United States Patent Application: 0140128486

In point of fact, our headline notwithstanding, Saudi Arabia can now make both plastics and at least one gasoline blending component from Carbon Dioxide - - and, from Coal, by the way, as they themselves specify deep in the full Disclosure of the United States Patent Application we submit to you herein.

An advance excerpt from line item "106" of the Disclosure:

"coal, biomass or municipal solid waste is fed to the syngas generation unit. The syngas generated is contacted with a first catalyst composition (catalyst A) to obtain a first product stream";

 

is the only place where the Saudi invention which is the subject of this dispatch explains where the "Syngas", the catalytic treatment of which is the focus the technical exposition we bring to you herein, might come from. Their suggestion relates to a process like that disclosed, for only one example, in our report of:.

California Hydrogasifies Coal & Carbon-Recycling Wastes | Research & Development | News; concerning:

"United States Patent 7,500,997 - Steam Pyrolysis ... to Enhance the Hydro-Gasification of Carbonaceous Materials; 2009; Assignee: The Regents of the University of California; Abstract: A process and apparatus for producing a synthesis gas for use as a gaseous fuel or as feed into a Fischer-Tropsch reactor to produce a liquid fuel in a substantially self-sustaining process. In one embodiment, a slurry of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasification reactor to generate methane rich producer gases which are fed into a steam pyrolytic reformer to generate synthesis gas comprising hydrogen and carbon monoxide. A portion of the hydrogen is used as the internal hydrogen source. The remaining synthesis gas is either used as fuel to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor to produce liquid fuel. In another embodiment of the invention, carbonaceous material can be heated simultaneously in the presence of both hydrogen and steam to undergo steam pyrolysis and hydro-gasification in a single step. Claims: A process for converting carbonaceous material to energetic gases ... wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer".

However, the owner of this Syngas processing innovation is Saudi Basic Industries Corporation, aka "SABIC", of Riyadh, the largest company headquartered in that part of the world; and, as seen for one example in our report of:

Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development | News; concerning:

"United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; 2012; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics.Claims: A process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, consisting essentially of chromium as active substituent, optionally at least one alkali metal or alkaline earth metal as promoter, and alumina as support";

they have some other, perhaps more intriguing, options for obtaining such "Syngas".

In any case, we see herein that once SABIC has produced Syngas, from whatever source, they are able, in a comprehensive process, to convert that Syngas into a full range of hydrocarbon products.

And, note, we won't be reproducing many of the technical details. The complete exposition is extensive and detailed, and, it requires access to referenced illustrations for complete understanding.

Those illustrations are accessible via auxiliary links associated with this patent publication on the United States Patent and Trademark Office's web site.

We limit both our excerpts and our intent herein to focus, simply, on demonstrating that hydrocarbon synthesis gas, a blend of Carbon Monoxide and Hydrogen, as we might produce, as via the above references, from either Coal or Carbon Dioxide, can be, in one industrial process - -  that, as Saudi Arabia emphasizes, can be completely   "integrated" - -  converted into literally anything and everything - -  fuels and chemical raw materials - - we are now reliant on natural petroleum for our supply of.

As explained in excerpts from the initial link in this dispatch to:

"United States Patent Application 20140128486 - Process for Producing Ethylene and Propylene from Syngas

(First, don't be misled by the title. The technology to be disclosed herein goes well beyond "Ethylene and Propylene", as we will explain in closing excerpts and appended comments. The implications for the productive utilization, and permanent chemical consumption, via the companion process of the above-cited "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture", of Carbon Dioxide, are rather astonishing - - as are the implications for freedom from OPEC oil enslavement and an abundance of jobs for anyone who can lay their hands on a little Carbon Dioxide.) .

Patent US20140128486 - Process for Producing Ethylene and Propylene from Syngas - Google Patents

Process for Producing Ethylene and Propylene from Syngas - Karim, Khalid

Date: May 8, 2014

Inventors: Khalid Karim, et. al., Saudi Arabia

Assignee: Saudi Basic Industries Corporation, Riyadh

Abstract: The present invention relates to a process for producing ethylene and propylene from syngas, the process comprising the steps of:

a) contacting syngas with a first catalyst composition to obtain a first product stream comprising ethylene, propylene and aliphatic hydrocarbons having 4 or more carbon atoms,

b) splitting the first product stream into a second product stream comprising at least 90% of said aliphatic hydrocarbons having 4 or more carbon atoms and a third product stream comprising ethylene and propylene,

c) separating ethylene and propylene in the third product stream so as to form a first ethylene stream and a first propylene stream and:

d) converting the second product stream into a fourth product stream comprising ethylene and/or propylene.

