CA1056598A - Process for treating solid carbonaceous fossil fuels and the products thus prepared - Google Patents

Abstract

Abstract of the Disclosure Solid carbonaceous fossil fuels such as coal, lignite and peat are treated with an aqueous medium containing a novel catalyst to remove undesirable constituents and pro-duce valuable products. The catalyst is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully controlled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous colloidal suspension of the reaction product, admixing a micelle-forming surfactant with the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form catalyst-containing micelles.
In one variant, combustible sulfur and nitrogen compounds and alkali metal ash are removed, and the resulting treated fuel may be used in urban areas where strict air pollution regulations must be met. The coal, lignite and peat react with water and/or the components thereof when treated with an aqueous medium containing the catalyst, and/or are oxidized or otherwise chemically changed to produce valuable organic chemicals which are soluble in one or more solvents including the aqueous treating medium, water soluble and water insoluble organic extraction solvents, aqueous solutions of organic and inorganic acids and aqueous solutions of organic and inorganic bases. The treated insoluble particles of coal, lignite and peat remaining after extraction with one or more of the above solvents have ion exchange properties and are useful as an absorbent or adsorbent for liquid phase organic and inorganic compounds and for removing organic and inorganic acidic components from gaseous mixtures in a manner similar to activated carbon. In a further variant, particles of a fossil fuel containing metal values are treated with an aqueous medium in the presence of the catalyst, and thereafter the treated particles are separated from the aqueous medium and extracted with an aqueous leach solution in which the metal values are soluble. The solubilized metal values are recovered from the resulting leach liquor following prior art hydrometallurgical techniques. In still a further variant, the solid particles of the treated coal, lignite and peat, or components thereof.
are treated and solubilized in the aqueous catalyst suspension to produce a novel aqueous solution which has highly unusual and unexpected properties. The resultant solution has unique germicidal, medicinal and synergistic properties, and it also has important applications in agriculture and animal husbandry.

Description

105~59~3 ~

~he Background of the Invsntion The Field of the Invention This invention broadly relates to an improved process for treating solid ~ossilized carbonaceous~fuels with an aqueous medium in the ~resence of a novel catalyst. The invention further relates to the removal of com~ustible sul~ur and nitrogen compounds and other undesirable con-stituents from solid ~ossilized fuels, and the solubilization and recovery of metal and non-metal values therefrom. In one o~ its more specific variants, the invention is concerned with the preparation of solvent soluble organic compounds and ~n activated solid carbonaceous residue from solid fossil fuels. In another variant, the invention is concerned with the solubilization of solid carbonaceous ~ossil fuels or components thereof in an aqueous medium containing the aforementioned catalyst to thereby produce a novel a~ueous solution whi~h has highly unusual and unexpected properties.

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-The Prior Art .

Solid fossilized carbonaceous fuels such as coal, lignite and peat are products o~ the gradual aecomposition of vegetable matter without free access of air. Bituminous andanthracite coal, and to some extent lignite, are thought to have been formed in the pre~ence of moisture at elevated temperature and pressure. Most authorities believe that coal passes through successive stages of peat, lignite or brown coal, sub-bituminous and bituminous or soft coal, and anthracite or hard coal under conditions o increasing temperature and pressure. The carb~n content increases on a weight percent basis as the vegetable matter is transformed from peat into anthracite coal, and much of the carbon is combined with other elements such as hydrogen, sulfur, nitrogen and alkali metal, alkaline earth metal or heavy metal values.
Solid fossilized carbonaceous fuels and especially coal comprise high molecular weight ~hree-dimensional cyclic structures which contain predominantly six membered rings.
For example, it is known that coal contains bikumin and humin which have large, flat, aromatic lamellar structures that differ in molecular weight, degree o aromaticity, oxygen ; content, nitrogen content and the degree of cross-linking.
Volatile matter, fusain, mineral matter, moistura, pyritic sulfur, inorganic sulfates, and organic sulfur ana nitrogen compounds also are present. Fusain is a mineral charcoal which is consumed during burning in the presence o sufficient l~S~9~

oxygen for complete combustion and the mineral matter remains behind as ash. Fusain, mineral matter and inorganic sulfates do not contribute to atmosphexic pollution upon complete combustion of the coal. ~owever, the presence of combustiblé
~ulfur such as pyritic sulfur and organic sulfur compounds results in the formation of sulfur oxides which, upon reaction wikh atmospheric moisture, produce highly corrosive sulfurous acid and/or sulfuric acid. Combustible nitrogen compounds also present simi~ar problems. As a result, urban areas have strict air pollution regulations which require that the sulfur content vf solid fossilized carbonaceous fuels be reduced to about 0.5% by weight or less of combustible sulfur so as to control atmospheric pollution.
The prior art processes for reducing the combustible sulfur content of solid fossilized carbonaceous fuels are expensive and require elaborate equipment, costly chemicals or vigorous reaction conditions such as high temperatures and pressures. As a result of the inherent deficiences of the prior art desulfuriæation processes, the coal industry has long sought an efficient low-cost process for removing com-busti~le sulfur from coal~
Solid fossilized carbonaceous fuel also has been treated heretofore to produce organic chemicals, solid carbonaceous products such as coXe and activated carbon, and liquid hydrocarbon fuels. For example, coke is produced by ~L~f~
f~
heating coal at a~out 1,000-1,300F, in a retor~O The coke thus produced i5 a hard porous residium consisting largely of carbon admixed with mineral ash and other nonvolatile ~onstituents of the original coal. Volatile byproducts are produced such as coal gas, coal tar, coal tar ch~micals and ammonia. The low temperature carbonization of coal at temperatures of about 500-700F. produces products which differ substantially from those obtained at the higher carbonization temperatures.
~evertheless, both processes involve crac~ing of the large molecules of the coal to produce a solid residue consisting largely of carbon and mineral ash, and volatile constituents such as coal gas and normally liquid byproducts.
Liquid and yaseous fuels have ~een produced from coal by the Bergius Process. The early Bergius process usually consisted of mixin~ powdered coal with heavy tar from pre-vious runs and approximately 5% of iron oxide as a catalyst.
The pasty mass thus produced was heated with hydrogen at about 450-490F. for around two hours at a pressure of approxi-mate~y 3,000 pounds per square inch. There has ~een much

2~ research in this area in an effort to produce petroleum-like materials from coal. The more recent processes use different and more effecti~e catalysts and the reaction mixture is either in liquid or gaseous phase. In all of the processes, the coal is subjected to drastic processing conditions.
Activated car~on has been produced heretofore from coal using a combînation of high temperature and various chemicals ~(~5~S~
to convert the raw coal into an activated carbon residue. Some processes invo~ve subjecting finely divided raw coai to high pressures and temperatures and traatment in the presence of steam alone or in combination wi.tb chemicals. In ~he latter process, the pressure is often reduced very quickly causing the steam that has penetrated the coal particles to expand rapidly. This ruptures bonds within the coal particles and increases the available surface area and porosity.
~here are large d~posits of solid fossilized car-bonaceous materials in the United States which contain small percentages of valuable metal values or non-metal values.
~xamples of these deposits include uranium-bearing lignite and coal which are estimated to contain a substantial percentage of all knowm uranlum reserves discovered to date. Orien other valua~le metal values are present such as molybdenum, cobalt, zirconium; germanium and the }ike. Selenium and other - valuable non-metal values also are present in some deposits~
Entixely satisfactory prior art processes were not available heretofore for solubilizing and recovering these metal values and/or non-~etal values. For example, one prior art practice involves burning heavy metal-bearing lignite and recovering the ash which contains the metal values, and then processing the ash into a commercial form of the metal values for sale such as uranium oxide, vanadium oxide, mvlybdenum oxide, and the like. In accordance with another prior art practice, the fossil fuel is heated ln a closed system in th~e presence of hydrogen and under drastic reaction conditions includi~g high temperature and pressure, with or without a catalyst, to produce a liquid petroleum-like material and a solid residue which contains the metal values. The residue is separated r~m the liquid and gaseous products, and is further processed ~i in accordance with prior art practices to reco~er the metal values in the form of a marketable commercial product.
~~11 of ~he processes discussed above which havé been lp used heretofore for converting solid fossilized car~onaceous fuels into more valuable products involve the use of elaborate ~equipment, numerous processing steps, large quantities of processing chemicals which are not readily recycled, and ; drastic reaction conaitions. As a result, the processes available heretofore have been costly to pra~tice and in some instances uneconomical.
It has also been proposed to use solid carbonaceous fossil fuels as fertilizer, and the presence of fungistatic and bacteriostatic ingredients has been suggested. However, entirely satisfactory processes were not available heretofore to produce acceptable commercial products on a reproducible basis.
The Summary of the Invention.
The present invention overcomes the a~orementioned and still other disadvantages of the prior art aDd provides a ~ s~s~
novel process for upgrading solid fossiliæed carbonaceous uels and producing ~aluable products therefrom. The treat-ing conditions are comparatively mild, and it i5 not necessa~y to use unusually high temperatures, pressures, expensive processing chemicals, elaborate apparatus, or other costly items.
Thus, the present invention provides a process for treating solid fossil fuels~ with an aqueous medium comprising intimately contacting solid fossil uel in particu-late form selected from the group consisting of coal, lignite, peat and admixtures thereof with an aquaous medium containing a catalytically effective amount of a catalyst, the solid fossil fuel having active sites therein which react with at least one component o~ the aqueous medium under liguid phase conditions in the presence o the catalyst, the particles o~ the solid fossil uel being inti-mately contacted with the a~ueous medium under liquid phase conditions until active sites thereof react with at least one component of the aqueous medium, the catalyst being prepared by a process comprising admixing a water soluble alkali metal silica~e with an aqueous medium containing a di~solved substance which is a source of calcium ion and a dissolved substance which is a source of magnesium lon, the aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-4 and 1 x 10 1 mole per lit~r each of calcium ion and magnesium ion, the aqueous medium containing said dissolved sub-stances in amounts to provide a molar ratio of calcium ion to r~ - 9`_ I

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magnesium ion between about 2.0:1.0 and ~.0:2.0;
the alkali mekal silicate having an alkali metal oxide to silicon dioxide ratio between about 0~9:1.0 and le~s than 2.0:1.0 and being admixed with the aqueous medium in an amount of about 0.05-2 moles per liter, reacting the alkali metal silicate with said dis-solved su~s~ances providi~g calcium~ion ~and ~l~agnësium ion ko produce an aqueous suspension of finely diviaed particles of the reaction product, admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said finely divided particles upon agitating the aqueous medium, and agitating the aqueous medium containing the finely divided particles and surfactant to form said catalyst micelles.

