the unreduced catalyst be exposed to dry reducing agents such as H2 and CO unless absolutely cold. At the start up of the plant, the catalyst must be activated, which is mainly a reduction of Fe2O3 to Fe3O4. The reduction will take place at a temperature above 250C but the temperature should not be allowed to exceed 400C during the reduction, in order not to decrease the activity of the catalyst. When new, the catalyst can operate at a gas inlet temperature of 350C. Afterwards, the optimum inlet temperature will be higher, but as long as the outlet temperature has not reached 470C, the activity will decrease only slowly. The cold catalyst can be heated by steam alone, both when oxidised and reduced. Drops of liquid water on hot catalyst may result in disintegration of the catalyst.

ii) LT Shift Converter: The LT shift converter, R-1205, contains 115.9 m3 of Topse LK-821 catalyst consisting of oxides of copper, zinc and aluminium in two beds. On top of the LK-821, 6.10 m3 of Topse LSK is placed as a chlorine guard. The LSK catalyst will also protect the catalyst bed against droplets of condensing steam. As the catalyst is extremely sensitive to chlorine, which may be liberated from the HT shift catalyst, but to a certain extent also from the refractory in the secondary reformer during the first period of operation, the LT shift converter is bypassed during this stage until the gas is practically free of chlorine as well as sulphur. The chlorine will normally be present in process steam, quench water and process air in very small amounts. Besides chlorides, sulphur and gaseous Si-compounds are poisons. When the catalyst is in a reduced stage, temperatures above 250C must normally be avoided unless the catalyst is old. The normal operating temperature is between 200C and 240C. A short exposure to 300C will have no adverse effect on the catalyst.

2) Carbon Di Oxide Removal: CO2 is removed by absorption in hot aqueous solution containing approx. 27-29 wt % potash, 1 wt% Glycine, 1 wt% Diethylamide and 0.50 wt% Vanadium Pent oxide. The solution is known as Giammarco

P a g e | 13 Vetrocoke. The potash is partially converted into potassium bicarbonate. The solution contains Glycine as activator and Vanadium Oxide as corrosion inhibitor. The reason for keeping the solution hot is to increase the rate of absorption and keep the bicarbonate in the solution. Another advantage is that the temperature is approx. the same in the absorber and in the regenerator, i.e. the boiling temperature of the solution at the pressure prevailing in each of the two regenerators. Thus, it is not necessary to supply

site view

HP Regenerator

LP Regenerator

CO2 Absorber

The gas is passed to the CO2 absorber, F-1303. In the absorber, the gas flows upwards against a descending stream of GV solution. Approx. 16 % of the solution is introduced above the top bed at 65C, whereas the remainder is introduced at about 106C below the top beds. The CO2 absorption occurs according the following reaction mechanism:

CO2 + H2O CO3- - + H2O CO3- - + CO2 + H2O

HCO3- + H+ HCO3- + OH2HCO3-

(1) (2) (3)

The reaction rate of (3) is determined by (1), which is the slowest step. The presence of the activator is the cause of the quick transfer of gaseous CO2 into the liquid phase by means of the Glycine carbonate formation according to the reaction:

H2NCH2COO-

CO2

OOCNHCH2COO- + H +

(4)

The activator effect is much higher than the one relating to the carbonate concentration. At high temperature and in presence of OH-, the carbonate is hydrolysed and the activator is restored. The gaseous CO2 transferred into the liquid is ponderably absorbed by the potassium carbonate. The absorption is carried out in two stages: In the first stage, where the bulk of CO2 is absorbed, the high temperature increases the reaction rate and the solution used for absorption on this stage is partly regenerated. In the second stage, a stream of strongly regenerated solution is utilised. At the lower

P a g e | 14 temperature, the CO2 vapour pressure of the solution is further reduced to meet the low CO2 slippage in the purified gas (about 0.10 mole %, dry basis). The rich solution leaving the absorbed bottom is expanded through the expansion turbine connected to the semi lean solution pump and it feeds the top of the first regenerator, F-1301, operating at 1 kg/cm2g. On account of depressurization, a part of the CO2 is flashed off. A stream of the rich solution extracted from the top of F-1301 is further depressurized and enters the top of the second regenerator, F-1302, operating slightly above atmospheric pressure. The remainder of the rich solution flows down through F1301 in counter current with steam and the remaining CO2 is removed by stripping. A semi lean solution is extracted from the intermediary tray of F-1301 at 124C and flashed across the level control valves and enters F-1302. The solution is collected on a take-off tray and feeds the semi lean solution pump. Lean solution transferred from F-1301 bottom at 127C is flashed across a set of level control valves and enters F-1302 bottom just below the semi lean solution take-off tray. The solution is collected in F-1302 bottom to feed the lean solution pump. Steam developed by flashing from lean and semi lean solutions (which is practically pure steam) is used as stripping steam to regenerate the rich solution fed to the top of F-1302. According to this technology, more than half of the stripping steam supplied to F-1301, is recovered as flashing steam and works in double effect in F-1302. The overhead condensate necessary for keeping the water balance in the CO2 removal unit is introduced at the suction of the lean solution pump. The CO2/steam mixture leaving the top of F-1301 is partly condensed in the DMW preheater, E-1313. The condensate is separated in B-1304 and sent to B-1305, 1st OH condensate separator for F-1302. The CO2/steam mixture from F-1301 is finally cooled to 40C in E1305 and the condensate is separated in B-1303. The CO2/steam mixture leaving the top of F-1302 is partly condensed in the DMW preheater, E-1308. The condensate is separated in B-1305 and is partly recycled to the CO2 removal unit. The CO2/steam mixture from F-1302 is finally cooled to 40C in E-1304 and the condensate is separated in B-1307. The condensate from B-1307 is sent to the process condensate recovery section for further treatment. The CO2 stream leaving B-1307 is compressed to about 1 kg/cm2g by the CO2 booster and subsequently mixed with CO2 from B-1304. After final cooling in E-1305 and separation of condensate in B-1303, the CO2 is sent to the urea plant.

3) Methanation: After the CO2 removal unit, remaining traces of CO and CO2 must be removed, since these compounds are poisonous to the ammonia synthesis catalyst. This is done in the Methanator, R-1311 and the reactions involved are the reverse of the reforming reactions:

CO + 3H2 CO2 + 4H2

CH4 +

H 2O +

Heat Heat

CH4 + 2H2O +

Determining parameters for the methanation reaction are- besides the activity of the catalyst- the temperature, the pressure and the steam content of the process gas. Low temperature, high pressure and low steam content tend to favour the methane formation. However, within the allowable temperature ranges, the equilibrium conditions are so favorable that practically the catalyst activity determines the efficiency of Methanation. The higher the temperature, the better the efficiency, but at the same time it means a shorter lifetime for the catalyst. Furthermore, in case of a possible breakthrough of CO2 (or CO) to the Methanator, which would result in a high temperature rise, a low inlet temperature is to be preferred as this limits the temperature rise somewhat in connection with the lower activity. After the Methanator, the gas normally contains less than 10 ppm CO + CO2. The temperature rise will normally be about 25C.

P a g e | 15 The Methanator, R-1311, is provided with two catalyst beds, each 2650 m high containing a total of 60 m3 catalyst. Initially only the upper bed will be loaded with 30 m3 catalyst. The catalyst foreseen is the PK-5. This catalyst has approx. the same characteristics as the reforming catalysts, being a nickel catalyst on a ceramic base. As the reactions take place at much lower temperatures than those prevailing in the reformers, the catalyst must be very active at lower temperatures whereas the performance of the catalyst at higher temperatures is of minor interest. The catalyst is very sensitive to sulphur, arsenic and chlorine compounds. Steam without hydrogen would oxidise the catalyst and should therefore, not be used for heating, cooling or purging. Furthermore, it should not be exposed to condensing steam as the catalyst will disintegrate. The catalyst is activated simply by heating it up with the gas, it normally treats. The content of CO and CO2 in the gas used for activation should be as low as possible, preferably below 2 mole % CO + CO 2 to minimise the temperature rise. The adiabatic temperature rise is about 75C per mole % CO and 60C per mole % CO2. The methanation reaction starts at about 240C, but in order to ensure a sufficiently low content of CO and CO2 in the effluent gas, the operating temperature would be from 280C to 350C, depending on the catalyst activity and the gas composition. The methanation catalyst should not be exposed to catalyst temperatures above 420C for long period of time.

D) Ammonia Synthesis Section: 1) Chemistry Involved: The ammonia synthesis takes place in the S-200 radial flow converter, R-1501, according to the following reaction:

3H2 +

N2

2NH3 + Heat

The reaction is an equilibrium reaction and therefore, only part of H 2 and N2 can be converted into NH3 by passing through the catalyst bed. The composition of the gas at chemical equilibrium is influenced by pressure and temperature. High pressure and low temperature tend to favour the ammonia formation. However, the reaction velocity is very much enhanced by high temperature operation. There is an optimum level for catalyst temperature at which the maximum production is obtained. At higher temperatures, the equilibrium percentage (which is the theoretical highest obtainable percentage of NH3) will be too low, while at lower temperature, the reaction temperature will be too slow. The synthesis unit is designed for a maximum pressure of 245 kg/cm 2g and the normal operating pressure is about 220 kg/cm2g. The normal operating temperature in the two catalyst beds is within the range from 370C to 520C. A considerable amount of heat is liberated by the reaction (about 750 Kcal/kg produced NH 3) and the major part of the heat is utilised for production of HP steam and preheat of HP boiler feed water. According to the fact that the reaction is an equilibrium reaction, only a partial conversion can be obtained and it is necessary to recycle the unconverted synthesis gas to the converter. Approx. 30 % of the H2 and N2 contained in the synthesis gas at converter inlet are converted into ammonia per pass. In addition to the converter, the synthesis loop includes a recirculating compressor (integrated with the synthesis gas compressor) as well as equipment for steam production, BFW preheat, for cooling of the synthesis gas and condensation as well as separation of ammonia. The converter effluent gas is cooled in a number of steps; Ist in the waste heat boiler from the converter exit temperature of about 455C to 350C then in the boiler feed water preheater to 274C followed by hot heat exchanger and the two chillers to 12C. The condensed ammonia is separated from the circulating synthesis gas in a separator. Make-up gas is introduced between the two chillers.

P a g e | 16

The converter R-1501 is a radial flow type converter with the gas flowing through the two catalyst beds in radial direction. The converter contains a total of 104.50 m3 catalyst, Topse type KMR. As already mentioned, the converter has two catalyst beds. The first bed has a catalyst volume of 27.75 m3 and the second bed contains 76.74 m3 catalysts. The nominal diameter of the catalyst granules in both beds are 1.50 mm to 3.00 mm. The catalytic bed activity of the small particles is very high and the special advantage of the radial converter is to allow the use of the small particles without a prohibitive pressure drop. The catalyst is loaded with prereduced catalyst, type KMR, in both beds. This is a normal ammonia catalyst (KM) reduced and stabilised by a superficial oxidation during manufacture (O2 content about 2 % of catalyst weight). The catalyst is stable in air below 100C. Above 100C, it will react with air and spontaneously heat up. The catalyst is activated by reducing the iron oxide surface layer to free iron. This reduction is normally carried out with circulating synthesis gas. Although, the KMR catalyst can be used at temperatures up to about 530C to 550C, it should be noted that the lower the catalyst temperatures are in operation, the slower the decrease in catalyst activity and accordingly the catalyst lifetime will be prolonged. The temperature out of the first catalyst bed should be about 510C and should not exceed 530C. Compounds containing oxygen such as water, carbon monoxide and carbon-di-oxide are all poisons to the catalyst and small amounts of these catalyst poisons causes a considerable decrease in catalyst activity. When entering the synthesis loop, the make-up gas is saturated with water vapours and contains maximum 10 ppm of CO + CO2.

2) Process Conditions: (i) Gas Composition- During normal operation, the composition of the make-up gas and the circulating
synthesis gas at converter inlet is as follows: Gas Make-up Circulating Synthesis Gas

P a g e | 17 (Mole %) Hydrogen (H2) Nitrogen (N2) Argon (Ar) Methane (CH4) Ammonia (NH3) 74.09 24.73 00.30 00.88 -(Mole %) 64.23 21.41 02.36 06.39 05.61

The gas composition may be characterised by: - The content of Ammonia. - The content of inert gases (Ar and CH4). - The H2 to N2 ratio. - The purity.

