EP0057577B1 - Méthode pour l'amélioration, la liquéfaction et la récupération de charbon et d'autres matières carbonées solides, ainsi que les produits améliorés de charbon - Google Patents
Méthode pour l'amélioration, la liquéfaction et la récupération de charbon et d'autres matières carbonées solides, ainsi que les produits améliorés de charbon Download PDFInfo
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- EP0057577B1 EP0057577B1 EP82300449A EP82300449A EP0057577B1 EP 0057577 B1 EP0057577 B1 EP 0057577B1 EP 82300449 A EP82300449 A EP 82300449A EP 82300449 A EP82300449 A EP 82300449A EP 0057577 B1 EP0057577 B1 EP 0057577B1
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- coal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/005—General arrangement of separating plant, e.g. flow sheets specially adapted for coal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/14—Flotation machines
- B03D1/1443—Feed or discharge mechanisms for flotation tanks
- B03D1/1456—Feed mechanisms for the slurry
Definitions
- This invention relates to a process for the beneficiation of coal and solid carbonaceous fuel materials, and more particularly to an improved process for the beneficiation and enhanced recovery of coal.
- coal Regardless, however, of the form in which the coal is ultimately employed, the coal must be cleaned because it contains substantial amounts of sulfur, nitrogen compounds and mineral matter, including significant quantities of toxic metal impurities. During combustion these materials enter the environment as sulfur dioxides, nitrogen oxides and compounds of toxic metals. If coal is to be accepted as a primary energy source, it must be cleaned to prevent pollution of the environment.
- chemical coal cleaning techniques are in a very early stage of development.
- Known chemical coal cleaning techniques include, for example, oxidative desulfurization of coal (sulfur is converted to a watersoluble form by air oxidation), ferric salt leaching (oxidation of pyritic sulfur with ferric sulfate), and hydrogen peroxide-sulfuric acid leaching.
- Other methods are also disclosed in the above-noted reference to the Encylopedia of Chemical Technology, Vol. 6, pages 314-322.
- coal is first cleaned of rock and the like and pulverized to a fine size.
- the pulverized coal now in the form of a water slurry, is then contacted with a mixture comprising a polymerizable monomer, and a polymerization catalyst.
- the resultant surface treated coal is highly hydrophobic and the oleophilic and is thus readily separated from unwanted ash and sulfur using oil and water separation techniques.
- hydrophobic coal can be readily further dehydrated to very low water levels without employing costly thermal energy.
- the clean, very low moisture content coal resulting from this process can then be employed as is, i.e. as a dry solid product, or further processed to advantageous coal-oil or coal-aqueous mixtures.
- froth flotation process which consists of agitating the finely divided coal and mineral suspension with small amounts of frothing reagents in the presence of water and air.
- the frothing reagents assist the formation of small air bubbles that collect the hydrophobic coal particles and carry them to the surface.
- the hydrophilic mineral matter is wetted by water and drawn off as tailings.
- the recovery of fine.coal residuals in coal cleaning refuse water using conventional froth flotation is so poor that the procedure is seldom practiced commercially.
- a further problem associated with the beneficiation and recovery of coal is the variety of kinds of coal that are naturally found. That is, for example, it is well known that the so-called low rank coals do not respond well to beneficiation using conventional flotation processes, particularly because the beneficiated products do not float well.
- the invention seeks to fulfil such aims by providing a process for the beneficiation and recovery of coal which comprises the steps of pulverising the raw coal or other carbonaceous fuel, forming the pulverised coal or other carbonaceous fuel into an aqueous slurry and subjecting the slurry to intensive mixing under conditions of higher shear in the presence of a water insoluble organic liquid, and thereafter recovering the pulverised coal or other fuel particles from the slurry, characterised in that the said water insoluble organic liquid is benzene xylene toluene or other light hydrocarbon oil boiling in the range 40-80°C, cyclohexane, pyridine or ethyl acetate, or a mixture of two or more thereof.
- a process which further includes the steps of further cleaning the treated coal or other solid fuel particles in one or more froth flotation steps by admixing the treated coal product with an aqueous froth flotation medium to form a froth phase containing the treated coal or other fuel, separating the coal-containing froth phase from the continuous aqueous phase, and recovering the treated coal or other fuel particles from the separated froth phase.
- aqueous slurry of pulverised coal or other solid fuel particles there are added to the aqueous slurry of pulverised coal or other solid fuel particles during or prior to the intensive agitation and/or in any subsequent flotation step one or more monomeric organic compounds capable of undergoing free radial polymerisation in situ on the pulverised fuel particles, thereby to render such particles hydrophobic and oleophilic, a free radical polymerisation initiator and a free radial polymerisation catalyst which are effective to cause the said in situ polymerisation of said monomeric organic compound or compounds.
