EP0057577B1 - Method for the beneficiation, liquefaction and recovery of coal and other solid carbonaceous materials and beneficiated coal products - Google Patents
Method for the beneficiation, liquefaction and recovery of coal and other solid carbonaceous materials and beneficiated coal products Download PDFInfo
- Publication number
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- coal
- froth
- zone
- process according
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003245 coal Substances 0.000 title claims abstract description 173
- 238000000034 method Methods 0.000 title claims abstract description 80
- 239000007787 solid Substances 0.000 title claims abstract description 25
- 238000011084 recovery Methods 0.000 title description 24
- 239000003575 carbonaceous material Substances 0.000 title description 9
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 230000008569 process Effects 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000000284 extract Substances 0.000 claims abstract description 14
- 239000002609 medium Substances 0.000 claims abstract description 13
- 239000012736 aqueous medium Substances 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 40
- 238000005188 flotation Methods 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 26
- 239000000446 fuel Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 239000008346 aqueous phase Substances 0.000 claims description 22
- 238000009291 froth flotation Methods 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 239000004449 solid propellant Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000002685 polymerization catalyst Substances 0.000 abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 10
- 239000007921 spray Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 239000003209 petroleum derivative Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 239000003077 lignite Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010742 number 1 fuel oil Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 e.g. Substances 0.000 description 3
- 239000011953 free-radical catalyst Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003250 coal slurry Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 239000011135 tin Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Chemical class 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010038743 Restlessness Diseases 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- BXOBFMUWVVHLFK-QXMHVHEDSA-N [(z)-octadec-9-enyl] 2-methylprop-2-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)C(C)=C BXOBFMUWVVHLFK-QXMHVHEDSA-N 0.000 description 1
- ASAPXSLRMDUMFX-QXMHVHEDSA-N [(z)-octadec-9-enyl] prop-2-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)C=C ASAPXSLRMDUMFX-QXMHVHEDSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical class [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Chemical class 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- XSSIBEAEHKRFSG-UHFFFAOYSA-N cyclohexane;pyridine Chemical compound C1CCCCC1.C1=CC=NC=C1 XSSIBEAEHKRFSG-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003828 free initiator Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000005609 naphthenate group Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical class 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000003476 subbituminous coal Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- FHYUCVWDMABHHH-UHFFFAOYSA-N toluene;1,2-xylene Chemical compound CC1=CC=CC=C1.CC1=CC=CC=C1C FHYUCVWDMABHHH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
- 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.
- Known resources of coal and other solid carbonaceous fuel materials in the world are far greater than the known resources of petroleum and natural gas combined. Despite this enormous abundance of coal and related solid carbonaceous materials, reliance on these resources, particularly coal, as primary sources of energy, has been for the most part discouraged. The availability of cheaper, cleaner burning, more easily retrievable and transportable fuels, such as petroleum and natural gas, has in the past cast coal to a largely supporting role in the energy field.
- Current world events, however, have forced a new awareness of global energy requirements and of the availability of those resources which will adequately meet these needs. The realization that reserves of petroleum and natural gas are being rapidly depleted in conjunction with rising petroleum and natural gas prices and the unrest in the regions of the world which contain the largest quantities of these resources, has sparked a new interest in the utilization of solid carbonaceous materials, particularly coal, as primary energy sources.
- As a result, enormous efforts are being extended to make coal and related solid carbonaceous materials equivalent or better sources of energy than petroleum or natural gas. In the case of coal, for example, much of this effort is directed to overcome the environmental problems associated with its production, transportation and combustion. For example, health and safety hazards associated with coal mining have been significantly reduced with the onset of new legislation governing coal mining. Furthermore, numerous techniques have been explored and developed to make coal cleaner burning, more suitable for burning and more readily transportable.
- Gasification and liquefaction of coal are two such known techniques. Detailed descriptions of various coal gasification and liquefaction processes may be found, for example, in the Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition (1980) Volume 11, pages 410-422 and 449-473. Typically, these techniques, however, require high energy input, as well as the utilization of high temperature and high pressure equipment, thereby reducing their widespread feasibility and value.
- Processes to make coal more readily liquefiable have also been developed. One such process is disclosed in U.S. Patent No. 4,033,852. This process involves chemically modifying the molecular structure of the coal, the effect of which alters its morphology and thus renders a portion of the coal more readily liquefiable than the natural forms of coal.
