First Foundation Day Indian Institute of Chemical Engineers

CHALLENGES & INNOVATIONS IN TECHNOLOGY OF AMMONIA UREA PLANTS

Dr. U. S. Awasthi Managing Director Indian Farmers Fertiliser Cooperative Ltd.

Introduction

Chemical Fertilisers played the key role to meet the on going demand of food grain production for the faster growing human population. Chemical fertilisers provide three primary nutrients:

Nitrogen (N) Phosphorous (P2O5) Potash (K2O)

Nitrogenous Fertilisers

Urea is one of the major nitrogenous fertilisers. Others are Ammonium Sulphate, Ammonium Chloride, Ammonium Nitrate etc. With time, technologies have undergone tremendous developments resulting in reduction in capital cost and energy consumption thereby leading to lower cost of production. Ammonia is the intermediate product in Urea production. Efficient production of Ammonia has greatest impact on Specific Energy consumption as 80% energy for Urea production is consumed for Ammonia production.

Development in Ammonia Technology

Innovation in Technology for further improvement

Development of special alloys reduced the size and weight of equipment and enhanced the capacity of plant In 1960s, use of centrifugal compressors made possible large single train ammonia plants of 1000 or even 1500 tpd capacity.

Present level is around 7.0 Gcal/tonne of Ammonia and capacity increased to 2000 TPD. Successive improvements in ammonia production lowered the cost of production resulting in liberal use of fertiliser in crop production.

First commercial production : 1913 in Germany. plant size was 25 to 30 tpd cost of production was very high.
Ammonia technology

Development in Ammonia Technology

By incorporating the latest technology energy requirement for Ammonia plants has reduced to 7 GCal/ tonne from earlier 10 GCal/tonne. Further improvement is possible as the theoretical energy requirement is 4.5 GCal/tonne of Ammonia.
Reduction in specific energy consumption in Ammonia Plants 11
GCal per Tonne of Ammonia

10 9 8 7 6
1960 1970 1980 1990 2000

Technology

Various available Technologies for Ammonia are as below:

Haldor Topsoe (HTAS) Kellogg Brown Root (KBR) ICI CF Braun Uhde

Technology

The thrust area for future process technologies are:

Low specific energy consumption Innovative, yet proven technology Superior economic performance Reducing the emission of Green House Gases (GHG) Looking for various cost effective feed stocks

Challenges being faced by Fertiliser industry

Major challenges are:

Availability of Feed Stock Reduction in Specific Energy Consumption Innovations in Technology

Availability of Feed Stock

For efficient production of Fertiliser, availability of feed stock and its prices are most important. Natural Gas is preferred feed stock as it is clean and efficient as compared to liquid fuels. More than 70% of World production of Urea is based on Natural Gas. In India about 67% Urea capacity is based on Natural Gas and balance 33% on Naphtha & Fuel Oil.

Feed Stock World Reserve

World Oil reserves at present estimated to be 3 trillion barrels and expected to last for 40 years with the reserve to current production rate. No major discoveries of oil in last few years. Total reserves of Natural Gas in the world are about 6040 TCF. With the reserve to present production rate the reserves will last up to 70 years.

Feed Stock : India

In India, the total proven Natural Gas reserves are 26 TCF and with present production rate Gas reserves will last up to 27 years. New explorations by M/s GSPCL, M/s Reliance & ONGC in KG basin are adding to its reserves. At present, the supply of Natural Gas is around 75 MMSCMD to various industries. Present allocation of Natural Gas to Fertiliser Industry is around 29 MMSCMD against demand of 33 MMSCMD.

Feed Stock : India .

Sector wise split of Natural Gas Demand in India
Others, 10% Domestic Fuel, 3% Fertiliser, 33% Industrial Fuel, 11%

Power, 43%

Feed Stock : India .

Fertiliser industry needs around 35 MMSCMD additional Natural Gas for following purposes:

To meet the shortfall of Natural Gas in Gas based plants To convert the Naphtha/FO/LSHS based plants to Gas based Additional requirement for proposed expansions

Additional requirement may be met either by importing LNG or sourcing gas from recent Gas discoveries.

Feed Stock : India .

