KR20200015663A - Method of preparing light oil from extra heavy oil using unsupported NiMoW sulfide dispersed catalyst - Google Patents
Method of preparing light oil from extra heavy oil using unsupported NiMoW sulfide dispersed catalyst Download PDFInfo
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- KR20200015663A KR20200015663A KR1020200012520A KR20200012520A KR20200015663A KR 20200015663 A KR20200015663 A KR 20200015663A KR 1020200012520 A KR1020200012520 A KR 1020200012520A KR 20200012520 A KR20200012520 A KR 20200012520A KR 20200015663 A KR20200015663 A KR 20200015663A
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- catalyst
- molybdenum
- tungsten
- oil
- heavy oil
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 239000000295 fuel oil Substances 0.000 title claims abstract description 53
- 239000003921 oil Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title abstract description 3
- LCSNMIIKJKUSFF-UHFFFAOYSA-N [Ni].[Mo].[W] Chemical compound [Ni].[Mo].[W] LCSNMIIKJKUSFF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000010779 crude oil Substances 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 230000005484 gravity Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000005486 sulfidation Methods 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 abstract description 16
- 239000000571 coke Substances 0.000 abstract description 15
- 238000000354 decomposition reaction Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 229910003294 NiMo Inorganic materials 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 13
- 238000003795 desorption Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- YZVRMKZSTUSOJF-UHFFFAOYSA-N molybdenum;nickel;sulfanylidenetungsten Chemical compound [Ni].[Mo].[W]=S YZVRMKZSTUSOJF-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940060799 clarus Drugs 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/023—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
본 발명은 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용한 초중질유로부터 경질유를 제조하는 방법에 관한 것으로 보다 상세하게는 수소화 분해 반응에 담지체를 사용하지 않고 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용하여 경질유를 제조하는 방법에 관한 것이다.The present invention relates to a process for preparing light oil from super heavy oil using a sulfided nickel-molybdenum-tungsten dispersion catalyst without using a carrier, and more particularly, sulfidation without using a support in a hydrocracking reaction. A process for producing light oil using a treated nickel-molybdenum-tungsten dispersed catalyst.
국내의 경우 휘발유, 경유뿐만 아니라 다양한 석유화학원료를 원유로부터 생산하고 있다. 현재까지 시추가 용이하고 휘발유, 경유 및 납사 성분이 많이 포함된 경질 원유를 주로 사용하고 있었으나, 이러한 고급 경질 원유의 매장량이 한계에 도달함에 따라 경질유 기반의 석유화학에서 중질유 또는 초중질유 기반으로 패러다임의 전환이 있을 것으로 예상된다. In Korea, various petrochemical raw materials are produced from crude oil as well as gasoline and diesel. Until now, light crude oil, which is easy to drill and contains a lot of gasoline, diesel, and naphtha components, has been mainly used.However, as the reserves of these high-grade light crude oil have reached their limits, light oil-based petrochemicals have become a paradigm based on heavy or ultra heavy oil. It is expected that there will be a transition.
또한, 전 세계 원유 수요 예측량은 2010년 약 8천만 배럴/일로 중국, 인도 등 아시아와 중남미 신흥 발전국의 소비량 증가로 인해서 매년 1.7% 가량 증가할 것으로 내다보며 2015년경에는 9천만 배럴을 넘어설 것으로 전망되고 있다. 소비원유 중 전세계적으로 경질유(light distillate)와 중질유(middle distillate) 소비량이 많을 뿐만 아니라 증가폭도 각각 2.8%와 4.4%로 다른 생산품에 비해 높은 경향을 나타내고 있다. 특히 중남미와 아시아 태평양지역의 신흥 발전국들의 발전과 함께 경질유 및 중질유의 소비는 더욱 증가할 것으로 예상된다. In addition, the global oil demand forecast is expected to reach about 80 million barrels / day in 2010, which is expected to increase by 1.7% every year due to the increase in consumption in emerging economies in Asia and Latin America such as China and India. It is expected. In addition to the consumption of light and middle distillate in the world of crude oil, the increase is 2.8% and 4.4%, respectively, which is higher than other products. In particular, with the development of emerging economies in Latin America and the Asia-Pacific region, light and heavy oil consumption is expected to increase.
상기와 같은 문제를 해결하기 위해 경질유분을 대체할 에너지원에 대한 다양한 연구가 진행 중에 있으나, 기존의 생산 설비를 이용할 수 있는 에너지 개발이 쉽지 않기 때문에 현 시점에서 매장량이 풍부한 오일 샌드 또는 베네수엘라의 초중질유에 대한 관심이 매우 높은 상황이다.In order to solve the above problems, various researches on energy sources to replace light oil are underway, but it is not easy to develop energy that can use existing production equipment. There is a high interest in heavy oil.
