CN102482582A - 煤的催化提取方法 - Google Patents
煤的催化提取方法 Download PDFInfo
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- CN102482582A CN102482582A CN2010800382627A CN201080038262A CN102482582A CN 102482582 A CN102482582 A CN 102482582A CN 2010800382627 A CN2010800382627 A CN 2010800382627A CN 201080038262 A CN201080038262 A CN 201080038262A CN 102482582 A CN102482582 A CN 102482582A
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- Prior art keywords
- coal
- coke
- solvent
- catalyzer
- pitch
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 91
- 239000003245 coal Substances 0.000 title claims abstract description 89
- 238000000605 extraction Methods 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000011135 tin Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 239000010948 rhodium Substances 0.000 claims abstract description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052699 polonium Inorganic materials 0.000 claims abstract description 5
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- 239000011669 selenium Substances 0.000 claims abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000000571 coke Substances 0.000 claims description 65
- 239000011331 needle coke Substances 0.000 claims description 32
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- 239000011305 binder pitch Substances 0.000 claims description 10
- 239000011302 mesophase pitch Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
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- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 64
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- 239000000284 extract Substances 0.000 description 37
- 239000002994 raw material Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 26
- 239000011280 coal tar Substances 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 19
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- 239000003921 oil Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000003610 charcoal Substances 0.000 description 9
