Fuel Processing Technology 88 (2007) 493 500 www.elsevier.

com/locate/fuproc

Gas-to-liquid technologies: India's perspective

Tirupati Reddy Keshav, S. Basu
Department of Chemical Engineering, Indian Institute of Technology Delhi, New Delhi 110016, India Received 29 June 2006; received in revised form 14 December 2006; accepted 15 December 2006

Abstract Gas-to-liquid (GTL) technologies are capable of converting gas to clean, useful liquid hydrocarbons and thus suitable for addressing problems of remote gas utilization, increase in crude oil price, depletion of fossil fuel and environmental pollution. The Indian state of Tripura is considered to be the richest province with 26 billion cubic meters of gas reserves. Neighboring country Myanmar has huge gas reserves but these reserves remain unutilized mainly because of land-locked situation. GTL is a well developed and proven technology and it is an important option for moving natural gas to the market place. GTL options include not only the well-known production of FischerTropsch synthesis liquids but also the production of oxygen containing fuels, fuel additives and chemicals, such as methanol and DME. An alternative, promising option to convert surplus gas is the direct route of methane conversion, which is more energy efficient than the indirect route since it bypasses the energy intensive endothermic steam reforming step of syngas formation. On-site conversion to liquid products of commercial importance using direct route would make transportation of these natural deposits much more economical and practical. In this paper an attempt has been made to review recent developments in syngas technologies, direct routes of methane conversion into useful liquids, and status of both existing and future developments in GTL industry around the world. Finally challenges in GTL technology are discussed. 2006 Elsevier B.V. All rights reserved.
Keywords: GTL; Syngas technology; Direct conversion of methane; Oxygenates

1. Introduction India is both a major energy producer and consumer. India currently ranks as the world's eleventh greatest energy producer, accounting for about 2.4% of the world's total annual energy production, and as the world's sixth greatest energy consumer, accounting for about 3.3% of the world's total annual energy consumption. Despite its large annual energy production, India is a net energy importer. India's natural gas reserves are currently estimated at about 2932 trillion cubic feet (tcf), which is about 0.5% of the world's total gas reserve estimates. Most of these reserves lie in Tripura, offshore close to northwest of Mumbai in the Arabian Sea and onshore state of Gujarat and Godavari basin in the state of Andhra Pradesh. Tripura is considered to be the country's richest province in terms of gas reserves, which are estimated to be more than 26 billion cubic meters (bcm), but most of the fields have remained unexplored due to lack of market in the land-locked province [1]. Only 27% of this is marketable through pipe line and the rest is surplus.
Corresponding author. Tel.: +91 11 26591526; fax: +91 11 26581120. E-mail address: sbasu@chemical.iitd.ac.in (S. Basu). 0378-3820/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2006.12.006

The state-owned exploration company has earlier discovered gas at six locations in the north-eastern provinces: Baramura, Rokhia, Agartala Dome, Gojalia, Tichna and Maicherra. Further, in the adjacent country, Myanmar, huge gas reserves are found and mainly remain unutilized because of the lack of market demand in the area and as well as uneconomical proposition in transporting through pipe line. India is not in the top 20 of the world's greatest natural gas consumers, but it is changing fast because of industrial development and huge demand in energy. Natural gas demand has the highest rate of growth compared to any other primary fuels in India; the demand is growing at about 4.8% per year and is forecasted to rise to 1.2 tcf per year by 2010 and 1.6 tcf per year by 2015. A historical summary of natural gas production and consumption in India is shown in Table 1. According to the International Energy Outlook-2005 forecast, natural gas is going to be the highest growing primary energy source. The consumption of natural gas is projected to increase by nearly 70% between 2002 and 2025, with the most robust growth in demand expected among the emerging developing countries. In this article the existing GTL technologies have been reviewed and direct route to gas-to-liquid conversion is recommended to