The Detailed Description of the ; Invention Including the Presently Preferred Variants and Embodiments Thereof In practicing the present invention, a solid carbona-ceous fossil fuel~in particulate form is intimately contac~ed~
with an aqueous medium containing a catalytically effective amount of a novel catalyst to be described more fully hereinafter. The solid fossil fuel is preerably coal, lignite, peat or admixtures thereof, and it has active sites which are capable of reacting with at least one component of the aqueous medium in the pre-sence of the catalyst. The partiales of the fossil uel are contacted with the aqueous medium under liquid phase conditions until substantially all or a desired proportion of the active sites react with the aqueous medium. Thereafter the ;~ .. . ..

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particles of fossil fuel may be further treated as ~ill be -described more fully hereinafter. It will be appreciated ~ that there are cer~ain variants of the invention which produce preferred results and these variants will likewise be discussed more fully hereinafter.
The fossil fuel need not be pretreated prior to~
treating with the aqueous medium other than, when desired, ~rushing or otherwise reducing it to a suitable particle ..
size. The particle size is not critical and may vary over 10. -wide ranges as the aqueous medium has remarkable penetration properties and is capable of penetrating large lumps. The particle size may be, for example, from 1 inch to -300 ~ mesh (~yler screen) and preferably is about -10 mesh to -200 ; mesh, and for many applications is from -50 mesh to -100 mesh.
It is understood that particles as iarge as 2, 3 or 4 inches, . and often mine run ossil fuel, may be treated but longerperiods of contact with the aqueous medium may be necessary to allow sufficient time for adequate penetration and reaction. Also, particle sizes smaller than -300 mesh may be treated but the expense of grinding the coal to such a fine particle size usually.outweighs any advantages that are.gained.
The particles of fossil fuèl are intimately contacted with the aqueous medium under liquid phase conditions and in the presence of a sufficient volume of ~3S~9~ .

the aqueous medium to assure that the particles are conveniently and easily contacted therewith. The voltume ratio of the aqueous medium to the particles of fossil fu~l may vary - ; over wide ranges. It is usually preferred that the aqueous meditun be present in sufficient volume to allow the particles to be easily ~gitated therein such as ~y means of a prior art stirring or agitating device.
The concentration of the catalyst in the aqueous medium also may vary over a wide range as it is only necessa~y that a catalytic amount be present. Suitable catalyst ~oncentrations are dis~ussed more fully hereinater. For oxample, the concentrated catalyst solution as produced by Example I may be diluted with approximately 30-~000 ~olumes of water and for better results in s~me instances with a~out 100-200 volumes of water to theraby arrive at a satisfactor~ aqueous treating medium~
rhe pH value of the aqueous trea~iny medium also may vary over wide ran~es such as from about 1 to 13.5~
The initial pH value is preferably greater than 7, and is usually a~out 8~ There is a tendency ~or the pH
value to decrease as the reaction proceeds. If desired, the pH value o~ the aqueous medium may be adjusted as the reaction proceeds by addition of a base such as alkali m tal hydroxide to thereby partially or fully restore the initial pH valtle, but this is not essentialO

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The temperature of treatment may likewise vary over wide ranges and may be, for example, between the freezing point and the boiling point of the aqueous medium under the existing pressure conditions. Usually atmospheric pressure is preferred, and in such instances, the aqueous medium may have a temperature of approximately 0C. to 100C. and is often about 20-60C. Surprisinglyf lower temperatures of treatment such as 0-10 C. appear to enhance the rate and degree of oxidation and thus lower temperatures may be preferred in instances where a maximum am~unt of oxidation is desired. Higher temperatures than 100C. may be emp-oyed under superatmospheric pressure.
For example, pro~ided that the pressure is sufficient under the existing temperature to maintain liquid phase conditions, the temperature may be 100-200C.
or higher. ~evertheless, such extreme reaction conditions are not necessary and are usually avoided.
Ine~pensive reaction vessels or open vats, with or without agitatoræ ancl other simple auxiliary equipment, ~0 are satisfactory and may be used with good results. The period of treatment may be varied over wide ranges. It is only necessary that the aqueous medium be intimately contacted with the fossil fuel particles for a period of time sufficient for the reaction to vccur and continued treatment is not deleterious. The minim~um period of treatment will vary t~ some extent with the remaining conditions, such as the particle size of the fossil fuel, the concentration of the catalyst, the pH value of the aqueous medium and the reaction temperatureO The period S of treatment may vary, for examp~e, from approximately 5 minutes or less to 24 hours or more but it ~s usually from a~out 15 minutes to 2 hours. As a general rule, the ~-amount of oxidation increases with time provided all of the remaining conditions of treatmenk remain the same.
Solid carbonaceous fossil fuels such as coal, lignite and peat ha~e active car~on atoms or active sites.
Examples of the acti~e sites include carbon-to-carbon double or triple bonds, carbon~to-oxygen bonds, carbon-to-sulfur bonds, car~on-to-nitrogen bonds, carbon-to-metal bonds, carbon attached to an electronegative group, and carbon bonded or otherwise attached or attracted to a dissimilar substrate which is a component of the fossil fuel. The catalyst o~ the present invention causes the liquid water in the a~ueous treating medium to exhibit very unusual and heretofore unrecognized properties in the presence of fossil fuels having the aforementioned active carbon atoms or active sites. While the exact nature of the reaction is not known at the present time, it appears that water or some component o water reacts with or alters the a~tive car~on atoms or active sites to there~y produce pronounced chemical and~or physical changes~ For example~ the fossil fuel may be 1~5~
oxidized to produce useful organic oxidation products such as carboxylic acids and hydroxycarboxylicacids. It is also possible to fix nitrogen in the form of organic compounds by treating the fossil fuel in the presence of an atmosphere containing elemental nitrogen. Additionally, combustible sulfur, nitrogen, and other deleterious substances are altered to permit their removal by prior art techniques such as by extraction in the aqueous treating medium or with solvents subsequent to the treatmentO
Additionally, metal values present in the fossil fuel are solubiIized or rendered soluble upon extraction with solvents thereby allowing the metal values to be concentrated and recoveredO The treated particles also have a much higher water content than béfore treatment~ The aqueous treating medium following treatment contains the water soluble constituents of the treated fossil fuel particles.
The treated particles also undergo physical changes as well as chemical changes. For example, certain chemical or physical bonds existing wi*hin the particles are broken upon treatment with the aqueous medium. The resultant treated fossil fuel may be crushed, ground or otherwlse reduced to a more finely divided form with little effort.
It is also possible to easily separate and remove non-carbonaceous material such as mineral matter from the particles and thereby further reduce the concentration of undesirable sulfur and nitrogen compounds and ash-forming constituentsO In instances where the fossil fuel is a - 15 ~

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car~onaceous ore containing valuable metal values, the , treatment in the aqueous medium solubilizes or otherwise renders the metal values more susceptible to solvent ~xtraction and concentration by prior art hydrometallurgical te~hniques. ,' When the aqueous medium containing the novel catalyst is contacted with the fossil fuel, there is a pexiod of activation during which there is little or no reaction. ~his activation period may ~e eliminatea or Ieduced markedly by pre-treating the fresh catalyst suspension with a small portion of the fossil fuel, or b~ using a recycled catalyst solution from a pre~ious ; treatment. In a,preferred variant, all or part of the aqueous catalyst suspension is recycled so that an activated catalyst is always available for contacting with fresh portions of the fossil fuel. The activatea aqueous catalyst suspension thus produced is much more effecti~e and has properties which differ substantially from those of the initially prepared catalystO
The agueous treating medium containing the water soluble constituents of tha treated ~ossil fuel is separated from the particles~ When desired, all or a portion of the separated treating medium may be recycled and used to treat additional fossil fuel as aforementïoned. The resultant treated particles are changed in appearance and acquire S~

the physical appearance and properties of weathered ~oxidized) fossil fuels such as Leonardite. The separated particles may be washed with water and then ~tracted with various solvents to recover organic compounds and other desired constituents therefrom. The soluble constituents in the aqueous medium may be recovered therefrom by precipitation, such as by precipitation with a mineral acid, or other techniques may be employed such as by evaporating the water and precipitating the desired constituents from the conentrated liquor.
The treated particles contain large amounts of water and the ex~ess water and organic compounds may be - - - remo~ed therefrom simultaneously by extracting with a water soluble organic solvent. Examples of suitable ~ater soluble organic sol~ents include the water soluble alcohols and especially those containing about 1-4 carbon atoms, the water soluble ketones and especially those containing about 1-4 carbon atoms, water soluble polyhydroxy compounds such as the glycols, and other similar water soluble organic solventsO
The treated fossil uel is intimately contacted with tha water soluble organic solvent under liquid phase conditionsO
The temperature of extraction may vary between the freezing -point and the boiling point of the solvent, but is preferably about room temperature or at a moderately elevated tPmperature.

