EP0106130B1 - Coal-aqueous mixtures and process for preparing same - Google Patents
Coal-aqueous mixtures and process for preparing same Download PDFInfo
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- EP0106130B1 EP0106130B1 EP83108876A EP83108876A EP0106130B1 EP 0106130 B1 EP0106130 B1 EP 0106130B1 EP 83108876 A EP83108876 A EP 83108876A EP 83108876 A EP83108876 A EP 83108876A EP 0106130 B1 EP0106130 B1 EP 0106130B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003245 coal Substances 0.000 claims description 123
- 239000002245 particle Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- -1 glycol oleate ester Chemical class 0.000 claims description 26
- 239000004094 surface-active agent Substances 0.000 claims description 26
- 239000002736 nonionic surfactant Substances 0.000 claims description 21
- 239000002562 thickening agent Substances 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 claims description 4
- 229920001285 xanthan gum Polymers 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
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- 235000010493 xanthan gum Nutrition 0.000 claims description 3
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- 229920002907 Guar gum Polymers 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
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- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 229940095098 glycol oleate Drugs 0.000 claims 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 25
- 239000007787 solid Substances 0.000 abstract description 18
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- 229920000642 polymer Polymers 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 8
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- 239000000126 substance Substances 0.000 description 7
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- 238000011282 treatment Methods 0.000 description 6
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- 125000005263 alkylenediamine group Chemical group 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
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- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002359 Tetronic® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MUQFNNWFNCSSEJ-UHFFFAOYSA-N CN(C)[N](C)(C)OC Chemical compound CN(C)[N](C)(C)OC MUQFNNWFNCSSEJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
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- 229920000881 Modified starch Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000003995 emulsifying agent Substances 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229920013746 hydrophilic polyethylene oxide Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229920013818 hydroxypropyl guar gum Polymers 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Classifications
-
- 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
Definitions
- the present invention relates to a method for forming coal-aqueous mixtures.
- Coal as an energy source is in abundant supply. It is estimated that in the United States there is more energy available in coal than in petroleum, natural gas, oil shale and tar sands combined. The substitution of coal for natural gas and oil on a large scale would therefore seem a ready-made solution to our energy problems. Unfortunately, however, unlike oil and gas consumption, coal use is limited not by reserves or production capacity but rather by the extraordinary industrial and regulatory difficulties of burning it in a convenient, efficient and environmentally acceptable manner.
- a number of techniques are being explored to provide coal as a more useful energy source.
- One such technique employs gasification methods such as destructive distillation, to effect the conversion of coal to a gas of low or medium calorific value.
- gasification methods such as destructive distillation, to effect the conversion of coal to a gas of low or medium calorific value.
- high pressure hydrogenation is utilized to liquefy coal to make it more suited for transport, burning and the like.
- Another technique suggested, and the one to which the present invention relates, is the technique whereby solid coal particles are dispersed in a fluid carrier medium, such as fuel oil or water to form coal-aqueous or coal-oil mixtures.
- Coal-oil and coal-aqueous mixtures are distinct systems, each having its own difficulties of formulation.
- coal and oil are relatively compatible, coal and water are not.
- the initial dispersing of the coal in the continuous water phase especially large amounts of coal, represents a challenging obstacle.
- stabilizing i.e. keeping the coal from settling out of the water phase, must be also achieved.
- coal mixtures offer considerable advantages. They are more readily transported than dry solid coal, are more easily stored and are less subject to the risks of explosion by spontaneous ignition, the latter being a significanat factor in handling coal.
- providing coal in a fluid form can permit its burning in apparatus normally used for buring fuel oil. This can greatly facilitate the transition from fuel oil to coal as a primary energy source, another highly desirable result.
- U.S. Patent No. 4,251,229 is an example of coal-oil mixtures stabilized with high molecular weight adducts of alkylene oxide and an alcohol, an amine, a carboxylic acid or phenol having at least three active hydrogens.
- oil is the continuous carrier phase and accordingly, the stabilization of the coal, as emphasized repeatedly therein, in the continuous oil phase, is essentially the only concern.
- U.S. Patent No. 4,242,098 discloses aqueous coal slurry compositions containing water soluble polymers, which are thickeners, such as xanthan gum, hydroxypropyl guar gum or poly(ethylene oxide) having a molecular weight over 100,000.