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Table 1 Dry natural gas production and consumption in India, 19932003 (in tcf) 1993 Production Consumption 0.53 0.53 1994 0.59 0.59 1995 0.63 0.63 1996 0.70 0.70 1997 0.72 0.72 1998 0.76 0.76 1999 0.75 0.75 2000 0.79 0.79 2001 0.85 0.85 2002 0.88 0.88 2003 0.96 0.96

make use of the unexploited natural gas reserves in the Indian state of Tripura and finally problems related to GTL technologies are discussed. 1.1. What is GTL? GTL fuels are produced from natural gas, coal, and biomass using the FischerTropsch synthesis (FTS) process. The potential route to obtain clean liquid fuels based on FTS is shown in Fig. 1. The liquids produced include naphtha, diesel, and petrochemical feedstocks. The resulting GTL diesel can be used neat or blended with today's diesel fuel in existing diesel engines. This provides an opportunity to reduce dependence on petroleum-based fuels and reduce tail pipe emissions. Different routes to convert methane into useful liquid hydrocarbons include (1) indirect methane conversion and (2) direct methane conversion. At present, commercial technologies are based on indirect route that consists of multistep reaction processes. These processes include five key steps: (i) air separation, (ii) gas processing, (iii) syngas production, (iv) conversion of syngas to a syncrude or oxygenate (FischerTropsch Synthesis) and (v) upgradation of syncrude by hydroprocessing to marketable products. Fig. 2 represents the flow sheet that illustrates the above five steps. Direct conversion of methane, the principal component in natural gas, to liquid fuels and chemicals of commercial importance has been the subject area of recent research and development activity throughout the world. The direct route of methane conversion is considered more energy efficient than the indirect route since it bypasses the energy intensive endothermic steam reforming step of syngas formation. Natural gas deposits (containing 6595% methane) located in the remote areas of India can be converted to liquid products on site using direct route and that would make transportation of these natural gas deposits much more economical and practical. The reviews on recent developments in syngas technologies through direct routes of methane conversion and status of both existing and future developments of GTL industry are presented below. 2. Syngas production technologies Syngas, the starting point for much of the organic chemical industry and for the production of liquid fuels, is derived from coal, natural gas or biomass. The estimate of the world's fuel reserves is as follows: petroleum 5775 Quads (Q), gas 5137 Q, coal 30,100 Q [2]. Levenspeil [3] and Heng and Idrus [4] reviewed the possibilities of using coal and natural gas as source of syngas for future motor fueling and gas-based petrochemicals. The preparation of syngas is the most capitalintensive part of a GTL-complex. It may account for in the order of 40% of the total investment (including air separation unit) in

a GTL-complex. Hence, there is a considerable incentive to optimize and further develop syngas production technologies for the purpose of cost reduction. The various syngas production technologies are partial oxidation (catalytic/non-catalytic), steam reforming, auto-thermal reforming, compound reforming and ceramic membrane reforming. Available processes for the production of syngas for GTL plants are based on steam reforming, partial oxidation or a combination of both. The most attractive and economical technology is considered to be oxygen blown auto-thermal reforming (ATR), which has been commercialized by Haldor Topse at a steam to carbon (S/C) ratio of 0.6 [5]. A GTL plant in Europe has been in commercial operation for more than 3 years, and another plant with a capacity of 17,000 bbl/d was commissioned in July 2004 in South Africa with excellent operating records. Other plants are close to start-up or in advanced stages of engineering and construction in Qatar and Nigeria. 2.1. Reforming reactions Out of the processes currently finding commercial applications, the most fruitful has been steam reforming of natural gas [6]. In this process, a multi-tubular reactor is filled with catalyst and heat is added from the exterior. CH4 H2 O CO 3H2 ; H 0 298K 205:92kJ=mol CH4 CO2 2CO 2H2 ; H 0 298K 247:32kJ=mol This process is extremely productive, but it poses a number of problems like extensive energy consumption, high H2/CO ratio of the syngas ranging from 3 to 5, and high construction costs. 2.2. Partial oxidation method In comparison to the steam reforming method, the reactor in the partial oxidation (POX) method is simple. A distinguishing characteristic of the partial oxidation method is that the energy consumption is low because the reaction is exothermic [7]. CH4 1=2O2 CO 2H2 ; H 0 298K 35:25kJ=mol Some drawbacks of POX are high outlet temperature (1500 C) from the reactor leading to high cost of the reactor materials and soot formation. 2.3. Auto-thermal reforming method In the auto-thermal reforming (ATR) method, the reactions of both partial oxidation and steam reforming are integrated into