Major discovery in Krishna Godavari (KG) basin in Bay of Bengal is expected to produce around 80 MMSCMD Gas from 2008 onwards. Demand supply gap of Natural Gas induces the search for different alternative feedstock for production of Urea. Some of the alternative feedstock are :

Coal bed Methane Coal Gasification : Above ground & Underground Gas Hydrates

Alternative Feedstocks
Coal Bed Methane (CBM):

A gas similar to natural gas with 90% methane which is trapped inside Coal Bed and is an eco-friendly source of energy. In India approximately 850 BCM of CBM Gas reserves are estimated. In the coming years, around 21 MMSCMD gas is expected to be produced through CBM with an approximate cost of 5.5 US$ / MMBTU.

Alternative Feedstocks
Coal Gasification : Above ground / Underground Coal gasification is a viable option for Urea production with delivered coal price of 2.5 US$/MMBTU. Underground Coal gasification (UCG) is in-situ gasification of coal in the seam. It is achieved by injecting oxidants, gasifying the coal and bringing the product gas to the surface through boreholes drilled from surface. India has large reserve of coal and lignite at un-mineable depth which can be tapped through UCG. The lignite reserve at Mehsana-Ahmedabad block in Gujarat alone contain recoverable gas reserve of 15,000 Billion cubic meter equivalent of natural gas utilizing UCG. ONGC and GAIL are exploring the possibility of exploiting coal gas by UCG technology.

Alternative Feedstocks
Gas Hydrates Gas hydrates, generally found in deep sea at a water depth of 650 to 750 meter, are basically methane molecules trapped in ice. So far, World estimates have converged on a consensus value of about 21,000 trillion cubic meters of methane in natural gas hydrates which is more than 100 times of world NG reserve. The drilling/coring for gas hydrates is a very specialized activity and India will be third country in the world to do so, after USA and Japan. Pilot test production is planned to be carried out in India by 2009/10. Research work is under progress at various parts of world to find out a suitable technology for production of gas from gas hydrates in a safe, economical and environmentally acceptable way.

Reduction in Specific Energy Consumption

In India, huge quantity of Oil and Gas need to be imported to meet its energy requirement. Limited availability of feed/fuel make the prices much higher. For Indian Fertiliser Industry, it is imperative to reduce specific energy consumption to remain competitive. New technologies are incorporated from time to time to modify the existing plants to improve energy efficiency. For example, IFFCO Kalol was commissioned in 1975 with a design energy consumption of 10.2 GCal, still operating continuously after 31 years of commissioning at more than 100% capacity utilisation with a reduced energy level of 8.2 GCal per tonne.

Specific Energy

IFFCO always endeavored to implement latest energy saving schemes in its plants. IFFCO plants are among the most efficient plants in India and even in the world Major Energy Saving Schemes implemented by IFFCO are as below:

Revamping of existing CO2 removal system with two stage aMDEA process which resulted in reduction of CO2 slip to 10~50ppm from earlier level of 600 700 ppm and energy saving to the tune of 0.21 GCal/MT. Process Condensate Stripper using MP process steam which eliminate emission to the atmosphere complementary with added benefit of process water, CO2 and Ammonia recovery. Installation of Process Steam Super heater.

Specific Energy

Introduction of Pre-reformer High efficiency turbines for all critical drives High efficiency catalyst Accelerated start up techniques Introduction of Distributed Control System Addition of S-50 Converter which has resulted in energy saving to the tune of 0.13 GCal/MT of Ammonia

Energy Consumption Trend in Ammonia Plants of IFFCO

9

GCal/MT Ammonia

8.8

8.6

8.4

8.2

8 2000-01

2001-02

2002-03

2003-04

2004-05

2005-06

2006-07 (Targetted)

Innovations in Existing Ammonia Plants

With the advancement of technology, present Specific Energy Consumption in modern Ammonia plant came down to 7.0 GCal per tonne of Ammonia. Further research being carried out to reduce energy and with the implementation of new improvements, the energy is expected to reduce up to 6.5 GCal per tonne of Ammonia.

