Review pubs.acs.

org/CR

Advances in Coal Gasication, Hydrogenation, and Gas Treating for the Production of Chemicals and Fuels
Christopher Higman*, and Samuel Tam

Higman Consulting GmbH, 65824 Schwalbach, Germany Advanced Energy Systems Division, Oce of Fossil Energy, U.S. Department of Energy, Washington, D.C. 20585, United States
3.7.2. Hydrogasication 3.7.3. Chemical Looping 3.7.4. Other 4. Gas Treating 4.1. Desulfurization 4.1.1. Zinc 4.1.2. Iron 4.1.3. Calcium 4.1.4. Other Sorbents 4.1.5. COS Hydrolysis and Removal 4.2. Trace Element Removal 4.2.1. Mercury 4.2.2. Arsenic and Selenium 4.3. Water Gas Shift (WGS) 4.3.1. Alternative Catalysts 4.3.2. Reactors 4.4. HydrogenCarbon Dioxide Separation 4.4.1. CO2 Sorbents 4.4.2. Hydrogen Membranes 5. Chemicals from Syngas 5.1. Ammonia 5.2. Hydrogen 5.3. Methanol and Derivatives 5.3.1. Methanol Derivatives 5.4. Ethanol 5.5. Oxo Alcohols 5.6. Monoethylene Glycol (MEG) 5.7. Substitute Natural Gas (SNG) 5.8. Liqueed Petroleum Gas (LPG) 5.9. FischerTropsch Synthesis 5.10. Direct Reduced Iron (DRI) 6. Chemicals from Pyrolysis Byproducts of Gasication 7. Direct Hydrogenation to Liquids 7.1. Process Description 7.2. Commercial Plant 7.3. Research and Development (R&D) Activities 8. Conclusions Author Information Corresponding Author Notes Biographies Acknowledgments Abbreviations and Acronyms 1690 1690 1690 1690 1691 1692 1692 1692 1692 1692 1693 1693 1693 1693 1694 1694 1694 1694 1694 1694 1695 1695 1695 1695 1696 1696 1696 1696 1697 1697 1697 1697 1697 1698 1698 1698 1699 1699 1699 1699 1699 1700 1700

CONTENTS
1. Introduction 2. Background to Gasication 2.1. Chemistry and Thermodynamics 2.2. Process Realization 2.2.1. Operating Temperature 2.2.2. Bed Type 3. Gasication Research and Development 3.1. Coal Properties Relevant to Gasication 3.1.1. Reactivity of Coal and Other Chars 3.1.2. Behavior of Mineral Matter 3.2. Coal Preparation and Feeding 3.2.1. Fines Reduction in Crushing Facilities 3.2.2. Slurry Feeding Systems 3.2.3. Dry Feeding Systems 3.2.4. Dry Solids Pumps 3.2.5. Cogasication of Alternative Feedstocks 3.3. Gasication Reactors 3.3.1. Fixed Bed Gasiers 3.3.2. Fluid Bed Gasiers 3.3.3. Entrained Flow Gasiers 3.3.4. Reactor Containment 3.3.5. Two-Stage Gasication 3.3.6. Other Issues 3.4. Contaminant Species in Raw Syngas 3.4.1. Nitrogen Species 3.4.2. Alkali Metals 3.4.3. Trace Elements 3.5. Syngas Coolers 3.5.1. Radiant Coolers 3.5.2. Quench Systems 3.6. Primary Gas Cleaning 3.6.1. Solids Removal from Raw Syngas 3.7. Alternative Congurations 3.7.1. Catalytic Gasication
2013 American Chemical Society

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Special Issue: 2014 Chemicals from Coal, Alkynes, and Biofuels Received: April 6, 2013 Published: October 21, 2013
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Nomenclature References 1700 1700

Review

1. INTRODUCTION World ammonia production in 2010 is reported to be 159 million tons per annum,1 of which Chinese coal-based production is estimated to be 39 million tons.2 This amounts to about 25% of total worldwide production. A similar situation obtains for methanol. Global capacity is reported as 69 million tons per annum,3 of which coal-based capacity, again mostly in China, is estimated as 27 million tons or about 39% of the world total. While much of this methanol is further processed to conventional methanol derivatives such as formaldehyde, solvents, methyl tert-butyl ether (MTBE), and acetyls, other markets have opened up in recent years. Newer methanol derivatives include dimethyl ether (DME), gasoline via the ExxonMobil MTG (methanol to gasoline) and similar processes, and olens. Other chemicals being manufactured on an industrial scale from coal-derived synthesis gas (H2 + CO or syngas) include oxo alcohols, monoethylene glycol (MEG), substitute natural gas (SNG), and FischerTropsch liquids. It is almost exactly 100 years since the start-up of Carl Boschs rst industrial synthetic ammonia plant in Oppau, Germany, on Sept 9, 1913.4 The hydrogen for this plant was produced from coal using the water gas process. The capacity was 30 metric tons per day (t/d), modest compared with the 3300 t/d units being oered today. However, this was not the beginning of chemicals from coal gasication. In 1910 Kietaible5 discussed the manufacture of both hydrogen and formic acid from generator gas or water gas. At the time, the development of airships was seen as a mass market for coalbased hydrogen production. Formic acid was used as an intermediate for synthetic dyestus and oxalic acid. Coal tar based chemistry is even older, but it is not the subject of this review. Chemicals production from syngas, whether generated by coal gasication or steam reforming of natural gas, is a major and largely mature industrial activity with a broad range of commercial licensors. Much research and development takes place in the commercial laboratories of such companies and is therefore not accessible in the same manner as academic research. Nonetheless the results of this work become visible through the patent literature and with each further improvement in the industrial processes. Coal gasication is but one means of generating synthesis gas. The synthesis of chemicals from syngas is largely independent of the source of the syngas, so that most developments applicable to syngas from steam reforming of natural gas are applicable to syngas generated from coal gasication. This review will therefore focus on advances in gasication and associated gas treatment technology with only brief mention being made of the chemicals that can be manufactured from the treated syngas. Synthetic fuels have been included in the denition of chemicals, so brief mention is also made of FischerTropsch synthesis. Direct hydrogenation of coal is however discussed in more detail. Coal gasication is used in the power industry in the integrated gasication combined cycle (IGCC) conguration, but this cannot be considered as part of the chemical industry and is therefore not discussed. The demands placed particularly on gas treatment are dierent, but many of the techniques described here will nd their way into advanced IGCCs,
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particularly those incorporating carbon capture. Scho et al. have reviewed the research and development needs for IGCC, and the reader is referred to that source for further detail.6 Although many of the techniques used for coal gasication have their analogues in biomass gasication, the dierences, both in the combustible material and in the associated mineral matter, call in many cases for dierent solutions in detail. Therefore, while this review will occasionally mention biomass gasication as a starting point for chemicals manufacture, e.g., under the heading of cogasication, there is no attempt to cover the topic in a comprehensive manner. As referred to above, the coals-to-chemicals industry is an established and mature industry. It will therefore be an aim of this review to look at potential advances in this light, examining the status quo of industrial practice and identifying what improvements are needed or could be useful and relating work performed in the past ve years to those needs.

2. BACKGROUND TO GASIFICATION Gasication can be described as the conversion of any carbonaceous feedstock into a gaseous product with a useful chemical heating value.7 Initially the focus was on devolatilization and pyrolysis since the 19th century town gas market was mainly for lighting, where a high hydrocarbon content was of benet. For modern chemical synthesis applications a heavy hydrocarbon free gas mainly consisting of hydrogen and carbon monoxide is desired, so the emphasis is on the partial oxidation reactions.
2.1. Chemistry and Thermodynamics

The principle reactions which take place during the gasication of pure carbon are those involving carbon, oxygen, and hydrogen and in particular their compounds carbon monoxide, carbon dioxide, water (or steam), and methane. Simplifying coal to pure carbon, the most important reactions are partial oxidation:
C + 1 2 O2 CO
0 H298K = 111 MJ/kmol

(1)

CO oxidation:
CO + 1 2 O2 CO2
0 H298K = 283 MJ/kmol

(2)

water gas reaction:

C + H 2O(g) CO + H 2
0 H298K = +131 MJ/kmol

(3)

and Boudouard reaction:

C + CO2 2CO
0 H298K = + 172 MJ/kmol

(4)

In gasication processes the reactions involving free oxygen are essentially complete. The carbon conversion is usually 95% or higher, whereby the failure to reach 100% conversion is due to nonthermodynamic eects. At the high temperatures at which most processes operate, the reactions reach close to equilibrium and the nal gas composition is determined by the CO shift reaction:
CO + H 2O(g) CO2 + H 2
0 H298K = 41 MJ/kmol

(5)

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Review

Figure 1. Sequence of reactions in coal gasication. [Adapted with permission from Reimert, R. and Schaub, G. Gas Production. In Ullmanns Encyclopedia of Industrial Chemistry, 5th ed.; VCH: Weinheim, Germany, 1989; Vol. A12, p 215. Copyright 1989 Wiley-VCH.]

Table 1. Characteristics of Dierent Categories of Gasication Process [Adapted with Permission from ref 7. Copyright 2003 Elsevier.]
category ash conditions typical processes feed characteristics size acceptability of nes acceptability of caking coal preferred coal rank operating characteristics outlet gas temperature oxidant demand steam demand other characteristics dry ash Lurgi, SEDIN moving bed slagging BGL uid bed dry ash Winkler, HTW, CFB, TRIG agglomerating KRW, U-Gas, AFB entrained ow slagging Shell, GEE, E-Gas, Siemens, KT, and others; see Table2 <200 m unlimited yes

1/42 in. limited yes (with stirrer)

1/42 in. better than dry ash yes (with stirrer)

1/41/2 in. good possibly

1/41/2 in. better yes

any

any

low

any

any (dry feed); high (slurry feed)

low (450650 C) low high hydrocarbons in gas

low (450650 C) low low hydrocarbons in gas

moderate (9001050 C) moderate moderate lower carbon conversion

moderate (9001050 C) moderate moderate lower carbon conversion

high (12501600 C) high low pure gas, high carbon conversion

and the steam methane reforming reaction:

CH4 + H 2O(g) CO + 3H 2
0 H298K = +206 MJ/kmol

(6)

Coal is of course much more complex than pure carbon. The accepted sequence of events in coal gasication can be summarized as in Figure 1. In an initial pyrolysis phase, volatiles are driven o from the coal. Vapor phase reactions proceed quickly. The heterogeneous char gasication is the determining factor in the overall reaction kinetics. Temperatures of gasication reactors are typically suciently high that methane is usually the only hydrocarbon present in any appreciable quantity. It is however possible that pyrolysis products survive and are contained in the synthesis gas, particularly in counterow moving bed reactors. The pressure and temperature of the gasier have an inuence on the gas composition. The contents of CH4 and CO2 in the synthesis gas increase with increasing pressure. As the gasication temperature increases, the methane content drops and the H2/CO ratio shifts toward increasing CO. Typical industrial gasication processes today operate in the range 2580 bar depending on application. At these pressures, temperatures of above 1250 C are required in order to produce a synthesis gas with a low (<0.5 mol %) methane content. While an increased methane content is benecial for, e.g., substitute natural gas (SNG) production, it would be counterproductive for synthesis of other chemicals such as ammonia or methanol, where methane is an inert. Nonetheless,
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even low temperature uid bed processes operating around 950 C generate suciently little methane that, where considerations determined by the quality of the coal to be gasied indicate their use, they are used. Many chemical synthesis processes such as those for methanol and ammonia are conducted at high pressures80 to 100 bar or higher. For such applications it is advantageous to perform the gasication at high pressure, since this will reduce the compression energy requirement of the overall integrated process.
2.2. Process Realization

In the practical realization of gasication processes a broad range of reactor types has been and continues to be used. The most important dierentiating characteristics are discussed in sections 2.2.1 and 2.2.2. 2.2.1. Operating Temperature. Operating temperature, i.e., whether to apply a slagging or nonslagging operation, is fundamental to the design concept of a gasication system. In many cases the temperature is dictated by the bed type. Entrained ow gasiers all operate at slagging temperatures; uid bed gasiers operate in the nonslagging mode. However, the moving bed oers a choice between, e.g., the Lurgi dry bottom gasier and the BGL slagging gasier. For slagging gasiers the temperature must be high enough that the slag is a free-owing liquid, which can be extracted through a slag tap at the bottom of the gasier. For nonslagging gasiers the temperature must be suciently lower than the ash softening temperature that sintering and agglomeration into larger
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Chemical Reviews particles are avoided. In between these two temperature regimes is an eective no-go zone in which sticky ash will create operating problems in any system. 2.2.2. Bed Type. As described by this author elsewhere,8 Gasication reactors are generally classied according to bed type as listed in Table 1 and portrayed in Figure 2:9 moving bed

Review

Figure 2. The three major types of gasier. [Reprinted with permission from ref 9. Copyright 1993 EPRI.]

gasiers, uid bed gasiers, and entrained ow gasiers. Only a few gasiers fall outside this classication. Further details of the classication system are provided below.8 Moving bed gasiers (also called xed bed gasiers...) are characterized by a bed, in which the coal moves slowly downward under gravity as it is gasied by a blast or oxidant, which generally, but not universally, moves countercurrent to the coal. In such a countercurrent arrangement, the hot synthesis gas from the gasication zone is used to preheat and pyrolyze the downward owing coal. [This arrangement reduces the oxygen consumption,] but pyrolysis products as well as moisture brought into the reactor with the coal are present in the product synthesis gas. [Depending on coal quality and other circumstances, the methane content of the dry syngas can be anything between 5 and 15 mol %.] The outlet temperature of the synthesis gas is generally low, even if higher temperatures are reached in the heart of the bed. Moving bed processes operate on lump coal. An excessive amount of nes, particularly if the coal has strong caking properties, can block the passage of the upowing syngas. Fluid bed gasiers oer extremely good mixing between feed and oxidant, which promotes both heat and mass transfer. This ensures an even distribution of material in the bed, and hence a certain amount of only partially reacted fuel is inevitably removed with the ash. This places a limitation on the carbon conversion of uid bed processes. The operation of uid bed gasiers is generally restricted to temperatures below the softening point of

the ash, since agglomeration of soft ash particles will disturb the uidization of the bed.... Sizing of the particles in the feed is critical: material which is too ne will tend to become entrained in the syngas and leave the bed overhead. This is usually partially captured in a cyclone and returned to the bed. The lower temperature operation of uid bed processes means that [they handle reactive feedstocks such as low rank coals and biomass better than bituminous coals. The methane content of the syngas is in the range 27 mol %.] [As a means to improve carbon conversion, some gasiers contact the ash with an additional stream of oxidant as it is extracted from the gasier. This provides additional carbon burn o from the ash. The temperature rises at this point, and the ash particles form agglomerates.] Entrained ow gasiers operate with feed and [oxidant] in cocurrent ow. The residence time in these processes is short (a few seconds). The feed is ground to a size of 200 m or less to promote mass transfer and allow transport in the gas. Given the short residence time, high temperatures are required to ensure a good conversion and therefore all entrained ow gasiers operate in the slagging range [(i.e., above the melting temperature of the ash)]. The high temperature operation creates a high oxygen demand for this type of process. An advantage of entrained ow gasiers is that they do not generally have any specic technical limitations on the type of coal used.... Additionally, the ash is produced in the form of an inert slag or frit, which can be used as a construction material. This is achieved with the penalty of additional eort in coal preparation as well as the high oxygen consumption, especially in the case of coalwater slurries and/or coals with a high moisture or ash content. Where the fusion temperature of the ash is high, in particular higher than acceptable for a refractory lining, then it is possible to add a uxing agent to allow operation at a lower temperature.

3. GASIFICATION RESEARCH AND DEVELOPMENT The only recent review of gasication developments is that of Mondal et al.10 This however focused largely on state-of-the-art technologies in the commercial sector, with little emphasis on research. A typical gasication process comprises a sequence of several unit operations, which can be described in a generalized form as in Figure 3. The format of this review will follow this sequence, starting with the coal itself, following through with dierent feeding methods, the gasication reactors themselves, syngas cooling, and primary cleaning (particulate and halide removal).
3.1. Coal Properties Relevant to Gasication

A good understanding of the properties of the feedstock is a prerequisite to the successful design and operation of a gasier.

Figure 3. Typical sequence of operations in a gasication process.