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This extraction usually removes most o the absorbed water and organic compounds. In instances where the extracted fossil fuel contains organic compounds which are not - soluble in the organic solvent, then they may be extracted with a water insoluble organic solvent such as normally liquid hydrocarbons and especially those containing about S 12 carbon atoms, normally liquid halogenated hydrocarbons and especially those containing about 4 8 carbon atoms, and normally liquid ~ractions deri~ed from petroleum such as petroleum ether, gasoline~ Xerosene, gas oil, and diesel fuel. This second ~xtraction with the water insoluble -organic solvent is likewise carried out under liquia phase conditions ~nd at temperatures between the freezing point and boiling point of the sol~ent under the existing pressure, and prefera~ly at approximately room temperature or at a moderately elevated temperature.
Th2 resultant extracted solid fossil fuel residue is substantially free of organic compounds produced ~y the treatment but contains inorganic compounds which may ~e removed by extraction. The extracted residue i5 separated from the organic solvent and the inorganic compounds may be recovered therefrom by extraction with water soluble ~ases and/or acidsO The extracted organic compounds may be separated from the aforementioned water insolu~le organic solvents by distillation or fractio~ation. It is usually 9~ , desira~le to acidify the organic solvent-water solution before distillation. It is possible to separate the extracted or~anic compounds from the water so1uble organic solvent by agitating with a water insoluble solvent as aforementioned~ When this is done, some of th~ extracted organic compounds dissolva in the water insoluble organic solvent and form one layer. Another layer of extracted organic compounds separates as a semi-- ~olid layer, and the water content of the extraction mixture separates as a third layer. The water layer may be drawn off and discarded, and the upper two layers may be separated individua~ly or as a mixture from which the watar insolu~le solvent is separated by distillation or fractiona~ion~ Tha resultant organic compounds or coal 15 ~ chemicals are valuable raw materials for ths production of prior art organic compounds.
The organic solvent extracted residue may be further extracted with an aqueous acidic solution of an organic and/or inorganic acid. Examples of water soluble acids incluae hydroch10ric acid, nitric acid, sul~uric acid, phosphoric acid and water soluble organic acids such as formic acid, acetic acid, propionic acid, and trichloroacetic acid. Extraction with the aqueous acid results in the removal of compounds containing metal vzlues and other inorganic constituents~ ~n instances where the - -- lg -- .

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treated fossil fuel contains metal ~alues or non-metal ~alue_ such as uranium, cobalt, vanadiumf molybdenum, zirconium~
germanium or selenium, then surprisingly the desired values may be solubilized and recovered by prior art hydrometallurgical techniquesO The treatment of the fossil uel with tha catalyst suspension alters the metal and non-metal values and renders them amenable to solu~ilization aDd extraction in the acidic leach æolution whereas prior to the treatment, the matal values ~an not be easily solubilized and extractea.
The organic solvent extracted residue also may be ~urther extracted with an aqueous base. Examples of water s~luble bases which may be used include sodium hydroxide, ~, potassium hydroxide and ammonium hydroxide. The aqueous solution o the base may be intimately contacted with the fossil fue~ residueand any amphoteric metal values and sol~le non-metal values may be removed, or other soluble inorganic constituents. -The extraction step with the aqueous base may either precede or follow the extraction step with the acidic solution depending upon the substances to be removed.
As was true of the acid extraction step, valuable metal or non-metal va~ues may be recovered from the leach solution following prior art hydrometallurgical techniques.
The resultant extracted fossil fuel residue now has th desirable properties of activated charcoal or activated car~on. For exa~ple, the extracted residue may be used to 5~

absorb acidic gases such aY hydrogen chloride, hydrogen fluoride~ hydrogen bromide, hydrogen sulfide, sulfur ~ioxideO
-sulfur trioxide, carbon dioxide and halogens including chlorine, fluorine, and bromine~ The acidic gases may be absorbed by passing a gaseous stream containing the substance to be a~sorbed ~hrough a contained body of the extracted fossil fue~ residue following a technique analogous to that emp~oyed with activated ~arbon or activated charcoal. When the fossil fuel residue ~as reached its absorption capacity, it may be regenerated and thexea~ter reused by intimately contacting it with an aqueous solution of a base such as aqueous sodium hydroxide, potassium ~ydroxide, or ammonium hydroxide. This is a convenient method of preparing salts of the acidic substance and especially hypohalite salts.
The extracted fossil fuel residue is also capable of absorbing large quantities of normally liquid hydrocarbons.
Thus, the extracted particles may be used to absorb petroleum or liquid fractions derived therefrom and thereby control oil spills. The extracted particles are lighter than water, and in instances where the oil is present in the form of an oil slick floating on the water, the floating axtracted ; particles are in intimate contact therewith and absorb the oil. The resultant solid residue and the absor~ed oil content may be easily separated from the water by skimming, filtration 2S or other suita~le separation process.

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In a further variant of the invention~ the fossil fuel is treated with an oxidizing agent before, during or f~llowing treatment wi~h the aqueous medium contain-ing the catalyst to thereby aid in solubilizing additional organic c~mpounds. The oxidizing agent may be air, elemental oxygen, ozone, peroxides such as hydrogen peroxide or the alkali metal peroxides, or other suitable oxidizing agents.
The ~ossil fuel is reacted wikh the oxidizing agent in an amount to partially oxidize or artificially weather it without co~bustion. For example, air or elemental oxygen may be bubbled through the aqueous medium while in contact with the fossil fuel, or the fossil fuel may be intimately contacted with air or elemental oxygen at ele~ated tempexature prior to treatment with the aqueous medium. Also, the extracted fossil ~uel particles rom which the organic and/or inorganic constituents have been removed may be partially cxidized by intimately contacting the same with an oxidant to produce additional oxygenated organic compounds. The oxygenated organic compounds thus produced may be recovered by the afore-mentioned extraction steps.
In a urther variant of the invention, the extractedfossil fuel is subjected to destructive distillation to produce organic compounds. The resultant organic compounds are not the same as are produced when destructively distilling the original fossil fuel. T~us, the treatment of the fossil fuel alters ~-o~s~

the chemical composition and allows novel destructi~e distilla- ' ;
tion products to be produced. ~ ' The treated fossil fuel is also useful in the -preparation of a synthetic fertilizer. The fertilizer may be prepared by'adding to the treated fossil fuel a phosphate-containing compound such as phosphoric acid or the alkaline earth metal salts thereof, a nitrogen containing compound such as ammonia, ammonium salts or nitrates, and a potassium-ff~ffontaining compound such as potassium chloride. This is prefera~ly done while the treated,fossil fuel is wétted with the aqueous treating medium. The resultant fertilizer has trace elements and humus contained in the fossil ~uel in addition to the added phosphorous, nitrQgen and potash and it - is remar~ably effective. Lignite, and especially weathered lignite such as ~eonardite, is especially useful in preparing - fertilizers.
The extracted fossil fuel is substantially free of deleterious pollutants such as combustible sulfur and nitrogen compounds and it may be used as a premium fuel.
Very little of the heat ~alue is lost and it may be burned in coal-burningurnaces in a manner analogous to coal. The treated fossil fuel may be pelletized if desired prior to burning.
The combustion gases are substantially free of sulfur dioxide or trioxida and thus the fuel meets stxict standards in this respect. In instances where the treated fossil fuel is _ 23 - -~os~

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used for ~iring boil~rs, the tube life is increased very mar~edly -due to the absence of coxrosive contaminating substances which tend to shorten tube life.
The oxidation o the fossil fuel and the formation of acidic organic compounds may ~e enhanced by treating with -~
~he aqueous catalyst ~uspension at temperatures approaching - tha freezing point, such as about 0-10C~ and preferably about 0-4C. The degree of oxidation is also controlled to some extent by the materials used in constructing the reaction ~essel and the materials of construction of auxiliary apparatus in contact therewith such as agitators. Surprisingly, con~tructi~g the equipment rom nonconductors of electricity such as polyolefins results in a maximum degree of oxidation under a given set of operating conditions. Constructing the e~uipment from good conductors of electricity such as steel and other metals results in a minim~um de~ree of oxidation or a given set o treating conditions, whereas constructing the equipment rom glass or ceramic materials results in an inter-m~diate degree o oxidation. The reason for this unusual phenomenon is not fully understood at the present time but it is obvious that the three products difer mar~edly. Thus, the process o the present invention is capable of controlling the level of oxidation under a gi~en set of reaction conditions.
It is not a~ways necessary nor desirable to separate _ 24 ~

the catalyst ~uspension from the treated fossil fuel. For example, in some instances it is advantageous to evaporate the water content of the a~ueous suspension, either ~t atmospheric pressure or preferably under reduced pressure, to thereby deposit the catalyst micelles on the treated fossil fuel parti-cles. When this is done, addition o~ water thereto reactivates the catalyst micelles and the particles are subjected to a further treatment with the a~ueous catalyst suspension. This variant is especially advantageous in instances where it is desired to prepare the solution of the treated fossil fuels to be described hereinafter.
In a further variant of the invention, the solid particles of the treated fossil ~uel, or components thereof, are further treated and solubilized in tha aqueous catalyst suspension to produce a novel agueous solution which has highly unusual and unexpected properties. The term 'rsolution" as used herein when referring to this product is intended to embrace finely divided suspended substances which are not in true solution. The resulting solution has, for example, uni~ue germicidal, medicinal, and synergistic properties, and it also has important applications in agriculture and animal husbandryO Additionally, the resultant s~lution may be used in practicing the applicant's invention disclosed and claime*
in copending Canadian applications Serial No. 238,234, 238,235, -238,237 and 238,245, all of which were filed on Octo~er 24, 1975 by the present applicant, and in Canadian Patent ~o.
1,039,610, which issued on Octo~er 3, 1978 to the present appli-cantO