(ii) Ammonia Concentration at Converter Inlet- The ammonia content in the synthesis gas at
converter inlet is of importance for the conversion obtained in the converter. A low NH3 concentration at converter inlet gives a high reaction rate and thus high production rate. The ammonia concentration at converter inlet is depending on the cooling level in the refrigeration chillers and the operating pressure. 5.6 % NH3 at converter inlet corresponds to 12C at a pressure of 209 kg/cm2g in the NH3 separator.

(iii) Inert Gases- The make-up gas contains small amounts of Ar and CH4. These gases are inert in the
sense that they pass through the synthesis converter without undergoing any chemical changes. The gases will accumulate in the synthesis loop and a high inert level, i.e. high concentration of inert gases will build up in the circulating synthesis gas. The inert level will increase until the constant addition of inert gases with the make-up is counter balanced by a constant removal of same quantity of inert gases from the loop. Part of the inerts will be dissolved in the liquid product which is separated from the synthesis gas in the ammonia separator. The quantity of inert gases leaving the loop this way is proportional to the inert concentration as well as to the operating pressure. This quantity is not sufficient to remove all the inert gases introduced with the make-up gas and therefore a purge gas flow shall be established to remove the main part of the inerts. An inert level of this order would, however, reduce the reaction rate considerably and it is therefore more economic to purge a certain amount of the circulating synthesis gas from the loop and thereby remove the main part of the inert gases. In the present case, 14420 Nm 3/h of the synthesis gas is constantly purged from the loop at normal conditions. The purge is taken after the first ammonia chiller, where the concentration of inert gases is high.

(iv) H2/N2 Ratio- By the synthesis reaction, 3 volumes of H2 react with 1 volume of N2 to form 2
volumes of NH3. Furthermore, some H2 and N2 are removed from the synthesis loop with the purge gas and a small amount leaves the loop dissolved in the liquid product. However, compared with the amount of H2 and N2 removed by the synthesis reaction, these amounts are very small. It is therefore, a consequence of the reaction scheme of the synthesis reaction that a change in the H2/N2 ratio of the make-up gas will result in a much higher change in the H2/N2 ratio of the circulating synthesis gas. The H2/N2 ratio of the make-up gas should normally be in the range of 2.95 to 3.00. The synthesis loop is designed for operating at the H 2/N2 ratio of 3.0, but special conditions may make it favourable to operate the loop at a slightly different ratio in the range of 2.5 to 3.5. When the ratio is decreased to 2.5, the reaction rate will increase slightly (but fall again for ratios below 2.5), while on the other hand, the circulating synthesis gas will be heavier. Therefore, the pressure drop through the loop will increase and the efficiency of the ammonia separator may decrease, leading to an increased ammonia concentration at converter inlet.

P a g e | 18 The H2/N2 ratio should be kept as constant as possible. It should be noted that the composition of the synthesis gas will change slowly when a small adjustment of the make-up gas has been made and one should allow the system time enough to find its new equilibrium before making further corrections.

(v) Reaction Temperature- The temperature in the two catalyst beds are usually 370C to 520C. At
the inlet of the catalyst layer, a certain minimum temperature of 360C to 380C is required to ensure a sufficient reaction rate. If the temperature at the catalyst inlet is below 360C, the reaction rate may become so low that the heat liberated by the reaction becomes too small to maintain the temperature in the bed and the reaction will quickly extinguish itself if proper process adjustments (lowering the gas circulation and/or closing the cold shot) are not made immediately. On the other hand, it is desirable to keep the catalyst temperatures as low as possible to prolong the catalyst life. It is therefore, recommended that the catalyst inlet temperature be kept somewhat above the minimum temperature. It is anticipated that the synthesis gas enters the first catalyst bed at a temperature of maximum 400C. As the gas passes through the bed, the temperature increases to a maximum temperature at the outlet from the first catalyst bed, which is normally the highest temperature in the converter called the hotspot. The temperature of the hotspot is up to 520C. The gas from the first bed is cooled in the interbed heat exchanger using part of the cold inlet gas to the first bed in order to obtain a temperature of approx. 380C before the second bed. In the second bed, the gas outlet temperature is approx. 455C.

(vi) Operating Pressure- The synthesis loop is designed for a maximum pressure of 245 kg/cm2g and it
is foreseen that the synthesis loop can operate at a pressure of 220 kg/cm2g when operating at design production rate, design inert level and design gas composition. The actual operating pressure is not directly controlled and is dependent on the other process conditions, notably production rate, inert level, ammonia concentration at converter inlet, H2/N2 ratio and catalyst activity. The production rate increases with rising pressure and for a given set of process conditions, the pressure will adjust itself so that the production rate corresponds to the amount of make-up gas fed into the loop.

UNIT III

PROCESS DESCRIPTION AND NORMAL OPERATION

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A) Desulphurization: Desulphurization is a two step process-

1) Hydrogenation-

Organic sulphur is converted into Hydrogen Sulphide (H2S) over the hydrogenation catalyst in the HDS reactor, R-1201. Organic sulphur is reduced to less than 0.05 ppm (by

volume).

2) Absorption- The absorption of formed Hydrogen Sulphide takes place in two Zinc Oxide (ZnO)
absorbers, R-1202 A/B, arranged in series with R-1202 B acting as guard. R-1202 has been designed to operate for at least one year based on the design sulphur content in Natural Gas of 10 ppm volume as Hydrogen Sulphide. Inlet temperature of hydrogenator is 390-400 C. Reasons for a possible insufficient desulphurization are given below:

Insufficient Hydrogenation1) Too low temperature in hydrogenator. 2) Too low recycle hydrogen flow. The hydrogen content in the mixture of natural gas and recycle gas
has to be at least 2 % by volume and has to be increased if carbon oxides are present.

3) The Tk-251 catalyst has lost its activity. Insufficient Absorption 4) The HTZ-3 catalyst of the absorber, R-1202 A, is loaded with sulphur.
5) Water vapour is present in the feed gas, which gives an unfavourable equilibrium.

B) Reforming Section: Construction features of Primary Reformer

P a g e | 20 The primary reformer, H-1201, is the HALDOR TOPSE A/S Single Row Type, having an induced draught box heater and vertically installed catalyst tubes. The total number of catalyst tubes is 288, each with a heated length of 11,370 mm. and an outer/inner diameter of 152 mm/132 mm. The catalyst tube is made of an alloy having approx. 25% Chromium, 35% Nickel plus Niobium and Titanium. The tubes are loaded with a total of 44.8 m3 of catalyst, of which 11.2 m3 is TOPSE R-67R-7H catalyst placed in the upper part of tubes and remaining 33.6 m3 is TOPSE R-67-7H catalyst placed in the lower part of the tubes. The reformer is provided with 576 forced draught wall burners. Each burner is able to liberate a maximum of 337,000 Kcal/h whereas during normal operation average heat liberation will be 269,600 Kcal/h. All hot parts of reformer have been insulated by ceramic materials to reduce the heat loss to a minimum.

1) Primary Reformer: The preheated gas/steam mixture enters the primary reformer, H-1201, at about 34 kg/cm2g and 507 C. It passes the inlet hairpins and flows down through the catalyst tubes. The temperature rise of the process gas inside the catalyst tubes is in the range of 300 C. The reformed process gas containing about 11 mole % (dry basis) of methane passes through the outlet hairpins and enters the hot collectors (or sub collectors). Every two reformer sections (one from each chamber) have one hot collector. From the hot collectors, the process gas enters a common cold collector and the transfer line to the secondary reformer, R-1203.

2) Secondary Reformer: It includes mixing and combustion of the primary reformed process gas with process air, takes place in the secondary reformer, R-1203. The process gas (32 kg/cm2g, 800C) enters the secondary reformer at the top, where it is mixed with the preheated process air (32 kg/cm2g, 527C). The reaction between air (Oxygen) and process gas is a combustion where all the added oxygen is utilised, raising the temperature to about 1200 C. During the subsequent passage of the catalyst bed containing 39m 3 of TOPSE RKS-2-7H, the temperature decreases to about 990C which is the outlet temperature. The pressure is 31kg/cm 2g and the methane content is reduced from about 11 mole % to 0.30 mole % (dry basis).

P a g e | 21

Secondary Reformer

Primary Reformer

Defects of the insulation may cause the design temperature to be exceeded, with possible damage to the secondary reformer shell as a result. In order to warn of this risk factor, the secondary reformer should be coated with thermo-indicative paint. All piping with internal insulation such as cold collector, transfer line and the connection between secondary reformer and waste heat boiler should be painted with thermo-indicative paint.

C) Waste Heat Recovery Section (WHS): The Waste Heat Recovery Section comprises nine coils. The two upper coils (E-1201 and E1202 A) receive flue gas only from the primary reformer while the remaining coils receive flue gas also from the steam super heater, H-1203. During normal operation, the flue quantities are about 177,000 Nm 3/h from the reformer (1000C) and about 32,000 Nm3/h from the auxiliary steam super heater (852C). The flue gas temperature upstream, E-1201, is about 995C. The flue gas is cooled to about 845C by preheating the process gas and steam mixture from 374C to 507C. In the coil, E-1203 A, high pressure steam is superheated from approx. 366C to 425C, cooling the flue gas from 797C to 631C. The coil E-1204 A is the last NG Preheater coil where natural gas to the desulphurization section is preheated from 315C to 397C by cooling the flue gas to about 607C. The first HP steam superheater coil, E-1203 B, superheats saturated HP steam (115 kg/cm 2g, 321C) to 366C by cooling the flue gas to about 400C. The flue gas is cooled from 400C to about 369C by preheating process air from 169C to 300C in E1202 B. Cooling of flue gas from 319 to 161C takes place in the combustion air preheater, E-1205, where the combustion air is preheated from 88C to 281C. The final cooling of the flue gas takes place in the NG preheater E-1204, where NG is preheated from 80C to 129C. It is important to have a surplus of oxygen in the flue gas, as the reformer tubes require a non reducing atmosphere. During normal operation, the surplus of combustion air is 5 % corresponding to 0.8 mole % of oxygen in the flue gas. The flue gas fan increases the flue gas pressure from about 400 mm water gauge below atmospheric pressure to atmospheric pressure making it possible to emit the flue gas

P a g e | 22 through stack. During normal operation, the fan is driven by a steam turbine, mounted at one end of the shaft. Steam is added to the process air during the stepwise shutdown and when the air flow is stopped, the two process air coils are fully protected by steam.

i) Process Gas Cooling And HP Steam Production: The reformed process gas leaving the secondary reformer, R-1203, flows to the front end waste heat boiler, E-1206, which has been integrated with the transfer line. The Waste Heat Boiler is of the fired tube-type and comprises two compartments. The total process gas flow passes the first compartment, whereas the second compartment is provided with an internal bypass, controlling the outlet temperature of the process gas. The process gas inlet temperature to waste heat boiler is about 990C. In the second compartment, the process gas is cooled down to the inlet temperature of the high temperature CO converter, R-1204. During normal operation, this temperature is about 360C. The high pressure steam production in the front end takes place on shell side of the two boilers, E1206 and E-1207. The latter is placed downstream of the high temperature CO converter, R-1204. The steam is produced at 115 kg/cm2g corresponding to a boiling temperature of 321C. During normal operation, about 215 T/h of high pressure Boiler Feed Water at about 275C is fed to the steam drum.

ii) Boiler Feed Water (BFW): Conductivity (at 25C & before pH <1 s/cm adjustment with NH3. Total Dissolved Solids (TDS) Iron Copper Silica SO42- + SO32ClpH (at 25C) Dissolved Oxygen Hydrazine Organic Matter Oil <0.5 mg/kg <0.02 mg/kg <0.003 mg/kg <0.02 mg/kg <0.02 mg/kg <0.1 mg/kg >9.0 <0.02 ppm 0.02-0.05 ppm Corresponding to <5 mg KMnO4/kg H2O <0.5 mg/kg

Further a small amount of phosphate solution is added to the steam drum.

iii) Steam: Steam Quality: Solids Conductivity (at 25C) SiO2 Total Iron Na + K Copper As above <0.2 s/cm <0.02 mg/kg <0.02 mg/kg <0.01 mg/kg <0.003 mg/kg

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iv) HP Steam Superheating: The superheating of the high pressure steam from the waste heat boilers in the front end and ammonia loop takes place in the two superheater coils, E-1203 A/B, in the waste heat section and in the auxillary steam superheater, H-1203. The saturated HP steam (115 kg/cm2g, 321C) flows to the first steam superheater coil, E-1203 B, where it is superheated to about 366C. In the second superheater coil, E-1203 A, the HP steam is superheated to about 425C. During normal operation, about 270 T/h of HP steam is passed to the auxillary steam superheater, H1203, where it is superheated from about 425C to 515C. The superheater unit comprises a refractory lined radiant section with a flue gas duct connected to the waste heat recovery section. The radiant section has been installed with a number of burner units.

