BASIC COAL CHEMISTRY FOR COAL TO LIQUIDS

Coal is a generic term referring to a family of solid fossil fuels with a wide range of physical and chemical compositions. Coal is formed from large accumulations of plant materials that have been preserved from complete decay and later altered by chemical and physical conditions in the accumulation. Coal is actually a heterogeneous rock composed of different kinds of organic matter which vary in their proportions in different coals, and no two coals are absolutely identical in nature, composition or origin. One proposed generalized definition of coal is: "Coal is a compact stratified mass of metamorphosed plants which have, in part, suffered arrested decay to varying degrees of completeness." The organic material in coal was formed from plant debris which has been laid down in a peat swamp, over many millions of years. These swamps were extremely large, and it has been calculated that the thick brown coal seams were originally formed from wood and plant debris. With time, the plant debris was covered with sediments, and undergone various changes of temperature and pressure which produced a sequence of coals beginning with peat and terminating with anthracite. Coal seams occur in two main types of deposit: the first is a sequence of coal seams (possibly as many as 20 or 30 seams found in strata 500 to 1000 m thick. Each strata is of great extent and relatively moderate in thickness. The thickest individual seams in this type of deposit or coalfield seldom exceeded 4 m. For example, in Great Britain, the average thickness of a coal seam is about 1 m. These seams were deposited in the Debonian Period (350 400 million years ago), when the flora consisted of lycopods and small ferns submerged in shallow lagoons. In this case, the thin coaly sections are separated by sequences of rock (shales, sandstones, limestones). In the Lower Carboniferous Period (310-280 million years ago), the appearance of conifers in thick forest swamps resulted in the deposition of thick economical seams. In North America, this age is often referred to as the bituminous coal period. Two mechanisms have been suggested that favor peat formation and the accumulation of enormous quantities of vegetable matter involved. The in-situ mechanism postulates the growth of extensive forests in swamps. The trees and other vegetation died, and lay where they fell. In the course of geologic time, the very slow sinking of the site allowed a continuous thickness of decaying woody material to accumulate. In due course, the site was buried under silt when the forest was submerged by abrupt subsidence and the incursion of silt laden water. In most of the large coalfields in the Northern Hemisphere the in-situ mechanism is the only possible explanation of the occurrence of very extensive, roughly parallel, and generally uniform coal seams of low inorganic content. The other mechanism for coal formation is called the drift mechanism. This mechanism postulates vegetation to have been carried (drifted) by moving water (for example a great river system) from the growing area to a remote shallow water site in which it accumulated and was eventually submerged and buried. In general these types of seams are too rich in mineral mater, spores, and pollen to form economic coal deposits. In both mechanisms, the gradually increasing weight of the accumulating inorganic layer buried in the peat caused consolidation of the peat. The pressure effect increased as successive layers of deposits were built up in the course of geologic time. The effect of pressure resulting from overburden (overlaying layers) and also in the course of geologic time, of other pressure effects and of temperature elevation, both resulting from movements of the earths crust, caused further profound changes in the buried peat. By these means, a whole series of types of coal was formed, each member of the series representing a different extent of metamorphosis of the peat deposit.

All coal contains two major constituents simply referred to a useful bits and useless bits as defined below: USEFUL BITS: These are the parts of the coal which are of direct benefit to a process because they can produce heat, or be used as a source of carbon. This part is usually termed the "organic" part of the coal substance, and originated mainly from the carbon in the original plant material. USELESS BITS: These are those parts of the coal which have no value to the utilization of the coal. Two materials are present in this category: The "inorganic" part of the coal substance, is present in the form of "minerals" which remain in the coal substance by virtue of inert substances contaminating the plant material as it was being laid down in the peat swamp, and are present in the form of minerals (which produce ash). The coal "moisture" which is retained within the porous coal structure, and on the coal surface. Some other organic constituents including nitrogen, and organic sulfur. The basic composition of the useless and useful bits of coal (and non-coal) is illustrated below in a simple box diagram shown in Figure x.x. It should be noted that some of the carbon, hydrogen and oxygen are the only useful bits of the coal. Some of the carbon and all the hydrogen and oxygen report to the volatiles, and the balance of the carbon reports to the fixed carbon during combustion or gasification. Figure x.x

The systematic variation of the properties of coal with rank, and the possibility of measuring these properties by laboratory test means to be able to assess the suitability of various coals for industrial purposes, and has led to the creation of a number of different types of classification systems. Each system type is intended to allow many properties of coal to be reduced from knowledge of two or three easily measured features, or to allow classification of the industrial use outlets for a specific coal to be decided from knowledge of a limited range of properties