- the treated coal particles recovered by froth flotation are treated to remove residual water and liquid organic medium therefrom and then treated under conditions of high shear mixing with further organic liquid optionally containing additional polymerizable monomer, a polymerization catalyst and polymerization initiator, to provide both a super-clean beneficiated coal product and a liquid coal extract.
- Fig. 1 illustrates the basic sequence of steps for carrying out processes of the present invention.
- it is initially preferred to reduce raw mined coal or other solid carbonaceous materials to a fine diameter size and to remove the unwanted rock, heavy ash and the like materials collected in the mining operation.
- raw coal which has previously been crushed and removed of rock and heavy ash such as by using breakers, jigs and the like, is introduced to pulverization zone 10 through conduit 21 where the raw coal is pulverized and initially cleaned, usually in the presence of water, which may be introduced through line 23.
- the coal is ground employing conventional equipment, such as, for example, ball or rod mills.
- additives assist in rendering the ash more hydrophilic, which facilitates the separation thereof.
- Typical additives which can be introduced through a separate line 25 or through either of lines 21 or 23 and which are useful for purposes herein, include conventional inorganic and organic dispersants, surfactants, and/or wetting agents.
- Preferred additives for this purpose include sodium carbonate, sodium pyrophosphate, and the like.
- the coal-aqueous slurry formed in pulverization zone 10 is typically one having a coal to water ratio of from about 1 to about 19 and preferably about 1:4 parts by weight, respectively. Also, ratios of 2:1 (coal to water) are also contemplated. 1:1 (coal to water) is also preferably used. If utilized, water conditioning additives as hereinbefore described are employed in small amounts, usually, for example, from about 0.025 to about 5%. While it is generally recognized that more impurities are liberated as the size of the coal is reduced, the law of diminishing returns applies in that there is an economic optimum which governs the degree of pulverization.
- the coal is generally desired to grind the coal to a particle size of from about 48 to about 300 mesh Tyler: 0.295 to 0.05 mm, preferably about 80% of the particles being finer than about 200 mesh size (0.074 mm).
- any type coal can be employed in the process of the present invention.
- these include, for example, bituminous coal, sub-bituminous coal, anthracite, lignite and the like.
- Other solid carbonaceous fuel materials such as oil shale, tar sands, and the like are also contemplated for treatment by the process herein.
- the term "coal” is also intended to include these kinds of other solid carbonaceous fuel materials.
- the present process is particularly well suited for beneficiating low rank coals, e.g. lignite, low rank bituminous, sub-bituminous and peat.
- the coal-aqueous slurry, which exits pulverization zone 10 through conduit 29 is fed to a high shear, i.e. high speed agitation, zone 12 wherein the pulverized coal is contacted, at a temperature of from about 40°C to about 95°C preferably 50-80°C for a period of from about 15 seconds to about 15 minutes and admixed under high speed agitation, with an organic water insoluble liquid medium added by means of any of reagent tanks 1, 2 or 3. It has been found herein that the presence of the organic water insoluble liquid at this stage in the process results in a "deep" cleaning of the coal, especially with coals which are generally very difficult to clean, such as the aforementioned low rank coals.
- the organic water insoluble liquid operates to drive the moisture (if present) from the coal, thus allowing reaction with the polymerizable reaction composition (in sub-bituminous and lignite it is believed that the water of hydration offers ⁇ -barrier to surface reaction) which leads to heterogenous separation of the organic phase from the water and accordingly enhances ash separation.
- the beneficiated coal recovered from zone 12, via line 31, after removal of residual water and liquid hydrocarbons, by drying and solvent extract techniques (if desired), for example, has a low moisture content of from about 5% to about 30%, a low ash content of from about 1% to about 10% and a low sulfur content of from about 0.1 to about 6%, preferably 0.3 to 2%, depending on the coal feed.
- This product is a highly desirable one and is therefore suitable for use as is or may be further treated and cleaned in accordance with the following discussion encompassing further embodiments of the present invention.
- Water-insoluble organic liquids which are suitable in high shear mix zone 12 are generally any solvents or other fluid medium which will sufficiently wet the coal to permit ash separation.
- water insoluble organic liquids suitable for the purposes of this invention are low boiling liquids, i.e. boiling point from about 40°C to about 80°C.
- Such liquids include benzene, toluene, xylene, hydrocarbon oils, pyridine cyclohexane, ethyl acetate and mixtures thereof.