- United States Patent No. 4,217,109 discloses a technique for cleaning and dispersing coal in water utilizing dispersing agents which by selective adsorption impart different electrical charges to the carbon particles and the impurities.
- the dispersing agents taught are polyelectrolytes, such as alkali metal and ammonium salts of polycarboxylic acids and polyphosphates.
- U.S. Patent No. 4,358,293 dated November 9, 1982 discloses the surprising discovery that certain polyalkyleneoxide nonionic surfactants are excellent additives for forming coal-aqueous mixtures having high coal solids concentrations. It is also disclosed therein that polyalkyleneoxide nonionic surfactants of high molecular weight having a hydrophobic portion, and a hydrophilic portion, the hydrophilic portion being comprised of at least about 100 ethylene oxide repeating units, provide coal-water dispersions having very high coal solids concentrations of about 70% by weight coal, or higher, when the surfactant is present in an amount sufficient to disperse the particulate coal in water.
- the resultant mixtures are free- flowing and are adapted to provide coal in a form ready for transport, storage and clean-burning.
- the surfactants employed can differ in chemical structure so long as they are of the selected type, are of sufficient molecular weight and are comprised of at least about 100 units of ethylene oxide.
- coal-aqueous slurries prepared in accordance with the present invention are characterized by high solids content, excellent long term storage stability and other advantages which will become apparent hereinafter.
- the present invention relates to a method for forming a coal-aqueous mixture in which a polyalkylene oxide non-ionic surfactant having a hydrophobic portion and hydrophilic portion, said hydrophilic portion being comprised of at least 100 units of ethylene oxide is admixed under stirring with water and particulate coal is admixed thereto under further agitating, characterized in that (i) the admixing of the surfactant with water is effected under low speed agitation conditions (500 to 1500 rpm), (ii) the admixing of the particulate coal to the admixture resulting from step (i) is effected under medium speed agitation conditions (1000 to 3000 rpm), and (iii) the resultant coal containing the mixture of step (ii) is agitated under high speed conditions (3000 to 6000 rpm).
- coal-aqueous slurries obtained by the present invention are comprised of coal or other carbonaceous material as the dispersed solid; water as the carrier medium; and a polyalkyleneoxide nonionic surfactant, as further described herein.
- polyalkyleneoxide nonionic surfactant connotes all compositions, compounds, mixtures, polymers, etc. having in whole or in part an alkylene oxide repeating unit of the structure: and having a hydrophobic portion and a hydrophilic portion and which does not dissociate or ionize in solution.
- These surfactants have a polymeric portion comprised of repeating units of ethylene oxide of the general formula:
- polyalkyleneoxidè nonionic surfactant compositions employed in this invention are of high molecular weight, i.e., 4,000 or higher, depending on the particular surfactant employed, are hydrophilic and are comprised of at least 100 repeating units of the ethylene oxide monomer.
- the surfactants utilized have a hydrophobic portion and a hydrophilic portion and are nonionic. Being nonionic, these compositions are generally not subject to ionization in aqueous solutions of acid or alkali.
- Suitable hydrophilic polyalkyleneoxide nonionic surfactants for use in this invention are the commercially available glycol ethers of alkyl phenols of the following general formula I: wherein R is substituted or unsubstituted alkyl of from 1 to 18 carbon atoms, preferably 9 carbon atoms; substituted or unsubstituted aryl, or an amino group and n is an integer of at least 100.
- nonionic surfactants are available in a wide array of molecular weights depending primarily on the value of "n", i.e., the number of ethylene oxide repeating units. Surprisingly, it has been found that these surfactants of a high molecular weight of 4,000 or higher wherein "n" is at least 100, or higher are particularly effective as dispersants for forming coal-aqueous mixtures to high coal solids concentration requiring little if any further additives, to form highly flowable liquids.
- glycol ethers of formula I Procedures for the preparation of the glycol ethers of formula I are well known and are described, for example, in United States Patents Nos. 2,213,477 and 2,496,582. Generally, the production of these compositions involves the condensation of substituted phenols with molar proportions of ethylene oxide monomer.
- polyalkyleneoxide nonionic surfactants suitable for use in the invention include the glycol ethers of alkylated phenols having a molecular weight of at least 4,000 of the general formula: wherein R is substituted or unsubstituted alkyl of from 1 to 18 carbon atoms, preferably 9 carbon atoms; substituted or unsubstituted aryl, or an amino group, and n is an integer of at least 100.