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Chemical Reviews The properties most relevant to a particular operation will depend, at least to some extent, on the type of gasier employed, but in all cases it will be necessary to adapt the operation to allow for changes in the feed. While the determination of much coal characterization data is a routine matter, often performed by and available from sellers and traders, char reactivity will in almost all cases need to be assessed by the gasier designer or operator. Similarly, while the ash fusion temperature data is often available from the seller, this can provide only an indication of the likely operation temperature. For slagging gasiers the viscositytemperature relationship will have to be determined. For xed and uid bed gasiers the need is to have an understanding of the onset of clinkering. Both these areas, char reactivity and the behavior of mineral matter in coal, continue to be the subjects of intense investigation. 3.1.1. Reactivity of Coal and Other Chars. Feedstock reactivity generally receives more consideration in connection with uid bed gasiers, and it is often assumed that entrained ow gasiers operate at temperatures suciently high that the rate of reaction is determined by bulk diusion rather than inherent reactivity. While this may be true, it is still necessary to have a good understanding of the apparent reactivity at high temperature. On the scale-up of the 26 bar Texaco gasier for the Polk Power Station, the expected carbon conversion was 97.598%, but actual performance was in the low to mid 90% range.11 This has been attributed to insucient residence time in the reactor.12 The same references note that the carbon conversion dropped further on gasifying a fuel containing 55% petroleum coke, which has a much lower reactivity than coal. There is unfortunately no clear standard for reporting reactivity, so numerical data is often dicult to compare or interpret. The most common procedure is to determine reactivity at atmospheric pressure under CO2 or steam, but as discussed below, even the preparation of the char can have an inuence on the result. However, for lack of a standard it is always necessary to report the conditions under which the measurement was made to avoid any misinterpretation. There is an awareness of a need to determine reactivities under conditions similar to those obtaining under actual industrial conditions. Studies have been performed under absolute pressures in the range 2025 bar. Roberts and Harris found reduced reaction rates with an increased CO partial pressure.13 An investigation of reactivity of petroleum coke under a CO2 atmosphere without CO did not reveal any pressure inuence.14 In a dierent investigation char was prepared under dierent pressures up to 20 bar and then gasied at atmospheric pressure under steam.15 The chars generated under pressure were found to be more reactive, but further work will be needed to determine the eect of pressure and gas composition. It should however be noted that all this work has been conducted at temperatures in the 8001000 C range. This provides insights appropriate to uid bed processes, but for entrained ow gasiers operating in the 14001600 C range, these investigations will need to be extended. Some work has been performed at higher temperatures, but then mostly at atmospheric pressure. One such was the determination by Zhan et al. of the catalytic eect of black liquor on the gasication reactivity of petroleum coke,16 which was conducted up to 1400 C, but this must be considered as a special case and unlikely to be able to nd direct transfer of applicability to other situations.
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Review

The diculty of transferring results from reactivity studies of one coal to another coal is the reason that so much work is performed in this area. Liu et al. found that the rate of heating during pyrolysis inuenced the reactivity of Binxian coal char.17 Faster pyrolysis at higher temperatures increases the reactivity. On the other hand, demineralization of the coal with HF and HCl prior to pyrolysis reduced the reactivity when it was treated otherwise similarly. Reactivity is usually measured with CO2 as the gasifying medium, but some have used steam against the background of generating a hydrogen-rich gas.18,19 Tay and Li compared the results of gasifying with pure CO2 and a gas containing 4000 ppm O2 in Ar, both at 800 C.20 Although both atmospheres are oxidizing, the reactivities of the chars prepared in pure CO2 were of a much higher magnitude than of those prepared in the O2/Ar atmosphere. 3.1.2. Behavior of Mineral Matter. 3.1.2.1. Ash Fusion Temperatures. The ash fusion temperature (AFT), usually characterized by the initial deformation temperature (IDT) as dened by standard test procedures (e.g., ASTM D1857), is an important coal characteristic for any gasication process. For uid bed processes it determines the upper limit for the operating temperature, since above this temperature agglomeration of the particles is likely. For entrained ow processes the temperature must be above the uid temperature (FT) to allow the molten ash to be drawn o as a molten slag. Note that entrained ow processes will actually operate at signicantly above FT, since, as discussed below, the slag viscosity requirements will demand this. There has been much eort devoted to determining a method to predict the AFT from the chemical composition of the ash, but the validity of the results obtained has generally been limited to coals of similar origin to that used to test the proposed model, at least with any degree of accuracy. Recent work with thermochemical equilibrium models such as FactSage has brought the goal nearer.2123 While each of these studies concentrated on coals from a specic region and the correlations of measured data with predicted results were reasonable, there are still limitations. Song et al.24 systematically varied the amounts of SiO2, Al2O3, CaO, Fe2O3, and MgO added to some Chinese coals under an inert (Ar) atmosphere and generally found good agreement in the shape of a temperaturecomponent plotin particular the component concentration required to achieve the minimum AFTbut the absolute values for the predicted AFT still show some deviation from the measured values. Even with such a deviation, results like these will provide a good guide to determining the optimal ux addition rates. It should be noted also that Song et al. also demonstrated the dierence in AFT predictions under inert and reducing atmospheres,24 so this also provides an additional reason to take care in applying absolute temperatures derived from FactSage to a particular industrial situation. 3.1.2.2. Viscosity. As mentioned above, slag viscosity is the determining factor for the operating temperature of an entrained ow gasier, since the slag must not only be liquid, but also suciently free-owing that it can easily ow out of the reactor as a liquid. Generally, a viscosity of 25 Pas or lower is considered to be suitable. The temperature at which the slag reaches this viscosity is known as T25. As with the AFT, there is a need to be able to correlate the viscosity with the chemical composition of the slag. When looking at a plot of slag viscosity against temperature such as that in Figure 4, at suciently high temperatures the slag behaves as a Newtonian uid. As the temperature drops, there comes a point as the slag nears the
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Review

3.1.2.4. Sintering. When examining viscosity and related phenomena in connection with a xed bed or uid bed gasier, the focus of attention is at the lower end of the IDT to FT range. As shown in Figure 5, while ash is heated toward its IDT,

Figure 4. Viscositytemperature curves of coal ash samples. [Reprinted from ref 34. Copyright 2012 American Chemical Society.]

solidication temperature, where this is no longer so. This temperature is known as the critical temperature or Tcv. A theoretical model to calculate slag viscosity developed by Urbain et al.25 and modied by Kalmanovitch and Frank26 has been shown to give good results for slags in the Newtonian region27 above Tcv. Extensive empirical work to determine the Tcv was performed on the system SiO2Al2O3CaOFeO for a wide variety of Australian coals.28 Work continues in this area and in particular comparisons are made with data derived from FactSage; however, much of this is related to specic circumstances.2933 The transition from a Newtonian uid at Tcv is attributed to the onset of crystallization of species in the slag during cool down. Understanding this process can assist in the prediction of Tcv. Yuan et al. measured the viscosity on cooling various slags from 200 C over the uid temperature to a temperature at which the viscosity had increased markedly.34 In parallel these slags were simulated with FactSage. For coal ash samples rich in Al2O3 and SiO2, mullite was the rst solid phase to form, even at temperatures above 1600 C; for those with more CaO and Fe2O3, anorthite was the rst solid phase to form. Nakano et al used a synthetic ash mixture to simulate a coalpetroleum coke (petcoke) mix.35 With a high proportion of petcoke, the rst solid phase is karelianite (V2O3). The presence of mullite, which was predicted by FactSage, was not observed, even with a lower proportion of petcoke. 3.1.2.3. CharSlag Transition. Carbon conversion rates in uid bed gasication tend not to be as good as for entrained ow gasiers. Values of 9295% are typical unless there is an agglomeration stage to improve them. On the other hand, there can be some advantage to limiting the conversion rate. In a series of ash deposition experiments, under both oxidizing36 and gasication37 conditions, Li et al. determined that, as char particles were gasied, there was a transition point at which the deposition rate of the mineral matter on an impingement plate increased rapidly. Increasing the conversion rate beyond this charslag transition point will therefore increase the likelihood of fouling of a syngas cooler. This work provides the background to the empirically determined industrial practice in oil gasication, whereby carbon conversion is deliberately not increased beyond a value of about 99.099.5% depending on ash content, since doing so will cause ash deposition in the cooler.
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Figure 5. Comparison of liquid slag proportion of sample (FactSage) with ASTM ash fusion measurements. [Diagram adapted from ref 38 with the kind permission of Sasol Technology (Pty) Ltd.]

some components become liquid before the bulk mineral reaches this state.38 It is the behavior of this partially melted mixture of liquid and crystalline solid that is responsible for agglomeration and sintering.3941 Agglomeration and sintering cause disturbances in both uid bed and xed bed gasiers. As the ash approaches its fusion temperature, individual ash particles tend to swell, become soft, and on contact can stick to one another. In a uid bed continued agglomeration can create large particles that are no longer supported by the upow and fall out of the bed. In a xed bed gasier, large pieces of agglomerated material can blind a portion of the bed, forcing the upward ow of gas around it, and the char immediately above it is not converted. If sintered material is too large, then it cannot pass out through the grate. Despite these concerns, it is desirable to operate the gasier at as high a temperature as reasonable in order to maintain a high rate of carbon conversion. For a uid bed gasier the safety margin is typically around 100150 C relative to the IDT. Current work to improve the understanding of the sintering process includes looking at the eect of dierent mineral components in dierent atmospheres. Jing et al. examined the sintering temperature of ash from a Jincheng coal under dierent atmospheres and at dierent temperatures.42 Under all atmospheres the sintering temperature decreases with increasing pressure. For this coal the sintering temperature under a reducing atmosphere was lower than under an oxidizing or inert atmosphere. Nel at al. compared the sintering temperatures and compressive strength when heating a model coal mineral mixture under dierent atmospheres.43 Like Jing they found that an inert (N2) atmosphere produced a lower sintering temperature than an oxidizing atmosphere. Being heated in air, the compressive strength was increased over the range 400900 C due to the formation of CaSO4. Under N2, there was insucient oxygen for CaSO4 to form, and the increase of compressive strength was not observed.
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Chemical Reviews 3.1.2.5. Kinetics. Most current work on the correlation between slag properties and chemical composition has been based on the calculation of thermodynamic equilibrium of the minerals. Wang et al. have examined the kinetic behavior of two dierent coals with diering AFTs and found considerable dierences. In particular, the content of Na2O, K2O, and CaO can inhibit the rate of mullite formation. Further work will be necessary to develop these observations into a more widely applicable model.44 3.1.2.6. Surface Tension. Besides viscosity there are other properties of the liquid slag which are needed for modeling and design of gasiers and high temperature particulate removal equipment. Melchior et al. have investigated the eect of pressure up to 10 bar on surface tension,45 a property for which hitherto only data under atmospheric pressure has been available in the literature.
3.2. Coal Preparation and Feeding

Review

One of the greater challenges in any gasication process is that of charging a pressurized gasier vessel with a solid coal feedstock.46 This has to be performed with due consideration for the safety of the system, since any failure or leakage runs the risk of discharging ammable and toxic syngas into the surroundings. For entrained ow gasiers both wet and dry systems for size reduction, pressurizing, transporting, and measuring coal feed ow have been developed and are in industrial use. Nonetheless, there is still considerable incentive to improve the eciency, reliability, and cost of these systems and that has been the focus of research in this area. As described elsewhere,8 In a dry feed system the coal is ground to a size of about 100 m and simultaneously dried in a roller mill similar to those used in conventional pulverized coal units. The pulverized coal is pressurized in a lock hopper system and deposited into a feed vessel, from which it is transported by pneumatic conveying. For ammonia production the carrier gas is typically pure nitrogen from the air separation unit (ASU), but for many other chemical applications where nitrogen is undesirable, CO2 is used. Generally a dry feed system contributes to a higher gasier eciency. However the amount of carrier gas required for the pneumatic transport of the coal into the gasier increases with pressure. The economic limit for dry feed systems is generally considered to be about 40 bar. For low rank coals a pre-drying system upstream the mills may be necessary. For wet feed systems the slurry is made in a rod mill into which pre-crushed (2 in.) coal and water are fed. The coal is ground in a wet milling process to a size of about 100 m. The slurry is pumped to the reactor pressure typically by a membrane piston pump, which allows gasier operation at up to 80 bar. This can be an advantage for some chemical applications. The need to evaporate the water from the slurry in the gasier reduces the eciency of slurry fed systems. In the case of low rank coals the high inherent moisture of the coal does not contribute to the transport properties of the slurry, so that it is superimposed on to the about 35% free water content. The total water content entering the gasier can then become so large that economic operation with a slurry feed is impossible. 3.2.1. Fines Reduction in Crushing Facilities. One of the rst steps in any gasication process is size reduction to at least
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a transportable size of about <50 mm. Whether the gasication facility is located at the mine, as are for instance the Sasol facilities in South Africa, or remotely, there is likely to be an incentive to minimize the production of nes. Typical traded coal sizes are 2 in. maximum top size and maximum 30% 2 mm.47 Moving bed gasiers such as those of Lurgi and BGL (British GasLurgi) can only accept a small to moderate amount of nes (<57%) without the risk of the nes blocking part of the bed and causing channeling of the gas around the blockage.48 Such channeling is associated with the material in the blocked area not being converted and also possible breakthrough of oxygen through the channel into the syngas. Fines that arise out of the coal preparation must therefore either be directed to a large pulverized coal boiler, such as at the Dakota Gasication SNG plant,49 or be briquetted to make them suitable for feeding to the gasier, such as in the Hulunbeier BGL ammonia plant in Inner Mongolia.50 In plants without briquetting facilities considerable eort is devoted to minimizing the nes make during precrushing and transport activities. In order to support such activities at the Sasol coal-to-liquids plant in Secunda, South Africa, work is being conducted at North-West University (South Africa) to gain a better understanding of the comminution characteristics of South African coals.51 A similar situation obtains with uid beds, though the desired size range is smaller (26 mm), and similar work has taken place to dene how one can minimize nes generation during the process of size reduction with an impact crusher.52 The study determined that the rotational speed of the crusher is a relevant though weak parameter over which the operator does have some control, but recognizes that the quality of the feed coal to a crushing system is the most important factor. 3.2.2. Slurry Feeding Systems. Coalwater slurries for slurry-feed gasiers typically have a solids content of 6268%.53 The water in the slurry must be evaporated in the gasier, which contributes to the lower eciency of such systems compared with a dry feed system. The limitation to reducing the water content is generally the viscosity of the slurry, which must be typically less than 10001200 mPas at a shear rate of 100 s1. Viscosities higher than this create practical problems for ltering and pumping. In an industrial application, there is usually a buer tank containing 812 h holdup between slurry manufacture and gasier. The solids should not settle out in the buer tank or in the pipelines of the system. Another critical property of the slurry is therefore its stability. The use of surfactants and in particular ammonium lignosulfonate as an additive to achieve a higher solids content while maintaining an acceptable viscosity is well-known.54 Further eorts continue to be made to increase the solids content of coalwater slurries. Additives that have been investigated include black liquor,55,56 sewage sludge,57,58 algae,59 ethanol,60 and natural plant extracts.61 The motivation for much of this work is however disposal of wastes and examining the eect of coslurrying waste streams with the coal. Black liquor is, perhaps unsurprisingly, benecial; sewage sludge, having a high degree of inherent moisture, reduces the overall solids content of the slurry at an acceptable viscosity, though Wang et al. did observe an improvement in the stability characteristics of the slurry.62 Liu investigated the eect of limestone addition as a means of desulfurization in connection with slurry feed combustion.63 This data is applicable also, when limestone is added as a
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Chemical Reviews uxant. The eect of adding small quantities of limestone to the coal has a minor detrimental eect on slurry quality, both increasing viscosity and reducing stability, but these eects increase rapidly with increasing proportions of limestone. Another approach has been to pretreat the coal prior to slurrying. This is potentially particularly attractive for low rank coals, since generally much lower solids concentrations can be achieved than with high rank coals. Yu et al. performed a hydrothermal dewatering on two dierent Chinese brown coals.64 In one case the solids concentration was increased from 45.7 to 59.5 wt %, and in the other case it was increased from 53.7 to 62.1 wt %. This brings a brown coal slurry into almost the same range as a typical optimized slurry.65 The Electric Power Research Institute (EPRI), Palo Alto, CA, has proposed an alternative approach to reducing the eciency loss attributable to the evaporation of the continuous phase of the slurry, namely, to replace the water by liquid CO2, which has a lower heat of evaporation.66 EPRI recently received a contract from the U.S. DOE to pursue this work further.67 3.2.2.1. Slurry Feed Injectors. Another aspect of slurry feed gasiers that has received continuous development attention is the relatively short life of the feed injectors or burners. Eastman Chemicals reported improving their feed injector life from a record 91 days in 200168 to 122 days in 2003.69 Although further improvements have been made since (e.g., Zhou reports 150 days70), the contrast with the 12 year life of a dry feed burner remains remarkable. This author attributes at least part of this dierence to the instability of the ame pattern caused by the ashing of the liquid phase and the resultant thermal fatigue on the burner face. Much of the improvement to date has been accomplished by improved materials of construction and minor geometrical changes, but addressing this basic issue has not been so well discussed in public. Attempts at developing an understanding of the ow patterns in the breakup are in progress,71 but there is still a need for a model based on the underlying physics.72 Superimposing the ashing eects on such a model remains a task for the future. GE has announced an improvement program, the results of which have been incorporated into the design for the recently (September 2012) started-up Edwardsport IGCC.73 3.2.3. Dry Feeding Systems. 3.2.3.1. Milling. Dry feeding systems for entrained ow gasiers use the same milling equipment as is used for conventional pulverized coal boilers and benet from incremental improvements made for the boiler market. 3.2.3.2. Lock Hoppering of Pulverized Coal. The conventional method of moving dry solids from a region of low pressure to one of high pressure is to use lock hoppers. A typical conguration is shown in Figure 6.74 Pulverized coal is stored in the atmospheric storage bin. One of the lock hoppers is depressurized and the valves between it and the storage bin are opened allowing coal to be charged to the lock hopper. The lock hopper is then blocked in and pressurized to the pressure of the feeding vessel. The valve to the feeding vessel is then opened and the coal is discharged. The lock hopper is again blocked in and depressurized, restarting the cycle. The second lock hopper works on a similar, but staggered cycle to smooth out the supply of coal to the feed vessel. The whole operation is controlled electronically with appropriate safeguards against valve malfunction and the like. In terms of reliability and maintenance the lock hopper system is considered to be one of the most critical parts of a dry feed gasication system. The key issues are the risk of bridging,
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Figure 6. Typical lock hopper arrangement for pulverized coal. [Reprinted with permission from ref 74. Copyright 2013 Siemens Fuel Gasication Technology GmbH & Co. KG.]

