United States Patent: 4263141

We treat several interrelated issues concerning the conversion of Coal into liquid hydrocarbon fuels in this dispatch.

First, as we have earlier discussed, an extensive, truly extensive, body of documentation exists which describes and explains how "synthesis gas", or, "syngas", a blend of, primarily, Carbon Monoxide and Hydrogen, can be processed and catalyzed, and be made thereby to form virtually any variety of hydrocarbon, whether liquid or gas.

 

 

However, despite the, now quite literally, more than a thousand documented attestations of the fact that synthesis gas can be made from Coal, and/or virtually any other Carbon-based material, including biomass and Carbon Dioxide, which we have already brought to your attention, there is an even far larger body of records originating from within the global petroleum industry concerning the catalytic conversions of syngas, where the sources of the syngas are, though most often left unstated, implied to be conventional petroleum sources. However, those sources are sometimes specified to include the highly-carbonaceous and Coal-like petroleum refinery residues, sometimes labeled "asphaltenes", or, "resids", that are the by-products of some conventional refining processes.

Herein, through multiple related links and excerpts, we wanted to again drive home the point that, yes, Hydrogen-Carbon Monoxide synthesis gas can be efficiently catalyzed and made to form any type or sort of hydrocarbon we might want; and, yes, we can most definitely make such synthesis gas efficiently from our abundant domestic Coal.

First, from a Germany-based corporate source we have previously cited, we reintroduce a Coal syngas conversion technology we previously made specific report of more than a year ago, as seen in:

Germany Makes Gasoline from Coal Syngas Via Methanol | Research & Development.

Our original treatment of the US Patent which is the subject of that report was overly-brief.

We wanted to illuminate it a bit more fully herein; and, to emphasize it's import by the inclusion, following, of some additional links and excerpts which provide clear and plain description of how such a blend of Carbon Monoxide and Hydrogen synthesis gas, which can be so efficiently condensed into our most favorite form of liquid hydrocarbon, can be generated in a straightforward process from our abundant Coal:

"United States Patent 4,263,141 - Process of Producing Gasoline from Synthesis Gas

Date: April, 1981

Inventor: Friedrich Moller, et. al., Germany

Assignee: Metallgesellschaft AG, Frankfurt am Main

Abstract: A process for the catalytic production of gasoline hydrocarbons from synthesis gas comprising carbon oxides and hydrogen is disclosed wherein the synthesis gas is fed initially to a methanol synthesis and thereafter effluent from the methanol synthesis is converted to gasoline hydrocarbons in a gasoline synthesis stage. The invention resides in that the entire effluent from the methanol synthesis stage is fed to the gasoline synthesis stage and at least a portion of the residual gases from the gasoline synthesis stage comprising carbon oxides, hydrogen, methane and minor amounts of C2 -C4 hydrocarbons is fed to the methanol synthesis stage together with fresh synthesis gas.

(As we have previously documented from other sources, some products of synthesis gas conversion, even  Methanol itself, can be recycled back into, variously, both the syngas generation and syngas catalyzation processes themselves, to influence the types of hydrocarbon products ultimately produced. And, fresh syngas can be added to intermediate products prior to subsequent catalyzation for the same purpose.)

Claims: A process of producing gasoline hydrocarbons (C5+) from a synthesis gas containing mainly carbon oxides and hydrogen, comprising the steps of:

(a) feeding said synthesis gas into a methanol synthesis zone containing a methanol synthesis catalyst and producing a methanol containing product, said catalyst being indirectly cooled by boiling water under a pressure of 15 to 90 bars to maintain its temperature in the range of 200 to 300C, said water being supplied from a first reservoir to said methanol synthesis zone and recycled to said first reservoir.

(Note: The specified temperatures and pressures might seem quite high. But, our review of available literature indicates that current Coal-fired power plants now generate and utilize Steam at pressures in excess of 100, even up to 150, bars; and, at temperatures in the range of 350 to 500C. So, the operating parameters of  "United States Patent 4,263,141" are well within the limits of current industrial practice.)  