Claims: A process for producing ethylene and propylene from syngas, the process comprising the steps of a) contacting syngas with a first catalyst composition to obtain a first product stream comprising ethylene, propylene and aliphatic hydrocarbons having 4 or more carbon atoms, b) splitting the first product stream into a second product stream comprising at least 90% of said aliphatic hydrocarbons having 4 or more carbon atoms and a third product stream comprising ethylene and propylene, c) separating ethylene and propylene in the third product stream so as to form a first ethylene stream and a first propylene stream and d) converting the second product stream into a fourth product stream comprising ethylene and/or propylene. 

(And) wherein the fourth product stream comprising ethylene and/or propylene is mixed with the first product stream.

The process ...  wherein the first product stream and the third product stream further comprise methane, ethane and propane and wherein step c) comprises the steps of: c1) removing methane from the third product stream to obtain a fifth product stream comprising ethane, ethylene, propane and propylene, c2) separating the fifth product stream into a sixth product stream comprising ethane and ethylene and a seventh product stream comprising propane and propylene, c3) removing ethane from the sixth product stream to form the first ethylene stream and c3') removing propane from the seventh product stream to form the first propylene stream.

(We presume your familiarity with "methane, ethane and propane", as produced herein from "Syngas", as can be derived from both Coal and Carbon Dioxide, and, with their utility and economic importance. Concerning the targeted products made from synthesis gas herein, "ethylene" and "propylene", see:

Ethylene - Wikipedia, the free encyclopedia; "Ethylene is widely used in chemical industry, and its worldwide production (over 109 million tonnes in 2006) exceeds that of any other organic compound"; and:

Propene - Wikipedia, the free encyclopedia; "Propene, also known as propylene.Propeneis the second most important starting product in the petrochemical industry after ethylene. It is the raw material for a wide variety of products. Manufacturers of the plastic polypropylene account for nearly two thirds of all demand. Polypropylene is, for example, needed for the production of films, packaging, caps and closures as well as for other applications".

They are immensely important polymer manufacturing raw materials with an almost vast worldwide demand. And, the CO2 consumed in the generation of synthesis gas used in the production, as herein, of the initial "ethylene" and "propylene" would remain forever, permanently, chemically and productively "sequestered" in the valuable end-product polymers.)  

The process ... wherein propane removed from the seventh product stream in step c3') is dehydrogenated into propylene and mixed with the seventh product stream.

The process ... wherein methane removed from the third product stream of step c1) is added to the syngas (and) wherein ethane removed from the six product stream in step c3) is added to the syngas.

(Concerning the immediately above, it seems likely that the by-product "methane", after it has been "removed" from the product stream, isn't just "added to the syngas", but, as in:

Saudia Arabia CO2 + Methane = Hydrocarbons + Syngas | Research & Development | News; concerning:

"United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas; 2008; Inventors: Agaddin Mamedov, et. al., Saudi Arabia; Assignee: Saudi Basic Industries Corporation; Abstract: Process for producing benzene, ethylene and synthesis gas, comprising the steps of: i) introducing a starting gas flow comprising methane and carbon dioxide into a reactor; ii) oxidizing the methane in the reactor at certain reactor conditions optionally using a first catalytic material and/or and additional oxidant; and: iii) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor;

is actually reacted with even more Carbon Dioxide to make even more "synthesis gas".)

The process according to (foregoing claims) wherein the first catalyst composition is unsupported and comprises cobalt; manganese; and at least one element selected from the group of lanthanum and phosphorus (in specified combination with one or more elements selected from) sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti) and zirconium (Zr).

The process according to any (of the foregoing claims) wherein said syngas has a hydrogen (H2) to carbon monoxide (CO) molar ratio of about 1-4.

The process according to any (of the foregoing claims) wherein the first product stream is produced by Fischer-Tropsch synthesis.

(Again, as explained most recently in our report of:

Bayer Improves Fischer-Tropsch Hydrocarbon Synthesis | Research & Development | News; concerning:

"United States Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis; 2013; Inventors: Ralph Schellen, et. al., Germany and Texas; Assignee: Bayer Intellectual Property GmbH, Germany; Abstract: The present invention relates to a multistage adiabatic process for performing the Fischer-Tropsch synthesis at low temperatures, in which the synthesis is performed in 5 to 40 series-connected reaction zones under adiabatic conditions. Claims: Process for preparing liquid hydrocarbons from the process gases carbon monoxide and hydrogen";

the "Fischer-Tropsch synthesis" was developed in Germany back in the 1920's, in order to make "liquid hydrocarbons", i.e., transportation fuels, from Coal, via an initial gasification that converted Coal into the syngas blend of Carbon Monoxide and Hydrogen. Such liquid hydrocarbon fuels remain the primary product of the "Fischer-Tropsch synthesis"; and, what is being disclosed herein by Saudi Basic Industries Corporation is a way in which, first, the initial products of a "Fischer-Tropsch synthesis" can be tailored, so to speak, through selection and application of certain catalysts and processing conditions, and, how the byproducts of a process that is producing, basically, liquid hydrocarbon fuels, the "first product",  from "Syngas", and which byproducts include Methane and other light hydrocarbons, can be further processed to generate additional products of value, such as the "Ethylene" and "Propylene".)