D) Carbon Monoxide (CO) Conversion Section: IntroductionThe CO conversion section comprises the two CO converters and equipment for process gas cooling and separation. The main part of the CO is converted into CO2 shift reaction-

CO + H2O

CO2 + H2 + Heat

The heat evolved is used primarily for steam production and boiler feed water preheat. The process gas leaving the CO conversion section contains about 0.3 mole % (dry basis) CO.

i) High Temperature CO ConversionThe quantity of reformed process gas entering the high temperature CO converter, R-1204, is approx. 285,000 Nm3/h with a steam to dry gas ratio of approx. 0.53. The inlet pressure is approx. 30.6 kg/cm 2g and temperature 360C. The high temperature CO converter comprises two beds containing a total of 92 m3 SK-201 catalyst. The process gas enters the top of the converter and flows downwards. Temperatures are measured by six thermocouples in the upper bed and two in the lower bed. The outlet temperature of the gas is approx. 427C.

ii) Low Temperature ConversionThe gas leaving the high temperature CO converter is cooled in the waste heat boiler; E-1207, the trim heater, E1209 and the HP boiler feed water preheater, E-1210 A/B. The total process gas flow entering the low temperature CO converter, R-1205, is 284,000 Nm3/h with a content of 3.0 mole % (dry basis) of CO. The process gas enters the top of the converter at 200C. The low temperature converter consists of two beds containing a total of 115.9 m3 of LK-821 with a top layer of LSK catalyst (6.1 m3). The temperature over here, are measured by eight thermocouples. The process gas leaves the converter at about 221C and 29 kg/cm2g containing approx. 0.25 mole % CO (on dry basis). The converter is provided with a bypass. The bypass is taken into operation during start-up and shutdown. The process gas inlet to the CO2 removal section is 158C.

iii) Operation of the CO conversion sectionThe optimum inlet temperature required for both CO converters is dependent on the catalyst activity and therefore the temperatures have to be increased as the catalyst ages. This means about 20C between start and end-of-run conditions for the HT shift and about 10C for the LT shift. During

P a g e | 24 operation it is especially important that the inlet gas temperature to the LT shift be well above the dew point, as condensation may cause damage to the catalyst.

E) Carbon-Di-Oxide Removal Section: The shifted process gas contains about 18 vol % (dry basis) CO2 when entering the CO2 removal section. This content is reduced to about 0.10 vol % by absorption in hot K2CO3 solution (HPC solution). The loaded HP solution is regenerated by stripping off the CO2 and is then recirculated. The heat contained in the CO2/steam mixture is used for preheating of Demineralised Water.

F) Methanation Section: Methanation- The process gas (approx 173,500 Nm3/h) from the CO2 removal section still contains
about 0.10 vol % CO2 and 0.30 vol % CO (dry basis) and, as this content of carbon oxides is poisonous to the ammonia synthesis catalyst, it is converted into methane (CH4) in the Methanator, R-1311, by use of H2.

CO2 + 4H2 CO + 3H2

CH4 + 2H2O + Heat CH4 + H2O + Heat

Both reactions are exothermic and the temperature across the Methanator bed will increase (approx. 18C). The inlet temperature to the Methanator is about 320C, obtained by cooling the Methanator outlet gas in the gas/gas exchanger, E-1311 A/B and by heat exchanging part of the inlet gas with part of the process gases upstream the LT shift in the trim heater, E-1209. From the separator, B-1306, the process gas (28 kg/cm2g, 65C) enters the tube side of the gas/gas exchanger, where it is preheated to about 310C. The exchanger outlet flow is divided into two streams by means of the two manually operated valves. About 25 % of the gas flow is passed to the trim heater, E-1209, where It is heated to 340-350C and returned to the main stream. The major part of Methanation takes place in the upper bed which is provided with four thermocouples. Two are used to measure the layer bed temperature and outlet gas temperature. The Methanator gas enters the shell side of E-1311 A/B, where it is cooled to about 90C.

Final Cooling And Methanation- The inlet temperature to the make-up synthesis gas compressor is
about 38C and the cooling to this temperature takes place in the final gas cooler, E-1312, by means of cooling water. In the final separator, B-1311- about 1300 kg/h of process condensate is separated from the process gas. Downstream of the separator, the process conditions of the process gas, still containing about 415 Nm3/h of water vapour, are measured. The make-up gas flow is about 163,000 Nm3/h.

G) Compressor Section: Introduction- The compressor section consists of three compressor groups. Each compressor group
includes a compressor with driver, a condenser, various auxillary equipments and a local control panel. The following compressors are installed in the compressor area-

1) Process Air Compressor With turbine (K-1421/TK-1421)- During normal operation, about 54,000
Nm3/h of atmospheric air is compressed to 33 kg/cm2g and added to the secondary reformer and process air. From the last stage of the compressor, the air is passed to the two process preheater coils, E1202 A/B, in the waste heat recovery section. At reduced load, the compressor speed can be reduced corresponding to about 70 % of removal flow without activation of the vent valve. The steam turbine, TK-1421, has been provided with an inlet for LP steam in order to utilize excess LP steam.

P a g e | 25

2) Make-up Synthesis Gas Compressor With Turbine (K-1431/TK-1431)- The process gas from the
Methanation section is compressed from about 26 kg/cm 2g to 211 kg/cm2g before introduction to the ammonia synthesis loop. The compression is carried out by means of make-up synthesis gas compressor, K-1431, comprising several stages and a recirculator. During normal operation, the inlet gas flow is about 163,150 Nm 3/h at a temperature of 38C and the outlet flow about 160,400 Nm3/h at 38C. After the first stage, a flow of about 1850 Nm 3/h is extracted. The hydrogenation gas is added to the natural gas upstream the desulphurization section. Before leaving the compressor section, the recycle gas is depressurized to about 44 kg/cm2g. The recirculation serves to compensate for the pressure drop of the circulated synthesis gas in the ammonia loop. The inlet flow about 591,000 Nm3/h at 208 kg/cm2g and 35C and the discharge pressure & temperature are 222 kg/cm2g and 43C respectively. The recirculator is provided with a bypass. The steam turbine driving the make-up synthesis gas compressor consists of two parts. The first part is a back pressure turbine driven by HP steam (105 kg/cm2g, 510C). The second part is the condensing turbine driven by superheated MP steam at 37 kg/cm2g, coming from the back pressure part. During normal operation, the turbine is fed with about 260 T/h HP steam and the major part of the outlet MP steam flow is used as supply for the MP steam grid, whereas the remaining 28 T/h is sent to the condensing turbine. The outlet conditions of the exhaust steam are 0.14 kg/cm 2 abs and 52C.

3) Ammonia Booster Compressor Group (K-1441/Tk-1441K-1442/Tk-1442)- The two ammonia

booster compressor, K-1441/K-1442, installed in parallel, are of the screw type, the both being motor driven. The compressors are lubricated by oil flooding. The suction conditions of each compressor are 0.02 kg/cm2g and -30C & the discharge conditions are 4.5kg/cm2g and 38C. Depending on the cooling load in the ammonia synthesis one or both the compressors K-1441/K-1442 may be in operation. If all or most of the product ammonia is sent to storage (3 kg/cm2g, -32C), both compressors will be running, whereas if the ammonia is sent to urea directly (25 kg/cm2g, 14C), only one compressor will be needed. The capacity of K-1441/K-1442 is controlled by a pressure controller with a normal set point of 1.02 kg/cm2abs referring to the common suction line of the compressors. The set point may be adjusted from the central control room. The controller operates in split range on:

i) The return bypass valve common for the two compressors, and ii) The sliding valves on both compressors. Normally control will be by the slide valve with the bypass
valve fully closed. Upward changes of capacity will be slow and the slide valve will be able to follow. A decrease in capacity may occur sharply, in which case, the bypass valve will compensate for change. In case of very low pressure in suction line, a second compressor with a set point of 1.0 kg/cm 2abs will take over acting on a bigger bypass valve.

4) Ammonia Refrigeration Compressor Group (K-1451/TK-1451)- The turbine driven ammonia

refrigeration compressor, K-1451, is a two stage centrifugal compressor with one casing. It is installed in the ammonia refrigeration circuit as the second compression group. The first stage of K-1451 receives ammonia from the second ammonia chiller, E-1507, the inert gas chiller, E-1509 and from the discharge of the ammonia booster compressor group, K-1441/K-1442. The suction conditions are 4.5 kg/cm2g and 22C. After cooling in the intercooler, the ammonia from the first stage is further compressed by the second stage of K-1451, which also receives ammonia from the first chiller, E-1506 and make-up gas chiller, E-1514. The suction conditions for the second stage are 7.2 kg/cm 2g and 30C. The compressed ammonia from the K-1451 is sent to the ammonia condensers, E-1510 A/B at 17.2 kg/cm2g and 109C. Total ammonia flow is about 43 T/h. Each stage of K-1451 has been provided with an anti-surge bypass. The driver of K1451 is a condensing turbine, TK-1451, which consumes MP steam at 37 kg/cm2g and 381C. Exhaust steam conditions are 0.14 kg/cm2abs and 52C. The turbine can be operated at variable speed.

P a g e | 26

H) Ammonia Synthesis Section: 1) Introduction of Make-Up Synthesis Gas- The make-up synthesis gas flow, which is in the order of
160,400 Nm3/h, leaves the make-up synthesis compressor group at 211 kg/cm2g and 38C. The make-up synthesis gas is further cooled in the make-up gas chiller, E-1514, giving an outlet temperature of 23C. The mixing of synthesis gas and recirculated synthesis gas takes place between the first ammonia chiller, E-1506 and the second ammonia chiller, E-1507. The addition decreases the temperature of the mixture to about 19C, due to partial evaporation of the ammonia already condensed. The final condensing takes place in the second ammonia chiller, where the gas/liquid mixture (about 666,000 Nm3/h) is cooled to the separation temperature of 12C.

2) Ammonia Separation and Synthesis Gas Recirculation- The gas/liquid mixture is separated in the
ammonia separator, B-1501. During normal operation about 591,000 Nm3/h of gas leaves the top as recirculating gas and about 56,300 Nm3/h of liquid ammonia leaves the bottom. The recirculated synthesis gas leaves the top of the ammonia separator at 12C and is passed to the shell side of the cold heat exchanger, E-1505. The gas is preheated to about 35C by heat exchange with converter effluent gas. The preheated gas is sent through the recirculation part of the make-up synthesis gas compressor, K-1431, where it is compressed from about 208 to 222 kg/cm2g. The gas is further preheated from 43C to the converter inlet temperature (244C).