(b) withdrawing steam from said first reservoir,

(c) subjecting the entire methanol containing product of step (a) to a gasoline synthesis stage containing a gasoline synthesis catalyst and producing a gasoline containing product, said gasoline synthesis catalyst being indirectly cooled by a cooling liquid and maintained at a temperature of about 250 to 400C,

(d) recycling said cooling liquid through an external heat exchanger zone,

(e) withdrawing heat from said liquid in said heat exchanger zone by means of boiling water under pressure from and recycled to a second reservoir,

(f) feeding fresh water into the first reservoir and feeding part of the boiling water from said first reservoir by a pumping means into said second reservoir, withdrawing steam with a pressure of at least 100 bars from said second reservoir.

(g) cooling the gasoline containing product of step (c), from said product separating gasoline hydrocarbons and a residual gas comprising carbon oxides, hydrogen, methane and minor amounts of gaseous hydrocarbons of the C2 to C4 range, at least a portion of said residual gas being fed together with said synthesis gas into said methanol synthesis zone.

A process ... wherein the product from step (c) is heat exchanged with methanol synthesis product of step (a) whereby to heat the methanol and cool the product of step (c).

(Note, again: Un-reacted syngas and some products of the synthesis reactions can be recycled back into various stages of the process to good effect. Also, as in other of our reports, the catalytic reactions that condense syngas into Methanol, and which then transform Methanol into higher hydrocarbons, are most often exothernic. They generate heat which has to be controlled and withdrawn, and which can be recycled into other, endothermic, processes within the overall system in order to achieve greater efficiencies.)

A process ... wherein the methanol synthesis stage is prepared in the presence of a catalyst comprising 40 to 60 atomic percent of copper, 10 to 20 atomic percent of vanadium and 20 to 50 atomic percent of zinc and/or manganese.

(As in most of the Coal and Carbon conversion technologies we have documented for you, the catalysts needed are neither too exotic nor too expensive. They might not be dirt cheap, but we don't need diamond dust or crushed pearls to get this done. There is no economic argument against it.)

Background and Field: This invention relates to a catalytic process of producing gasoline hydrocarbons (C5+) from a synthesis gas which consists mainly of carbon oxides and hydrogen and which is subjected to methanol synthesis first and to gasoline synthesis thereafter.

Such processes are known (in specified prior art)

In such processes, methanol and water are condensed from the effluent gas from the methanol synthesis reactor and part of the remaining effluent gas is then recycled to the synthesis stage. That recycled gas contains carbon oxides, hydrogen and methane and in a mixture with fresh synthesis gas is fed to the methanol synthesis stage. Residual gases become available also in the gasoline synthesis stage, separately from the methanol synthesis stage, and contain gaseous hydrocarbons and must also be separated and re-used in the process.

It is an object of the invention to carry out the known processes in a simple manner at low cost.

The synthesis gas for use in the process according to the invention can be produced in known manner, provided that the synthesis gas contains at least 88% by volume of carbon oxides and hydrogen and that the volume ratio of H2 to (2 CO+3 CO2) is at least 1.

(Note that it is perfectly acceptable to have more Carbon Dioxide than Carbon Monoxide in the synthesis gas. We won't belabor here what should be the obvious implications of that fact, but rest assured that we'll beat them to death for you in future reports. Further, we don't have to have a surplus of free Hydrogen, which implies even additional economies.)

Such synthesis gas can be produced by a ... gasifying treatment of coal with oxygen and water vapor.

Suitable processes of gasifying coal have been described in United States Patents Number. 4,056,483 and Number 3,937,620 ..., which the disclosures are hereby incorporated by reference."

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And, even though we once intended to get the above-referenced US Patents to you via separate reports, as we did, though too casually, with our above United States Patent 4,263,141, our plans were thwarted by one of our communication breakdowns.

