Methanol feedstock

In the DME column (4), DME is separated from the top and condensed. The DME is cooled in a chilling unit (5) and stored in a DME tank (6) as a product. Water and methanol are discharged from the bottom and fed to a methanol column (1) for methanol recovery. The purified methanol from this column is recycled to the reactor after mixing with feedstock methanol. 

Methanol is a clean-burning liquid that can be used to power electricitygenerating turbines or as a fuel for automobiles and other vehicles. It can also be a feedstock for a variety of chemicals 14). Though most methanol is produced from natural gas, it can be produced from syngas derived from other feedstocks. Methanol contains no sulfur and produces very little nitrogen oxide pollutants when burned, making it one of the cleanest combustion fuels. 

Water and methanol are discharged from the bottom and fed to a methanol column (1) for methanol recovery. The purified methanol from this column is recycled to the reactor after mixing with feedstock methanol. 

Instead of using pure methane as a feedstock methanol, which undergoes the same reaction although at a much lower temperature (350°C), can be used. 

The present chemical outlets for methanol in the more traditional regions are rather well known and are even reaching maturity, as for formaldehyde and acetic acid to a lesser degree. There are some distinct chemical uses, however, that could provide new and alternative outlets for methanol somewhere in the more distant future. Producing various chemicals from feedstock methanol can result in a better value-added ratio than using methanol for fuels. Listed here are some of the routes to higher valued chemical products ... 

Thus, the further economic and environmental benefits arising from the use of natural gas encouraged an alternative route for olefins production by using relatively inexpensive methanol, which is deemed to be a readily stored and manageable intermediate product for the use of natural gas. Methanol to olefins (MTO) represents a real paradigm shift as the whole process is new and the feedstock, methanol, is different from the conventional feedstocks directly available from fossil resources, namely naphtha, liquid pressurized gas (LPG), or ethane [1]. 

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

Methanol. If methanol is to compete with conventional gasoline and diesel fuel it must be readily available and inexpensively produced. Thus methanol production from a low-cost feed stock such as natural gas [8006-14-2] or coal is essential (see Feedstocks). There is an abundance of natural gas (see Gas, natural) woddwide and reserves of coal are even greater than those of natural gas. 

Produced from a.tura.1 Ga.s, Cost assessments of methanol produced from natural gas have been performed (13—18). Projections depend on such factors as the estimated costs of the methanol production faciUty, the value of the feedstock, and operating, maintenance, and shipping costs. Estimates vary for each of these factors. Costs also depend on the value of oil. Oil price not only affects the value of natural gas, it also affects the costs of plant components, labor, and shipping. 

Ethanol. Accurate projections of ethanol costs are much more difficult to make than are those for methanol. Large scale ethanol production would impact upon food costs and have important environmental consequences that are rarely cost-analyzed because of the complexity. Furthermore, for corn, the most likely large-scale feedstock, ethanol costs are strongly influenced by the credit assigned to the protein by-product remaining after the starch has been removed and converted to ethanol. 

The term feedstock in this article refers not only to coal, but also to products and coproducts of coal conversion processes used to meet the raw material needs of the chemical industry. This definition distinguishes between use of coal-derived products for fuels and for chemicals, but this distinction is somewhat arbitrary because the products involved in fuel and chemical appHcations are often identical or related by simple transformations. For example, methanol has been widely promoted and used as a component of motor fuel, but it is also used heavily in the chemical industry. Frequendy, some or all of the chemical products of a coal conversion process are not isolated but used as process fuel. This practice is common in the many coke plants that are now burning coal tar and naphtha in the ovens. 

The only other petrochemical feedstock of significant commercial use is methane (natural gas) which is used primarily to produce ammonia and methanol. Consumption factors are about 28 GJ and 31 GJ per metric ton, respectively (58,300 and 64,700 BTU/lb) (8). Approximately... 

Liquid-phase oxidation of lower hydrocarbons has for many years been an important route to acetic acid [64-19-7]. In the United States, butane has been the preferred feedstock, whereas ia Europe naphtha has been used. Formic acid is a coproduct of such processes. Between 0.05 and 0.25 tons of formic acid are produced for every ton of acetic acid. The reaction product is a highly complex mixture, and a number of distillation steps are required to isolate the products and to recycle the iatermediates. The purification of the formic acid requires the use of a2eotropiag agents (24). Siace the early 1980s hydrocarbon oxidation routes to acetic acid have decliaed somewhat ia importance owiag to the development of the rhodium-cataly2ed route from CO and methanol (see Acetic acid). 

Liquid Fuels via Methanol Synthesis and Conversion. Methanol is produced catalyticaHy from synthesis gas. By-products such as ethers, formates, and higher hydrocarbons are formed in side reactions and are found in the cmde methanol product. Whereas for many years methanol was produced from coal, after World War II low cost natural gas and light petroleum fractions replaced coal as the feedstock. 

There are some chemicals that can be made economically from coal or coal-derived substances. Methanol and CO are used to make acetic anhydride and acetic acid. Methanol itself can be made from synthesis gas over a copper-2inc catalyst (see Feedstocks, coal chemicals). 