- benzene and toluene are preferred, toluene being most preferred.
- the clean coal from high shear mix zone 12 may be further cleaned in accordance with the present invention to provide an even cleaner, i.e. a "super clean" coal product.
- a "super clean" coal product This is accomplished in accordance with the process outlined by Fig. 2.
- the coal containing mixture exiting high shear mix zone 12 is fed to a first flotation zone 14 through line 31.
- the coal-organic liquid mixture is contacted and admixed with an aqueous medium.
- This aqueous medium in flotation zone 14 may comprise simply water or in addition to water other surface treating additives may be present.
- the aqueous medium of flotation zone 14 may comprise a chemical treating mixture comprised of water, a polymerizable monomer and polymerization catalyst. These ingredients can be introduced, for example, to zone 14 through lines 33, 35 and 37, respectively. If desired, a further amount of organic liquid hereinbefore (and hereinafter) described, can also be added to the aqueous medium of zone 14 such as via line 39. This organic liquid may be the same or different from that employed in high shear mix zone 12; preferably, it is the same.
- the coal containing mixture from zone 12 is sprayed, most preferably through a pressure spray nozzle, into flotation zone 14. Spraying further facilitates the separation of ash from coal by assisting in breaking up any flocs of coal which may include trapped ash. Moreover, in order to encourage frothing it is also preferred herein to spray the surface treating ingredients into flotation zone 14 such as through line 33 (water), 35 (monomer) 37 (catalyst) and 39 (catalyst initiator). Frothing takes place in flotation zone 14 thus providing a floating coal froth phase and an aqueous phase.
- Fig. 4 illustrates a unit 55 which is suitable as a froth flotation vessel useful in zone 14 or any of flotation and flotation recovery zones employed in the present process.
- the coal-organic liquid mixture is sprayed into the vessel through line 29 and through spray nozzle 61.
- the treating reagents may be added by way of lines 33, 35, 37 and 39. As indicated hereinabove and although not shown in Fig. 4, these ingredients may be fed to the vessel through spray nozzles also.
- These agents can be added directly to the liquid media in the pulverization zone, in the organic liquid medium or in water or separately in lines leading to the zones or vessels.
- a particularly effective technique for separating the treated coal particles from unwanted ash and sulfur in the water phase comprises an aeration spray technique wherein a coal froth phase is formed by spraying or injecting the treated coal- water slurry into the surface of cleaning water.
- the coal slurry is injected through at least one spray nozzle at pressures, for example, at from about 15-20 psi (103 to 138 kPa) at a spaced-apart distance above the water surface into the water surface producing aeration and a frothing or foaming of the coal particles, causing these particles to float to the water surface for skimming off.
- the surface treating conditions utilized in zone 14 will, of course, vary depending upon the specific reactants employed. Generally, however, any conditions which result in the formation of a hydrophobic and oleophilic surface on the coal can be utilized. More specifically, typical conditions include, for example, temperatures in the range of from about 10°C to about 90°C, atmospheric to nearly atmospheric pressure conditions and a contact time, i.e. reaction time, of from about .02 to about 10 minutes. Preferably, the chemical reaction is carried out at a temperature of from about 15°C to 60°C and atmospheric pressure for about 2 minutes.
- the coal froth phase, which ensues in zone 14, is readily separated from the aqueous phase, which is also formed therein, by conventional means, for example, skimming.
- the beneficiated solid coal product resulting at this point in the process is even further cleaned of impurities, including ash and sulfur. Preferably, however, it is fed to further flotation zone 16 through line 41 for further cleaning.
- the aqueous phase remaining in zone 14, which contains residual coal particles or fines and ash is removed from zone 14 and sent to flotation recovery zone 20 through line 43.
- the aqueous phase from zone 14 is preferably fed to zone 20 through a pressure spray nozzle, thereby facilitating further frothing.
- Recovery zone 20 comprises an aqueous medium typically contained in a froth flotation unit as illustrated in Fig. 4 herein. It has been surprisingly discovered that in contrast to prior art froth flotation recovery operations, merely admixing, preferably by spraying, the aqueous phase from zone 14 into the aqueous medium of zone 20, causes a significant quantity of the residual coal fines to float, which permits for greater recovery than customarily achieved by processes used heretofore. While it is not completely understood, it is believed that this advantage results from the unique surface treating beneficiation process employed in the present process, wherein the surface of the coal becomes highly hydrophobic and oleophilic.