초중질유란, 미국석유협회가 정한 API(American Petroleum Institute) 값 기준으로 10°이하를 갖는 원유를 말하며, 베네수엘라 산(産) 원유 및 오일샌드에서 추출한 원유 성분인 역청(bitumen)이 초중질유에 해당된다. 또한, 원유를 증류할 때 발생하는 감압잔사유(vacuum residue) 역시 매우 낮은 API 값을 가지기 때문에 초중질유로 분류될 수 있다.Ultra-heavy oil refers to crude oil having 10 ° or less based on API (American Petroleum Institute) value set by the American Petroleum Institute. Bitumen, a crude oil extracted from Venezuela crude oil and oil sand, corresponds to ultra heavy oil. do. In addition, the vacuum residue generated when distilling crude oil can also be classified as super heavy oil because it has a very low API value.
중질유의 분해법으로는 접촉분해법, 수소화분해법 및 열분해법 등과 같은 다양한 방법이 존재한다. 초중질유의 경질화를 위한 열분해 공정은 고온의 열을 통해 탄소-탄소(C-C) 결합을 끊어 점도를 낮추거나 코크의 생산을 통해 액상의 수소/탄소(H/C) 분율을 높이는 쪽으로 연구가 진행되고 있다. 상기와 같은 열분해법은 초기 운전비용이 적게 들고 비교적 용이한 방법에 해당되어 많이 이용되고 있으나, 과량의 탄소 손실에 의해 공정 효율이 떨어지며 수소의 손실이 발생해 고급 원유의 생산이 어렵다는 단점이 존재한다. There are various methods of cracking heavy oils such as catalytic cracking, hydrocracking and pyrolysis. Pyrolysis process for hardening super heavy oil is carried out to lower the viscosity by breaking the carbon-carbon (CC) bond through high temperature heat or to increase the hydrogen / carbon (H / C) fraction of the liquid phase through the production of coke. It is becoming. The above pyrolysis method is used because it has a low initial operation cost and is a relatively easy method. However, there is a disadvantage in that the production efficiency of high-quality crude oil is difficult due to the loss of process efficiency and the loss of hydrogen. .
또한, 수소화 분해법에서 다양한 촉매들의 가능성이 보고되고 있으나, 초중질유와 같이 보다 더 극한의 조건에서 분해반응을 일으키기에 촉매의 내구성이 충분하지 않거나 초중질유의 금속 성분에 의해 촉매성능이 상실되는 문제점이 있다.In addition, the possibility of various catalysts has been reported in hydrocracking, but the catalyst is not sufficiently durable to cause decomposition reaction under more extreme conditions such as ultra heavy oil, or the catalyst performance is lost due to the metal component of the super heavy oil. have.
따라서, 수소를 효율적으로 이용할 수 있는 촉매 및 분해 공정의 개발에 대한 중요성이 대두되고 있다. Thus, the importance of developing catalysts and decomposition processes that can utilize hydrogen efficiently has emerged.
종래 기술(비특허문헌 1)에 따르면, 제올라이트 촉매에 귀금속을 담지한 중질유 생산 방법에 대하여 기재하고 있으나, 상기와 같은 종래 기술은 초중질유의 분해 조건에서 사용되기 어려운 담지체를 포함하고 있다.According to the prior art (Non-Patent Document 1), a method for producing heavy oil in which a noble metal is supported on a zeolite catalyst is described, but such a prior art includes a support that is difficult to be used in decomposition conditions of ultra heavy oil.
이와 같은 기술적 배경 하에서, 본 발명자들은 예의 노력한 결과, 초중질유로부터 경질유를 제조하는 방법을 개발하기에 이르렀다.Under these technical backgrounds, the present inventors have made efforts to produce a light oil from super heavy oil.
본 발명의 목적은 초중질유의 수소화 분해 반응에 담지체를 사용하지 않은 니켈-몰리브데늄-텅스텐 분산형 촉매를 적용하여 경질유를 제조하는 방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing light oil by applying a nickel-molybdenum-tungsten dispersed catalyst which does not use a carrier in the hydrocracking reaction of super heavy oil.