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Fig. 1. Potential routes to clean liquid fuels based on the FischerTropsch synthesis (FTS) process. BTL: biomass to liquid; CTL: coal to liquid.

one reforming reactor. The advantage of this method is syngas of higher pressure is obtained than that by the steam reforming method. On the other hand, the drawbacks are that a large volume of CO2 is produced and the top of the combustion compartment reaches high temperatures close to 2000 C. Bakkerud [5] demonstrates that the ATR technology holds promises for further improvements, both as a stand-alone technology and in combination with Haldor Topse exchange reformer (HTER). These technologies will be the dominant, at least for the next 510 years. Among the radical technologies emerging, CO2-methane reforming (CMR) shows promising results. However, with substantial issues still to be solved, CMR is not considered as a real competitor to ATR or combinations of ATR/HTER within the next 10 years. 2.4. Compound reforming method The compound reforming method combines the steam reforming reactor with the auto-thermal reactor. A major feature of this method is that the early-stage steam reforming reaction and the late-stage automatic-thermal reforming reaction take place in separate devices. As a result, the advantage is that the low-pressure gas at the outlet of steam reforming reaction is transformed into high-pressure gas by means of auto-thermal reforming. The production cost is reduced because the compressor is not required. On the other hand, the requirement of two reactors increases the capital expenditure. 2.5. Catalytic partial oxidation (CPOX) and ceramic membrane reforming The concept of the process and the flow sheet of a GTLcomplex based on CPOX or ATR is similar. In CPOX, no burner

is used and all the chemical reactions take place in a catalytic bed membrane reactor. Recently, an elaborate pilot study on CPOX of methane to syngas in tubular membrane reactor made of Ba0.5Sr0.5Co0.5Fe0.5O3 was reported by Lu et al. [8]. They achieved 92% methane conversion, 90% CO selectivity with LiLaNiOx/-Al2O3 catalyst in the membrane reactor with 15.5 ml/cm2 minimum O2 permeation flux at a steady state and at a temperature of 1123 K and pressure of 5 atm. A syngas production rate of 79 ml/cm2 minimum was obtained. Further new developments of CPOX catalyst and membrane reactor are reported by Chowdhury et al. [9] and Hu et al. [10]. 2.6. Economic analysis and performance comparison of syngas technologies An evaluation of the economy of five types of synthetic gas production technologies has been presented in Table 2. It is clear that CPOX is the best technology based on the factors presented in Table 2. The evaluation was based on a comparison of economy in the production of 2500 tpd of methanol. On the other hand, the reactor performance of different technologies has been presented in Table 3 [11]. Here, the performance of POX is the best in terms of CO yield and H2 to CO ratio. 3. Direct conversion of methane into useful products The C-1 chemical industry has made remarkable progress in the 20th century and become an important branch of the petrochemical industry. The main achievements in this area are summarized into three phases: (i) syngas manufacturing processes from natural gas, (ii) liquid phase carbonylation technology of CH3OH and related catalyst systems and (iii) indirect conversion of C-1 raw materials to C2H4, C2H5OH,

Fig. 2. Main steps in the GTL process plant through indirect route.

