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The Ammonia Industry Today A Business and Technology Update

Dr. M.P. SUKUMARAN NAIR, FIE
The Travancore Cochin Chemicals Ltd., Cochin, India. E-mail: mpsn@dataone.in The ammonia industry, which provides the basic input to the production of nitrogenous fertilisers, is one of the most developed segments of the chemical processing industry. Ever since the invention of the Haber-Bosch process in 1913 and its subsequent development spanning over 90 years into the modern ammonia industry, fixation of atmospheric nitrogen as ammonia and its subsequent conversion to agrochemicals contribute to meet around 40% of the worlds protein needs. Supply-demand trends The ammonia industry consumes around 1.2% of the worlds energy resources and over the past three decades there has been a significant improvement in the energy efficiency, safety and environmental friendliness of ammonia production. Thus the specific energy consumption, waste generation, greenhouse gas emission and accident rate in the ammonia industry has shown marked downtrends. Aggregate world fertiliser consumption is 153-mt (million tons) of nutrients in 2005-06. This indicates a growth of 3.9% from the levels in 2004-05. The nitrogen supply/demand balance in 2006 was tighter mostly due to increased fertiliser consumption in Asia. The International Fertiliser Association (IFA), based in Paris, projects a global demand of 184.2-mt by 2011-12, i.e., an average annual growth rate of 2.6%. Global ammonia capacity is expected to grow to 204-mt by 2015 from the current level of 177-mt. Major growth centres are Middle East, North Africa and East Asia who have a ready access to cheap natural gas resources. World production of ammonia in 2006 stands at 148-mt, 90% of which directly goes to manufacture mineral fertilisers. The IFA, estimated that in terms of cumulative growth of demand over supply (total capability of ammonia) between now and 2011, the growth in supply will be 1.8% annually, compared with a growth in demand of 1%. A surplus is expected to emerge by 2007 and to increase substantially by 2011, assuming that all an-

About the Author

Dr MP Sukumaran Nair is Managing Director of the state-owned chlor-alkali major, Travancore-Cochin Chemicals Ltd., Cochin. He has over three decades of experience in the fertiliser industry at the Fertilisers and Chemical Travancore (FACT), Indias pioneer fertiliser and chemical manufacturing, engineering design and consultancy organization. He is well experienced in process plant operation, process design, troubleshooting and management, in the chemical processing industry and has published more than 70 technical/management papers. Dr. Nair is a Fellow of the Institution of Engineers (India), was Chairman of its Cochin Center and a Member of the American Institute of Chemical Engineers (AIChE). He is also very closely associated with various professional bodies and institutions and serves on several expert advisory committees to the Central and State Governments.
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Table 1 World ammonia situation 2003 Country China India USA Russia Ukraine Canada Trinidad Indonesia Others World total
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[Million tons] Country USA India S Korea France Belgium Imports 5.415 1.085 0.841 0.609 0.477

Production 30.207 12.595 8.768 9.113 3.934 3.646 3.574 4.254 32.70 108.79

Country Russia Trinidad Ukraine Indonesia Canada Qatar S Arabia Netherlands Others World