so that when a discharge valve opens the hopper does not discharge, and the reliability of the valves themselves. Avoiding bridging is usually accomplished by aeration with an inert gas such as nitrogen as shown in Figure 6. As described by Lu et al., the pulverized coal is typical of a Geldart Type C powder that is dicult to uidize.75 Dierent technologies include dierent solutions in detail and are also the subject of continuous incremental improvement.76 As described below, there can be reasons to use CO2 rather than nitrogen as inert gas. Lu et al. also investigated the eect of changing the aeration gas to CO2.77 At low pressures, CO2 was much less eective as a uidizing agent than air. However, already at 4 bar the dierence was much less noticeable. A comparison at the typical 2540 bar of a dry feed gasier has not been identied. The valves operate on a cycle of typically about 30 min. They can be expected to be subject to erosion by the passing coal, but at the same time they may not leak even after continuous use, since this would defeat the pressure cycling, which is the whole basis of the lock hoppering process. 3.2.3.3. Pneumatic Conveying. The actual feeding of coal to the burner of a dry feed entrained ow gasier is by pneumatic conveying from the feed vessel as shown in Figure 6. Transport is in the dense phase, in which a density of 350450 kg coal/ m3 carrier gas is achieved.78 Initially this dense feed conveying was performed with nitrogen as carrier gas, since in the gasication environment this was a readily available inert gas. Typically the nitrogen appears in a concentration of about 6% in the raw syngas. For ammonia (or power) applications, this is not harmful. For other applications such as methanol, SNG, or FischerTropsch synthesis, this level of inert material in the synthesis gas is undesirable: compression energy for the inert component of the syngas is consumed to no good purpose and the amount of syngas accompanying the inert purge is also a loss to the system. In such cases CO2 is used as carrier gas. In applications where nitrogen is undesirable, there is usually a CO2 removal unit in the syngas processing, which provides a source of carrier gas as well as a means of adjusting the stoichiometry of the gas for the synthesis. However, care must be taken in the design of systems suitable for CO2. Cong et al. have investigated the characterdx.doi.org/10.1021/cr400202m | Chem. Rev. 2014, 114, 16731708

Chemical Reviews istics of pulverized coal pneumatic conveying using alternatively CO2 and air and report several dierences.79 For the same solids mass ow rate, the required CO2 gas ow rate is higher than that of air. One result is a 20% increase in energy demand to transport the same mass of solids, when using CO2. Part of this work included the study of ow patterns and pressure signals in a horizontal pneumatic conveying line.80 They found multiple ow patterns and were able to correlate the ow patterns with pressure signals providing a means of characterizing the ow patterns and their variation. This oers potential for improved monitoring of the dense ow pneumatic transport and early warning of operational disturbance. 3.2.3.4. Lock Hoppering for Fixed Bed Gasiers. Lock hoppering of lump coal for xed bed reactors, while sharing the same basic pressure cycle, is much simpler than for pulverized coal supply to an entrained ow gasier. The lock hopper discharges directly into the reactor and is built integrally with it. However, the gas losses from the lock hopper depressurization are syngas, rather than an inert gas. The safety considerations and cost of these losses are therefore of even more concern than in the case of the entrained ow gasiers. In some cases the lock gas is simply burned in a are; in others it is recompressed and added to the syngas. The scale of these losses is increased with pressure, and for the 100 bar xed bed demonstration unit Ruhr 100, twin lock hoppers were installed. The cycles of the two lock hoppers were integrated so that the depressurization gas of the one hopper could be used as pressurizing gas for the otherat least until pressure equalization was achieved. This arrangement achieved a 70% savings in pressurizing gas.81 The rst twin locks on an industrial scale were implemented on a BGL gasier at Schwarze Pumpe, Germany, in 2001.82 They are included in the design of the recently announced Lurgi Mark Plus gasier, an up-scaled version of the previous Mark IV design.83 3.2.4. Dry Solids Pumps. One potential means of reducing the capital cost of dry feeding is the use of so-called dry solids pumps. The rst concepts were developed in the 1980s.84,85 The Stamet Posimetric Pump shown in Figure 786 has one moving part: a spool comprising two disks on a shaft which rotates within a housing. An abutment, extending between the disks to the hub, separates the inlet from the outlet. Material entering the pump becomes locked or bridged between the disks and is carried around by their rotation. This principle of lockup means the pump experiences virtually no

Review

Figure 7. Stamet dry solids pump. [Reprinted from ref 86.]

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wear. The abutment forces material from between the disks, preventing material being carried around for an entire rotation. It also makes the pump self-cleaning.87 The technology has been developed to operate at 70 bar (1000 psig). It was acquired in 1997 by GE as part of a strategy to extend the GE gasication technology to include a low rank coal capability. While low pressure pumps have found industrial applications, integration into a gasication plant has yet to be demonstrated. An alternative, linear conguration has been developed by Pratt & Whitney Rocketdyne (PWR) using the same physical principle of a pressure seal formed by the compacted solids.88,89 A 400 t/d demonstration unit has been tested,90 and a rst industrial application is expected in 2013. In addition to its pump PWR has developed an ultradense phase injector and feed system.91 A third system of mechanical transport from a low pressure space to a high pressure space has been developed by Thomas Koch Energi.92 This was originally developed as a feeder for biomass gasiers, but its capability is now extended to include pulverized coal. 3.2.5. Cogasication of Alternative Feedstocks. There is considerable interest in cogasication of nonfossil feedstocks, both biomass and wastes, as a means of reducing the CO2 impact of coal gasication. Large-scale tests of biomass addition to design coal feedstocks have been performed in industrial gasiers, both slurry feed at the 250 MWe Polk Power Station in Florida (ref 11, Appendix G) and dry feed at the 250 MWe Buggenum, The Netherlands, IGCC and also at the ELCOGAS 300 MWe IGCC in Puertollano, Spain.93 At the Buggenum plant up to 40% biomass has been added to the feed, though not without issues.94 Limitations at Buggenum included the nitrogen supply for carrier gas, the increased CO2 content of the syngas, and increased fouling of the syngas cooler. Buggenum built a dedicated biomass feed facility, which has been used for normal operation with about 20% biomass addition since its construction. Polk identied a similar need for a separate feed facility, but did not implement it. Also xed bed gasiers have demonstrated a capability of processing alternative fuels, particularly wastes. The BGL gasier at the SVZ (Sekondar rohsto-Verwertungszentrum) waste treatment plant located at Schwarze Pumpe, Germany, was designed from the beginning to process about 7080% municipal solid waste (MSW) and demonstrated that capability at an industrial scale. The Lurgi dry bottom gasiers at Vre sova, Czech Republic, have been able to operate satisfactorily with 10% waste tire addition to the normal lignite feed. The low reactivity of the tire char causes an increased carbon in ash at higher addition rates, though short-term increases of up to 20% can be accommodated.95 A limitation of all these large-scale empirical tests is that they have had to take place under the constraints of an operating plant without the opportunity necessarily to develop a deeper understanding of the interaction of the dierent fuels. This is particularly the case for the entrained ow gasiers, which operate at a suciently high temperature that many of the issues such as tar make are not relevant. The xed bed gasiers make too much tar to allow the behavior of mixed feeds to be clearly identiable. It is therefore not surprising that most of the work on cogasication takes place in the midrange temperatures typical of uid bed gasiers. Under these conditions the tar make typical of biomass gasiers remains an issueeven with coal addition.
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Chemical Reviews Pinto et al. have examined the results of cogasication of various coals with pine, bagasse, refuse-derived fuel, and polyethylene wastes in a pilot-scale uid bed gasier operating with air or oxygensteam mixture at 850 C.9699 In all cases tars were produced, though in varying amounts depending on the quality of the noncoal component of the fuel. A gas cleanup system using two xed beds of dolomite and Ni-based catalyst was used. Tars were reduced to below 1% in all cases after the dolomite and were not detected downstream the Ni catalyst. Vel ez et al.100 and Alzate et al.101 have conducted tests with steam gasication of coalsawdust pellets. It is important to develop a good understanding of how trace elements, particularly those introduced by waste addition, will behave. For instance, Zhang et al. investigated gasication of a coalsewage sludge mixture in dierent proportions.102 The sewage sludge itself contained about 2.85 wt % phosphorus. Organic phosphorus, nonapatite inorganic phosphorus (NAIP, not Ca-bound phosphorus), and apatite phosphorus (AIP, Cabound phosphorus) account for 9.0, 73.0, and 18.0 wt % of the total phosphorus, respectively. They found that while the bulk of the organic phosphorus volatilized already during the pyrolysis stage, there was little obvious volatilization of inorganic phosphorus until about 1200 C. Thus most of the phosphorus was bound in the slag after gasication. Aigner et al. performed cogasication of wood and coal in a 100 kWth pilot dual uid bed indirect gasier in diering proportions to study the eect of varying the proportions of biomass and coal.103 All gas components show a linear relationship with linearly changing fuel ratios. No synergetic eects of cogasication between coal and biomass were found. Zhu et al. looked at the eect of blending ratio on pyrolysis in a strawcoal mixture.104 They also found no synergies in the char yield from the pyrolysis. There was, however, an increase of gasication reactivity with increased ratio of wheat straw-tocoal. 3.2.5.1. Cogasication with Petroleum Coke. Cogasication of petroleum coke (petcoke) with coal is already practiced industrially, particularly in locations where the petcoke has low value. The ELCOGAS dry feed IGCC in Puertollano, Spain, was designed for a 50:50 mixture of petroleum coke and high ash, low sulfur coal. The principle lesson learned from that plant specic to the petcoke feed was that more attention to the detail design of the grinding equipment was necessary.105 The Wabash and Polk slurry feed demonstration IGCCs were originally designed only for a range of coals. Since the conclusion of the DOE demonstration program in January 2000, the Wabash plant has operated on 100% petcoke with the addition of only 23% limestone or boiler bottom ash ux.106 Polk has operated on a coalpetcoke ratio of about 45:55 since 2001 (ref 11, p 1-28). The principle limitation on increasing the petroleum coke feed at Polk is the capacity of the sulfur recovery unit. Nonetheless, cogasication of petcoke and coal continues to attract research attention. Petroleum coke is much less reactive than coal. There are multiple reasons for this. The BET specic surface area of petcoke is much lower than that of coals; there is little alkaline or alkaline earth material with catalytic activity for gasication in the ash; the ash with its typically high vanadium content has a very high fusion temperature. This all results in the need to operate the gasier at higher temperature to achieve a high carbon conversion similar to what one would achieve with a bituminous coal. Economically, the higher oxygen demand removes part of the benet of petroleum coke as a
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cheap fuel. In refractory-lined gasiers a higher operating temperature may be undesirable in order to maintain a longer refractory lifetime, so a low single pass conversion may have to be accepted. For a single stage gasier such as Polk, a high carbon fraction of the slag stream is separated from the slag and recycled to the gasier.107 In a two-stage gasier, the char recycle will be larger. It is against this background that the continued eorts to nd improvements must be understood. Vejahati et al. have followed up earlier work on cogasifying oil sand coke with Albertan coal, but they failed to nd any synergies.108 There is however no indication of the ash content or composition in the coal, so it is dicult to evaluate this nding. On the other hand, Zhan et al. investigated the inuence of blending methods on the cogasication reactivity of petroleum coke and lignite and found wet grinding to be more benecial than dry milling.109 The lignite used was a high ash (18.24 wt %) material with 12.6 wt % CaO in the ash. The loss of weight with time as measured with TGA was improved against that of undiluted petcoke in both cases, but this eect was much more marked in the case of wet grinding. This is attributed to the improved mixing achieved with wet grinding.
3.3. Gasication Reactors

3.3.1. Fixed Bed Gasiers. Still today more syngas is produced using the Lurgi xed bed dry bottom gasier or derivatives than any other. Locations using it are however few but large, being located in South Africa, the United States (North Dakota), Czech Republic, and China. It is therefore not surprising that research is largely limited to these countries and to coals specic to them. One of the most important techniques in developing a further understanding of xed bed reactors is the turn out, in which the contents of a shut-down reactor is sampled while slowly removing it through the grate. Bunt and Waanders have performed studies on the basis of this technique examining the fate of the principle reacting elements (C, H, N, O, S) over the depth of the reactor bed as well as the changes in the ash speciation. It was found that, in the oxidation zone, ash components oxidize also and in the case studied consumed 2.5% of the total oxygen supplied to the reactor.110 van Dyk et al. pursued this phenomenon and have developed a correlation between oxygen capture tendencies and CaO content valid for South African Highveld coals.111 In a second study Bunt and Waanders observed development of particle size through the reactor. Of the +25 mm particles, 85% had already broken up into ner size fractions in the upper, drying, and slow pyrolysis zones.112 In a third study they and Wagner found inuences of dierent petrographies on the behavior of coal particles in the reactor.113 A similar turn-out exercise performed on two gasiers operating on North Dakota lignite showed that about twothirds of the reactor volume was taken up with drying and devolatilization of the coal. Nonetheless the high reactivity of the lignite char allowed it to be gasied with an overall carbon conversion of 98% within a third of the remaining space.114 Skhonde et al. used the results from a gasier turn-out to follow the behavior of sulfur in a xed bed gasier.115 A second technique used to see the eect of particle size on gasication is the small-scale pipe reactor, which can be moved from the vertical position to the horizontal and opened up axially to allow sample taking and visual inspection of the bed prole.116
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Table 2. Characteristics of Commercial Entrained Flow Gasication Processes [Reprinted with Permission from ref 7. Copyright 2003 Elsevier.]
process Koppers-Totzek Shell SCGP Preno Siemens GE Energy E-Gas MHI OMB MCSG TPRI HT-L Tsinghua EAGLE
a

stages 1 1 1 1 1 2 2 1 1 2 1 2 2

feed dry dry dry dry slurry, drya slurry dry slurry, drya slurry dry dry slurry dry

ow up up up down down up up down down up down down up

reactor wall jacket membrane membrane membrane refractory refractory membrane refractory, membranea refractory membrane membrane refractory, membranea membrane

syngas cooling syngas cooler gas quench and syngas cooler water quencha gas quench and syngas cooler water quencha water quench radiant coolera water quench or radiant cooler two-stage gasication two-stage gasication water quench or syngas cooler water quench two-stage gasication water quench water quench two-stage gasication

oxidant O2 O2 O2 O2 O2 O2 air/O2 O2 O2 O2 O2 O2 O2

In development.

One of the byproducts of a xed bed gasier is known as dusty tar, condensed heavy hydrocarbons from the pyrolysis stage contaminated by particulate matter carried over in the syngas from the gasier bed. van Dyk et al. investigated this material as a potential feed to a liquids gasier.117 The viscosity of the tar is very high (>1000 cP at 80 C), but can be reduced to <300 cP by milling, addition of waste solvent streams, or both. For the South African coal from which this dusty tar is produced, the ash fusion temperature is >1350 C, but it can be reduced to 1250 C using an 8% CaO ux. Any eect of the ux addition on the dusty tar viscosity is not reported. While most work on xed bed gasication is performed at locations close to industrial facilities, it is interesting to note that an air-blown pilot plant was started up successfully in Italy in 2009 and has been operated in two campaigns since.118 The focus of this work is the development of small-to-medium-scale equipment (1015 MWth). Fixed bed gasiers are notoriously dicult to model accurately, so any published advance on existing models can be of benet to the community. One such is that of Grieco and Baldi,119 who based their model on the work of Hobbs et al.,120 while removing some of the simplifying assumptions. 3.3.2. Fluid Bed Gasiers. Fluid bed gasication is largely the realm of low rank coals and biomass. The results of Cao et al., who investigated cogasication of methane with coals of various ranks, show clearly the superior performance of low rank coals compared with higher rank coals, when gasied in a uid bed reactor. Under essentially similar conditions in the same uid bed gasier, they obtained carbon conversions of 94.7 and 93.6% for lignite and subbituminous coal, respectively, and 68.5 and 82.9% for two dierent bituminous coals.121 One industrial scale technology, the high temperature Winkler (HTW) process, was developed for Rhenisch lignite.122 KBR/Southerns TRIG transport integrated gasier was developed primarily with Powder River Basin (PRB) subbituminous coal in mind,123 and the rst industrial application in the 524 MWe Kemper County IGCC is for Mississippi lignite.124 However, some work on uid bed gasication continues to be performed on bituminous coals. Duan et al. explored the eects of oxygen/carbon and steam/coal ratios as well as a high temperature gasication agent supply to an air-blown 70 mm circulating uid bed (CFB) gasier operating on Huaibei bituminous coal at 3 bar. While the trends shown by varying the
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operating mode were as might be expected, the carbon conversion did not exceed 90% in any of the runs performed.125 Ju et al. performed similar studies on an 800 mm industrial scale atmospheric CFB unit with a Xuzhou bituminous coal.126 The carbon conversion was also much lower that would be desired in an industrial application. The addition of an agglomerating stage to a uid bed gasier is one approach to addressing the low carbon conversion rates typical of uid bed gasiers operating on high rank coals. Thompson reports carbon conversions of up to 99% in a U-Gas plant operating on feeds ranging from run-of-mine bituminous coal through high ash subbituminous coal to a high moisture lignite.127 Unfortunately, it is not clear with which of the various feedstocks this high conversion rate was achieved. Liu et al. have developed a simulation model of the ash agglomerating uidized bed (AFB) gasier, which compares well with the test results of a pilot plant operating on Jincheng anthracite.128 In this case also, carbon conversion is below 90%. Dual uidized bed (DFB) systems are well-known from biomass gasication.129 A particular attraction of the system is the ability to produce a medium BTU gas (350450 MJ/kmol) without the use of an oxygen plant. Experience with coal is however limited. The DFB unit in Gussing, Austria, was originally designed for biomass (wood chip) feed and is normally operated thus. Coal feed has however been tested with success. Zhang et al. report that application of the DFB principle to coal is also being developed in both Japan and China.130 In particular, Wang et al. have initiated work in this direction. They operated a pilot DFB plant initially with air and then backed o some of the air with steam. Although the results indicate that operation in a purely steam-blown gasication mode is possible, the plant was not operated in this manner during the campaigns reported.131 3.3.3. Entrained Flow Gasiers. Most coal gasication processes developed since 1950 are entrained ow, slagging gasiers operating at pressures of 2080 bar. They have been selected for the majority of industrial-scale IGCC applications with hard coal feed. An overview of currently oered entrained ow gasiers is shown in Table 2. Each of these gasiers is in operation at industrial scale in numbers varying from 1 to over 100. (The rst 170 MWe industrial-scale EAGLE gasier is currently in planning with start-up scheduled for 2017.132) Each technology owner continues to make incremental improvements to secure a
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Figure 8. (left) Refractory lining and (right) membrane wall. [Reprinted with permission from ref 7, 2nd ed.; Figure 6.6, p 210. Copyright 2008 Elsevier.]