- In addition to gasification and liquefaction, other methods for converting coal to more convenient forms for burning and transporting are also known. For example, the preparation of coal-oil and coal-aqueous mixtures are described in the literature. Such liquid coal mixtures offer considerable advantages. In addition to being more readily transportable than dry solid coal, they are more easily storable, and less subject to the risks of explosion by spontaneous ignition. Moreover, providing coal in a fluid form makes it feasible for burning in conventional apparatus used for burning fuel oil. Such a capability can greatly facilitate the transition from fuel oil to coal as a primary energy source. Typical coal-oil and coal-aqueous mixtures and their prepration are disclosed in U.S. Patent No. 3,762,887, U.S. Patent No. 3,617,095 and U.S. Patent No. 4,217,109 and British Patent No. 1,523,193.
- 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.
- Accordingly, chemical as well as physical coal cleaning (beneficiation) processes have been extensively employed. In general, physical coal cleaning processes involve pulverizing the coal to release the impurities, wherein the fineness of the coal generally governs the degree to which the impurities are released. However, because the costs of preparing the coal rise exponentially with the amount of fines produced, there is an economic optimum in size reduction. Based on the physical properties that effect the separation of the coal from the impurities, physical coal cleaning methods are generally divided into four categories; gravity, flotation, magnetic and electrical methods.
- In contrast to physical coal cleaning, 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.
- A recent promising development in the art of chemical coal benefication is disclosed in our copending European Patent application No. 81300152.6 (Publication No. 0032811), and in United States Government Report No. 2694 entitled "Fuel Extension by Dispersion of Clean Coal in Fuel Oil". In summary, according to this coal benefication process, 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. Moreover, the 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.
- In any coal cleaning process, whether it by physical or chemical, the recovery of maximum yields of useable product is always an important economic concern. Much effort has also been devoted to the recovery of the huge amounts of residual coal.
- One recovery method, for example, which has been developed is the 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. However, 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.
- Accordingly, other methods for the improved beneficiation and enhanced recovery of coal, including residual coal fines, would obviously be very desirable. Of particular importance is a method which not only provides for an improved beneficiated product in high yield but also which is suitable for the beneficiation and good recovery of low rank coals not normally suitable for beneficiation. In addition, other processes for the liquefaction of coal would also be welcome, not to mention the desirability for a process which has the capability of achieving all the aforementioned goals but also provides for the liquefaction of coal and moreover the recovery of clean liquefiéld coal product.
- 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.
- Other embodiments herein are achieved by 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.
- In a particularly preferred technique 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.
- In yet another modification, 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.
- The process of this invention is further described with reference to the accompanying drawings in which:
- Figure 1 is a block diagram illustrating one embodiment of the process of the present invention.
- Figure 2 is another block diagram illustrating a preferred embodiment of the process of the present invention.
- Fig. 3 is a further block diagram schematically illustrating another preferred embodiment of the present invention.
- Fig. 4 is a schematic illustration of a preferred vessel in which raw coal is subjected to surface treatment and/or froth flotation according to the present process.
