United States Patent: 5952540

We've documented many times, as in, for just a couple of examples:

Korea CO2 to Methanol & Dimethyl Ether | Research & Development | News; concerning: "United States Patent 6,248.795 - Dimethyl Ether and Methanol from Carbon Dioxide; 2001; Inventor: Ki Won Jun and Kyu Wan Lee, Daejeon, KR; Assignee: Korea Research Institute of Chemical Technology; Abstract: This invention relates to the process of preparing from carbon dioxide a mixture of dimethyl ether and methanol which are useful as clean fuel or raw materials in the chemical industry. More particularly, this invention relates to the process of preparing dimethyl ether and methanol in high yield without by-products such as hydrocarbons by means of chemical conversion of carbon dioxide"; and:

 

Korea Improves CO2 Recycling | Research & Development | News; concerning: "Catalytic Hydrogenation of CO2 into Hydrocarbons; Support Effects on Fe and Fe-K Catalysts"; Ki-Won Jun, Soo-Jae Lee, Myuong-Jae Choi and Kyu-Wan Lee; Catalysis Division; Korea Research Institute of Chemical Technology;Taejon, Korea; Intoduction: Since accumulation of carbon dioxide in the atmosphere is now regarded as one of the major reasons of the Global Warming, interest in the re-utilization of carbon dioxide is on the increase. It is desirable for the reutilization of carbon dioxide to develop the technology for the hydrogenation of carbon dioxide to valuable materials such as light olefins or liquid hydrocarbons";

that Korea, that is, South Korea, has a well-established interest in the development of technologies for the practical, profitable consumption and utilization of Carbon Dioxide, in the synthesis of gaseous and liquid hydrocarbons, and, of fuel alcohols.

Such positive utilization of Carbon Dioxide - - which opponents, many of whose motives we must now hold suspect, of our economically essential use of Coal in the generation of abundant and affordable electric power use as their primary weapon in their war against Coal - - can, simply, be done.

Many of the Korean innovations for such use of Carbon Dioxide specify that it is to be transformed into fuel alcohols and hydrocarbons through direct reaction with elemental, molecular Hydrogen, with the  CO2 conversion technologies being distinguished by the different types of catalysts specified, and the  different ranges of products thus produced.

And, since we most recently documented, in our report of: 

Penn State Solar Energy Extracts Hydrogen from H2O | Research & Development | News; concerning: "United States Patent Application 20140251819 - Methods for Hydrogen Gas Production; September 11, 2014; Inventors: Bruce Logan, et. al., PA, IL and South Korea; Assignee: The Penn State Research Foundation, University Park, PA; Abstract: According to aspects described herein, methods and systems provided by the present invention for hydrogen gas production include a RED (reverse electrodialysis) stack including one or more RED subunits, and use of a saline material including a heat regenerable salt. The salinity driven energy, provided by the one or more RED subunits, completely eliminates the need for an external power source to produce hydrogen gas";

that we in the US, and in Korea, are getting better and better at using various chemical/physical processes and environmental energies to extract elemental Hydrogen from the abundant and ever-renewing water, H2O, molecule, we wanted to bring you herein further report of Korean developments in the productive consumption of Carbon Dioxide - - in processes which employ elemental Hydrogen, through various catalytic systems, to chemically "reduce" CO2 in reactions which produce valuable hydrocarbons.

We selected the two prior reports of Korean CO2 utilization developments for citation above since two of the principals named, Ki-Won Jun and Kyu-Wan Lee, are named, respectively, as the lead named inventors of the two CO2-to-hydrocarbon recycling technologies we present to you herein.

First, from fully a decade and half ago, we have the plainly and directly titled:

"United States Patent 5,952,540 - Process for Preparing Hydrocarbons

Process for preparing hydrocarbons - Korea Research Institute of Chemical Technology

Date: September 14, 1999

Inventors: Kyu Wan Lee (and) Ki Won Jun, et. al., Korea

Assignee: Korea Research Institute of Chemical Technology, Daejeon, KR

Abstract: This invention relates to a process for preparing hydrocarbons, in particular hydrogenation of carbon dioxide over Fe-K/Al2O3 (Iron-Potassium/Aluminum Oxide) catalyst, which is reduced in hydrogen and activated in the mixture of carbon dioxide and hydrogen.

(At this point in the Disclosure, prior applicable patented art is cited by the inventors. One of the two technologies identified as being precedent to this CO2-to-Hydrocarbon technical development is that seen in our report of:

Exxon Recycles CO2 to Gas and Liquids | Research & Development | News; concerning: "United States Patent 5,140,049 - Method for Producing Olefins from H2 and CO2; 1992; Inventor: Rocco Fiato, et. al.;  Assignee: Exxon Research and Engineering Company, NJ; Abstract: This invention relates to a process for producing C2 -C20 olefins from a feed stream consisting of H2 and CO2 using an iron-carbide based catalyst";

wherein it was explained how hydrocarbons of higher molecular weight than just substitute natural gas Methane, a common product of reactions between CO2 and Hydrogen, could be formed from CO2-H2 blends by, much as herein, specific catalyst compositions.)