competitive advantage. The focus of most such improvements is reduced cost and enhanced reliability, availability, and maintainability (RAM) performance. Eorts are devoted both to the gasication process as it takes place in the gasication chamber as described here and to equipment-oriented aspects discussed in the following sections. As discussed in section 3.2.2.1, the atomization performance of a slurry burner is critical for the satisfactory performance of the gasier. Yu et al.,133 Zhao et al.,134 and Jakobs et al.135 have all investigated and improved on the performance of their own burners, but the results are, as might be expected, all specic to those designs. Flow patterns in the reactor space are important. In order to achieve a good rate of carbon conversion, the distribution of residence time for individual particles must be maintained close to the average residence time. Particles with a low residence time leave the reaction chamber before the carbon is fully reacted, lowering the overall conversion rate. Opposed burners used by various designers (Shell, Uhde, and the East China University of Science and Technology (ECUST)) address this issue. On the other hand, diametrically opposed burners can be a cause of ame instability as determined by Li et al.136,137 unless suitable measures are taken. The eect of ow pattern on temperature distribution is equally important to maintain the integrity of the containment system. Yan, Yu, and co-workers have measured the temperature distributions in a bench-scale gasier with opposed burners.138,139 Although short-term operation with two burners is sometimes suggested,140 their work identies that this is not advisable and runs the risk of shortening the life of the unused burners or refractory. They recommend feeding inert gas through the unused burners during such an operation. 3.3.4. Reactor Containment. A reactor containment system is required as a means of protecting the pressure shell from the reaction temperature. Three systems have been applied industrially: (i) refractory lining, (ii) a water-cooled membrane wall between the reaction space and the pressure shell, and (iii) a water jacket integral with the pressure shell. A refractory lining has the lowest capital cost, but for slagging gasiers it requires regular maintenance. The life of the hot face is typically 1824 months depending on gasier operating conditions.
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The membrane wall is covered by a layer of solidied slag. The liquid slag then ows down the wall of solid slag as shown in Figure 8. A membrane wall has a considerable higher rst cost than a refractory lining, but once installed, little maintenance is required. Membrane walls can have an expected life of 20 years or more. 3.3.4.1. Refractory Linings. Refractory linings have long been recognized as a leading cause of reduced availability of entrained ow gasiers.141 Traditionally chrome and zirconium oxides have been the materials used. Depending on operational circumstances (temperature, slag composition) refractory life has been typically in the range of 1824 months. With the acceptance of a signicantly reduced carbon conversion rate achieved by operating at a reduced temperature, this has been extended to 40 months as illustrated by the experience from the Polk IGCC shown in Figure 9. The mode of failure is a mixture of erosion and spalling.

Figure 9. Plot of refractory liner life against carbon conversion at Polk Power Station. [Reprinted from ref 11, p 5-7.]

Work conducted at the U.S. DOE Albany Laboratories showed that the main cause of shortened refractory life was slag penetration of the refractory and that the addition of phosphate to the high chrome refractory material could reduce this penetration.142 The concept was developed further, and test bricks were installed in panels in industrial gasiers.143 The resistance to spalling was denitely improved, and this material is now being oered commercially. The laboratory also stated that work was proceeding on a nonchrome refractory solution. In parallel, the U.S. DOE Pacic Northwest Laboratory has been examining other inuences on refractory life, taking an
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Chemical Reviews integrated approach to include modeling and process optimization.144 In work focused on a novel steelmaking process involving integration of petroleum coke gasication and direct reduction of iron (DRI), Puente-Ornelas et al. found that magnesium aluminate could be an eective nonchrome addition to reduce slag penetration into an alumina refractory.145 Alumina refractories have been used in oil gasication with success for over 50 years, but have little resistance to coal slags, so it will be interesting to see how this idea develops further. General Electric (GE or GE Energy) has patented the addition of manganese oxide to the feedstock to improve refractory life.146 GE has advertised that it is using a proprietary advanced refractory material for the recently constructed gasiers at Edwardsport, IN, but no details have been released.147 3.3.4.2. Membrane Walls. An alternative to the refractory wall is a water-cooled membrane wall. Seggiani developed a model of the slag ow down the membrane wall for the Preno gasier in Puertollano,148 which has provided a starting point for many researchers. This model was used to predict the eects of changes in the gasier operating conditions, considering both operating temperature and slag property changes. After such perturbations, it was estimated that the slag layer would take about 2 h to reach the new steady state condition. Li et al. used a simplied, steady-state version of this model to simulate the slag layer on the membrane wall of the TPRI (Thermal Power Research Institute) two-stage membrane wall gasier and found good agreement with practice in the pilot plant.149 Liang et al. performed a similar exercise in comparing its model of heat transfer behavior and slag deposition with a pilot plant.150 In follow-up work Lin, Liang, and co-workers extended their model to include more detail on the geometrical eects of studs and ns in the wall. With this they then investigated the stresses in the solid slag layer, both in steady state151 and during transitions.152 With this model it is possible to estimate the rate of change of operating parameters that can be achieved without risking cracking of the solid slag layer. Slag deposition on the walls of a boiler is undesirable for a number of reasons, not least of which is reduced heat transfer and loss of eciency. It is therefore not surprising that eorts are being made to understand the mechanisms involved and develop numerical models to be able to predict slag formation and deposition under these conditions.153,154 Yong and Ghoniem155,156 modied Seggianis model by assuming a cubic temperature prole across the molten slag layer, combined this with the steady-state slag ow model of Wang et al,.157 and included their own slag capture prediction criterion. They incorporated these submodels into a CFD (computational uid dynamics) model of a pilot-scale pressurized oxy-fuel combustor, but the same methodology could be applied also to a membrane wall gasier. For the gasication situation Ni et al. have developed a submodel to predict slag deposition and applied it both to membrane wall and refractory lined systems.158,159 3.3.5. Two-Stage Gasication. Eciency can be increased by gasifying in two stages. As shown in Figure 10, only part of the feed is gasied with oxygen in the rst stage. This rst stage operates under slagging conditions, and slag is withdrawn at the bottom. In the second stage the hot syngas is reacted with the remainder of the feed. The second stage feed is dried,
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Figure 10. Two-stage gasication. [Reprinted with permission from ref 8. Copyright 2008 Academic Press.]

devolatilized, and partially gasied. These second stage reactions are all endothermic. The unreacted char leaves the second stage entrained in the gas, the temperature of which is below the ash fusion temperature. The char laden gas can be cooled in a convection cooler and is separated from the char in a cyclone or lter (or both in series). The separated char is recycled to the rst stage, where the gasication of the carbon is completed. In this manner the ash associated with the second stage feed is also molten and discharged from the rst stage as slag. In typical state-of-the-art two-stage gasication processes, between 10 and 50% of the feedstock is introduced into the second stage. Phillips 66 is developing a system capable of accepting 100% feedstock to the second stage and operating the rst stage on recycled char only.160 For these conditions Tsang and Keeler report an exit temperature from the second stage of 400700 C, eliminating the need for a syngas cooler. At these temperatures some residual pyrolysis products can be expected in the gas. As a complement to this development, a low temperature tar conversion catalyst has been developed. Tar conversion of 100% is claimed at 400 C in the presence of sulfur.161 The catalyst is also CO shift active. Whether a selective mode of operation without shift is possible is unclear. Conventional two-stage gasication operates the rst stage with the total oxygen ow, injecting further coal into the second stage to eect a chemical quench. Zhang et al. at Tsinghua University in Beijing have introduced a dierent, oxygen staged gasication concept.162 The conguration is basically a conventional slurry feed downow quench gasier with a single top-mounted burner. The novelty lies in the fact that only about 85% of the total oxygen is supplied through the main burner, with the rest being injected through side-mounted horizontal jets at the bottom of the ame zone. The rst industrial scale (500 t/d) units with this design went into operation in 2006 with a refractory lining.163 However, the main focus of Tsinghuas subsequent development for industrial application has been on the use of a membrane wall without the staged oxygen feed. 3.3.6. Other Issues. 3.3.6.1. Fluxing. Flux addition to reduce the slag IDT is a well-known and commonly used technique in coal gasication and other processes. The Eastman Chemical Co. has operated a coal-to-methanol and acetyls plant since 1984. During this time the company has performed much development work to improve operations. In a recent paper it has reported on optimizing the ux to expand
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Chemical Reviews the range of suitable gasication fuels for their plant.164 The most important nd was the recognition that Mg-based uxes such as olivine can achieve better results in viscosity reduction than the more commonly used Ca-based uxes. Li et al. also investigated the eect of Mg-based uxes on an Anhui coal. They found that a reduction of the IDT from 1398 to 1350 C could be achieved with only 2.8 mass % Mg-based ux compared with 6.2 mass % Ca-based ux.165 3.3.6.2. Carbon in Slag. Carbon conversions of 9899.5% can be achieved in entrained ow gasiers. Much of the unconverted carbon is intimately associated with the slag and may be inaccessible to any oxidant which could convert it. Studies have been made to understand the partition of the unconverted carbon between coarse slag, ne slag, and, where relevant, y slag and the nature of the association with the mineral matter. There are three main routes in slag formation in a gasier. Coarse slag is derived from the slag which accumulates on and ows down the reactor wall before entering the slag quench chamber (which may or may not serve also as gas quench depending on gasier design). Finer particles of mineral matter also enter the slag quench and are designated as ne slag. A third stream is the y slag that leaves the gasier with the syngas. This may be collected separately in a dry lter or washed out in a scrubber. In the latter case the rundown water is usually mixed with the quench water blowdown, so the ne slag is a mixture from two sources. Zhao et al. examined the slag material from a downow slurry-feed quench gasier.166 Montagnaro et al. performed a similar exercise for an upow dry-feed gasier with syngas cooler and dry ltration.167 The basic ndings were directionally similar in that there was much more carbon in the ne slag than in the coarse slag and that the mechanism by which the carbon is entrained in the coarse and ne slags is dierent. The carbon in coarse slag has become surrounded by slag after impact. It has not had the same residence time in contact with the gas and is more reactive than the carbon associated with the ne slag. Gu et al. also examined the y slag from two Texaco gasiers and found that the carbon in the slag was more reactive than the parent coal char.168 The y slag is an important dierence between the two gasication processes. The y slag from the quench gasier is removed from the gas in the scrubber and mixed with the ne slag. Unfortunately, it is not clear whether this y slag was drawn from the scrubber rundown or, like the material examined by Zhao et al., the mixed ne slag from the quench. In the case of the upow gasier it is collected separately and was found to contain very little carbon (5 mass %). Independently of these studies of material from industrial gasiers, Shannon et al. have adopted an analytic approach to determining the mechanism by which carbon particles become trapped in the liquid slag layer on a gasier wall.169 3.3.6.3. Temperature Measurement. In an ideal situation, the control of a gasier operation would be by temperature control. This is done in uid bed reactors, where the temperature is usually less than 1000 C. The conditions inside an entrained ow gasier, however, make the direct measurement of temperature extremely dicult. In refractorylined gasiers thermocouples have been used extensively for oil gasication, but only have an average lifetime of about 6 months.170 In a coal gasier the expected lifetime would be even shorter due to slag attack on the ceramic sheath. Alternative, indirect methods such as using the methane
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content in the syngas to infer the temperature are used but are too slow to detect rapid upset conditions. Texaco made considerable eorts to develop a pyrometer for operation in a pressurized environment.171 Diculties to be overcome included maintaining a line of sight through the liquid slag on the gasier wall and understanding to what exactly the temperature measurement relatedgas, ungasied particles, or the opposite wall. The system was tested at the Polk Power Station gasier, but was not taken into industrial service. A dierent optical system was developed at about the same time using a single-crystal sapphire disk, but it has also not achieved commercial success. The search for a reliable and robust system that can be used in a gasier control system continues. A group at Stanford University has with support from EPRI developed a laser-based system that has been tested at a pilot-scale coal gasier at the University of Utah. A further test campaign was planned for November 2012 in the U.S. National Carbon Capture Center (NCCC) at Wilsonville, AL.172 3.3.6.4. Online Ash Analysis. Gasier control operates typically by mass ratio control between the oxidant supply and the feedstock to the gasier. This is often referred to as the oxygen-to-carbon (O/C) ratio, but in reality it is at best only an approximation, since any change in the coal quality cannot be factored in to the coal ow measurement. An increase in ash content of the coal at constant measured O/C ratio will lead to a higher real O/C ratio in the gasier and thus to a higher operating temperature. A change in the slag viscosity characteristics for the feed coal may require a higher operating temperature to maintain a free-owing slag ow out of the gasier. Ash quantity and ash quality are at present determined oine in a procedure taking some hours, so even with a good feedstock management system, a ne control is not possible. There is therefore considerable incentive to develop an online coal characterization device, which will allow more precise control of the gasier. Eastman Chemical Co. recognized the potential for such a device in its own operations, focusing in the rst place on ash composition and its eect on slag viscosity.173 Nonetheless this technology has not found use in other parts of the industry. An alternative approach using laser-induced breakdown spectroscopy (LIBS) is currently being developed at Lehigh University with support from EPRI.174 The project includes the development of an articial neural network model to relate the elemental composition as measured by LIBS to the IDT of the mineral matter. Field results in an operating power plant showed the LIBS technology to be accurate and repeatable within the requirements of a industrial operation. Laboratory validation of the technology under coalwater slurry conditions is proposed as a next step before application in a gasication environment.
3.4. Contaminant Species in Raw Syngas

3.4.1. Nitrogen Species. During gasication nitrogen species in the coal tend to form ammonia, hydrogen cyanide, and nitrogen. There is little published work on this topic specic to gasication, and much of the process has to be deduced from work primarily aimed at understanding NOx formation in a combustion situation. Both ammonia and HCN are potentially important impurities in process condensate from all gasication processes. In the Lurgi xed bed gasication process and also in the KBR/Southern TRIG uidized bed process,175 sucient ammonia may be formed that it is
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Chemical Reviews worthwhile recovering it as anhydrous ammonia for commercial gain. In many entrained ow gasiers the quantities of ammonia are insucient for this to be attractive. In such cases the ammonia is stripped out of the water and combusted in the sulfur recovery unit.176 Park et al. showed that increasing concentrations of steam inuence the distribution of nitrogen species in the syngas, in particular resulting in the increase of NH3 at the expense of N2.177 McKenzie et al. also found that steam played a vital role in converting a large proportion of coal-N into NH3. However, the importance of this eect decreased with increasing coal rank.178 Both these ndings are consistent with the industrial practice described above. Tsubouchi and Ohtsuka have pointed out the catalytic roles of metal cations, in particular Ca2+ and Fe3+, in secondary reactions of volatile nitrogen and char nitrogen,179 specically during pyrolysis. The presence of these ions, whether in the native coal or subsequently added to previously demineralized coal, aids the conversion of coal-N to N2 at the expense particularly of NH3. 3.4.2. Alkali Metals. 3.4.2.1. Alkalis in Fixed and Fluid Beds. Some lignites have a high content of sodium, in many cases present mostly as sodium chloride. In xed bed gasiers this has led to excessive clinkering. Extensive tests were performed using central German lignite with about 2.1 mass % Na (in coal, 18 mass % in ash). These tests were only partially successful, and the measures taken aected the economics negatively.180 Lignite with about 68% sodium in ash is successfully gasied in North Dakota, but also in this case great care has to be exercised to avoid excessive clinkering.181 In uid beds the present of alkalis can create the conditions for agglomeration. Dahlin et al. encountered agglomeration and depositing problems in a uid bed transport gasier when gasifying the same North Dakota lignite.182 The agglomeration was attributed to vaporization of the sodium species and the formation of sticky sodium silicates in combination with the bed material. Tests were made with a broad range of various sorbents, initially in the laboratory. Kaolin was determined to have the best potential and operation without deposition was successfully demonstrated during a 300 h test run in a pilot plant.183 3.4.2.2. Alkali Metals in Syngas. Much investigation into the presence of alkali metals in syngas is motivated by biomass gasication issues, but the knowledge gained can be of considerable use to coal gasication applications as well. While alkali metals can show useful catalytic eects in the gasication process itself, many species formed in the gasier leave it in the vapor phase and present issues in the immediate downstream equipment. Sodium compounds are known to condense out in syngas coolers causing fouling and possibly even blockage. Conventional removal of alkalis in a barrier lter requires prior cooling to about 450 C to ensure they are in the solid phase, which poses a limitation to hot gas cleanup concepts. Blas ing and Muller have investigated the release of alkalis, sulfur, and chlorine in an eort to generate a basic understanding of the phenomena, both in a batch process184 and in a drop tube reactor under helium with 5 mol % oxygen.185 The main alkali species present in the gas were NaO, KOH, NaCl, and KCl. Furthermore, they found, like others, that lignites with high Al and Si contents had a high retention capability for alkali metal species, especially for hydroxides, under gasication like conditions at 1400 C. Weindlich and
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Muller reviewed a wide variety of potential sorbents including bauxite, kaolin, and sand. They concluded that kaolin with an Al2O3/SiO2 ratio between 1/5 and 1/3 was an eective sorbent for reducing alkali metal chlorides to below 100 ppbv.186 The sorbent can then be extracted from the gas on a high temperature ceramic lter. Matsuoka et al. have investigated the behavior of alkali and alkaline earth metals in gasication of low rank coals. While Ca species were found to interact with inherent clay minerals to form complex aluminosilicates, dispersed species of Na and K mostly vaporized and no interaction with inherent minerals was observed.187 3.4.3. Trace Elements. Trace elements in coal are typically dened as those with concentration of less than 1000 ppmw in the mineral matter. Many of these trace elements present risks to the environment or to synthesis catalysts, and it is necessary to have a good understanding of their fate in a gasier and downstream processing. This understanding is an important prerequisite to the development of an eective design to mitigate such risks. The reducing atmosphere in a gasier will cause a dierent speciation from that known from combustion. Furthermore, details of gasication processes such as operating pressure and temperature as well as the primary gas treatment (solids and halide removal) will lead to dierent partitioning, so each process must be considered individually. Trace elements are contained in the coal in dierent forms and are associated with dierent main elements, both organic and inorganic. Although most gasication processes operate at temperatures which destroy such association, this is not always the case. Wang et al.188 and Vejahati et al.189 have presented reviews examining correlations between trace elements and main elements in coal. Font et al. have examined the partitioning of trace elements at the ELCOGAS Preno IGCC in Spain.190 They found mercury to be consistently only in the gas phase, but the partitioning of arsenic and selenium exhibited considerable variation. The proportion of arsenic reporting to the gas phase varied between 0.01 and 42%. The slag contained only about 5% in all four measurement campaigns with the variation being taken up by the y ash. Vapor phase selenium varied between 5 and 23% of the totalagain with most of the rest in the y ash. A correlation was found between the Cl content of the gas and the amount of these volatiles, which is attributed to the formation of low boiling chlorides. Conversely, increasing the amount of calcium was found to decrease the amount of vapor phase heavy metals, presumably by preferentially binding the Cl. Li et al also found indications that the increase of volatility of mercury correlated with the halogen content of the coal.191 One must expect that the partitioning characteristics of a quench gasier or a two-stage gasier will be dierent from those of a single-stage upow gasier. While there is a limited amount of data on partitioning available from the Polk and Wabash IGCCs, further detailed studies of such systems need to be performed. Considerable work has been undertaken by Bunt and Waanders on industrial xed bed gasiers in conjunction with Sasol to determine partitioning and speciation of Hg, As, Se, Cd, and Pb192 as well as of Cu, Mo, Ni, and Zn193 and of Ba, Co, Cr, Mn, and V.194 In all cases the behavior in the drying and devolatilization zones of the reactor were considered separately from the gasication and combustion zones. This work was accompanied by FactSage equilibrium calculations, which in most cases showed reasonable agreement. Discrepdx.doi.org/10.1021/cr400202m | Chem. Rev. 2014, 114, 16731708

