Than sch ang l vn ln ca ngnh nng lng (xem thm bi Than sch, STINFO s ny).

. Vo nm 1920 hai nh nghin cu ngi c l Franz Fischer v Hans Tropsch ti Vin Hong Wilhelm thc hin mt sng ch, tng hp nhin liu dng lng t than (c th c t g v nhiu loi nguyn liu sinh khi khc) vi nguyn l c bn l phng trnh phn ng ha hc sau: (2n+1)H2 + nCO = CnH2n+2 + nH2O vi cht xc tc da trn st v cobalt. V phi phn ng trn l nhin liu lng. Nhng tc cht ban u trong phn ng trn (CO v H2) c th sn xut c t vic nung than hay nguyn liu sinh khi theo phn ng: C + H2O = H2 +CO Vo thi im , d n trin khai phng php ny b ct vo ngn ko do gain thnh sn phm qu t so vi gi thnh du ha v vic t than trc tip cha lm cho con ngi kinh hi bi nhim. Tuy vy, loi nhiu liu lng ny tng c s dng nhng rt hn ch c trong Th chin th 2. Cui thp nin 1940, Cng ty Sasol c thnh lp di ci tn Cng ty Than v Du kh Nam Phi, vi mc ch p dng phng php Fischer-Tropsch gip Nam Phi c th t cung t cp nhin liu mc cao nht thng qua cc nh my kh ha than. Gia thp nin 1950, khi chnh sch phn bit chng tc khin cho nc ny ngy cng b c lp vi th gii, nh my kh ha than theo phng php FischerTropsch vi quy m thng mi u tin c khnh thnh ti Sasoburg. Gn 80 nm sau ngy c sng ch, nm 1999, nhin liu lng c t phng php Fischer-Tropsch c khng lc Hoa K mt ti trc tnh hnh gain due th tng v phi i mt vi nhng tnh ton: ring khng lc Hoa K ngn n 2,6 t gallon nhin liu my bay hng nm, tr gain 4,5 t USD, cn cc hng hng khng dn s Hoa K th tiu th mi ngy 53 triu gallon, nu nhn cho 365 ngy = 19 t 345 triu gallon, qu l mt con s khng l. Kt qu l vo ngy 27/9/2006, khng lc Hoa K ln u tin th nghim loi nhin liu tng hp ny trn mt pho i bay B-52, song ch 2/8 ng c m thi v vi t l pha 50-50 (nhin liu tng hp-xng). Kim nh mi trng, kt qu l gim 50% kh thi so vi trc y. Tip n, vo ngy 15/12/2006, khng lc Hoa K thng bo hon tt chuyn bay th nghim ca my bay B-52 vi tm ng c c s dng loi nhin liu mi: hn hp nhin liu tng hp theo phng php Fischer-

Tropsch. Hoa K c k hoch nghin cu hon thin cng ngh sn xut ln loi nhin liu ny nhm n mc tiu nm 2025: dng k thut cng ngh thay th hn 75% lng due m nhp khu t Trung ng. Nhp chut vo tm kim trn trang Google vi t kha Fischer-Tropsch, c rt nhiu ti liu hin ra. l nhng ti liu v phng php FischerTropsch c ng dng hoc ang c nghin cu tip tc m rng ng dng ti nhiu nc nh c, Trung Quc, n , Philipine, v ch vi phng php Fischer-Tropsch c t gn 100 nm trc, rt nhiu nc vch ra con ng gii quyt vn ln hin nay: khng hong nng lng v nn nhim mi trng ton cu. Th mi thy con ng i vo cuc sng tht thnh thang cho nhng sng to ch thc. Fischer-Tropsch diesel The Fischer-Tropsch process is one of the advanced biofuel conversion technologies that comprise gasification of biomass feedstocks, cleaning and conditioning of the produced synthesis gas, and subsequent synthesis to liquid (or gaseous) biofuels. The Fischer-Tropsch process has been known since the 1920s in Germany, but in the past it was mainly used for the production of liquid fuels from coal or natural gas. However, the process using biomass as feedstock is still under development. Any type of biomass can be used as a feedstock, including woody and grassy materials and agricultural and forestry residues. The biomass is gasified to produce synthesis gas, which is a mixture of carbon monoxide (CO) and hydrogen (H2). Prior to synthesis, this gas can be conditioned using the water gas shift to achieve the required H2/CO ratio for the synthesis. The liquids produced from the syngas, which comprise various hydrocarbon fractions, are very clean (sulphur free) straight-chain hydrocarbons, and can be converted further to automotive fuels. Fischer-Tropsch diesel can be produced directly, but a higher yield is achieved if first Fischer-Tropsch wax is produced, followed by hydrocracking. Fischer-Tropsch diesel is similar to fossil diesel with regard to a.o. its energy content, density and viscosity and it can be blended with fossil diesel in any proportion without the need for engine or infrastructure modifications. Regarding some fuel characteristics, Fischer-Tropsch diesel is even more favourable, i.e. a higher cetane number (better auto-ignition qualities) and lower aromatic content, which results in lower NOx and particle emissions. For the production of Fischer-Tropsch diesel the main technological challenges are in the production of the synthesis gas (entrained flow gasifier). These barriers also apply to other gasification-derived biofuels, i.e. bio-methanol, bio-DME and