- the substituents of the alkyl and aryl radicals can include halogen, hydroxy, and the like.
- nonionic surfactants are the poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) or, as otherwise described, propoxylated, ethoxylated propylene glycol nonionic surfactant block polymers having a molecular weight of at least 6,000 of the general formula: wherein a, b and c are whole integers and wherein a and c total at least 100.
- Still other polyalkyleneoxide nonionic surfactants suitable for use in the invention are the block polymers of ethylene and propylene oxide derived from nitrogen-containing compositions such as ethylene diamine and having a molecular weight of at least 14,000 of the general formula: wherein Ri is an alkylene radical having 2 to 5 carbon atoms, preferably 2; R 2 is alkylene radical having 3 to 5 carbon atoms, preferably 3; a, b, c, d, e, f, g and h are whole integers; and e, f, g and h total at least 100.
- the coal-aqueous mixture compositions of the invention herein are characterized by having a high coal solids content and a relatively low viscosity of 2,000 to 6,000 mPa-S (2,000 to 6,000 centipoise) or lower as measured, e.g., in a Brookfield viscometer, model #RVT, fitted with a number 3 spindle, at 100 r.p.m. even at solids level of 70% by weight, or higher, based oon the total weight of the mixture.
- These compositions can also include amounts of conventional flow modifying materials, such as thickeners, glues, defoaming agents, salts, etc., depending upon the use intended.
- the products of the invention contain only minor amounts of surfactant additives in the order of 0.1 to 3.0 percent by weight. They further contain particulate coal as the dispersed solid in an amount from 45 to 80 percent; water as the carrier medium in an amount of from 19.9 to 52 percent and, if desired, from 0.1 to 2 percent of a thickener or thickeners; 0.01 to 2 percent of a defoaming agent and 0.1 to 2 percent of salts, anti-bacterial agents, caustic or other additive flow control agents, all of the percentages given being based on the total weight of the mixture.
- glycol ethers of the type generally described in formula I are the nonylphenoxy(polyethyleneoxy)ethanol compositions of the formula: wherein n is 100 or higher.
- surfactants of this type are supplied by the GAF Corporation under the designations IGEPAL O CO-990 and IGEPAL O CO-997.
- Other commercially available surfactants of this type are supplied by the Thompson-Hayward Chemical Co. under the designation T-Det @ N-1 00, and Whitestone Chemical Co. under the designation ICONOL O NP-100.
- polyalkyleneoxide nonionic surfactants useful in the invention are the well known poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) nonionic surfactant block polymers.
- These surfactants comprise the block polymers of ethylene oxide and propylene oxide with the repeating units of propylene oxide constituting the hydrophobic portion of the surfactant, and the repeating units of ethylene oxide constituting the hydrophilic portion of the surfactant.
- block polymer compositions are of the general formula II: wherein a, b and c are whole integers and wherein a and c total at least 100.
- compositions can be prepared, and are commercially available, in a variety of molecular weights, depending primarily on the number of repeating units of propylene and ethylene oxide. It has been found that these block polymers having a molecular weight of at least 6,000 and comprising at least 100 repeating units of ethylene oxide are excellent additives for dispersing coal in a water carrier to the desired high coal solids concentrations of 45 to 80 percent, preferably about 70 percent coal particles, based on the weight of the total mixture.
- poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) nonionic surfactants suitable for use in the invention are those wherein a, b and c are integers and a and c total 100 or higher.
- these block polymers are prepared by a controlled addition of propylene oxide to the two hydroxyl groups of propylene glycol to form the hydrophobe, followed by the controlled addition of ethylene oxide to "sandwich" in the hydrophobe between the two hydrophilic polyethyleneoxide groups.
- nonionic surfactants of this type (Formula II having the requisite number of at least 100 units of ethylene oxide are available from the BASF-Wyandotte Corporation under the PLURONIC * designation, Series Nos. F-77, F-87, F-68, F-88, F-127, F-98, and F-108. These compositions have at least 100 ethylene oxide units, as per the following table of these PLURONIC surfactants:
- a further group of polyalkyleneoxide nonionic surfactants suitable as coal dispersants herein are the nitrogen containing block polymers of the general formula III: wherein R 1 is an alkylene radical having 2 to 5 carbon atoms, preferably 2; R 2 is alkylene radical having 3 to 5 carbon atoms, preferably 3; a, b, c, d, e, f, g and h are whole integers; and e, f, g and h total at least 100.