Chemical Reviews ancies were found, however, for As, attributed to condensation phenomena during countercurrent ow not included in the FactSage model used. While the results will not be applicable to other gasier types, the theoretical underpinning of the measurements will allow good estimation of similar gasiers operating on dierent coals. This work was followed up by a comparison of the behavior of Hg, As, Se, Cd, and Pb in similar gasiers operating on Dakota lignite.195 Despite dierences in feed concentrations and mode of occurrence of these metals in the lignite and despite the lower operation temperatures required for lignite gasication, the partitioning behavior was found to be generally similar. In particular, As was shown to be the least volatile. If one considers the work of Font et al. at ELCOGAS,190 then the inuence of halides may need to be considered, particularly given the relatively high chloride content of the North Dakota lignite. Note that in a laboratory-scale xed bed gasier Li et al. found some temperature eect on the volatility, particularly of Pb and As under a CO2 atmosphere.196 In a related project Wagner et al. investigated the overall mercury mass balance across the total Sasol petrochemical complex.197 Whereas Bunt and Waanders had drawn their balancing envelope around the gasier only, the wider study also determined that the mercury retention in the tar removal from the syngas was minimal (less than the ash). Essentially all the mercury in the raw syngas is captured as a solid in the Rectisol plant prior to processing in the FischerTropsch synthesis, leaving the conventional coal-red auxiliary boilers as the primary mercury emission source from the plant. It is interesting to note the contrast with the adsorption of mercury on y ash in the primary gas cleaning at the ELCOGAS plant described above.
3.5. Syngas Coolers

Review

High temperature gas cooling is one of the critical design aspects of any entrained ow slagging gasier. The gas leaving the reaction chamber contains y slag, small entrained droplets of molten ash, which on cooling pass through a plastic, sticky phase before solidifying. This temperature range between freeowing liquid and dry solid poses diculties for heat exchange, since the y slag will tend to adhere to any heat transfer surface with which it comes into contact as it cools. Techniques to bridge this no-go zone must ensure that no sticky ash comes into contact with heat exchange or other surfaces, while it is in this intermediate temperature range. This can be achieved in a number of ways, including quenching with water or cooled syngas. 3.5.1. Radiant Coolers. One approach to addressing the problem of sticky ash is the use of a radiant cooler. Flow patterns in such a cooler are designed to minimize impingement of slag particles onto the heat exchange surfaces so that they do not adhere and foul the surfaces. Such a ow pattern inhibits convective heat transfer; thus radiant heat transfer is predominant. Texaco used such designs in its SAR198 and Cool Water199 development and demonstration plants. This solution was also implemented at the industrial scale at the Polk 250 MWe Power Station and included lessons learned from the earlier two plants.200 The use of radiant heat transfer, while addressing the fouling issues, does not provide a high heat ux, so radiant coolers tend to be large and expensive. The cooler (shell plus internals) for Polk weighs 740 t. By and large the objectives set for the Polk unit were met. The design exit temperature was 1400 F [760 C], but despite not using the
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soot blower system, the exit temperature is consistently below 1350 F [732 C].201 Virtually all of the slag and about half the y ash are collected in a water pool (sump) located at the bottom of the cooler. The balance of the y ash continues to be entrained in the gas stream, which leaves the radiant cooler through two exit ducts to two conventional shell and tube convective heat exchangers. Despite the low measured gas temperatures, the y ash is still sticky and accumulates on the inlet tube sheet of the convective syngas cooler, which has been a constant source of unplanned maintenance. Research in this area has focused on optimizing heat transfer so as to reduce the overall weight and cost of such units and also gaining a better understanding of the ow patterns and y ash behaviorin particular so as to protect the downstream equipment. General Electric (successor to Texaco) has further developed the Polk design for a new 2 309 MWe plant in Edwardsport, IN, which started up in October 2012. The radiant cooler design used at Edwardsport will raise approximately 30% more steam than the radiant cooler at Tampa. The diameter of the radiant cooler will be 0.6 m (2 ft.) or 10% less than that at Tampa, but the overall length will be 2.75 m (9 ft) more while maintaining the overall weight of 740 t.202 In addition, GE has modied the sump of the radiant syngas cooler (RSC) into a water quench, by submerging the gas outlet of the cooler.203 This eliminates all risk of y ash fouling in the downstream equipment. This concept was already considered after the Cool Water experience204 and further rened.205,206 Details of the actual execution in Edwardsport, however, have not been published. The East China University of Science and Technology (ECUST) has published results of its modeling of a radiant cooler.207 This provides useful insights, because such calculations were previously kept as proprietary knowledge of the vessel manufacturers. The ow pattern results compare well with a cold ow model.208 It is noteworthy that the particle temperature prole is calculated separately from that of the gas.209 However, the temperature prole within the particles is not yet addressed. When looking for explanations of the experience at Polk, the possibility of a warmer, soft core surrounded by a cooler thin solid shell, which is damaged on impact, needs to be considered. A start-up case with lower pressures and higher velocities would also be of benet. The existing work provides a good basis for such additional studies. Siemens has also been developing a radiant cooler to oer in conjunction with its dry-feed gasier.210 As with the GE design, the radiant cooler is followed immediately by a water quench to reduce fouling risks. The Siemens design retains its existing spray quench system rather than submerged quench. The U.S. National Energy Technology Laboratory has initiated a program to explore ways to mitigate and better manage syngas cooler plugging and fouling.211 Initial analytical work has started, and associated laboratory work will proceed during 2013. 3.5.2. Quench Systems. The alternative to syngas cooling by steam raising is a water quench. Quench systems are cheaper than syngas coolers, but in power applications failure to use the hot syngas for steam raising will carry a 23% points eciency loss. For most chemical applications a CO shift is requiredat least for part of the gas stream. Typically the syngas exits the quench water saturated at 200 C or higher. This is then available for the CO shift, so the performance penalty is less.
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Chemical Reviews Most chemical applications will include a quench cooling system. There are two dierent designs: the submerged quench with dip tube as practiced by, e.g., GE Energy and the spray quench of which the Siemens gasier is an example. Shell and Uhde, both of which had previously oered exclusively steam-raising coolers, have both announced the development of quench designs. The rst Uhde quench gasier will be in a biomass-toliquids demonstration plant in France. 212 Shell has a demonstration plant under construction in Nanjing.213
3.6. Primary Gas Cleaning

Review

induced by the reverse pulse cleaning. In addition, the dust is never fully removed from the candle surface, so dust ingress into the lter structure after each cleaning pulse is avoided. Chen et al. have proposed a new quality control method for ceramic lter candles using a nondestructive dynamic characterization technique.219
3.7. Alternative Congurations

The raw syngas exiting a gasier includes some residual entrained solids in the form of y slag. Furthermore, chlorine in the feedstock is mostly present in the gas as vapor-phase HCl. Removal of solids and chlorides from the raw syngas is usually considered as part of the complete gasication process and as such is supplied by all the gasication technology vendors. Particulate removal may be performed wet, in a scrubber, or dry with a candle lter. The wet systems combine particulate removal and chloride removal in a single step. The scrubber rundown, or black water, must be cooled and cleaned. While the water handling in the dry systems is much simpler, the candle lter itself is a source of maintenance cost. In any case, a water wash to remove chlorides is required downstream the lter. In contrast to wet particulate removal, the wash water is largely free of particulate matter. 3.6.1. Solids Removal from Raw Syngas. Dry solids removal by ltration is used in many dierent process congurations. Compared with wet systems, it has the advantage of simplifying the treatment of process condensate and the water used to remove halides downstream from the lter. In uid bed processes, e.g., TRIG or U-Gas, the purpose is basically similar, though the solids are y ash rather than y slag. In two-stage gasiers, e.g., E-Gas or MHI, the task is dierent, in that the solids comprise char and ash which are to be recycled to the gasier rst stage. Heidenreich has reviewed the current status of hot gas ltration, and the reader is referred there for details.214 In some entrained ow processes, e.g., Shell and Preno, the recovered y slag can be sold as a byproduct, though quality control is important. Font et al. have developed a quick method for determining the glass content of y ash.215 Industrial experience is generally in the temperature range up to 250 C, although there are examples of higher operating temperatures, e.g., downstream the Var namo biomass gasier, where the temperature was 350400 C.216 Although ceramic candles have the capability of operating at 800 C or higher, process application in gasication is limited to about 450 C. Above this temperature the risk of some of the alkalis passing through in the vapor phase is considered too high. Both ceramic (Shell, Preno) and sintered metal (E-Gas) candles are used in industrial operations. As part of the development of the TRIG process, Southern Company Services tested various materials including iron aluminide and silicon carbide.217 Sharma et al. have reviewed recent developments and also discussed ideas for further research.218 These include adding adsorbents to syngas at high temperatures to x the alkalis and halides, thus allowing full exploitation of the high temperature capability of ceramics (cf. Blas ing and Muller in section 3.4.2.2). They also introduce the concept of a pulseless lter with continuous partial removal of the solids. This has the advantage of eliminating the stress cycling on the candles
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A number of alternative congurations have been considered and in some cases been applied industrially. Plasma gasication has been applied in a number of plants for waste gasication, but not industrially with coal. Underground gasication is advocated by some, and a demonstration unit in Australia has in fact produced small quantities of FischerTropsch liquids.220 The issues are however mainly of a geological nature and therefore not discussed here. 3.7.1. Catalytic Gasication. One approach which has attracted attention over the years is that of catalytic gasication. This approach utilizes the favorable equilibrium for methane at low temperatures. Conventional uid bed processes operating in the 8001000 C range produce a gas with a methane content in the range 36 mol %. A catalytic gasication process can operate in the range 600700 C, producing signicantly more methane.221 Such a process was developed by Exxon between 1978 and 1981 but not pursued to industrial maturity.222 This technology has been developed further by Great Point Energy, Inc., including its use for petroleum coke gasication.223 However, little of a technical nature has been published on these developments. It is generally well documented that potassium salts exhibit a higher catalytic eect than calcium.224,225 In a comparison between potassium salts and calcium salts, Zhang et al. found that calcium salts provided a maximum conversion rate in the low conversion range, while potassium salts were more eective as the conversion increased.226 However, there is substantial catalyst degeneration and loss of potassium salts by catalyst volatilization or formation or water-insoluble compounds such as KAlSO4 after contact with the mineral matter in the coal.227 In this respect calcium compounds are far less sensitive and this has maintained the interest in calcium as a catalyst. However, also in this case it is necessary to have a suitable means of catalyst recovery for reuse. Much of the calcium is present as water-insoluble calcium carbonate after gasication, so organic or inorganic acids may be used for calcium recovery. Zhang et al. have used crude vinegar, a light fraction of the liquids derived from biomass pyrolysis.228 The results were superior to the equivalent technique with acetic acid. Furthermore, it was found that the use of crude vinegar could improve the catalytic activity of the indigenous crystalline calcium in a bituminous coal. Wang, Jiang, and co-workers have also been researching catalytic gasication, but the aim is to minimize the methane make while still using K2CO3 as catalyst, but they limit the methane make by separating pyrolysis and partial oxidation of the resulting char.229 Further deactivation of the catalyst could be reduced by the addition of Ca(OH)2.230,231 This concept has been extended to catalytic gasication of petroleum coke, and an optimum temperature for hydrogen production of around 750 C was determined.232 Sharma et al. have investigated the catalytic gasication of HyperCoal, a coal that has been separated from its ash content by solvent extraction. The gasication rate was examined over
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Chemical Reviews the temperature range 775650 C with a K2CO3 catalyst. Gasication with HyperCoal derived from a bituminous coal was slow at 650 C, but the catalyst showed no signicant degradation after being recycled four times.233 HyperCoals made from a subbituminous coal and a lignite were also tested under similar conditions. HyperCoals produced from low rank coals showed a higher reactivity, and it may be possible to gasify them at temperatures below 650 C.234 Methane content remains low and the steamcoal ratio can be used to inuence the H2/CO ratio of the product gas.235 A gas suitable for methanol and other chemicals could be produced by adding CO2 to the steam.236 3.7.2. Hydrogasication. Hydrogasication, the direct gasication of coal with hydrogen to methane (SNG), was the subject of extensive work in the 1970s and 1980s. In particular, Rheinbraun, owner of much of the Rhenish lignite deposits in Germany, developed it to the point of building a 10 t/h pilot plant, which operated from 1983 to 1986.237 Work on this development was not pursued further because of unattractive economics. The concept or aspects thereof have been reexamined since then from time to time, most recently by Tomeczek and Gil.238 3.7.3. Chemical Looping. Chemical looping is a designation for a group of processes in which a solid carrier, typically a metal oxide, is oxidized in one reactor (oxidizer) and is transported to a second reactor (reducer), where it gives up its oxygen in a reaction with fuel. The carrier is then returned to the rst reactor to be reoxidized. This basic concept as shown in Figure 11 can be used in a wide variety of

Review

While considerable progress has been made with gaseous fuels, devising an implementation for a solid fuel which overcomes the limitations imposed by the solidsolid mass transfer requires considerable ingenuity.243 Initial eorts were therefore focused on applying the chemical looping process as a means of converting a desulfurized syngas generated in a conventional gasier to separate streams of hydrogen and carbon dioxide.244246 Tests were performed with solid fuels in the 10 kW unit at Chalmers, and the results showed some promise.247 This work is still ongoing.248 Research has also been initiated into direct chemical looping combustion of coal (CDCL) at Ohio State University (Figure 12). A 25 kW subpilot unit ran for over 200 h in January 2013.

Figure 12. Coal direct chemical looping (CDCL). [Reprinted from ref 250. Copyright 2012 American Chemical Society.]