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- 238000006555 catalytic reaction Methods 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 230000003111 delayed effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
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- 238000004231 fluid catalytic cracking Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002010 green coke Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
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- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 230000001737 promoting effect Effects 0.000 description 2
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- 238000013517 stratification Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 230000006378 damage Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
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- 238000005272 metallurgy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- -1 thomel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
- C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/02—Multi-step carbonising or coking processes
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
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- C04B2235/40—Metallic constituents or additives not added as binding phase
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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Abstract
用于由煤的提取生产碳材料的方法,所述方法包括形成煤、溶剂和催化剂的混合物,所述催化剂选自钼、锡、钛、锆、铪、钍、硒、碲、钋、铁、钴、镍、钌、铑、钯、锇、铱、铂、含有任何前述元素的催化-活性化合物和配位化合物、和它们的组合和混合物。
Description
本发明以授予号DE-FC26-03NT41874在美国能源部(DOE)的支持下作出。政府对本发明具有某些权利。然而,本文表述的任何主张、发现、结论或建议为申请人的,并且不必然反映DOE的观点。
发明背景
技术领域
本发明涉及可用于包括生产石墨电极、特种石墨或碳阳极的应用的焦炭。更具体地,本发明涉及一种用于由煤的溶剂提取物生产具有所选的热膨胀系数(CTE)的焦炭的方法,所述焦炭用作呈现期望的热膨胀系数的石墨产品的原料。
背景技术
碳电极(尤其是石墨电极)在钢工业中用于熔融在电-热炉中用于形成钢的金属和补充成分两者。通过将电流通过至少一个(更通常,多个)电极并在电极和金属之间形成电弧,产生熔融基材金属所需的热量。通常使用超过100,000安培的电流。同样,在铝熔炼操作中采用碳阳极,并起到引导电流通过铝土矿或其它铝矿到阴极床的作用。
石墨电极以及碳阳极和特种石墨的制造需要选择煅烧的焦炭填料和粘合剂如沥青,用于有效和经济的操作。通常,将焦炭填料与粘合剂混合、成型和烘焙,以形成单个的固体物质。常规级别的焦炭或海绵焦炭适于铝工业中的碳阳极,并且必须满足某些要求,包括硫、灰分和金属含量低。特别关注钒和镍的存在,它们可充当氧化催化剂。由于碳阳极在电解产生铝金属中被消耗,在全球基础上需要大量优质焦炭。在石墨电极中使用的焦炭具有必须建立长程订单(order)的额外要求。由于它们的高度结晶性质,这些焦炭看起来是针状的。虽然比起碳阳极,石墨电极以较小的规模生产,但是它们仍然是钢和其它金属工业的关键商品。