The main categories for classifying coal are:

1. The broad classification into three major classifications, namely lignite, sub-bituminous, and
bituminous to identify the type of resource reserve available 2. 3. Classification based on coal type to indicate the origin of the coal (coal petrology) Classification based on coal rank. This is perhaps the most useful for commercial use of coal

The different types of coal that are clearly recognizable by their different properties and appearance can be arranged in order of their increasing metamorphosis and hardness from the original peat material as indicated in Table x.x below. Table x.x COAL TYPES Metamorphosis/Appearance Peat Brown Coal Lignite Sub-bituminous Bituminous Semi-bituminous Anthracite Hardness Soft Soft Soft Hard Hard Hard Hard

Each member of this series represents a greater degree of maturity than the preceding one, and this degree of maturity is referred to as the rank of the coal. A coal of a certain level of maturity or degree of metamorphosis from peat is said to be of certain rank. For example, sub-bituminous coal is of higher rank than brown coal, lignite is of lower rank than bituminous coal, anthracite is of the highest coal rank. Brown coals are dark brown in color and have a marked woody or fibrous structure. As mined, they contain 40-60% moisture. Their carbon content (dry ash free basis) is relatively low (being 65-69%). Lignites are closely related to brown coals, and lignite/brown coal names tend to be loosely applied such that at times, confusion arises. Technically, lignites are black in color, they contain 20-40% moisture as mined, and their carbon content is 63-75% daf. The calorific value of lignite is low (25% MJ/kg daf) and they yield 40-60% of volatile matter on carbonization. A first cut analysis of coal rank characteristics is shown below in Table x.x Table x.x FIRST CUT COAL RANK CHARACTERISTICS Material/Properties Moisture (as found),% Moisture (air dried),% Dry, ash free composition,% Carbon Hydrogen Oxygen Wood 30-60 10-15 50 6.0 43 Peat 90+ 20-25 55-65 5.5 32 Lignite 20-40 15-25 65-73 4.5 21 Sub-bit. Coal 10-20 10-20 73-78 6.0 16 Bituminous/Semibit Coal 13-1 13-1 78-92 5.3 8 Anthracite 2-3.5 2-3.5 92-96 2.5 4

The data in Table x.x shows the rank members of the peat to anthracite series displays a steady decrease in the water content of the coal with increasing rank, and suggests a steady increase in the content in

combustible matter (dry mineral mater free) basis to a situation in the semi-bituminous coals at which the moisture content (air dried basis) is only 1%. Further increase in rank toward the anthracites is accompanied by a reversal of this trend. Pure coal free from water and inorganic mineral matter (dry, mineral matter free or dmmf) shows a steady increase in its proportion of carbon and a steady decrease in its oxygen content through the whole range of increasing rank. The proportion of hydrogen decreases as the rank increases to a low values in the more mature lignites. The interval of rank from the lignites to the sub-bituminous coals, the progressive change in hydrogen content is interrupted. Instead of declining, the hydrogen content of coals abruptly increases in this interval and then resumes its stead reduction to a minimum value in the anthracites. Other properties of coals change systematically with the rank of the materials. The calorific value (dry, ash-free basis or daf) increases steadily with an increase in rank to a maximum in the semi-bituminous range, and then tends to decline slightly in the anthracites. The amount of tar and gas that coals produced when they are heated decreases as the rank increases. Thus anthracites (higher rank coals) evolve less than 10% of their weight as volatile matter when heated and almost all is in the form of gas. These progressive changes in composition with increases in the degree of methmorphism form the basis for all classifications based on rank. One of several ranking systems is summarized in Table x.x below for the U.S. (ASTM) Classification system. Table x.x US (ASTM) COAL CLASSIFICATION Class I. Anthracite II. Bituminous 1. 2. 3. 1. 2. 3. 4. 5. III Sub-bituminous IV. Lignitic 1. 2. 3. 1. 2. Group Meta-anthracite Anthracite Semianthracite Low volatile bituminous Medium volatile bituminous High volatile A bituminous High volatile B bitumiinous High volatile C bituminous Sub-bituminous A Sub-bituminous B Sub-bituminous C Lignite A Lignite B Fixed carbon (% dmmf) > 98 92-98 86-92 78-86 69-78 <69 Calorific Value (Btu/lb mmmf) Agglomerating character Nonagglomerating Commonly agglomerating Agglomerating

> 14000 13000-14000 11500-13000

10500-11500 9500-10000 8300-9500 6300-8300 <6300

Nonagglomerating

Both brown coals and lignites are non-caking. A major utilization difficulty with both lignites and brown coals is their high moisture content. When air dried, they disintegrate to powder, which is convenient for pulverized fuel combustion. They oxidize readily and if totally dried, tend to ignite at relatively low temperatures during the drying operation. They can be briquetted after partial drying. Successful briquettes can be made either without the addition of an added binding material or with the help of additions of pitch or tar.

