Right up front, we have to report, that, in the course of our research for this dispatch, we stumbled across a public statement that is, of course, so obvious that we all have just pretty much come to accept, without comment or protest, the fact of it. But, on further reflection, as we worked on our composition herein, the true import of it - - in light especially of our own reportage on Coal liquefaction technology as made public by the West Virginia Coal Association, and the ongoing Coal Country public press silence, a veritable blackout, on the issue - - began to loom much larger and compelled us to comment.
First, we remind of the Nobel Prize-winning "Bergius process" for direct Coal hydrogenation and liquefaction, wherein Coal is reacted, at high temperature and pressure, directly with Hydrogen; more about which can be learned, for a few examples, in our reports of:
West Virginia Coal Association | Bergius 1928 Coal Liquefaction | Research & Development; concerning: "United States Patent 1,669,439 - Process for Distilling and Liquefying Coal; 1928; Inventor: Friedrich Bergius, of Heidelberg, Germany; Abstract: This invention relates to improvements in a correlated process for distilling and liquefying coal"; and:
West Virginia Coal Association | CoalTL Wins Nobel Prize - in 1931 | Research & Development; wherein it's explained that Friedrich Bergius was awarded the Nobel Prize in Chemistry for developing a process whereby Coal can be reacted at high pressure with molecular Hydrogen, in the presence of catalysts and an oil derived from the process itself, and be thereby converted into liquid and gaseous hydrocarbons.
And, the reference to the Bergius process that has caused us much reflection is one found in what has become an almost ubiquitous source of broadly-disseminated public knowledge, the Wikipedia. As in:
Bergius process - Wikipedia, the free encyclopedia; wherein we're told, in an article of commendable detail, that: "During WWII the United States conducted secret research in converting coal to gasoline at a facility in Louisiana, Missouri. Located along the Mississippi river, this plant was producing gasoline in commercial quantities by 1948. The Louisiana process method produced automobile gasoline at a price slightly higher than, but comparable to, petroleum based gasoline but of a higher quality. The facility was shut down in 1953 by the Eisenhower administration after intense lobbying by the oil industry. The Louisiana MO operation began about 1946 using captured German technology. The objection to it by big oil in Houston was that the cost estimates for commercial production were so low that the corporations' oilfield resources would be rendered worthless, therefore the program had to be terminated to protect the profits of big oil".The Wikipedia is careful to document their sources via appended reference links; and, we know from our own research and reportage that all the above is true. We've made previous report, long ago, on the Missouri Coal conversion plant. But, consider:
Sixty years ago, it was established by our own United States Government that "commercial quantities" of "gasoline", a gasoline of "higher quality" than, and of a "price ... comparable to", gasoline derived from petroleum, could be made from Coal, using a form of the Bergius process, which was used on a broad scale by Germany during WWII to produce hydrocarbon fuels. But, the Government of the United States of America was cowed into terminating, and apparently hiding evidence of, their successful, profitable conversion of Coal into Gasoline because "big oil in Houston" objected to it; "the program had to be terminated to protect the profits of big oil".
And, we want here to quote - - for the half-dozen members of the Coal Country press who have been our primary addressees over these past nearly half-dozen years, for these reports on the truth that Coal can, cleanly and efficiently, be converted into anything we now mortgage our grandchildren's future to the inimical alien nations of OPEC to keep ourselves supplied with in the here and now, and, in particular, for one of those members of the press for whom we have documented other momentous things, as well - - one of America's great liberators:
"A time comes when silence is betrayal." - - Martin Luther King.
By our way of thinking, that time for some of you, at least one of you, for multiple reasons, has come and gone. For others of you, maybe not; but, you're on the clock.