石墨电极通常使用针状焦炭填料与沥青粘合剂组合来制造。针状焦炭为具有针状、各向异性微观结构的焦炭品级。目前用于生产如石墨电极和碳阳极的制品的大多数焦炭作为在石油精炼厂中通过延迟焦化方法得到的副产物而生产。延迟焦化可通过热降解机理将多种重石油馏分转化为馏出物燃料,其中碳在延迟焦化器的内腔上沉积。虽然在延迟焦化器操作期间的工艺条件可影响焦炭的品质,但是重要的考虑是液体进料的化学性质和组成。仅某些石油馏分会可靠地生产期望的焦炭。这通过以下事实证明:在延迟焦化器中生产的焦炭中仅约四分之一可看作阳极级别并且小得多的百分比可看作针状级别。
石墨电极所需的高度取向(或“各向异性”)的焦炭由相对低API比重的高级芳族油生产。比起更加脂族的原料,这些油还倾向于更高的焦炭产率。
为了产生可承受期望的超高功率处理量的石墨电极,针状焦炭必须具有低电阻率和低热膨胀系数(CTE),同时当石墨化时还能生产相对高强度制品。针状焦炭指定的CTE值常规如下测定:将已研磨,煅烧的焦炭与沥青粘合剂混合,挤出焦炭/沥青共混物以形成电极,接着热处理电极至约3000℃,以使电极石墨化。随后对石墨化的电极测量CTE值。
针状焦炭的特定的性质主要取决于原料的选择,在一定程度上取决于其中将适当的碳原料转化为焦炭的焦化方法中的参数控制。通常,通过级别水平系统进行针状焦炭的分类,所述级别水平作为在某个温度范围内CTE的函数而区分。例如,高级针状焦炭通常分类为在约100℃-约400℃的温度范围内具有小于约1.00×10-6/℃的平均CTE,而常规级别针状焦炭在约100℃-约400℃的温度范围内具有约1.00×10-6/℃-约1.25×10-6/℃的平均CTE。使用膨胀计或电容方法(描述于G.Wagoner等人,Carbon Conference 1986 Proceedings,第234页,Baden-Baden,1986),在挤出(即,纵向)方向测量使用焦炭填料生产的石墨化电极的CTE值。
如上所述,为了将针状焦炭转化为石墨,应通常在约2000℃-约3500℃的范围将含有针状焦炭的制品(例如,电极)加热,以将针状焦炭转化为石墨结晶结构,同时消除挥发性杂质。这种杂质不利地提高所形成的石墨电极的CTE,并且当施加电流时可导致电极膨胀。膨胀将改变电极的电弧放电性质,使得该方法不太有效或可能导致电极破裂。
适用于高性能石墨电极的低CTE针状焦炭主要由石油-衍生的原料生产。出于该目的,原料应为高度芳族的,在焦化后提供良好的碳收率,并且灰分和不熔化的固体非常低。通常在石油针状焦炭的生产中,流体催化裂化(FCC)倾析油用作含有约0.02%-约0.04%重量的灰分的原料。灰分的主要组成是由倾析油的初始裂化剩余的FCC催化剂。该FCC催化剂提高所得到的电极的热膨胀特性,从而必须除去催化剂用于由石油针状焦炭生产低CTE石墨电极。结果是,许多个体已开发了除去灰分颗粒的方法,以降低所得到的电极的CTE。例如,在Eguchi等人的美国专利号5,695,631中公开了一种用于生产石油针状焦炭的方法,该方法包括过滤、离心和/或静电聚集,以从倾析油中除去实质部分的FCC催化剂。
虽然使用基于石油的针状焦炭可导致形成具有较低CTE的石墨电极,但是使用基于石油的针状焦炭具有显著的缺点。一种该缺点为由于石油价格持续上涨,石油-衍生的针状焦炭可能短缺。此外,适用于产生低CTE石墨电极的石油针状焦炭的供应商少并且有限。另外,由于为了从倾析油中除去显著部分的灰分所需的过滤,石油针状焦炭的成本被推向更高。
一种不同的方法为使用基于煤的原料来提供用于石墨电极的针状焦炭。在该方法中,煤焦油由用于从煤生产冶金焦炭的焦化方法衍生。煤焦油作为塔顶馏出物产品得到,并且含有不熔化的碳质固体,该不熔化的碳质固体通过基于气体的碳化以及由于煤移行(carryover)而形成。这些剩余的固体干扰形成针状焦炭时大区域中间相的产生,转而导致形成高CTE焦炭。
尽管存在这些固体,由于煤焦油高度芳族并且具有高碳收率,煤焦油是用于生产焦炭的期望的原料。通过修改的康拉逊残炭(MCC)测试测定,煤焦油的碳收率通常为约10%-约30%。然而,为了由煤焦油得到低CTE焦炭,必须采用物理固体分离方法来除去构成焦油的最多10%的不期望的固体。
其中已从用于制备针状焦炭的煤焦油中除去固体的实例包括Misao等人的日本专利号JP19850263700,其中将喹啉-不溶性组分从用于延迟焦化以生产针状焦炭的煤焦油和/或煤焦油沥青中除去。
在Masayoshi等人(德国专利号DE3347352)中,描述了一种用于生产针状焦炭的方法,其中在氢化催化剂存在下,通过氢化纯化煤焦油原料,直至达到至少15%重量的脱氮比率。
不利用煤焦油,已开发了利用煤焦油馏出物来生产中间相沥青的方法。Lewis等人的美国专利号4,317,809描述了一种其中在450℃下在750psig下将煤焦油馏出物加热5小时以形成中间相沥青的方法。中间相沥青的总产率低于期望,并且对于用于工业延迟焦化方法,认为所用的压力太高,工业延迟焦化方法通常在低于约100psig操作。