- the coal froth phase which ensues in zone 20 is recovered therefrom through line 45 and recycled to either pulverization zone 10 or high shear mix zone 12 (not illustrated) or directly to flotation zone 14 via line 31 (as shown) for further treatment therein.
- the aqueous phase resulting in zone 20 may be drawn off and sent to a waste disposal unit (not illustrated) or preferably is fed to a further recovery zone 22 as shown.
- Frothing and/or flotation aids, which assist in the formation of small air bubbles, may be added to recovery zone 20 or 22 for enhanced coal phase separation.
- the coal froth phase from zone 14 is, at the same time, introduced to a further flotation zone 16, again preferably through pressure spray nozzles, in line 41.
- Zone 16 is also comprised of an aqueous medium.
- the coal froth phase, which forms in zone 16 is separated from the aqueous phase which is also formed in zone 16, and preferably introduced to a third flotation zone 18, through line 47, as shown in Fig. 2.
- zone 18 is also comprised of an aqueous medium.
- a coal froth phase and an aqueous phase also ensues in zone 18.
- the coal froth phase is skimmed from flotation zone 18 and then may be fed through line 83 to a drying zone 48 such as a centrifuge or other solvent and/or water removal technique, and used as is.
- This coal is a "super clean" coal product having a very low ash content of from about 0.5 to about 10%, and a very low moisture content of from about 0.2 to about 15%.
- Such a coal product is extremely desirable in the formation of coal-aqueous and/or coal-oil mixtures.
- the aqueous phases formed in each of these zones are also continuously removed and introduced for further processing as illustrated in Figs. 2 and 3. That is, the aqueous phase from zone 16 is recycled to zone 14 in a countercurrently flowing stream via line 49, whereby residual coal particles are again subjected to treatment in zone 14. Similarly, the aqueous phase in zone 18, is recycled in a countercurrently flowing stream via line 51 to zone 16 for further processing therein. At the same time, as described before, the aqueous phase from zone 14 is continuously removed therefrom and introduced to flotation recovery zone 20 by way of line 43.
- the resultant coal froth phase in zone 20 is removed therefrom and recycled to flotation zone 14 for further treatment by way of lines 45 and 31.
- the aqueous phase formed in zone 20 is continuously removed and preferably fed to second flotation recovery zone 22 through line 53.
- the coal froth phase which ensues in zone 22 is removed therefrom and is continuously recycled in counter-current flowing stream to recovery zone 20 via line 55.
- the aqueous phase in zone 22 is disposed of via line 57 and typically sent to a waste treatment unit 44 as depicted in Fig. 3.
- water may be the only ingredient utilized in the aqueous mediums contained in flotation zones 14, 16 and 18 and flotation recovery zones 20 and 22, it is contemplated herein, particularly in zones 14,16 and 18 but also in zones 20 and 22, to employ, in addition to water, small amounts of the hereinbefore-mentioned surfactants, dispersing and/or wetting agents, particularly sodium carbonate and sodium pyrophosphate, polyeri- zable monomer, such as the same or different monomer which may have been employed in the initial surface treatment mixture in flotation zone 14, a small amount of liquid organic carrier, such as fuel oil, a coal derived oil or any of the heretofore and hereinafter recited organic liquids, and a small additional amount of polymerization catalyst, such as the free radical catalyst and/or initiator.
- surfactants particularly sodium carbonate and sodium pyrophosphate
- polyeri- zable monomer such as the same or different monomer which may have been employed in the initial surface treatment mixture in flotation zone 14
- residence times of the materials being treated, washed and/or recovered in each of the foregoing identified zones will, of course, vary depending upon the amounts and materials utilized. Residence times which result in optimum frothing and separation of phases are most desirable. Generally, however, any residence time which is sufficient to result in a coal froth phase and an aqueous phase may be utilized. More specifically, these times range from about 0.2 to about 30 minutes.
- the super clean coal 50 is now introduced to an extraction procedure wherein further modified and liquefied coal products are produced which are cleaned of even further amounts of inorganic and organic sulfur.
- the extraction procedure involves high shear agitation, which may include a single stage or a series of high shear mixing stages and treatments.
- the super clean coal from zone 18, either before drying or after drying is fed via line 59 to high shear mix 24 wherein the coal is admixed under high speed agitation, with an organic liquid medium comprising an organic liquid, a polymerizable monomer, a free radical catalyst and free radical initiator.
- an organic liquid medium comprising an organic liquid, a polymerizable monomer, a free radical catalyst and free radical initiator.
- the resultant product is fed via line 101 to a separation zone 26, commonly a centrifuge, wherein the liquids fraction is separated from the solids fraction.