본 발명은 상기 과제를 해결하기 위하여, The present invention to solve the above problems,
(a) 초중질유 및 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐(NiMoWS) 분산형 촉매를 혼합하여 혼합물을 생성하는 단계;(a) mixing a sulfided nickel-molybdenum-tungsten (NiMoWS) dispersed catalyst without the use of ultra heavy oil and a support to produce a mixture;
(b) 상기 혼합물에 수소를 첨가하는 단계; 및(b) adding hydrogen to the mixture; And
(c) 상기 수소가 첨가된 혼합물을 380 ~ 500 ℃ 에서 수소화 분해하는 단계;(c) hydrocracking the mixture to which the hydrogen is added at 380 to 500 ° C;
를 포함하는 경질유의 제조 방법을 제공한다.It provides a process for producing light oil comprising a.
본 발명에 따르면, 상기 초중질유는 API(American Petroleum Institute) 비중이 1 ~ 10˚인 원유, 역청(bitumen), 감압잔사유(vacuum residue) 또는 이의 혼합물로부터 선택될 수 있다.According to the present invention, the super heavy oil may be selected from crude oil, bitumen, vacuum residue or mixtures thereof having a specific gravity of 1 to 10 ° API (American Petroleum Institute).
본 발명에 따르면, 상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 몰리브데늄/텅스텐의 몰비율은 0.1 내지 3.5일 수 있다.According to the present invention, the molar ratio of molybdenum / tungsten of the sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier may be 0.1 to 3.5.
본 발명에 따르면, 상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매는,According to the present invention, the sulfided nickel-molybdenum-tungsten dispersed catalyst that does not use the carrier,
텅스텐 전구체와 몰리브데늄 전구체를 혼합하는 단계;Mixing the tungsten precursor and the molybdenum precursor;
상기 혼합 후 암모니아 용액을 첨가하는 단계;Adding ammonia solution after the mixing;
상기 암모니아 용액 첨가 후 니켈 전구체를 혼합하는 단계; 및Mixing the nickel precursor after the ammonia solution is added; And
상기 니켈 전구체 혼합 후 H2S/H2 가스를 사용하여 300 ~ 500 ℃에서 황화 처리(sulfidation)하는 단계;를 통해 제조될 수 있다.After mixing the nickel precursor H 2 S / H 2 gas using a sulfiding (sulfidation) at 300 ~ 500 ℃; can be prepared through.
본 발명에 따르면, 상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 크기는 100 nm 내지 1 ㎛일 수 있다. According to the present invention, the size of the sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier may be 100 nm to 1 μm.
본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용한 경질유의 생산방법은 중질유의 분해 반응에 일반적이고, 상업적으로 사용되는 NiMo/Al2O3 촉매에 비하여 높은 반응성을 가지고 초중질유를 효율적으로 분해하여 경질유를 생산할 수 있으며, 높은 액상 생성물의 수득률은 물론, 담지체를 사용한 촉매에 비해 코크 생성을 억제하며 아스팔텐의 분해에서도 높은 활성을 나타낸다.The process for producing light oil using the sulfided nickel-molybdenum-tungsten dispersion catalyst without using the carrier according to the present invention is generally used for the decomposition of heavy oil, and commercially used NiMo / Al 2 O 3 catalyst. Compared with the high reactivity, the heavy oil can be efficiently decomposed to produce a light oil. The yield of high liquid products, as well as the suppression of coke formation compared to the catalyst using the carrier, are also high in the decomposition of asphaltenes.
도 1은 다공성 담지체 촉매와 콜로이드성 또는 분자성 촉매에 따른 끓는점이 525 ℃ 이상인 잔유의 전환율 및 이에 포함된 아스팔텐의 전화율을 나타낸 것이다.
도 2는 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 HRTEM 이미지이다.
도 3은 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 XRD 분석 결과를 나타낸 것이다.
도 4는 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 합성한 후 TEM-EDX mapping 분석을 통해 각각의 성분들이 잘 분산되어 있음을 확인한 결과를 나타낸 것이다.
도 5는 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용한 초중질유의 분해 과정을 나타낸 것이다.
도 6은 초중질유에 포함된 아스팔텐의 구조를 나타낸 것이다.
도 7은 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 H2-TPD(H2-temperature programmed desorption) 결과를 나타낸 것이다.
도 8의 a)는 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용하여 분해된 생성물의 성분 함량을 나타낸 것이고, 도 8의 b)는 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용하여 분해된 상용 액상 생성물(나프타+중질유+가스오일)의 질량분율을 나타낸 것이다.
도 9는 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매를 이용하여 얻어진 고상 생성물(코크)과 아스팔텐 전환율을 나타낸 것이다.Figure 1 shows the conversion of the residual oil having a boiling point of 525 ℃ or more and the conversion of asphaltenes contained therein according to the porous carrier catalyst and the colloidal or molecular catalyst.
