We've made numerous reports concerning the operation of a Coal liquefaction pilot plant, and the conduct of associated research activities, by the old Union Carbide Corporation in South Charleston, West Virginia.
Those good works, as seen, for just two examples, in:
West Virginia Hydrocracks Coal Liquids with Brute Force | Research & Development; concerning: "United States Patent 2,913,397 - Hydrogenolysis of Coal Hydrogenation Products; 1959; Inventors: James Murray, et. al., South Charleston and Nitro, WV; Assignee: Union Carbide Corporation, NY; Abstract: This application relates to chemical processes. More particularly it relates to an improvement in processes for obtaining chemicals from coal", and:
Charleston, WV, Coal + Steam = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 3,988,237 - Integrated Coal Hydrocarbonization and Gasification of Char; 1976; Inventors: Hubert Davis, Charles Albright, et. al.; all of West Virginia; Assignee: Union Carbide Corporation, NY;
Abstract: An integrated continuous process for the production of liquid and gaseous fuels wherein coal particles are hydrocarbonized with a hydrogen-rich gas supplied by a gasification process employing two separate and interconnected zones for combustion and gasification and wherein char produced by the hydrocarbonization of the coal particles provides the feed for the gasification zone".
continued, largely unheralded and unnoted by the Coal-mining citizens of West Virginia, over the course of multiple decades.
We've also, separately, disparaged at some length the energy-wasting concept of manufacturing Ethanol, through processes of fermentation, from agricultural produce and other botanically-derived materials.
Not only is such "Corn" Ethanol wasteful of energy, for a number of reasons, it also, again for a number of reasons, does nothing to reduce CO2 emissions; and might, in fact, if all the energy-demanding and Carbon Dioxide-generating processes of cultivation, harvesting, fermentation and distillation were properly accounted for, actually add a net amount of CO2 to humanity's overall emissions.
As it happens, one of the focuses of Union Carbide's Coal hydrogenation work in West Virginia was on the conversion of Coal first into Alcohols, and, then, the conversion of those Alcohols into Gasoline, as seen in:
WV Coal to Methanol to Gasoline to Zeolite Catalysis | Research & Development; which reports: "United States Patent 4,499,327 - Production of Light Olefins; 1985; Inventor: Steven Kaiser, South Charleston, WV; Assignee: Union Carbide Corporation, CT; Abstract: The process for the production of light olefins from a feedstock comprising methanol (and) ethanol (as) may be manufactured from ... from synthesis gas (which) may be derived by the combustion of ... coal."
And, herein, a West Virginia scientist in the employ of Union Carbide tells us specifically how we can make such a "feedstock comprising methanol (and) ethanol", which are part of a special group of alcohols known technically as "alkanols", "from synthesis gas" produced from Coal.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent 4,333,852 - Production of Ethanol and Methanol Directly from Synthesis Gas
Date: June, 1982
Inventor: Barbara Warren, Charleston, WV
Assignee: Union Carbide Corporation, CT
Abstract: Alkanols are selectively produced as the major product directly from synthesis gas under mild conditions using a homogeneous ruthenium catalyst, a halogen or halide promoter and a phosphine oxide compound as solvent.
(Though a precious metal, "ruthenium" isn't all that hard to get. And, it is often specified as a component of catalysts used in hydrogenation and hydrocracking operations by the petroleum industry.)
Claims: A catalyst for the direct production of ethanol or mixtures thereof with other alkanols ... by the reaction of carbon monoxide and hydrogen comprising (a) a ruthenium compound, (b) a promoter, and (c) an organic phosphine oxide solvent wherein said ... promoter (b) is elemental iodine or bromine or a compound thereof which is capable of generating hydrogen iodide or hydrogen bromide during said reaction.
(We've many times made report on the use of bromine, iodine and chlorine, i.e., "halogen", compounds in processes similar to that above. An example would include:
Shell Oil Cracks Coal with Zinc Halide | Research & Development; concerning: "United States Patent 3,764,515 - Process for Hydrocracking Heavy Hydrocarbons; 1973; Assignee: Shell Oil Company, NY;
Abstract: There is disclosed a process for hydrocracking coal or other heavy hydrocarbon fractions employing a molten catalyst system, including a mineral acid that is stable at reaction conditions, and a metal halide catalyst selected from zinc chloride, bromide or iodide, antimony bromide or iodide, tin bromide, titanium iodide, arsenic bromide or iodide, mercuric bromide or iodide, gallium bromide, or bismuth bromide".