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Table 2 Comparison of economy by reforming method Important factors NG consumption volume (GJ/t-MeoH) Oxygen consumption volume (m3/t-MeoH) CO2 emissions volume (103 t/y) Relative costs SMR 32 POX 31.56 530 380 100 375 95 ATR 30.6 460 355 8595 CR 30 280 290 8085 CPOX 2930 270300 250270 7080

using the acidic ion-exchange method. The conversion of methane and composition of liquid hydrocarbons formed over ZSM-5 and metal loaded ZSM-5 has been shown in Table 4. They concluded that Cu loaded HZSM-5 is a potential catalyst for the conversion of methane to liquid hydrocarbons. The existence of silanol groups gave positive impacts on the methane conversion and the successful production of gasoline from methane depends on the amount of aluminum present in the zeolite framework and the strength of Bronsted acid sites. 3.2. Synthesis of methanol, dimethyl ether (DME) and other oxygenates Methanol is a major chemical building block used today to manufacture formaldehyde, methyl-tertiary butyl ether (MTBE), acetic acid and a wide range of other chemical products. In the past decades, several reviews were published on direct conversion of methane into oxygenates [2128]. Recently a good review by Otsuka and Wang [29] appeared on this topic. Otsuka and Wang [29] highlighted the recent novel approaches to the partial oxidation of methane over both homogeneous and heterogeneous catalysts into useful oxygenates with an emphasis on the selective formation of methanol in the presence of H2. Methanol production processes are currently available under license from many companies including ICI, Haldor Topse, Lurgi, MW Kellogg, and Mitsubishi. DME production technology is available from Haldor Topse, Mitsubishi, Lurgi and Toyo Engineering. The processes for conversion of methanol to olefins (MTO) have been developed both by UOP and Norsk Hydro, and ExxonMobil. MTO was developed as a second step in a twostep process to convert low-cost natural gas to ethylene and propylene. DME and propylene produced from methanol will increase the value of natural gas considerably and will offer an exciting potential of growth and a high earning. Lurgi's MegaMethanol technology [30] brings down the net methanol production cost below US $50 per ton, wherever low-cost natural gas is available. This opens up a completely new field for downstream products like DME, propylene and synfuels. Based on simple fixed-bed reactor systems, conventional processing elements and operating conditions including commercially manufactured catalysts, Lurgi's MegaDME, MTP and MtSynfuels technologies provide attractive ways to monetise natural gas. The Topse DME process combines
Table 3 Performance comparison of syngas technologies CO, % yield 50 70 85 92 96 100 Ratio of H2 to CO SMR 0 3 0 0 0 0 ATR 0 0 2.4 0 0 0 POX 0 0 0 1.8 0 0 COPOX 0 0 0 0 1.9 0 GTL best 0 0 0 0 0 2.2

CH3COOH and liquid fuels via syngas. As a whole, the basis of the above achievements is the syngas manufacturing technology. Since the 1970s, the syngas manufacturing technology has also been developed with a greater pace, but it is still considered as a high investment as well as a high energy consuming process. In the following sections new processes based on catalytic route and their developments for the direct conversion of CH4 to liquid hydrocarbon have been discussed. 3.1. Methane to liquid hydrocarbons over ZSM-5 and metal loaded ZSM-5 Many researchers have studied the applicability of HZSM-5 and modified ZSM-5 zeolites to the conversion of methane to liquid hydrocarbons [1219]. But the results of their research are still confined to low conversion and selectivity. The direct partial oxidation of methane to liquid hydrocarbons was first reported by Han et al. [12,13]. However, methane conversion and liquid hydrocarbon selectivity were too low, and the major product was COx (CO and CO2). They concluded that only Cu, Ni, Zn and Ga-ZSM-5 catalysts could produce liquid hydrocarbons by methane oxidation if the methane or ethane dehydrogenation and olefin oxidation functions of the metals are in balance. Pak et al. [19] reported a reaction of methane with oxygen that led to a high liquid hydrocarbon yield (80%) using two reactors and a recycle system. Unfortunately, this process needed two reactors and many separators to separate the desired products from the diluted product streams. Hamid et al. [20] studied propane aromatization using modified ZSM-5 zeolites loaded with gallium prepared by the acidic ionexchange method. In their work, gallium was observed to be distributed on the catalyst surface, in the pores and more importantly gallium occupied the aluminum positions in the framework of ZSM-5. Eventually maximum activity and aromatics selectivity were observed for samples with the highest non-framework dispersed gallium species concentration, which was associated with zeoliteBronsted acidic sites as bifunctional dual sites. From the studies of Han et al. [12,13], metal HZSM-5 catalysts were found to be encouraging for conversion of methane to liquid hydrocarbon because of: (a) the oxidation of methane to methyl species, (b) the dehydrogenation of paraffin gas to olefin and the dehydrogenation of alicyclic liquid hydrocarbons to aromatic and (c) the oligomerization of ethylene and propylene to oligomers (C+5). Amin and Anggoro [21] used the ZSM-5 zeolite, which was modified by loading it with Cr and Cu from the first-row transition group and with Ga