Sub-bituminous coals are intermediate in rank between mature lignites and the hard, bituminous coals. They usually have 10-20% of moisture when air dried and, on the pure coal basis, 73% to about 79% of carbon. On carbonization they are quite non-caking but yield some 45% of volatile combustion products. Their hydrogen content is relatively high and may reach 6%, whereas the organic matter of mature lignite has substantially less than 3% hydrogen. Bituminous coals constitute the bulk of the hard coals and are also the principal type of coal. The moisture content (air-dried basis) of this type of coal varies widely according to the level of rank. Commonly the lowest rant bituminous coals contain some 13% of moisture (air-dried basis), while the highest rank varieties of this class of coal have approximately 1% of moisture. The yield of volatile matter on carbonization also is very sensitive to changes in rank. The range of carbon contents (daf) is from 78-90$%, and in response to the same increase in rank, the yield of volatile matter falls from 40-20% (daf) The calorific value of these coals is high and increases with increasing rank from 32-37 MJ/kg (daf). The lower rank bituminous coals (lower carbon content) are noncaking, but the phenomenon of fusibility appears for the first time among coals in this class. This rheological behavior on carbonization is first seen in, for example, British coal seams by the bright coals of 83% carbon content. Caking power in this class of coals increases with increasing rank, and the bituminous class includes the strongest coking coals known. Semibituminous coals can be regarded as a transition class between the bituminous and anthracite coals. They are all of low inherent moisture content (0.7-1.5%), high in carbon (90-93% daf) and low in volatile matter yield (20-10%). The term inherent moisture is equivalent to moisture on an air dried basis. This class also contains coals covering a wide range of caking power from strongly caking to non-caking varieties, but the semibituminous class caking power decreases with increasing rank. Anthracites are now very much less widely distributed than are the bituminous coals; many coalfields based on anthracite are now exhausted. Coal Gasification Coal gasification is a process in which solid coal is converted into gaseous state. This new gaseous state is still combustible, and can be used to fuel power plants, make chemicals, and even to create fertilizer. Several gasification technologies are well established. These technologies gasify coal with oxygen in an exothermic reaction to produce a combustible gas consisting of carbon monoxide, hydrogen, and some methane and carbon dioxide. This combustible mixture can be used as a fuel, and usually this is with a gas turbine to produce electricity, or it can be used to make a synthetic natural gas or chemical feedstock. Sometimes pure oxygen is used in a process termed oxygen gasification, or air may be used in air gasification, and then the product gas also contains nitrogen. Steam can be added to the oxidant stream to increase the amount of hydrogen in the gas produced. Alternatively, water can be added as a liquid when the coal is injected in the form or a coal-water slurry. Coal may be used as a feedstock, but the technique is applicable to any hydrocarbon, including natural gas and heavy refinery residues. Coal Water Slurries Coarse (>1 mm diameter) coal water slurries can be used as feedstocks for gasification and as a feedstock for direct coal injection into blast furnaces. The attraction of the coal water slurry is its complete independence on an oil supply: coal oil slurries are also an effective means of extending oil supplies. Coal water slurry is simply produced by mixing pulverized coal with water together with a small amount of a surfactant and a stabilizing agent. The coal particle diameters used are generally about 100 microns or slightly less, but micronized coal particle sizes are, as the name suggests of the order of 1 micron. The resulting liquid looks like a black oil but feels like water and smells like coal. There are two major reasons for investigating the suitability of the use of coal water slurries as fuel. First, the fuel can be stored and burned in a similar way to heavy fuel oil with only a few minor plant modifications and second, coal water mixtures can easily be transported in pipelines.