Exports 2.4999 3.251 1.467 1.257 0.674 0.349 0.372 0.476 3.431 13.777

Others World

5.35 13.777

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and imports to India, which was stopped in 2000, restarted in 2003 and may go up to 16-mt by the end of the 11th plan due to spurt in demand of the order of 8.4% and closure of around 3.4-mt of urea capacity following the changes in the fertiliser pricing policy, which went wholly against naphtha and fuel oil based plants. Even though China does not have proven source of natural gas or easy access to LNG, it is the largest coal producer in the world. Hence China continues its ammonia expansion program by planning 10 coalbased plants to produce 3.7-mt of ammonia per annum. On the contrary, two major Indian coal based ammonia plants, which contributed significant expertise to coal gasification technology, were closed down due to lack of viability. Looking at the international scenario, one feels that India may have to again relook at this technology to meet our growing needs of fertilisers. The Indian ammonia industry has an installed capacity of 12.8-mtpa and production during 2003-04 was 12.595-mt. Around 61% of ammonia produced is based on natural gas. Of the 38 plants in existence, 35 are now operating and three are closed down due to lack of viability under the new fertiliser pricing policy. 15 plants operate in the private sector, 14 in the public sector and six in the cooperative sector. Besides a domestic production of 12.595-mt, India imported around 1.33-mt of ammonia during 200304. With the recent hike in the price of crude oil in the international markets, the price of feedstock for ammonia production natural gas and naphtha has gone up considerably. In India, the prevailing price of natural gas along the HaziraVijaipur-Jagdishpur (HVJ) pipeline is US$3.0-4.5 per million British thermal units (mBtu), whereas that of fuel oil is around US$12 per mBtu and for naphtha in the range of US$14-18 per mBtu. The increasing liquid feedstock price has put tremendous pressure on naphtha and fuel oil based plants and some of these plants are closed, while others operate incurring heavy losses. International trade In 2005, around 19-mt of liquid ammonia was traded around the world. Major exporters are Middle East (Saudi Arabia, Bahrain & UAE), former Soviet Union (Russia & Ukraine), Canada, Germany, Netherlands, Indonesia and Trinidad. The US, India, South Korea, Western European countries, Jordan and Latin American countries import bulk of the ammonia produced in these countries. Ammonia trade, at 19.5mt during 2006, accounted for almost 13% of global production. It has increased significantly over the years and is expected to touch 23-mt by 2015. Even though world ammonia production increased by 7% in 2004 and 3% in 2005, availability of cargo was restricted in the inter-regional trade due to capacity constraints and rising maritime freight rates. Major centres of production are the Former Soviet Union (FSU) and Middle East, where natural gas is available in abundance. Major importers of ammonia are India and the US. Around 62% of the 8.476mt of ammonia exported from the Middle East comes to India. During the last year there has been an increase in demand also from the US, which accounts for 41%
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nounced capacity projects are completed in time. The global nitrogen supply and demand balance shows the current surplus of 5-mt of N rising to 17-mt by 2011. During the period from 2006 to 2011, new projects and expansions will add about 33-mt of ammonia capacity, of which 60% would be located in consuming countries. In terms of regional distribution, China, West Asia, Egypt, Algeria will contribute close to most of the new capacity additions during this period. The higher cost of natural gas prevailing in North America, West and Central Europe, North-East Asia and India do not provide any incentives for investments in modern, large and cost-competitive capacity in the region. Instead, the gas-rich regions of West Asia, Russia and the Caribbean will continue to provide strong business perspective for sustained investments in the industry. In addition, several plants remain idle in the US and India due to highcost feedstock, be it gas or liquid. Indian scenario China and India, major importers of urea till late 1990s, have developed substantial indigenous production capabilities and curtailed imports. China even started exporting around 1-mt of urea in 2001. Consequently, global capacity build up was curtailed for some years following the loss of demand from India and China. The situation is now slowly changing

Indian ammonia production (Thousand tons)

Figure 1: Trends in Indian ammonia production

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of total imports of ammonia. Asian demand during 2007, led by India, followed by Pakistan, Bangladesh, also remains strong, Price trends The price of ammonia is highly volatile with the lowest recorded price being US$106 per ton CFR India in October/December 2002 and the highest being US$326.27 per ton CFR India in January/ March 2004. The average price reigned in the range of US$117-304 per ton CFR India. Raw materials Natural gas Natural gas, predominantly methane, CH4, is the best feedstock for ammonia production. A recent survey shows that 71% of worlds ammonia capacity is built on natural gas. Other feedstock include naphtha, LPG and refinery gases (5.6%), fuel oil and liquid residues (3.7%) and coal, coke and coke oven gas (19%). Developments in coal gasification suggest that it is likely to again come up as a prime feedstock for ammonia, especially under the hitherto unprecedented increase in the price of oil and gas. Liquefied natural gas Natural gas is also traded around the world in the form of liquefied natural gas (LNG) and also as piped gas through cross-country gas pipelines. Major exporters of LNG are located in Middle East, Russia, South East Asia, Australia, Algeria, Nigeria, Canada and Mexico. Major importers of LNG are Japan, European Union, US, South Korea and Taiwan. Most of the long distance natural gas pipelines are located in Europe and North America. Natural gas enjoys a price advantage over other feedstock, but use has been restricted for long primarily because of restricted availability (mostly at close proximity to oil fields); and huge investments needed for liquefaction, transport of the cryogenic liquid, re-gasification
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and pipeline infrastructure at the consumer s end. This situation has slowly changed over the past few years, as more and more LNG terminals are coming up in different countries. Compressed natural gas Compressed natural gas (CNG) is slowly emerging as a low cost option as feedstock to ammonia plants. Technology for CNG capture, transport and delivery is proven and is suited for capture of natural gas from stranded gas fields. Furthermore, investment requirements on infrastructure are low, compared to LNG terminals. Transport of gas as CNG is simple and easy to implement, as majority of the investment is in shipping. CNG is cheaper than LNG for distances up to 3,500-km; beyond that, however, the cost of CNG becomes more than that of LNG, because of the ability to transport more gas as LNG (three times the volume of gas) per shipment. With the assured availability of CNG, coastal ammonia plants based on naphtha or fuel oil may find it feasible to consider a change of feedstock to regain financial viability. Other feedstock Other feedstock used for ammonia manufacture includes light hydrocarbons like liquefied petroleum gas (LPG), fuel oil, refinery residues and coal. All these feedstock are yet to prove technical and commercial viability in modern large capacity plants. Table 2 Feedstock prices: India 2006 [US$ per mBtu] Feedstock Naphtha Fuel Oil Coal Natural Gas Price 18.5 12.2 1.40 3.5-4.5 GAIL & Petronet 10.82 Shell LNG