SMR steam methane reforming; ATR auto-thermal reforming; POX: partial oxidation; COPOX: ConocoPhillips partial oxidation.

T. Reddy Keshav, S. Basu / Fuel Processing Technology 88 (2007) 493500 Table 4 The methane conversion and composition of liquid hydrocarbons over ZSM-5 and metal loaded ZSM-5 (basis: 200) Catalyst ZSM-5 Cr-ZSM-5 Cu-ZSM-5 Ga-ZSM-5 CH4 conversion 10.8 21.0 15.6 18.5 Gasoline range 72.4 70.5 80.2 70.1 n-paraffins 13.5 9.0 8.0 7.0 Iso-paraffins 22.3 23.0 20.0 17.0 Olefins 53.4 55.0 57.0 58.0 Aromatics 10.8 13.0 15.0 18.0

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C+ 11 range 27.6 29.5 19.8 26.9

the production of methanol from natural gas and the conversion into DME in a single plant, with an integrated synthesis section. The DME process includes the Topse auto-thermal reforming process followed by a proprietary synthesis design. The DME synthesis technology takes place in gas phase in fixed-bed reactors. Both the auto-thermal reformer technology and the DME synthesis technology accommodate very large single line capacities, and thus permit significantly large economy of scale. A single line capacity exceeding 7000 million tons per day (MTPD) DME is possible. A new process for DME synthesis is being developed by NKK Corp. using a slurry reactor recently. 3.3. Gas to ethylene (GTE) technology The GTE technology consists of a direct conversion of methane into ethylene and/or hydrogen. It has been conceived by a research team at Texas A&M University [31]. The process consists of two reaction steps and one separation step to produce ethylene. The process can operate economically with natural gas flow as low as 300 kSCMD up to any desired capacity. SynFuels International Inc. has licensed the technology to commercialize it, and the company has constructed a pilot plant capable of processing 3 kMCMD. The cost of a commercial 300 kSCMD plant should be in the US$5075 million range. The cost of the liquids should be about US $2528 per barrel. 4. Status of GTL developments The construction and operation of commercial and pilot/ demonstration scale plants has enhanced the level of GTL experience. Several companies have large-scale plant operating experience: (1) Exxon Mobil has experience due to both the New Zealand gas-to-gasoline plant, and its 200 barrels per day (bpd) Baton Rouge demonstration plant. (2) Sasol has very extensive and large-scale experience with several coal-based FTS processes. (3) Shell's experience is primarily due to its GTL plant in Bintulu, Malaysia. (4) Other companies such as BP, Syntroleum, Rentech and Conoco are in the process of acquiring experience with large-scale 70400 bpd pilot plants. Fleisch et al. [32] give a good summary about global commercialization activities indicating that today's operating and announced GTL projects represent about one million bpd capacity via FTS, of which 35,000 bpd is operating, and about 125,000 bpd for oxygenate production through conversion of ethylene. 4.1. Sasol (South Africa, 1955) The Sasol plant produces liquid fuel from syngas, which is derived from coal. Although syngas is not generated from