So, herewith, are links to and excerpts from some explanations, by other German scientists, of just how we might go about making for ourselves some of the so-useful blends of "carbon oxides and hydrogen" wherein "the volume ratio of H2 to (2 CO+3 CO2) is at least 1", as found in:

"United States Patent: 4056483 - Process for Producing Synthesis Gas

Date: November, 1977

Inventors: Gerhard Baron, et. al., Germany

Assignee: Metallgesellschaft AG, Frankfurt am Main, and Ruhrgas AG, Essen

Abstract: In the production of a synthesis gas comprising carbon monoxide and hydrogen, by a process comprising gasifying a solid fuel under a pressure of about 5-150 bars by a treatment with oxygen and water vapor ... , the improvement which comprises further reacting the water vapor-containing raw gas ... with oxygen in a succeeding reactor to produce an intermediate product gas ... , and freeing the intermediate product gas from sulfur compounds. A dust fuel and/or liquid hydrocarbon can be added to the raw gas as such or after prereaction with oxygen, the addition advantageously taking place in the succeeding reactor. The reactor may contain a granular bed of a catalyst such as nickel, cobalt or chromium oxide and/or sulfide, and/or a contact material or catalyst support such as an oxide, spinel or silicate of aluminum and/or magnesium. The bed can be fluidized or otherwise mechanically moved.

The resulting gas is suited for use as a starting material in a methanol ... or Fischer-Tropsch synthesis.

Claims: The production of a synthesis gas comprising carbon monoxide and hydrogen, by a process comprising gasifying coal ... under (specified conditions) with oxygen and water vapor ... .

(And, then) feeding said raw (product) gas without cooling same, into a second reaction zone and reacting it non-catalytically with oxygen under (specified conditions, and) cooling the intermediate product gas and freeing it from sulfur compounds.

The process ... wherein at least part of the heat of reaction required in the first reaction zone for producing the intermediate product gas is supplied by ... electric resistance heating.

(Note, we've earlier documented that "electric resistance heating" can be utilized to provide the heat needed to effect an initial Coal gasification, thus preventing the production of any unnecessary Carbon Dioxide through the partial oxidation of the Coal to generate the heat. And, as documented in:

Mountaineer Wind Energy Center - Wikipedia, the free encyclopedia; which reports that: "Mountaineer Wind Energy Center is a wind farm on Backbone Mountain in Preston and Tucker counties in the US state of West Virginia. When it came online in December 2002, Mountaineer was the first wind farm in West Virginia, and the largest east of the Mississippi River. Mountaineer Wind Energy Center is owned and operated by Florida Power & Light. Exelon Generation purchases the power produced by Mountaineer and markets it across the Mid-Atlantic region"; and, in:

Another Energy Bonanza for Coal Country | Research & Development; concerning: "West Virginia Geothermal; A Large Green Energy Source Beneath Northeastern West Virginia; Southern Methodist University, 2010; New research produced by Southern Methodist University ... suggests that the temperature of the Earth beneath the state of West Virginia is significantly higher than previously estimated and capable of supporting commercial baseload geothermal energy production"; and, in:

http://hydropower.inel.gov/resourceassessment/pdfs/states/wv.pdf; which contains the: "U.S. Hydropower Resource Assessment for West Virginia; 1998; Prepared for the U.S. Department of Energy"; wherein it is revealed that there are very nearly forty available but undeveloped sites in West Virginia where significant amounts of hydroelectric power could be generated;

we have some options for obtaining the CO2-free juice we might want to help us undertake the CO2-free generation of an "intermediate product gas" from Coal by using "electric resistance heating".)

The process ... wherein the gasifying agent for gasifying the solid fuel includes carbon dioxide in addition to the oxygen and water vapor.

(And) wherein the reaction in the succeeding reactor is carried out in the presence of oxygen gas and carbon dioxide.