Background and Description: The present invention relates to a process for producing ethylene and propylene from syngas using a catalyst composition.

Gaseous mixtures comprising hydrogen (H2) and carbon monoxide (CO) can be converted into a hydrocarbon product stream by a catalystic process known as Fischer-Tropsch synthesis (F-T synthesis).

The most common catalysts useful in F-T synthesis ("F-T catalysts") are based on Fe and/or Co, although Ni- and Ru-based catalysts have also been described ... . Generally, Ni-based catalysts are relatively more selective for producing methane whereas Co-, Fe- and Ru-based catalysts are more selective for hydrocarbons having at least two carbon atoms (C2+ hydrocarbons). Moreover, the selectivity for C2+ hydrocarbons can be increased by decreasing the H2:CO ratio, decreasing the reaction temperature and decreasing the reactor pressure.

It has been previously described that unsupported cobalt-manganese oxide catalysts can be used as an F-T catalyst having an improved selectivity for C3 hydrocarbons and a suppressed CH4 (methane) selectivity ... .

It was the disadvantage of the prior art that F-T synthesis of hydrocarbon products always result in a mixture of desired products and less desired products.

It was an object of the present invention to provide an improved process for producing a higher yield of ethylene and propylene from syngas.

The solution to the above problem is achieved by providing the embodiments as described herein below and as characterized in the claims. Accordingly, the present invention provides a process for producing ethylene and propylene from syngas, the process comprising the steps of a) contacting syngas with a first catalyst composition to obtain a first product stream comprising ethylene, propylene and aliphatic hydrocarbons having 4 or more carbon atoms, b) splitting the first product stream into a second product stream comprising at least 90% of said aliphatic hydrocarbons having 4 or more carbon atoms and a third product stream comprising ethylene and propylene, c) separating ethylene and propylene in the third product stream so as to form a first ethylene stream and a first propylene stream, d) converting the second product stream into a fourth product stream comprising ethylene and/or propylene.

Integrated Process

In the process according to the present invention, the syngas is first contacted with a first catalyst composition to be converted to a first product stream, preferably by Fischer-Tropsch synthesis. The first product stream comprises ethylene, propylene and aliphatic hydrocarbons having 4 or more carbon atoms.

The first product stream may further comprise other components such as methane, ethane, propane, aromatic hydrocarbons and CO2.

(Keep in mind, again, that, as per our above citation of our report concerning: "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas; 2008; Inventors: Agaddin Mamedov, et. al., Saudi Arabia; Assignee: Saudi Basic Industries Corporation"; the lower-value products "methane ... and CO2" can subsequently be reacted together and made to form additional amounts of the "Syngas".)

Preferably, the aliphatic hydrocarbons having 4 or more carbon atoms essentially consist of aliphatic hydrocarbons having 4-10 carbon atoms, more preferably 4-8 carbon atoms, more preferably 4-6 carbon atoms. The term "essentially consist of" in this context may mean at least 95 wt %, at least 99 wt % or at least 99.5 wt %.

The aliphatic hydrocarbons having 4 or more carbon atoms may comprise e.g. butane, butene, pentane, pentene, hexane and hexene. The aliphatic hydrocarbons having 4 or more carbon atoms preferably comprise 1-butene and 1-hexene.

The first product stream is split into two product streams: a product stream of aliphatic hydrocarbons having 4 or more carbon atoms and a product stream of aliphatic hydrocarbons having 3 or less carbon atoms. This step may be done by a depropanizer, which is well-known to the skilled person.

The first product stream is split into a second product stream comprising at least 90 wt % of said aliphatic hydrocarbons having 4 or more carbon atoms and a third product stream comprising ethylene and propylene. The second product stream preferably comprises at least 95 wt %, more preferably at least 99 wt % or more preferably at least 99.5 wt % of said aliphatic hydrocarbons having 4 or more carbon atoms. The remainder of the second product stream is the component of the first product stream. Most preferably, the third product stream consists of the aliphatic hydrocarbons having 4 or more carbon atoms.

The third product stream comprises ethylene and propylene. In the cases where the third product stream comprises other components, said other components are preferably mostly other aliphatic hydrocarbons having 3 or less carbon atoms such as methane, ethane and propane. Preferably, the third product stream comprises at least 90 wt %, more preferably at least 95 wt %, more preferably at least 99 wt % or more preferably at least 99.5 wt % of aliphatic hydrocarbons having 3 or less carbon atoms.

Ethylene and propylene are separated from the third product stream so as to form a first ethylene stream and a first propylene stream.