Claims: A process for preparing hydrocarbons by hydrogenation of carbon dioxide over a catalyst, wherein said catalyst is Fe-K/.gamma.--Al2O3 ... and including ... about.50 weight % of Fe to total catalyst weight and wherein prior to said hydrogenation said catalyst is reduced under hydrogen gas and activated under a mixture of hydrogen and carbon dioxide. 

(By "reduced", they mean chemically reduced, that is, de-oxidized. They do that by first pumping just Hydrogen through it. The blend of Hydrogen and Carbon Dioxide follows.)

The process ... wherein said reduction is performed by flowing hydrogen on the (specified catalyst) at 300 (to about) 500 C (and at about) 10 atmosphere (pressure, and) wherein said activation is performed by flowing the mixture of hydrogen and carbon dioxide on (the catalyst) at 200 (to).about.400 C (and) 10 (to).about.40 atmosphere (pressure)... .

The process ... wherein said hydrogenation is preformed by flowing mixture gas (H2 /CO2 on a 1 to about 5 volume to volume ratio) into the reactor at 200 (to) about 500 C (and) 1.(to) about.100 atmosphere (pressure, in a blending gas mixture, and) wherein said mixture gas contains one or more selected from the group which is consisted of nitrogen, argon and helium. 

The process ... wherein said reactor is a fixed bed reactor, a fluidized bed reactor or slurry type reactor.

Background and Field: This invention relates to a process for preparing hydrocarbons, in particular, to a process for preparing hydrocarbons by hydrogenation of carbon dioxide over Fe-K/Al2O3 catalyst, which is reduced under hydrogen atmosphere after (being)activated in mixture of carbon dioxide and hydrogen. 

A possible contribution to reducing carbon dioxide accumulation would be the chemical transformation of carbon dioxide into valuable compounds or fuel using suitable catalysts. This would provide a means of recycling carbon dioxide exhausted from combustion of fuel (and) 
the effective conversion of carbon dioxide to hydrocarbons ... . 

Processes for preparing hydrocarbons by hydrogenation of carbon monoxide have been studied widely and applied in commercial quantity. Catalysts and technology used for the hydrogenation of carbon monoxide also can be applied to hydrogenation of carbon dioxide. But chemical properties of carbon monoxide and carbon dioxide are quite different from each other, so the yield of hydrocarbons, especially hydrocarbons having 2 or more carbon atoms (hereinafter called "C2+ hydrocarbons") is extremely low. 

It requires emergently new catalyst for preparing hydrocarbons in high yield without forming of by-product such as carbon monoxide. 

There are two general methods for preparing C2+ hydrocarbons using carbon dioxide. The first method is comprised of two- step reactions, that is, conversion of carbon dioxide to methanol and continuous conversion of the methanol to hydrocarbons. The second method is reacting carbon dioxide with hydrogen to obtain hydrocarbons directly. 

The inventors of this invention have investigated a new method for preparing hydrocarbons, especially C2+ hydrocarbons by hydrogenation of carbon dioxide.

In the process according to this invention, the conversion of carbon dioxide was raised much more than 50%, the yields of hydrocarbons and C2+ hydrocarbons are more than 50% and 45% respectively, and carbon monoxide generation is minimized.

Summary: The object of this invention is to provide a new process for preparing hydrocarbons which are valuable in chemical industry. 

The other object of this invention is to provide a new process for reducing the emission of carbon dioxide into the atmosphere. 

This invention relates to a process for preparing hydrocarbon by hydrogenation of carbon dioxide over catalyst, wherein said catalyst is pretreated Fe-K/Al2O3 with reduction and activation".

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The full Disclosure goes on at considerable length documenting the fact that converting Carbon Dioxide into substitute natural gas Methane and alcohols through reaction with elemental Hydrogen is so commonplace and so well understood as to be almost unremarkable, and, that the end product of a Hydrogen-CO2 reaction should preferentially be higher-molecular weight hydrocarbons.

In the process of this invention, those higher-weight, "C2+ hydrocarbons" comprise right around half of the product mixture.

In any case, Lee and Jun, and their colleagues, followed up very nearly a decade later with a complete description of an apparently improved CO2-to-Hydrocarbon catalyst, one obviously evolved from that identified in the above "United States Patent 5,952,540 - Process for Preparing Hydrocarbons". It is an even better catalyst for performing the CO2-to-Hydrocarbon synthesis which they do, as they state, intend for use in the process of "United States Patent 5,952,540".