Such metal halides disassociate in those processes to "yield" the halide, and would constitute Carbide's specified "compound(s) ... capable of generating hydrogen iodide or hydrogen bromide".)
Description and Background: Within the past decade the price of crude oil, the basis for most petroleum products, has increased significantly in addition its availability in needed quantities has at times been severely curtailed. This has created many problems to the manufacturers and consumers leading to attempts to reduce reliance on crude oil as the basic starting material. A major product dependent on adequate supplies of crude oil is ethanol, which has been manufactured in significant quantities by the hydration of ethylene derived from petroleum or crude oil. The increased cost of crude oil are, however, making this process less economical at a time when the demand for ethanol for use in fuels, such as gasohol, or as an intermediate for producing other organic compounds, such as ethylene (from dehydration), is increasing at an unpredictable rate. Thus, much effort is being expended to the development of alternate processes for the production of ethanol at economically acceptable costs from other sources.
While the production of ethanol by the well known fermentation process is well established, this process competes with the use of the starting materials generally used, grains and sugars, as foodstuffs. Further, in many instances the feedstocks are not readily available at the plant site and the processes are multi-step procedures requiring provisions for fermentation, distillation and disposal of residual solid wastes. To attempt to supply the anticipated demand for ethanol solely by additional fermentation plants could result in a significant disruption in the amount of feed grain available for human needs.
As a result methods which do not severely disrupt these needs are preferred.
Such procedures involve the use of synthesis gas, a mixture of carbon monoxide and hydrogen. This is an alternate feedstock which is inexpensive and increasingly desirable because it can be derived from non-petroleum sources such as coal.
Basically the known processes involve the catalytic homologation of methanol with synthesis gas at elevated temperatures and pressures, with most processes yielding a mixture of products that are subsequently separated.
(We thought that we had previously made report of the use of Coal-derived synthesis gas in the conversion, the "homologation", of Methanol into Ethanol, but we cannot, at this time, find such a reference in the West Virginia Coal Association R&D archives. We will make a point of further documenting such technology for you in the near future. It was, it seems, a process well-known in certain informed circles.)
To our present knowledge there is no single reference that can be said to individually teach how to selectively produce ethanol at commercially significant efficiencies directly from synthesis gas.
(That might have been true in 1982, and, as seen in:
LeHigh University Converts Coal to Ethanol for USDOE | Research & Development; concerning: "Ethanol Synthesis and Water Gas Shift Over Bi-functional Sulfide Catalysts; 1992; Lehigh University (for) the USDOE Pittsburgh Technology Center. (Abstract:) The objective of the proposed research is to investigate and develop a novel catalytic process for the conversion of coal-derived synthesis gas into high octane CI-C 4 alcohols, especially ethanol";
our USDOE, despite the accomplishments of Union Carbide we report herein, was, ten years later, still trying to find better ways to go about it.)
Summary and Description: It has now been found that ethanol can be produced selectively as the major product directly from synthesis gas under mild conditions using a homogeneous catalyst. The catalyst system contains a ruthenium compound, an halogen or halide promoter (preferably based on iodine or bromine) and a phosphine oxide compound as solvent. One can also include other promoters, if desired.
The present invention is directed to a catalytic process in which ... ethanol is directly and selectively produced in a homogeneous process, and to the catalyst compositions used in such process.
In the process of this invention ethanol is obtained as the major product directly from synthesis gas under mild conditions using a homogeneous ruthenium catalyst. Methanol, propanol, ethylene glycol and methane are the significant by-products, all of which can be separated and recovered, or recycled, if desired.
The invention is advantageous when compared to other known processes when the intent is to produce a mixture of compounds, e.g. alkanols, for fuel use in that it is a one-step, homogeneous, direct process from synthesis gas to yield a mixture high in alcohols that can be used with a minimum of purification. Thus the use of this invention for the manufacture of compositions useful as fuels is of significant importance in today's economy."
-------------------
And, it seems more than likely, does it not, that such a "synthesis gas" - - - which Union Carbide demonstrates herein can be used to "manufacture ... compositions useful as fuels", which fuels are "of significant importance in today's economy", with "today" being very nearly thirty years ago, and which "synthesis gas" Union Carbide specifies, as in our above reference to "US Patent 3,988,237 - Integrated Coal Hydrocarbonization and Gasification of Char", "may be derived by the combustion of ... coal" - - - would have an even greater, far greater, "importance", today, with all that's happened since, and, especially, in West Virginia, where the technology was invented, in the very heart of US Coal Country?