- Referring to the drawing, Fig. 1 illustrates the basic sequence of steps for carrying out processes of the present invention. Thus, in the practice 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. As shown in Fig. 1, 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 throughconduit 21 where the raw coal is pulverized and initially cleaned, usually in the presence of water, which may be introduced throughline 23. The coal is ground employing conventional equipment, such as, for example, ball or rod mills. It is generally desirable, although not necessary to the present process, to employ certain water conditioning or treating additives in the pulverization operation. Such additives assist in rendering the ash more hydrophilic, which facilitates the separation thereof. Typical additives which can be introduced through aseparate line 25 or through either oflines - 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. In any event, for the purpose of this invention, it 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. Typically, 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. Thus, for the purposes of this invention, the term "coal" is also intended to include these kinds of other solid carbonaceous fuel materials. Moreover, it has been found herein that 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 throughconduit 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 ofreagent tanks - Thus, the beneficiated coal recovered from
zone 12, vialine 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. Generally, 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. For the purposes of this invention, benzene and toluene are preferred, toluene being most preferred. It has been found that the presence of the organic liquid such as toluene, in the highshear mix zone 12, increases the recovery of clean coal by up to about 30%. Other additives and/or reagents including monomer, catalyst (described in greater detail hereinafter) may also be added to the high shear mix zone, if desired, by means of any oftanks - 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. This is accomplished in accordance with the process outlined by Fig. 2. Thus, referring to Fig. 2, the coal containing mixture exiting highshear mix zone 12 is fed to afirst flotation zone 14 throughline 31. Inflotation zone 14; the coal-organic liquid mixture is contacted and admixed with an aqueous medium. This aqueous medium inflotation zone 14 may comprise simply water or in addition to water other surface treating additives may be present. That is, for example, the aqueous medium offlotation 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 throughlines zone 14 such as vialine 39. This organic liquid may be the same or different from that employed in highshear mix zone 12; preferably, it is the same. - In a preferred embodiment of the present invention, the coal containing mixture from
zone 12 is sprayed, most preferably through a pressure spray nozzle, intoflotation 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 intoflotation zone 14 such as through line 33 (water), 35 (monomer) 37 (catalyst) and 39 (catalyst initiator). Frothing takes place inflotation 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 inzone 14 or any of flotation and flotation recovery zones employed in the present process. In this unit, the coal-organic liquid mixture is sprayed into the vessel throughline 29 and throughspray nozzle 61. The treating reagents may be added by way oflines - 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. Briefly, according to this method 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 tofurther flotation zone 16 throughline 41 for further cleaning. Concomitantly, the aqueous phase remaining inzone 14, which contains residual coal particles or fines and ash, is removed fromzone 14 and sent toflotation recovery zone 20 throughline 43. Similar to the manner described hereinbefore for the introduction of materials tozone 14, the aqueous phase fromzone 14 is preferably fed tozone 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 fromzone 14 into the aqueous medium ofzone 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. - In furtherence of the process of the present invention and as shown in Fig. 2, the coal froth phase which ensues in
zone 20 is recovered therefrom throughline 45 and recycled to eitherpulverization zone 10 or high shear mix zone 12 (not illustrated) or directly toflotation zone 14 via line 31 (as shown) for further treatment therein. The aqueous phase resulting inzone 20 may be drawn off and sent to a waste disposal unit (not illustrated) or preferably is fed to afurther recovery zone 22 as shown. Frothing and/or flotation aids, which assist in the formation of small air bubbles, may be added torecovery zone - In the continuance of the process herein, the coal froth phase from
zone 14 is, at the same time, introduced to afurther flotation zone 16, again preferably through pressure spray nozzles, inline 41.Zone 16 is also comprised of an aqueous medium. The coal froth phase, which forms inzone 16 is separated from the aqueous phase which is also formed inzone 16, and preferably introduced to athird flotation zone 18, throughline 47, as shown in Fig. 2. Likeflotation zones zone 18 is also comprised of an aqueous medium. Thus a coal froth phase and an aqueous phase also ensues inzone 18. - The coal froth phase is skimmed from
flotation zone 18 and then may be fed throughline 83 to a dryingzone 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. - Simultaneous with the continuous formation, separation and removal of the coal froth phases from
zones zone 16 is recycled tozone 14 in a countercurrently flowing stream vialine 49, whereby residual coal particles are again subjected to treatment inzone 14. Similarly, the aqueous phase inzone 18, is recycled in a countercurrently flowing stream vialine 51 to zone 16 for further processing therein. At the same time, as described before, the aqueous phase fromzone 14 is continuously removed therefrom and introduced toflotation recovery zone 20 by way ofline 43. As indicated before, the resultant coal froth phase inzone 20 is removed therefrom and recycled toflotation zone 14 for further treatment by way oflines zone 20 is continuously removed and preferably fed to secondflotation recovery zone 22 throughline 53. The coal froth phase which ensues inzone 22 is removed therefrom and is continuously recycled in counter-current flowing stream torecovery zone 20 vialine 55. The aqueous phase inzone 22 is disposed of vialine 57 and typically sent to awaste treatment unit 44 as depicted in Fig. 3. - While water may be the only ingredient utilized in the aqueous mediums contained in
flotation zones flotation recovery zones zones zones 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. - Furthermore, the 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.