3) Ammonia Conversion- The approx. converter inlet gas composition is as shown below:
Hydrogen (H2) Nitrogen (N2) Ammonia (NH3) Methane (CH4) Argon (Ar) 64.24 mole % 21.41 mole% 05.60 mole % 06.02 mole % 02.73 mole %

The main inlet flow to the converter, R-1501, is divided before introduction through the two inlet nozzles. The inlet gas passes upwards through the annular space between the pressure shell and the insulated basket. Thereby, pressure shell is kept relatively cool. The temperature profile of the shell may be followed by using the 11 thermo elements mounted on the shell. Nine of the thermo elements are installed at three levels, each comprising three elements and two are mounted just above the inlet gas nozzles. From the annular space, the non converted gas enters the tube side of the inter bed heat exchanger, where it is heated up to the inlet temperature of the first catalyst bed (370C). This temperature is adjusted by the cold shot flow. The adjustment is carried out by adding a small flow of cold converter inlet gas (passed through the centre tube) to the hot gas leaving the tubes of the inter bed heat exchanger. The unconverted gas then passes downwards through the screen panels between the converter basket wall and the first catalyst bed and enters the catalyst bed through a large number of small holes. The heat of reaction for the ammonia conversion increases the temperature of the partly converted gas and the gas is cooled on the shell side of the inter bed heat exchanger. The outlet temperature of the gas from the first bed (inlet temperature of inter bed exchanger) is measured by six thermo elements placed in three thermocouple along the bed. The outlet gas temperature from the inter bed heat exchanger is equivalent to the inlet temperature to the second catalyst bed i.e. about 380C. After passing the second catalyst bed, the converted gas leaves the converter through the bottom piece. The temperature over here is about 455C. During start up, the

P a g e | 27 bottom piece is exposed to relatively high temperature as the synthesis gas from start-up heater, H1501, is introduced through this part. Therefore the design temperature is 480C (at 245 kg/cm2g). The approx. composition of the converted gas is shown below: Hydrogen (H2) Nitrogen (N2) Ammonia (NH3) Methane (CH4) Argon (Ar) 51.90 mole % 17.30 mole% 20.80 mole % 06.90 mole % 03.10 mole %

4) Cooling Of Converter Effluent Gas- The converter effluent gas is cooled in six steps prior to purge
gas removal, make-up synthesis gas addition and final condensing of ammonia. The purpose of cooling taking place in the first five heat exchangers is firstly to save as much refrigeration energy as possible in the subsequent ammonia chillers and secondly top preheat converter inlet gas. The converter effluent gas passes the tube side of the six heat exchangers and the anticipated cooling temperatures are shown: Heat Exchanger E-1501: Loop Waste Heat Boiler E-1502: BFW Preheater E-1503: Hot Heat Exchanger E-1504: Water Cooler E-1505: Cold Heat Exchanger E-1506: First Ammonia Chiller Effluent Gas Inlet/Outlet Temp. (C) 455 / 350 350 / 273 273 / 63 63 / 39 69 / 30 30 / 23

In order, not to accumulate methane and argon (Inert Gases) introduced with the make-up synthesis gas into the ammonia loop, a small purge gas flow is removed at the outlet of the first ammonia chiller. Downstream of the purge point, the make-up synthesis gas is added to the outlet flow of chiller where ammonia is partly condensed and cycle is repeated.

5) Ammonia Let Down And Flash- The liquid ammonia leaving the separator, B-1501, is depressurized
from about 209 kg/cm2g before entering the ammonia let down vessel, B-1502. The depressurization is carried out in two steps with about 75 % in one of the two valves and about 25 % across restriction orifice. The let down vessel serves as a separator where the major part of methane and argon dissolved in ammonia is flashed off as let down gas. Besides inerts, the let down gas contains hydrogen, nitrogen and ammonia. The major part of ammonia is recovered by condensation in the let down gas chiller, E1508 and separation in the knock out drum, B-1508, from which, the liquid ammonia is returned by gravity to the let down vessel. The let down vessel temperature and pressure are 13.8C and 25 kg/cm2g. The product ammonia flow to the urea plant is approx. 56,000 kg/h. The liquid ammonia is depressurized to 0.05 kg/cm 2g, which is the operating pressure of the flash vessel, B-1503. Owing to the reduced pressure, part of the liquid ammonia is evaporated and fed into the refrigeration circuit. The rest of the ammonia is passed to the

P a g e | 28 ammonia section by means of one of the two ammonia product pumps. The flash temperature is the saturation temperature corresponding to the operating pressure. The product ammonia leaving the product pumps has a pressure of about 4 kg/cm2g and a temperature of about -32.5C.

6) Refrigeration Circuit- The purpose of the refrigeration circuit is to provide the necessary cooling
capacity the ammonia synthesis loop. The circuit operates at three compression steps, one condenser step and three depressurization steps. The three chiller levels are distributed as follows :

i) The high chiller level (7.4 kg/cm2g, 18.8C) where cooling of make-up synthesis gas (E-1514) and
condensation of ammonia from converter effluent gas (E-1506) takes place.

ii) The medium chiller level (4.7 kg/cm2g, 7.5C) where final condensation of ammonia (E-1507) from the
mixture of make-up synthesis gas and converter effluent gas takes place. Furthermore, ammonia is recovered from inert gas (E-1509) by condensation.

iii) The low chiller level (0.19 kg/cm2g, -30C) where ammonia is recovered from purge gas (E-1511) and
let down gas (E-1508). The flash vessel, B-1503, is the connection between ammonia synthesis loop and refrigeration circuit and has two purposes:

i) To flash off inert gases passed through the refrigeration circuit to the ammonia accumulator, B-1510,
where the main part is removed by purging.

ii) To cool down the ammonia product.

Saturated ammonia vapour from the purge gas chiller and the let down gas chiller is mixed with evaporated ammonia (containing H2, N2, CH4 and Ar) from the flash vessel. The mixture passes the Knock out drum before entering the ammonia booster compressors. The gaseous ammonia leaving the booster compressors is mixed with evaporated ammonia from the second ammonia chiller, E-1507 and the inert gas chiller, E-1509. After separation in the knock out drum, the ammonia is fed to the first stage of ammonia refrigeration compressor. The suction pressure of this compressor corresponds to the pressure of the second ammonia chiller (4.8 kg/cm2g). The outlet flow from the first stage is mixed with evaporated ammonia from the first ammonia chiller, E1506 and make-up gas chiller, E-1514. The mixture passes the knock out drum and enters the second stage of the refrigeration compressor. The inlet pressure is 7.2 kg/cm2g and the outlet conditions are 17.2 kg/cm2g and 109C. The gaseous ammonia is cooled and condensed in the two ammonia condensers, E-1510 A/B, installed in parallel and liquid ammonia at 41.9C is then passed to the ammonia accumulator. The accumulator level is maintained by adjustment of the ammonia flow from the second ammonia chiller to be evaporated in the flash vessel. The accumulator is equipped with an off gas heater, E-1512, which serves to cool down the ammonia from 41C to 37C. The heated medium is off gas compressing purge gas, let down gas and inert gas heated up from -25C to 11C. A small purge flow (about 2850 Nm3/h) containing ammonia vapour and the major part of the gases introduced into the refrigeration circuit by flashing, is taken from the top of the accumulator. The purge flow is passed to the inert gas chiller, E-1509, where most of the ammonia is condensed. The inert gas/ammonia mixture is separated in the knock out drum, downstream of the inert gas chiller and the ammonia is returned by gravity to the accumulator. The inert vent gas is passed to the off gas header. The liquid ammonia from the bottom of E-1514 is split into two flows, one to the second ammonia chiller, E-1507 and one to the inert gas chiller, E-1509, both operating at the medium chiller level. The ammonia flows are depressurized to the operating pressure (4.7 kg/cm2g).

P a g e | 29 Part of the liquid ammonia from E-1507, is passed to the two chillers connected in series and operating at low chiller level. The first of these chillers is the purge gas chiller, E-1511. The operation of the refrigeration circuit very much depends on whether the product ammonia is sent to the ammonia storage. The two extreme cases with either 100 % production to urea plant or 100 % production to storage represents a difference in refrigeration compressor load of approx. 2000 KW. Owing to the poisonous nature of ammonia, all safety valves discharge pipes and all vent & drain lines are connected to an ammonia blow down system, which includes the ammonia vent drum. When in operation, gaseous ammonia leaves the top of the vent drum and is passed to the flare stack through the vent stream.

7) Off Gas from Ammonia Synthesis Loop & Refrigeration Circuit- Off gas is the designation of the
combined flow of purge gas and let down gas. As already described, the purge gas flow and let down gas flow come from the ammonia synthesis loop, whereas the inert gas comes from the refrigeration circuit.

i) Purge Gas- The purge gas leaves the top of the knock out drum after separation of recovered
ammonia (about 600 kg/h). Downstream of the knock out drum, about 11,000 Nm3/h of purge gas is depressurized.

ii) Let Down Gas- The knock out drum receives let down gas from E-1508 at 25 kg/cm2g and -25C. The
flow of the let down gas is normally 1000 Nm3/h. About 260 kg/h of liquid ammonia is returned from knock out drum to the let down vessel.

iii) Inert Gas- The purge flow from the ammonia accumulator is ammonia vapour/inert gas mixture. The
major part of ammonia is recovered and returned and the inert gas leaving the knock out drum is passed to the off gas header. Although the gas mixture is designated inert gas, it contains only CH 4 & Ar but also H2, N2 and NH3. It is anticipated that the inert gas flow passed to the off gas header is about 280 Nm 3/h at 16 kg/cm2g and 12C. The following table gives the approx. gas compositions of purge, let down and inert gas in mole%: Gas Hydrogen (H2) Nitrogen (N2) Ammonia (NH3) Methane (CH4) Argon (Ar) Purge Gas 64.60 21.50 01.50 08.50 03.90 Let Down Gas 51.60 21.20 06.90 15.70 04.60 Inert Gas 14.40 09.40 42.70 29.50 04.00

The total of gas amounts to about 12,200 Nm3/h, which is passed to the off gas heater, E-1512. The off gas heater is a U-bundle heat exchanger mounted in the ammonia accumulator. By heat exchange with ammonia, the off gas is heated up from -25C to 15C. Although most of ammonia is recovered from the gases before mixing, the off gas still contains about 2.90 mole % ammonia. This content of ammonia has to be removed before the off gas is used as secondary fuel in the primary reformer and this is done in the ammonia wash section.

8) Operation of Ammonia Synthesis Loop- The major process variables characterizing the behaviour
of the ammonia loop are:

i) Gas Composition- At normal operation, the gas composition of the make-up synthesis gas is as:

P a g e | 30

Gas Hydrogen (H2) Nitrogen (N2) Argon (Ar) Methane (CH4) Ammonia (NH3)

Make-up syn gas (mole %) 74.20 24.77 00.30 00.73 00.00

Circulation syn gas (mole %) 64.24 21.41 02.73 06.02 05.60

The gas composition may be characterized by its content of ammonia and inert gases (CH 4 & Ar), the H2 to N2 ratio and the purity. The purity of the gas (i.e. the content of catalyst poisons) has been dealt with previously.

ii) Ammonia Concentration at Converter Inlet- The ammonia concentration at the inlet of the
converter is of importance to the conversion obtained. A low ammonia concentration at inlet gives a high production capacity due to high reaction rate. The ammonia concentration depends on the operating pressure and cooling level in the refrigeration chillers, especially the second ammonia chiller. With a temperature of 12C and a pressure of 209 kg/cm2g in the ammonia separator, the content of ammonia in the circulating syn gas is 5.6 mole %.

iii) Inert Gas Level- Make-up gas contains small amount of Ar and CH4. These gases are inert in the
sense that they pass through the ammonia synthesis converter without undergoing any chemical changes. The inert gases are accumulated in the ammonia synthesis loop until addition of inert gases is counterbalanced by removal of the same quantity of inert gases from the loop. A small part of the inert gases will be dissolved in the liquid product which is separated from the synthesis in the ammonia separator. The quantity of Ar & CH4, leaving in this way is proportional to the inert gas concentration and the operating pressure. With a constant addition of inerts, removal by dissolution in ammonia is not sufficient to remove all inerts and therefore a continuous purge flow has to be established. The purge gas is taken after the first ammonia chiller, E-1506, where the concentration of inert gases is high. The purge gas flow in the normal case is 10,956 Nm3/h corresponding to an inert level of 8.75%.

iv) H2/N2 Ratio- By the synthesis reaction, 3 volumes of H2 react with 1 volume of N2 forming 2 volume
of NH3. Besides the consumption of the synthesis gas, some N 2 and H2 are removed with the purge gas and furthermore a small amount leaves the ammonia loop dissolved in the liquid product. However, these amounts are extremely small compared to the N 2 and H2 removed by the synthesis. Therefore, it is evident that the H2 to N2 ratio of the synthesis make-up gas shall be close to 3:1. Normally, the ratio shall be within the range of 2.953.05 and even small changes in the H2/N2 ratio of the make-up gas results in major changes in the H2/N2 ratio of the circulating synthesis gas. The ammonia synthesis loop is designed for operation at a H 2/N2 ratio 3.0, but special conditions may make it favourable to operate the loop at a slightly different ratio in the range of 2.503.50. When the ratio is decreased 2.70 to 2.90, the reaction rate increases slightly (but falls again for ratio below 2.50) while on the other hand, the circulating synthesis gas heavier, causing an increase in the pressure drop of the loop and a decrease in the efficiency of the ammonia separator (due to the changed ratio between gas and liquid densities). When operating the ammonia synthesis loop, the H 2/N2 ratio shall be kept as constant as possible and this ratio is determined and controlled by the H 2/N2 ratio of the make-up synthesis gas. It is worth noting that when a small adjustment of the H2.N2 ratio of make-up gas has been made, the composition of the circulating synthesis gas will change only very slowly. It is therefore,