biohydrogen. The synthesis gas is produced by a high-temperature gasification, which is already used for coal gasification. Biomass has different properties than coal and, therefore, several process changes are necessary. First, the biomass pretreatment and feeding need a different process, because milling biomass to small particles is too energy-intensive. Moreover, small biomass particles can also aggregate and plug feeding lines. Pretreatment processes like torrefaction or pyrolysis (which produces a liquid oil) could be developed to overcome these problems. Second, due to the higher reactivity of biomass (compared to coal) the gasification temperature might be decreased, resulting in higher efficiencies, but this will require different gasification and burner design. Third, the ash composition in biomass is different from that in coal, which results in different ash and slag behaviour, which is an important factor in the gasifier and still needs to be studied thoroughly. This ash and slag behaviour is also important for the cooling of the syngas, for which innovative development is desired. Other research topics are the cleaning and conditioning of synthesis gas, development of several types of catalysts, and the utilisation of by-products such as electricity, heat and steam. In Germany, a pilot production facility for Fischer-Tropsch liquids from biomass is currently in operation. Technical Note: Fischer-Tropsch Process The Fischer-Tropsch process often comes up in the discussion of new technologies for producing liquid fuels from solids or gases. The Fischer-Tropsch process produces high value, clean-burning fuels. FT fuels can be used in conventional engines with no modification and have improved combustion which reduces emissions, but may have a lower fuel economy. The resulting fuels are colorless, odorless and low in toxicity. FT fuels have less sulfur, nitrogen oxide, carbon monoxide and particulate matter emissions than petroleum fuels. The Fischer-Tropsch (FT) process was first developed in Germany in the 1920's. It was used in Germany during WWII and was brought to prominence by Sasol in South Africa to produce oil and gasoline from coal, referred to as coal to liquids (CTL), when they were boycotted during apartheid and where it is still used. Exxon, Rentech, Sasol and Shell offer commercial processes. Shell has a commercial plant in operation converting natural gas to diesel fuel, referred to as gas to liquids (GTL), and several smaller plants are in operation. The FT process requires a feed stream consisting largely of carbon monoxide and hydrogen. Thus gasification is the first step of coal liquefication or production of Fischer-Tropsch fuels from biomass such as corn stover (corn stalks), wood or

switch grass. The feed gas, referred to as syngas, is produced in a gasifier by heating the gas to a temperatures greater than than 700oC. Bycarefully controlling the oxygen content the hydrocarbons in the feedstock are broken down to carbon monoxide and hydrogen. The Fischer-Tropsch process converts the feed gas into liquid organic compounds, carbon dioxide and water. The conversion takes place in the presence of a catalyst, usually iron or cobalt. The temperature, pressure and catalyst determine whether a light or heavy syncrude is produced. For example at 330C mostly gasoline and olefins are produced whereas at 180 to 250C mostly diesel and waxes are produced. Each company has proprietary FT technology, but a common theme is that most use a slurry-phase reactor with a cobalt-based catalyst. Exceptions are Shell and BP, whose processes use a fixed-bed reactor, and Rentech, Inc. (Denver, CO; www.rentechinc.com), which uses an iron-based catalyst. Most companies use autothermal reforming (ATR) rather than steam reforming because it is less expensive, especially when scaled up. "When you double the capacity of a steam reformer, you need double the number of tubes, so you pay about twice the price," The partial oxidation route of reforming provides the desired 2:1 ratio and is the preferred route in without consideration of other needs. There are two routes: one uses oxygen and produces a purer syngas without nitrogen; the other uses air creating a more dilute syngas. However, the oxygen route requires an air separation plant that increases the cost of the investment. Steam reforming is carried out in a fired heater with catalyst-filled tubes that produces a syngas with at least a 5:1 hydrogen to carbon monoxide ratio. To adjust the ratio, hydrogen can be removed by a membrane or pressure swing adsorption system. Helping economics is if the surplus hydrogen is used in a petroleum refinery or for the manufacture of ammonia in an adjoining plant. There are mainly two types of F-T reactors. The vertical fixed tube type has the catalyst in tubes that are cooled externally by pressurised boiling water. For a large plant, several reactors in parallel may be used presenting energy savings. The other process uses a slurry reactor in which pre-heated synthesis gas is fed to the bottom of the reactor and distributed into the slurry consisting of liquid wax and catalyst particles. As the gas bubbles upwards through the slurry, it is diffused and converted into more wax by the F-T reaction. The heat generated is removed through the reactor's cooling coils where steam is generated for use in the process. The resulting organic compounds are a synthetic form of petroleum, analogous to a crude oil, and can be converted into many petroleum products including diesel and

