WVU CTL Tech & Fuel From Garbage

 
"United States Patent 4618736"
 
For reasons that we'll explain, we refer to this US Patent for converting cellulose into liquid fuel, awarded more than 20 years ago to British inventors, as a "WVU CTL Tech(nology)".
 
We are compelled to excerpt extensive passages from this Patent, and we trust you will agree that some of the implications are significant, for a number of reasons, and the excessive verbiage thus worthwhile.
 
Our comments are interspersed parenthetically throughout, and appended.
 
As follows:
 
"A process for converting cellulose-containing refuse into a fuel comprising forming a suspension of said cellulosic material in a polycyclic hydrogen donor substance and hydrogenating the suspension at elevated temperature and pressure in the presence of a catalyst to produce a mixture of gaseous, liquid and solid hydrocarbons having a low oxygen content and correspondingly high calorific value."
 
(First of all, "cellulose-containing refuse" would include scrap wood, sawdust, some crop wastes, sewage plant sludge and, yes, Intel's and News-Registers, post-, or pre-, reading. And, the "polycyclic hydrogen donor substance" is revealed to be "Tetralin" - 1,2,3,4-tetrahydronaphthalene - which is at the heart of WVU's West Virginia Process for liquefying coal and converting it into liquid fuels. - JtM)
 
"Filing Date: 08/06/1985
Assignee: Salford University Industrial Centre Limited (Manchester, UK) 
Inventors: Benn, Frederick R. (Sale, GB2); Mcauliffe, Charles A. (Altrincham, GB2)
Application Number: 06/763049
Publication Date: 10/21/1986
Filing Date: 08/06/1985  

It is well known that cellulose can be hydrogenated at elevated temperature and pressure in the presence of a metal catalyst in an oil solvent to form a mixture of gaseous, liquid and solid products. It is also known that certain hydrogen donor substances such as tetralin can be used to extract soluble components from coal and to facilitate hydrogenation of the soluble components."

(Never mind that "It is well known that cellulose can be hydrogenated" into liquid hydrocarbons. DO note that, in 1985, it was "known that certain hydrogen donor substances such as tetralin can be used to extract soluble components from coal and to facilitate hydrogenation of the soluble components." Not so well known in the United States, apparently. - JtM)

"It has now been discovered that cellulose can be hydrogenated in the presence of a hydrogen donor substance such as tetralin even though cellulose is not soluble in tetralin, to yield a product having a low oxygen content and high calorific value."

(So, the coal liquefaction and hydrogenation solvent, tetralin, specified by WVU in their coal liquefaction technology, can hydrogenate cellulose and thus help to convert it into more valuable hydrocarbons with "high calorific value". - JtM)  

"According to the invention there is provided a process for the production of hydrocarbons from cellulosic material comprising the steps of forming a suspension of cellulosic material in a liquid polycyclic hydrogen donor substance, said liquid polycyclic hydrogen donor substance being a non-solvent for the cellulosic material, subjecting the suspension to increased pressure and elevated temperature to bring about hydrogenation of the cellulosic material and produce a mixture of gaseous, liquid and solid hydrocarbons having an oxygen content below 10% by weight, separating the mixture of hydrocarbon and recovering the liquid polycyclic hydrogen donor substance from the liquid phase."

(We have in other reports, via other citations, suggested that tetralin might have some potential to be recyclable, as in: "recovering the liquid polycyclic hydrogen donor substance from the liquid phase".- JtM)

"The preferred polycyclic hydrogen donor substance is tetralin. Other useful hydrogen donor substances include partially reduced polycyclic aromatic compounds such as dihydroanthracene and dihydrophenanthrene; and crude polycyclic aromatic fractions. Crude polycyclic aromatic fractions may, if desired, be treated before use to partially hydrogenate them but it is economically advantageous to omit such partial hydrogenation."

We won't herein quote references or include reference links, but: "partially reduced polycyclic aromatic compounds such as dihydroanthracene and dihydrophenanthrene; and crude polycyclic aromatic fractions" are all components of coal and coal tar, or can be readily produced from them. Those compounds, extracted from coal, accordingly, can be added to the liquefied and hydrogenated cellulose to increase productivity of the overall liquid fuel production system.