However, there are some disadvantages to overcome, such as increase of wear to pumps and atomizers due to the abrasive nature of the coal particles, blockage of mechanical components, flame instability, and flow problems during storage and pumping. The techniques that have been used for the utilization of heavy fuel oil combustion have been applied to the combustion of coal water slurries. This is because after the coal has been mixed with sufficient water to achieve the required viscosity, there are certain similarities with heavy fuel oil with regard to both the rheology and to the combustion mechanism. The key feature that has emerged from slurry-droplet combustion studies is that small coal particles originally present in the slurry can agglomerate, especially in large droplets, resulting in chars larger in size than if the original coal had been burned directly as pulverized fuel. The implication is that a longer combustion time is required than for pulverized fuels or oil. The viscosity of the fuel and the quality of atomization that can be achieved are therefore crucial factors. The relative proportions of coal and water that can form a suitable fuel are restricted by several factors. The coal must be present as a large fraction of the mixture, but in order to produce a practical flowing liquid fuel capable of being pumped and atomized, the presence of a certain amount of water is necessary. The highest coal loading that will still provide a slurry that satisfies operational requirements, particularly flame stability criteria, appears to be less than 80%. For this reason, most of the coal water slurries that have been investigated so far contain between 60-74% by mass of pulverized coal. Not only coal loading but also the maximum size of the largest coal particles and the size distribution of the particles can affect both the rheology of the slurry and also the combustion efficiency, since the smaller coal particles have a more rapid burn-out. However, the economic benefits in combustion efficiency and ease of slurry handling gained by grinding the coal to a finer size are offset to a certain extent by the higher cost of pulverizing the coal. Therefore a typical coal water slurry contains about 70% mass of coal pulverized to minus 200 mesh or finer, with about 1% mass of additive. Thers are various dispersants, surfactants, neutralizers, or stabilizers that, when present in small concentrations have the ability to alter the rheological properties of the liquid mixture and thus allow a larger coal loading. They also prevent the coal and water from separating out by sedimentation during storage and prevent bacterial growth. The presence of about 1% of an additive has been found to not greatly affect combustion performance compared with combustion of similar slurry without the additive. Carbon conversion efficiency is slightly lower with an additive present, and atomization characteristics and the emission in the product gas or criteria pollutants are similar. Gasification The gasification of coal can be summarized in five simple basic chemical reactions. a) Gasification with oxygen and air (partial combustion).

b) Combustion with oxygen

c) Gasification with carbon dioxide (Boudouard reaction)

d) Gasification with seam (water gas reaction)

e) Gasification with hydrogen (hydrogasification reaction)

Note that the enthalpies of reaction for these equations are for standard conditions and the enthalpy of formation for carbon used is 12.5 kJ/mol; to account for the fact that coal carbon differs from graphite carbon. These reactions are endothermic, i.e. require heat in order to proceed. Therefore the heat required for this desired reactions is supplied by the complete or partial combustion of a small proportion of the coal in oxygen or air. Thermodynamic and kinetic estimations in regards to coal gasification processes are important in the design of gasifiers and plants that utilize them. Measurement of these properties is very difficult because of the complex nature and the high number of variables associated with gasification (i.e. coal BTU content, coal composition, variations in temperature, pressure, etc.). There is a balance between the extent of combustion and gasification processes that is controlled by the products required and the reaction temperature and pressure. Methane may be the preferred product and is favored by low temperatures. The production of hydrogen gas is one of the more valuable aspects of gasification. As fossil fuels, especially oil, availability decreases, both the energy and transportation sectors will begin to rely more on hydrogen related fuels. Gasification provides an alternative to hydrolysis, a process to separate water into hydrogen and oxygen that is currently uneconomical and consumes fossil fuels. The production of hydrogen gas and/or carbon monoxide through coal gasification is becoming an important commercial process. If a certain H2/CO mixture is desired, a blend of coal, steam, and O2 is fed into the gasifier. The exact ratio of these reactants is heavily dependent on how reactive the coal is, the specific operating capacities of the gasifier, and the chemical makeup of the desired product. As the gasifier begins to operate at higher temperatures, the amount of CO produced increases. The product gas is oftentimes passed through what is called a CO shift converter (the reaction shown below) to produce the final desired ratio.

Additionally, coal gasification produces syngas, which is the combustible gas used to fuel a boiler. Also, syngas can be used to make liquid fuels, or gaseous fuels that are used in non-power generation technology. Other exothermic reactions reactions taking place in the gasifier include methanation and pyrolysis.

CO + 3H2 = CO2 + H2 4CnHm = mCH4 + (4n-m)C

Two gas phase reactions that are important for determining the final gas composition are the water gas shift reaction and the methanation reactions. The water gas shift reaction has influence on the H2/CO ratio, which can be important if the gasification gas is to be used for chemical synthesis.