Figure 11. Chemical looping combustion. [Reprinted with permission from ref 242. Copyright 2010 Elsevier.]

applications including combustion and gasication and both with gaseous or solid fuels. Chemical looping combustion (CLC), in which the nitrogen from the combustion air is discharged from the oxidizer and the CO2 from the fuel is discharged from the reducer, opens the way to an elegant method for CO2 capture.239 There is also a considerable amount of research devoted to chemical looping reforming (CLR) for syngas and hydrogen applications.240 Most early work focused on gaseous fuels in either CLC or CLR mode using dual uid bed technology for the reactors. Important centers for this development were Chalmers University, Gothenburg, Sweden, The Technical University of Vienna, and CSIC, Zaragoza, Spain, which cooperated with Alstom and BP on a project to build and operate a 10 kW reactor at Chalmers. Synthesis gas production by chemical looping reforming of natural gas has been demonstrated in pilot scale operation at scales between 10 and 145 kWth.241,242
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Solid fuel conversion was nearly 100% and the purity of the CO2 stream was over 99%.249 Plans are in place to install a 250 kW pressurized version of the technology at the NCCC later in 2013. Questions still remain to be answered. While the fate of impurities such as sulfur, chlorine, and nitrogen compounds has been considered at least in simulations,250 issues such as the fate of pyrolysis products also need addressing. Moghtaderi has reviewed process developments in chemical looping in 2011, and the reader is referred to this for more detail.251 Chemical looping is still in an early stage of development, and considerable work remains before it becomes an industrial process which can convert coal into hydrogen or syngas. Nonetheless the potential is apparent. 3.7.4. Other. The main gasi cation reactions are endothermic and part of the fuel is combusted to provide the necessary heat. It is therefore not surprising that alternative forms of heat to feed the reaction have been considered. Using solar energy is one possibility which could increase the eciency of coal usage by, potentially, some 30%. Piatkowski and Steinfeld worked with a 5 kW bench scale xed bed reactor operating in batch mode.252 Maag and Steinfeld have extrapolated results from a 3 kW reactor to model a 10 MW particle ow reactor.253 Molten bath gasiers were known from the 1980s, using both molten iron (e.g., Klockner) and molten slag (e.g., SaarbergOtto). Little work has been performed since then, but Li et al. have tested three dierent Chinese coals in a slag bath. It is unclear whether they intend to pursue this further.254

4. GAS TREATING Raw syngas from coal gasication contains sulfur species, hydrogen chloride, ammonia, HCN, and volatile species of various trace metals such as mercury, arsenic, and selenium. At
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Chemical Reviews Table 3. Specications for Various Synthesis Gases

product ammonia H2/CO total S <100 ppbv poisons CO + H2O < 20 ppmv O2+ CO2 < 10 ppmv Cl < 100 ppbv P, As halides, As halides < 10 ppbv NH3 < 10 ppmv HCN < 10 ppbv Fe/Ni carbonyls < 10 ppbv C2H2 < 5 ppmv unsaturates < 300 ppmv O2, strong acids, HCN, dienes other H2/N2 = 3.0 inerts < 2%

Review

source a, b, c

hydrogen (by methanation) methanol

2.0 (H2+CO2) 2.05 (COCO2)

<100 ppbv <100 ppbv

CO + CO2 < 2% O2 < 1% CO2 3%

d c, e

oxo alcohols MEG (for cryogenic H2CO separation) SNG FischerTropsch (dependent on process)

1.0 1.5 3.0 1.32.6

H2S, COS, organosulfur <100 ppbv <20100 ppbv <10 ppb to <1 ppmv

CO2 < 0.5% CO2 < 100 ppmv H2O < 10 ppmv

halides, As NH3, HCN < 1 ppmv halides < 10 ppbv alkaline metals < 10 ppmv tars, phenols Hg, As, Se N2 < 6% preferred < 1% CH4 34%

DRI

0.5 (CO + H2) >2 (CO2 + H2O) preferred > 11

<0.3% preferred < 100 ppmv

Reference 285. bVancini, C. A. Synthesis of Ammonia; Macmillan: London, 1971. cSpath, P. L.; Dayton, D. C. Preliminary ScreeningTechnical and Economic Assessment of Synthesis Gas to Fuels and Chemicals with Emphasis on the Potential for Biomass-Derived Syngas; Report TP-510-34929; U.S. DOE-NREL: Golden, CO, December 2003. dMuller, W. D. Gas Production. In Ullmanns Encyclopedia of Industrial Chemistry, 5th ed.; VCH: Weinheim, Germany, 1989, Vol. A12, p 245. eReference 323. fBahrmann and Bach. Oxo synthesis. In Ullmanns Encyclopedia of Industrial Chemistry, 6th ed.; Wiley-VCH: Weinheim, Germany, 2003; Vol. 24, p 553. gBoerrigter, H.; den Uil, H.; Calis, H.-P. Green Diesel from Biomass via FischerTropsch Synthesis: New Insights in Gas Cleaning and Process Design. Presented at Pyrolysis and Gasication of Biomass and Waste. Expert Meeting, Strasbourg, October 2002. hReference 358.
a

high temperatures also alkalis can be present. Chlorides as well as part of the ammonia and HCN are generally removed in a water wash. Alkalis can be removed either wet in a scrubber or dry in a particulate lter. These processes are generally integral to the gasication process as described above. Gas purication processes are devoted to removing the sulfur species and the remaining traces according to the requirements of the downstream synthesis process. The H2/CO ratio of a raw syngas produced from coal is in many cases too low for the requirements of the synthesis process. In such cases shifting the CO with steam to H2 and CO2 will be needed, probably with a subsequent CO2 removal step. The CO shift is usually classied as syngas conditioning. Gas treatment includes both purication and conditioning. Typical requirements of various syntheses are listed in Table 3, and these specications provide the basis for purication and conditioning processes.
4.1. Desulfurization

Sulfur in raw synthesis gas generally reports as H2S and COS, with the latter representing anything between 5 and 10% of the total sulfur. In some cases such as the Lurgi xed bed gasier other species such as thiols may be present in small (ppmv) quantities. Given the fact that sulfur is a poison to a wide variety of catalysts, its removal down to parts-per-billion levels is an important part of any coal-to-chemicals complex. State-ofthe-art technology uses regenerable physical or chemical solvents such as methanol (Rectisol process), dimethyl ethers of polyethylene glycol (Selexol process), or amines. The
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physical solvents have the advantages of being able to remove H2S and COS to a residual 110 ppmv (Selexol) or even 0.1 ppmv (Rectisol), of being selective, and of having a (relatively) low energy demand for solvent regeneration; it is acknowledged, however, that they are very expensive in capital cost. Amine washes generally require much less capital expenditure, but have a very high steam demand for solvent regeneration. In view of this cost situation, for a long time there has been considerable interest in developing alternative systems that can oer Rectisol performance at MDEA [methyl diethanolamine] cost.255 A number of dierent approaches have been applied to nding a solution to this task, but most of them have been based on adsorption technologies. Performing this task at temperatures described as warm (250500 C) or hot (>750 C) has an added attraction for power applications, since avoiding dropping the temperature below the water dew point can improve the cycle eciency by up to 3% points. Comprehensive reviews of development in adsorption technologies have been published by Cheah et al. in 2009256 and by Meng et al. in 2010.257 Both these reviews focused largely on the use of metal oxides in biomass gasication applications, but many of the issues are the same as for coal. One major dierence is that coal-based syngas is likely to contain signicantly more sulfur than syngas from biomass. This will shift the economic break-even point between adsorption and absorption technologies in favor of the latter. The other principal dierence is in the content of trace elements, which may or may not impact the ecacy of a particular adsorbent. Metals considered in these reviews include
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Chemical Reviews

Review

Figure 13. RTI high temperature desulfurization process. [Reprinted with permission from ref 259. Copyright 2012 RTI International.]

those of zinc (also zinc ferrite and zinc titanite), copper, calcium, manganese, iron, and some rare earths. 4.1.1. Zinc. The work on regenerable zinc oxide based adsorbents that has progressed furthest toward commercial application is that of RTI International. The quantities of sulfur in a coal-based synthesis gas will require a regenerable sorbent. While zinc oxide has many advantages and is regularly used as a disposable sorbent in xed bed polishing application, it has proved insuciently abrasion resistant to be used successfully in a uid bed. RTI have developed a ZnO/ZnAl2O4 sorbent that demonstrates an attrition rate (as dened by ASTM D5757-95) of less than 2.258 This is used in a transport reactor, in which H2S and COS are picked up by the sorbent in the riser. The sulfur on the sorbent is oxidized to SO2 in the regenerator before the sorbent is recycled to the riser again (Figure 13). A 460 m3n/h gas throughput pilot unit was eld-tested for about 3000 h on a slipstream from the quench gasier of Eastman Chemicals Co.s methanol plant at Kingsport, TN, in 2005/2006. The plant was operated at dierent pressures between 21 and 40 bar in the temperature range 425540 C. With a sulfur inlet concentration of 0.70.9 mol %, purities in the range 58 ppmv H2S + COS could be achieved. A larger, 54 000 m3n/h demonstration unit is under construction to process about 30% of the gas from the gasier with radiant cooling at Tampa Electrics 250 MWe Polk Power Station. This is part of a carbon capture demonstration, which is planned to start up in early 2014 and operate for 50008000 h259. This is about half the size of what might be considered a typical ammonia or methanol plant. Schmidt et al. have investigated the potential for using S Zorb, a ZnNi-based sorbent used for gasoline desulfurization as a gas, in a warm syngas cleanup environment.260,261 Initial work was concerned with conrming the sulfur loading and activity in a H2, CO, and H2O atmosphere in the laboratory. Further work has now been performed on determining the impact of NH3 and HCl on sulfur removal.262 Ammonia appears to pass through the sorbent without detrimental eect. HCl is adsorbed and breaks through simultaneously with H2S. 4.1.2. Iron. An alternative adsorbent to zinc is iron. In one sense this is not a new technology, since the use of iron sponge (iron oxide typically on a wood chip carrier) was a traditional means of reducing sulfur in town gas in late 19th and early 20th century town gas plants. Irons wide availability and
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low cost still provide an incentive to develop a version of the process that meets modern environmental requirements. One such eort263 including the use of coal ash as a carrier264 is taking place at Taiyuan University of Technology. 4.1.3. Calcium. Limestone and other calcium-based sorbents are attractive as sorbents on account of their low cost and wide availability, even if the equilibrium residual sulfur is higher than with a zinc-based sorbent. They are often used as in-bed sorbents in uid bed gasiers [see ref 257]. For example, limestone has been used in the transport gasier at the Power Systems Development Facility (PSDF), Wilsonville, AL.265 Ruggeri et al. propose a xed bed of CaOMgO for bulk desulfurization and simultaneous tar cracking in the syngas.266 The solid phase is regenerated and recycled with the H2S recovered as a separate stream suitable for treatment in a Claus plant. A second stage wash with Ca(OH)2 solution is used to reduce the residual sulfur content of 0.1 ppmv. 4.1.4. Other Sorbents. Rare earths have also been suggested as potential sorbents for H2S, e.g., by Liu et al.267 and Dooley et al.268 A further possibility is the use of activated carbon as suggested by Itaya et al.269 and by Zhou et al.270 4.1.5. COS Hydrolysis and Removal. Various H2S absorption technologies, among them amines and Selexol, have a much reduced capability of removing COS compared with H2S. This is often addressed by selective hydrolysis of COS to H2S and CO2. Conventional catalysts are however sensitive to poisoning by halides,176 and thus in a conventional lineup, COS hydrolysis takes place downstream the water wash. The need to raise the temperature of the gas again in order to maintain sucient superheat over the water saturation temperature is a cause of ineciency. Honjo et al. discussed the development of a halide resistant catalyst in 2008.271 Yoshida then reported on the results of 16 000 h of operation in an industrial environment. It has operated without replacement since 2007, and during that period it has regularly achieved 95% COS conversion in the presence of up to 100 ppm halides.272 Zhou et al. have investigated the use of a FeMnCe mixed oxide sorbent to remove COS at high temperature (280320 C).273 The work included varying ratios of H2:CO:CO2, but did not investigate the eect of halides. Li et al. have suggested using AlNa promoted activated carbon for the removal of carbonyl sulde at low temperature (4070 C).274
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Chemical Reviews
4.2. Trace Element Removal

Review

As described in section 4.1, one of the primary attractions of warm gas desulfurization is that, in power systems, the avoidance of cooling the gas to ambient or subambient temperatures can provide a signicant increase in cycle eciency. If, however, removal of other trace elements such as mercury or CO2 requires gas cooling, then much of the benet of warm gas desulfurization is lost. There is therefore strong interest from the power sector to operate all trace element removal at higher temperatures. Whether this is of signicant benet for chemical applications or not remains to be seen. Where compression is required, e.g., for ammonia synthesis, a low suction temperature is desirable to reduce compression energy requirements. Furthermore, without cooling there would still be substantial quantities of steam in the gas, which would cause diculties of one sort or another for most synthesis processes. Nonetheless, there may be some scope for cost saving with warm gas cleanup, even without the cycle benets available to power applications. 4.2.1. Mercury. Mercury removal from natural gas on sulfur impregnated activated carbon at ambient temperatures has been a mature technology in LNG (liqueed natural gas) plants for decades.275 While not often used in syngas applications, one example is Eastman Chemical Co.s coal-to-methanol plant in Kingsport, TN, where it has been in place since 1983. Mercury capture is reported to be 9095%276 and is certainly sucient to prevent contamination of the highly sensitive downstream acetyl operation.277 However, as noted above, ambient operation would vitiate the advantages of warm gas desulfurization. Couling et al. have performed a thermodynamic screening of metal oxides and metal suldes as sorbents for elemental mercury at elevated temperatures.278 A number of these showed promise as mercury sorbents in principle, but not in syngas service because they react with hydrogen. Pavlish et al. have tested monoliths with an undisclosed coating at temperatures in the range 180 260 C with promising results.279 Granite et al. found that palladium on alumina had signicant potential for mercury removal from syngas at temperatures in the 200370 C range.280 Further work has shown that palladiumalumina sorbents for high-temperature capture of mercury have potential to remove also arsenic.281 A series of tests has been performed at the U.S. National Carbon Capture Center on real syngas from a TRIG pilot-scale gasier between 2008 and 2011. The results show promise in that with 5% Pd on Al2O3 100% removal of Hg, As, and Se was achieved for up to 642 h. With 2% Pd operating at 260265 C and 14 bar, nearly 100% Hg removal could be maintained for 1011 h. A further test is planned for 2013 at a low Pd loading and higher syngas ow rates.282 It has been noticed that carbonyl sulde can be formed catalytically on Pd/-Al2O3 sorbents.283 Gupta has reported on a multicontaminant control process, which also uses an unspecied adsorbent for mercury removal. A 5 MWe equivalent slipstream from the Polk warm desulfurization demonstration plant mentioned above is under construction.284 Wagner at al.197 report that the Rectisol gas cleaning process [in the Sasol coal-to liquids (CTL) complex] is a functional sink that removes mercury from the crude gas as a solid. It is removed during maintenance cleaning and disposed of as per requirements for mercury containing waste. 4.2.2. Arsenic and Selenium. Arsenic and selenium are two further volatile metals that can occur in untreated syngas.
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Arsenic is a catalyst poison for ammonia285 and other synthesis catalysts. It can also be found as a deposit on gas turbine blades, which creates the need for additional safety precautions during maintenance operations (ref 11, p 1-67). Selenium can nd its way into wastewater streams.176 Gupta259 reports that adsorbents for arsenic and selenium are included in the 5 MWe equivalent multicontaminant control process demonstration at Polk described above. Poulston et al. have extended their work on Hg adsorption on a PdAl2O3 sorbent to include AsH3. Tests with a simulated syngas at temperatures between 204 and 288 C were encouraging, showing very high removal eciencies and an arsenic adsorption capacity in excess of 7 wt % [of total sorbent].286 This work will be continued in 2013 as part of the testing at NCCC mentioned above. Riess and Muller made their investigations at much higher temperatures (800 C) as an extension of their work on high temperature alkali removal. The focus was therefore on sorbents already screened for that program. A broad range of sorbents has shown potential for retention of arsenic such as y ash, bauxite, -Al2O3, and corundum as well as coppercontaining sorbents.287
4.3. Water Gas Shift (WGS)

The water gas shift reaction

CO + H 2O(g) CO2 + H 2
0 H298K = 41 MJ/kmol

(7)

is a long-known and well-understood reaction. It was present in the ow sheet of Boschs rst ammonia plant in 1913.288 Nonetheless, it is still the subject of a considerable body of research. There are three groups of catalysts used industrially: (a) The CoMo-based sour shift catalyst is the most widely used of the three downstream of coal gasiers. It operates in the sulded state and typically requires between 500 and 800 ppmv H2S in the feed gas to maintain it in this state. There are, however, indications that the loss of activity in the nonsulded state is not as great as previously assumed.289 (b) The Fe-based sweet shift (also known in the context of steam reforming plants as high temperature shift) catalyst is found in a number of gasication plants downstream the desulfurization unit. (c) The Cu-based low temperature shift catalyst is extremely sensitive to sulfur poisoning and there is only one known application in a gasication plant.290 Many plants operating with sour shift have full quench cooling downstream of the gasier. This can provide a steamto-CO ratio of about 3:1 in the saturated synthesis gas depending on pressure. This is more than sucient steam to drive the reaction to equilibrium, and typically in a three-stage unit with intercooling a residual CO slip of about 0.7 mol % can be achieved. This is advantageous for ammonia syngas or hydrogen, but hardly necessary for methanol or Fischer Tropsch applications. For gasication processes using syngas cooling for steam generation, the steam has to be added back into the gas, which impacts negatively on the energy balance of the plant. The steam serves not only to provide a driving force for the equilibrium reaction but also to suppress undesirable side reactions, such as carbon or methane formation. Catalyst vendors such as Haldor Topse,291 Johnson Matthey,292 Clariant, and Lianxin293 have therefore been making eorts to
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Chemical Reviews reduce the steam requirement for CO shift. In all of these cases very little detail has been published for commercial reasons. 4.3.1. Alternative Catalysts. Besides the application in bulk chemicals such as ammonia and methanol, the water gas shift reaction has also been considered as a step in producing hydrogen for fuel cell applications. Hwang et al. describe some disadvantages of the conventional catalysts for this application. They require long-term activation procedures, are pyrophoric, and are intolerant of poisons, condensation and oxidation.294 Further, there could be additional advantages to operation at lower temperatures. Various workers are therefore looking at noble metal catalysts for this application, particularly CeO2supported Pt295 and Pd,296 but also with other support systems.297 The extent to which all the issues listed by Hwang et al., in particular poisoning, are addressed remains for future work. Haryanto et al. have looked at the use of Ni as a WGS catalyst. Activity for WGS at 450 C was found to be good. Although a loss of eciency for hydrogen production due to methane formation was noted, there was no discussion of the associated exotherm. This will need to be addressed before Ni can become a contender for this application.298 4.3.2. Reactors. A dierent route to improving the eciency of the CO shift process is to remove one of the products continuously from the reaction space. This causes the shift reaction equilibrium to move toward the product side, thus increasing the conversion. Two approaches have been taken. Sorption-enhanced water gas shift (SEWGS) is a method by which CO2 is captured on a sorbent in the reactor. The reactor is taken oine cyclically and the CO2 desorbed. Multiple reactors with staggered cycles ensure continuous operation. Allam et al. screened many dierent potential sorbents before identifying a promoted hydrotalcite as showing the highest cyclic capacity for removal of CO2 under the conditions of interest.299 This was tested rst in a single column unit and then demonstrated in a multicolumn unit. The resulting performance did not reach levels predicted through modeling and required for economic value.300 However, there is continued interest in the concept,301 including the use of alternative sorbents.302 Steen has reported on a dierent eort which in 2012 was at the sorbent screening and evaluation stage.303 An alternative is to incorporate a membrane into the reactor and extract hydrogen from the reaction space. 304 306 Compared with SEWGS, the concept has the advantage of being continuous and of avoiding the mechanical issues of high temperature switching valves. On the other hand, it requires a suitable hydrogen membrane which exhibits a high hydrogen ux rate, mechanical strength, and resistance to poisons. The focus of work on this concept is therefore the development of suitable membranes, which is discussed in section 4.4.2.
4.4. HydrogenCarbon Dioxide Separation