P a g e | 31 recommended that the system shall be allowed sufficient time to find its new equilibrium before further corrections and adjustments are made.

v) Reaction Temperature- The temperature in the catalyst beds are usually in the range of 360-530C.
At the top of catalyst layer, a certain minimum temperature of 350-360C is sufficient to ensure a sufficient reaction rate. If the temperature at catalyst inlet is below 350C, the reaction rate may become so low that the heat liberated by the reaction rate is too small to maintain the converter temperature and the reaction is quickly extinguished. This can be avoided by proper process adjustment such as lowering of the circulation rate or closing of the cold shot valve. On the other hand, it is desirable to keep the catalyst temperature as low as possible to prolong the catalyst life and therefore, a catalyst inlet temperature of 10C above the maximum temperature is a recommendable compromise. It is anticipated that the circulating synthesis gas will enter the first catalyst bed at a temperature of about 370-380C for an old catalyst and as the gas passes through the catalyst layer, the temperature increases to a maximum temperature of 510-520C at the outlet of the catalyst bed. This temperature is normally the highest temperature in the converter called the hot spot. The hot spot temperature should never exceed 550C. The gas leaving the first catalyst bed is cooled in the inter bed heat exchanger by means of converter feed gas. The gas is cooled to 380C before entering the second catalyst bed. The temperature of the converted gas at outlet of the second catalyst bed is about 455C.

vi) Circulation Rate- The capacity of the ammonia synthesis loop with regard to production rises with
increasing circulation rate. However, the ammonia production per cubic meter of circulation synthesis gas, which is proportional to the difference in temperature between converter outlet and inlet, will decrease.

vii) Operating Pressure- The ammonia synthesis loop is designed for a maximum pressure of 245
kg/cm2g and the loop is foreseen to operate at a pressure of 200-220 kg/cm2g. The actual operating pressure is not directly controlled and depends on the other process conditions notably production rate, circulation flow, inert level, ammonia concentration at converter inlet, H 2/N2 ratio and catalyst activity. The production rate increases with rising pressure and for a given set of process temperature, the process will adjust itself so that the production rate corresponds to the make-up synthesis gas fed to the loop. The loop pressure is increased by increasing the make-up gas flow to the loop, by decreasing the circulation rate, by increasing the inert level, by increasing the ammonia concentration at converter inlet or by changing the H2/N2 ratio away from the optimum. Furthermore, increased catalyst age (decreasing activity) raises the loop pressure.

vii) Boiler Feed Water Preheat and HP steam Production- Production of HP steam and preheat of
boiler feed water are carried out by heat exchange with converter effluent gas in the loop waste heat boiler, E-1501 and the loop BFW preheater, E-1502. The BFW preheater operates in parallel with the BFW preheater, E-1210 A/B, with the inlet conditions: 125 kg/cm2g and 178C approx. The outlet temperature from E-1502 is about 275C. The main part of the preheated BFW is passed to the steam drum of the waste heat boiler in the front end and the rest is passed to the loop waste heat boiler, E1501. In the boiler, the converted synthesis gas is cooled from about 455 to 350C. The boiler produces HP steam at 115 kg/cm2g and 321C and the shell side design conditions are 130 kg/cm2g and 340C. The BFW inlet flow is controlled by a three element boiler feed water control loop, which implies that the BFW flow is adjusted in accordance with both level and steam flow rate variations.

I) Ammonia Wash Section: i) Ammonia Absorption- The ammonia wash section serves to recover most of the ammonia contained
in the off gas from the ammonia synthesis section and by reduction of ammonia content in the

P a g e | 32 secondary fuel to the primary reformer, the flue gas emitted from the stack, H-1204, has only a negligible content of nitrogen oxides. The off gas is introduced to the lower part of the ammonia absorber at a pressure of 15 kg/cm2g and a temperature of 15C. The gas passes up through the two packed beds filled with 1.5 inch stainless steel pall rings and is washed with lean solution from the bottom of the distillation column. The inlet temperature of the lean solution is about 40C and the outlet temperature of the rich solution containing about 10 wt % ammonia, is about 30C. The purified off gas leaves the absorber at the top at a temperature of about 43C. The pressure drop of the off gas across the column is in the range of 0.2 kg/cm2g. The approx. inlet and outlet compositions of the off gas are shown: Gas Hydrogen(H2) Nitrogen (N2) Ammonia (NH3) Methane (CH4) Argon (Ar) Water (H2O) Off Gas inlet (mole %) 62.40 21.20 02.90 09.60 03.90 00.00 Off Gas Outlet (mole %) 63.80 21.70 00.10 09.80 04.00 00.60

ii) Ammonia Distillation- The rich solution at about 20 kg/cm2g and 156C is introduced at tray no. 12
in the distillation column, having a total of 20 valve trays. The heat necessary for evaporation of the dissolved ammonia is provided by raising steam at 20 kg/cm2g and 213C in the reboiler, E-1521, using condensing MP steam (37 kg/cm2g, 381C) as heating medium. The overhead product of the distillation column contains mainly ammonia vapour, but also minor amounts of non-condensable gases such as N2, CH4 and Ar. These non-condensable gases are liberated in the ammonia condenser, E-1522. The pressure at the top of the column is 19.7 kg/cm2g.

iii) Circulation Of Rich/Lean Solution- Before entering the distillation column, the rich solution is
preheated to 156C by heat exchange with lean solution in the rich/lean solution exchanger, E-1523 A/B. The lean solution used for washing out the ammonia in the absorber leaves the bottom of the reboiler at 20 kg/cm2g and 213C. The temperature is the saturation temperature of water at the operating pressure of the reboiler. The hot lean solution is cooled down to about 70C, in the rich/lean solution exchanger and further cooling takes place in the lean solution cooler, E-1524. The outlet temperature of the ammonia absorber inlet temperature is about 40C. Before being introduced to the absorber, the lean solution is depressurized to about 15 kg/cm2g.

iv) Operation Of the Ammonia Wash Section- During normal operation of the ammonia wash
section, the ammonia content of the purified off gas has to be 0.10 to 0.20 mole %. The inefficient operation can be caused due to:

a) Low Circulation Rate- If the water circulation rate is too low; this may be observed by an increased
outlet temperature. When increasing the circulation rate, the steam input to the reboiler has to be adjusted accordingly.

b) Insufficient Regeneration (Distillation)- Insufficient regeneration of the circulating solution may

be caused by too low distillation temperature or too high pressure. The stripping efficiency is favoured by high temperature, but as the purity of the product ammonia is favoured by low temperature, the extent of a temperature increase is limited. When necessary, the temperature is increased by increasing

P a g e | 33 the steam flow to the reboiler. If the pressure is too high, the water content of the overhead product is increased and this is not desirable.

J) Process Condensate Stripping Section: i) Introduction- The condensate stripping section treats process condensate from the three separators,
B-1302, B-1301 and B-1311 and vetrocoke overhead condensate from the condensate pumps. The condensate stripping removes a substantial part of the ammonia, CO2 and CH3OH from the condensate, before this is passed to the boiler feed water preparation unit. The stripping takes place in the process condensate stripper, F-1321, placed on top of the process condensate stripper. The CO2 stripper is provided with one packed bed containing 1.5 inch stainless steel pall rings. The process condensate stripper is a distillation column having 28 valve cap trays. The condensate is introduced on tray no. 20. The stripping medium is low pressure steam at 2.5 kg/cm 2g and 150C from the header. The CO2 stripper operates at a pressure of 2.4 kg/cm2g and the process condensate stripper at a pressure of 2.4-2.6 kg/cm2g. The temperature range is between 130-140C.

ii) Carbon-Di-Oxide Stripping- The vetrocoke overhead condensate (about 17 T/h) is transferred by
the vetrocoke overhead condensing pumps to the condensate exchanger, E-1321, in the process condensate stripping section. Before entering E-1321, it is mixed with the process condensate final gas separator (about 1300 kg/h). In E-1321, the condensate is preheated to 117C by heat exchange with the stripped process condensate. The preheated condensate is introduced above the packed bed of the CO2 stripper. The process condensate leaving the two separators, B-1302 and B-1301, is depressurized through the level control valves controlling the separator levels. The entire flow is further depressurized and introduced above the packed bed of CO2 stripper. The major part of CO2 is liberated during passage of the packed bed in F-1322, by stripping with LP steam from F-1321, introduced to the bottom of F-1322. The liberated CO2 is vented to the atmosphere at the top of F-1322, whereas the condensate leaves the bottom of F-1322 and is introduced at tray no. 20 of F-1321.

iii) Process Condensate Stripping- The low pressure stream flow to the process condensate stripper
(about 18 T/h) is introduced into the bottom of F-1321. The quality of the purified process condensate can be determined by analysing samples taken at the sample points. In case of insufficient quality, it is necessary to improve the stripping by increasing the steam input. The stripped process condensate leaves the bottom of stripper column at 139C. It is first cooled to 124C in the condensate exchanger, E1321 and then it is cooled to about 86C by preheating of Natural Gas (NG) in the NG preheater, E-1217 and by preheating of combustion air in the combustion air preheater, E-1218. E-1217 and E-1218 are parallel on the condensate side. Finally, the stripped process condensate is cooled to 40C in the stripped condensate cooler, E-1323 A/B. the cooled and purified condensate is pumped to the BFW preparation unit using one of the two stripped condensate pumps.

iv) Condensate Stripper Overhead System- The mixture of water vapour, ammonia, CO2 and MeOH
leaves the top of the stripper column at about 2.4 kg/cm 2g and 136C. The vapour mixture is partially condensed in the DM water preheater, E-1325, where the heat of condensation is recovered by preheating of DM water for the ammonia plant and for the off sites. If the flow of DM water through E1325 is too low to remove the necessary amount of heat from the overhead vapour, the condensate stripper overhead exchanger, E-1322 (air cooler), is put in line. E-1322 is located upstream of E-1325 and is normally bypassed. The partially condensed overhead mixture is passed from E-1325 to the condensate stripper of separator, B-1321, from where the liquid is refluxed to the top of condensate stripper, F-1321, by means

P a g e | 34 of one of the reflux pumps. To obtain a proper deaeration of the Dm water in the deaerators, the DM preheating temperature should not be allowed to increase much above 119C. Therefore, if the DM water preheating temperature tends to increase above 119C by preheating in E-1325, the duty of E1325 should be decreased by passing part of the overhead vapour through the air cooler, E-1322. In case of too high DM water preheating temperature, one or more fans on E-1327 can be put in operation to balance the need of cooling. E-1322 can fully substitute E-1325. The concentrated impure vapours are purged from B-1321 and are depressurized to atmospheric pressure and completely condensed in the recycle condenser E-1324. The exit temperature from E-1324 is 40C. The condensate is passed to the atmospheric condensate recycle separator, B-1322, from where the liquid is transferred by one of the condensate recycle pumps to the process steam line and thus recycled to the primary reformer. The atmospheric vent pipe from B-1322 is provided with a LP steam connection to avoid risk of blocking with solid ammonium carbamate, which might be formed at low temperature.

K) Steam Generation System: i) Introduction- The steam generation system is not to be considered a limited geographical area
containing a few pieces of equipment. On the contrary, this section includes all facilities necessary for preheating and deaeration of DM water, pumping, preheating and distribution of BFW and production, superheating and distribution of steam. The BFW used for high pressure steam production in the process boilers has a pressure of 130 kg/cm2g and a temperature of 275C. The HP steam at 115 kg/cm2g and 321C is produced in the process waste heat boilers E-1206, E-1207 and E-1501. The total production of saturated HP steam from these boilers is about 270 T/h, of which 21 % or 58 T/h comes from the loop waste heat boiler, E-1501. The rest comes from the two front end boilers, E-1206 and E-1207, having a common steam drum. The combined steam flows from the process boilers are superheated in two steps. The first part of the superheater takes place in two superheater coils, E-1203 A/B, placed in the waste heat section, H-1202 and the steam outlet temperature is about 425C. The second part of the steam superheat is carried out in the auxillary steam superheater, H-1203, from which, the steam leaves at 515C. The auxillary steam superheater is a NG fired heater, where the produced flue gas is mixed with flue gas from the primary reformer in the waste heat section. During normal operation, the ammonia plant is autonomous with regard to steam production and steam consumption. However, during start up, emergency shut down and for balance purposes. The steam production is adjusted by the auxillary boilers in the off sites.

ii) Preheating and Deaeration Demineralisation Water (DM water)- The total DM water flow
(about 400 T/h) is pumped from the storage to the ammonia plant. The water is preheated from approx. 40C to 106C in the four preheater, E-1308, E-1313, E-1303 and E-1306, placed in the CO2 removal section. The DM water is further preheated to 119C in E-1325 in the process condensate stripper section. About 125 T/h is sent to the offsite boilers, whereas the remaining is sent to the deaerator B1601, where most of the dissolved oxygen is stripped off by means of saturated LP steam. The deaerator consists of 111 m3 tank provided with a packed tower, which contains 2 inch stainless steel slotted rings. During normal operation, the DM water is introduced above the bed and the stripping steam below the bed. During start up, steam is introduced at the bottom of the tank to heat up the stored quantity of water. The deaerator level normally corresponds to a volume of 86 m3 of water. During normal operation, about 272 T/h of DM water is sent to the deaerator, which operates at 1.40 kg/cm 2g. The required quantity of LP steam necessary for the deaeration and for heating up the DM water from 119C to 126C is about 4.8 T/h. The outlet temperature of the DM water going to the BFW pumps is measured and the quality is determined by analyzing samples. The pH of water is also continuously monitored.