Because of the hydrogen in the gas phase, hydrogenation of carbon also occurs, so that the gasifier gases also contain some methane. Methane is also produced by the reaction of carbon monoxide and hydrogen. The methanation reaction increases the calorific value of the gas, but is very slow except at high pressure. Synfuels The United States uses over 380 million gallons of gasoline per day, but the majority of crude oil consumption comes from foreign sources. On the other hand, coal is abundant in the United States, and US coal reserves are expected to last until 2100. For these reasons, coal is an attractive alternative energy source to oil. However, as most of the fuels we use are in the form of liquids and gases, there is mismatch in energy forms. These factors make developing coal derived fuels, or synfuels, an attractive option. Synfuels, or synthetic fuels, are fuels derived from coal through a number of chemical processes. For example, synthetic crude oil is a complex mixture of hydrocarbons, somewhat similar to petroleum, obtained through coal liquefaction (discussed later). Synthetic crude oil generally differs in composition from petroleum, usually containing more aromatic hydrocarbons than petroleum and thereby resulting in a higher hydrogen-to-carbon ration. Synthetic diesel fuel can also be derived from coal, and is in fact more promising as its properties extremely similar to diesel derived from crude oil. Other alternative fuels derived from coal, methanol and dimethyl ether, are currently being researched and will be discussed in detail below. What are synfuels? Synfuels, or synthetic fuels, are gaseous, liquid, or solid fuels that do not occur naturally. Such fuels can be made from coal, tar sand, or oil shale. There are several routes by which synthetic fuels can be prepared from coal. Gasification can yield clean gases for combustion or synthesis gas that has a controlled ration of hydrogen to carbon monoxide. Another route is coal liquefaction, which involves increasing the hydrogen-to-carbon atomic ratio considerably (from about 0.8 to 1.5-2.0) to produce a low-sulfur, ash-free liquid product that is comparable to crude oil or gasoline. Liquefaction of coal can be carried out in two ways:

1. Indirectly, by reconstructing liquid molecules from a synthesis gas by Fischer-Tropsch or

methanol synthesis reactions or

2. Directly, by chemically adding hydrogen to the coal matrix under conditions of high pressure
and temperature. Synfuels can be obtained through gasification or liquefaction of coal. There are two methods for deriving liquid fuel from coal: direct coal liquefaction (DCL) and indirect coal liquefaction (ICL). While the DCL process creates a liquid fuel directly from coal, ICL involves gasifying the coal first and then using the resulting syngas to produce liquid fuel.

Direct Coal Liquefaction

Source: www. accessscience.com

In direct coal liquefaction, coal is first crushed and slurried in a process-derived solvent, then heated and pumped to typical reaction conditions, in the range of 425-500C and 140-300 atm. Depending on the process, a catalyst may be added to the liquefaction step, or the solvent may be hydrogenated to improve hydrogen transfer to the coal. As the coal is heated to reaction temperatures, thermal cracking occurs. At liquefaction temperature, chemical bonds are broken (cracked), generating free-radical fragments which can participate in secondary reactions combining with hydrogen to produce liquids. Control of these secondary reactions is important in achieving high conversions and good selectivity to distillable liquid products. During liquefaction, heteroatoms in the coal (oxygen, nitrogen, and sulfur) are also liberated, principally as carbon oxides, water, ammonia, and hydrogen sulfide. Although more efficient (by as much as 10%) than indirect coal liquefaction, direct coal liquefaction programs were abandoned by the United States government during the 1980s for numerous reasons. The most serious problem is that fuels produced by the process contain high levels of polycyclic aromatic hydrocarbons (PAHs) which inhibit complete combustion and result in the release of unburned exhaust emissions. Because additional energy input is needed to refine the synthetic oil produced for it to be usable, companies have little incentive to capture CO2 due to cost efficiencies . Indirect Coal Liquefaction

The 3 basic steps of indirect coal liquefaction:

The coal is gasified . The resulting gas is adjusted (i.e., H2 content is increased, H2S and CO2 are removed). The CO and H2 in the synthesis gas are catalytically reacted to form liquids.