Review

The main focus of this interest is IGCC with carbon capture and hydrogen generation for fuel cells rather than chemical applications. Nonetheless, as these technologies develop and mature, it is possible that they could nd a place in chemical production. The two areas of attention are high temperature CO2 sorbents and hydrogen membranes. 4.4.1. CO2 Sorbents. RTI International has included the development of a CO2 adsorbent operating under warm conditions in its multicontaminant control suite. A 0.5 MWe equivalent pilot scale unit is to be included as part of the 50 MWe warm gas desulfurization demonstration at the Polk IGCC, mentioned already.307 TDA Research Inc. has tested a (undisclosed) high temperature CO2 sorbent at the NCCC, Wilsonville, AL, over 200 cycles, achieving over 98% CO2 removal from desulfurized syngas at temperatures above 200 C.308 Hassanzadeh and Abbasian tested various magnesium-based sorbents. They found that a natural dolomite modied by semicalcining and then impregnated with potassium gave the best results, with operation in the temperature range 300450 C.309 Some sorbents primarily developed for SEWGS may be used outside the shift reactor as well. 4.4.2. Hydrogen Membranes. Much eort has been invested in palladium membranes by, e.g., Zhang, Qiao, and coworkers,310,311 and also by Karellas et al.312 Tests with 4.5 kg/h sulfur-free syngas have been conducted at the NCCC on a palladium membrane supplied by Worcester Polytechnic Institute.308 However, concerns about the potential cost of using palladium have led others to look for alternatives. Jack et al. have developed a dense (undisclosed) metal membrane that operates at near water gas shift conditions. A 12 lb/day (5.4 kg/d) subscale engineering prototype plant was built and tested on industrial quality syngas at the Eastman Chemical plant at Kingsport, TN. One set of 5 ft (1.5 m) tubes operated over a range of 16 dierent conditions for 250 h and the ux stability previously determined in the laboratory was conrmed. A 250 lb/day (113 kg/d) process development unit was planned to be operated during 2012, and a 410 t/d precommercial module is planned for 2015.313 Dolan et al. have developed a range of vanadium based alloys, which demonstrate improved ux at a practical membrane thickness and reduced cost.314316 In particular, alloying with nickel and titanium is used to address the problem of hydrogen embrittlement encountered with pure vanadium, while maintaining the high hydrogen solubility that vanadium oers. The NCCC has tested carbon membranes supplied by Media Processing Technology and polymer membranes from Membrane Technology & Research as well.308 Others have performed laboratory testing of ceramics, e.g., Othman et al.317 and Vaitsi et al.318

Current technology for separating hydrogen and CO2 is generally based on CO2 absorption in the same solutions as used for desulfurization. The principal alternative technology for providing pure hydrogen is pressure swing adsorption. Both these technologies operate at ambient or even subambient temperatures. As discussed above for desulfurization, the necessary cooling can be a considerable source of ineciency, where it is not required for other reasons. There is therefore substantial interest in H2/CO2 separation at high temperatures.
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5. CHEMICALS FROM SYNGAS The production of chemicals from syngas is largely independent of the source of the syngas, so most developments applicable to syngas generated by steam reforming of natural gas are applicable to syngas generated from coal gasication. It is therefore not intended at this point to review general developments in the eld of chemical syntheses from syngas. However, small dierences in syngas quality according to source can have an eect on the detail design of synthesis units and these will be mentioned.
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Chemical Reviews
5.1. Ammonia 5.3. Methanol and Derivatives

Review

Most gasication-based ammonia plants have a liquid nitrogen wash as the nal treatment process before the synthesis unit proper. Others have a pressure swing adsorption for nal hydrogen purication. In both cases there are two dierences to the syngas produced by a traditional steam reformer plant. First, there is no residual water vapor in the gas. This leads to a minor simplication in the synthesis unit, in that it is not necessary that the water be removed in the product ammonia to protect the catalyst. One side eect of this is that the product ammonia is absolutely water-free. This high purity ammonia is known to be a cause of stress corrosion cracking (SCC). Commercial anhydrous ammonia from a steam reformer plant contains about 0.2 wt % water, which is sucient to suppress the SCC.319 Water may need to be added to coalbased ammonia in order meet commercial specications. Second, the gas is essentially inerts-free, with the exception of perhaps traces of helium. There is therefore no need for a continuous inerts purge. It is also worth noting that there is more CO2 available from a coal-based ammonia plant than from a steam reformer plant. Under the right circumstances this can be used to increase urea output.
5.2. Hydrogen

Methanol synthesis takes place by the reaction of hydrogen with carbon oxides according to the following reactions:
CO + 2H 2 CH3OH
0 H298K = 91 MJ/kmol

(8)

and
CO2 + 3H 2 CH3OH + H 2O(g)
0 H298K = 50 MJ/kmol

(9)

In hydrogen production from natural gas by steam reforming and CO shift, the state-of-the-art process for nal purication is pressure swing adsorption (PSA) which extracts 99.9+ mol % hydrogen from the shifted syngas, leaving a combustible tail gas which contains not only H2, CO, and CH4, but also all the CO2. In principle one could do the same with desulfurized syngas from coal. However, it is necessary to consider that the CO2 content of the PSA feed would be of the order of magnitude of about 3540 mol % instead of the 16 mol % or so with a steam methane reformer. Untreated as feed to a PSA plant, this gas would require very large beds, the hydrogen yield would be low, and the tail gas would be incombustible. A bulk CO2 absorption unit is therefore often seen upstream of the PSA unit in coal-tohydrogen ow sheets, so as to keep the PSA tail gas combustible. An alternative to PSA after a CO2 absorption unit is methanation of the residual carbon oxides, which provides a better hydrogen yield at the expense of a lower purity.320 There are few examples of pure hydrogen production from coal (unless one counts the ammonia plants mentioned above), but the synergy between the need for hydrogen for hydrotreating and hydrocracking in oil reneries and disposal strategies for residue disposal has led to the construction of a number of oil gasication to hydrogen plants. Two prominent examples are the Motiva Renery in Convent, LA, which uses the Texaco (GE) process, and the Shell Pernis Renery in The Netherlands, which uses the Shell process. Both these plants use methanation as the nal purication step. The largest coalto-hydrogen facility is the approximately 225 000 m3n/h hydrogen supply to the Shenhua Direct Coal Liquefaction plant at Erdos, Inner Mongolia. The syngas is supplied by two Shell coal gasiers fed with about 2250 t/d coal each. The purication process applied is unknown. The Long Lake, Canada, asphalt gasiers provide the feed gas for what is claimed to be the worlds largest single train PSA hydrogen unit.321 A 600 000 m3n/h hydrogen unit is currently under construction at Jamnagar, India, as part of Reliance Industries petroleum coke gasication complex.322
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An ideal synthesis gas specication would have stoichiometric ratio (H2CO2)/(CO + CO2) of about 2.03 and a CO2 content of about 3 mol %.323 It should be emphasized that this is an optimized gas quality and that a conventional natural gas steam reformer plant would have a CO2 content of around 7 mol %, whether with an optimized combined reforming lineup or not. Coal gasication produces a gas too carbon rich for methanol synthesis, so a degree of CO shift and CO2 removal will in any case be necessary. As a result, it is possible to provide an optimum gas with less CO2 content than from a steam reformer. As can be seen from reactions 8 and 9, shifting the educt to more CO and less CO2 increases the overall heat release. Isothermal reactors are therefore preferred for gasication-derived syngas, even by those that have in the past oered adiabatic reactors for steam reformer plants. Alternatives to the classic gas phase equilibrium reactors have been considered or developed. An example is the slurry phase LPMEOH process, which was demonstrated at a scale of 235 t/ d between 1997 and 2002 using syngas from the Eastman Kingsport coal gasication plant. A particular advantage claimed for this technology is the ability to handle a CO-rich gas, such as may occur during transients in a coal-based facility. However, commercial application of LPMEOH is linked to commercialization of IGCC [power plants],324 so no further commercial scale plant has been built in the 10 intervening years. Another alternative often considered is taking conversion beyond equilibrium by removing methanol during the reaction.325 More recently, van Bennekom et al. have developed the concept of in situ condensation and observed the phenomenon in a view cell.326 5.3.1. Methanol Derivatives. Methanol quality from coalderived syngas is the same as from a natural gas fueled plant. There is therefore no technical dierence in the processing of methanol to DME, olens, or gasoline which is dependent on the source of the syngas. There is, however, probably an economic dierence, in that where natural gas is available, there may be less need to use the syngas route to these chemicals. LPG, a product for which DME is a substitute, may be available from the gas condensate. Olens can be produced by steam cracking of ethane more economically than from methanol. In the past the largest markets for methanol were as an intermediate in the manufacture of formaldehyde, methyl tertbutyl ether (MTBE), and acetic acid.327 In recent years (2005 2010) usage of methanol for gasoline blending and dimethyl ether production has increased substantially. 5.3.1.1. Dimethyl Ether (DME). The largest use of DME is as a substitute or extender for LPG, which takes up about 65% of world production.328 It is also used as a propellant gas for sprays. DME is an intermediate in the production of gasoline and olens from methanol. It is also a potential clean burning diesel substitute. The European Union BioDME project has operated a eet of trucks for over 700 000 km in Sweden using
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Chemical Reviews

Review

Figure 14. Coal to MEG block ow diagram. [Reprinted with permission from ref 341. Copyright 2013 ASIACHEM.]

DME produced from syngas derived from black liquor gasication.329 DME is conventionally produced by dehydration of methanol. Starting from coal, this route involves adding water at the CO shift stage, which is then removed in the dehydration. Haldor Topse has developed a route directly to DME on the basis of the stoichiometry
3H 2 + 3CO = CH3OCH3 + CO2
(10)

thus avoiding the addition and subsequent removal of the water.330 Others including Nie et al.331 have investigated catalysts for this route as well. 5.3.1.2. Gasoline. Mobil (now ExxonMobil) developed the methanol-to-gasoline (MTG) process in the 1970s and built a rst industrial 14 500 bpd (1700 t/d) plant in New Zealand in 1985, which operated for 12 years before production stopped for commercial reasons. A rst coal-based 2500 bpd (290 t/d) MTG plant was built in Jincheng, Shanxi, China, and started up in 2009. This plant has incorporated all the learning from the plant in New Zealand.332 Other plants are in various stages of planning. Haldor Topse uses the integrated syngas-to-DME route described above in its TIGAS integrated gasoline process. A 1 t/d pilot plant has been operated for over 7000 h. A 23 bpd (2.7 t/d) pilot plant to operate on biomass-derived syngas at the Gas Technology Institute, Des Plaines, IL, was scheduled for start-up in 2012 with all testing to be complete by November 2013.333 5.3.1.3. Olens. Methanol can be converted to olens by essentially the same mechanisms as for MTG, namely dehydration to DME and subsequent further dehydration to the hydrocarbon. Three versions developed in the 1990s have matured to industrial-scale processes. The UOP/Norsk Hydro MTO process uses a uid bed technology. Four licenses have been sold for plants in China, the rst of which is expected to come on stream in 2013.334 The Dalian Institute of Chemical Physics DMTO uid bed process was used for the Shenhua Bautou 600 000 t/a olen plant, which started commercial operation in 2011. The Lurgi propylene selective MTP process uses a xed bed and is included in two plants in China which started up in 2011/2012. A third plant has been ordered.335
5.4. Ethanol

catalyst, or indirect, either via homologation of methanol or hydrogenation of acetic acid. Ethanol can be synthesized over a Ru catalyst, but both yield and selectivity are poor. This is conrmed by a more recent paper by Chen et al., who were able to achieve some improvement by supporting a Ru/Mn catalyst on modied SBA-15 molecular sieves.337 The selectivity to ethanol increased from 9.3 to 12.8% compared with an amorphous silica-supported catalyst. Clearly considerably more work will have to be performed, if ethanol is to be synthesized directly from syngas, whether biomass or coal-derived. On the other hand, Sterin and Fotheringham have recently (September 2012) announced the successful development of a commercial technology for ethanol production via syngas.338 Technical details have not been revealed, but on the basis of their presentation and the patent literature, e.g., Johnston et al.,339 it can be assumed that the technology applies the acetic acid hydration route.
5.5. Oxo Alcohols

Oxo alcohols are produced by reacting syngas with an olen to produce an aldehyde and hydrogenating the aldehyde to obtain the alcohol. Commercial products range from C6 to C12 alcohols for use as plasticizers and surfactants. Syngas volumes are generally small compared with methanol or ammonia plants, so a dedicated coal gasifer to generate the required syngas is unlikely to be economical. The Sasol higher alcohols plant producing 120 million t/a mixed C12/C13 alcohols is claimed to be part of the rst commercial route used anywhere for manufacturing surfactant alcohols from coal.340
5.6. Monoethylene Glycol (MEG)

Interest in syngas to ethanol has primarily been in the context of biofuels, providing a possible route to ethanol from those parts of plants not currently accessible to fermentation technologies, cellulosic ethanol . However, the issues surrounding the synthesis of ethanol from syngas remain the same, whether the source of the syngas is biomass or coal. Subramani et al. have reviewed the search for an ecient catalytic process for the conversion of syngas to ethanol.336 The discussion looked at three main routes: direct synthesis on a Ru
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Conventionally, ethylene glycol has been produced by hydration of ethylene oxide either directly or via ethylene carbonate. In recent years a route from synthesis gas has been developed in China. As shown in Figure 14,341 the process starts by splitting the synthesis gas so that the CO can be oxidized with methyl nitrite to produce dimethyl oxalate (DMO). The hydrogen is used to convert the DMO to MEG and methanol.342 The methanol is separated from the MEG and recycled. Methyl nitrite is prepared by oxidizing the nitric oxide recycled from the carbonylation step by reaction with methanol and oxygen. The only feedstocks consumed are CO, hydrogen, and oxygen. The rst 200 000 t/a plants in Tongliao, Inner Mongolia, and Xinxiang, Henan, are in operation. Eight more, including four pilot plants, are in various stages of commissioning, and a further nine are under construction.343
5.7. Substitute Natural Gas (SNG)

Kopyscinski et al. have reviewed the status of SNG technologies from 1950 to 2009,344 and it is not intended to repeat this work in this article. However, the commercial environment in which SNG technology nds itself in 2013 has changed so dramatically since then that a discussion of intermediate
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Chemical Reviews developments is more than appropriate. Whereas the price of natural gas in the United States (Henry Hub) was between $10/MMBTU and $12/MMBTU in the summer of 2008,345 it has fallen to below $3/MMBTU for most of 2012. This has been due to a combination of the rapid development of shale gas production and a generally reduced economic activity. Kopyscinski et al. include a list of 15 announced SNG projects, 12 of which were in the United State, most of them due to be in service by 2012 or 2013. The changed price situation has meant that not one of these 12 has entered construction. On the other hand, the successful start-up of one of the three Chinese projects identied in the list (Hexigten) was announced in 2012.346 Furthermore, projects not yet identied in 2009 are well into construction, for example, at Guangyang, South Korea, which is due to start up at the end of 2013.347 These two projects use the Davy HICOM and Topse TREMP processes, respectively. Other plants are also under construction in China. Other technological developments have taken place as well. Lurgi in cooperation with BASF has upgraded the technology used since 1984 in the North Dakota SNG plant. The Lurgi HT Methanation process uses an advanced catalyst capable of operation at 650 C. The ow sheet has a recycle around two adiabatic methanation reactors followed by a single polishing reactor.348 Ruggeri has presented an alternative ow sheet proposed by Foster Wheeler and Clariant (formerly Sud Chemie), which eliminates the gas recycle, places the CO shift within the SNG unit, and removes CO2 after methanation.349 Both these developments are essentially incremental improvements on existing technologies where the main advance has been in the catalyst. Others have taken a more radical approach to the key issues of heat removal and carbon management. Gotz et al. are developing a slurry-phase reactor operating at a temperature of between 280 and 300 C. A Ni Al2O3 catalyst is suspended in an inert uid through which the gas is bubbled.350,351 Conversion rates in a single isothermal reactor are good; the gas hourly space velocity (GHSV) is, however, low and the subject of the main development eort. The current focus is on biomass applications, so reactor size is unlikely to be a limitation. Ryi et al. have developed a nickel membrane which can be installed in a thin plate reactor.352 Liu et al. have made ceramic plates coated with nickel catalyst as the rst step toward the development of a microchannel reactor.353
5.8. Liqueed Petroleum Gas (LPG)

Review

FischerTropsch with iron catalyst (ARGE) is included in the plant at Sasolburg, South Africa, which also used coal gasication for syngas generation from its inception in 1955 until it was replaced by natural gas feed in 2004. Both plants use (or used) Rectisol acid gas removal and provide a solid base of experience for iron catalyst with coal gas. Other industrial scale FT facilities, such as Bintulu, Malaysia, and Oryx and Pearl in Qatar use low temperature FT with cobalt catalyst in conjunction with natural gas feed. Cobalt catalysts are known to be more sensitive than iron catalysts. At present (2012) there are no industrial scale FT units with cobalt catalyst operating on coal gas, although a number of projects with this combination are being considered. It is expected that these projects will include additional adsorbents to protect the catalyst from the various trace elements that may be in the coalbased syngas.
5.10. Direct Reduced Iron (DRI)

It may be debatable whether a metallurgical syngas application can be considered as chemical. Nonetheless, for the sake of completeness, its application to direct reduced iron is mentioned here. Historically, industrial applications of the DRI process have used dry (CO2) reforming of natural gas to supply the reducing gas. There has been some interest in the use of coal as a source of syngas, particularly in locations short of natural gas, but it is only recently that the rst plant has been constructed in Angul, India, with start-up planned for 2013.357 It is preferred that the reduction ratio, (CO + H2)/(CO2 + H2O), be greater than 11, but values as low as 2 are acceptable.358 The preferred methane content of 34% should also be noted, since this can inuence the gasier selection. Small amounts of sulfur up to 0.3% are acceptable, but lower values are preferred, since sulfur removal downstream will add to the costs.