Feedstock Purification Manufacture of Synthesis Gases Hydrogen, Ammonia, Methanol, product bulletin. United Catalysts, Inc., Louisville, Ky. 

Synthesis Gas Generation Routes. Any hydrocarbon that can be converted into a synthesis gas by either reforming with steam (eq. 4) or gasification with oxygen (eq. 5) is a potential feedstock for methanol. 

This excess hydrogen is normally carried forward to be compressed into the synthesis loop, from which it is ultimately purged as fuel. Addition of by-product CO2 where available may be advantageous in that it serves to adjust the reformed gas to a more stoichiometric composition gas for methanol production, which results in a decrease in natural gas consumption (8). Carbon-rich off-gases from other sources, such as acetylene units, can also be used to provide supplemental synthesis gas. Alternatively, the hydrogen-rich purge gas can be an attractive feedstock for ammonia production (9). 

The high cost of coal handling and preparation and treatment of effluents, compounded by continuing low prices for cmde oil and natural gas, has precluded significant exploitation of coal as a feedstock for methanol. A small amount of methanol is made from coal in South Africa for local strategic reasons. Tennessee Eastman operates a 195,000-t/yr methanol plant in Tennessee based on the Texaco coal gasification process to make the methyl acetate intermediate for acetic anhydride production (15). 

Noncatalytic partial oxidation of residual fuel oil accounts for the remainder of world methanol production. Shell and Texaco ate the predominant hcensors for partial oxidation technology (16) the two differ principally in the mechanical details of mixing the feedstock and oxidant, in waste heat recovery, and in soHds management. 

The nameplate capacity of worldwide methanol plants is given by country in Table 2 (27). A significant portion of this capacity is based on natural gas feedstock. Percent utilization is expected to remain in the low 90s through the mid-1990s. A principal portion of this added capacity is expected to continue to come from offshore sources where natural gas, often associated with cmde oil production, is valued inexpensively. This has resulted in the emergence of a substantial international trade in methanol. In these cases, the cost of transportation is a relatively larger portion of the total cost of production than it is for domestic plants. 

Other Markets. The use of methanol in the production of formaldehyde, MTBE, and acetic acid [64-19-7] accounts for approximately two-thirds of the worldwide demand for methanol. Methanol is used as feedstock for various other chemicals, such as dimethyl terephthalate (DMT)... 

The advent of a large international trade in methanol as a chemical feedstock has prompted additional purchase specifications, depending on the end user. Chlorides, which would be potential contaminants from seawater during ocean transport, are common downstream catalyst poisons likely to be excluded. Limitations on iron and sulfur can similarly be expected. Some users are sensitive to specific by-products for a variety of reasons. Eor example, alkaline compounds neutralize MTBE catalysts, and ethanol causes objectionable propionic acid formation in the carbonylation of methanol to acetic acid. Very high purity methanol is available from reagent vendors for small-scale electronic and pharmaceutical appHcations. 

In addition to these principal commercial uses of molybdenum catalysts, there is great research interest in molybdenum oxides, often supported on siHca, ie, MoO —Si02, as partial oxidation catalysts for such processes as methane-to-methanol or methane-to-formaldehyde (80). Both O2 and N2O have been used as oxidants, and photochemical activation of the MoO catalyst has been reported (81). The research is driven by the increased use of natural gas as a feedstock for Hquid fuels and chemicals (82). Various heteropolymolybdates (83), MoO.-containing ultrastable Y-zeoHtes (84), and certain mixed metal molybdates, eg, MnMoO Ee2(MoO)2, photoactivated CuMoO, and ZnMoO, have also been studied as partial oxidation catalysts for methane conversion to methanol or formaldehyde (80) and for the oxidation of C-4-hydrocarbons to maleic anhydride (85). Heteropolymolybdates have also been shown to effect ethylene (qv) conversion to acetaldehyde (qv) in a possible replacement for the Wacker process. 

Oxidation of cumene to cumene hydroperoxide is usually achieved in three to four oxidizers in series, where the fractional conversion is about the same for each reactor. Fresh cumene and recycled cumene are fed to the first reactor. Air is bubbled in at the bottom of the reactor and leaves at the top of each reactor. The oxidizers are operated at low to moderate pressure. Due to the exothermic nature of the oxidation reaction, heat is generated and must be removed by external cooling. A portion of cumene reacts to form dimethylbenzyl alcohol and acetophenone. Methanol is formed in the acetophenone reaction and is further oxidized to formaldehyde and formic acid. A small amount of water is also formed by the various reactions. The selectivity of the oxidation reaction is a function of oxidation conditions temperature, conversion level, residence time, and oxygen partial pressure. Typical commercial yield of cumene hydroperoxide is about 95 mol % in the oxidizers. The reaction effluent is stripped off unreacted cumene which is then recycled as feedstock. Spent air from the oxidizers is treated to recover 99.99% of the cumene and other volatile organic compounds. 

Biofuels. Biofuels are Hquid fuels, primarily used ia transportation (qv), produced from biomass feedstocks. Identified Hquid fuels and blending components iaclude ethanol (qv), methanol (qv), and the ethers ethyl /-butyl ether (ETBE) and methyl /-butyl ether (MTBE), as well as synthetic gasoline, diesel, and jet fuels. 

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