natural gas, commercialization of liquids from syngas using the FT technology is very relevant to the development of gas-toliquid technology. At both Sasolburg and Secunda, synthesis gas is produced from coal using Sasol/Lurgi fixed-bed dry bottom gasifiers. The production potential of the Sasol plant is around 135,000 bpd. Future GTL plants using Sasol FT technology would use auto-thermal reforming technology supplied by Haldor Topsoe. 4.2. Mossgas (South Africa, 1993) Mossgas (Pty.) Ltd., a South African government-owned company, has 13 years experience in converting offshore natural gas to GTL fuels. The process to produce the synthetic diesels consists of three basic steps: (i) production of syngas by steam reforming of natural gas; (ii) high temperature FTS to form an olefinic synthetic distillate, synthol light oil (SLO) from syngas; (iii) conversion of lighter olefinic gasses produced by the FTS process to the Mossgas conversion of olefins to distillate (COD) unit. Olefins are oligomerized over COD-9 catalyst to form quality distillates and gasoline components. The synthol light oil (SLO) and COD distillates once hydrotreated are distilled to produce quality diesel fuels. It produces a range of high quality sulphur-free and eco-friendly fuels in the largest GTL facility in the world. The production potential of the Mossgas plant is around 22,500 bpd. Liquid products are produced from syngas using FTS technology licensed from Sasol. Mossgas produces petrol, diesel, kerosene, liquid petroleum gas (LPG) and fuel oil, as well as a range of anhydrous alcohols. 4.3. Shell (Malaysia, 1993) Shell's state-of-the-art proprietary GTL process, the Shell Middle Distillate Synthesis (SMDS), is currently used in Shell's Bintulu plant in Malaysia. This is the world's first and only integrated low-temperature FischerTropsch GTL plant at a commercial scale. The three main process stages used in SMDS are syngas manufacture, FTS synthesis and hydrocracking, which are common to most gas-to-liquid technologies. The plant converts 100 million standard cubic feet per day (MMSCFD) of natural gas into 12,500 bpd of middle distillates (gasoil, kerosene, naphtha) and specialty products. The plant started operations in May 1993. In 1997, an explosion in the air separation unit damaged the plant. The plant was rebuilt and production restarted in mid-2000. Since then the plant has been operating at full capacity. Building on the experience of the lowtemperature FTS catalyst used at Bintulu, and further success in research work, Shell has developed a new second generation catalyst. When used in the Shell proprietary multi-tubular

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reactor, this catalyst yields more than 90% selectivity for desirable middle distillate products. Its activity is sufficient to provide a reactor capacity of around 9000 bpd, compared to the existing reactor capacity of 3000 bpd. The breakthrough in the low-temperature FTS catalyst used in the SMDS synthesis stage has markedly increased process productivity. This, coupled with the valuable experience gained from the operations and commercial-scale testing program at Bintulu, provided a sound basis to scale-up the SMDS technology from the current 12,500 to around 73,000 bpd. In October 2003, Shell signed a Heads of Agreement with Qatar Petroleum to build the world's largest GTL plant in Ras Laffan, Qatar, which will produce 140,000 bpd of products primarily naphtha and transport fuel. The project will be developed in two phases with the first phase operational in 2009 producing around 70,000 bpd of GTL followed by the second phase which will be completed two years later. This project provides further evidence of Shell's leadership in GTL technology and provides Qatar with an attractive alternative to commercialize their enormous gas reserves. 4.4. Syntroleum in Australia Syntroleum's GTL process has been under development since the 1980s. Syntroleum has developed highly active cobaltbased FTS catalysts to convert syngas produced from air fed auto-thermal reactor. The catalysts have been developed for a multi-tubular fixed-bed reactor and slurry reactor to be used in the Sweetwater GTL Project, Australia. The Sweetwater project is an 11,500 bpd plant that will employ the Syntroleum process to convert natural gas into ultra-clean, high performance, sulfurfree synthetic specialty products, such as lubricants, industrial fluids and paraffins, as well as synthetic transportation fuels. The plant will be located on the Burrup Peninsula in Western Australia. In summary at present, there are nine commercial GTL projects worldwide at various stages of planning and development for the period 2009 to 2015 that could bring to market an additional capacity of 580,000 bpd [33]. Six of the nine confirmed GTL projects are located in Qatar as joint ventures based on an integrated development and production sharing agreement (DPSA) with major international oil companies. By 2011, Qatar is set to produce about 394,000 barrels of GTL products per day, the equivalent of 68% of the total confirmed new capacity. A list of Qatar's GTL ventures [11] is shown in Table 5. Based on both the announced GTL plants and a
Table 5 GTL joint venture projects in Qatar Project ConocoPhillips ExxonMobil Marathon Oryx Pearl(Shell) QP/Sasol Chevron Total Initial capacity (bpd) 80,000 154,000 60,000 34,000 70,000 130,000 528,000 Start date Delay 2011 Delay 2005 2009 Delay Full capacity (bpd) 160,000 154,000 120,000 100,000 140,000 130,000 804,000