- Alternatively and preferably in another embodiment of the present invention, 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. - Thus, referring to Fig. 3, the super clean coal from
zone 18, either before drying or after drying, is fed vialine 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. After admixture in zone 24, the resultant product is fed vialine 101 to aseparation zone 26, commonly a centrifuge, wherein the liquids fraction is separated from the solids fraction. - The organic liquid employed in the extraction procedure (in any of
zones 24, 28 or 32) may be water insoluble such as those used inzone 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 asolvent removal zone 34, illustratively shown as an evaporator unit, throughline 61. The solids portion fromzone 26 is introduced vialine 103 to a further highshear 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 ofzones zone 28 is fed vialine 105 to aseparation zone 30 wherein the liquids fraction is separated from solids. The liquids portion is sent tosolvent removal zone 34 vialine 63 and the solids portion is fed vialine 107 to a third highshear 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 inzone zone 32 is fed throughline 67 to aseparation zone 95 wherein the liquids fraction is separated from solids. The liquids portion is sent, vialine 65, tosolvent 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 atline 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. Generally, to remove residual solvent, the product is forwarded to asolvent removal zone 36, such as a steam distillation unit. The resultant drysolid 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%. - As shown in Fig. 3, 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 vialine 71 may be collected in a condensingzone 38 wherein the condensed solvent is then recycled by way ofline 73 to aholding tank 40 whereby solvent contained therein is recycled vialine 75 to highshear mix zone 12. Solvent removed inzone 36 is sent back to highshear mix zone lines zone 42. Water coming fromwaste treatment unit 44 is recycled to holdingtank 40 vialine 79, which water is in turn recycled topulverization zone 10 vialine 81. - Any polmerizable monomer can be employed in the process herein where so specified. While it is more convenient to utilize monomers which are liquid at ambient temperature and pressure, gaseous monomers which contain olefinic unsaturation permitting polymerization with the same or different molecules can be used. Thus, monomers intended to be employed herein may be characterized by the formula XHC=CHX' wherein X and X' each may be hydrogen or any of a wide variety of organic radicals or inorganic substituents. Illustratively, 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.
- 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
- 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.
- The catalysts employed in the practice of the present invention are any such materials commonly used in polymerization reactions. Typically, for the purposes of this invention, 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. Thus, illustratively, 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.
- Moreover, free radical polymerization systems commonly employ free radical initiators which function to help initiate the free radical reaction. For the purposes herein, any of those disclosed in the prior art, particularly those disclosed, for example, in U.S. Patent No. 4,033,852, incorporated herein by reference, may be used. Specifically, some of these 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(N03)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 soluble or water insoluble liquid organic mediums utilized herein in the various zones 0.25 to 2% based on the weight of solid carbonaceous material, 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.
- All percentages hereinabove are based on the weight of dry coal unless otherwise specified.
- 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.
- It is also to be understood herein that 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.
- In order that those skilled in the art may better understand how the present invention is practiced, the following Example is presented by way of illustration and not by way of limitation.
- 200 grams of lignite coal 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. No. 2 fuel, (.25%) oleic acid (0.125%), hydrogen peroxide (200 ppm) and 100 ppm of methyl isobutylcarbinol (frothing agent). 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.
- All the recovered coal froth phases are combined and vacuum filtered.
- 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). To the remaining filter cake is added THF, copper naphthenate, hydrogen peroxide und oleic acid in the amounts specified above and the mixture is high shear agitated. (In the alternative, only THF need be used or THF and catalyst and/or initiator, etc.).' The extraction procedure, i.e. vacuum drying, as described before is carried out. This high shear procedure is carried out 3 more times. The liquid extracts are combined, and the solid residual coal portion is finally dried under vacuum, thereby recovering the THF which can be recycled for use in the extraction procedure. All percentages and ppm in this example are based on the weight of dry coal in the process.