gasoline. Alternatively hydrogen can be recovered by further processing, resulting in only carbon dioxide and hydrogen with no hydrocarbons in the product stream. The primary interest at the present time is to produce low sulfur diesel fuel. Production of diesel fuel requires little processing from the FT crude, has low sulfur and aromatic content, high cetane number and and it burns exceptionally clean in a diesel engine. The process is known for high capital cost and high operating and maintenance costs. Recent refinements in the process by the commercial suppliers and government research have improved the process and reduced these costs. It becomes practical when "green" transportation fuels are desired and/or when petroleum fuels become high priced. With current prices of gasoline and diesel, FT fuels are competitive, Hirsch, P43, when produced on a large scale. Updated to include more details 6/20/05

5 Things You Need to Know About The Fischer-Tropsch Process by Bill Siuru 07/03/2008 Why Fischer-Tropsch Synthetic Fuel? Synthetic fuels represent an interesting alternative to petroleum, which can sometimes be in short supply and, as is the case today, also quite expensive. One of the most high-profile ways to create synthetic fuel is through what's known as the Fischer-Tropsch (F-T) process. It was invented in the 1920s by Franz Fischer and Hans Tropsch, scientists at Kaiser Wilhelm Institute. The F-T process was initially used to help solve Germany's need for fuel in the midst of a petroleum shortage by converting coal, which was abundant in Germany, into synthetic fuels. Both Germany and Japan used this ersatz fuel during World War II. By 1944, Germany was producing 124,000 barrels of synthetic fuels daily at 25 F-T plants. After the war, research was continued in the U.S. by German scientists as part of Operation Paperclip. During South Africa's economic isolation because of Apartheid, Sasol used the process to meet the country's energy needs using both natural gas and coal as feedstocks.

How the F-T Process Produces Fuel The Fischer-Tropsch process converts carbon monoxide and hydrogen, called synthesis gas or syngas, into liquid hydrocarbon fuels like synthetic diesel and jet fuel. Prior to the T-F process, the coal, gas, or biomass is gasified to produce this syngas using intense heat and pressure, turning these feedstocks into hydrogen and carbon monoxide. Synthetic fuels burn cleanly so they offer improved environmental performance along with addressing energy diversity.

Many Raw Materials can be Used Some of the more promising applications for the F-T process include coal-to-liquid (CTL), gas-to-liquid (GTL), and bio-to-liquid (BTL) technologies. The latter would mean a less carbon-intensive alternative that could not only use agricultural feedstocks but also waste biomass materials.

Alternatives Become Attractive as Fuel Prices Climb While the Fischer-Tropsch process is a well proven technology, it requires a large capital investment in equipment followed by high operation and maintenance costs. Also, the gasification to create carbon monoxide and hydrogen is very energy intensive. However, as petroleum prices spiral upward, making synfuels from coal, natural gas, and biomass become more economically competitive. Along with advanced energy companies focusing exclusively on alternative fuels, many oil companies also have dedicated synthetic fuel development programs in place. Shown here is traditional diesel (left) and clean F-T diesel produced by Shell.

Diverse Use of Synthetic Fuels Audi has used Shell's GTL diesel in the R10 TDI Le Mans racers for the past two seasons. In fact, many automakers have explored using synthetic GTL fuels in their

quest to decrease future environmental impact. Since jet fuel and diesel are both kerosene based and quite similar, GTL fuel can also be used in civilian and military aircraft. For example, the USAF has already flown a B-52H bomber and C-17 Globemaster III transport on a 50-50 blend of JP-8 jet fuel and F-T fuel produced in a natural gas-to-liquid process by Syntroleum. The USAF intends to certify every one of its aircraft models for the fuel by 2011. This is a major step in the U.S. military's goal of obtaining about half of its aviation fuel from alternative sources by 2016 to reduce its dependence on foreign-sourced crude oil. Bill Siuru is a retired USAF colonel who has been writing about automotive technology for nearly 40 years. He has a bachelor's degree in automotive engineering, a PhD in mechanical engineering and has taught engineering at West Point and the U.S. Air Force Academy.