In any case, as we've documented in a number of reports, including, for one example:
West Virginia Coal Association | Exxon 1982 CoalTL Uses WVU CoalTL Hydrogen Donor Solvent | Research & Development; concerning: "US Patent 4,345,989 - Catalytic Hydrogen-donor Liquefaction Process; 1982; Assignee: Exxon Research and Engineering Company; Abstract: Coal or a similar solid carbonaceous feed material is converted into lower molecular weight liquid hydrocarbons by contacting the feed material with a hydrogen-donor solvent ... and molecular hydrogen ... . The hydrogen-donor solvent used in preparing the slurry ... will normally be a coal-derived solvent, preferably a hydrogenated recycle solvent";
various entities have continued to improve upon the basic Bergius process, wherein Coal, suspended in a Coal-derived oil which serves as a Hydrogen donor, or transfer, solvent, is treated under suitable reaction conditions through exposure to "molecular hydrogen". And, as seen for example in:
West Virginia Coal Association | California Rocket Scientists Liquefy Coal | Research & Development; concerning: "US Patent 4,169,128 - Coal Liquefaction Apparatus; 1979; Assignee: Rockwell International Corporation; Abstract: Disclosure is made of an apparatus for reacting carbonaceous material with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels wherein the reaction involves injection of carbonaceous material such as pulverized coal entrained in a minimum amount of gas and mixing the entrained coal at near ambient temperature with a separate source of heated hydrogen"; and:
West Virginia Coal Association | USDOE Improves Direct Coal Hydrogenation and Conversion | Research & Development; concerning: "United States Patent 4,735,706 - Process and Apparatus for Coal Hydrogenation; 1988; Assignee: The United States of America; Abstract: In the coal liquefaction process, an aqueous slurry of coal is prepared containing a dissolved liquefaction catalyst. A small quantity of oil is added to the slurry and then coal-oil agglomerates are prepared by agitation of the slurry at atmospheric pressure. The resulting mixture of agglomerates, excess water, dissolved catalyst, and unagglomerated solids is pumped to reaction pressure and then passed through a drainage device where all but a small amount of surface water is removed from the agglomerates. Sufficient catalyst for the reaction is contained in surface water remaining on the agglomerates. The agglomerates fall into the liquefaction reactor counter currently to a stream of hot gas which is utilized to dry and preheat the agglomerates as well as deposit catalyst on the agglomerates before they enter the reactor where they are converted to primarily liquid products under hydrogen pressure.
alternative Coal direct hydro-treating processes have been developed by various entities, wherein Coal is exposed directly to Hydrogen gas, with the Hydrogen transfer solvent, if used at all, is used in smaller quantities.
And, we see herein another example of such Coal hydrogenation and conversion technology, as developed by our own United States Department of Energy, via excerpts from the initial link in this dispatch to:
"United States Patent 4,155,832 - Hydrogenation Process for Solid Carbonaceous Materials
Patent US4155832 - Hydrogenation process for solid carbonaceous materials - Google Patents
Date: May, 1979
Inventors: John Cox and Wayne Wilcox, Richland, WA
Assignee: The United States of America
Abstract: Coal or other solid carbonaceous material is contacted with an organic solvent containing both hydrogen and a transition metal catalyst in solution to hydrogenate unsaturated bonds within the carbonaceous material. This benefaction step permits subsequent pyrolysis or hydrogenolysis of the carbonaceous fuel to form gaseous and liquid hydrocarbon products of increased yield and quality
Government Interests: The invention described herein was made in the course of, or under, a contract with the United States Department of Energy.
(All indications are that this technology was developed at, or in partnership with, the USDOE's Pacific Northwest National Laboratory:
Pacific Northwest National Laboratory; and: Pacific Northwest National Laboratory - Wikipedia, the free encyclopedia; "Pacific Northwest National Laboratory (PNNL) is one of the United States Department of Energy National Laboratories ... . The main campus of the laboratory is in Richland, Washington. PNNL scientists conduct basic and applied research and development to strengthen U.S. scientific foundations (to, among other things) increase the U.S. energy capacity and reduce dependence on imported oil".)
Claims: A method of hydrogenating solid carbonaceous fuels that contain unsaturated carbon to carbon bonds, the carbonaceous materials are selected from coal, lignite, wood (and) comprising:
- providing an organic solution containing a nickel Zeigler catalyst prepared from a nickel carboxylate reacted with an alkyl aluminum in an anhydrous, organic solvent to provide a homogeneous catalytic solution;
- treating the catalytic solution with a source of hydrogen to form a hydrogen-containing complex with the transition metal; and
- contacting the solid carbonaceous material with the catalytic solution to hydrogenate the unsaturated carbon bonds.