P a g e | 35

iii) Chemical Dosing Units- The installed chemical dosing units are a hydrazine dosing unit, an
ammonia water dosing unit and a phosphate dosing unit. All units comprise a preparation tank equipped with an electrically driven stirrer and a set of electrically dosing pumps.

A) Hydrazine- The addition of hydrazine to the BFW downstream of the deaerator serves to remove
remaining traces of oxygen. The removal of oxygen follows the reaction:

H2N=NH2 + O2

N2 + 2H2O

Each of the two dosing pumps has been provided with a running lamp signal, making it possible to check the operational status of this dosing unit,

B) Ammonia Water- The ammonia water solution is also added to the BFW downstream of the
deaerator. The addition is required to adjust the pH, which has to be in the range of 9-10.

C) Phosphates- The phosphate solution serves as a corrosion inhibitor. It is added to each of the two
boilers, front-end and loop boiler. The phosphate solution to the front-end boiler is added to the steam drum, B-1201 by means of dosing pumps, whose running status, is indicated by on/off signals. The preparation tank for hydrazine and ammonia water are equipped with high vents due to the unpleasant nature of these chemicals.

iv) High Pressure Boiler Feed Water Pumps- The DM water leaving the deaerator is sent to the high
pressure boiler feed water pumps, P1601 A/B/C, of which P-1601 B is on backpressure steam turbine drive and the rest two are on electric motor drive. Normally P-1601 B and one of the motor driven pumps are in operation, the third pump being in auto-start standby mode. Each of the pumps has been provided with an extraction nozzle making it possible to extract a maximum of 20 m 3/h of BFW at 70 kg/cm2g. This extraction flow is used as quench water in the HP/MP steam let down stations. Part of the quench water is further depressurized to about 15 kg/cm2g. This quench water is used in the MP/LP steam let down stations and as flashing water in the vetrocoke section. The BFW pumps, P-1601 A/B/C, are multistage (no. of stages=11) pumps and they supply HP BFW to the three process boilers E-1206, E-1207 and E-1501. Each pump is capable of handling a rated flow of 200 m3/h. During normal operation, the flow is about 290 m3/h with the discharge conditions 130 kg/cm2g and 126C.

v) Boiler Feed Water Distribution- The High Pressure BFW (130 kg/cm2g and 126C) leaving the pump
P-1601 A/B/C, is passed to the BFW header where it is used as follows:

A: Boiler Feed Water for E-1211 A/B B: Quench water between the two HP steam superheater coils, E-1203 A/B, in the waste heat recovery
section.

C: Flushing water in the Vetrocoke section. The MP quench water conditions are approx. 70 kg/cm 2g and
126C and it is used as: 1- Quench water for the HP/MP steam conversion. 2- Quench water for the MP quench station- steam addition to HT CO converter, R-1204, heating steam to the boilers E-1202, E-1207 and MP steam addition to the process gas line upstream of the Vetrocoke reboiler. 3- Depressurization to LP quench water header. The LP quench water conditions are approx. 15 kg/cm2g and 126C and it is used as:

P a g e | 36 1- Quench water for the MP/LP steam conversion. 2- Desuperheating of LP steam. 3- Sealing and flushing water in the Vetrocoke section.

vi) Blow Down Section- In order to maintain the quality of boiler water, primarily with respect to the
content of salts (phosphates), each of the three boilers, E-1206, E-1207 and E-1501 has been provided with a boiler water blow down system. The operational principle implies that a continuous blow down flow is taken fro, each steam drum and occasionally a blow down flow is taken from the bottom part of the boilers, where the salts tend to accumulate. The flashing blow down flame are passed to the blow down vessel, B-1603, where saturated LP steam at 3.5 kg/cm2g is separated from steam condensate. The LP steam is fed to the LP steam header and the condensate is routed to the cooling water pump basin. During normal operation of the ammonia plant, the continuous blow down rate is 1 % of the inlet boiler feed water flow, but this rate is increased during start-up. It is anticipated that the intermittent blow down valves are operated once per day during normal operation and once per shift during normal startup, but boiler water analysis may indicate that the frequency has to be increased. It must be strongly emphasized that keeping the BFW quality is extremely important for the performance of all steam driven rotating equipment, in particular the condensing turbine. Therefore, regular analysis of BFW shall be carried out and corrective measures taken in case of deteriorating BFW quality.

vii) HP/MP Steam Conversion System- During normal operation of the ammonia plant, the necessary
quantity of MP steam is extracted from the synthesis gas compressor turbine. However, in order to keep the steam conversion valve hot and ready for operation, a small amount (0.5 T/h) is passed through each of the manually operated bypass valves. In case of total trip of the synthesis gas compressor group, the surplus of HP steam (about 230 T/h) has to be rapidly (within 1 sec) converted with MP steam in order to ensure uninterrupted flow of process steam to the reformer. To fulfil these two operational requirements, the HP /MP steam conversion system comprises three steam valves-two large and one small-along with quench water injection valves for control of the MP steam temperature.

viii) MP/LP Steam Conversion and LP Steam Saturation- During normal operation, it is not
necessary to convert MP steam to LP steam, as the LP steam requirement is covered by the backpressure turbines. The MP/LP steam conversion is controlled by the LP steam header pressure controller. During normal operation, the process conditions are 3.5 kg/cm2g and 225C, but the deaerator, B-1601 and the process condensate stripper, F-1321 are fed with saturated LP steam at the process conditions: 3.5 kg/cm2g and approx. 150C.

ix) Steam Export and Import- Provisions have been made, both to export and import superheated HP
steam, to export MP steam and to export LP steam. During normal operation, an export of about 18 T/h of superheated HP steam is foreseen. During normal operation, no export of LP steam is foreseen.

UNIT IV

DESCRIPTION OF CATALYSTS

P a g e | 37

1) Topse Hydrodesulphurization Catalyst (Type TK-250 and TK-251): In cases where the feedstock contains organic sulphur and in particular stable sulphur compounds like thiophenes or organic sulphides, it is necessary to include a hydrodesulphurisation (HDS) step in which these compounds are converted to hydrogen sulphide (H2S). The typically low quantities of hydrogen sulphide can then be removed by the sulphur absorbent, which follows downstream of the HDS catalyst. The Topse catalyst mostly used for this purpose is TK-250, which is installed in a large number of hydrogen, ammonia and methanol plants around the world. The catalyst consists of cobalt/molybdenum on a high surface area alumina carrier.

Main Features: High Activity- The alumina carrier for TK-250 has been designed to yield a high and stable surface area. The result is a higher catalyst activity on a volume basis when compared to conventional extruded solid particles or shapes. High Mechanical Strength- The mechanical strength of extruded particles cannot be measured with
accuracy. However, many years of industrial experience shows that TK-250 never suffers mechanical damage during loading, operation, or unloading of the catalyst.

Low Pressure Drop- Topses leading position as supplier of ring shaped hydroprocessing catalyst to
the refining industry allows us to also offer the associated advantages to the field of fine purification of steam reforming feedstocks. Above all, the ring shape of TK-250 ensures a large void volume of the packed bed, which in turn provides a low pressure drop and a considerably increased tolerance for buildup of contaminants.

Presulphiding- For final desulphurisation of hydrocarbon feed to hydrogen, ammonia and methanol
plants it is normally not feasible to presulphide the TK-250 catalyst. The higher activity gained through the presulphiding is not required and would be gradually lost again when operating on feedstock with low sulphur content. Only in case of a feedstock with high content of olefins or very high hydrogen content is it recommended to presulphide the TK-250 catalyst.

2) Topse Steam Reforming Catalyst (R-67R-7H/R-67- 7H):-

P a g e | 38 R-67 and its 7 holes variant R-67-7H are especially high active catalysts for reforming of gaseous feedstock. Their high activity would be advantageous for all reforming furnaces but is particularly of interest for such furnaces which are designed and operated at high space velocity and heat fluxes above the order of 60000 Kcal/hm2 (22000 Btu/ft2h). The use of a high active catalyst will prevent the occurrence of hot brands in the upper part of furnace and in addition decrease the general tube skin temperature level. The catalyst is loaded dry into the tubes by means of socks or canisters. The catalyst can also be loaded into tubes filled with water. The prereduced catalysts R-67R and R-67R-7H can be loaded like the unreduced catalyst, as they are stable in air up to 80C. If for any reason, the prereduced catalyst is exposed to higher temperature, the resulting oxidation and consequent temperature increase will be undramatic and harmless to the catalyst. In cases where it is suspected that the catalyst activity has decreased somewhat due to sulphur poisoning, it may be advisable to delay the introduction of gas, say until the outlet temperature reaches 650-700C in order to take the advantage of the partial removal of sulphur by steaming. The reformer outlet temperature refers to side-fired or terrace-fired furnaces, where the temperatures increase gradually from top towards bottom. In the top-fired furnaces, during start up conditions with low flow and little or no heat of reaction in the tubes, a temperature maximum may well be found at the level of the flames. In such furnaces, higher than desirable temperatures may be present in the top part of the tubes, even when the outlet temperature is not higher than the level recorded. Therefore, it is suggested for operation of such furnaces to correct the recommended outlet temperatures towards lower figures. A correction of approx. 50 to 100C is suggested.

3) Topse Activated Zinc Oxide Catalyst (Type HTZ):In ammonia, methanol, hydrogen and other plants having a steam reforming unit, it is imperative to remove sulphur efficiently from the hydrocarbon feed in order to prevent poisoning of the nickel catalyst in the reformer. Desulphurisation is commonly initiated by a hydrogenation step where organic sulphur compounds are converted into hydrogen sulphide (H2S). The hydrogen sulphide is then quantitatively absorbed on zinc oxide down to or in some cases even below the equilibrium level according to following reaction:

ZnO (s) + H2S (g)

ZnS (s) + H2O (g)

For this purpose, Topse offers a series of zinc oxide absorbents designated HTZ-3, HTZ-4 and HTZ-5. The HTZ Series has made Topse a leading supplier of zinc oxide absorbents to the industry providing very high absorption capacity for all applications.

HTZ-3- It is Topses standard sulphur absorbent used for removal of hydrogen sulphide and to some
extent also certain organic sulphur compounds depending on operating temperature. HTZ-3 is characterised by its very high purity (>99% zinc oxide), which together with a high bulk density ensures an absorption capacity up to 510 kg/m3 (31.5 lbs/cu. ft.). As a result of the high density and purity, HTZ-3 typically provides 20-30% more zinc oxide for a given volume purchased than other commercial zinc oxide products corresponding to a 20-30% longer lifetime operating at the same conditions. HTZ-3 is recommended for operating in the temperature range 300-400C (570-750F) and for gases containing more than a few ppm sulphur.

HTZ-4- It is especially promoted sulphur absorbent. HTZ-4 has absorption properties very similar to HTZ3, but in addition it is capable of absorbing carbonyl sulphide (COS) even at ambient temperature. HTZ-4 is composed of approximately 90% zinc oxide, the balance being mainly alumina (Al2O3). HTZ-4 is recommended in cases where all or part of the sulphur in the feed is present as carbonyl sulphide and where no hydrogenation catalyst is placed upstream the zinc oxide. The reaction is initiated by hydrolysis of carbonyl sulphide, catalysed by alumina:

P a g e | 39

COS ZnO

+ +

H 2O H 2S

H 2S + ZnS +

CO2 H 2O

The humidity present in the feed gas will normally be sufficient for the reaction. The absorption capacity of HTZ-4 is, like for HTZ-3, reduced at low temperatures.