We have previously documented, from other sources, the fact that cellulose and coal can be converted synergistically together into liquid fuel raw materials, in a coordinated and partially-shared process stream that enhances and improves the efficiency of production. The importance of this additional documentation is that it further confirms the fact that coal liquefaction industry could not only supply our national liquid fuel needs through full utilization of our most abundant natural resource, but: Coal liquefaction could also lead us into a "cleaner" environment, and a more "renewable" liquid fuel supply, through the inclusion both of solid wastes, such as sewer sludge, that otherwise pose problems of disposal, and of botanically-derived cellulose, in it's various forms, that provides an inherent, integral route for the recycling of environmental Carbon Dioxide. 

Coal can do all of that.

Russia - Coal Ash Liquefies Coal

 
 
We had earlier informed you that Exxon-Mobil, in their "MTG" (r) process, were converting Methanol, manufactured from coal, into Gasoline through the mediation of their "ZSM" zeolite catalyst. They are commercializing that technology, as we've documented, in China and, perhaps, New Zealand.
 
We have also documented for you that zeolites can be found, and "mined", in abundance, from coal ash accumulations.
 
We submit the enclosed in further support of that knowledge. Please understand, as we have earlier explained, that "hydrotreatment", as used herein, is somewhat synonymous with "hydrogenation". Hydrogen is being added to high-carbon coal products to effect their transmutation into liquid hydrocarbons. West Virginia University, in their "West Virginia Process" for coal conversion, as we understand it, uses the Hydrogen-donor solvent, Tetralin, to liquefy and "hydrogenate" coal into such synthetic "petroleum".
 
There are, though, as we've tediously repeated, numerous ways in which to skin the coal conversion cat, and thus make the United States self-sufficient in liquid fuels. Herein, as excerpted below, is even more information on how yet another coal use waste can be employed to help make that happen:
 
"Catalytic properties of high-silica zeolites in hydrotreatment of coal liquefaction products 

Andrey A. Krichko, Anatoly S. Maloletnev, Olga A. Mazneva and Sergey G. Gagarin

Institute of Fossil Fuels, GSP-1, Leninsky Prospekt 29, Moscow 117 910, Russia 

Abstract

Catalytic activities of high-silica zeolites of ZSM type and also bi-zeolite catalysts HY-ZSM and LaY-ZSM in the hydrotreatment of a wide fraction of liquefaction products from brown coal (328–698 K boiling range) were determined. All the zeolites were modified by Mo and also Pd, Co and Ni loading. It was shown that ZSM use provides an opportunity to hydrogenate nitrogen compounds selectively in the presence of sulfur compounds. Removal of phenols does not restrict the general hydrotreatment process. A considerable increase in activity was found on changing from ZSM to the bi-zeolite systems HY-ZSM and LaY-ZSM."

And, we must affirm yet again that Carbon Dioxide, as well, can be "hydrotreated", hydrogenated, as we have thoroughly documented, into additional hydrocarbon, fuel, liquids.

"Focus on Practical US Energy Policy" - Intelligencer / News - Reg

 
""More attention should be given to a variety of technologies such as those involving carbon sequestration and enhanced recovery methods for oil and gas", Manchin pointed out."
 
 
If you've followed our posts/correspondence, you know, or should know, that "carbon sequestration and enhanced recovery methods for oil and gas" are a waste of a potentially-valuable coal-use byproduct. They would be undertaken at great expense to the people who mine and use coal, in unthinking and obeisant support of the withering, but increasingly greedy and parasitic, grotesque vampire our oil industry, with all it's major players, has become.
 
Why don't you publicly reveal the truth of the matter, as you must by now, from our posts, know it; and, thus, give Governor Manchin a stake made of coal to ram through the vampire's heart, instead of a public forum from which he can, in misguided innocence, promote it's insidious, self-centered, delusional and damaging agenda?
 
During the last election cycle, you published a fanciful product entitled, as we recall, "Obama No Friend Of Coal".
 
Again: Given what you must, from our published research, by now know - - about the very real potential of  established technologies that do exist to convert WV's abundant coal, and to recycle Carbon Dioxide, into the liquid transportation fuels our nation desperately needs - - and, given also your silence thus far on those issues, should you not now publish a cathartic mea culpa entitled "Myer No Friend Of Coal"?
 