(First, note the element of sustainability and Carbon recycling through the inclusion of "wood". Second, "Ziegler catalyst"s are well-known in industry. See:
Ziegler–Natta catalyst - Wikipedia, the free encyclopedia. Third, since we require "a source of hydrogen", as we've documented now many times, as, for one example, in:
West Virginia Coal Association | General Electric 2010 Hydrogen from Sunlight and Water | Research & Development; concerning: "United States Patent 7,820,022 - Photoelectrochemical Cell and Method of Manufacture; 2010; General Electric Company; Abstract: A photoelectrochemical cell ... to produce gaseous hydrogen and oxygen (from water)";
we're getting pretty good at using environmental energy, such as sunlight, to extract Hydrogen from plain old Water.)
The method ... wherein the solid carbonaceous fuel is contacted with the catalytic solution at a temperature less than 400 C (and, more specifically) between 150 to 350 C.
The method ... wherein the organic solution includes a liquid solvent of liquefaction products of the solid carbonaceous material.
(The "solvent", in other words, is a Coal-derived liquid made in the process itself.)
The method ... wherein the solid carbonaceous material following the hydrogenation reaction is heated to a temperature substantially in excess of 300 C to produce gaseous and liquid hydrocarbon products (and) wherein the solid, hydrogenated carbonaceous material is heated to a temperature of 400 (to) 500 C. at about 100-200 atmospheres pressure in the presence of a transition metal catalyst and a source of hydrogen to provide hydrogenolysis of the carbonaceous material resulting in gaseous hydrocarbons, liquid hydrocarbon and solid char containing residual carbonaceous material.
(So, like the original Bergius process, this technology does, in the end, require the application of some pretty high temperatures and pressures. Such high pressures will limit the size of individual reaction chambers. although, as can be learned via the full Disclosure of the above-cited, later "United States Patent 4,735,706 - Process and Apparatus for Coal Hydrogenation", direct Coal hydrogenation technology continued to improve, with a reduction in the severity of the needed reaction conditions.)
The method ... wherein the solid char containing residual carbonaceous material is contacted with steam and oxygen to produce a gas containing hydrogen and carbon monoxide as a source of hydrogen for treating the catalytic solution.
(Actually, since we can supply the Hydrogen via a process like that seen in the above-cited "United States Patent 7,820,022 - Photoelectrochemical Cell and Method of Manufacture", we can, instead, treat "the solid char containing residual carbonaceous material" in another process like that seen in our report of:
West Virginia Coal Association | Pittsburgh USBM Recycles CoalTL Residue | Research & Development; concerning: "United States Patent 2,634,286 - Hydrocarbon Synthesis Gas from Coal; 1953; Assignee: The United States of America; Abstract: This invention relates to the production of synthesis gas and more particularly to the production of a low-sulfur content mixture of carbon monoxide and hydrogen by gasifying the char obtained as a byproduct of the direct hydrogenation of coal ... . The low-sulfur content synthesis gas produced by gasification of this low-sulfur content char will find one of it's most advantageous uses in processes such as the Fischer-Tropsch ... to form liquid and gaseous hydrocarbons";
which was designed and intended by the US Bureau of Miners to convert just such still-carbonaceous residues from a direct Coal hydrogenation process, indirectly, into even more hydrocarbons.)
A method of converting solid carbonaceous material, that includes unsaturated carbon to carbon bonds, selected from coal, lignite (and) wood ... to liquid and gaseous hydrocarbon fuels comprising:
- contacting said solid carbonaceous material with a liquid catalytic solution in the presence of a source of hydrogen at a first temperature below 350 C to hydrogenate unsaturated carbon bonds within the solid carbonaceous material, said catalytic solution including an organic solvent and a complex compound selected from the group consisting of the carbonyls, hydrocarbonyls and Ziegler-type catalytic compounds of the group VIII transition metals;
- separating said liquid catalytic solution from said hydrogenated, solid carbonaceous material, and recycling said catalytic solution with dissolved catalyst into contact with fresh carbonaceous material;
- heating said hydrogenated, solid carbonaceous material to a second temperature in excess of said first temperature in the presence of a hydrogen containing gas to break carbon to carbon bonds and form liquid and gaseous hydrocarbon fuels.