reasonable projected rate of plant construction, the total GTL production could reach 12 million bpd by 2015. 5. GTL challenges Erection of GTL plant to a commercial level is very complex and challenging in nature. There exist challenges at various levels that range from process design to construction of plant, product sales, licensing and performance guarantees. The commercial GTL process consists of five stages: (1) air separation, (2) gas cleaning, (3) syngas production, (4) FischerTropsch synthesis, and (5) hydrocracking. An excellent account of details about various technical challenges in all the individual units of GTL plant has been given by Brook [34]. To improve Capex, efficiency and reliability will involve various types of technical challenges, which are discussed below. Air separation unit (ASU) has been one of the key factors governing the single-train GTL plant capacity. Three major technical challenges associated with the ASU are sizes of the compressor, type and arrangement of compressor drivers and cooling arrangements. The largest available ASU capacity is currently around 3600 tpd. The current capacity of a single-train GTL plant is about 17,000 bpd consuming 3500 tpd of oxygen. The future single-train capacity with 5000 tpd oxygen would increase the GTL plant capacity around 25,00030,000 bpd. A 5000 tpd oxygen plant will require approximately 870,000 m3/h of air. The long term reliability of the ASU with this large compressors remains to be proven. The capacity has been limited by the size of the main air compressor and the limitations in design of the cold box/column. In a GTL application any large main air compressor would require shaft power between 70 and 90 MW. The selection of driver whether it is steam turbine, gas turbine electric motor, or a combination of both is challenging. The reliability of these machines especially on a single-train GTL plant is also a major hurdle to be overcome. It is possible to use electric motor drives but the current maximum size motor is limited to around 65 MW for a high speed motor. The other challenge is integration of internal utilities. The key high grade energy users in a GTL plant are natural gas reformer, oxygen/steam generator, product-workup fired heaters and recycle compressors. A large amount high grade energy is produced from high-pressure steam coming out of syngas heat recovery system and fuel gas from several sources. There is a possibility of a large-scale low grade energy generation from FTS synthesis. In syngas production technologies, currently the ATR fits best in terms of H2 to CO ratio and higher GTL train capacity. In ATR, reactants at high temperature will reduce the oxygen consumption and increase the reactor capacity. Similarly a further increase in capacity can be gained by reduction of steam to carbon (S:C) ratio. However high temperatures and lower S:C ratio lead to further challenges in burner and reactor design and in the selection of material for the downstream heat recovery equipment where metal dusting could be a problem. In catalytic partial oxidation using direct route catalyst, 100% thermodynamic conversion is possible, but the conversion must be stopped at the stage of catalytic partial oxidation of byproduct (H2/CO) prior to complete combustion.