2 is an HRTEM image of a sulfided nickel-molybdenum-tungsten dispersed catalyst without using a carrier according to the present invention.
Figure 3 shows the results of XRD analysis of the sulfided nickel- molybdenum-tungsten dispersed catalyst without using the carrier according to the present invention.
Figure 4 shows the results of confirming that each component is well dispersed through the TEM-EDX mapping analysis after synthesis of sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier according to the present invention. will be.
Figure 5 shows the decomposition of super heavy oil using a sulfided nickel- molybdenum-tungsten dispersed catalyst without using a carrier according to the present invention.
Figure 6 shows the structure of asphaltenes contained in super heavy oil.
Figure 7 is a sulfided using no carrier according to the present invention nickel-shows the H 2 -TPD (H 2 -temperature programmed desorption) results of tungsten dispersed catalyst-molybdenum.
Figure 8a) shows the component content of the product decomposed using a sulfided nickel-molybdenum-tungsten dispersion catalyst without using the carrier according to the present invention, Figure 8b) of the present invention The mass fraction of a commercial liquid product (naphtha + heavy oil + gas oil) decomposed using a sulfided nickel-molybdenum-tungsten dispersion catalyst without using a carrier according to the present invention is shown.
FIG. 9 shows the conversion of solid product (coke) and asphaltene obtained using a sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier according to the present invention.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐(NiMoWs) 분산형 촉매를 이용하여 초중질유로부터 경질유를 제조하는 것을 특징으로 하는 경질유 제조방법 및 초중질유로부터 경질유를 제조하기 위한 담지체를 사용하지 않은 분산형 황화 처리된 니켈-몰리브데늄-텅스텐(NiMoWS 또는 NMWS로 표시) 분산형 촉매에 관한 것이다.The present invention relates to a process for producing light oil from ultra heavy oil using a sulfided nickel-molybdenum-tungsten (NiMoWs) dispersion catalyst which does not use a carrier, and to prepare light oil from ultra heavy oil. It relates to a disperse sulfided nickel-molybdenum-tungsten (denoted NiMoWS or NMWS) dispersive catalyst without the use of a carrier for the same.
본 발명에 있어, 분산형 촉매란 분산된 형태(well dispersed)의 촉매를 의미하는데, 촉매의 분산 정도는 촉매의 활성에 직접적인 영향을 미치기 때문에 중요한 요소가 된다.In the present invention, a dispersed catalyst means a well dispersed catalyst, which is an important factor because the degree of dispersion of the catalyst directly affects the activity of the catalyst.
구체적으로 본 발명은, (a) 초중질유 및 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐(NiMoWS) 분산형 촉매를 혼합하여 혼합물을 생성하는 단계; (b) 상기 혼합물에 수소를 첨가하는 단계; 및 (c) 상기 수소가 첨가된 혼합물을 380 ~ 500 ℃ 에서 수소화 분해하는 단계;를 포함하는 경질유의 제조 방법을 제공한다.Specifically, the present invention comprises the steps of: (a) mixing a sulfided nickel-molybdenum-tungsten (NiMoWS) dispersed catalyst without the use of ultra-heavy oils and carriers to produce a mixture; (b) adding hydrogen to the mixture; And (c) hydrocracking the mixture to which the hydrogen is added at 380 to 500 ° C.
본 발명에 따르면, 상기 초중질유는 API(American Petroleum Institute) 비중이 1 ~ 10˚인 원유, 역청(bitumen), 감압잔사유(vacuum residue) 또는 이의 혼합물로부터 선택될 수 있다.According to the present invention, the super heavy oil may be selected from crude oil, bitumen, vacuum residue or mixtures thereof having a specific gravity of 1 to 10 ° API (American Petroleum Institute).
본 발명은 초중질유의 수소화 분해 반응에 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매(NiMoWS)를 이용하여 경질유를 제조하는 방법으로, 종래 담지체에 담지된 촉매에 해당하는 유동식 접촉 분해 촉매(FCC)를 사용하여 중질유를 분해하는 방법과 구별된다.The present invention is a method for producing light oil using a sulfide-treated nickel-molybdenum-tungsten dispersed catalyst (NiMoWS) in the hydrocracking reaction of super heavy oil, a fluid catalytic cracking catalyst corresponding to a catalyst supported on a conventional carrier. (FCC) to separate heavy oils.