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It is understood that the fossil fuel solutions described hereinafter, which contain the catalyst suspension as an ingredient, may be substituted ~or the aqueous catalyst sus-pension per se which is used in the aforementioned Canadian Patent and pending Canadian applications. It is only necessary to substitute a like amount of the solution of this in~ention for the aquaous catalyst suspension of the prior inventions hased upon the weight of the catalyst present in each instance.
~he fossil fuel solutions described hereinater may be prepared from coal, lignite or peatO However, the solutions prepared from lîgnite produce superior results and thus are presently preferred. Accordingly, the discussion appearing hereinafter may be directed specifically to the use of lignite but it is understood that the invention is not necessarily limited theretoO
The lignite is first treated with the a~ueous cata-lyst suspension following the aforementioned genaral procedure to produce a catalyst treated lignite productO It is usually preferred that the aqueous catalyst suspension be evaporated, preferably under vacuum, to thereby deposit the catalyst micelles on the lignite particles and produce a dry treated lignite product for subsequent useO In such instances, ~3S~9~

it is oDly necessary to add water to reacti~ate the catalyst micelles and thereby further treat the lignite particles. In i~stances where the catalyst suspension was removed from the treated particles, then it is necessary to further treat the lignite particles with additional catalyst suspension ! It is also usually preferred to use a concentrated catalyst suspension, such as that produced in Example I prior to dilution.
The catalyst suspension used in the further treatment either contains su~ficient alkali metal base to form water soluble salts of the organic acids that are produced, or additional alkali metal hydroxide may be added for this purpose. Ammonium hydroxide also may be used. Additionally, in instances where the lignite initially treated has not been oxidized or - weathered, it is usually preferred to add an oxidizing agent at some stage of the treating process. This may be duriny the first treatment of the lignite, or it may be during a sub-sequent treat~ent with the aqueous catalyst suspension. Also, ~he treated lig~ite particles may be extracted with organic solvents and/or aqueous solutions o~ acids or bases prior to solubilization. Regaraless, of the specific procedure which is followed, the lignite particles are treated with the aqueous catalyst suspension in the presence of sufficient base such as alkali metal hydroxide and/or ammonium hydroxide to result in ~he formation of humin salts or other organic acid salts~
The concentrations o the catalyst suspension and the _ 27 -s~

dissolved solids in the solution may vary over ex~remely wide ranges. In a number o~ instances, the concentrations thereof are determined to some extent ~y the end use of the solution.
Some uses require very dilute solutions~ whereas other uses require much more concentrated solutions. Also, it is often advantageous to market a concentrated solu~ion which is . diluted by the customer at the time of use to save packaging and shipping costs. As a general rule, the concentration of catalyst solids in the solution is within the ranges aforementioned for the aqueous treating medium. The concentration of dissolved lignite in the solution may be from about 0.1 part per million to about 10% by weight, or higher. Solutions containing at least ~00 parts per million of dissolved lignite, and pre-~erably about 600-700 parts per million or more exhibit pronounced bactèriostati~ and/or fungistatic properties~
Solutions ~or general use in agriculture a~d anima~ husbandry need contain only about 0.5-lO0 parts per million o dissolved ligniter althou~h more concentrated solutions may be pro~ided initially for dilution. As a general rule, the solutions usuall~
~0 contain 1% or less of dissolved lignite.
l~le solutions o the sQlid carbonaceous fossil ~uel are useful in a num~ex of diverse fields. This is thought to be due in part to the prssence of trace elments and organic compounds used by the growing vegetation which was the precursor of the coal, lignite and peat. The treatment of the fossil fuel with the aqueous catalyst alters the structure thereof and liberates and makes availa~le ~he trace elements and other substances contained therein. The ~olution contains substances which have properties characteristic of hacteriocides and fungici~es and which are capable of protecti~g seeds, plants during their growth, and animals con~uming the plants. Other use~ul su~stancas also are present such as ~io-regulators which control the rate of growth and especially ; growth ac~elerators, and su~stances which enhance the resistance of the plants to ad~erse con~itions of growth or stress such as freezing, drought, physical damage to foilage and transplanting.
~he solutions of the fossil f~lel have the followiny uses in agriculture:
1. Soil treated with a dilute aqueous solution of the solu~iliged fossil fuel is markedly more fertile than untreated soil and the increase in ; fertility cannot be attri~uted to the plant ~ood contenk of the solution. It appears that formerly I unavailable nutrients in the treated soil become available for use by growing plants ollowing treatment with the solution. This increases the effective concentration o~ availa~le nutrients in the soil and thereby increases the fertility and promotes the ~rowth o~ plants.
2. Adaition of the solution to the soil appears to cause the soil to a~tract and hold moiskure. Laboratory tests prove ~hat temperatures as high as 350F. are necessary to remove all of the water from the treated soil. The water is retained at temperatures far in excess ~f the ~oiling pointO
3. The solubilized lignite is largely in the f~rm of salts of humic acid and other carboxylic acids. Treatment of soil with the solution thus adds humus and the other aforementioned desirable substances.

4. Seeds sprayed with the lignite solution when in the seed bed sprout ~aster and have a higher germination rate than untreated seeds. The seedlings also have a very rapid growth rate and may be transplanted earlier.

5. Cuttings placed in a dilute solution of lignite form sufficiant roots for transplanting much more rapidly than the same cuttings placed in untreated water.
~ 6. Plants treated with the lignite ~olution withstand drought better than untreated plants.
7O Plants treated with the lignite solution grow much larg~r than untreated plants, and the ~uality of the produce is as good or better than that from u~treated plants or seeds.
8. ~lants such as potatoes sprayed with the lignite solution re~over faster after a hard -.
_ 30 ~

~05~5~

freeze than do untreated plants. Crops such as potatoes may be planted much earlier in the Spring and in some instances even in the Fall.
The lignite solution is also useful in the storage of crops. Lignite solutions sprayed on corn in non~airtight storage having a moisture content of 25%
eliminate mold and rot. The traated corn also has a sweet silage-like odor and samples show the protein content ~ increased from 9% to 12~/o due to the growth thereon of a protein-; 10 yie~ding yeast. There was also some evidence of an increase i~ sugar content. Cubes formed from new mown hay and treated wi~h the lignite solution did not spoil when exposed to the alements whereas untreated cubes did spoil. Grain and forage ~ appears to be more palatable and digestible when sprayed with the lignite solution than when untreated. Tests with a fungi inperfecti grown on liyno-cellulose treated with the lignite solution showed that protein is produced at low cost which is suitable for use as animal feed.
~he catalyst treated fossil fuels, and especial-y catalyst treated lignite, are useful as animal feed supp~ements.
The fossil fuel solutions also may be similarly used. It is only necessary to add the treated fossil fuel or solution to the standard feed mixture in an amount of, for example, -approximate~y 1-10% and preferably approximately 5%. Animals eating the feed grow faster and with less disease than animals 1051j59~
fed untreated feed.
The lignite solution has medicinal and synergistic properties which render it useful in animal husbandry appli-cations. For example, it may be synergistically combined with antibiotics in the treatment o~ foot-rot in sheep and cattle and pink eye or cancer eye in catt~e. It is also useful in relieving stress and infection in weaning calves and pigs, in the treatment of burns, cuts, bruises, and sprains, in the treatment of ketosis in sheep.

~he prepaxation of the novel catalyst used in practicing the present invention is described hereinafter.

.

_ 32 -105~S~
PREPARATION OF THE CATALYST

The catalyst used inpracticing the present invention may be prepared as described below. In the presently preferred process for preparing an aqueous suspension of the catalyst, a water soluble alkali metal silicate is admixed and reacted with an aqueous solution of a wa~er soluble dissolved substance which is a source of calcium ion and a water soluble dissolved substance which is a source of magnesium ion to produce a finely divided or colloidal suspension of the reaction product. The aqueous solution contains the dissolved substances initially in amounts to provide between about I x l0 4 and l x 10~l mole per liter each of calcium ion and magnesi~m ion, preferably between about l x 10-3 and l x 10-2 mole per liter, ànd for lS still better results betweèn l x l0 3 and 6 x 10-3 mole per liter. The dissolved substances should also be present in amounts to prov1de a molar ratio of calcium ion to magnesium ion between about 2.0:l.0 and l.0:2.0, and preferabLy about l.5:l.0 and 1.0:l.5. For-best ~0 results, the aqueous medium should contain the dissolved substances in amounts to provide between about 2.5 x l0 and 3.0 x l0 mole per liter each of calcium ion and magnesium ion, and the molar ratio of calcium ion to magnesium ion should be about l.0:l.0, e. g., 2.9 x -3 _3 l0 mole per liter o-f calcium ion and 2.7 x l0 mole pex liter of magnesium ion. The alkali metal silicate should have an alkali metal oxide to silicon dioxide ratio be~ween about 0.9:l.0 and less than ~S~55~
2.0:1.0, and pr~fera~ly between about 0.9:1.0 and 1.2:
1Ø The alkali metal silicate should be admi~ed with the aqueous medium in an amount of about 0.05 2 moles per liter, preferably about 0.1-1 mole per liter, and for still better results about 0.2-0.5 mole per liter. For best results, the alkali metal silicate should be an alka~i metal meta-silicate having an alkali metal oxide to silicon dioxide ratio of about 1:1, and it -should be admixed with the aqueous medium in an amount to provide about 0.2-0.3 mole per liter, e.g., about 0.25 mole per liter.
Examples of sources of calcium ion and magnesium ion for use in preparing the aqueous solution include mineral acid salts such as the halides, sulfates, bisulfates, nitrites, and nitrates of calcium and magnesium. ~he chlorldes are usually the preferred halides, and both calcium and magnesium chloride are soluble and may be used. Magnesium sulfate and bisulfate are soluble and o~ten are the preferred sources of magnesium ion. Calcium sulfate is only slightly soluble in water and usually is not a preferred source of calcium ion, but calcium bisulfate is somewhat more soluble. While calcium and magnesium nitrite or nitrate are soluble in water and may be used, these substances are not preferred in most instances. The sources o~ calcium ion and magnesium ion are dissolved in the aqueous medium in amounts to provide calcium ion and magnesium ion within the above ranges. Complete ionization is assumed when calculating the quantities s5'~
to be dissolved and any desired order of addition is satisfactory. For example, the source of calcium ion may be added to the aqueous medium before, during or after the source o magnesium ion.
S The alkali metal silicate to be admixed with the aqueous medium is preferably a water soluble sodium or potassium silicate having an alkali metal oxide (M20) to silicon dioxide (SiO2) mole ratio between - about 0.9:1.0 and less than 2.0:1.0, and preferably between about 0.9:1.0 and 1.2:1~0. The best results are usually obtained with an alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1:1. Elydrated alkali metal silicates dissolve faster and should be used for best results when the alkali metal silicate is added in solid form. In instances where an anhydrous al~ali metal silicate is used, it may be desirable to dissolve it in water and then add the solution to the aqueous medium. Sodium metasilicate is preferred and usually a hydrated sodium metasilicate such as the pentahydrate gives the best results.
Carbonate ion and/or bicarbonate ion should not be present in the aqueous medium in substantial concentrations as the ~alcium ion and magnesium ion are pr~cipitated in the form of their respective carbonates.