Further, the second product stream is converted into a fourth product stream comprising ethylene and/or propylene. The fourth product stream may be split into a second ethylene stream and a second propylene stream. The first and second ethylene and/or the first and second propylene stream may be combined.

The process according to the present invention has an advantage that ethylene and propylene are obtained in two ways. Ethylene and propylene are directly obtained from the syngas by a conversion using the first catalyst composition. Furthermore, the aliphatic hydrocarbons having 4 or more carbon atoms from the first product stream is converted to ethylene and/or propylene. Hence, the process according to the present invention results in an overall high yield of ethylene and/or propylene.

Preferably, the fourth product stream comprising ethylene and/or propylene is mixed with the first product stream. This may be done by feeding said fourth product stream back to the unit for splitting the first product stream into the second and the third product streams, e.g. depropanizer. During the conversion of the second product stream, aromatics may also be produced, mainly benzene, toluene and xylene. Before the fourth product stream is mixed with the first product stream, these aromatics are preferably separated from the fourth product stream".

------------------------------- 

Again, this is a "SABIC" technology for processing "Syngas", as can be made via the process of SABIC's above-cited "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture", from Carbon Dioxide.

The purpose of our subject, "United States Patent Application 20140128486 - Process for Producing Ethylene and Propylene from Syngas", is to maximize the production of the polymers and plastics precursors, "Ethylene and Propylene", from the Syngas.

And, as noted earlier in our excerpts, other valuable hydrocarbons, like Methane, are co-produced in the course of the Syngas catalytic conversion.

But, the technology, and it's potentials, go far beyond that. Don't miss what is also co-produced in this multi-step process, as emphasized in our final excepted paragraph.

Along with the Ethylene and Propylene, which Sabic is trying to make more, specifically, of, we obtain, "during the conversion of the second product stream", the products "benzene, toluene and xylene", which is a trio of compounds you will in the literature see abbreviated as "BTX"; and, the significance of that is, literally, immense.

Sadly, we won't be able to document that fact for you with a link. We were working on this dispatch when we were struck with an electrical disaster that has ruined our ability to access the internet. We, in our isolated little outpost, aren't even certain we'll be able to transmit this dispatch as an email once it is complete. And, we simply don't have the resources to ourselves correct the problems, or to hire others to effect the necessary repairs.

However: Should you be one of what we now suspect to be the lonely few who actually care, we suggest you look up "BTX" in the nearly-omniscient Wikipedia. What you will discover is, that, while some portion of the BTX spectrum can be used for one component of Gasoline blending stock, the rest of it can be used, in various combinations, as the raw material stream from which other plastics and polymers, including, but not limited to, Polystyrene, Polycarbonate, Nylon, Polyurethane and Polyester, can be synthesized. And, those would be in addition to the "Ethylene and Propylene" which can also be produced directly, by the process of our subject, "United States Patent Application 20140128486 - Process for Producing Ethylene and Propylene from Syngas", from "Syngas", and, which "Syngas" can be produced directly by the companion Saudi Arabia Basic Industries Corporation technology: "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture".

We know that confrontational attitudes are growing in Coal Country with regards to the US EPA and their proposed "Carbon" regulations to be imposed on our economically vital Coal-fired power generation industries - with "Carbon" meaning Carbon Dioxide.

If the EPA must be confronted, then confront them with the facts: As herein, Carbon Dioxide is a valuable raw material resource which can be chemically and profitably consumed in the synthesis of an amazing array of plastics and polymers, the world-wide demand for which is collectively vast.

The Carbon Dioxide so utilized could put a comparably huge number of people to work, whereas Carbon Dioxide simply barred from being co-produced during the generation of affordable and abundant electric power from Coal would put a great number of people out of work; and, would cripple our national economy while doing so by denying other industries access to that affordable and abundant electric power. 

As we've documented in many prior reports, our United States Department of Energy and our United States Navy have developed processes comparable to the Saudi's "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture". And, there are many technologies available in the United States of America and around the world for processing such "Syngas" to produce hydrocarbons.

The SABIC process of our subject herein, "United States Patent Application 20140128486 - Process for Producing Ethylene and Propylene from Syngas", might be a particularly sophisticated example of such technology, but, it is not the only one. 

The primary difference, as we see things, between it and the others that are available is, that, the Saudi Arabians are already making preparations to put it into industrial, commercial practice, while the citizens of the United States of America haven't even been deemed worthy enough to be informed that such practical, profitable, and win-win, solutions to the Carbon Dioxide debate exist.

While we squander our time and our energy in rancorous confrontation, Saudi Arabia will simply be opening a new mint and printing more money - with ink and on bills made figuratively from Carbon Dioxide. And, again given that the USDOE and the US Navy have comparable technologies in hand, the fact that no one capable of doing so seems to have the will to sound the alarm for the US Coal Country public seems horribly sad.


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