Table 3 Natural gas prices 2006 [US$ per mBtu] Country Arab Gulf Russia Trinidad Venezuela Western Europe N.America Indonesia Australia Price 0.75 1.5 1.5 1.25 6 7.5 2 2

Technology update On the technology front, there is little change in the ammonia flow-sheet and layout of plant equipment, ever since the steam hydrocarbon reforming process, developed in the 1960s, was accepted as the most efficient and economic process route in the industry. At the same time, it is pertinent to note that every process stage and unit operation in the plant has undergone significant innovations and considerable improvements with a view to better the economics of operation by increasing efficiencies, lowering environmental burden, upgrading operational safety and reducing overall risk. Partial oxidation of light and heavy hydrocarbons, which was prevalent in the industry in the 1960s, is staging a strong comeback, incorporating the latest advances in gasification fostering clean technologies. The current trend in the ammonia industry is to go for higher single stream plants. Single stream plants having capacities in the range of 2,500-3,000 tons per day (tpd) have become operational. Capacities up to 5,000-tpd are being planned by major technology suppliers. This achievement has become possible on account of the continuous effort in optimizing and improving ammonia synthesis technology. The benefit of going for bigger plants is to realize advantages of economy of scale. Doubling the size of a single-train plant has the potential to reduce the capi173

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presence of cobalt molybdenum (Comox) catalyst. The H2S from the feedstock stream is adsorbed on palletized zinc oxide, to form zinc sulphide. The hydrogen is normally provided by the synthesis section, and the zinc sulphide remains in the adsorption bed, which are deactivated over a period and then replaced. ZnO + H2S ZnS + H2O

Figure 2: Indian naphtha price (Rs per ton)

Figure 3: Indian ammonia price (US$ per ton)

The catalyst is manufactured from high purity raw materials, essentially free of arsenic and chlorine, which might poison downstream catalysts. The sulphur pick-up rate is very much dependent on temperature, porosity and surface area of the zinc oxide pellets. A normal life of 57 years for the desulphuri-zation catalyst is usual. Adiabatic pre-reforming Adiabatic pre-reforming is used for easing the burden of the endothermic tubular reforming. Besides, it improves the efficiency of the overall reforming process and many a problem generally encountered in conventional tubular steam reformers are eliminated. Prereformer catalyst is nickel based on magnesium alumina spinel oxide and is characterized by high reforming activity, improved tolerance for sulphur and greater resistance to carbon formation at low steam to carbon ratios. Such catalysts are available for heavy hydrocarbon feedstock from natural gas to naphtha. Tubular reforming The desulphurized gas feed may contain less than 0.1-ppm sulphur and is mixed with superheated process steam. This mixture is heated to 500-600C and introduced to the primary reformer. The reformer is usually a rectangular tubular furnace in which the feedstock steam mixture is heated using externally fired burners. The primary reformer tubes conChemical Weekly

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Figure 4: Ammonia average energy consumption (Mcal per ton)

tal-related cost of production by about 20%.The following sections discuss some of the recent technology developments. Feedstock sulphur removal Feedstock natural gas and light hydrocarbon invariably contains small quan174

tities of sulphur compounds, which would poison most of the process catalysts downstream in the plant. Consequently, these compounds are removed from the feed-gas by hydrogenating it at 350-400C when the sulphur compounds are converted to hydrogen sulphide (H2S) in a desulphuriser, in