Liqueed petroleum gas (LPG) is not currently considered as a fuel to be derived from synthesis gas. Nonetheless Ma et al. have investigated this possibility. The route to LPG is via methanol, dehydration to DME, further dehydration to olens, and hydrogenation of the olens using a mixed catalyst at 30 40 bar.354 While the 7380% selectivity for the C3/C4 fraction may present some encouragement, direct use of DME is more likely to nd favor, since in at least one major market, rural fuel supplies, DME is already establishing itself as a direct competitor of LPG, where a coal derived product is required.
5.9. FischerTropsch Synthesis

FischerTropsch (FT) synthesis of hydrocarbons from synthesis gas is a wide subject, and for details the reader is referred to standard works.355,356 It is however important to review the interface between synthesis gas production and the synthesis itself. High temperature FischerTropsch with iron catalyst (originally Synthol, later SAS) is the mainstay of Sasols coal-based complex in Secunda, South Africa. Low temperature
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6. CHEMICALS FROM PYROLYSIS BYPRODUCTS OF GASIFICATION Countercurrent updraft gasiers such as those of Lurgi, Sasol, or BGL use hot synthesis gas from the gasication zone to pyrolyze the incoming coal. A part of these pyrolysis products is carried out with the raw syngas and is condensed and removed in a water wash. Heavy, non-water-soluble hydrocarbons are separated from the aqueous gas liquor phase. The quantities of these materials can be sucient to make it worthwhile to recover at least part as salable byproducts. Typical of industrial installations such as those of Sasol or Dakota Gasication is recovery of ammonia, phenol, and cresylic acid.181,359 In the Sasol Secunda facility the tar is distilled and hydrotreated to recover naphtha and distillate as blending components for the renery. In particular, the high density distillate produced was an important feature, since it provided the main source of diesel density in the renery (ref 356, p 198). Sasol continues to explore new ways of exploiting this pyrolysis material in cooperation with various partners.360362 Pan, Long, and co-workers have also performed characterization studies on medium-temperature gasication of coal tar.363,364 Further opportunities for chemical production from tars generally are described elsewhere.365,366 7. DIRECT HYDROGENATION TO LIQUIDS The alternative to the indirect (syngas and FischerTropsch) route from coal to automotive fuels is the direct hydrogenation of coal to liquids (DCL). The hydrogenation of coal at high
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Chemical Reviews pressures to form liquid hydrocarbons was rst patented by Friedrich Bergius in 1913,367 the same year that Carl Bosch started up his rst commercial ammonia plant in Oppau. Later, in 1931, the two men were joint recipients of a Nobel Prize in recognition of their contributions to the invention and development of chemical high pressure methods.368 After much development work, Bergius sold his patents to BASF (later IG Farben) in 1925. The rst demonstration commercial plant was built at the Leuna site in central Germany next to the existing ammonia plants in 1927. In the 1930s and 1940s this plant was expanded and 12 others were built in Germany, to provide a domestic source of high octane fuel to the military. After 1945, wide availability of petroleum caused interest in the technology to wane until the oil boycott of the mid-1970s. From 1976 to 2000, the United States government invested heavily in the development and demonstration of technologies related to direct coal liquefaction and other coal conversion technologies. During this time, pilot and demonstration facilities ranging from 30 to 1800 barrels per day of liquid fuel were built and operated in the United States. During the same period of time, pilot-scale work was also performed in Germany, the United Kingdom, and Japan. Eorts were focused on developing better catalysts, reactor design, better materials of construction for higher temperature and higher pressure operation, and overall heat recovery and integration. A number of these processes were developed to the point where the next logical step would have been a commercial or semicommercial scale demonstration plant. This included the HTI catalytic twostage liquefaction process in the United States, the NEDOL process in Japan, and the IGOR+ process in Germany. However, in the early 1990s, the low price and abundant supply of crude oil stopped most of the demonstration programs. A brief overview of developments in China, including comparisons with FischerTropsch CTL technologies, was prepared by Liu et al.369
7.1. Process Description

Review

using conventional petroleum rening methods. Unreacted hydrogen is recovered for recycle from the gas phase. Heavy vacuum gas oil (VGO) is extracted from the bottoms, the remainder of which is recycled as slurry. A side stream can be removed to the deashing unit to avoid excessive buildup in the system. The actual chemical reactions that take place inside the DCL reactor are complex. The general belief is that the coal is rst broken up into large fragments. These are preasphaltene and asphaltene materials. These high molecular weight materials are further broken down into smaller compounds with less than 15 carbon atoms through the catalytic hydrocracking reaction. An important part of optimizing the process is based on matching rates of cracking and hydrogenation in order to avoid the production of undesirable products. The performance of the reactor is mostly dependent on the catalyst, operating temperature, and pressure. The product selectivity is most aected by the type of catalyst and its age. The operating temperature aects the reaction rates. The overall reactor pressure changes the partial pressure of hydrogen and ammonia. Partial pressure of hydrogen has the most dominant impact on the overall conversion. Increase of the partial pressure of ammonia has a negative eect on the conversion.
7.2. Commercial Plant

The basic sequence of operations in a typical DCL process is described in Figure 15.370 The coal feedstock is slurried with hydrocarbons and fed to the liquefaction section. The coal reacts under high pressure with hydrogen, the makeup part of which may come from a coal gasication based hydrogen plant. Depending on the process the slurry may include a hydrogendonor solvent. The hydrogenated product is further hydrotreated to produce a synthetic crude, which can be worked up

Only one commercial DCL plant has been built since 1945. That is the Shenhua plant in Inner Mongolia. In 1997, HTI had signed an agreement with Shenhua Clean Coal Technology Development and China Coal Research Institute to execute a feasibility study for constructing a DCL plant in China. In June 2002, Shenhua agreed to apply the HTI technology for the rst phase of a three-phase multibillion dollar direct coal liquefaction project. The HTI process consists of two backmixing reactors using a proprietary dispersed superne iron catalyst (Gelcat) plus a xed-bed in-line hydrotreater. The reactor operating pressure is 170 bar and temperature is in the range 400460 C.371 Finally, Shenhua built a 1 080 000 t/a (25 000 bpd) plant located at Erdos, Inner Mongolia, China, with their own DCL technology.372,373 The plant was started up successfully in 2008. The total project cost was 10 billion Yuan (US$1.5 billion), and it consumes about 3.5 million t/a coal.374
7.3. Research and Development (R&D) Activities

Figure 15. Block ow diagram of direct coal to liquids process. [Adapted with permission from ref 370. Copyright 2009 Headwaters Technology Innovation Group.]
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R&D activities in direct coal liquefaction have continued. This section will focus on summarizing the DCL R&D activities in the past 510 years. Their results have led to much improved catalyst, reactor design, and product upgrading. In 2010, Headwaters Inc. (owners of HTI) and Axens (part of the IFP group), both of whom had contributed engineering design and technical services to the Shenhua project, announced the formation of a Direct Coal Liquefaction Alliance.375 The alliance combines Headwaters slurry catalyst technology and CTL research facilities including the 3 t/d DCL pilot plant with the Axens ebullated-bed H-Coal Process and proprietary catalyst.376378 Additional work by this group includes the development of a process that comprises two successive direct liquefaction stages in ebullated bed reactors followed by a xed-bed hydrocracking stage.379 This process can produce excellent quality fuel bases (kerosene and diesel). HTI also oers a similar conguration.380 They employ a homogeneous iron-based catalyst that simplies the design of the ebullated bed reactor. Similar reactors were installed in the commercial DCL plant in Inner Mongolia, China. A further
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Chemical Reviews development is a multistage catalytic process for DCL.381383 The fresh hydrogenation catalyst is rst used to reduce heteroatoms (S, N) from the coal-derived liquids in the downstream hydrotreater. Then, this catalyst is cascaded and reused in the rst low temperature DCL reactor and the second high temperature reactor. The countercurrent ow of the catalyst and the reactor euents allow the production of very low contaminant coal liquids. In 19951996, HTI conducted successfully the proof-of-concept runs in their 3 tons of coal/ day pilot plant under this catalytic multistage liquefaction (CMSL) conguration.384 David Moulton of Southwest Research Institute has patented a process concept that mixes syngas with coal in a single-stage DCL reactor.385 The presence of syngas and the catalyst promotes in situ water gas shift (WGS) reaction. Thus, a separate WGS reaction step is avoided. The concept also applies to carbonaceous material such as any type of coal and/ or biomass containing plant and/or animal matters for conversion to a synthetic fuel. ExxonMobil has patented a process and apparatus that produce acetylene from a feed stream of low hydrogen content hydrocarbons such as coal.386 The feed is blended with methane which is partially combusted inside the DCL reactor. Accelergy Corp. has developed an integrated coal/biomassto-liquid (ICBTL) system that has a low greenhouse gas footprint for converting coal or coal and biomass to liquid fuels.387391 Coal is converted to liquids by the proprietary DCL process, and the liquids are upgraded to produce premium fuels. The CO2 produced by the process is used to produce algal biomass and photosynthetic microorganisms in a photobioreactor. The biomass residues and coal could be gasied to produce hydrogen and syngas for the DCL process. Some or all the algal biomass and photosynthetic microorganisms are used to produce a natural biofertilizer. China Fuel (Huaibei) Bioenergy Technology Development Co. Ltd. is developing a process for producing liquid hydrocarbon fuel from coal.392 Cellulose is used to assist the coal hydrolysis, and the hydrolyzed product could be further hydrogenated to lighter liquid hydrocarbon fuel. Coprocessing coal with other carbonaceous materials has shown a positive synergistic eect on converting coal to liquid fuels. West Virginia University has suggested a method and systems for liquefying coal utilizing a hydrogenated solvent, including hydrogenated vegetable oil, a rubber material, sewage material, and pipeline crude oil.393 Frontier Applied Sciences,394 Nippon Steel Chemical Co.,395 and Synfuels China Co.396 have also proposed similar concepts. China Petroleum & Chemical Corp. employs a similar process conguration to convert low rank coal to liquid fuels.397 The catalytic converter is separated into two reaction zones. The catalyst is regenerated by steam striping and followed with coke burning. Zhaoqing Shunxin Coal Chemical Industry S.T. Co. uses the same approach except that it does not regenerate the catalyst.398 While most of the above work is concentrated on issues of optimizing the core conversion process, other aspects of DCL technologies are also attracting attention. The inuence of hydrothermal pretreatment has been investigated by groups in Japan399,400 and in China.401 Another eld being studied is the use of the heavy residue from DCL. Various dierent approaches are being taken such as further hydrogenation to recover further product402,403 gasication which would reduce
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the feed requirement for hydrogen production404,405 or even direct application as an asphalt modier.406,407

8. CONCLUSIONS
The production of chemicals from coal via gasication is a large and mature industry. Nonetheless, research continues in both academic and commercial organizations to develop the technology further. The most important focus today is the economics, for which improvements in capital costs, in energy eciency, and in operational reliability and availability are all major factors. Also, as with all coal-based technologies, minimizing the carbon footprint remains a task requiring further work.

AUTHOR INFORMATION
Corresponding Author

*E-mail: chris@higman.de.
Notes

The authors declare no competing nancial interest.

Biographies

Chris Higman received his bachelors degree in mathematics at the University of Oxford, U.K., in 1966 and later obtained his M.Sc. in mechanical engineering from the University of the Witwatersrand, Johannesburg, South Africa. He began his engineering career in South Africa in 1966, where he worked in the water and power supply industries. Here in 1967, he made his rst contact with gas manufacture on the start-up of an atmospheric, air-blown, xed bed gas producer. Chris joined Lurgi in 1975, and his rst project for the company on was the process integration and later the start-up of an ammonia plant in North Germany based on the gasication of petroleum residues. He was associated with Lurgi for nearly 30 years, mostly in the eld of complete chemical plants based on gasication. These included various ammonia, methanol, and synfuels (GTL) plants as well as the basic design of the hydrogen and power facility at Shells Pernis renery in The Netherlands. He occupied various positions in corporate management including that of Managing Director of Lurgi India. Since retiring from Lurgi he has worked as an independent consultant specializing in gasication and other syngas technologies. He has a number of patents and has authored many articles in the eld. He is coauthor, with Maarten van der Burgt, of the book Gasification.
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Chemical Reviews DRI ECUST EPRI FT FT GE GHSV HTW IDT IGCC LIBS LNG LPG MDEA MEG MSW MTBE MTG MTO MTP NCCC PRB PSA PSDF PWR RAM RSC SAR SCC SEWGS SNG SVZ TGA TPRI TRIG VGO WGS

Review

In the past 30+ years, Mr. Tam has been active in research and development, engineering, project management, and commercial development related to the conversion of coal and natural gas to power, chemicals, and liquid transportation fuels. Mr. Tam is the Director for Advanced Energy Systems Division in the Oce of Fossil Energy of the U.S. Department of Energy. His current responsibility is to oversee the R&D activities in advanced coal gasication, advanced turbines, solid oxide fuel cells, oxycombustion, and coal and biomass to liquids. Before he joined DOE in September 2009, he was the Director of Technology at Headwaters and was responsible for developing the commercial coal-to-liquid projects. Prior to joining Headwaters, Mr. Tam spent 17 years with Bechtel and its aliated companies. He was responsible for providing technology and engineering support in the chemical, natural gas, and oil rening EPC business. In his last position, he was the Vice President of Process Technology in Clean Fuels and Chemicals from natural gas and coal. With Standard Oil of Ohio (now BP), he was the lead process engineer and project leader in various synfuel projects in the early 1980s. He also spent more than 5 years in research and production with Dow Chemical Co. in Midland, MI. Mr. Tam is a Professional Engineer registered in the state of Michigan. He received B.Sc. and M.Sc. degrees in chemical engineering from The Ohio State University.

ACKNOWLEDGMENTS C.H. wishes to express his thanks for support from the EnglerBunte-Institute, Karlsruhe Institute of Technology, in particular from Prof. Thomas Kolb and Dr. Siegfried Bajohr. S.T. wishes to thank Joseph Wong of DOE for his support in the literature search. ABBREVIATIONS AND ACRONYMS AFB agglomerating uidized bed AFT ash fusion temperature ASU air separation unit BET BrunauerEmmettTeller BGL British GasLurgi BTU British thermal unit (=1.0551 kJ) CDCL coal-direct chemical looping CFB circulating uidized bed CFD computational uid dynamics CLC chemical looping combustion CLR chemical looping reforming CTL coal to liquids DCL direct coal to liquids DFB dual uidized bed DME dimethyl ether DMTO Dalian methanol to olens DOE (U.S.) Department of Energy
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direct reduced iron East China University of Science and Technology Electric Power Research Institute uid temperature FischerTropsch General Electric or GE Energy gas hourly space velocity high temperature Winkler initial deformation temperature integrated gasication combined ccycle laser-induced breakdown spectroscopy liqueed natural gas liquid petroleum gas methyl diethanolamine monoethylene glycol municipal solid waste methyl tert-butyl ether methanol to gasoline methanol to olens methanol to propylene U.S. National Carbon Capture Center Powder River Basin pressure swing adsorption Power Systems Development Facility Pratt & Whitney Rocketdyne reliability, availability, and maintainability radiant syngas cooler Synthesegasanlage Ruhr Stress corrosion cracking sorbent enhanced water gas shift substitute natural gas Sekondar rohsto -Verwertungszentrum Schwarze Pumpe GmbH thermogravimetric analysis Thermal Power Research Institute transport integrated gasication vacuum gas oil water gas shift

NOMENCLATURE m3n/h volumetric ow rate in m3 at a reference condition of 0 C and 1.013 25 bar MWe electrical output of power plant in MW MWth thermal rating of a gasier in MW, usually related to the gasier feed REFERENCES
(1) Index Mundi. http://www.indexmundi.com/en/commodities/ minerals/nitrogen/nitrogen_t12.html (accessed Jan 26, 2013). (2) China National Chemical Information Center. http://www. fertmarket.com/newsabout.aspx?id=38 (accessed Jan 26, 2013). (3) Jackson, C. The Methanol Institute, Washington, DC. Personal communication, Jan 18, 2012. (4) Roggersdorf, W. Im Reiche der Chemie: 100 Jahre BASF; Econ Verlag: Dusseldorf, Germany, 1965; p 82 . (5) Kietaible, C. Das Generatorgasseine Erzeugung und Verwendung; A. Hartlebens Verlag: Vienna, 1910; p 337 . (6) Scho, R.; Booras, G.; Higman, C.; Holt, N.; Kubek, D.; Sorensen, J.; Todd, D. 2012 Integrated Gasication Combined Cycle (IGCC) Research and Development Roadmap: Technology Development for Improved Performance and Economics; Report 1023867; Electric Power Research Institute: Palo Alto, CA, October 2012. (7) Higman, C. A. A.; van der Burgt, M. Gasication; Elsevier: Amsterdam, 2003.
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