Just wondering. But, you did get the title of our current subject right. It is way past time for us to "Focus on Practical US Energy Policy". It would be policy founded in coal conversion technology.
   
(PS. We are still researching the issue, but, aside from the fact that expensive and wasteful  "sequestration" of CO2 is of unproven, even wildly speculative, effectiveness and permanence, the concept seems to be much younger and newer than the far more practical, Nobel-winning, Sabatier technology for actually recycling CO2 into valuable hydrocarbon fuels.)
 

Coal Tech Related Info

 
 
Herein another piece of the coal conversion puzzle we discovered while clearing/consolidating our coal-to-liquid files.
 
If you'll recall, one route, as is being commercialized by Exxon-Mobil, to convert coal into gasoline involves first making methanol from coal, as is being accomplished, as we've documented, in various places around the world, including the US, and then converting the methanol, via zeolite catalysis, into gasoline.
 
Zeolites, as it happens, can be manufactured from coal ash.
 
Additional comment follows the excerpt:  
 
"A two-step process for the synthesis of zeolites from coal fly ash 

G. G. Hollman, G. Steenbruggen and M. Janssen-Jurkovic

Faculty of Earth Sciences, Department of Geochemistry, Utrecht University, PO Box 80021, 3508 TA Utrecht, The Netherlands 

Abstract

The conversion of fly ash into zeolites by incubation of the fly ash with alkaline solutions is a well known process which, however, usually results in a zeolitic product which still contains significant amounts of residual fly ash. Presented here is a method by which part of the silicon in fly ash can be used for the synthesis of a maximum of 85 g of pure zeolite per kg of fly ash prior to the residual being converted into zeolite by the traditional method. The cation exchange capacities ranged from 3.6 to 4.3 meq/g for the pure zeolites and from 2.0 to 2.5 meq/g for the zeolite containing residual fly ash. Tests showed that the pure zeolites are suitable for the removal of ammonium and heavy metal ions from waste water."

First, the article is just one example of the rather abundant literature available on the manufacture of zeolites from coal ash. It is, it seems, a well-known technology.

But, not only can fly ash provide the necessary zeolite catalyst to convert coal-derived methanol into gasoline via Exxon-Mobil's process, related zeolites from coal combustion residue can also help us clean up the Nitrogen ("ammonium") and heavy metals that might be produced in the waste streams of a coal conversion facility, or a coal-fired power plant using exhaust gas scrubbers.   

It's just another example, Mike, of the fact that coal science is much further advanced than is popularly known, or even, perhaps, professionally realized. Many of the inherent problems, as in pollution issues, have been solved, while many of the great potentials, as in liquid fuel conversion, remain largely undeveloped.

Non-Blog CO2 Recycling Via Cellulose with CoalTL

 
We might have sent you this reference in another format previously, but I couldn't find it in our files or on "Joe the Miner". We found it as we were clearing/consolidating our records, and Joe thought it to be of interest/importance and asked me to send it out. It is, he says, another demonstrated technology where coal combustion/liquefaction by-products, specifically CO2, can be reclaimed and recycled into more liquid fuels through biological/botanical agents.
 
More than that, he thinks the inventors are using, though they don't seem to name it, the same Hydrogen-donor solvent that WVU uses in the WV Process for coal liquefaction.
 


Title:  Liquefaction of cellulose
Patent ID:  US5336819
Issue Date:  August 09, 1994
Abstract:

The conversion of cellulose to hydrocarbon fuel, particularly fuel oil can be carried out using a polycyclic hydrogen donor substance. The present invention rests on the discovery that a light cut of the product oil can be used in place of the polycyclic hydrogen donor substance thus making it much easier to run the process continuously.

Inventor(s): 
McAuliffe;  Charles A.  (Manchester,  GB2) , Email and Contact Information
Benn;  Frederick R.  (Manchester,  GB2) Email and Contact Information
Assignee:  Man-Oil Limited;  (Manchester,  GB)
Agent: 
Salter & Michaelson
 
Claim(s):

We claim:

1. A process for converting cellulose to hydrocarbon product comprising subjecting the cellulose to a temperature of from 320.degree. to 380.degree. C. and a pressure of at least 40atmospheres in the presence of a nickel catalyst and a cellulose derived oil without the use of any additional reducing species to produce said hydrocarbon product; said cellulose derived oil being obtained from said hydrocarbon product.

