Synthesis Gas. James G. Speight

Waxes Methanol Dimethyl ether Ethylene Polyolefins Propylene Polyolefins Acetic acid Methyl acetate Acetate esters Polyvinyl acetate Acetic anhydride

      Figure 2.1 Potential products from synthesis gas produced from gasification of carbonaceous feedstocks.

Coal has been the primary feedstock for gasification units for many decades. However, there is a move to carbonaceous feedstocks other than coal for gasification processes with the concern on the issue of environmental pollutants and the potential shortage for coal in some areas (except in the United States) as well as concerns related to the effect of increased coal use on the environment. Nevertheless, coal use still prevails and will continue to do so for at least several decades into the future, if not well into the next century (Speight, 2013).

      In fact, gasification plants are cleaner with respect to standard pulverized coal combustion facilities, producing fewer sulfur and nitrogen byproducts, which contribute to smog and acid rain. For this reason, gasification appeals as a way to utilize relatively inexpensive and expansive coal reserves, while reducing the environmental impact. Indeed, the mounting interest in coal gasification technology reflects a convergence of two changes in the electricity generation marketplace: (i) the maturity of gasification technology, and (ii) the extremely low emissions from integrated gasification combined cycle (IGCC) plants, especially air emissions, and the potential for lower cost control of greenhouse gases than other coal-based systems. Fluctuations in the costs associated with natural gas-based power, which is viewed as a major competitor to coal-based power, can also play a role. Furthermore, gasification permits the utilization of a range of carbonaceous feedstocks (such as crude oil resids, coal, biomass, and carbonaceous domestic and industrial wastes) to their fullest potential. Thus, power developers would be well advised to consider gasification as a means of converting a carbonaceous feedstock to gas.

      Liquid fuels, including gasoline, diesel, naphtha and jet fuel, are usually processed via refining of crude oil (Speight, 2014a, 2017). Due to the direct distillation, crude oil is the most suited raw material for liquid fuel production. However, with fluctuating and rising prices of crude oil, coal-to-liquids (CTL) and biomass-to-liquids (BTL) processes are currently starting to be considered as alternative routes used for liquid fuels production. Both feedstocks are converted to synthesis gas which is subsequently converted into a mixture of liquid products by Fischer-Tropsch (FT) processes. The liquid fuel obtained after FT synthesis is eventually upgraded using known crude oil refinery technologies to produce gasoline, naphtha, diesel fuel and jet fuel (Dry, 1976; Chadeesingh, 2011; Speight, 2014a, 2017). Gasification processes can accept a variety of feedstocks but the reactor must be selected on the basis of feedstock properties and behavior in the process. The future depends very much on the effect of gasification processes on the surrounding environment. It is these environmental effects and issues that will direct the success of gasification.

      Clean Coal Technologies (CCTs) are a new generation of advanced coal utilization processes that are designed to enhance both the efficiency and the environmental acceptability of coal extraction, preparation and use (Speight, 2013). These technologies reduce emissions, reduce waste, and increase the amount of energy gained from coal. The goal of the program was to foster development of the most promising clean coal technologies such as improved methods of cleaning coal, fluidized bed combustion, integrated gasification combined cycle, furnace sorbent injection, and advanced flue-gas desulfurization.

      In fact, there is the distinct possibility that within the foreseeable future the gasification process will increase in popularity in crude oil refineries – some refineries may even be known as gasification refineries (Speight, 2011b). A gasification refinery would have, as the center piece, gasification technology as is the case with the Sasol refinery in South Africa (Couvaras, 1997). The refinery would produce synthesis gas (from the carbonaceous feedstock) from which liquid fuels would be manufactured using the Fischer-Tropsch synthesis technology.

In fact, gasification to produce synthesis gas can proceed from any carbonaceous material, including biomass. Inorganic components of the feedstock, such as metals and minerals, are trapped in an inert and environmentally safe form as char, which may have use as a fertilizer. Biomass gasification is therefore one of the most technically and economically convincing energy possibilities for a potentially carbon neutral economy.

      The manufacture of gas mixtures of carbon monoxide and hydrogen has been an important part of chemical technology for approximately a century. Originally, such mixtures were obtained by the reaction of steam with incandescent coke and were known as water gas. Eventually, steam reforming processes, in which steam is reacted with natural gas (methane) or crude oil naphtha over a nickel catalyst, found wide application for the production of synthesis gas.

      A modified version of steam reforming known as autothermal reforming, which is a combination of partial oxidation near the reactor inlet with conventional steam reforming further along the reactor, improves the overall reactor efficiency and increases the flexibility of the process. Partial oxidation processes using oxygen instead of steam also found wide application for synthesis gas manufacture, with the special feature that they could utilize low-value feedstocks such as heavy crude oil residues. In recent years, catalytic partial oxidation employing very short reaction times (milliseconds) at high temperatures (850 to 1000^oC) is providing still another approach to synthesis gas manufacture (Hickman and Schmidt, 1993).

      In a gasifier, the carbonaceous material undergoes several different processes: (i) pyrolysis of carbonaceous fuels, (ii) combustion, and (iii) gasification of the remaining char. The process is very dependent on the properties of the carbonaceous material and determines the structure and composition of the char, which will then undergo gasification reactions.

      As crude oil supplies decrease, the desirability of producing gas from other carbonaceous feedstocks will increase, especially in those areas where natural gas is in short supply. It is also anticipated that costs of natural gas will increase, allowing gasification of other carbonaceous feedstocks to compete as an economically viable process. Research in progress on a laboratory and pilot-plant scale should lead to the invention of new process technology by the end of the century, thus accelerating the industrial use of gasification processes.

      The conversion of the gaseous products of gasification processes to synthesis gas, a mixture of hydrogen (H₂) and carbon monoxide (CO), in a ratio appropriate to the application, needs additional steps, after purification. The product gases – carbon monoxide, carbon dioxide, hydrogen, methane, and nitrogen – can be used as fuels or as raw materials for chemical or fertilizer manufacture.