Innovations in existing plants

Some of the improvement on which work is in advanced stage are as below: Advanced Instrumentation, Computation and Control Modernisation of Primary Reformer either as a auto thermal reactor or as heat exchanger by using heat of secondary reformer which will eliminate CO2 emission caused by fuel firing.. New and advanced catalyst in low pressure converter Flame less oxidation (FLOX) type burners with lower NOx emission. Special Oxide Dispersion Stabilized (ODS) alloys with higher creep resistance as Primary Reformer Tube material. Fuel cells as a source of electrical energy replacing the captive power plant of Ammonia/Urea complex.

Innovations in Conventional Technologies of Ammonia

At present, reducing the cost of plant by increasing the plant capacity is the major thrust in Conventional Ammonia process. To overcome the constraints in increasing the plant capacity beyond 2000 metric tons per day following development in Technology made. Uhdes Dual Pressure Ammonia Technology MEGAMMONIA

Uhdes Dual Pressure Ammonia Technology

Main feature:

Introduction of once through synthesis reactor at an intermediate pressure level in synthesis gas loop makes synthesis and separation of Ammonia possible in between compressor casing. The front-end process not to be modified. Make up gas from front end is compressed in the low pressure (LP) casing of the syngas compressor at a discharge pressure of 110 bar and then passes through the newly developed three bed, inter-cooled, once-through converter which will produce one third of total ammonia. Effluent from this converter is cooled and 85% of ammonia produced is separated from gas.

Brief Process Detail:

Uhdes Dual Pressure Ammonia Technology

Brief Process Detail

Highly active well proven KATALCO 74-1 (Iron based) catalyst is used in once through converter which is specifically developed for low-pressure synthesis. In the next step, the remaining syngas is compressed to the operating pressure of the synthesis loop (up to 210 bar) in the syngas compressors high-pressure (HP) casing and ammonia is then produced following conventional process steps. There are no major deviations from established process conditions.

Uhdes Dual Pressure Ammonia Technology

Benefits: Significant reduction of synthesis gas volume flow in high pressure loop. Hydrogen yield is superior Significant increase in plant capacity (+65%) Energy consumption decreased by 4% A 3300 mtpd plant can be built with no critical equipment exceeding the sizes of a current 2000 mtpd plant Uhdes 3300 MTPD Ammonia Plant based on Dual Pressure Technology has been commissioned for SAFCO in Saudi Arabia. Considerable reduction in cost of production of Ammonia

MEGAMMONIA

Designed jointly by M/s Lurgi and M/s Ammonia Casale for large scale production capacity of 4000 MTPD Ammonia Brief Process Detail: Ammonia is produced by using natural gas, steam and air as feedstock following five principal steps as below:
i.

ii.

iii.

Air separation: 95% oxygen and 99.99% pure nitrogen is produced from air. Catalytic Partial Oxidation : Desulphurised natural gas, after addition of steam is first preheated in a fired heater and then reformed over a Nickel oxide catalyst to CO, H2 and CO2 following partial oxidation. CO-Shift: Reformed gas is passed through two beds of conventional HT shift catalyst (Copper promoted Iron / chromia based) in series to convert remaining CO to H2 and CO2.

MEGAMMONIA
Process details Gas Purification: CO2 is removed by absorption in cold iv. methanol and other impurities like CO, CH4 and Ar are removed by washing the gas with liquid nitrogen. Ammonia Synthesis: The extremely high purity of ammonia v. synthesis gas results in higher conversion of gas per pass, lower circulator duty and lower refrigeration duty. Benefits: Reduce the capital cost by approx. 18-20% Operating cost is expected to be lower around 12-15% over the most advanced conventional technology. CO2 emission is expected to reduce by around 30% as compared to other conventional technologies.

Innovations in Unconventional Technologies in Ammonia production

A lot of research is being carried out to develop new unconventional technologies for the production of Ammonia with the main focus as below:

Development of environment friendly, efficient and economical production of Ammonia. Development of technologies for using renewable sources of energy like bio-mass, solar energy etc.

Innovations in Unconventional Technologies in Ammonia production

HydroMax Technology

Alchemix Corporation, USA has developed the HydroMax Technology for hydrogen production. Hydrogen is produced at very low cost utilizing Steam and carbon from cheaper/inexpensive sources like coal, municipal waste, biomass and petroleum coke etc. in presence of metal like Iron. In the first step, steam reacts with molten iron to form iron oxide and hydrogen and in second step, iron oxide is reduced back to pure metal by adding carbon. Iron simply act as a carrier for oxygen. Both process steps, hydrogen production and reduction of iron oxide back into iron, occur in the same reactor at the same temperature of 1250C.