As seen in:

"United States Patent: 7157404 - Catalyst for Preparing Hydocarbon

Catalyst for preparing hydrocarbon - Korea Research Institute of Chemical Technology

Date: January 2, 2007

Inventors: Ki-Won Jun, Jin-Soo Wang, Kyu Wan Lee, et. al., Korea

Assignee: Korea Research Institute of Chemical Technology, Daejeon

Abstract: The present invention relates to a catalyst for preparing hydrocarbons of carbon dioxide and more particularly, the Fe--Cu--K/gamma.--Al2O3 catalyst prepared by impregnation which enables producing hydrocarbons in high yield for more than 2000 hours due to its excellent activity and stability.

Background and Field: The present invention relates to a catalyst for preparing hydrocarbons by hydrogenation of carbon dioxide and more particularly, the Fe--Cu--K/.gamma.--Al2O catalyst prepared by impregnation which enables producing hydrocarbons in high yield for more than 2000 hours due to its excellent activity and stability. 

Carbon dioxide is one of the so-called greenhouse gases (and) recycling of carbon dioxide into useful hydrocarbons would help to alleviate the problem of our diminishing hydrocarbon resources. 

In order to convert carbon dioxide to useful hydrocarbons, the inventors have disclosed a process for preparing hydrocarbons (as via the catalyst and process disclosed in the above-reported "United States Patent 5,952,540 - Process for Preparing Hydrocarbons"). 

However, when Fe--K/.gamma.--Al2O3 catalyst has been used for more than 800 hours, the conversion rate of carbon dioxide to hydrocarbons is decreased by more than 10% and productivity of hydrocarbons is also decreased by more than 20%. On top of that, formation of undesirable carbon monoxide and methane gas are extremely increased by 70% and 30%, respectively.

(Note, again: It is relatively easy to synthesize substitute natural gas Methane, and industrially-valuable Carbon Monoxide, from Carbon Dioxide, but such otherwise intriguing products herein are "undesirable". The intent herein is to make more hydrocarbons of greater intrinsic value from Carbon Dioxide.)

Summary: In view of the above considerations, the inventors herein have intensively studied to solve deactivation of a catalyst for preparing hydrocarbons out of carbon dioxide by hydrogenation. As a result, the inventors realized that depositions of carbonaceous material such as coke on the surface of the catalyst is a major cause of deactivation of Fe--K/.gamma.--Al2O3 catalyst as disclosed in United States. Patent Number. 5,952,540 and thus, addition of Copper can provide excellent stability of the catalyst for more than 2000 hours to prepare hydrocarbons by suppressing depositions at carbonaceous on the surface of the catalyst. 

Therefore, the object of the present invention is to find a catalyst which not only gives satisfactory activity values but at the same time provides long-term resistance to deactivation by depositions of carbonaceous. Thus, the Fe--K--Cu/.gamma.--Al2O3 catalyst prepared by adding Copper ... provides that it decreases coke deposits thereon and exhibits sufficient activity, satisfactory yield of hydrocarbons even after using more than 2000 hours and good stability". 

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The initial process of "United States. Patent Number. 5,952,540", referring to our excerpts from it, was already making higher-weight hydrocarbons out of Carbon Dioxide at a rate, as it were, wherein the desired hydrocarbons comprised about 50% of the final product mix.

That's not bad for an industrial process to begin with, especially when the byproducts include the less desired, but still industrially useful, Carbon Monoxide and substitute natural gas Methane.

The catalyst composition later designed, and then disclosed in "United States Patent 7,157,404" improves the Carbon Dioxide conversion and hydrocarbon production rates to some unspecified degree, and, perhaps more importantly, greatly extends the service life of the catalyst, thus enabling much longer continuous production runs.

At this point near closing, we could cite some of our prior reports concerning similar hydrocarbon synthesis technologies which consume Carbon Dioxide as the basic raw material, and which have been developed elsewhere in the world, including in the United States of America by the United States Government itself. 

But, we'll spare you that tedium this time around to conclude with some thoughts that we've repeated as well so many times that they, too, are no doubt tedious. 

Clearly: Carbon Dioxide, as it is co-produced in only a small way - no matter what you've been told, no matter what you've been led to believe - relative to some all-natural and un-taxable sources of it's emission, such as the Earth's global and inexorable processes of planetary volcanism - from our use of Coal in the generation of reliable and affordable electric power, can be seen and treated as a valuable raw material resource.

As disclosed by a team of accomplished scientists in Korea, and as officially confirmed by technical experts in the employ of our United States Government, we can consume and utilize Carbon Dioxide, as recovered from whatever handy source, in an efficient process using what should be an inexpensive catalyst and capable of operating continuously for extended periods of time, into valuable hydrocarbons.

And, for everyone who presents themselves as being concerned about US energy independence, and/or about the health and viability of our economically-essential Coal-fired power generation industries, and/or about our environment, at least insofar as the issue of Carbon Dioxide emissions is concerned:

"A time comes when silence is betrayal". - Martin Luther King, Jr.


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