The free carbonate ion and/or bicarbonate ion concentra-tions in the aqueous medium should not exceed about 10 ~s~s~ r parts per million by weight based upon the combined weight of the water and the ingredients added thereto and for this reason, the alkali metal silicates should be substantially free of carbonate ion and bicarbonate S ion. A small amount of preciptated calclum carbonate and/or magnesium carbonate may be present in the aqueous medium provided additional calcium ion and magnesium ion are available to meet the above defined - concentration~.
Distilled water and/or deionized water are usually preferred over a natural or untreated water when --preparing the aqueous medium. In in~tances where water is used which contains su~stantial lnitial concentrations of alkaline earth metal ions, then this should be taken into consideration in calculating the amounts of the sources of calcium ion and magnesium ion which are necessary to arrive at the final concentrations previously discussed.
An electrolyte which aids in the preparation of colloidal suspensions may be present in the aqueous medium at the time of admixing the alkali metal silicate therewith. Examples of electrolytes include those used in preparing prior art colloidal suspensions such as the alkali metal halides,sulfates and bisulfates.
25- Sodium chloride, sodium sulfate and sodium bisulfate are usually preferred. The electrolyte should be added in small amounts such as, for example, about 0.00001 0.1 mole per liter, hut often larger or smaller amounts may be present.
The conditions under which the alkali metal silicate is admixed with the aqueous medium and reacted - with the sources of calcium ion and magnesium ion are not critical provided the reaction mixture is maintained in the liquid phase. The reaction temperature may be, ~or example, between the freezing point and boiling point of water under the existing pressure conditions. At atmospheric pressure, the temperatur~ is usually about 10-90C and often a more convenient temperature is about 20-50C. In many instances, ambient or normal room temperature is satisfactory.
The degree o~ agitation is not critical, and mild to vigorous agitation may be employed during addition of the alka~i metal silicate. For the best results, the aqueous medium should be agitated sufficiently to assure rapid and uniform admixing of the alkali metal silicate.
After completing the addition of the alkali metal silicate, when desired the agitation may be continued for a sufficient period of time to assure complete reaction and aging of the resulting colloidal suspension, such as for approximately 1-5 minutes to one hour or longer.
Upon admixing the alkali metal silicate with the aqueous medium, it takes on a turbid appearance but in most instances no significant amount of visible precipitate is f~rmed. The colloidal suspension of the reaction product thus produced should be strongly basic and may have a pH value of, for example, approximately ~s~

.

10-14 and preferably about 11-13, a~d for best results about 12. In view of this, the initial p~ value of the aqueous medium containing the dissolved sources of calcium ion and magn~sium ion is of importance and should be about 6-9 and preferably about 7-8. When necessary, it is possible to adjust the pH value of the aqueous medium to the foregoing levels either before during or after addition of the alkali metal silicate by adding bases such as sodium or potassium hydroxidel or mineral acids such as sulfuric or hydrochloric acid.
The colloidal suspension may be stored for several weeks or longer while awaiting the further treatment described hereinafter. In instances where the colloidal suspension is to be stored over a substantial period of time, the p~l value should be maintained at the above described level and the storage vessel is preferably a tightly capped polyethylene bottle or other inert plastic container which prevents the contents from absorbing carbon dioxide from the atmosphere.
~he colloidal suspension of the reaction product is not suitable for use as a catalyst as prepared and it should be agitated sufficiently in the presence o~ a micelle-forming surfactant to form catalyst-containing - micelles~ ~he degree of agitation, the length of 2~ the agitation period, and the amount of the micelle-forming surfactant that is present in the colloidal 5~i9~3 suspension are controlled at levels fa~orable to the formation of micelles. For example, the surfactant may .
be present in an amount of about OoOOl~O~l mo~e per liter and preferably about 0.03-0.07 mole per liter for most surfactants. Smaller or larger amounts may be effective with some surfactants such as 0.0001 mole per liter or less, or 0.2 mole per liter or more. About 0.05 mole per litèr often gives the best results with many surfactants.
The minimum period of agitation and the minimum degree of agitation that are required for micelle formation varies somewhat with temperature and the type and amount of surfactant. As is well understood in this ; art, gradually increasing these Yariants in the presence of an effective amount of the~micelle-forming surfactant will result in micelle formation when the proper levels are reached. As a general rule, longer periods of agitation and~or more vigorqus ayitation are required to form micelles at lower temperatures approaching the freezing point of the colloidal suspension than at higher temperatures approaching the ~oiling point. In instances where the aqueous suspension has a temperature of approximately 50-90C., then mild agitation over a period of about 10-60 minutes is satisfactory. Often longer or shorter periods of mild to vigorous agitation may be employed such as from about 1-5 minutes to several hours _ 3~ ~

at temperatures ~arying, respectively, between the ~oiling point and the fre~zing point. When desired, the agitation may be continued long after the catalyst-containing micelles are formed as continued agitation does not seem to have an adverse effect.
As a general rule, the micelle-forming surEactants known in the prior art may be used in practicing the presenk in~ention~ Micelle-forming surfactants used in the emulsion polymerization of monomeric organic compounds are dis~losed .
in the text Synthetic Ru~ber, by G. S. Whitby, et al, John Wiley & Sons, Incorporated, ~ew York (1954), and surface active agents in general are disclosed on pages 418-424 o~ the text Organic ChemistrY~ Fieser and Fieser, 2nd Edition, Reinhold Publishing Corporation, ~ew York~ ~ew York ~1950). Examples of surfactants disc~osed in the above texts include the alkali metal soaps of long chain fatty acids, and especially the sodium and potassium soaps of fatty acids containing about 14-2~ car~on atoms and preferably about 16-l8 carbon atoms, and the sodium and potassium soaps of the rosin acids, abietic acid and the derivatives thereof. Other micelle-forming surfactants include fats and oils such as corn oil, cotton seed oil, castor oil, soy bean oil and safflower oil which have been fully or parti-ally saponified with alkali metal bases ko _ 40 -,1 ~o~

produca mixtures including saponified long chain fatty acids, the mono- or di-glycerides thereof, and glycerin.
Examples of synthetic micelle-forming surfactants include the sulfonates of long chain alcohols prepared by hydrogenation of naturally ocurring fats and oils of the abo~e types and especially sulfonated long chain alcohols containing about 10 20 and preferably about 12-14 carbon atoms, the alkali metal salts of the monosulfonates of monoglycerides such as sodium glyceryl monolaurate sulfonate~
the sulfonates of succinic acid esters such as dioctyl sodium sulfosuccinate and the alkylaryl alkali metal sulfonates. Spècific examples of presently preferred micelle-forming surfactants include sodium and potassi~m sulforicinoleatel tetrahydronaphthalene sul~onate, 1~ octahydroanthrace~e sulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate, alkyl benzene su~fonic acid and potassium benzene sulfonate.
Sulfated long chain hydroxycarboxy]ic acids containing about 14-25 carbon atoms and preferably about 16-18 carbon atoms, and sulfated fats and oils containing hydroxycarboxylic acids of this type produce exceptionally good micelle-forming surfactants. At least 25~ of the hydroxyl groups and preferably at least 50~ should be sulfated, and up to 95-100~ may be sulfated. It is usually preferred that the sulfated oils and/or long chain hydroxycarboxylic acids be neutralized with an alkali metal .