2. A process as claimed in claim 1, characterised in that the hydrocarbon product oil is recycled for treatment with further cellulose in a continuous process.

3. A process for converting cellulose to hydrocarbon comprising subjecting the cellulose to a temperature of from 320.degree. to 380.degree. C. and a pressure of at least 40 atmospheres in the presence of a nickel catalyst and a cellulosederived oil without the use of any additional reducing species, said cellulose derived oil comprising a light fraction.

4. A process for converting cellulose to hydrocarbon comprising subjecting the cellulose to a temperature of from 320.degree. to 380.degree. C. and a pressure of between 40 atmospheres and 150 atmospheres in the presence of a nickel catalystand a cellulose derived oil without the use of any additional reducing species.

5. Hydrocarbon obtained from the process as claimed in claim 4.

6. A continuous process for converting cellulosic material to hydrocarbon fuel oil comprising subjecting the cellulosic material to a temperature of from 320.degree. to 380.degree. C. and a pressure of at least 40 atmospheres in the presenceof a nickel catalyst and a cellulose derived aromatic liquefaction solvent to produce a hydrocarbon product, separating aromatic hydro-carbon oil from the hydrocarbon product and recycling at least a portion of said separated aromatic oil for use thereofas said aromatic solvent, said portion of said aromatic oil being recycled with further cellulose.

7. A process for converting cellulosic material to hydrocarbon fuel oil comprising subjecting the cellulosic material to a temperature of from 320.degree. to 380.degree. C. and a pressure of at least 40 atmospheres in the presence of a nickelcatalyst and a cellulose derived aromatic liquefaction solvent to produce a hydrocarbon product, separating aromatic hydro-carbon oil from the hydrocarbon product and recycling at least a portion of said separated aromatic oil for use thereof as saidaromatic solvent, the recycled portion of said separated aromatic oil comprising a distillation fraction of said separated oil cut from 200.degree. C. to 300.degree. C. at atmospheric pressure.

8. A process for converting cellulosic material to hydrocarbon fuel oil comprising subjecting the cellulosic material to a temperature of from 320.degree. to 380.degree. C. and a pressure of between 40 atmospheres and 150 atmospheric in thepresence of a nickel catalyst and a cellulose derived aromatic liquefaction solvent to produce a hydrocarbon product, separating aromatic hydro-carbon oil from the hydrocarbon product and recycling at least a portion of said separated aromatic oil foruse thereof as said aromatic solvent.

9. The hydrocarbon oil product produced by the method of claim 8.



Description:

This is a continuation-in-part of application Ser. No. 07/382,654 filed as PCT/GB00058, Feb. 1, 1988 and publishedas WO 88/05807, Aug. 11, 1988, now abandoned.

This invention relates to the liquefaction of cellulose.

U.K. Patent Specification No.2089831 describes a process for liquefaction of cellulose which comprises hydrogenation of the cellulose in the presence of a polycyclic hydrogen donor substance such as tetralin at elevated temperature and increasedpressure. The product comprises a mixture of solid, liquid and gaseous hydrocarbons. The polycyclic hydrogen donor substance is recovered and used in the treatment of further cellulose.

It has now been discovered that the liquefaction of cellulose can be effected by replacing the polycyclic hydrogen donor substance with cellulose derived oil.

According to the invention there is provided a process for converting cellulose to hydrocarbon comprising subjecting the cellulose to elevated pressure and temperature in the presence of a liquefaction solvent characterised in that during atleast part of the process the liquefaction solvent is wholly a cellulose derived oil.

Further, the process of converting cellulose is carried out without the addition of water or the use of additional reducing species, such as a specific hydrogen donor solvent or a reducing gas. In this regard, it has even been found that inactual practice, the addition of a reducing gas can have a deleterious effect on the process by causing improper mixing and irregular flow through process vessels due to slugging and surging.

By the invention, therefore, the requirement for addition of a specific polycyclic hydrogen donor solvent is rendered unnecessary and hence the separation of polycyclic hydrogen donor solvent from the product is no longer required. In apreferred embodiment of the invention a part of the liquid aromatic hydrocarbon product oil from the process is used for the treatment of further cellulose. Thus the invention can very easily be operated continuously in which a predetermined quantity ofproduct oil is recycled for the treatment of fresh cellulose. It will be understood, however, that, even in a continuous process, the cellulose derived oil used in the invention does not have to be recycled from the product of the process actually beingoperated. The cellulose derived oil can, if desired, be taken from another suitable source. For example the oil can be obtained from another like process according to the present invention or a process as described in U.K. Patent SpecificationNo.2089831.