Catalysis in the Refining of FischerTropsch Syncrude

By Arno de Klerk (University of Alberta, Edmonton, Alberta, Canada) and Edward Furimsky (IMAF Group, Ontario, Ottawa, Canada), RSC Catalysis Series, No. 4, Royal Society of Chemistry, Cambridge, UK, 2010, 294 pages, ISBN: 978-184973-080-8, 121.99, US$205.00, 139.95 (Print version); e-ISBN: 978-184973-201-7 (Online version)
Reviewed by Stewart Brown Johnson Matthey Precious Metals Marketing, Orchard Road, Royston, Hertfordshire SG8 5HE, UK
Email: stewart.brown@matthey.com

Platinum Metals Rev.,

2011, 55, (4), 263

doi: 10.1595/147106711x593717

Download Article View References View Reviewer Profiles

Introduction

Catalysis in the Refining of Fischer-Tropsch Syncrude is the fourth book in the Royal Society of Chemistry's Catalysis Series. Written by Arno de Klerk and Edward Furimsky from the University of Alberta and the IMAF group in Ontario, Canada, respectively, this book provides a review of the somewhat neglected area of refining and upgrading catalysts, rather than the more widely published area of Fischer-Tropsch synthesis itself (1). This book provides an excellent and comprehensive evaluation of the catalytic processes for syncrude conversion to useful products such as fuel and oils. The book consists of eleven chapters, which are well presented and divided into easily manageable segments. The writing style is very clear and explains the processes concisely and simply. The first two short chapters put syncrude refining into context within the Fischer-Tropsch process as a whole and allow non-specialists to quickly grasp the technology. The remaining chapters take the reader on a logical and well thought out journey through the Fischer-Tropsch production of syncrude; the upgrading of waxes, oxygenates and crude; the catalysis of the refining process; the commercial products obtained during the process; and finally a review of the current patent literature and future perspectives.

Fischer-Tropsch Processes

Fischer-Tropsch is the process whereby synthesis gas (hydrogen and carbon monoxide) is converted into a mixture of hydrocarbons, oxygenates, water and carbon dioxide. The hydrocarbons thus produced can be refined and used in place of more conventional liquid fuels derived from crude oil. Synthetic fuel can be produced by a variety of methods, with gas-to-liquid (GTL), coal-to-liquid (CTL) and biomass-to-liquid (BTL) being the most widespread. An outline of a Fischer-Tropsch facility is summarised in Figure 1.

Fig. 1.

A simplified flow diagram of a Fischer-Tropsch-based facility (some liquid pyrolysis products may be produced, represented by the dashed line) (Reproduced by permission of The Royal Society of Chemistry)

Fischer-Tropsch synthesis has been carried out predominantly using iron- and cobalt-based catalysts since the 1930s, having been commercialised in Germany in 1936 to provide transport fuel for the coal rich, oil poor nation. South Africa has since become the largest user of Fischer-Tropsch technology, developed in response to international sanctions that prevented the import of crude oil, and nearly the entire country's diesel is currently produced from coal by this method ( 2). In the present book, Chapters 3 and 4 provide a good technical overview of and background to the chemistry of Fischer-Tropsch reactions. These chapters concentrate on how different reaction and catalyst conditions affect the composition of the syncrude (Figure 2). Chapter 3 concludes with an examination of current industrial Fischer-Tropsch processes. The message is that this area of chemistry is not just an academic pursuit, but rather a key technology for future energy security and fuel production. The table of production facilities provides a timeline from the first facilities employed by Germany during the Second World War right up to the gigantic Shell Pearl GTL plant in Qatar. This plant began shipments of its GTL Gasoil product in 2011 with full production scheduled for 2012. In Chapter 4, the reader is taken in more detail through the initial processing steps of Fischer-Tropsch synthesis and how the syncrude produced differs from that obtained from conventional crude oil. The differences in chemical composition are vital in understanding which downstream refining and upgrading processes are required to produce useful commercial products.

Fig. 2.