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82300449T ATE19649T1 (en) | 1981-01-29 | 1982-01-28 | METHOD OF IMPROVING, LIQUEFICATION AND RECOVERY OF COAL AND OTHER SOLID CARBON-CONTAINING MATERIALS AND IMPROVED CARBON PRODUCTS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23005281A | 1981-01-29 | 1981-01-29 | |
US230052 | 1981-01-29 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0057577A2 EP0057577A2 (en) | 1982-08-11 |
EP0057577A3 EP0057577A3 (en) | 1983-11-30 |
EP0057577B1 true EP0057577B1 (en) | 1986-05-07 |
Family
ID=22863765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82300449A Expired EP0057577B1 (en) | 1981-01-29 | 1982-01-28 | Method for the beneficiation, liquefaction and recovery of coal and other solid carbonaceous materials and beneficiated coal products |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0057577B1 (en) |
JP (1) | JPS57147596A (en) |
AT (1) | ATE19649T1 (en) |
AU (2) | AU551441B2 (en) |
CA (1) | CA1175767A (en) |
DE (1) | DE3270923D1 (en) |
ZA (1) | ZA82214B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008000037A1 (en) * | 2006-06-30 | 2008-01-03 | Newcastle Innovation Limited | A separation process and system |
WO2008025088A1 (en) * | 2006-08-30 | 2008-03-06 | Ian Raymond Brake | Coal flotation method |
WO2020117810A1 (en) * | 2018-12-05 | 2020-06-11 | Controlamatics Corporation | A process for producing clean coal using chemical pre-treatment and high shear reactor |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0219569B1 (en) * | 1985-10-23 | 1988-05-11 | The Standard Oil Company | Method for the beneficiation of low rank coal and products obtained thereby |
US4441889A (en) * | 1981-01-29 | 1984-04-10 | Gulf & Western Industries, Inc. | Coal-aqueous mixtures |
CA1194304A (en) * | 1981-05-28 | 1985-10-01 | Lester E. Burgess | Beneficiated coal, coal mixtures and processes for the production thereof |
CA1214039A (en) * | 1982-09-30 | 1986-11-18 | George E. Snow | Process for the beneficiation of carbonaceous matter employing high shear conditioning |
US4605420A (en) * | 1984-07-02 | 1986-08-12 | Sohio Alternate Energy Development Company | Method for the beneficiation of oxidized coal |
DE3426395A1 (en) * | 1984-07-18 | 1986-01-23 | Basf Ag, 6700 Ludwigshafen | AQUEOUS COAL DISPERSIONS |
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 (en) * | 1985-03-28 | 1985-11-26 | ||
WO2011075163A1 (en) | 2009-12-18 | 2011-06-23 | Ciris Energy, Inc. | Biogasification of coal to methane and other useful products |
SG184940A1 (en) * | 2010-04-21 | 2012-11-29 | Ciris Energy Inc | Solubilization of carbonaceous materials and conversion to hydrocarbons and other useful products |
DE102013107865A1 (en) * | 2012-07-26 | 2014-01-30 | Studiengesellschaft Kohle Mbh | Process for direct coal liquefaction |
WO2017174973A1 (en) * | 2016-04-04 | 2017-10-12 | Allard Services Ltd | Solid-liquid crude oil compositions and fractionation processes thereof |
CN112058500B (en) * | 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 | Beneficiation method for comprehensively utilizing magnetite concentrate flotation desulfurization foam products |
CN112916195B (en) * | 2021-03-11 | 2023-01-20 | 重庆工程职业技术学院 | Coal mining washing equipment |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017491A1 (en) * | 1979-04-06 | 1980-10-15 | Mobil Oil Corporation | Method for producing a solid fuel for small furnaces and solid fuel produced thereby |
EP0032811A2 (en) * | 1980-01-22 | 1981-07-29 | The Standard Oil Company | A process for the beneficiation of coal and beneficiated coal product |
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 |
US4355999A (en) * | 1978-12-20 | 1982-10-26 | Atlantic Richfield Company | Process for agglomerating coal |
US4282004A (en) * | 1978-12-20 | 1981-08-04 | Atlantic Richfield Company | Process for agglomerating coal |
EP0015736B1 (en) * | 1979-03-05 | 1983-09-21 | The Broken Hill Proprietary Company Limited | 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 ZA ZA82214A patent/ZA82214B/en unknown
- 1982-01-13 AU AU79475/82A patent/AU551441B2/en not_active Ceased
- 1982-01-13 AU AU79476/82A patent/AU551442B2/en not_active Ceased
- 1982-01-28 AT AT82300449T patent/ATE19649T1/en not_active IP Right Cessation
- 1982-01-28 DE DE8282300449T patent/DE3270923D1/en not_active Expired
- 1982-01-28 EP EP82300449A patent/EP0057577B1/en not_active Expired
- 1982-01-29 JP JP57014271A patent/JPS57147596A/en active Pending
- 1982-01-29 CA CA000395218A patent/CA1175767A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017491A1 (en) * | 1979-04-06 | 1980-10-15 | Mobil Oil Corporation | Method for producing a solid fuel for small furnaces and solid fuel produced thereby |