일반적인 중질유(heavy oil)의 수소화 분해 반응(hydrocracking)의 온도 조건은 약 270 ~ 400 ℃ 인 반면, 초중질유(extra heavy oil)의 수소화 분해 반응의 온도 조건은 약 370 ~ 500 ℃ 로서 중질유의 분해 반응 조건보다 상대적으로 더 가혹한 조건을 요구한다. 또한, 초중질유는 중질유에 비하여 과량의 금속 및 황 성분을 포함하기 때문에 분해 반응에 사용되는 촉매의 강한 내구성이 요구된다.The temperature condition of hydrocracking of heavy oil is about 270-400 ° C, whereas the temperature condition of hydrocracking of extra heavy oil is about 370-500 ° C. Requires conditions that are relatively harsher than conditions. In addition, since super heavy oil contains excess metal and sulfur components compared to heavy oil, strong durability of the catalyst used for the decomposition reaction is required.
중질유의 경우 아스팔텐(asphaltene)과 같은 중질 물질(heavy material)이 거의 존재하지 않으며, 니켈 또는 바나듐과 같은 금속 성분이 매우 미량 포함되어 있다. 또한, 물성 역시 초중질유에 비해 우수하기 때문에 코크(coke)의 발생량도 상대적으로 적다. 따라서, 산화알루미늄과 같은 담지체를 적용하여 분해 반응을 위한 비표면적을 증가시킴과 동시에 산성을 띄는 담지체를 사용함으로써 촉매의 활성을 증가시킨다.In the case of heavy oil, there are almost no heavy materials such as asphaltene, and very small amounts of metal such as nickel or vanadium are included. In addition, since physical properties are also superior to that of super heavy oil, the amount of coke is relatively low. Therefore, by applying a carrier such as aluminum oxide to increase the specific surface area for the decomposition reaction and at the same time to increase the activity of the catalyst by using an acidic carrier.
다만, 담지체는 표면에 미세 기공을 다수 포함하고 있으며, 상기 기공 내에 분해 반응의 활성 구성요소인 니켈, 몰리브덴 또는 헤테로폴리산 등을 포함하고 있는 형태를 취하고 있다. 따라서, 도 1에 나타난 바와 같이, 담지체를 포함하는 촉매를 초중질유의 수소화 분해 반응에 사용할 경우, 아스팔텐과 같은 중질 물질이 담지체의 기공 안으로 침투하여 질량 이동 제한(mass transfer limitation)이 발생하고, 초중질유에 포함된 과량의 금속 성분에 의해 코크(coke)가 발생하게 되어 담지체의 기공을 막게되는 결과, 촉매의 활성이 소멸되는 문제점이 발생한다. 또한, 아스팔텐은 코크를 생성시키는 전구체로 알려져 있어 아스팔텐의 분해를 통한 경질유로의 반응 유도가 본 반응에서의 중요한 요소가 될 수 있다.However, the carrier includes a large number of fine pores on the surface, and has a form containing nickel, molybdenum or heteropoly acid, etc., which are active components of the decomposition reaction in the pores. Therefore, as shown in FIG. 1, when a catalyst including a support is used for hydrocracking of super heavy oil, a heavy material such as asphaltene penetrates into the pores of the support, thereby causing mass transfer limitation. In addition, coke is generated by the excess metal component contained in the ultra-heavy oil, which prevents the pores of the carrier, resulting in the disappearance of the activity of the catalyst. In addition, asphaltenes are known as precursors to produce coke, so induction of reactions into light oil through decomposition of asphaltenes may be an important factor in this reaction.
따라서, 본 발명은 초중질유의 수소화 분해 반응을 위해 담지체에 담지되지 않으며, 초중질유에 포함된 과량의 금속 성분의 담지체로의 침착에 의한 촉매의 비활성이 야기되지 않으며, 상기 촉매로 금속성분이 침착되더라도 공촉매(co-catalyst)로서 작용할 수 있다.Therefore, the present invention is not supported on the support for the hydrocracking reaction of the ultra heavy oil, and does not cause the inactivation of the catalyst by deposition on the carrier of the excess metal component contained in the ultra heavy oil, Even when deposited, it can act as a co-catalyst.
본 발명에 따른 담지체를 사용하지 않은 황화 니켈-몰리브데늄-텅스텐 (NiMoWS)분산형 촉매를 이용하여 초중질유를 분해할 때, 생성되는 고상(solid), 액상(liquid) 및 기상(gas) 생성물의 수득률을 통해 촉매의 활성 정도가 결정된다. 초중질유의 수소화 분해 반응에 촉매를 사용하지 않는 경우보다 담지체를 사용하지 않은 황화 니켈-몰리브데늄-텅스텐 (NiMoW)분산형 촉매를 사용할 경우, 액상 생성물의 수득률이 증가하며, 고상 및 기상 생성물의 수득률이 감소한다. Solid, liquid and gas produced when cracking super-heavy oil using a nickel sulfide-molybdenum-tungsten (NiMoWS) dispersion catalyst without using the carrier according to the present invention. The yield of the product determines the degree of activity of the catalyst. The use of nickel sulfide-molybdenum-tungsten (NiMoW) dispersing catalysts without carriers yields higher yields of liquid products than solid catalysts and gaseous products rather than catalysts for hydrocracking of heavy oils. Yield is reduced.