Fischer-Tropsch reactor technologies in industrial applications (Reproduced by permission of The Royal Society of Chemistry)

Platinum Group Metals in the Upgrading of Fischer-Tropsch Syncrude

Chapter 5 is where the main topic of the book really gets going, it is by far the largest chapter in the whole book with over 120 pages devoted to it. Here the reader is provided with a review of the technical detail behind the catalysis of upgrading Fischer-Tropsch syncrude. The chapter is split into four main sections corresponding to the most widely utilised conversion technologies. These are: a. b. c. d. oligomerisation, isomerisation and hydroisomerisation, cracking and hydrocracking, hydrotreating.

Although this chapter contains the most significant amount of information, it only concerns the upgrading of syncrude rather than the refining. Catalytic reforming, which is an important platinum group metal (pgm) utilising process in refineries, is mentioned in a later chapter. In terms of pgm usage, all but the oligomerisation section contain numerous references to pgm-catalysed processes. The subsections proceed in a logical fashion, describing first the background and mechanism of each process, then the various catalysts used. The use of platinum and palladium as promoters in various zeolite, silica-alumina, phosphate and sulfonated zirconia catalysts is given considerable coverage, well illustrated by graphs and tables detailing conversion, yield and selectivity relationships with various feedstocks. The catalytic mechanisms detailed throughout this book are very clear, giving the reader an understanding of the chemistry behind the refining and upgrading processes. The vast range of different temperatures, pressures, feeds, catalysts and other factors are emphasised, giving a good feel for the complexity of syncrude upgrading. The authors compare and contrast these different factors and clearly show the effect of each on the final products. Each section gives a solid introduction and mechanistic outline to each process, followed by an examination of the commercial aspects and a comprehensive review of the current literature regarding catalyst developments. They conclude with a comparison of the various modes of deactivation for different catalysts and conditions. This is an area often neglected when concentrating on activity, yields and selectivity.

Refining Catalysts

Chapter 8, despite being somewhat shorter than Chapter 5, nevertheless contains an excellent review of refining catalysts, such as those employed in reforming, a significant area of pgm demand. The first part of the chapter demonstrates the differences between conventional oil refineries and those employing Fischer-Tropsch technology. The generic plant designs illustrated at the beginning of the chapter highlight the major differences in how the various refined fractions are produced and again drives home the message that to produce high quality fuels and oils using Fischer-Tropsch synthesis requires specialised equipment, processes and catalysts to deal with the different chemistries of syncrude and conventional crude oil. The first table in Chapter 8 highlights this further by examining the current conventional conversion processes and their compatibility with Fischer-Tropsch refineries. There are two subsections dedicated to the use of platinum on acidic alumina and on non-acidic zeolite respectively, highlighting the importance of platinum for the production of synthetic fuels. The higher amounts of oxygenates in Fischer-Tropsch feed have been shown to deactivate the acidic support, although it is very compatible with the non-acidic L-zeolite catalyst (Figure 3). The much lower sulfur content of the feed is a distinct advantage over conventional crude feedstocks.

Fig. 3.

End-on adsorption of n-alkanes on platinum/L-zeolite which results in 1,6-ring closure and aromatisation (Reproduced by permission of The Royal Society of Chemistry)

The final chapters examine the commercial products obtained from Fischer-Tropsch syncrude, the current patent literature and future perspectives in this technology. The authors do a very good job of putting the catalysis reviewed in the preceding chapters into a commercial context, whilst showing what the future may hold for this exciting area. The final chapter makes the interesting point that Fischer-Tropsch plants have historically been built to deal with issues of energy security. Going forward it appears that investment will be driven by both the requirement to produce fuels from alternative carbon sources and the price differential between conventional crude and that produced by Fischer-Tropsch technology.

Conclusions

The authors state that a review of catalysis in the refining of Fischer-Tropsch syncrude is the main objective of the book. This objective has been achieved admirably, providing an accessible and comprehensive review of Fischer-Tropsch refining catalysis from the fundamental chemistry to the commercial aspects and applications. The reader is required to have a general understanding of chemistry and catalysis, and the book will appeal both to those looking to gain initial exposure to this topic, and to readers with greater knowledge of the subject. The use of the pgms features strongly throughout the book, dominating the chapters on upgrading and refining syncrude. Overall, this book will be of interest to a wide audience, from those involved in the academic pursuit of improving the catalysis to those involved with the commercial development of Fischer-Tropsch refining. It is clearly an exciting area to be involved with and the potential to provide an alternative to conventional fuel sources is something that the authors convey particularly well.

Catalysis in the Refining of Fischer-Tropsch Syncrude LINK http://dx.doi.org/10.1039/9781849732017