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tain nickel catalyst and are externally heated by fuel to provide the energy for the endothermic reaction. Typical reformer outlet temperature is in the range of 815-900C so that the methane slip is kept low. Reformer exit methane equilibrium is favoured by higher tube outlet temperature, higher steam to gas ratio and a lower exit pressure, all of which have tremendous technological and economic implications. A 5.5C rise in the tube outlet temperature contribute to a reduction of 1.3% of the feed input and an equal increase in steam generated in the waste heat recovery section. Metallurgical limitations of tubes, endothermic heat requirements and economics of downstream pressure operations limit the choice of designers. Steam carbon ratio, the molar ratio of steam to the reactive carbon contained in the hydrocarbon maintained in the primary reformer varies from 2.8 to 3.4 from natural gas to naphtha. A higher steam carbon ratio drives the reaction closer to the equilibrium and reduces hydrocarbon slip. CH4 + H2O CO + H2O CO + 3 H2 CO2 + H2; mechanical strength and the catalyst shall have a large surface area. Alkalipromoted catalysts prevent carbon formation in the steam reformer and prevent hot band formation when reforming naphtha or natural gas. Developments in furnace tube metallurgy The reformer tube which is usually designed for a limiting creep rupture life of 100,000 hours, operate under severe conditions of the oxidizing environment, and in a very hot atmosphere containing corrosive oxides of sulphur, nitrogen and particulates. The tube material is also under strain of carburization and metal dusting and is subjected to extensive cyclic thermal and pressure shock loadings. Thus the chosen material shall have proven mechanical strength, high temperature corrosion resistance and shall be amenable to casting and welding. Moreover, it must be easily available at affordable cost to the operators. The development of furnace tube alloys from HK 40 to the wide variety of modern super alloys is indeed a search DH = + 206.3 KJ/mole DH = - 41.2 KJ/mole to fulfil one or more of the above daunting tasks. Cast alloys are the prime choice as they tolerate significantly higher concentrations of carbon, silicon, tungsten, molybdenum, etc., which are added to enhance mechanical properties and enhance corrosion resistance. In the above process the metal working of the cast tubes become difficult. Another form of elevated temperature degradation of austenitic stainless steels is sensitization caused by the precipitation of chromium carbides, preferentially at grain boundaries. It may occur during fabrication from the heat of welding, improper heat treatment or through service exposure.

Report

Nature of tube failures in primary reformers are creep rupture, stress rupture, bowing or hot bands. Common causes of reformer tube failures are over-firing, thermal shocks, condensation of steam over the catalyst and impact of thermal and pressure cycling in case the start up and shutdown are frequent. Hence monitoring the health of the tube becomes an important aspect of reformer operations. Regular assessment of the tube wall temperature, maintaining a well-defined burner flame geometry and ensuring even flow through the tubes help to achieve a better tube life. Physical condition of the tubes may be assessed during annual turnarounds with the help of non-destructive testing (NDT) methods for creep detection, such as eddy current, ultrasonic or laser profilometry methods. Now-a-days, the economic choice of tube metallurgy is based on life cycle costing. Several reformers are revamped using improved metallurgy of the tube material with increased creep rupture strength and improved carburization resistance and drastically reduced plant outage. Thus, it has been well established that it is more cost effective to specify a material that will provide an extended life, particularly in areas that are difficult to repair or in components that would cause major shut-downs in case of failure as the primary reformer tubes. In these situations, the original cost of the material may be insignificant compared to the loss of production caused by the use of a lower cost, but less proven material. The gas heated reformer or the tandem reformer is developed to replace the tubular reformer with a heat exchanger having tubes filled with the reforming catalyst. The effluents from the secondary reformer provide the heat requirement for the reforming reaction. Though it has several advantages over the con175

Two important developments in the reforming technology that took place over the years relate to catalyst and metallurgy of the reformer tubes. Both these developments are driven by the necessity to adapt a wide variety of feedstock available today and to attain increased energy efficiency under demanding process conditions. A very high and stable catalytic activity is needed for favourable heat transfer and lower pressure drop in the tubes. It is possible to significantly increase throughput under constant pressure drop and stable tube wall temperatures. The carrier of the catalyst shall have good
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ventional tubular reformer it is yet to gain acceptance in modern large capacity plants. The flue gas leaving the radiant box has a temperature of about 1100C. Only 50-60% of the heat supplied is directly used in the process. The remaining enthalpy of the flue gas is recovered in the flue gas heat recovery train to pre-heat the incoming feedstock, for steam generation, superheating steam and for other process requirements. The flue gas leaves the convection section and is sent to the atmosphere at 100-200C and this is the main source of emissions from the plant. It contains mainly CO2 and small amounts of nitrogen oxides (NOx), CO and SO 2. Secondary Reforming Secondary reforming is partial oxidation of residual methane in the process gas from primary reformer. Hot process air is added to the gas stream through a specially designed burner into the reactor, because of which internal combustion takes place. The extent of primary reforming is adjusted so that the air supplied to the secondary reformer meets both the heat balance and the stoichiometric synthesis gas requirement. The gas/air mixture is then passed over a nickel containing catalyst where the reforming reaction proceeds to near completion. 2CH4 + O2 (+4N2 )

Figure 5: Ammonia Flow Sheet - Natural Gas Reforming

CO Conversion The cooled reformed gas contains 1215% CO, balance being hydrogen, nitrogen, CO 2 and small amounts of argon and methane (dry basis). Most of the CO is converted to CO2 by passing the process gas through a bed of iron oxide/chromium oxide catalyst at around 370-400C in a DH = - 71.4 KJ/mol