- the organic liquid employed in the extraction procedure may be water insoluble such as those used in zone 12 or they may be water soluble or mixtures thereof.
- Typical organic liquid mediums used in the extraction process include toluene-alcohol mixtures, benzene-alcohol mixtures, xylene- alcohol mixtures, ethanol, methanol, isopropyl alcohol, methyl ethyl ketone, cyclohexane, pyridine, dimethylformamide, tetrahydrofuran (THF) and the like. THF is preferred.
- the liquids fraction from separation zone 26 is fed to a solvent removal zone 34, illustratively shown as an evaporator unit, through line 61.
- the solids portion from zone 26 is introduced via line 103 to a further high shear mix zone 28 wherein the coal is admixed under high speed agitation with further organic liquid.
- This organic liquid medium may or may not contain the same ingredients, e.g., monomer, catalyst initiator, as used in zone 24. These ingredients including the organic liquid medium, may be added to any of zones 24, 28 or 32 via reagent tanks 4, 5 and/or 6.
- the product resulting from zone 28 is fed via line 105 to a separation zone 30 wherein the liquids fraction is separated from solids.
- the liquids portion is sent to solvent removal zone 34 via line 63 and the solids portion is fed via line 107 to a third high shear mix zone 32 wherein the coal product is again admixed under high speed agitation with further organic liquid hydrocarbon medium which again may or may not contain the same ingredients used in zone 26 and 28.
- the product resulting from zone 32 is fed through line 67 to a separation zone 95 wherein the liquids fraction is separated from solids.
- the liquids portion is sent, via line 65, to solvent removal zone 34.
- the residual hydrocarbon solvent present in the liquids fraction is removed in zone 34 and a liquefied coal extract product is recovered at line 66.
- This combined liquefied coal extract is a highly beneficiated coal product of the present invention and is a low ash (from about 0.1 to about 2%), preferably 0.2 to 1 %, low sulfur (from about 0.1 to about 3%), preferably 0.2 to 1% and high BTU carbon product.
- This liquid extract may be used as a very desirable source of energy and in addition is a valuable feedstock for organic products, particularly aromatic products.
- the extract which contains some of the extracting solvent can be a fluid true liquid or further evaporated to a viscous fluid. If evaporated to dryness, it can become a redissolvable solid.
- the solid coal which exits separation zone 95 is another product of the present invention.
- the product is forwarded to a solvent removal zone 36, such as a steam distillation unit.
- the resultant dry solid coal 69 is a highly beneficiated product having an ash content of from about 0.5 to about 10%; a sulfur content of from about 0.5 to 1 and a moisture content of from about 2 to 8%.
- the process herein includes provisions for recycling many of process reagents, solvents, etc. That is, for example, solvent which is removed from drying zone 48 via line 71 may be collected in a condensing zone 38 wherein the condensed solvent is then recycled by way of line 73 to a holding tank 40 whereby solvent contained therein is recycled via line 75 to high shear mix zone 12. Solvent removed in zone 36 is sent back to high shear mix zone 24, 28 or 32 via lines 77, 77A and 77B after being condensed in zone 42. Water coming from waste treatment unit 44 is recycled to holding tank 40 via line 79, which water is in turn recycled to pulverization zone 10 via line 81.
- such monomers include ethylene, propylene, butylene, tetrapropylene, isoprene, butadiene, such as 1,4-butadiene, pentadiene, dicyclopentadiene, octadiene, olefinic petroleum fractions, styrene, vinyltoluene, vinylchloride, vinylbromide, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide, acrolein, maleic anhydride, maleic acid, fumaric acid, abietic acid and the like.
- butadiene such as 1,4-butadiene, pentadiene, dicyclopentadiene, octadiene, olefinic petroleum fractions
- styrene vinyltoluene
- vinylchloride vinylbromide
- acrylonitrile methacrylonitrile
- acrylamide methacrylamide
- a preferred class of monomers for the purposes of the present invention are unsaturated carboxylic acids, esters, or salts thereof, particularly those included within the formula wherein R is an olefinically unsaturated organic radical, preferably containing from about 2 to about 30 carbon atoms, and R' is hydrogen, a salt-forming cation such as an alkali metal, alkaline earth metal or ammonium cation, or a saturated or ethylenically unsaturated hydrocarbon radical, preferably containing from 1 to about 30 carbon atoms, either unsubstituted or substituted with one or more halogen atoms, carboxylic acid groups and/or hydroxyl groups in which the hydroxyl hydrogens may be replaced with saturated and/or unsaturated acyl groups, the latter preferably containing from about 8 to about 30 carbon atoms.