HTZ-5- It consists (like HTZ-3) of more than 99% zinc oxide. However, pore volume and surface area are
much higher for HTZ-5 than for HTZ-3. The high surface area makes HTZ-5 very suitable for absorption of hydrogen sulphide at low temperatures and/or low hydrogen sulphide content in the gas. As mentioned, the sulphur pick-up rate is very temperature dependent, but the pick-up rate also depends on porosity and zinc oxide surface area. Therefore, at low temperatures, it is possible to obtain a higher sulphur pickup per m3 (cu. ft.) with HTZ-5 than with HTZ-3, even though the bulk density of HTZ-5 is approximately 25% lower than that of HTZ-3.

4) Topse Secondary Reforming Catalyst (Type RKS-2/RKS-2-7H):RKS-2/RKS-2-7H catalyst is supplied in 110 litres steel drum. The usual care when handling and storing catalyst drums should be exercised also for RKS catalyst. The main parts are:

i) Drums should be handled as gently as possible. They should preferably be transported in upright
position and never be rolled.

ii) Drums can be stored outdoors but should be protected against rain and against moisture from
ground. The lower drums in a stack should therefore, be placed on logs or pallets and the stacks covered by a plastic or canvas sheets.

iii) If the catalyst is to be stored for long time i.e. more than some months, indoor storage is
recommended.

5) Topse High Temperature Shift Catalyst (Types Sk-201 and SK-12):The catalyst is supplied either in big bags or in easy to handle polyethylene lined steel drums of 100 litres nominal capacity. The drums are fitted with a totally removable lid. In case, the drums are stored outdoors, the lower drums should be placed on logs or pallets and the drums should be covered by a plastic or canvas sheet. Also big bags should be protected from the elements in case of outdoor storage. Every care should be taken to exclude foreign material during the charging operation. Dust from the catalyst contains compounds which may irritate throat and nose. Therefore, protective clothing and dust masks should be used when handling the catalyst especially in confined environments or inside the reactor.

6) Topse Low Temperature Shift Catalysts (LSK/LK-801 or LK-801; LSK/LK-821 or LK-821):The catalyst is supplied either in big bags of approx. 1000 litres (35 cu. ft.) or in easy to handle steel drums of approx. 110 litres (3.9 cu. ft.) nominal capacity. The drums are lined with polyethylene and equipped with a removable lid. Indoor storage is recommended. In case, the catalyst containers (big bags and/or drums) are stored for a short period, they should be placed on logs or pallets and covered by a plastic or canvas tarpaulin. Big bags should never be stacked.

P a g e | 40 Dust from the catalyst contains compounds which may irritate the skin, eyes and respiratory system. Therefore, the catalyst should be handled in a way which minimizes dust formation. A fresh air supply to inside of the converter vessel should be established. Dust masks should be used when handling the catalyst especially within the converter vessel. Furthermore, it is recommended that the workers handling the catalyst wear gloves and goggles.

7) Topse Methanation Catalyst (Types PK-3 and PK-5):The catalyst is supplied in easy to handle steel drums of approx. 110 litres (3.9 cu. ft.) nominal capacity. The drums are lined with polyethylene and equipped with a removable lid. Indoor storage is recommended. In case, the catalyst containers (big bags and/or drums) are stored for a short period, they should be placed on logs or pallets and covered by a plastic or canvas tarpaulin.Nickel Carbonyl, Ni(CO)4, is a highly toxic compound which may form by reaction between the nickel of the catalyst and the CO of the process gas. It is obvious that if it is necessary for man to enter a methanation reactor, the reactor should be purged especially carefully and the person should wear an air mask and skin protection. Initial symptoms of nickel carbonyl poisoning are headache, dizziness, nausea, vomiting, fever and breathing problems. A person suffering, should be hospitalized immediately.

UNIT V

OFFSITE PLANTS

P a g e | 41

1) Bore well, Raw water storage and Pumping System: The plant is away from the river and no lake is available in the nearby vicinity. Thus subsoil water is the only source of raw water supply. It is estimated that normal requirement of raw water at 100 % capacity will be around 1000 m3/h. The raw water is used in the following section:

i) Water Demineralization Plant for preparing Boiler Feed Water for producing HP steam. ii) Cooling Tower make-up. iii) For fire Protection system. iv) For cleaning plant area. v) For drinking purpose (plant as well as township).

2) Cooling Water System (Crosscurrent Induced Draft): The systems using water as coolant are called as cooling water systems. They control temperature and pressure by transferring heat from hot process fluids to the cooling water, which carries the unwanted heat away. During process, the cooling water gets heated up and must be either cooled before it can be used again or replaced with fresh make up water.

Cooling tower is basically a tower containing treated wood as filling material. Filling material is piled up in the tower from the distribution basin. Water falls on the filling and breaks into fine droplets. Fan mounted on top of tower, induces air into the tower through air louvers, placed on either side of the tower. Across this air flow, water drops fall through fillings. The filling plays the role of enlarging the heat transfer area between water and air.

P a g e | 42 Evaporation is the main cooling mechanism. Water cannot be cooled below the wet bulb temperature of entering air. The wet bulb temperature represents the minimum temperature that the water would attain after infinite time of contact between water and air in cooling tower. Design Basis of Cooling Tower Unit: Hot water temperature at cooling tower inlet Cold water temperature at cooling tower outlet Air wet bulb temperature Cooling water flow rate Cooling water pressure at plant outlet Flow rate of fresh water make up to cooling water Chemical Dosing Unit: 43.5C 33.5C 29C 20,500m3/h 3.5 kg/cm2g 400 m3/h

(a) Sulphuric Acid Dosing Unit- This unit is common for both ammonia and urea plant cooling towers.
To maintain pH of circulating cooling water within special limits, sulphuric acid is added and a sulphuric acid dosing unit has been provided.

(b) Chlorination Unit- This unit is common for both ammonia and urea plant cooling tower. The
chlorine house is capable of accommodating 12 nos. of filled chlorine cylinders, each containing 1000 kg of liquid chlorine.

3) DM Water Treatment Plant: Sub oil water is not fit for use directly as boiler feed water because the mineral contents present in the water gets deposited on the internals of the boiler. This deposited layer is highly non-active and acts as insulator which is very essential for maximising thermal efficiency of the boilers. Modern high pressure boilers need feed water, which should be of high degree of purity and conditioned with certain chemicals. Water treatment plant produces DM water of high purity for boiler feed. Ion exchange process is adopted here for producing DM water. The raw material along with treated turbine condensate of ammonia/urea plant and treated process condensate of ammonia plant is treated in three streams of DM section; each stream of 234 m3/h. Provisions for treating the following condensates from process plant is kept in the DM water section:

i) 124 m3/h turbine condensate from ammonia plant, 22 m3/h turbine condensate from urea plant and
53 m3/h steam condensate from urea plant are treated in two streams of active carbon filters, each having capacity of 100 m3/h and then fed to inlet to mixed bed units of DM section.

ii) 108 m3/h ammonia plant process condensate is treated in two streams, each having active carbon
filter and then taken to raw water buffer tank for further treatment in DM section. The normal and maximum capacity of each stream is 55/110 m3/h.

iii) 62 m3/h urea plant process condensate is treated in carbon filters, strong acid action and mixed bed.
Each carbon filter is operating at normal/maximum flow rate 31/62 m 3/h and all other equipment of capacity 62 m3/h.

P a g e | 43

4) Gas Turbine, Service Boiler and HRSG: a) Gas Turbine Generator- The gas turbine, like any other heat engine, is a device for converting part
of a fuels chemical energy into useful available mechanical power.

GTG operates on natural gas as fuel. The exhaust gases are sent to heat recovery steam generators (2 nos.).

GTG Manufacturer Type Capacity Net Output

2 nos. (1 running and 1 standby) M/S BHEL, Hyderabad Frame V, Model PG 5371 PA 26.4 MW at ISO base rating 20.7 MW at site conditions

A typical gas turbine installation consists of a power section, gear box and accessories such as a starter, fuel control lubrication system, gas conditioning skid, etc. The power section includes a centrifugal air compressor, an axial turbine and a combustor. In combustor, fuel is burned, heating the air, which expands through the turbine, wheels drive the compressors and through the gear box, the generator.

b) Service Boilers- There are two numbers service boilers of capacity 100 MTPH each to generate high
pressure steam at 115 kg/cm2g at B.L. and 515C. The service boilers are designed to fire natural gas. The service boiler comprises a water cooled furnace, a convection bank, steam/water drums, headers for collecting and distributing water and steam, primary and secondary superheaters, deaerators, boiler feed water pumps, FD fans, etc.

P a g e | 44

c) Heat Recovery Steam Generator Units (HRSG)- Two numbers heat recovery steam generators,
each having capacity to generate 100 MTPH superheated steam at 515C and 115 kg/cm2g pressure based on exhaust gases from Frame-V Gas turbine sets (2 nos.) plus supplementary firing scheme. HRSG units have been supplied by M/S Thermax Babcock & Wilcox, Poona. The HRSG unit consists of and is arranged in the same casing as follows: - Supplementary Firing gas burners (8 nos.) - Superheaters - Evaporator with steam drum - Economizer It also consists of a bypass duct and vent stack.

5) Effluent Treatment Plant: The following effluents from the fertilizer complex have been considered:

i) Pretreated Water from plant areas(A) Demineralization unit effluent, after in plant neutralization; ii) Cooling Tower Blow-down(B) A non chromate cooling water conditioning system is provided. The cooling tower blow-down and
the filter back wash water, containing non-toxic chemicals and suspended solids within the tolerance limit imposed for discharge into inland surface water.

iii) Effluent normally treated in the production areas highlight(C) Condensate from ammonia plant- Normally the process condensate and the GV section
condensate are treated in a in-plant condensate stripping system and sent to DM water plant for further treatment and recycled to ammonia process.

(D) Process condensate from urea plant- Normally the condensate from urea plant is treated in an
in-plant hydrolyser and NH3 & CO2 are recovered. The treated condensate is sent to DMW plant.

iv) Effluent treated in the Waste Water Treatment Area(E) Oily waste water from urea plant and ammonia plant is pumped in the oily water pit in the ETP. In pit,
the oil is treated by discoil unit. The discoil collects floating oil in water and the accumulated oil is stored in drums. The clear water is now sent to guard pond.

v) Effluent collected in contaminated pond(F) Process condensate, GV overhead condensate from ammonia plant during upset conditions of process condensate stripping section and GV section floor washing. (G) Condensate from urea plant during upset conditions of hydrolysis section.

P a g e | 45

(H) Effluents from floor washing and drains in urea plant- Floor washing and drains from urea
plant are containing ammonia and urea is received in a RCC pit in urea plant and pumped to the effluent treatment section of effluent collection tank before treatment. The above effluent is treated in sand filter, steam stripper and then treated effluent is collected in balance pond.

6) Gas Metering Station: Natural Gas shall be available at the battery limit from Gas Authority Of India Limited (GAIL). Natural Gas at 65-73.2 kg/cm2g pressure and 15-40C temperature is available at GAIL Battery Limit and is passed through gas filters of 5 micron size to remove pipe line dust particles, gas heater to maintain temperature, pressure control valve to maintain pressure and flow meter assembly to measure flow of pressure of natural gas. Hence NG at 40 kg/cm2g pressure and 15-40C temperature is available at the B.L. Gas heater, which is a shell and tube heat exchanger, heated by LP steam. Following NG rate is available at B.L.: Minimum Normal Maximum 0.90 MM SCMD 1.80 MM SCMD 2.10 MM SCMD

Above NG from B.L. is sent for use to ammonia plant, GTG section, Auxiliary Boiler and Heat Recovery Steam Generations auxiliary burners. Analysis of Natural Gas: Constituents N2 CO2 C1 C2 C3 C4 C5 C6 C7 H2O S (max.) Gas Mole % 0.01 4.98 80.97 7.38 4.48 1.74 0.35 0.06 0.02 0.01 50 ppm

7) Pure Liquid Nitrogen Storage Unit: -

P a g e | 46 Two nos., 25000 litres each capacity, pure liquid nitrogen cold converters have been provided. These are vertical double wall cryogenic vessels. The inner vessel is of stainless steel and outer vessel is of carbon steel. The annular space is filled up with expanded perlite powder under vacuum. Whenever it is required to supply pure gaseous nitrogen from cold converters, the converter is pressurized to about 10 kg/cm2g with the help of pressurization coil. Liquid is drawn through valve, so that 2000 Nm 3/h pure gaseous nitrogen at 7 kg/cm2g at B.L. will be available. The liquid nitrogen outlet from cold converters is heated in two nos. of atmospheric vaporizers and then through electric heater to maintain temperature of nitrogen especially in winter season and supplied to consuming plants.