CO + 4H2 O (+4N2 )

The secondary reforming catalyst is nickel oxide on alumina support and has a high thermal resistance and stable activity. The gases exit from the secondary reformer at a temperature of around 950-1000C with most of the hydrocarbon in the feed converted to CO, CO2 and H2 together with added nitrogen. The process gas is then cooled to 350-400C in a process heat recovery steam boiler or boiler feed water heater.
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high temperature converter and then over a copper oxide/zinc oxide catalyst at about 200-220C in a low temperature converter. The residual CO content of the gas is 0.2-0.4%. CO + H2O CO2 + H2

steam, which was supplied at the primary reforming stage. Most of this steam is condensed by cooling the gas before it enters the CO2 removal system. The condensate normally contains 1500-2000 ppm of ammonia and 800-1200 ppm of methanol, as well as some CO2 and catalyst dust etc. In older plants, the process condensate is stripped in a column into which low-pressure steam is fed in at the bottom. A mixture of steam and gases is vented to the atmosphere, whilst the stripped condensate after polishing is used as boiler feed water. Medium temperature shift catalyst is DH = - 41.2 KJ/mol used as a replacement for the standard high temperature shift catalyst in amChemical Weekly

At this point, the gas contain mainly of H2, N2, CO2 and the excess process

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monia and hydrogen plants operating at very low steam to carbon ratios. Most low temperature shift catalysts in the market have high resistance to water and chlorine poisoning. Recently, the methanol by-product formation across LTS catalyst has become an environmental issue of increasing importance. The new generation LTS catalysts are capable of reducing methanol formation. A new development in the HTS shift converter is a specially designed boiler embedded in the catalyst beds for in situ heat removal which makes the reactor very efficient. Carbon dioxide removal The economics of hydrogen and ammonia manufacturing plants heavily depend on the efficiency and reliability of systems used for removal of carbon dioxide (CO 2) from process gas. During the last 30 years of the development of the technology, several innovations have taken place in this section of the plant, which has resulted in increase in efficiency of absorption, reduced CO2 slip of the order of a few parts per million by volume (ppmv), reduction in energy requirements for regeneration of CO 2, combating corrosion of plant equipment, emergence of non-toxic and environment-friendly solvent systems and activators for absorption, a shift from physical and chemical modes of absorption to a combination of both, improvements in mass transfer through better gas-liquid contact and so on. The converted gas usually contains about 18-22% CO2, which is then removed by chemical or physical absorption process. The solvents used in chemical processes are mainly aqueous amine solutions or hot potassium carbonate solutions. For physical absorption, solvents like glycol dimethyl ethers and propylene carbonate are used.
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Vanadium pentoxide, arsenic trioxide, piperazine and certain other compounds, depending on the process, are used as promoters or catalysts. In the amine processes, absorption of CO 2 takes place with the formation of amine adducts that are heat sensitive and are regenerated by heating the solution. In the physical absorption process, CO 2 is dissolved under pressure in methanol without combining in a chemical sense and regeneration take place by simple flashing of the solution. Pressure Swing Absorption is also employed for CO 2 removal in smaller plants. Apart from the solution for absorption and its characteristics, the design of the towers, its internal packing, solution distributors and redistributors, solution flow rates etc. are also important. Today, there are proven designs available for the process designer from proprietary suppliers, along with the right kind of technical back up for commissioning and troubleshooting, so that selection of the apt process becomes easy. Hot potassium carbonate process Hot potassium carbonate process is activated by diethanolamine (DEA) (3%). The solution is inhibited by vanadium pentoxide (V2O5) to reduce the corrosion impact. Usually the composition of the solution is of 30% of potassium carbonate plus 0.3 -1% of activator and the corrosion inhibitor. Improved amine activators with more stability and less prone to degradation are also developed by certain process licensors. K2CO3 + CO2 + H2 2KHCO3 + heat

Glycine Process The glycine processes use an aqueous solution mix of potassium carbonate, amino acetic acid (glycine) and diethanolamine. The carbonate content in the solution is usually around 29% by wt and both the activators together is less than 2%. The constituents of the solution are nontoxic. A two-stage absorption involving semi-lean (feed at the middle of absorber) and lean (top) solution is employed. The semi-lean flow is not cooled so as to increase the kinetics of the absorption process, whereas the lean flow is cooled to enhance the approach to equilibrium so that the CO2 slip is minimal.
H2N-CH2-COOH + CO2 + OOC-NH-CH2-COO + H -