_ 41 -1~.3~ B ~ ' ' base, and that the corresponding alkali metal salts be added to the colloidal suspension in tne ~orm of ~n aqueous solution. The aqueous solution may contain at least 25~
of water and preferably at least 35-40% by weight. Much larger percentages of water may be present when desired such a~ 75-80% or more by weight.
A very active catalyst is produced when using sulfated castox oil as the micelle-forming surfactant ~Turkey Red oil ). Sulfated castor oil which has been purified sufficiently to De of U.S.P. or medicinal ~rade produces an exceptionally active catalyst. For the best results, the castor oil is reacted with about an equal weight of concentrated sulfuric acid(e.g., 20~ by weight) at a temperature of approximately 25-30C. The mixture may be reacted for about two hours with stirring and is then neutralized with sodium h~droxide solution. The reaction mixture separates into three layers, i.e., an upper layer which is a water solution, an intermediate or oily layer, and a white curdy precipitate. q'he intermediate oily layer is separated fxom the upper and lower layers, and may be added to the colloidal suspension as the micelle-forming surfactant in an amount, for example, o~ 0. nol-o.
mole per liter, and pre~erably about 0.005 molQ per liter.
The activity of the catalyst may be increased very markedly by cooling the aqueous catalyst suspension to a temperature approaching the freezil-tg point such as 1~5~98 about 0-10 ~., and then warming over one or more cycles.
For best resul~s, the aqueous catalyst suspension should be ~rozen and thawed over one or more cycles. The reason for the increased catalytic activity is not fully understood at the p~esent time but cooling and then warming the aqueous catalyst suspension seems to increase the concentration of the catalyst-containing micelles and/or increases the catalytic activity thereof.
The aqueous suspension of the catalyst contains a relatively small percentage by weight of the active catalyst as produced. When desired, it may be concentrated hy e~aporating a portion of the water to produce a concentrated liquid catalyst suspension which may be - ~ stored and used more conveniently. It is also possible to prepare a dry catalyst concentrate by evaporating substantially all of the water. The preferred method of proc~ucing the dry catalyst concentrate is by flash evapoXation using a technique analogous to that employed in preparing powderéd milk. The catalyst concentrates produced upon partial or complete evaporation of the water content of the intially prepared aqueous suspension may be reconstituted by addition of water with little or no loss of catalytic activity. Preferably, the water is added to the dry catalyst concentrate under suficiently vigorous conditions of agitation to assure that the _ 43 -~:)5 ' catalyst micelles are resuspended and uniformly distributed.
The aqueous catalyst suspension may be used as produced for treating the coa~ lignite and peat, or it may be diluted wi~h approximately 2-10,000 parts by weight of water. For better results, the catalyst suspension as produced may be diluted with about 250-2,000 parts by weight of water, and preferably with about 500-1,000 parts by weight of water, and then used. It is only necessary that the coa~ lignite and peat be treated with a liquid phase 1, aqueous medium containing a catalytic amount of the catalyst.
The aqueous medium may contain, for example, about 0.0001-0.3%
by weight of the catalyst, but larger ox smaller amounts may be present when desirea~; Usua~ly the-a~usous mediu~ c~ntalns a~out 0.004-0.08% ~y weight of the oatalyst, and often 1~ about 0.006-0.007% by wsight gives tha best resultsr A
- ~urface active agent may be added thereto when desired as previously discussed. Alternatively the dry catalyst or liquid catalyst concentrate may be admixed with water and/or the surface activ0 agent to provide an effective catalyst concentration in the quantities previously discussedO The weight of the catalyst is calculated on a dry solids basis, i.e., he weight of the catalyst insredients in the a~ueous suspension as produced after removal o~ the water.

- ~4 -~(~S~5~

In a further variant of the process for preparing the catalyst, at least one dissolved subs~ance providing at least one amphoteric metal-containing ion is present in the aqueous medium at the time,of reacting the alkali ~etal silicate with the substances providing calcium ion and 'magnesium ion. The subetance or substances proviaing the : amphoteric metal-containing ion or ions may be present, : ' for example, in an amount sufficient to provide about 0.0001-1% and prefer~bly about 0.01-0.5% by weight when ~alculated as the amphoteric metal oxide and based upon the '. weight of the alkali metal silicate~ Preferred amphoteric metals include aluminum and/or zinc, and the preferred sources thereof include alkali metal aluminate and zincata , of which sodium aluminate and/or zincate usually give the best ; 15 results. The alkali metal aluminate and/or zincate may be added directly to the aqueous medium, or as the mineral acid salts, oxides and/or hydroxides which then for~l the alkali metal aluminate and/or zincate under the highly alXaline conditions that e~ist.
Surprisingly, an aqueous suspension of catalyst which was used previously in treating coal, lig~ite and peat in the process of the invention produces a more active catalyst than either aistilled water or deionized water. In one _ ~5 _ s~

preferred variant of the invention, spent aqueous catalyst suspension is recycled indefinitely in a process for treating the coal, lignite or peat with periodic additions of the chemicals necessary to maintain the desired concentration of the catalyst. The catalyst producad by this ~ariant exhibits greatly enhanced initial catalytic activity and rssults in a rapid attack on the acti~e sites of the coal, lignite and peat~ j The invention is further illustratad by the following speci~ic examples.
.
EX~MPLE }

- - This example illustrates one presently preferred process for preparing the novel c~talyst used in practicing .
the invention.

Anhydrous calcium chloride in an amount of 0.66 gram and maynesium sulfate heptahydrate in an amount o~
1.32 grams were dissolved in kwo liters of deionized water with stirring and warming until solution was complete.
Then 95 grams of sodium silicate pentahydrate having a molecular ratio o~ sodium oxide to silicon dioxide o~
1:1 were added to the solution with stirring and continued ~15~5~

warming to produce a wh~te colloidal suspe~sion of the reaction product.
After setting for 10 minutes, the colloidal suspension was heated to 80C. and sulfated castor oil in an amount of 201 grams was added with stirring~ The average molecular weight of the sulfated castor oil was 940 and it contained 50% of water. The turbidity lessened somewhat as the colloidal suspension was heated at 80-90~C. for one hour with vigorous stirring to produce catalyst micelles. The aqueous suspension of c~talyst micelles thus prepared had a viscosi.ty similar to that of water and it was used as the catalyst in certain Examples as noted hereinaftex~
A dr~ or solid catalyst concentrate was 1~ prepared ~n a further run by evaporating water from the initially prepared aqueous catalyst suspension. The resulting dry catalyst concentrate was resuspended in water and there was no substantial loss of catalytic aativity. In still other runs, the catalytic activi~y of the a~ueous suspension of catalyst as initially prepared, the diluted aqueous suspension of catalyst, and the reconstituted aqueous catalyst suspension was enhanced by ~reezing and tha~ing.
EXAMPLE II.
This example illustrates the preparatîon of additional catalyst suspensions.

- 47 ~

~5~
Five suspensions of the catalyst were prepared from the same ingredients as used in Example ~ and following the general procedure of Example I. The ratios of ingredients were varied as follows:
S Ing~edient Amount of Ingredient Run 1 ~un 2 Run 3 Run ~ Run 5 Deionized water 2 1 1~5 1 1.5 1 1.5 1 0.25 CaC12 0.66 g 0.5 g 0.5 g 1.0 g 0~5 g Mgso4.7El2o 1.32 g 1.0 g 1.0 g 2.0 g 1.0 g Na2si3'5M2 165 g 132 g 71 g 185 g 71 g Sulfated Castor lOO ml 150 ml 150 ml 200 ml 150 ml oil (approximately 50% by weight H20) The catalyst suspensions prepared by the above lS five runs were used in certain examples as noted hereinafter.
- EXAMPLE I~I
A portion of a c~ncentrated suspensi.on of catalyst prepared in accordance with Example I was diluted with 100 volumes of water. The resulting diluted catalyst suspension was used in treating small lumps of suh-bituminou~ coal in a ball mill.
The lumps of coal and the diluted catalyst suspension were fed ~o the ball mill at ambient temperature in the proportion o~ one pound of coal to one pound of catalyst suspension. The hall mill was rotated for 12 hours. Under these conditions, the coal los~ its crystalline appearance and ac~uired the physical appearance and properties of weathered ~S~g~

(oxidized) lignite or Leonardite.
Samples of the treated and untreated coal having - about thesame particle size were extracted with aquaous acetic acid and then with aqueous sodium hydroxide solution.
The solubility of the treated coal was markedly greater than that of the original coal. It was apparent that treating the ; coal with the catalyst suspension changed the chemical compo-sition and/or altered the bonds therein to produce both acid soluble and alkali soluble chemicals.
10 ~ A portion o~ the treated coal was exposed to ai~ for one hour at 100C. The initial oxidation was carried further, and a mixture of water soluble acidic compounds such as phenols, carboxy~ic acids, and hydroxycarboxylic acids, was produced and subsequently extracted with aqueous sodium hydroxide solution. The degree of oxidation achievea by this treatment was e~ui~alent ~o oxidizing the coal at 150~C. for a period of eig'nt hours in shallow pans with ~requent stirring~ Treating coal with the aqueous aatalyst suspension not only r~sulted in a remarkable degree of oxi.dation, but also seemed to activate the oxidizable sites whereby it was further oxidiæed by exposure to air in a minimum period of time and at low tempera-ture.
A substantial amount of gas was liberated in the ball mill while treating the coal and a significant pressure ~5 was built up. The off gases contained hydrogen cyanide, cyanogen, hydrogen sulfide, sulfur dioxide, sulfur trioxide and carbon dioxide. The composition of the off gases indicated that ~ 4g -~l~5~5~9~

the action o~ the catalyst suspension on the coal was one of oxidation.
A second portion of coal treated in the ball mill was extracted with acetone and then with benzene. Upon evaporating the solvents, a mixture of organic chemicals was ~btained in each instance and it was not possible to determine the exact chemical composition. However, the compounds were different from those obtained upon extracting the treated coal with àqueous acetic acid and aqueous sodium hydroxide.
A third sample of the treated coal was analyæed.
The treated coal contained substantially no alkali metal com-pounds or combustible sulfur and nitrogen compounds. The heating value was not changed signi~icantly and the treated coal is a low ~ulfur and low nitrogen containin~ fuel which may be burned in coal burning furnaces. Upon combustion, the treated coal produces ~ery little air pollution due to ~ulfur and nitrogen oxides and tube failure in furnaces is reduced to a minimum.
EX~MPLE IV
; 20 ~he five catalyst suspensions prepared by the ive runs of Example II were tested or catalytic activity follvw-ing the general procedure of Example III and were rated as active catalysts.
A portion or the catalyst suspension from each of the run~ was frozen and thawed~ When tested in accordance with the p~ocedure of ~xamp3e III, the frozen and thawed catalyst suspension had an even higher catalytic activity~