如美国专利号4,176,043中所描述的,可制备粘合剂沥青,其中将来自石油原料的高-芳族残余馏分与煤焦油馏分以1∶9-9∶1的重量比混合,并加热。在一个类似的方法中,将裂化油残余物与煤焦油沥青混合,随后使混合物在超过350℃的温度下经受热处理。裂化油残余物的软化点大于60℃,而煤焦油沥青的软化点大于80℃。在加热期间,将混合物保持与脱氢剂接触。
还可使用煤的溶剂提取完成焦炭和沥青的生产,其包括目的是向溶液中引入大多数煤块用于生产合成燃料的宽范围的方法或技术。最相关的方法不同地称为提取化学崩解、煤的溶剂提取或直接煤液化。在超过约350℃条件下和在适当的溶剂中,煤可转化为油或焦油样材料,适于作为焦炭原料。不变地,煤提取需要煤的碳与氢原子比降低,这可通过多种方式完成。煤升级越广泛,则其越可以形似沥青,并且由其衍生的焦炭越各向异性。
因此,期望由原料煤生产碳材料的溶剂提取方法,所述碳材料比如用于低CTE石墨电极的针状焦炭、具有所选的CTE的其它类型的焦炭、粘合剂或浸渍沥青包括中间相沥青、海绵焦炭和碳纤维,所述方法提供更大的效率、提高的碳材料生产速率和更高的产率。
发明概述
本公开提供了一种通过煤的溶剂提取独特地能够经济地生产期望的碳材料比如焦炭或沥青的方法。所公开的方法提供了催化提取,比起迄今为止观察到的方法,提供了更大的效率、提高了的碳材料生产速率和更高的产率。在一个实施方案中,所述方法生产针状焦炭,当掺入到例如石墨电极或碳阳极中时,在加热时耐膨胀,提供了改进的热稳定性和降低的CTE。
更具体地,所述方法涉及在催化剂存在下使用溶剂(比如芳族或氢化芳族烃)由煤进行提取。另外,所述溶剂可为非芳族烃。提高煤进入溶剂的溶解速率并且提供煤碎片升级措施的合适的催化剂的实例可包括钼、铁和锡的化合物。在所公开的方法中其它合适的催化剂包括周期表的任何IVa族金属元素:周期表的VIb族元素铬、钼和钨;和周期表的VIII族元素:铁、钴、镍、钌、铑、钯、锇、铱和铂;和Ib和IIb族元素比如铜和锌。合适的催化剂还包括催化-活性化合物和配位化合物以及含有任何前述物质的它们的任何组合。
在本公开方法的实践中,在催化剂存在下,将煤与溶剂混合。在一个实施方案中,将煤碾磨或另外研磨成为颗粒,以促进提取。在一个优选的实施方案中,煤应为颗粒形式,该颗粒的平均直径使得至少50%将通过100US目筛。在某些实施方案中,至少70%的煤颗粒将通过80US目筛。
通常,实现煤提取的溶剂和催化剂的量可取决于由其提取成分的煤的量和尺寸和用于实现提取的加工设备。例如,在一些实施方案中,溶剂与煤的重量比为约1∶1-约5∶1。在一个具体的实施方案中,溶剂与煤的重量比为约1∶1-约2∶1;在其它实施方案中,溶剂与煤的重量比为约2∶1-约5∶1。当煤的粒径使得至少70%的煤颗粒将通过80US目筛时,溶剂与煤的重量比需要仅为约2∶1-约5∶1。
同样,与当不存在催化剂采用的方法相比,采用的催化剂的量应为改进提取效率、生产速率或收率和足够的升级水平所需的量。催化剂与煤的重量比可为约0.01∶100-约5∶100。通常,催化剂与煤的重量比为约5∶100-约1∶100;在其它实施方案中,催化剂与煤的重量比为约0.1∶100-约0.01∶100。
在某些实施方案中,在溶剂和催化剂存在下,在涉及升高的温度(即,至少约325℃的温度)的反应条件下发生提取。通常,温度不必高于约500℃。另外,在某些实施方案中,在大气压下实现提取;在其它实施方案中,在升高的压力下实现提取,即,最高约5000psi(即,约340大气压)的压力。
此外,在某些实施方案中,在氢气气氛或惰性气氛(比如氮气)中实现提取反应。
通常,提取方法进行至少约0.5小时的时间;在优选的实施方案中,需要不大于约1小时从煤中提取显著量的期望的成分。在某个实际的实例中,催化剂的存在提供了在小于约1小时,更优选小于约0.5小时内,从煤中提取至少约85%,更优选最高约90%的期望的成分(即,提取物本身)。
因此,本公开的一方面是一种用于从煤中催化-中介的溶剂提取的方法。
本公开的另一方面是一种用于产生碳材料的方法,所述碳材料如用于低CTE石墨电极的针状焦炭、粘合剂或浸渍沥青,包括中间相沥青、海绵焦炭和碳纤维。
本公开的再一方面是一种用于煤的催化提取的方法,所述方法提供了更大的效率,提高的生产速率,以及碳材料的升级和更高的产率。
本公开的又一方面是一种用于从煤产生具有选择的CTE的焦炭的方法。
本公开的再一方面是一种使用所公开的方法,使用碳材料如针状焦炭和粘合剂和/或浸渍沥青,产生低CTE石墨电极的方法。
这些方面以及专业技术人员熟悉的其它方面,在一个实施方案中,焦炭可通过用于由煤的提取生产碳材料的方法而得到,所述方法包括形成煤、溶剂和催化剂的混合物,所述催化剂选自钒、铬、钼、钨、铁、钴、镍、铜、锌、锡和含有任何前述元素的催化-活性化合物和配位化合物、和它们的组合和混合物。