- These materials are prepared by the addition of a C 3 to C s alkylene oxide to an alkylene diamine under conditions to add two polyoxyalkylene groups to each of the nitrogen groups in the presence of a catalyst so as to polymerize the oxyalkylene groups into the desired long-chained polyoxyalkylene radicals.
- ethylene oxide is introduced and is added to the polyoxyalkylene groups to impart the desired hydrophilic characteristics to the compound.
- the agents are prepared by mixing the C 3 to C 5 alkylene oxide with the alkylene diamine at atmospheric or elevated pressures, at temperatures between about 50 to 150° centigrade and in the presence of an alkaline catalyst such as an alkali metal hydroxide or alcoholate.
- an alkaline catalyst such as an alkali metal hydroxide or alcoholate.
- the degree of polymerization or the size of the hydrophobic group is controlled by the relative proportions of C 3 to C s alkylene oxide and alkylene diamine, the alkylene oxide being introduced in a sufficient quantity to obtain a hydrophobic base weight of 2000 to 3600 units although other weights can be provided.
- compositions having the requisite number of at least 100 ethylene oxide repeating units are available from the BASF Wyandotte Chemicals Corporation under the TETRONIC@ designations Series Nos. 1107; 1307; 908 and 1508. These compositions have at least 100 ethylene oxide units, as per the following table of these TETRONIC surfactants.
- coals Any of a wide array of coals can be used to form the coal-aqueous mixtures of the invention, including anthracite, bituminous, sub-bituminous, mine tailings, fines, lignite and the like.
- Other finely divided solid carbonaceous materials may also be used, e.g., coke, prepared either from coal or from petroleum.
- coal is pulverized to approximately 90% finer than 0.044 mm (200 mech Tyler Standard screen size), although courser or finer particle sizes can be employed, if desired.
- the untreated pulverized raw coal is beneficiated, i.e., cleaned of amounts of ash and sulfur.
- beneficiated coal i.e., cleaned of amounts of ash and sulfur.
- mixtures formed of beneficiated coal offer considerable advantage. They are clean burning or relatively clean burning, and are more suited for burning in apparatus for powering utilities, home burners and the like without undue burdensome and expensive cleaning apparatus.
- any of a wide array of beneficiating treatments can be employed in preparing the particulate coals, including conventional heavy-media separations, magnetic seperation and the like.
- the preferred method for providing the beneficiated coal particles is by a chemical treatment process such as described in U.S. Patent No. 4,304,573.
- raw as-mined coal is ground in the presence of water to a particle size of about 200 mesh.
- the ground coal is treated in an aqueous medium with a monomeric compound, generally an unsaturated polymerizable composition such as readily available tall oil fatty acids in the presence of a metal initiator such as cupric nitrate; and minor amounts of fuel oil, all in an aqueous phase are also present.
- the ground coal so treated is made hydrophobic and oleophilic and is separated from the unwanted ash and sulfur by a froth flotation technique.
- the cleaned coal recovered from the preferred chemical treatment process now in the form of beneficiated coal particles, is suited for the coal-aqueous mixtures of the invention.
- These coal particles are characterized by having an ash content reduced to levels of 0.5 to 6.0% and a sulfur content reduced to levels of 0.5 to 2.0%.
- coal-aqueous mixture by first adding the surfactant to water together with other additives such as conventional defoaming agents, if desired. This admixing can be done with stirring at conditions of atmospheric or nearly atmospheric temperature and pressure. Thereafter, the particulate coal, preferably beneficiated coal particles, is added to the mixture to produce a coal-aqueous mixture of high coal solids content of 45 to 80% by weight coal, based on the total weight of the mixture at atmospheric or nearly atmospheric temperatures and pressures. If desired, thickeners can then be added to further stabilize the mixture to assist in preventing the coal particles from settling when the mixture is to be stored for extended periods.
- additives such as conventional defoaming agents
- the coal-aqueous mixtures can be prepared in a batch operation or in the continuous mode. In continuous production, the coal can be admixed with water in a first stage along with other flow control agents such as the surfactant. The compositions of the first stage can then be transferred continuously to a second stage wherein the thickener is added. Again, adding the thickener at the later stage results in reduced stirring requirements.
- the surfactant and other additives such as conventional defoaming agents, if desired, are first added to water and mixed, under low speed agitation conditions (500 rpm to 1500 rpm, preferably 1000 rpm) for a time of from 30 seconds to 3 minutes, preferably about 1 minute.