Description and Background: The present invention relates to methods for the benefaction, gasification and liquefaction of coal and other carbonaceous materials. The fuel materials contemplated include anthracite, bituminous and lignite coal along with other materials such as wood ... .
Previous methods for carrying out the processing of solid carbonaceous materials have employed solid catalysts of cobalt, iron, nickel, molybdenum and alloys such as cobalt-molybdenum. Since the coal or other carbonaceous material is also in solid form, it is difficult to obtain contact between the solid phases and the other reactants. Consequently, high temperatures have been used to break carbon to carbon bonds for hydrogen addition. This hydrogenolysis of the carbonaceous substrate can produce gaseous and liquid products.
In processes for the liquefaction of coal with a solid catalyst, organic liquids, often recycled product, are used as a media for catalyst-reactant contact. Hence these processes are characterized as heterogeneous catalytic reactions employing heterogeneous catalysts.
Various processes as the Bureau of Mines synthoil and others employ heterogeneous catalytic reactions in which hydrogen is reacted with materials within the coal at temperatures above about 400 C and pressures of 100-250 atmospheres. These reaction conditions promote hydrogenolysis in which carbon to carbon bonds are broken and hydrogen is added. In addition, other atoms such as oxygen, nitrogen and sulfur found in the carbonaceous materials are converted to water, ammonia and hydrogen sulfide. To the extent that these reactions remove sulfur and other pollutants, they can be desirable but otherwise they can be a nonproductive consumption of hydrogen.
Summary: (In) view of the problems associated with the prior art processes, it is an object of the present invention to provide a process for hydrogenating solid carbonaceous materials with a transition metal catalyst in organic solution.
It is a further object to provide a hydrogenation method for solid carbonaceous materials that can be performed at moderate conditions.
It is also an object of the present invention to provide a process employing a hydrogenation catalyst in an organic phase that can penetrate organic carbonaceous phases of the substrate material.
In accordance with the present invention, solid carbonaceous material containing unsaturated carbon to carbon bonds is contacted with an organic solution containing a dissolved transition metal catalyst and available hydrogen.
In more specific aspects of the invention, the solid carbonaceous material is contacted with the transition metal catalyst solution at moderate conditions including temperatures less than 350 C. The catalyst and solid hydrogenated material are separated in a liquid-solid separation step. The transition metal catalyst is preferably in the form of a complex molecule containing ligands such as carbonyls, hydrocarbonyls, or those present in a Zeigler catalyst form each having a hydrogen incorporation capability. Hydrogen for the reaction can be supplied as a separate gas .... ."
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And, to supply the needed "Hydrogen .... as a separate gas", so that we can utilize the Coal liquefaction residues as a source for hydrocarbon synthesis gas, keep in mind, again, that, as seen in:
West Virginia Coal Association | Panasonic Sunshine Extracts Even More Hydrogen from H2O | Research & Development; concerning: "United States Patent Application 20130075250 - Hydrogen Production Device; 2013; Assignee: Panasonic Corporation, (Japan); The present invention relates to a hydrogen production device for producing hydrogen through decomposition of water in a cell by irradiating an electrode including at least a photocatalytic semiconductor with light. (Hydrogen) production using a photocatalyst is a system for producing hydrogen directly from water and sunlight, and can convert the solar energy effectively into hydrogen energy";
we can, using environmental energy to drive the process, extract the Hydrogen efficiently from Water.
All in all, through our own government, We the People, own a process that can cleanly, efficiently, and, when combined with other known processes, completely, convert our abundant Coal into all forms of "liquid and gaseous hydrocarbon fuels".
As documented herein, we've known that officially to be true for more than three decades.
And, remember, finally, that:
"A time comes when silence is betrayal.