在又一实施方案中,这些方面以及专业技术人员熟悉的其它方面可通过以下方法而得到,所述方法包括通过以下由煤的催化提取生产煤提取物:形成煤、溶剂和催化剂的混合物,所述催化剂选自钼、锡、钛、锆、铪、钍、硒、碲、钋、铁、钴、镍、钌、铑、钯、锇、铱、铂、铬、钨、铜、锌、金、银、汞、含有任何前述元素的催化-活性化合物和配位化合物、和它们的组合和混合物;在加压下加热煤提取物,以得到原料焦炭;煅烧原料焦炭,以产生具有选择的热膨胀系数的焦炭;碾磨焦炭;将研磨的焦炭与煤焦油粘合剂沥青混合,以产生混合物;挤出混合物,以形成生料;烘焙生料,以产生烘焙的原料;和使烘焙的原料石墨化,以产生具有选择的热膨胀系数的石墨制品。
在又一实施方案中,这些方面以及专业技术人员熟悉的其它方面可通过以下方法而得到,所述方法包括通过以下由煤的催化提取生产煤提取物来生产具有选择的热膨胀系数的石墨产品:形成煤、溶剂和催化剂的混合物,所述催化剂选自钼、锡、钛、锆、铪、钍、硒、碲、钋、铁、钴、镍、钌、铑、钯、锇、铱、铂、铬、钨、铜、锌、金、银、汞、含有任何前述元素的催化-活性化合物和配位化合物、和它们的组合和混合物;在加压下加热煤提取物,以得到原料焦炭;煅烧原料焦炭,以产生具有选择的热膨胀系数的焦炭;碾磨焦炭;将研磨的焦炭与煤焦油粘合剂沥青混合,以产生混合物;挤出混合物,以形成生料;烘焙生料,以产生烘焙的原料;和使烘焙的原料石墨化,以产生具有选择的热膨胀系数的石墨产品。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中所述溶剂包含一种或多种烃。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中所述提取步骤在至少约325℃的温度下实现。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中所述提取步骤在约325℃-约500℃的温度下实现。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中所述提取步骤在最高约5000psi的压力下实现。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中所述提取步骤在氢气或惰性气体气氛中实现。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中提取步骤的溶剂与煤的比率为约1∶1-约5∶1。
本公开的又一方面是一种用于生产具有选择的热膨胀系数的石墨产品的方法,其中提取步骤的催化剂与煤的比率为约0.01∶1-约5∶100。
在又一实施方案中,这些方面以及专业技术人员熟悉的其它方面可通过产生具有选择的热膨胀系数的石墨制品的方法而得到,所述方法包括形成煤、溶剂和催化剂的混合物,所述催化剂选自钼、锡、钛、锆、铪、钍、硒、碲、钋、铁、钴、镍、钌、铑、钯、锇、铱、铂、铬、钨、铜、锌、金、银、汞、含有任何前述元素的催化-活性化合物和配位化合物、和它们的组合和混合物;提取混合物,从而形成煤提取;和在加压下加热煤提取物,以得到原料焦炭。
本公开的又一方面是一种用于通过以下生产具有选择的热膨胀系数的石墨产品的方法:煅烧原料焦炭,以产生具有选择的热膨胀系数的焦炭。
本公开的又一方面是一种用于通过碾磨焦炭来生产具有选择的热膨胀系数的石墨产品的方法。
本公开的又一方面是一种用于通过以下生产具有选择的热膨胀系数的石墨产品的方法:将研磨的焦炭与煤焦油粘合剂沥青混合,以产生混合物。
本公开的又一方面是一种用于通过以下生产具有选择的热膨胀系数的石墨产品的方法:挤出混合物,以形成生料。
本公开的又一方面是一种用于通过以下生产具有选择的热膨胀系数的石墨产品的方法:烘焙生料,以产生烘焙的制品;和使烘焙的制品石墨化,以产生具有选择的热膨胀系数的制品。
应理解的是,前述总的描述和以下详细描述两者提供了本公开的实施方案,并且旨在提供对要求保护的本发明的性质和特性的理解的综述或框架。
优选实施方案的详述
如上所述,在本公开方法的实践中,在催化剂存在下,将煤与溶剂(比如芳族、非芳族或氢化芳族烃)混合。采用的催化剂可包括任何钼、铁、锡、周期表的任何IVa族的过渡金属元素、周期表的VIb族的主族元素和周期表的VIII族元素,以及含有任何前述元素的催化-活性化合物和配位化合物。在一个优选的实施方案中,所述催化剂为钼。
在一个实施方案中,将煤碾磨或另外研磨成为颗粒,以促进提取。在一个优选的实施方案中,煤应为颗粒形式,该颗粒的平均直径使得至少50%将通过100US目筛。在某些实施方案中,至少70%的煤颗粒将通过80US目筛。实现煤提取的溶剂和催化剂的量可有利地取决于由其提取成分的煤的量和尺寸和用于实现提取的加工设备。例如,在一些实施方案中,溶剂与煤的重量比为约1∶1-约2∶1;在其它实施方案中,溶剂与煤的重量比为约2∶1-约5∶1。当煤的粒径使得至少70%的煤颗粒将通过80US目筛时,溶剂与煤的重量比需要仅为约2∶1-约5∶1。同样,与不存在催化剂时采用的方法相比,采用的催化剂的量应为改进提取效率、生产速率或收率所需的量。通常,催化剂与煤的重量比为约1∶100-约5∶100;在其它实施方案中,催化剂与煤的重量比为约0.1∶100-约0.01∶100。