- R is an olefinically unsaturated organic radical, preferably containing from about 2 to about 30 carbon atoms
- R' is hydrogen, a salt-forming
- Specific monomers conforming to the foregoing structural formula include unsaturated fatty acids such as oleic acid, linoleic acid, linolenic, ricinoleic, mono-, di- and tri-glycerides, and other esters of unsaturated fatty acids, acrylic acid, methyacrylic acid, methyl acrylate, ethylacrylate, ethylhexylacrylate, tertiarybutyl acrylate, oleylacrylate, methylmethacrylate, oleylmethacrylate, stearylacrylate, stearylmethacrylate, laurylmethacrylate, vinyl- stearate, vinylmyristate, vinyllaurate, soybean oil, dehydrated castor oil, tall oil, corn oil and the like.
- unsaturated fatty acids such as oleic acid, linoleic acid, linolenic, ricinoleic, mono-, di- and tri-glycer
- tall oil and corn oil are particularly advantageous.
- compositions containing compounds within the foregoing formula in addition containing, for example, saturated fatty acids such as palmitic, stearic, etc. are also contemplated herein.
- the amount of polymerizable monomer will vary depending upon the results desired. In general, however, monomer amounts of from about .0025 to about 2% by weight of carbonaceous materials are used.
- catalysts employed in the practice of the present invention are any such materials commonly used in polymerization reactions.
- any catalytic amount of those catalysts which are commonly referred to as free radical catalysts, or catalyst system (which can also be referred to as addition polymerization catalysts, vinyl polymerization catalysts or polymerization initiators) are preferred.
- catalysts contemplated herein include benzoyl peroxide, methylethyl ketone peroxide, tert-butylhydroperoxide, hydrogen peroxide, ammonium persulfate, di-tert-butylperoxide, tert-butylper- benzoate, peracetic acid and the like.
- free radical polymerization systems commonly employ free radical initiators which function to help initiate the free radical reaction.
- free radical initiators include, for example, sodium persulfate, potassium persulfate, silver acetate, ammonium persulfate, salts of noble metals such as platinum and gold, and salts of iron, zinc, arsenic, antimony, tin and cadmium.
- Particularly preferred initiators herein are copper salts, i.e.
- cuprous and cupric salts such as copper acetate, copper sulfate and copper nitrate. Most advantageous results can be obtained herein with cupric nitrate, Cu(N0 3 ) 2 .
- Other initiators contemplated herein include metal salts of naphthenates, tallates, octanoates, etc. said metals including copper, cobalt, mercury, chromium, manganese, nickel, tin, lead, zinc, iron, rare earth metals and mixtures thereof.
- the amounts of catalysts contemplated herein are within the range of 10 to 1000 ppm (based on the weight of the solid carbonaceous materials, such as dry coal).
- the amounts of water utilized in the various flotation zones and flotation recovery zones herein include from 65% to 95% based on the weight of carbonaceous material, such as dry coal.
- the coal resulting from reaction with the hereinbefore described polymerizable. mixture is extremely hydrophobic and oleophilic and consequently readily floats and separates from the aqueous phase.
- the floating hydrophobic coal is readily separable from the aqueous phase (for example, a skimming screen may be used for the separation) and can thereafter be readily introduced for further treatment as described hereinbefore.
- any of the zones illustrated in Figs. 1-3 may comprise a single vessel or zone or any number of vessels or zones arranged in a manner suitable and in accordance with carrying out the process of this invention as described herein. That is, for example, any number of high shear mix zones, flotation zones, etc. may be employed in series and arranged and employed in a monomer as shown herein in order to carry out the process of this invention.
- lignite coal 200 grams are pulverized in a wet . ball mill, containing 0.125% sodium carbonate, to 80%-200 mesh.
- the coal to water ratio in the pulverization zone is 1:2.
- 400 cc. of toluene and 200 ppm of cupric nitrate is added to the aqueous coal slurry.
- the entire admixture is placed in a blender and agitated under high shear conditions for 2-10 minutes.
- the blended admixture is removed from the blender and admixed with 4 litres of water in a flotation vessel or cell.
- the admixture is mixed for 4 minutes and the aqueous phase is drained from the vessel. 4 litres additional water is added to the vessel containing the coal froth and the mixture is agitated by the spray addition of further coal-aqueous slurry. This operation is repeated.
- THF tetrahydrofuran
- 50 grams of the vacuum dried coal is placed in a blender containing tetrahydrofuran (THF), 500 ppm copper naphthenate, 25 ppm hydrogen peroxide and 0.06% oleic acid.