In order to reach a state of affairs where it is possible to carry out the process of the present invention, should cellulose derived oil not be available, it may be necessary to carry out the process as described in U.K. Patent SpecificationNo.2089831 and utilise a polycyclic hydrogen donor substance until sufficient product oil has been obtained. In this embodiment of the invention product oil together with polycyclic hydrogen donor substance can be used. The proportions of polycyclichydrogen donor substance to cellulose derived oil do not appear to be critical. Thus starting from a process using a polycyclic hydrogen donor substance the proportion of cellulose derived oil in the recycle for treatment of fresh cellulose can beprogressively increased with corresponding reduction of the proportion of polycyclic hydrogen donor substance until the recycle consists entirely of product oil.

It is preferred that the cellulose derived oil used in the invention should comprise a light fraction of the liquid oil product obtained from cellulose by distillation, in particular a cut from 200.degree. to 300.degree. at atmosphericpressure. Although this is preferred, it is not necessary that the cellulose derived oil should consist entirely of a fraction in this range. It is not even essential that the composition of the cellulose derived oil used as starting material shouldremain uniform during the process. For example when the process is operated using recycled product oil it may happen that the proportion of light oil in the recycled oil gradually falls. When the performance of the recycled oil reaches an unacceptablelevel, for example if the oil becomes too viscous to handle, the proportion of light oil in the recycled oil can be increased by any suitable means.

The cellulose material for use in the invention can be derived from any source. Examples include cellulosic material from municipal refuse and waste biomass such as straw and sugar cane.

The process of the invention is preferably carried out in the presence of a catalyst- The preferred catalysts are heterogeneous catalysts such as nickel.

As stated previously the process of the invention is carried out at elevated temperature and increased pressure. The preferred temperature range is from 320.degree. to 380.degree. C. particularly preferred 350.degree. C. and pressure would be40.53 to 151.99 Bar (40 to 150 atmospheres).

The following Examples further illustrates the invention.

EXAMPLE I

100 grams of cellulosic material from municipal refuse were charged to a pressure vessel together with 400 grams of cellulose derived oil and 2 grams of catalyst. Air was exhausted from the vessel which was then heated to 350.degree. C. over aperiod of three hours and that temperature maintained for a further two hours. A pressure of 151.99 Bar (150 atmospheres) developed in the vessel.

The vessel was then cooled. The reaction products were as follows:

______________________________________ Solids (char) 2 g Oil 433 g Gas (including steam) 65 g ______________________________________

For continuous operation, therefore, 400 g of oil can be taken from the oil product and recycled for treating a further 100 g of cellulosic material. If the 400 g recycle contains too high a proportion of heavy oils the product oil can bedistilled and 400 grams of a light cut recycled.

EXAMPLE II

100 grams of cellulosic material from sugar cane bagasse were charged to a pressure vessel together with 390 grams of cellulose derived oil and 2 grams of catalyst. Air was exhausted from the vessel which was then heated to 380.degree. C. overa period of three and a half hours and that temperature maintained for a further two hours. A pressure of 177.32 Bar (175 atmospheres) developed in the vessel.

The vessel was then cooled. The reaction products were as follows:

______________________________________ Solids (char) 7 g Oil 415 g Gas (including steam) 68 g ______________________________________

EXAMPLE III

90 grams of cellulosic material from straw were charged to a pressure vessel together with 390 grams of cellulose derived oil and 1 gram of catalyst. Air was exhausted from the vessel which was then heated to 375.degree. C. over a period ofthree hours and that temperature maintained for a further one hour. A pressure of 7.18 Bar (165 atmospheres) developed in the vessel.

The vessel was then cooled. The reaction products were as follows:

______________________________________ Solids (char) 7 g Oil 415 g Gas (including steam) 59 g ______________________________________

This Example also illustrates a process which can readily be run continuously by recycling 390 g of product oil for treating a further 100 g of straw derived cellulosic material.

* * * * *

US Patent:  5336819