在溶剂和催化剂存在下,在涉及升高的温度(即,约325℃-约500℃的温度)的反应条件下发生提取。另外,在大气压力和约5000psi(即,约340大气压)之间的压力下实现提取。提取气氛可为氢气气氛或惰性气氛(比如氮气)。
在一些实施方案中,提取方法进行至少约0.5小时的时间;在优选的实施方案中,需要不大于约1小时从煤中提取显著量的期望的成分;实际上,催化剂的存在提供了在小于约1小时内从煤中提取至少约85%的期望的成分。
在提取方法之后,将混合物所暴露的任何升高的压力和/或温度释放;此外,如果不是在空气中实现提取,则将混合物从气氛中移除。随后使所得到的混合物经受分离方法,其中将固体从混合物的液体成分分离。该分离方法可涉及通过合适的过滤介质进行过滤、沉降、离心分离等。实际上,分离方法可包括多于一种前述技术。
在分离方法之后可回收溶剂和催化剂,并再循环或再利用。
煤提取物为重烃,其可用作原料用于产生具有所选CTE的碳材料。在某些实施方案中,第一步是选择具有相对高初始沸点的煤提取物。煤提取物的沸点可大于约280℃。此外,相对高沸点煤提取物应具有至少1%的焦化值,焦化值通过MCC测定。在选择相对高沸点煤提取物之后,煤提取物经历碳化步骤,其中施加压力和温度两者。将提取物材料加热至约450℃-约525℃的温度,温度优选约475℃。该温度通过以下达到:通过以约35℃/小时-约65℃/小时的速率逐步提高煤提取物的温度,在分批焦化操作中加热提取物,在一个具体的实施方案中,温度提高速率优选为约50℃/小时。一旦达到提取物材料的前述温度,将煤提取物在焦化容器中保持在该温度下约16小时-约25小时。在较低的特定温度下,可能需要较长的时间,以确保全部提取物转化为焦炭。或者,可将煤提取物连续进料至保持在450℃-约525℃的温度的焦化容器中,随后在该温度下保持至少3小时,以完成焦化方法。
碳化步骤导致将煤提取物材料转化为称为生焦炭或原料焦炭的材料。该生焦炭具有黑色块状外观,具有在碳化步骤期间放出挥发性气体而造成的可见的孔。使用该方法,生焦炭的产率为供给碳化步骤的初始煤提取物的约50%-约90%。在碳化步骤之后和煅烧步骤之前,可将生焦炭碾碎以提高焦炭的表面积,从而减少煅烧所需的时间。
煅烧步骤在比前述碳化步骤显著更高的温度下进行。该步骤包括在约1300℃-约1500℃的温度下加热碾碎的原料焦炭,更优选约1400℃-约1450℃。在该步骤中,将氢气以及焦炭中的显著部分的氮和硫除去,并将焦炭转化为碳结构。此外,通过以约300℃/小时-约400℃/小时的速率逐步提高原料焦炭的温度,在分批操作中达到该设定温度,在具体的实施方案中,理想地,该速率为约350℃/小时。对于工业操作,可将原料焦炭连续进料至煅烧器,在这里温度分阶段升高,以达到最终的值。
所得到的产品为具有所选CTE的产品,其具有使其良好适合生产所选的石墨产品的性质。使用本公开的方法,针状焦炭的产率可高达通过碳化步骤生产的原料焦炭的约95%,并且通常为至少约80%,甚至90%。本发明方法的最终的生产率为初始煤提取物的约50%-约90%。
由所公开的方法生产的具有所选CTE的焦炭可直接用于某些应用,或者可用于产生石墨产品。首先将焦炭碾磨以生产颗粒和粉末,随后与约15%-约35%重量的煤焦油粘合剂沥青热混合。随后在约90℃-约120℃的温度下挤出该混合物,以形成生料。通过加热煤焦油粘合剂沥青和碾磨的焦炭的热混合物,沥青中的颗粒熔融,引起热混合物变为流体,因此,对通过挤出、模塑或其它形成技术成型敏感。
随后将生料在约800℃-约900℃的温度下烘焙,以碳化生料的煤焦油粘合剂沥青成分。生料的烘焙将包含在粘合剂沥青材料中的挥发性材料驱除,使得所得到的原料具有更均匀的内部结构。
随后通过加热至约2600℃-约3400℃的温度使烘焙的原料石墨化,优选的温度为约3000℃。根据石墨制品的尺寸和应用两者,总的石墨化时间可短至几小时或长达数天。
通过本发明的方法生产的所得到的石墨制品可具有期望的CTE;在电极的情况下,具有相对低的CTE。具体地,通过使用如G.Wagoner等人,Carbon Conference 1986 Proceedings,第234页,Baden-Baden,1986所描述的电容方法,由本发明的方法得到的电极的热膨胀系数为约0.005ppm/℃-约0.150ppm/℃。
如上所讨论的,通过以专业技术人员熟悉的方式改变前述方法步骤,所述方法可被实施用于生产针状焦炭以外的碳材料,比如碳纤维、沥青包括粘合剂沥青、浸渍沥青和/或中间相沥青以及海绵焦炭。
本文描述的方法的优点在于煤提取物转化为沥青的产率最高约90%。同样这种沥青转化为焦炭的产率最高约60%。与此相比,由倾析油或煤焦油馏出物得到焦炭的产率仅为约10-20%。
因此,通过本公开方法的实施,通过包括煤的催化提取的方法制备碳材料,比起常规的溶剂提取方法,所述方法提供了更大的效率,提高的碳材料生产速率和更高的产率。
在本申请中涉及的所有引用的专利和出版物的公开内容通过引用结合到本文中。