Indirect coal liquefaction is preferred because it not only produces more refined fuel products that burn cleaner than DCL fuels, but also allows for cheaper more efficient capture of CO2 that would otherwise be emitted into the atmosphere. The potential to co-capture H2S and CO2 as a solution to acid gas management provides a very low cost solution to CO2 emissions. Fischer-Tropsch methods are the most widely in synfuel production today. Fischer-Tropsch Synthesis The Fischer-Tropsch synthesis was discovered in 1923 by F. Fischer and H. Tropsch at the Kaiser Wilhelm Institute for Coal Research in Mlheim , Germany . The reaction is highly exothermic, and the reactor must be designed for adequate heat removal to control the temperature and avoid catalyst deterioration and carbon formation. The synthesis processes based on the Fischer-Tropsch chemistry can be represented by the following reactions, Co catalysts 2n H2 + nCO = (CH2)n + nH2O Fe catalysts nH2 + 2nCO = (CH2)n + nCO2

which show polymeric addition of methylene groups to form a a distribution of linear paraffins and olefins. A broad range of molecular weights is usually produced, and the product includes branched, olefinic, and oxygenated compounds, depending on reactor type, operating conditions, and catalyst type. Products formed with iron catalysts contain more olefins than those formed in cobalt catalyst systems. The energy content of the products is between 37-51 kilocalories/mol of carbon (4,700-6,100 Btu/lb of product). Indirect coal liquefaction is preferred because it not only produces more refined fuel products that burn cleaner than DCL fuels, but also allows for cheaper more efficient capture of CO2 that would otherwise be emitted into the atmosphere. The potential to co-capture H2S and CO2 as a solution to acid gas management provides a very low cost solution to CO2 emissions. Fischer-Tropsch methods are the most widely in synfuel production today. Environmental Concerns As with any non-renewable resource, coal and coal derived fuels do not offer a permanent solution to the global energy problem. However, when oil reserves inevitably become depleted, using coal derived fuels can buy us more time to develop and perfect renewable energy sources. Emissions and Sulfur and Carbon Dioxide Removal Coal derived liquid fuels could have long term environmental benefits. The Fischer-Tropsch method provides a method, discussed in the next paragraph, to reduce sulfur and particulate matter emissions. Under the Clean Air Act, the EPA has regulated sulfur emissions from coal burning plants at 8.95 million tons annually, but coal derived fuels could provide a source of energy without sulfur emissions. This is especially important as more developing countries, with less stringent or non-existent emissions regulations, become industrialized and increase carbon fuel consumption. Because H2S removal is necessary in Fischer-Tropsch to protect synthesis catalysts as well as to limit SO2 emissions, sulfur levels in syngases entering the synthesis reactor must be below 1 ppmv. These levels are achieved through one of two methods--physical absorption by organic fluids or chemical reactions between amines and sulfur compounds. Physical absorption is the preferred process because syngases being passed through these systems are pressurized above 60 bars and the effectiveness of the system is proportional to the partial pressure of the gasses to be removed. This process allows H2S removal down to the 20 ppmv level at which point the syngas is passed over a zinc-oxide bed to bring H2S levels below 1 ppmv. But sulfur is not the only concern. Synfuel production releases significant amounts of mercury and other toxins that must be handled responsibly if their environmental effects are to be mitigated. Another major problem with the F-T method and the creation of coal derived fuels is the higher carbon content of coal per unit of energy. This higher ratio actually means that petroleum produce significantly less carbon emissions. Thus, it is not possible to convert the entire transportation market to synfuels until indirect coal liquefaction can be coupled with carbon sequestration. As already discussed, however, only indirect coal liquefaction allows for carbon dioxide capture. Direct coal liquefaction, on the other hand, which is emerging as the front-runner in China , does not easily allow capture and sequestration. Therefore China , with its booming economy and predicted rise in fuel demand will significantly add to the greenhouse gas problem by using this technology. And without any economic incentive to capture carbon during or after conversion, it is unlikely that the Chinese industry will seek sequestration of CO2 in the foreseeable future. Synfuels can potentially be a much better option environmentally than oil based fuels. Coupled with carbon sequestration, the Fischer-Tropsch fuels can usher in a new era of emissions-free energy. And with continuing research on direction coal liquefaction processes, the costs of implementing carbon sequestration with these processes should fall and become more viable. As synfuel technology becomes perfected, we can use synfuels to buy more time to develop renewable sources of energy.

While other alternative fuels are basically infeasible due to the high cost of modifying the current infrastructure (a problem with hydrogen methanol, or ethanol); Fischer-Tropsch diesel and gasoline can be transported through our already existing pipelines. These fuels can also be used in car engines currently on the market. For this reason, the Fischer-Tropsch process is the most feasible and most affordable fuel conversion method for countries such as the United States . These limitations are not a problem in developing nations such as China , where there is a lack of pre-existing infrastructure, especially in rural areas.