- the mixture is high shear blended for 2-10 minutes.
- the resultant admixture is vacuum filtered.
- the filtrate is roto-vacuum dried to concentrate the extract (residual water and toluene separate, i.e. water is obtained at the bottom of the vacuum flasks and the toluene evaporates).
- THF tetrahydrofuran
- copper naphthenate copper naphthenate
- hydrogen peroxide und oleic acid in the amounts specified above and the mixture is high shear agitated.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Combustion & Propulsion (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Liquid Carbonaceous Fuels (AREA)
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82300449T ATE19649T1 (de) | 1981-01-29 | 1982-01-28 | Methode zur verbesserung, verfluessigung und wiedergewinnung von kohle und anderen festen kohlenstoffhaltigen materialien sowie verbesserte kohleprodukte. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23005281A | 1981-01-29 | 1981-01-29 | |
US230052 | 1994-04-19 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0057577A2 EP0057577A2 (fr) | 1982-08-11 |
EP0057577A3 EP0057577A3 (en) | 1983-11-30 |
EP0057577B1 true EP0057577B1 (fr) | 1986-05-07 |
Family
ID=22863765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82300449A Expired EP0057577B1 (fr) | 1981-01-29 | 1982-01-28 | Méthode pour l'amélioration, la liquéfaction et la récupération de charbon et d'autres matières carbonées solides, ainsi que les produits améliorés de charbon |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0057577B1 (fr) |
JP (1) | JPS57147596A (fr) |
AT (1) | ATE19649T1 (fr) |
AU (2) | AU551441B2 (fr) |
CA (1) | CA1175767A (fr) |
DE (1) | DE3270923D1 (fr) |
ZA (1) | ZA82214B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008000037A1 (fr) * | 2006-06-30 | 2008-01-03 | Newcastle Innovation Limited | Système et procédé de séparation |
WO2008025088A1 (fr) * | 2006-08-30 | 2008-03-06 | Ian Raymond Brake | Procédé de flottation de charbon |
WO2020117810A1 (fr) * | 2018-12-05 | 2020-06-11 | Controlamatics Corporation | Procédé de production de charbon propre par utilisation d'un prétraitement chimique et d'un réacteur à haut cisaillement |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4441889A (en) * | 1981-01-29 | 1984-04-10 | Gulf & Western Industries, Inc. | Coal-aqueous mixtures |
CA1194304A (fr) * | 1981-05-28 | 1985-10-01 | Lester E. Burgess | Charbon enrichi, ses melanges et leur production |
CA1214039A (fr) * | 1982-09-30 | 1986-11-18 | George E. Snow | Methode d'enrichissement des matieres houilleres par conditionnement sous forme de brassage intense de leurs melanges |
US4605420A (en) * | 1984-07-02 | 1986-08-12 | Sohio Alternate Energy Development Company | Method for the beneficiation of oxidized coal |
DE3426395A1 (de) * | 1984-07-18 | 1986-01-23 | Basf Ag, 6700 Ludwigshafen | Waessrige kohledispersionen |
US4605494A (en) * | 1984-09-14 | 1986-08-12 | Sohio Alternate Energy Development Co. | Multistream, multiproduct, pressure manipulation beneficiation arrangement |
US4597858A (en) * | 1984-09-14 | 1986-07-01 | Sohio Alternate Energy Development Co. | Multistream, multiproduct beneficiation arrangement |
ZA852350B (fr) * | 1985-03-28 | 1985-11-26 | ||
DE3562627D1 (en) * | 1985-10-23 | 1988-06-16 | Standard Oil Co Ohio | Method for the beneficiation of low rank coal and products obtained thereby |
CN102822346A (zh) | 2009-12-18 | 2012-12-12 | 西里斯能源公司 | 煤至甲烷和其它有用产物的生物气化 |
NZ603129A (en) * | 2010-04-21 | 2014-05-30 | Ciris Energy Inc | Solubilization of carbonaceous materials and conversion to hydrocarbons and other useful products |
WO2014015861A1 (fr) * | 2012-07-26 | 2014-01-30 | Studiengesellschaft Kohle Mbh | Procédé de liquefaction directe du charbon |
CA3209907C (fr) | 2016-04-04 | 2024-04-09 | Arq Ip Limited | Compositions et procedes de petrole brut solide-liquide |
CN112058500B (zh) * | 2020-07-29 | 2022-03-11 | 中钢集团马鞍山矿山研究总院股份有限公司 | 一种磁铁精矿浮选脱硫泡沫产品综合利用的选矿方法 |