OOC-NH-CH2-COO- + H2O H2N-CH2-COO- + HCO3-

Methyl diethanolamine (MDEA) process Nowadays, the MDEA process is extensively used in ammonia plants for bulk CO2 removal. Several units are operating efficiently across the globe. This process has revolutionized technology hitherto for CO2 removal in terms of process economics, reliability, energy consumption and corrosion control. The solution consists of MDEA, a tertiary amine, piperazine, a cyclic amine, as activator, and water and it is less basic in nature compared to glycine or DEA. Absorption of CO2 by pure MDEA is quite low, but is enhanced by the presence of the activator and variation in the activator concentration allow shift in thermo-

2KHCO3 (absorption) K2CO3 + CO2 + H2O (regeneration)

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Methane is an inert gas in the synthesis reaction and the water formed is (CH2-CH2-OH)2-N-CH4+ + HCO3removed by cooling and condensing it. The gas after methanation and cooling contains hydrogen and nitrogen in the stoichiometric ratio of 3:1 and is called the synthesis gas. Ammonia synthesis Converter technology and synthesis catalyst have gone hand in hand to bring about higher energy efficiency in the synthesis section. Catalysts play a vital role in this development. Most plants have installed pre-reduced catalyst to minimize the time required for start up. The synthesis gas is compressed to 100-200 bars using centrifugal compressors, usually driven by high-pressure steam turbines. The reaction uses an iron catalyst at temperatures of 350-550C. Ammonia formation reaction is exothermic; heat thus generated is used for producing steam. Usually only 20-30% of the synthesis gas is converted with each pass through the converter, thus necessitating a loop arrangement for separating the ammonia from the converter effluent and also for admitting fresh make up gas to the system. During operation, inert gases contained in the synthesis gas (argon, methane etc.) tend to build up in the synthesis loop and is maintained at about 10-15% by a continuous purge. The purge gas is cooled to separate NH3 contained in it, scrubbed with water to remove remaining ammonia and is used as fuel in the reformer or sent for hydrogen recovery. DH = - 206 KJ/mol DH = - 165 KJ/mol The condensation of the product ammonia is achieved by a refrigeration system and the product ammonia is sent to storage. The liquefied product ammonia is either used directly in downstream plants or stored in tanks. These tanks are usually of the fully refrigerated type in the capacity range of 10,000-tons to 50,000-tons, pressurized spheres (3,000tons) and bullets (20-tons).
N2 + 3H2 >2NH3 DH = -91.8 KJ/mol

dynamic behaviour from a more physical to a more chemical nature. (CH2-CH2-OH) 2N-CH3 + CO2 + H2O A major constraint in the urea plant associated with natural gas based ammonia plant is that the carbon dioxide generated from the front end of the ammonia plant is not able to meet the requisite demand for the rated urea production. Several of such plants have put up units for recovery of carbon dioxide from primary reformer flue gas stream. This has contributed to reduction of green house gas (GHG) emission from the plant. ICI, which entered the ammonia technology arena in the mid-1990s with its novel Gas Heated Reformer (GHR) to replace the conventional tubular reformer, uses pressure swing absorption (PSA) for removal of carbon dioxide from the process gas stream. But for large capacity ammonia plants, PSA has not yet been proven economically. Methanation The gas from the absorber after CO2 removal contains only small amounts of CO and CO 2, which must be removed as it would poison the ammonia synthesis catalyst. This is achieved by the methanation reaction in which the CO and CO2 are converted to methane (CH4) and water by passing it through a reactor containing nickel catalyst at a temperature of around 350C. The development of efficient shift catalysts and more efficient CO2 removal systems have resulted in reduced operating temperature for the methanation catalyst. CO + 3H2 CO2 + 4H2
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The ammonia reaction equilibrium is favoured by low temperature and high pressure, But catalyzed reaction rates are increased by higher temperature and pressure and as a result, most ammonia synthesis loops utilize converters with multiple beds with inter bed cooling: A breakthrough in ammonia synthesis technology is the development of ruthenium metal based catalyst on a proprietary graphitic structure by MW Kellogg and BP. It has an intrinsic activity up to 20 times higher than the conventional iron based catalyst. It is capable of maintaining the high activity at relatively low temperature and pressure and operates over a wide range of hydrogen/nitrogen ratios. Another recent development in the ammonia catalyst technology is the granular wautite (non-stoichiometric ferrous oxide) catalyst with promoters as calcium (Ca), aluminium (Al), potassium (K), rare earth elements having a high activity at low temperature and pressure, faster reduction rate and increased mechanical strength and resistance to poisons. Modern ammonia converters are designed on the radial flow concept, which has inherently low pressure drop, high conversion per pass, heat removal between catalyst beds and enable use of smaller size catalyst. Thus the recircuChemical Weekly