상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 니켈/(몰리브데늄+텅스텐)의 몰비율은 0.1 내지 1인 것이 바람직하다.The molar ratio of nickel / (molybdenum + tungsten) of the sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier is preferably 0.1 to 1.
또한, 상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 몰리브데늄/텅스텐의 몰비율은 0.1 내지 3.5인 것이 바람직하고, 1.5인 것이 더욱 바람직하다.In addition, the molar ratio of molybdenum / tungsten of the sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier is preferably 0.1 to 3.5, more preferably 1.5.
상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매는, 텅스텐 전구체와 몰리브데늄 전구체를 혼합하는 단계; 상기 혼합 후 암모니아 용액을 첨가하는 단계; 상기 암모니아 용액 첨가 후 니켈 전구체를 혼합하는 단계; 및 상기 니켈 전구체 혼합 후 H2S/H2 가스를 사용하여 300 ~ 500 ℃에서 황화 처리(sulfidation)하는 단계;를 통해 제조될 수 있다.The sulfided nickel-molybdenum-tungsten dispersed catalyst that does not use the support may include: mixing a tungsten precursor and a molybdenum precursor; Adding ammonia solution after the mixing; Mixing the nickel precursor after the ammonia solution is added; And sulfidation at 300 to 500 ° C. using H 2 S / H 2 gas after mixing the nickel precursor.
또한, 상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 크기는 100 nm 내지 1 ㎛일 수 있다. In addition, the size of the sulfided nickel-molybdenum-tungsten dispersed catalyst without using the carrier may be 100 nm to 1 μm.
이하, 본 발명의 이해를 위하여 구체적인 실시예를 통하여 설명한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 하기의 실시예에 의해서 본 발명의 권리범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described with reference to specific examples. However, the following examples are merely provided to more easily understand the present invention, and the scope of the present invention is not limited by the following examples.
실험 방법Experiment method
담지체를Carrier 사용하지 않은 황화 처리된 니켈- Unused Sulfated Nickel 몰리브데늄Molybdenum -텅스텐 분산형 촉매(NiMoWS 또는 Tungsten dispersed catalyst (NiMoWS or NMWS로With NMWS 표시)의 제조 Manufacturing)
먼저, 텅스텐 전구체 (ammonium metatungstate (0, 0.16, 0.12, 0.08, 0.04, and 0.2 mole W, Sigma-Aldrich, ≥66.5%)), 몰리브데늄 전구체(Ammonium heptamolybdate (0.2, 0.04, 0.08, 0.12, 0.16, and 0 mole Mo, Sigma-Aldrich, 81.0-83.0%))와 증류수 (800 mL)를 혼합하여 90 ℃에서 교반하여 A 솔루션을 제조하였다. A 솔루션의 pH를 수산화암모늄 (약 600 ml, Sigma-Aldrich, 28.0-30.0% NH3 기준)을 첨가함으로써 약 9.8-10.0으로 유지시켰다. 다음으로, 니켈 전구체 (Nickel (II) nitrate hexahydrate (0.2 moles Ni, Sigma-Aldrich, 99.999%))를 90℃의 증류수 (100 mL)에 교반하여 용해시켜 B 솔루션을 제조하였다. 이어서 용액 B를 용액 A에 90℃에서 서서히 첨가할 때 침전이 관찰되었고, 용액을 100℃에서 8 시간 동안 환류시켰다. 현탁액을 실온으로 냉각 및 여과한 후(Whatman No. 1, 7 cm), 뜨거운 물로 세척하고 110℃에서 건조시켰다. 약 37.5-38.2 g의 물질이 회수되었다. 5 vol.