EP0032811A2 (en) * | 1980-01-22 | 1981-07-29 | The Standard Oil Company | A process for the beneficiation of coal and beneficiated coal product |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008000037A1 (en) * | 2006-06-30 | 2008-01-03 | Newcastle Innovation Limited | A separation process and system |
AU2007264411B2 (en) * | 2006-06-30 | 2012-07-19 | Newcastle Innovation Limited | A separation process and system |
WO2008025088A1 (en) * | 2006-08-30 | 2008-03-06 | Ian Raymond Brake | Coal flotation method |
WO2020117810A1 (en) * | 2018-12-05 | 2020-06-11 | Controlamatics Corporation | A process for producing clean coal using chemical pre-treatment and high shear reactor |
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 |
---|---|
CA1175767A (en) | 1984-10-09 |
JPS57147596A (en) | 1982-09-11 |
AU7947582A (en) | 1982-08-05 |
AU7947682A (en) | 1982-08-05 |
EP0057577A2 (en) | 1982-08-11 |
DE3270923D1 (en) | 1986-06-12 |
ZA82214B (en) | 1982-12-29 |
AU551442B2 (en) | 1986-05-01 |
EP0057577A3 (en) | 1983-11-30 |
AU551441B2 (en) | 1986-05-01 |
ATE19649T1 (en) | 1986-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4671801A (en) | Method for the beneficiation, liquefaction and recovery of coal and other solid carbonaceous materials | |
US4412843A (en) | Beneficiated coal, coal mixtures and processes for the production thereof | |
EP0057577B1 (en) | Method for the beneficiation, liquefaction and recovery of coal and other solid carbonaceous materials and beneficiated coal products | |
EP0057575B1 (en) | Method of forming stabilized coal-oil mixtures | |
US4564369A (en) | Apparatus for the enhanced separation of impurities from coal | |
US4406664A (en) | Process for the enhanced separation of impurities from coal and coal products produced therefrom | |
US4632750A (en) | Process for coal beneficiation by froth flotation employing pretreated water | |
JPH0138538B2 (en) | ||
US4583990A (en) | Method for the beneficiation of low rank coal | |
US4526585A (en) | Beneficiated coal, coal mixtures and processes for the production thereof | |
CA1214039A (en) | Process for the beneficiation of carbonaceous matter employing high shear conditioning | |
US4859318A (en) | Recovering coal fines | |
US4605420A (en) | Method for the beneficiation of oxidized coal | |
EP0066066B1 (en) | Beneficiated coal, coal mixtures and processes for the production thereof and an arrangement for producing a beneficiated coal product | |
EP0032811B1 (en) | A process for the beneficiation of coal and beneficiated coal product | |
EP0219569B1 (en) | Method for the beneficiation of low rank coal and products obtained thereby | |
CA1231689A (en) | Apparatus for the beneficiation of coal | |
EP0197164A1 (en) | Process for beneficiating coal employing low amounts of additives | |
JPH0453589B2 (en) | ||
JPS62106854A (en) | Coal preparation method of lower coal | |
NO851205L (en) | PROCEDURE FOR CREATING COALS. | |
NO854111L (en) | PROCEDURE FOR ENRICHING LOW QUALITY LOVE. | |
JPS61234961A (en) | Coal classification method using small amount of additive | |
JPS5898397A (en) | Coal deashing and granulation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE DE FR GB IT NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Designated state(s): AT BE DE FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19840503 |
|
ITF | It: translation for a ep patent filed | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: THE STANDARD OIL COMPANY |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE FR GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 19649 Country of ref document: AT Date of ref document: 19860515 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3270923 Country of ref document: DE Date of ref document: 19860612 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19891222 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19891229 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19891231 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19900115 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900125 Year of fee payment: 9 |
|
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19900131 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19900509 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19910128 Ref country code: AT Effective date: 19910128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19910129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19910131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19910801 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19910930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19911001 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
EUG | Se: european patent has lapsed |
Ref document number: 82300449.4 Effective date: 19910910 |