In order for the economics to be favorable, large scale facilities must be built. The most ideal projects
would have to be over a $1 billion investment. Also, in order for synfuel technologies to be a viable solution, there needs to be some sort of system of carbon sequestration and there are numerous economic as well as technological concerns regarding this. Other Possible Synfuels Methanol Methanol can function as a high-octane alternative fuel directly. MeOH is produced via two reactions: Water gas shift CO + H2O = CO2 + H2 (-40.9 kJ/mol) Methanol synthesis over CuO/ZnO/Al 2O3 catalyst CO + 2H2 = CH3OH (-90.7 kJ/mol) Methanol combustion releases formaldehyde, which has a lower potential to form ozone than unburned hydrocarbon emissions, it is a favorable alternative to conventional petroleum fuels. NO x emissions are also significantly lower due to a cooler flame when operated at the same compression ratio as gasoline. As with any fuel, there are of course some drawbacks to methanol as a transport fuel. Major problems include its corrosiveness, toxicity, low volumetric energy density, and most importantly, its affinity for water. This affinity for water makes a possible spill extremely dangerous, as MeOH could enter the drinking water supply, and because of its high toxicity, would be fatal in doses as small as 2 to 7 percent MeOH/liter of H2O, an amount that would not be detected by taste. Dimethyl Ether Dimethyl ether (DME) is a non-toxic and non-carcinogenic viable fuel alternative. DME could serve many uses, including an alternative to diesel fuels for transportation, liquefied petroleum gas for cooking, and as a potential source of electricity through diesel engine/generator sets. Dimethyl ether is currently produced through methanol dehydration which involves three key reactions: Water gas shift CO + H2O = CO2 + H2 (-40.9 kJ/mol) Methanol synthesis over CuO/ZnO/Al2O3 catalyst CO + 2 H 2 = CH 3 OH (-90.7 kJ/mol) Methanol dehydration over gamma-alumina catalyst 2 CH3OH = CH3OCH 3 + H2O (-23.4 kJ/mol)

Numerous corporations are currently working to develop a single-step slurry-phase reactor that will combine all three reactions to produce DME from coal-derived syngases in what is expected to be a cheaper, more efficient process. Dimethyl ether's similarities to diesel have been the subject of much research, to explore its viability as a diesel replacement. DME has a cetane number between 55-60, while standard diesel fuel has a cetane number between 45-55, making DME a suitable alternative to traditional diesel fuel. Studies show similar maximum speeds and accelerating performances for both diesel and DME. DME engines also passed current emissions regulations, with notable reductions in smoke and NOx as compared to diesel. The biggest problem with dimethyl ether is its poor lubricating properties. Diesel fuel functions as a lubricant for the fuel injection system as well as other components of diesel engines, and so to be considered a real alternative to diesel, a lubricating additive to DME is necessary for use in diesel engines. But Dimethyl ether could also serve another purpose. Dimethyl ether is a possible alternative for cooking fuel. Currently propane and butane, both poisonous because of their carbon monoxide and nitric oxide gas emissions, are being used as cooking fuels in countries such as India and China . These gases have caused major health concerns in the countries where they are used. Clean-burning DME offers a safe alternative fuel, and would eliminate most indoor air pollution, allowing this money to be allocated to other problems in the country. DME Development, Inc., a Japanese corporation made up of nine companies, has also realized the potential benefits of pushing DME in rural communities. The corporation is currently in the process of testing DME plants aimed at alleviated indoor air pollution problems. Synfuels offer a potentially environmentally-friendly, and on a large scale, cost-effective way to use the world's extensive coal reserves for much of our energy needs. This is becoming especially important as oil reserves dwindle. For countries with few oil resources and large coal reserves, like the United States and China , synfuels offer a way to utilize natural resources right at home and even out the trade imbalance that a foreign dependency on oil creates. We hope to see more research and government support of synfuels in the near future. Synfuels can be a viable fuel for the next several decades, allowing us to find a more permanent solution to the energy problem. CO2 in Gasification While gasification technology still produces CO2, it does so in a different manner than conventional coal burning plants. In normal carbon combustion (Equation 1), incomplete combustion oftentimes occurs, leaving the deadly carbon monoxide behind (Equation 2). This results in a decreased concentration of manageable CO2, making capture and consequent sequestration more difficult and expensive. Equation 1