Innovations in Unconventional Technologies in Ammonia production

HydroMax Technology Carbon-di-oxide and Hydrogen are produced in separate compartments and do not require CO2 removal system Cost of production is almost four times less than Steam Methane Reforming (SMR) production cost. Emission of green house gases is 34% less than SMR process. Clean and economic way to become energy independent for coal rich, oil poor nations like India. Demonstration of the novel aspect of HydroMax technology has been successfully conducted by M/s Alchemix, USA. They are in the process of building the 1st commercial HydroMax facility.

Innovations in Technologies
Biomass Pyrolysis / Gasification

Biomass like agricultural products including hardwood, softwood and other plant specifies may be used to produce hydrogen either by direct gasification or by pyrolysis to produce liquid bio-oil for reforming Direct biomass gasification takes place in three steps i.e. gasification, shift reaction and purification similar to coal gasification. In the gasification step, biomass is treated with steam in oxygen-blown or air blown gasifier to produce hydrocarbon gases, hydrogen, CO, CO2, tar and water vapor followed by shift reaction and purification to produce CO2 & H2.

Innovations in Technologies
Biomass Pyrolysis / Gasification

In case of Biomass Pyrolysis, biomass first thermally decomposed to liquid bio-oil at a temperature 450-550C called pyrolysis which is then steam reformed using a nickelbased catalyst at a temperature 750-850C followed by shift reaction to convert CO to CO2.

Biomass + energy Bio-oil + Char + Gas Impurities (Pyrolysis) Bio-oil+ H2O CO + H2 (Reforming) CO + H2O CO2 + H2 (Shift reaction)

Needs improvement in bio-mass feed preparation, reactor design. Work is under progress to design efficient fluidized and poison tolerant catalyst. Several pilot plant projects has proven the technology and its commercial viability is being studied.

Innovations in Technologies
Aqueous Phase Reforming (APR)

Produce hydrogen from renewable bio-mass derived feed stock like glycerol, sugars and sugar alcohols in place of fossil fuels for ammonia production. Reforming is done in liquid phase which generates hydrogen without volatilizing water. Aqueous solutions containing 10wt% glucose is converted to H2 and CO2 in a reforming reactor in presence of Pt & Pd bimetallic catalyst at around 220C. Occurs at pressure typically 15 to 60 bar where the hydrogenrich effluent can be effectively purified using either pressure swing absoption or membrane technologies.

Innovations in Technologies
Advantages of APR over conventional reforming APR is compatible with wet or water soluble feedstock Improved capability to reform without concominant reactant decomposition and carbon formation. Significant lower operating temperatures (220C vs 800C) enabling easier assimilation into heat sensitive. Generate 10 times more hydrogen per gram of catalyst than steam reforming process Low CO byproduct due to facilitated water gas shift. Virent Energy Systems, USA has got exclusive right to the APR process. US Department of Energy has taken up laboratory scale project.

Alternative technologies to source hydrogen

Hydrogen is the major constituent in the production of Ammonia. Present source of hydrogen is reforming of fossil fuels. Research is being carried out for production of hydrogen from alternative sources which are in different stages of development. This will reduce dependence on non renewable energy sources and will provide cleaner environment.

Alternative technologies to source hydrogen...

Use of Hydrogen
Methanol production and hydrogenation of fats Refining and desulphurization of oil

16%

24%

Ammonia production

60%

0%

40%

80%

Alternative technologies to source hydrogen...

Some of the alternative technologies under research to source hydrogen are as below: High Temperature Electrolysis

Electrolysis takes place at high temperature to break the water molecule using electricity for hydrogen production Economical and energy efficient than normal electrolysis at room temperature Cost of production reduces considerably as the energy required to break the water molecules decreases with rise in temperature. For large unit with centralized facility cost of production may be comparable with conventional technologies This process is highly dependant on electricity cost.

Alternative technologies to source hydrogen...