- the particulate coal preferably beneficiated coal particles
- moderate or medium agitation conditions 1000 rpm to 3000 rpm, preferably about 2000 rpm
- this time is in the range of from 5 minutes to 20 minutes.
- the agitation of the admixture is increased to a high speed (3000 rpm to 6000 rpm, preferably about 4000 rpm) for a time sufficient to disperse the coal, usually from 5 minutes to 15 minutes, preferably about 10 minutes.
- thickeners are then added to the slurry under the afore-described high speed agitation conditions, e.g. 4000 rpm, for a further time of from 1 minute to 3 minutes, preferably about 2 minutes.
- other ingredients such as viscosity stabilizers and antibacterial agents are then added to the formulation at said high speed agitation for a further time of from 1 minute to 3 minutes, preferably about 2 minutes.
- wetted out or wet as used herein it is meant that the surface of each coal particle is covered with water.
- Typical mixing or dispersiong apparatus employed herein include for example Premier Mill Co.'s Hi-Vispersator O High-Speed Disperser.
- the coal is allowed to be dispersed in a surfactant/antifoam solution at relatively low viscosity, while the surfactant is orienting at the coal-water interface.
- the anti-foam agent controls the level of foam caused by the surfactant being agitated in solution.
- the thickeners are added after the coal is adequately dispersed to impart the desired rheological and suspension properties from flocculating by forming a protective colloid.
- additives that can be added to the coal-aqueous mixture include defoaming agents, thickeners, salts, bases, other flow modifying agents and combinations of these materials.
- the defoaming agents that can be used are conventional and include both silicon and non- silicon containing compositions.
- a commercially available defoaming agent suitable for use in the mixtures is COLLOID 691, supplied by Colloids, Inc. This composition generally comprises a mixture containing mineral oil, amide and an ester.
- Thickeners can also be added to the mixture. They are added to increase the non-settling characteristics of the composition. Suitable thickeners include, for example, xanthum gum, guar gum, glue and the like. Other thickeners include, for example, alkali soluble acrylic polymers (e.g. ACRYSOL@ ICS-1 sold by the Rohm and Haas Company). Combinations of these thickeners are also contemplated herein. For the purposes herein, the thickeners are generally used in amounts ranging from 0.01 to 3.0% by weight, based on the total weight of the mixture.
- the polyalkyleneoxide nonionic surfactants are preferably mixed with water in a proportion of about 0.3 part by weight surfactant to 29.3, parts by weight, water at atmospheric or nearly atmospheric temperatures and pressures.
- a defoaming agent is also added to the water in an amount of about 0.03, part by weight, to assist in processing.
- the pulverized coal is then mixed with the water in a proportion of 70 parts by weight coal to 29.3 parts by weight of water to obtain a flowable liquid. If desired, to the mixture can then be added 0.12 to 0.15, part by weight, of thickener or thickeners to provide protection against settling.
- additives such as salts or bases, antibacterial agents such as formaldehyde, and the like, viscosity stabilizers, such as ammonia, can also be added in 0.2 to 0.3, part by weight, of the total mixture to further assist in dispersing the coal and providing the other obvious advantages.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- the following formulation is used to prepare an aqueous coal slurry in accordance with the improvement of the present invention.
- a high-speed disperser namely a High-Vispersator is used to stir, mix and disperse the materials into a stable homogeneous slurry.
- Ingredients 1, 2 and 3 are stirred together for one minute at low speed (1,000 rpm).
- the coal is added to this solution at medium speed (2,000 rpm) for a sufficient time to wet the coal particles and disperse the coal in ingredients 1, 2 and 3.
- the speed of the disperser is increased to high speed (4,000 rpm) for 10 minutes to further disperse the coal particles.
- Ingredients 5 and 6 are then added with the disperser at high speed. After two minutes ingredients 7 and 8 are added and the batch is considered complete after an additional two minutes of mixing at high speed. All mixing is carried out at atmospheric temperatures and pressures.
- coal-aqueous mixtures are readily provided having significantly high solid concentrations.