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When sundry catalysts, including Pt, Rh, Ru, Ir, Ni/Al2O3, or (rare earths) 2Ru2O7, are used in fixed-bed reactor to carry out CPOX, the methane conversion rate exceeds 90%, and the H2 selectivity rate is reported at 94% to 99%. However, there exist challenges in the process of catalytic partial oxidation, like, removal of heat generated by reaction, curtailment of heat generation, avoidance of selective gas phase reaction, and control of conversion rate through equilibrium management. The capacity of a slurry bed reactor developed for higher GTL train capacity is currently around 17,000 bpd. Although the improved catalyst activity would lower the amount of catalyst/barrel and increase the reactor capacity, this would lead to high reaction intensity and would impact the hydrodynamics of the slurry regime in the reactor. The high reaction intensity would require improvement in the heat removal system. This would lead to higher flows and thus gas distribution, catalyst disengagement and product separation would pose newer challenges in reactor design. The slurry bed reactors used are large and further increase in reactors size may be limited by capabilities in fabrication, manufacturing and transportation logistics. The capacity of the hydroprocessing unit in the refinery industry is around 80,000 bpd, and designing and upgrading the facility for FischerTropsch product for the increase capacity of 25,00030,000 bpd should not be a major concern. Recovery and recycling of GTL-FTS catalysts (cobalt and precious metal) will become an important issue with the increase in production of GTL products. Except in the air separation step, all other steps in GTL process require catalysts. FTS requires solid-phase catalysts containing a large amount of cobalt catalyst and traces of platinum group metals (PGM) or rhenium (promoter). A GTL plant with 100,000 bpd employing 20% cobalt catalyst with 0.1% PGM or rhenium as promoter would require about 500 tons of cobalt and 2.5 tons of PGM or rhenium. At an annual production of more than 200 tons of platinum and palladium, the effect on the market of these metals would be minor. However, considering an annual production of just over 20 tons of ruthenium and 4550 tons of rhenium, the GTL processes may affect the market dynamics of these two metals. Recycling of the spent catalyst is not only required because of the value of the base and precious metals, but may become mandatory to provide a sound, environmentally friendly solution for the large amounts of spent catalysts involved. Brumby et al. [35] discussed in great detail and pointed out the importance of recycling of GTL catalyst and challenges related to it. 6. Conclusions In India, natural gas is currently a minor fuel in the overall energy mix, representing only 6.5% of total primary energy consumption. India is rapidly expanding its infrastructure to facilitate consumption and import of gas. Overall, India's gas consumption is projected to grow at an average annual rate of 5.1% from 0.9 tcf in 2002 to 2.8 tcf in 2025. The power sector is projected to account for 70% of the total incremental growth in India's natural gas demand from 2002 to 2025. To meet future

energy requirement, India has to exploit the 73% of unused gas reserves in north-eastern states using GTL technologies as it is a land-locked area. GTL is a well developed and proven technology and it is an important option for moving natural gas to the market place. GTL options include not only the wellknown production of FTS liquids but also the production of oxygen containing fuels, fuel additives and chemicals, such as methanol and DME. Different strategies to convert methane into various liquid fuels have been explored and also commercial GTL plants in operation and their future activities have been presented. The conversion to liquid products of commercial importance using direct route would make transportation of these natural deposits much more economical and practical. With the combination of higher ASU capacity and reduction in oxygen consumption, the syngas unit capacity between 25,000 and 30,000 bpd is possible. The slurry bed reactor capacity using cobalt-based catalyst is currently around 17,000 bpd. Future challenge is to increase the slurry bed reactor capacity to match the increase in ASU and the syngas unit capacities to 25 30,000 bpd. The requirements for utilities increase with the increase in train capacity and thus heat integration and heat removal from the syngas and FTS units become more complex and the design of the utilities become more challenging. Acknowledgements The authors acknowledge the infrastructural help provided by IIT Delhi. One of the authors, Tirupati Reddy Keshav, acknowledges the Governing Body of Gayatri Vidya Parishad College of Engineering, AP, India for granting sabbatical leave to IIT Delhi for the year 20052006. References
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