8) Flare System: The ammonia plant has been provided with a flare header system, to which all vents containing inflammable gases have been connected. The main flare header is 28 inch connected to the flare stack. The flare stack is of a smokeless type and it has been provided with three constant burning ignition pilots and a molecular seal, which serves to prevent entry of air. The pilot burners are ignited by means of a flame front generator, which is remote operated. When burning gases contain higher hydrocarbons, there is a risk of incomplete combustion due to lack of oxygen. To prevent backfiring, a small amount of natural gas is continuously passed to the flare header and this flow is increased during cooling down of flare header after exposure to hot emissions.

ENVIRONMENT AND SAFETY

Safety: - The plant has a highly structured housekeeping scheme, a fire and safety department and an
excellent accident-prevention programme.

P a g e | 47 Highest priority is accorded to maintain high safety standards. Apart from holding regular fire drills, periodical emergency mock drills are conducted onsite. Safety audits are regularly undertaken by external experts and their recommendations are meticulously implemented. Gas monitoring and detection systems have been installed at toxic gas handling areas. Approved personal protective equipment of international standards is utilized for safe working. The Plant Safety committee and the Central Safety committee are very active. There is a widely publicized Safety, Health & Environment

Policy being diligently followed. "SAFETY FIRST, PRODUCTION MUST" is the motto of the organisation. KRIBHCO has adopted highest standards of safety. HAZOP study was conducted through an external agency and their recommendations are implemented. Mutual Aid Scheme has been formulated with neighboring industries, like Essar Gujarat, RIL, NTPC, ONGC and GAIL to tackle any emergency situation. A record 1009 continuous accident free days has been achieved. Regular safety audits are conducted at the plant site.

Environment: -

The Company believes in maintaining international standards for plant operation and environment preservation. In this pursuit, the Company has obtained systems certification from Interteck Systems Certification Mumbai, India for its Environment Policy (ISO-14001:2004). As a responsible corporate citizen, the Company remains committed to the total compliance of all applicable environmental, legal and other requirements, associated with manufacturing and marketing of Urea. Commitments:

Conservation of natural resources Optimum utilization of raw materials, energy, water and other inputs in the manufacturing process, so as to continuously reduce all types of pollution. Reducing the sound and dust level in manufacturing process to optimum levels. Continual improvement of environmental performances by adopting eco-viable technologies through active participation of trained and skilled associates. Minimizing the generation of process waste and maximizing recycling.

P a g e | 48

To develop and maintain the green belt in and around our premises as commitment to sustainable development

The Company submits regular compliance reports to statutory bodies like U.P. Pollution Control Board, Ministry of Environment and Forest as per the directives.

MATERIAL BALANCE OVER PRIMARY REFORMER: -

P a g e | 49

fig: Inside view of primary reformer

Data Provided: Natural Gas inlet = 48, 300 Nm3/h Steam Outlet = 129.80 T/h as 100 % steam Natural Gas Analysis (on dry basis): Constituents Methane (CH4) Ethane (C2H6) Propane (C3H8) Nitrogen (N2) Mole % or Vol. % 98.07 1.40 0.41 0.12

Outlet Reformed Gas Analysis (on dry basis):

Constituents Nitrogen (N2) Mole % or Vol. %

0.33 7.52

Carbon Monoxide (CO)

P a g e | 50

Carbon Di Oxide (CO2) Hydrogen (H2)

Methane (CH4)

10.72 68.10 13.33

Solution: Considering everything at Normal Temperature Pressure (NTP).

Basis: 48, 300 Nm3/h of NG Consider a single tube of primary reformer shown as below: S1 N Primary Reformer Tube

Burners

where- S1 = Steam Inlet N = Natural Gas Inlet S2 = Steam Outlet R = Reformed Gas Outlet

Catalyst Bed S2 R Reactions involved:

CH4 + 2H2O CO2 + H2

CO2 + 4H2 CO + H2O

(1) (2)

We know- 1 kmole = 22.414 Nm3 N = 48300 Nm3/h ; S1 = 129.8 Te/h

P a g e | 51 Calculating the volumetric flow rate (F) of each component in stream N : N2F1 = 48300 * (0.12/100) = 57.96 Nm3/h CH4F2 = 48300 * (98.07/100) = 47367.81 Nm3/h C2H6F3 = 48300 * (1.40/100) = 676.20 Nm3/h C3H8F4 = 48300 * (0.41/100) = 198.03 Nm3/h Total Carbon content in stream N = 47367.81 + (676.20 * 2) + (198.03 * 3) = 49314.30 Nm3/h Sum of Carbon content in stream R = 13.33 + 7.52 + 10.72 = 31.57 31.57 % of R = 49314.30 => R = 156, 205.21 Nm3/h

Steam Balance: Steam consumed by reaction (1) = 156205.21 * (10.72/100) * 2 = 33490.39 Nm 3/h Steam consumed by reaction (2) = 156205.21 * (7.52/100) = 11746.63 Nm 3/h Net Steam Consumed in both the reactions = 33490.39 + 11746.63 = 45237.02 Nm3/h Steam in = (129800 * 22.414)/18 = 159654 Nm3/h Steam Out = Steam in - Steam Consumed = 159654 - 45237.02 = 14416.97 Nm3/h Components of stream R : Components Nitrogen Carbon Monoxide Carbon Di Oxide Hydrogen Volumetric Flow rate (in Nm3/h) 515.48 11746.63 16745.20 106375.75

P a g e | 52 Methane 20822.15

Conversion of methaneXCH4 = CH4 in - CH4 out CH4 in = [(47367.81 - 20822.15)/47367.81] * 100

100

XCH4 =

56.04 %

P a g e | 53

Uses Of Ammonia
Fertilizer: Approximately 83% (as of 2004) of ammonia is used as fertilizers either as its salts or as solutions. Consuming more than 1% of all man-made power, the production of ammonia is a significant component of the world energy budget. Precursor to nitrogenous compounds: Ammonia is directly or indirectly the precursor to most nitrogen-containing compounds. Virtually all synthetic nitrogen compounds are derived from ammonia. An important derivative is nitric acid. This key material is generated via the Ostwald process by oxidation of ammonia with air over a platinum catalyst at 700850 C, ~9 atm. Nitric oxide is an intermediate in this conversion: NH3 + 2O2 HNO3 + H2O

Nitric acid is used for the production of fertilizers, explosives, and many organonitrogen compounds. Cleaner: Household ammonia is a solution of NH3 in water (i.e., ammonium hydroxide) used as a general purpose cleaner for many surfaces. Because ammonia results in a relatively streak-free shine, one of its most common uses is to clean glass, porcelain and stainless steel. It is also frequently used for cleaning ovens and soaking items to loosen baked-on grime. Household ammonia ranges in concentration from 5 to 10 weight percent ammonia. Fermentation: Solutions of ammonia ranging from 16% to 25% are used in the fermentation industry as a source of nitrogen for microorganisms and to adjust pH during fermentation. Refrigeration R717: Because of its favourable vaporization properties, ammonia is an attractive refrigerant. It was commonly used prior to the popularisation of chlorofluorocarbons (Freons). Anhydrous ammonia is widely used in industrial refrigeration applications and hockey rinks because of its high energy efficiency and low cost. The Kalina cycle, which is of growing importance to geothermal power plants, depends on the wide boiling range of the ammonia-water mixture. Ammonia is used less frequently in commercial applications, such as in grocery store freezer cases and refrigerated displays due to its toxicity. For remediation of gaseous emissions: Ammonia is used to scrub SO2 from the burning of fossil fuels, and the resulting product is converted to ammonium sulfate for use as fertilizer. Ammonia neutralizes the nitrogen oxides (NO x) pollutants emitted by diesel engines. This technology, called SCR (selective catalytic reduction), relies on a vanadiabased catalyst.

P a g e | 54 As a fuel: Ammonia was used during World War II to power buses in Belgium, and in engine and solar energy applications prior to 1900. Liquid ammonia was used as the fuel of the rocket airplane, the X-15. Although not as powerful as other fuels, it left no soot in the reusable rocket engine and its density approximately matches the density of the oxidizer, liquid oxygen, which simplified the aircraft's design. Ammonia has been proposed as a practical alternative to fossil fuel for internal combustion engines. The calorific value of ammonia is 22.5 MJ/kg (9690 BTU/lb) which is about half that of diesel. In a normal engine, in which the water vapour is not condensed, the calorific value of ammonia will be about 21% less than this figure. It can be used in existing engines with only minor modifications to carburettors/injectors. To meet these demands, significant capital would be required to increase present production levels. Although the second most produced chemical, the scale of ammonia production is a small fraction of world petroleum usage. It could be manufactured from renewable energy sources, as well as coal or nuclear power. It is however significantly less efficient than batteries. The 60 MW Rjukan dam in Telemark, Norway produced ammonia via electrolysis of water for many years from 1913 producing fertilizer for much of Europe. If produced from coal, the CO2 can be readily sequestered (the combustion products are nitrogen and water). In 1981 a Canadian company converted a 1981 Chevrolet Impala to operate using ammonia as fuel. Ammonia engines or ammonia motors, using ammonia as a working fluid, have been proposed and occasionally used. The principle is similar to that used in a fireless locomotive, but with ammonia as the working fluid, instead of steam or compressed air. Ammonia engines were used experimentally in the 19th century by Goldsworthy Gurney in the UK and in streetcars in New Orleans in the USA. Antimicrobial agent for food products: As early as in 1895 it was known that ammonia was "strongly antiseptic .. it requires 1.4 grams per litre to preserve beef tea. Anhydrous ammonia has been shown effective as an antimicrobial agent for animal feed and is currently used commercially to reduce or eliminate microbial contamination of beef. The New York Times reported in October, 2009 on an American company, Beef Products Inc., which turns fatty beef trimmings, averaging between 50 and 70 percent fat, into seven million pounds per week of lean finely textured beef by removing the fat using heat and centrifugation, then disinfecting the lean product with ammonia; the process was rated by the US Department of Agriculture as effective and safe on the basis of a study (financed by Beef Products) which found that the treatment reduces E. coli to undetectable levels. Further investigation by The New York Times published in December, 2009 revealed safety concerns about the process as well as consumer complaints about the taste and smell of beef treated at optimal levels of ammonia. As a stimulant: Ammonia has found significant use in various sports particularly the strength sports o weightlifting and Olympic weightlifting as a respiratory stimulant. Ammonia is commonly used in the illegal manufacture of Methamphetamine through a Birch reduction, The Birch method of making meth is dangerous because the alkali metal and liquid ammonia are both extremely reactive, and the temperature of liquid ammonia makes it susceptible to explosive boiling when reactants are added. Textile: -

P a g e | 55 Liquid ammonia is used for treatment of cotton materials, give a properties like mercerisation using alkalies. In particular, it is used for pre-washing of wool. Lifting gas: At standard temperature and pressure ammonia is less dense than atmosphere, and has approximately 60% of the lifting power of hydrogen or helium. Ammonia has sometimes been used to fill weather balloons as a lifting gas. Because of its relatively high boiling point (compared to helium and hydrogen), ammonia could potentially be refrigerated and liquefied aboard an airship to reduce lift and add ballast (and returned to a gas to add lift and reduce ballast). Woodworking: Ammonia was historically used to darken quartersawn white oak in Arts & Crafts and Mission style furniture. Ammonia fumes react with the natural tannins in the wood and cause it to change colours.

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REFERENCES
1) Original documentation prepared by HALDOR TOPSE A/S, Denmark, at the plant library. 2) Perry's Handbook For Chemical Engineers, Robert H. Perry & Don W. Green. 3) Unit Operations Of Chemical Engineering, Warren L. McCabe, Julian C. Smith, Peter Harriott. 4) Basic Principles and Calculations in Chemical Engineering, David Mautner Himmelblau, James B. Riggs. 5) Information about the catalysts from www.haldortopsoe.com 6) Images from www.image.google.com