~ 50 ~ 3 ~ ~

A portion of the frozen and thawed catalyst sus-pension rom Run 4 o Example II was evapo~ated to dryness and the dry residue was usad to prepare an aqueous catalyst ..
suspension in d~ionized waterO The càtalyst suspension con-tained 1 par~ of the dry residue for each 600 parts of deionized watèr and it was an effective catalyst when tested in accor-dance with the procedure of Example III.
-EXAMæLE V
This Example illustrates a ~urther presently pre-ferred process for preparing the catalyst of t~e invention.
~nhydrouscalcium chloride in an amount of 0.66 gram and magnesium sul~ate heptahydrate n an amount of 1.32 grams were dissolved in one liter of soft water heated to 80C.
Then 95 grams of sodium silicate pentahydrate was added to the resulting solution with stirring to produce a suspension of ~ine7y divided particles o~ the reaction product. The sodium silicate pentahydrate contained approximately 0.12 gram of aluminum when calculated as A1203 and a somewh~t smaller amount of zinc when calculated as ZnO.
The suspension of the reaction product was maintained at 80C. and stirred for one-halE hour. Then an aqueous solution prepared by admixing 75 grams of sulfated castor oil with 100 mililitexs of water was added slowly with stirring. The stirring was continued or one-half hour thereafter w~il0 maintainl~g the reaction mixture at 80C. to produce catalyst-containing micelles~

_ 51 -~s~
The sulfated castor oil contained 60 5-7% of organi-cally combined S03 on a dry basis, 0.9-1.1% of combined alkali when calculated as sodium oxide, no free alkali, and 50% ~ 1%
of material volatile at 105C. which was mostly waterO ~he average molecular weight of the sulfated castox oil molecule was approximately 400 grams per mole.
The above prepared suspension of catalyst was placed in plastic containers awaiting testing and use. The catalyst - suspension was tested in accordance with Example III and was rated as a superior catalyst~ It was possihle to add from 1,000 to 10,000 parts of water to a portion of the catalyst SUSpenSiQn and sti~l obtain excellent catalytic activity~
A furt~er portion of the catalyst suspension was frozen and thawed, and then tested in accordance with the procedure of Example I~I. The cooling and warming steps enhanced the catalytic activity.
A further portion of the catalyst suspension was admixed with commercially availahle surractants in quantities sufficient to serve as a laundry deter~ent. No detrimelltal effects were noted. It was also possible to add additional al~ali metal silicate haviny a mola ratio of sio2 to Na20 o~ 1.6:1 to 3:1 without detrimental effects. Thus, the aqueous catalyst suspension is sufficiently stable to allow a~dition of laundry detergents or builders such as a-kali metal silicates nitrilotriacetic acid and phosphates.

-- S~ --~.~5~
EX~MPLE VI
---- i The gPn~ral procedure of Example V was followed - ' with the exception of using 0.33 gram of anhydrous calcium chloride rather than 0.66 gram, 0.66 gram of magnesium sulate heptahydrate rather than 1.32 grams, and 45 grams of sodium silicate pentahydrate rather than 95 gra~s.
The remaining ingredients ana steps in the Example I procedure for preparing the catalyst were not changed.
The resulting catalyst suspension was approximately one-half as concentratea as that prepared in Example ~.
Upon testing in accordance with Example III, it was fo~lnd to be as e~ecti~a as the catalyst of Example V when calculated on a dry solid basis. 'It was also possible to add surfactants and alkali metal silica~es as described in Example V without adverse effect. Cooling the catalyst suspension to temperatures approaching the freezing point ox 'freezing, ollowed by warming or thawing, also had a beneficial effect upon the catalytic activity.
~ . , ~his Example illustrates the pr~paration of the fossil fuel solutions of the invention ~rom lignite.
~ignite from the Havelock Mine, New England, ~orth Dakota was ground to minus 60 mesh (Tyler Screen) and 200 grams thereof was admixed with 250 ml of a catalyst suspension prepared in accordance w,ith Example I and diluted with 1000 volumes of water~ The admixture was treated for 2 hours _ 53 -~05~

at room temperature (72F.) in a 1 quart Abbe Ball Mill using 3/4" ceramic balls. Followins the treatment, the reaction -mixture was filtered to obtain a glassy black pitch-like solid residue of treated lignite parti~les and a yellow li~uid treating solution having a pH of 6.7.
~he treated lignite particlas were extracted with acetone to producP a dark red solution and a residue of a~eto~e extracted particles. The acetone extracted particles were urther extracted with 3 M hydrochloric acid to ~btain a yellow-orange acidic extract solution and an acid extracted residue.
The acid ex~racted char was further treated with 1 M
sodium hydroxi~e solution and the mixture set to a jet-blac~
pitchlike substance. The solution was filtered with difficulty to yield a black thick liquid and a sodium hydroxide treated residue. ~en the residue was washed with water, the solid material peptiz~id and passed through the filter. Thus, substantia11y all of the liq~ite was solubilized.
X~MPLF, VIII
This Example illustrates the preparation of an aqueous solution of catalyst treated lignite.
Weathered lignite having a particle size of minus 80 mesh (Tyler Screen) was admixed in an amount of 50 pounds with 2.50 ml of the catalyst suspension prepared in accordance with Example I and 8 gallons of hot soft water having a *empexature of l~O~F. The admixture was heated and stirred and after five minutes, the pH value was approxirnatel~ 5 -5~-~05~

The admixture was allowed to set without heating or 12 hours and then 2 pounds of fla]ce caustic (78% sodium hydroxide) was added. The admixtuxe was stirred for approximately 5 minutes and the pH was 5-6. The wet catalyst treated li~nite was air dried and stored in a plastic container.
The above prepared catalyst treated lignite was admixed in an amount o~ 29~ grams with 307 grams of the catalyst suspension prepared in accordance with Example I. The resultant moist solid was stored in an airtight contailler while awaiting the preparation of a solution~ Thereaf~er, ~ ~rams of this admixture was added to one yallon o~ soft water, Substantially all of the treated lignite dissolved forming a dar~ opague blue-black solution~ The ~olution contained the catalyst in a concentration equivalent to diluting the catalyst suspension ~5 of Example I with 1000 volumes of water and it also contained 700 parts per million of the dissol~ed catalyst treated lignite.
The pE value was 7.
The above prepared lignite solution was tested on cultures of Staph~lococcus Aures ~gram positive) and ~0 Escherichia Coli (gram negative). The solution completely inhibited the growth of both Staphylococcus Aures and Escherichia Coli.
_AMP~E XI
This Example illustrates the treatment of Haveloc~
Mine lignite having a particle siæe such that 85% passed through a minus 85 mesh Tyler Scre~n.

An admixture of 70 pounds of the lignite, 300 ml of the catalyst suspension prepaxed in accordance.with Example I
and 8 gallons of soft water having a temperature of 150F.
was prepared. After 5 minutes of heating and stirring, the 5 . pH was 5 a~d 2.2 pounds of flake caustic soda (78% sodium hydroxide) was added. The pH of the resultant solution was 12 and after one-half hour of heating the pH was 11. The admixturP was allowed to set for 12 hours.
Thereafter 1./2 of the trQated lignite was air dried. A white encrustation appeared on the surface after drying. A second 1/2 portion of the treated Iignite was kept - moist with water for 2 days to determine if air oxidation continues provided the treated lignite is kept:moist and basic.
Upon;'testing, i~ was found that the air oxidation di.d continue.
A white encrustation formed on the surface of the treated lignite when dry. The remaining l/3 portion of the treated llgnite was admixed with 2 gallons of hot soft water and there-after lOG grams of sodium perborate was added. The temperat~re was 76C, Thereafter, the treated li.gnite was air dried in the ~20 sun and no white encrustation developed on the surface.

_ 56 -

Claims (56)

I CLAIM:

1. A process for treating solid fossil fuels with an aqueous medium comprising intimately contacting solid fossil fuel in particulate form selected from the group consisting of coal, lignite, peat and admixtures thereof with an aqueous medium containing a catalytically effective amount of a catalyst, the solid fossil fuel having active sites therein which react with at least one component of the aqueous medium under liquid phase conditions in the presence of the catalyst, the particles of the solid fossil fuel being intimately contacted with the aqueous medium under liquid phase conditions until active sites thereof react with at least one component of the aqueous medium, the catalyst being prepared by a process comprising admixing a water soluble alkali metal silicate with an aqueous medium containing a dissolved substance which is a source of calcium ion and a dissolved substance which is a source of magnesium ion, the aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-4 and 1 x 10-1 mole per liter each of calcium ion and magnesium ion, the aqueous medium containing said dissolved substances in amounts to provide a molar ratio of calcium ion to magnesium ion between about 2.0:1.0 and 1.0:2.0;
the alkali metal silicate having an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and less than 2.0:1.0 and being admixed with the aqueous medium in an amount of about 0.05-2 moles per liter, reacting the alkali metal silicate with said dissolved substances providing calcium ion and magnesium ion to produce an aqueous suspension of finely divided particles of the reaction product, admixing a micelle-forming surfactant with the aqueous medium in an amount to form catalyst micelles comprising said finely divided particles upon agitating the aqueous medium, and agitating the aqueous medium containing the finely divided particles and surfactant to form said catalyst micelles.