Equation 2

However, in the gasification process, the CO2 emerges prior to any combustion. Because it is a more thermodynamically efficient process, there is less CO, making the CO2 more easily captured and sequestered. The sequestration of CO2 will prove to be one of the most important facets of future energy production, but is outside of the scope of this report

Coal is not the only compound that is subject to gasification. Recent forays into the gasification of biomass, and oftentimes biomass combined with coal are offering promising outputs for future power production. Gasifying biomass simultaneously with coal is an option that could increase efficiency as well as bolster the production of "green power." "Co-firing biomass (i.e. wood waste) with coal may prove to be the lowest cost method for generating 'green power' in utility plant demonstrations. It also reduces the emissions of fossil-based CO2 . From a community service point-of-view, cofiring can provide an end use for low value or negative value products. These might include sawdust or other fine wood wastes produced by furniture mills, sawmills, and related industries in a generating plant's locale. Also, gasification has been used for years in the paper and pulp production industry. The resulting residue of the paper making process is a compound known as "black liquor." This relatively unreactive compound can be gasified through a self-catalyzing process to recreate other fuels. Black liquor gasification is a promising alternative for recovery of energy and chemicals from black liquor, a product of pulp and paper milling. Because the organic fraction of black liquor comes originally from plants, it is thought of as a renewable energy resource. Large-scale implementation of black liquor gasification technology through the use of IGCC technology maintains the potential for the production of up to 20,000 megawatts of green electricity in the United States. Alternately, using the syngas produced from black liquor gasification fuel for production of automotive fuels like biodiesel holds the potential to produce 280 million barrels of oil per year. This would displace more than 7% of U.S. oil imports with a domestically-produced, renewable fuel. However, the production of green electricity is beyond the scope of this report. Issues/Problems The main issues surrounding the implementation of gasification technology are price and building time. As mentioned above, the current price of producing and integrating gasifiers into energy plants is very high. Additionally, somewhat similar to the lengthy process of constructing a nuclear power plant, project developments take almost ten years. Thus, as energy demands continue to rise both domestically and globally, the construction of plants to meet those demands takes serious time. So, planning for future energy demands and beginning early construction accordingly is critical, especially as more strict emissions regulations increase the demand for clean energy. This further becomes a problem for developing countries that wish to utilize this cutting edge technology to support booming energy demands combined with increasingly stringent emissions regulations. While countries like the US and England enjoyed their periods of industrialization and emissions regulations, countries developing today are often times also stringently regulated. However, with populations in developing nations like India and China so high, the energy demands are astronomical and nearly impossible to meet economically. China is a country that is under particular strain, and they have committed to utilizing gasification technology to meet their future demands. If China continues their current energetic strategy, the following will happen: The country will become overly dependent on imported oil as a result of the rapidly growing demand for liquid fuels emerging from the transportation realm, Public health and environmental damages will occur and will lead to very large economic consequences Climate change impacts will become significant, making it impossible for China to make their contribution to mitigating greenhouse gas (GHG) emissions under current regulations

The plan to avoid these issues is the modernization of coal. Modernization of coal refers to using gasification technology in the following ways: produce synthetic gas for power clean fuels for transportation and cooking heat for both domestic and industrial heating applications replace coal combustion technology and oil imports

The implementation of gasification plants will achieve the above goals, but it will also create significant burdens on the current infrastructures in place in China. First, the railway system must be improved to transport the increased demand for coal. Second, the country currently lacks the necessary energy transportation lines to supply the desired locations. Dedication to expanding the accessible grid is crucial. Finally, a dedication to the widespread conversion of automobiles to using DME or in the longer term hydrogen, is the only way to truly curtail long term emissions. While the use of new power plants will aid significantly in this area, as the population continues to increase and additional automobiles hit the pavement, a cleaner car is needed. It is only through serious governmental commitment to solving the multitude of problems that will occur, as well as obtaining the necessary funding to build all these plants, that China can even expect a clear-aired future Conclusion In sum, gasification technologies are the coal combustion technologies of the future. Though there are many economic drawbacks, if the world wishes to continue to use coal and attempt to curtail harmful emissions simultaneously, gasification is their only answer. Additionally, gasification provides valuable synfuels, that can someday be implemented on a wide scale to fuel automobiles. Carbon sequestration is only possible if the carbon is first caught, and gasifiers greatly expedite this process. There is no panacea for the energy and environmental problems facing our planet, but coal gasification is a step towards that cure that the world must take soon.