CH4 + H2O CH4 + 2H2O

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lation rate and loop pressure drop remain low, resulting in a lower power requirement for compression. Most of the old plants are retrofitted with the new converter baskets to save energy and take away the strain of the loop equipment. The ammonia purge gas recovery (PGR) system is intended to recover considerable amount of hydrogen, which otherwise is lost as a fuel to the furnace. Designs based on both cryogenic technology and hollow fibre membranes have been successful. Though the former is more efficient in recovering hydrogen from the purge, the latter needs a lower investment. Partial oxidation of hydrocarbon or coal Partial oxidation processes using heavy fuel oil, vacuum residue from petroleum refining or coal offer an alternative route for ammonia production. Economics of the process depends on the relative availability, cost and quality of these feedstock and oxygen, in relation to investment costs and other factors such as the environmental need to use waste materials that are otherwise difficult to disposeoff. When the feedstock is heavy fuel oil with high sulphur content or coal, noncatalytic partial oxidation at around 50bar pressure and 1400C is employed for gasification. Steam is added to the gasifier to moderate the gasification temperature. A cryogenic air separation unit is needed to supply oxygen and nitrogen for the process. The reaction of the hydrocarbon with oxygen in the gasifier produces CO and hydrogen, as well as some CO2, CH4 and soot. After heat recovery from the hot and dusty gases in a specially designed boiler, soot is removed by scrubbing with water and separated as carbon slurry. Sulphur compounds in the feed are converted to hydrogen sulphide and sepaChemical Weekly

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rated from the process gas, using a selective absorption agent (which could be the same as in the CO 2 removal). The regenerated H 2S is then converted to elemental sulphur by the Claus sulphur recovery process. The CO is then converted to CO2 by the water shift reaction, upon passing through two beds of iron catalyst with intermediate cooling. The CO 2 is then removed by an absorption agent as in the case of the reforming route. The residual traces of CO and CO 2 are removed in the final purification of the gas by a liquid nitrogen wash. This results in a pure synthesis gas, to which more nitrogen is added to provide the stoichiometric hydrogen-nitrogen ratio for ammonia. As the synthesis gas so produced contain

only H2 and N2, without any inerts, there is no need for a purge in the ammonia synthesis loop and hence loop efficiency is better, compared to the steam reforming process. In coal gasification, the main stages are coal grinding and preparation of slurry for pulverization, in addition to those in the heavy fuel oil process. Higher initial investment needed and over one and a half times energy consumption over methane-steam reforming based ammonia plants render coal gasification technology for ammonia plants unviable. Still efforts are underway to see whether these disadvantages could be overcome by capitalizing on mega-capacities with the unprecedented hike in the price of petroleum feedstock.

Figure 6: Ammonia Flow Sheet - Heavy Oil Partial Oxidation

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covery and reduced carbon dioxide emissions. The advantages, besides an effective means of disposal of heavy refinery residues, also include better feedstock flexibility, a higher degree of operating reliability and efficiency for synthesis gas making through the gasification technology. The economy of the operation is attractive because of a higher level of system optimization and reduction in input costs at every stage. Developing countries like China and India where industrial and agricultural consumption and overall economic growth are increasing leaps and bounds depend mostly on imports for feedstock and fuel requirements of their refineries and downstream facilities such as fertiliser, power and petro-products. Refinery, fertiliser, power and petrochemicals are themselves major investment and high technology decisions and very often these units are put by different agencies and function as independent companies. Technology brings in lot of scope for exploiting the synergy within these units, which could play a major role in improving the bottom-line of current operations of these units. Plant reliability The improved reliability of the ammonia plant is contributed by the reliability of critical equipments such as reformers, boilers, converters, compressors, unit operations such as CO 2 removal, purge gas recovery and availability of better quality of catalysts with increased activity and life. The start-up time required for the plant has also been brought down over the years and technique of accelerated start up have been possible with the use of pre-reduced catalysts. The modern ammonia plant has registered a high degree of versatility with

Co-production of ammonia Gasification of residues from refining operations has become proven and well established through several installations in different countries. The process involves non-catalytic partial oxidation of the feedstock by oxygen from an associated air separation process to produce synthesis gas, a mixture of carbon monoxide (CO), hydrogen (H 2), and smaller quantities of carbon dioxide, sulphur dioxide and hydrogen sulphide, soot etc. The hot gases from the gasifier are cooled by generating steam by quenching with water to remove dust and particulate matter. Further, the hydrogen sulphides is separated by methanolamine or glycol wash. The recovered hydrogen sulphides and carbonyl sulphides (COS) are made to undergo the Claus reaction and sulphur is recovered in the elemental form and can be later used for production of sulphuric acid plants for fertiliser requirement. The entire sulphur in the residue is fixed as plant nutrient. Synthesis gas generated from the process is similar to that from other partial oxidation processes using Furnace Oil (FO) or Low Sulphur Heavy Stock (LSHS). Besides ammonia synthesis, it can also be used for methanol manufacture or power generation in the Integrated Gasification and Combined Cycle mode. For ammonia synthesis, the CO in the gas is to be converted to CO2 and it is to be stripped off. The hydrogen thus produced is mixed with nitrogen from air separation in a wash column to the specification of the ammonia synthesis gas. The refinery hydrogen requirement for desulphurisation and fuel upgradation can also be met from the synthesis gas through pressure swing adsorption. The environmental benefits associated with the combined operation are improved carbon recycle, total sulphur re180