2. The treated solid fossil fuel prepared by the process of Claim 1.

3. The process of Claim 1 wherein the solid fossil fuel is coal.

4. The process of Claim 1 wherein the solid fossil fuel is lignite.

5. The process of claim 1 wherein the solid fossil fuel is peat.

6. The process of claim 1 wherein in the process for preparing the catalyst, said ratio of calcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5.

7. The process of claim 1 wherein in the process for preparing the catalyst, said ratio of calcium ion to magnesium ion is about 1.0:1Ø

8. The process of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-3 and 6 x 10-3 mole per liter each of calcium ion and magnesium ion.

9. The process of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 2.5 x 10-3 and 3.0 x 10-3 mole per liter each of calcium ion and magnesium ion.

10. The process of claim l wherein in the process for preparing the catalyst, about 0.2-0.3 mole per liter of the alkali metal silicate is admixed with the aqueous medium.

11. The process of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and 1.2:1Ø

12. The process of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is alkali metal metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1Ø

13. The process of claim 1 wherein in the process for preparing the catalyst, about 0.001-0.1 mole per liter of the surfactant is admixed with the aqueous medium.

14. The process of claim 1 wherein in the process for preparing the catalyst, the surfactant comprises sulfated castor oil.

15. The process of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide between about 1 x 10-3 and 6 x 10-3 mole per liter each of calcium ion and magnesium ion, the ratio of calcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5, about 0.1-1 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 and 1.2:1Ø

16. The process of claim 1 wherein in the process for preparing the catalyst, the alkali metal silicate is ad-mixed with an aqueous medium containing said dissolved sub-stances in amounts to provide between about 2.5 x 10-3 and 3.0 x 10-3 mole per liter each of calcium ion and magnesium ion, the aqueous medium contains about equimolar amounts of calcium ion and magnesium ion, about 0.2-0.3 mole per liter of the alkali metal silicate is admixed with the aqueous medium, and the alkali metal silicate has an alkali metal oxide to silicon dioxide ratio of about 1.0:1Ø

17. The process of claim 16 wherein in the process for preparing the catalyst, the alkali metal silicate is sodium metasilicate having an alkali metal oxide to silicon dioxide ratio of about 1.0:1Ø

18. The process of claim 16 wherein in the process for preparing the catalyst, about 0.03-.07 mole per liter of the surfactant is admixed with the aqueous medium.

19. The process of claim 18 wherein in the process for preparing the catalyst, the surfactant comprises sulfated castor oil.

20. The process of claim 19 wherein in the process for preparing the catalyst, the alkali metal metasilicate is sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:1Ø

21. The process of claim 20 wherein in the process for preparing the catalyst, at least 25% of the hydroxy groups of the castor oil are sulfated, and about 0.03-0.07 mole per liter of the sulfated castor oil is admixed with the aqueous medium.

22. The process of claim 16 wherein in the process for preparing the catalyst, the alkali metal silicate is admixed with an aqueous medium containing said dissolved substances in amounts to provide about 2.9 x 10-3 mole per liter of calcium ion and about 2.7 x 10-3 mole per liter of magnesium ion, about 0.25 mole per liter of sodium metasilicate having a sodium oxide to silicon dioxide ratio of about 1.0:1.0 is admixed with the aqueous medium, the aqueous medium contains not more than 10 parts per million by weight of carbonate ion and bicarbonate ion, the surfactant comprises sulfated castor oil and at least 50% of the hydroxy groups of the castor oil are sulfated, and about 0.05 mole per liter of the sulfated castor oil is admixed with the aqueous medium.

23. The process of Claim 1 wherein the treated particles of fossil fuel are intimately contacted with an organic solvent under liquid phase conditions to extract organic compounds solubilized by the treatment.

24. The process of Claim 23 wherein the resulting solution of solubilized organic compounds is separated from the treated solid particles of fossil fuel and the dissolved organic compounds are recovered from the organic solvent.

25. The process of Claim 24 wherein the organic solvent is water soluble, the treated particles of fossil fuel are separated from the aqueous treating medium, and thereafter the solubilized organic compounds are extracted from the separated particles by intimately contacting the same with the organic solvent.

26. The process of Claim 24 wherein the organic solvent is water insoluble, the solubilized organic compounds are extracted from the treated particles by intimately contacting the same with the organic solvent in the pre-sence of the aqueous treating medium, and thereafter the organic solvent is separated from the aqueous treating medium and solid particles of fossil fuel.

27. The process of Claim 1 wherein solubilized organic compounds are extracted from the treated solid particles of fossil fuel by intimately contacting the same with an aqueous acidic medium.

28. The process of Claim 1 wherein solubilized organic compounds are extracted from the treated solid particles of fossil fuel by intimately contacting the same with an aqueous basic medium.

29. The process of Claim 1 wherein the treated solid particles are intimately contacted with an elemental oxygen-containing gas to further oxidize the fossil fuel and solubilize additional organic compounds.

30. The process of Claim 1 wherein the treated solid particles are subjected to destructive distillation and organic compounds are recovered from the resulting products of the destructive distillation.

31. The process of Claim 1 wherein the treated solid particles of fossil fuel are intimately contacted with an organic solvent under liquid phase conditions to extract organic compounds solubilized by the treatment, the extracted particles of fossil fuel are separated from the organic solvent, and thereafter the particles are intimately con-tacted with at least one aqueous medium selected from the group consisting of aqueous acidic media and aqueous basic media to extract additional solubilized organic compounds therefrom.

32. The process of Claim 31 wherein the particles extracted with the organic solvent are intimately contacted with an aqueous medium selected from the group consisting of aqueous acidic media and aqueous basic media to extract additional solubilized organic compounds in a second extraction step, the extracted particles are separated from the aqueous medium following the second extraction step, and thereafter the particles are intimately contacted with an aqueous medium selected from the group consisting of aqueous acidic media and aqueous basic media in a third extracting step to separate still additional solubilized organic compounds, the particles being intimately contacted with an aqueous acidic medium and an aqueous basic medium in the said second and third extraction steps, and the extracted particles being separated from the aqueous medium following the third extracting step.

33. The process of Claim 32 wherein solubilized organic compounds are recovered from the separated organic solvent, aqueous acidic medium and aqueous basic medium.

34. The process of Claim 31 wherein a gaseous mixture containing an acid forming gas is intimately con-tacted with the particles of fossil fuel from the last extraction step to absorb the said acid forming gas.

35. The process of Claim 34 wherein the gaseous mixture comprises at least one halogen in gaseous phase, and the halogen is absorbed by the particles

36. The process of Claim 35 wherein the particles of fossil fuel containing absorbed halogen are intimately contacted with aqueous base to regenerate the said particles and form the corresponding hypohalite salt.

37. The process of Claim 31 wherein particles of the fossil fuel from the last extraction step are inti-mately contacted with a liquid phase organic compound to absorb the same.

38. The process of Claim 37 wherein the liquid phase organic compound is selected from the group consisting of petroleum and fractions derived therefrom.

39. The process of Claim 1 wherein the particles of fossil fuel contain valuable metal or non-metal values, and the treated solid particles are intimately contacted with an aqueous leach solution in which the said metal or non-metal values are soluble selected from the group consisting of aqueous acidic media and aqueous basic media to produce a leach liquor containing the metal or non-metal values dissolved therein, and thereafter the said dissolved metal or non-metal values are recovered from the leach liquor.

40. The process of Claim 39 wherein the treated solid particles of fossil fuel are intimately contacted with aqueous mineral acid.

41. The process of Claim 39 wherein the particles of fossil fuel are intimately contacted with an aqueous solution of an alkali metal base.

42. The process of Claim 39 wherein the treated parti-cles of fossil fuel contain at least one metal or non-metal value selected from the group consisting of uranium values, cobalt values, vanadium values, molybdenum values, zirconium values, germanium values and selenium values.

43. The process of Claim 1 wherein the fossil fuel is treated with an oxidizing agent before, during or following treatment with the said aqueous medium containing the catalyst to thereby aid in solubilizing additional organic compounds.

44. The process of Claim 1 wherein the said particles of the solid fossil fuel are intimately contacted with the aqueous medium until active sites thereof are oxidized, and the said particles of the fossil fuel are treated in a vessel con-structed from an electrically conductive metal to thereby con-trol the degree of oxidation.

45. The process of Claim 1 wherein the said particles of the solid fossil fuel are intimately contacted with the aqueous medium until active sites thereof are oxidized, and the said particles of the fossil fuel are treated in a vessel which is an organic non-conductor of electricity to thereby control the degree of oxidation.

46. The process of Claim 1 wherein subsequent to treating the said particles of the fossil fuel with the catalyst containing aqueous medium, the aqueous medium is evaporated whereby the catalyst content thereof is deposited on the treated particles of the fossil fuel.

47. The catalyst containing particles of treated fossil fuel prepared by the process of Claim 46.

48. The process of Claim 1 wherein the treated fossil fuel particles are dissolved in an aqueous medium in the presence of the said catalyst and sufficient base to form soluble carboxylic acid salts from carboxylic acids contained therein.

49. The process of Claim 48 wherein the fossil fuel is treated with an oxidizing agent before, during, or follow-ing treatment with the said aqueous medium containing the catalyst to thereby aid in solubilizing additional organic compounds.

50. The process of Claim 48 wherein the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, and ammonium hydroxide.

51. The process of Claim 48 wherein the fossil fuel is lignite.

52. The process of Claim 49 wherein the fossil fuel is lignite.

53. The process of Claim 48 wherein the fossil fuel is peat.

54. The process of Claim 50 wherein the fossil fuel is lignite.

55. The process of Claim 49 wherein the fossil fuel is peat.

56. The process of Claim 50 wherein the fossil fuel is peat.