% H2S/H2 (60 mL/min)를 사용하여 4시간 동안 400℃ 및 1기압의 관형로(tubular furnace)에서 황화 처리(Sulfidation)하였으며, 이때, 촉매에서 물리 흡착된 가스를 제거하기 위해, 비활성 가스(N2)(60 mL/min)로 1시간 퍼징하여, 본 발명에 따른 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매(NiMoWS) 제조하였다. First, tungsten precursor (ammonium metatungstate (0, 0.16, 0.12, 0.08, 0.04, and 0.2 mole W, Sigma-Aldrich, ≥66.5%)), molybdenum precursor (Ammonium heptamolybdate (0.2, 0.04, 0.08, 0.12, 0.16) , and 0 mole Mo, Sigma-Aldrich, 81.0-83.0%)) and distilled water (800 mL) were mixed and stirred at 90 ℃ to prepare an A solution. The pH of the A solution was maintained at about 9.8-10.0 by adding ammonium hydroxide (about 600 ml, Sigma-Aldrich, based on 28.0-30.0% NH 3 ). Next, a nickel solution (Nickel (II) nitrate hexahydrate (0.2 moles Ni, Sigma-Aldrich, 99.999%)) was dissolved in distilled water (100 mL) at 90 ° C. to prepare a B solution. Precipitation was then observed when solution B was slowly added to solution A at 90 ° C. and the solution was refluxed at 100 ° C. for 8 hours. The suspension was cooled to room temperature and filtered (Whatman No. 1, 7 cm), washed with hot water and dried at 110 ° C. About 37.5-38.2 g of material was recovered. Sulfurization was carried out in a tubular furnace at 400 ° C. and 1 atm for 5 hours using 5 vol.% H 2 S / H 2 (60 mL / min), where the gas was physically adsorbed on the catalyst. In order to remove the, purged with inert gas (N 2 ) (60 mL / min) for 1 hour, a sulfided nickel- molybdenum-tungsten dispersed catalyst (NiMoWS) according to the present invention was prepared.
석유 정제 공정에서 수소 처리 및 수소 첨가 분해 반응을 위해 상업적으로 사용되는 NiMo/Al2O3 기반 촉매 (BASF)를 비교예로 준비하였다. 반응 시험 전에 NiMo/Al2O3 촉매를 분쇄하고 40-75 ㎛로 체질 한 후 400℃에서 5% H2S/H2 가스 하에서 4시간 동안 활성화시켰다.A NiMo / Al 2 O 3 based catalyst (BASF) commercially used for hydrotreating and hydrocracking reactions in petroleum refining processes was prepared as a comparative example. Before the reaction test, the NiMo / Al 2 O 3 catalyst was ground and sieved to 40-75 μm, and activated at 400 ° C. for 4 hours under 5% H 2 S / H 2 gas.
촉매의 특성 측정Characterization of the catalyst
황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매(NiMoWS)의 원소 함량 (W, Mo 및 Ni)은 ICP-OES (Thermo Scientific, iCAP 6300)로 측정하였으며, 촉매의 약식(abbreviated expressions)을 하기 표 1에 나타내었다.Elemental content (W, Mo and Ni) of sulfided nickel-molybdenum-tungsten dispersed catalyst (NiMoWS) was determined by ICP-OES (Thermo Scientific, iCAP 6300), and the abbreviated expressions of the catalyst Table 1 shows.
TEM 분석 및 EDX 원소 매핑은 300kV에서 작동되는 TEM 기기(Tecnai, G2 F30ST)를 사용하여 수행하였다. 분산된 NiMoWS(x) 샘플을 헥산 (Sigma-Aldrich, 95%)에 분산시키고 Cu 그리드 위에 떨어 뜨려 주변 조건에서 건조시켰다.TEM analysis and EDX elemental mapping were performed using a TEM instrument (Tecnai, G2 F30ST) operated at 300 kV. The dispersed NiMoWS (x) samples were dispersed in hexane (Sigma-Aldrich, 95%) and dropped on Cu grids and dried at ambient conditions.
XRD(Rigaku, D / MAX-2500V / PC 장비) 분석은 Ni-filtered Cu-Kα 방사선 (λ = 1.5418Å)을 사용하여 수행하였다. XRD 측정은 실온에서 10°에서 90°까지의 2-theta 범위 (2°/분의 스캐닝 속도)에 대해 얻어졌다.XRD (Rigaku, D / MAX-2500V / PC instrument) analysis was performed using Ni-filtered Cu-Kα radiation (λ = 1.5418 Hz). XRD measurements were obtained for the 2-theta range (scanning speed of 2 ° / min) from 10 ° to 90 ° at room temperature.