以上描述旨在使本领域技术人员能实施本发明。不旨在详述当阅读说明书后,对于技术人员显而易见的所有可能的变化和修改。然而,旨在所有这些修改和变化包括在以下权利要求所限定的本发明的范围内。除非上下文明确相反说明,否则权利要求旨在涵盖有效满足本发明目标的任何排列或顺序的所述要素和步骤。
因此,虽然已描述了用于煤的催化提取的新的和有用的方法的本发明具体实施方案,不旨在将这些参考解释为限制除以下权利要求所述以外的本发明范围。
Claims (9)
1.用于由煤的提取生产碳材料的方法,所述方法包括形成煤、溶剂和催化剂的混合物,所述催化剂选自钼、锡、钛、锆、铪、钍、硒、碲、钋、铁、钴、镍、钌、铑、钯、锇、铱、铂、铬、钨、铜、锌、金、银、汞、含有任何前述元素的催化-活性化合物和配位化合物、和它们的组合和混合物。
2.权利要求1的方法,其中所述碳材料包含针状焦炭、海绵焦炭、中间相沥青、粘合剂沥青、浸渍沥青、碳纤维、或它们的组合。
3.权利要求1的方法,其中所述溶剂包含一种或多种非芳族烃、一种或多种芳族烃、或它们的组合。
4.权利要求1的方法,其中所述提取在至少约325℃的温度下实现。
5.权利要求4的方法,其中所述提取在约325℃-约500℃的温度下实现。
6.权利要求1的方法,其中所述提取在最多约5000psi的压力下实现。
7.权利要求1的方法,其中所述提取在氢气或惰性气体气氛中实现。
8.权利要求1的方法,其中溶剂与煤的比率为约1∶1-约5∶1。
9.权利要求1的方法,其中催化剂与煤的比率为约0.01∶100-约5∶100。
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US4737261A (en) * | 1984-10-05 | 1988-04-12 | International Coal Refining Company | Process for the production of premium grade needle coke from a hydrotreated SRC material |
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2009
- 2009-08-21 US US12/545,140 patent/US20110044881A1/en not_active Abandoned
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2010
- 2010-08-20 GB GB1202542.5A patent/GB2485106B/en not_active Expired - Fee Related
- 2010-08-20 WO PCT/US2010/046121 patent/WO2011022620A1/en active Application Filing
- 2010-08-20 KR KR1020127007365A patent/KR20120064685A/ko not_active Application Discontinuation
- 2010-08-20 CN CN2010800382627A patent/CN102482582A/zh active Pending
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US20080017549A1 (en) * | 2006-05-24 | 2008-01-24 | Kennel Elliot B | Method of producing synthetic pitch |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106554793A (zh) * | 2014-01-21 | 2017-04-05 | 北京金菲特能源科技有限公司 | 一种通用型重质原料催化浆料加氢轻质化方法与装置 |
CN108698832A (zh) * | 2016-01-29 | 2018-10-23 | 西格里碳素欧洲公司 | 用于源自汽油或煤的焦炭的催化活性添加剂 |
Also Published As
Publication number | Publication date |
---|---|
GB2485106B (en) | 2013-07-10 |
WO2011022620A1 (en) | 2011-02-24 |
US20110044881A1 (en) | 2011-02-24 |
GB201202542D0 (en) | 2012-03-28 |
KR20120064685A (ko) | 2012-06-19 |
GB2485106A (en) | 2012-05-02 |
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