(Note: As in many other documents attesting to the fact we have already brought to your attention: Carbon Dioxide, reclaimed from whatever source, can be used as one of the agents of Coal gasification in a process designed to generate, from Coal, a synthesis gas suitable for the manufacture of hydrocarbons.)

It is an object of the invention to enable a processing of the raw gas and its conversion to a synthesis gas in a simpler manner and at lower costs. This is accomplished in that the water vapor-containing raw gas is reacted under a pressure of about 5-150 bars with free oxygen-containing gases in a succeeding reactor to produce an intermediate product gas, which leaves the reactor at temperatures between about 800 and 1400C, and this intermediate product gas is cooled and freed from sulfur compounds. As the raw gas is converted to the intermediate product gas, the hydrocarbons contained in the raw gas as well as the distributing phenols, fatty acids, and ammonia are converted mainly to hydrogen and carbon oxides by gasification and cracking and for this reason need not be separated from the raw gas. The reaction to produce the intermediate product gas is suitably effected under the pressure which is also maintained in the reactor for the pressure gasification of coal.

Dust fuels, particularly coal dust ... may preferably be gasified by a treatment with oxygen before or in the reactor for producing the intermediate product gas, and the gasification products may be fed to the reaction for producing the intermediate product gas. Exhaust gases and undesired by-products of other processes can also be processed by such thermal gasification treatment with oxygen. CO2 may be used as one of the gasifying agents in the production of the intermediate product gas."

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We are compelled to end our excerpts from US Patent 4,056,853 right there so that we can again emphasize the fact that additional Carbon Dioxide, contained in the "Exhaust gases" from "other processes can also be processed" in reactions with hot Coal, Steam, and Oxygen, in order to produce the desired blend of Hydrogen and Carbon Monoxide "product gas".

And, since both of our above subjects, US Patents 4,263,141 and 4,056,853, refer to it, following is yet another example of how Coal can be efficiently transformed into the "synthesis gas", which the process of USP 4,263,141 can so efficiently transform into "methanol" and "gasoline":

"United States Patent: 3937620 - Process and Apparatus for Gasifying Coal

Date: February, 1976

Inventor: Paul Rudolph, et. al., Germany

Assignee: Metallgessellschaft, AG, Franfurt am Main

Abstract: Coal is gasified under elevated pressures and temperatures in a reactor having a rotatably mounted grate and supply conduits for oxygen-containing and oxygen-free gasifying agents. The rotary grate contains an internal chamber adjacent to the bearing for the grate and one of the supply conduits is adapted to feed an oxygen-free fluid to this internal chamber. The uppermost portion of the rotary grate contains a substantially closed internal chamber which has a supply conduit for feeding an oxygen-free fluid thereto. A mixing chamber is positioned between the uppermost chamber and the chamber adjacent the bearing for the grate and is provided with passages which lead to the charge to be gasified. The mixing chamber communicates with the uppermost chamber as well as the chamber adjacent the bearing and also has a supply conduit for feeding gasifying agents containing free oxygen thereto. The process disclosed involves maintaining those portions of the rotary grate having the least resistance to free oxygen in a steam atmosphere.

Claims: Reactor for continuously gasifying coal ... with, as gasifying agents, oxygen and at least one oxygen-free gasifying agent such as water vapor or carbon dioxide."

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Note that US Patent 3,937, 620 specifies "at least one" of "water vapor or carbon dioxide" can be used, as a "gasifying agent" in addition to "oxygen".

Both H2O and CO2 can be used together in the gasification of Coal, as in other of our reports documenting the same fact to be true, in order to adjust and control the proportions of Hydrogen and Carbon Monoxide contained in the product synthesis gas.

That syngas can, thus, be tailor-made, so to speak, for use in the catalytic synthesis of a variety of hydrocarbon liquids and gases.

Which hydrocarbon liquids, as in the process of  US Patent 4,263,141, include Methanol and Gasoline.


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