Through Sulphur Iodine Cycle Based on Thermo-Chemical reactions and require only external heat source to operate. In the first step, Iodine and sulphur di-oxide react in water to form hydrogen iodine and sulphuric acid which are immiscible under the process condition and readily separated. Sulphuric acid is decomposed at about 850C releasing oxygen and recycling sulphur-di-oxide whereas hydrogen iodide is decomposed at about 350C releasing hydrogen and recycling iodine. Literally no effluent process as all reagents are recycling Approximate cost of hydrogen will be around 1.8 to 2.0 US$ per Kg of hydrogen which is almost comparable with cost of hydrogen produced by steam reforming of NG.

Alternative technologies to source hydrogen...

Hydrogen from Solar Energy Special titanium oxide ceramics can harvest sunlight and split water to produce hydrogen fuel. This is in early stage of research and efforts are needed to make the process economically viable. mechanism of plant based on Photosynthesis Manganese atom to break water into hydrogen and oxygen using sunlight is recently discovered by British Scientists. Hydrogen may be produced with the help of certain type of green Algae using solar energy. Refinements to the bio reactor design and genetically altering Algae could make this technology viable.

Alternative technologies to source hydrogen...

Hydrogen from Nuclear Energy

Nuclear energy has the potential to efficiently produce large quantities of hydrogen without producing greenhouse gases. Initiative to demonstrate the economic, commercialscale production is being taken. Nuclear energy can be utilized for the production of hydrogen through Sulphur-Iodine, High Temperature Electrolysis of water, Thermo Chemical water splitting etc.

Various Innovation in Urea Technology

Snamprogetti Urea Technology

Fertiliser plants based on Snamprogetti Urea Technology came into operation in India in early eighties and carried out various innovations with time to reduce energy for Urea production. The various innovations in Snamprogetti Urea Technology implemented in various fertiliser industries in Indian subcontinent are as under:

Installation of Pre-concentrator Installation of Pre-decomposer

Energy saving expected with above modifications is 0.09 GCal per MT of Urea.

Innovation in Urea Technology

ACES 21 Urea Technology Toyo Engineering Corporation (TEC) has developed their latest Urea synthesis technology, ACES 21, jointly with PT Pupuk Sriwidjaja, Indonesia. ACES 21 adopts two stage synthesis concept comprised by

A Vertical Submerged Carbamate Condenser (VSCC) functioning as carbamate condenser, HP scrubber and primary urea reactor A Vertical reactor, installed at ground level, to complete reaction from carbamate to Urea as secondary reactor A vertical falling film type stripper to decompose and separate unreacted carbamate and excess ammonia by CO2 stripping A HP ejector to supply driving force for HP loop circulation.

Innovation in Urea Technology

ACES 21 Urea Technology Advantages Less HP piping and construction materials owing to lower elevation layout, fewer and smaller HP vessels. Easier operation and maintenance Reduction of heat transfer area due to Vertical submerged configuration of Carbamate Condenser. Higher CO2 conversion of 63% Optimizing N/C ratios at different levels for the VSCC (N/C 2.9) and Reactor (N/C 3.7) at lower synthesis pressure i.e. 155 Kg/cm2g resulting in less energy consumption (10% or more). Based on ACES 21 Technology P.T. Pupuk Kujang Plant in Indonesia and Sichuan Chemical Works Ltd., China got commissioned successfully in 2005.

Innovation in Urea Technology

Stamicarbon MEGA Urea Plant Stamicarbon, the leading Urea process licensor, now ready to offer their latest developed Mammoth single train Urea plant up to a plant capacity 4500 TPD. The technology is based on Pool reactor/Condenser. Plant is equipped with medium pressure recycle stage without a separate Ammonia loop with the advantage of low water concentration in recycle carbamate resulting in high conversion and lower steam consumption. Investment cost involved for MEGA capacity concept is 7075% as compared with standard 2000 TPD Urea Plant. High pressure steam consumption is considerably less in MEGA Urea plants.

Conclusion

With the improvement in technology, the specific energy consumption vis--vis cost of production has reduced considerably over last two decade. Although, the conventional technologies are being improved continuously, but thrust should be given for improvement of unconventional technologies which promises use of renewable sources of energy and are environment friendly. To improve these technologies, industry and educational institutions should join hands for the brighter future.