Figure 7: Schematic diagram of refinery integrated fertilizer, power and petrochemicals combine Chemical Weekly

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regard to stream days. Over the years, annual turnarounds are planned considering the necessity of catalyst change after its end of run, for statutory inspection of boiler equipments or for other jobs that could not be taken up on-line. Certain plants have adopted a strategy to plan 30 days for yearly repairs and maintenance during a couple of years of continued operation. Nowadays most of the plants are on Distributed Control System (DCS)-based instrumentation and thus discrete analysis of past data and understanding the behavioural trends of equipments is easy. Real time process data reconciliation and validation help the operator to accurately model equipment and reactors. Such operator friendly programs for online performance monitoring are available at affordable costs. Several Indian plants have been successful in taking advantage of most of these reliability improvement tools. An expert group enquiring into the efficiency levels and energy consumption figures of ammonia and urea plants of the three largest producers in the world, found that energy consumption of Indian gas-based plants is better than similar plants in USA and China. In case of naphtha-based plants, the energy consumption figures are nearly equal on comparable basis. Safety, security and environmental status Remarkable improvement has been made in the operational safety of plants. A direct result of such efforts is that the harshness of the operating environment of the ammonia plant has been considerably reduced. To cite an example, the ammonia synthesis pressure was 350 atmospheres in the early 1960s and today is reduced to below 100 atmospheres with the help of catalysts with increased activity, better configuration of systems and use of more reliable equipment and process control instruments. Nowadays, every effort is
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made that the different sections of the ammonia plants are designed and built adhering to the inherent safety concepts to the extent possible. Once the plant is designed, a thorough Hazard and Operability (HAZOP) check is done at the design freeze stage and after construction of the plant. Later, the information is used to conduct a thorough risk analysis based on accepted techniques of process plant risk analysis. Adequate provisions are made to see that the risk arising out of the plant to the employees and the local community is maintained well within acceptable limits. Well laid down emergency management plans are also developed with inputs from these kinds of safety studies and are frequently tested through mock drills replicating probable worst case scenarios in the plant. In most plants, there are specific systems and guidelines intended for management of abnormal situations. There have been a number of accidents in the industry and several lessons were learned from such incidents. Every accident has been investigated, discussed at various international forums and remedial measures to prevent repetition of such occurrences in future have been incorporated in subsequent designs and changes in operation and maintenance philosophies have been brought in. In this context it is worthwhile to remember the meritorious contributions made by the Safety in Ammonia Plants and Related Facilities symposium organized annually by the American Institute of Chemical Engineers. The environment management facilities associated with the ammonia plant take care to see that emissions, effluents and solid waste are properly treated and disposed. These include spent catalysts, sludge from process equipment, debris from construction and insulation, oil sludge, process condensate, blow-down from cooling tower and boilers, spillage of CO2 removal solutions, gas leaks containing ammonia

and carbon oxides and flue gas from furnace. Another environmental concern from the plant is noise. Sources of noise in the ammonia plant are from the reformer furnace, blowers, air coolers, pumps, compressors and PSA units. Use of low noise burners, providing enclosures for the rotating equipments, noise attenuation insulation for air ducting etc. are some attempts to help to reduce noise in plants. Security of the plant is also a prime concern to the operator, in the context of increasing worldwide terrorism and there is a growing need for more detailed security guidelines to be adopted in process plants. Such guidelines may be issued by professional bodies of repute or by the Government. The facility management outlook has also undergone a sea change, so as to learn lessons from past failures, systematically investigate every failure of systems and equipment, practice risk-based inspection procedures and adopt reliability-centred maintenance techniques. On the operators side, on-line performance monitoring has become a commonly adopted practice for streamlining plant performance against targets. Predictive troubleshooting and preventive maintenance of equipments have been successful in reducing plant outages. Based on operating experience and research, common problems encountered in plants are addressed to achieve a reliable, efficient and sustainable operation. These include identifying best operating practices, exploring retrofit options available and suggesting methods for management of abnormal situations and thus achieving overall plant optimization. The driving force of production and innovation in the ammonia industry have become energy efficiency, environmental quality and economics of operation.
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