- the mixtures can be provided in a clean form ready for burning in utility burners, home burners and the like with little if any need for additional cleaning to remove ash and sulfur.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Carbon And Carbon Compounds (AREA)
- Devices That Are Associated With Refrigeration Equipment (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83108876T ATE33397T1 (de) | 1982-09-10 | 1983-09-08 | Waessrige gemische von kohlen und verfahren zu deren herstellung. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/416,606 US4441889A (en) | 1981-01-29 | 1982-09-10 | Coal-aqueous mixtures |
US416606 | 1989-10-10 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0106130A2 EP0106130A2 (en) | 1984-04-25 |
EP0106130A3 EP0106130A3 (en) | 1985-05-02 |
EP0106130B1 true EP0106130B1 (en) | 1988-04-06 |
Family
ID=23650620
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83108876A Expired EP0106130B1 (en) | 1982-09-10 | 1983-09-08 | Coal-aqueous mixtures and process for preparing same |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0106130B1 (da) |
JP (1) | JPS5964696A (da) |
AT (1) | ATE33397T1 (da) |
CA (1) | CA1200697A (da) |
DE (1) | DE3376219D1 (da) |
DK (1) | DK162654C (da) |
ES (1) | ES8502470A1 (da) |
GR (1) | GR79060B (da) |
PT (1) | PT77319B (da) |
ZA (1) | ZA836671B (da) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2178057A (en) * | 1985-07-19 | 1987-02-04 | Coal Ind | Improvements in slurries |
US5000872A (en) * | 1987-10-27 | 1991-03-19 | Canadian Occidental Petroleum, Ltd. | Surfactant requirements for the low-shear formation of water continuous emulsions from heavy crude oil |
US5263848A (en) * | 1986-11-24 | 1993-11-23 | Canadian Occidental Petroleum, Ltd. | Preparation of oil-in-aqueous phase emulsion and removing contaminants by burning |
US4978365A (en) * | 1986-11-24 | 1990-12-18 | Canadian Occidental Petroleum Ltd. | Preparation of improved stable crude oil transport emulsions |
US4983319A (en) * | 1986-11-24 | 1991-01-08 | Canadian Occidental Petroleum Ltd. | Preparation of low-viscosity improved stable crude oil transport emulsions |
US5083613A (en) * | 1989-02-14 | 1992-01-28 | Canadian Occidental Petroleum, Ltd. | Process for producing bitumen |
US5156652A (en) * | 1986-12-05 | 1992-10-20 | Canadian Occidental Petroleum Ltd. | Low-temperature pipeline emulsion transportation enhancement |
US4966235A (en) * | 1988-07-14 | 1990-10-30 | Canadian Occidental Petroleum Ltd. | In situ application of high temperature resistant surfactants to produce water continuous emulsions for improved crude recovery |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4358293A (en) * | 1981-01-29 | 1982-11-09 | Gulf & Western Manufacturing Co. | Coal-aqueous mixtures |
-
1983
- 1983-09-02 CA CA000436054A patent/CA1200697A/en not_active Expired
- 1983-09-07 ES ES525431A patent/ES8502470A1/es not_active Expired
- 1983-09-08 EP EP83108876A patent/EP0106130B1/en not_active Expired
- 1983-09-08 AT AT83108876T patent/ATE33397T1/de active
- 1983-09-08 DE DE8383108876T patent/DE3376219D1/de not_active Expired
- 1983-09-08 ZA ZA836671A patent/ZA836671B/xx unknown
- 1983-09-09 JP JP58165349A patent/JPS5964696A/ja active Granted
- 1983-09-09 PT PT77319A patent/PT77319B/pt not_active IP Right Cessation
- 1983-09-09 GR GR72414A patent/GR79060B/el unknown
- 1983-09-09 DK DK409683A patent/DK162654C/da not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DK409683A (da) | 1984-03-11 |
PT77319A (en) | 1983-10-01 |
JPH0316997B2 (da) | 1991-03-06 |
GR79060B (da) | 1984-10-02 |
ATE33397T1 (de) | 1988-04-15 |
DK162654B (da) | 1991-11-25 |
ES525431A0 (es) | 1985-01-16 |
EP0106130A2 (en) | 1984-04-25 |
CA1200697A (en) | 1986-02-18 |
PT77319B (en) | 1986-02-06 |
JPS5964696A (ja) | 1984-04-12 |
DK409683D0 (da) | 1983-09-09 |
ES8502470A1 (es) | 1985-01-16 |
ZA836671B (en) | 1984-04-25 |
EP0106130A3 (en) | 1985-05-02 |
DE3376219D1 (en) | 1988-05-11 |
DK162654C (da) | 1992-04-13 |
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