CN112916195B (zh) * | 2021-03-11 | 2023-01-20 | 重庆工程职业技术学院 | 一种煤矿开采洗选设备 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017491A1 (fr) * | 1979-04-06 | 1980-10-15 | Mobil Oil Corporation | Procédé de fabrication de combustible solide pour petits fourneaux et combustible solide ainsi produit |
EP0032811A2 (fr) * | 1980-01-22 | 1981-07-29 | The Standard Oil Company | Procédé d'amélioration du charbon et charbon ainsi amélioré |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4165969A (en) * | 1973-02-23 | 1979-08-28 | Ashland Oil, Inc. | High carbon content liquid fuels |
US4033852A (en) * | 1975-06-26 | 1977-07-05 | Polygulf Associates | Process for treating coal and products produced thereby |
ZA763874B (en) * | 1975-07-03 | 1977-05-25 | American Minechem Corp | Method for transporting coal |
GB1575413A (en) * | 1976-12-03 | 1980-09-24 | Shell Int Research | Method for agglomeration of coal fines |
AU530672B2 (en) * | 1978-06-23 | 1983-07-28 | Broken Hill Proprietary Company Limited, The | Beneficiation and dewatering of slurries |
US4282004A (en) * | 1978-12-20 | 1981-08-04 | Atlantic Richfield Company | Process for agglomerating coal |
US4355999A (en) * | 1978-12-20 | 1982-10-26 | Atlantic Richfield Company | Process for agglomerating coal |
DE3064870D1 (en) * | 1979-03-05 | 1983-10-27 | Broken Hill Pty Co Ltd | Method of recovering coal by coal handling operations and system therefor |
US4284413A (en) * | 1979-12-26 | 1981-08-18 | Canadian Patents & Development Ltd. | In-line method for the beneficiation of coal and the formation of a coal-in-oil combustible fuel therefrom |
US4306883A (en) * | 1981-01-29 | 1981-12-22 | Gulf & Western Manufacturing Company | Process for forming coal-oil mixtures under selected conditions of temperature and shear |
-
1982
- 1982-01-13 AU AU79475/82A patent/AU551441B2/en not_active Ceased
- 1982-01-13 AU AU79476/82A patent/AU551442B2/en not_active Ceased
- 1982-01-13 ZA ZA82214A patent/ZA82214B/xx unknown
- 1982-01-28 AT AT82300449T patent/ATE19649T1/de not_active IP Right Cessation
- 1982-01-28 EP EP82300449A patent/EP0057577B1/fr not_active Expired
- 1982-01-28 DE DE8282300449T patent/DE3270923D1/de not_active Expired
- 1982-01-29 CA CA000395218A patent/CA1175767A/fr not_active Expired
- 1982-01-29 JP JP57014271A patent/JPS57147596A/ja active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017491A1 (fr) * | 1979-04-06 | 1980-10-15 | Mobil Oil Corporation | Procédé de fabrication de combustible solide pour petits fourneaux et combustible solide ainsi produit |
EP0032811A2 (fr) * | 1980-01-22 | 1981-07-29 | The Standard Oil Company | Procédé d'amélioration du charbon et charbon ainsi amélioré |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008000037A1 (fr) * | 2006-06-30 | 2008-01-03 | Newcastle Innovation Limited | Système et procédé de séparation |
AU2007264411B2 (en) * | 2006-06-30 | 2012-07-19 | Newcastle Innovation Limited | A separation process and system |
WO2008025088A1 (fr) * | 2006-08-30 | 2008-03-06 | Ian Raymond Brake | Procédé de flottation de charbon |
WO2020117810A1 (fr) * | 2018-12-05 | 2020-06-11 | Controlamatics Corporation | Procédé de production de charbon propre par utilisation d'un prétraitement chimique et d'un réacteur à haut cisaillement |
US11591534B2 (en) | 2018-12-05 | 2023-02-28 | Controlamatics Corporation | Process for producing clean coal using chemical pre-treatment and high shear reactor |
Also Published As
Publication number | Publication date |
---|---|
ZA82214B (en) | 1982-12-29 |
AU7947682A (en) | 1982-08-05 |
DE3270923D1 (en) | 1986-06-12 |
ATE19649T1 (de) | 1986-05-15 |
EP0057577A3 (en) | 1983-11-30 |
EP0057577A2 (fr) | 1982-08-11 |
CA1175767A (fr) | 1984-10-09 |
AU7947582A (en) | 1982-08-05 |
AU551441B2 (en) | 1986-05-01 |
AU551442B2 (en) | 1986-05-01 |
JPS57147596A (en) | 1982-09-11 |
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