벨프로그램 (Bell, BELCAT-B)을 사용하여 H2-TPD(H2-temperature programmed desorption) 분석을 수행하였다. 촉매(50mg)를 U형 석영 튜브에 넣고 1시간 동안 30 mL/분의 헬륨 흐름 하에 200℃에서 전처리하였다. 샘플을 100℃로 냉각시키고, 10% H2/N2 가스를 30 mL/분의 유속으로 공급하고, 이를 1시간 동안 유지하였다. H2를 0.5 시간 동안 퍼지하기 위해 가스를 헬륨으로 전환하였다. 마지막으로, 촉매를 헬륨 유속 30 mL/min에서 10℃/min의 속도로 850℃로 가열하였다. 탈착된 가스는 질량 분석기 (Bell, BELMass)로 분석하였다.Bell program was performed (Bell, BELCAT-B) H 2 -TPD (H 2 -temperature programmed desorption) with the analysis. The catalyst (50 mg) was placed in a U-shaped quartz tube and pretreated at 200 ° C. under a 30 mL / min helium flow for 1 hour. The sample was cooled to 100 ° C. and 10% H 2 / N 2 gas was fed at a flow rate of 30 mL / min, which was maintained for 1 hour. The gas was converted to helium to purge H 2 for 0.5 h. Finally, the catalyst was heated to 850 ° C. at a rate of 10 ° C./min at a helium flow rate of 30 mL / min. Desorbed gas was analyzed by mass spectrometry (Bell, BELMass).
촉매 반응 시험Catalytic reaction test
감압잔사유(vacuum residue, VR)의 수소 첨가 분해 반응 시험은 오토클레이브 회분식 반응기 (Parr Instrument, 4598 Micro Reactor)를 사용하여 수행하였다. VR (30 g) 및 촉매 (40 mg)를 100 mL 반응기에 함께 첨가하였다. 반응기를 수소 가스 (+ 99.99 %)로 3회 세정하여 공기를 제거한 다음 내부 압력이 70 bar에 도달할 때까지 수소 가스로 채웠다. 이어서, 반응기를 400℃ (12.5℃/분)로 가열하였다. 반응을 1,000 rpm에서 24시간 동안 교반하면서 수행하였다(도 5 참조). 액체 및 고체 생성물은 종래 문헌(H.-J. Eom, D.-W. Lee, S. Kim, S.-H. Chung, Y.G. Hur, K.-Y. Lee, Hydrocracking of extra-heavy oil using Cs-exchanged phosphotungstic acid (CsxH3 - xPW12O40, x = 1-3) catalysts, Fuel, 126 (2014) 263-270.)에 기재된 방법대로 회수하였다.The hydrocracking reaction test of vacuum residue (VR) was carried out using an autoclave batch reactor (Parr Instrument, 4598 Micro Reactor). VR (30 g) and catalyst (40 mg) were added together in a 100 mL reactor. The reactor was washed three times with hydrogen gas (+ 99.99%) to remove air and then charged with hydrogen gas until the internal pressure reached 70 bar. The reactor was then heated to 400 ° C. (12.5 ° C./min). The reaction was carried out with stirring at 1,000 rpm for 24 hours (see FIG. 5). Liquid and solid products are described in the prior art by H.-J. Eom, D.-W. Lee, S. Kim, S.-H. Chung, YG Hur, K.-Y. Lee, Hydrocracking of extra-heavy oil using Recovered according to the method described in Cs-exchanged phosphotungstic acid (Cs x H 3 - x PW 12 O 40 , x = 1-3) catalysts, Fuel, 126 (2014) 263-270.).
생성물 (액체(l), 고체(s) 및 기체(g))의 수율은 하기 식 1 내지 식 3을 이용하여 계산하였다.The yield of the product (liquid (1), solid (s) and gas (g)) was calculated using the following formulas (1) to (3).
[식 1][Equation 1]
[식 2][Equation 2]
[식 3][Equation 3]
상업용 액상 제품의 수율(%)은 하기 식 4에 따라 계산하였다.The yield (%) of the commercial liquid product was calculated according to the following formula (4).
[식 4][Equation 4]
상기 식 4에서 10.4%의 값은 이미 VR 반응물에 함유된 경유의 중량% 이다. VR 특성은 하기 표 2에 기재된 바와 같다.The value of 10.4% in
C5-아스팔텐의 전환율은 하기 식 5에 따라 계산하였다.The conversion of C 5 -asphaltene was calculated according to the following equation.
[식 5][Equation 5]
n- 펜탄에 의해 분리된 아스팔텐 종은 C5-아스팔텐으로 표시되며, 아스팔텐의 구조는 하기 도 6에 나타내었다. 또한, 상기 식 5에서 23.1 %의 값은 VR 반응물에서 C5-아스팔텐의 질량 분율을 나타낸다.Asphaltene species separated by n-pentane are represented by C 5 -asphaltene, and the structure of the asphaltene is shown in FIG. 6. In addition, the value of 23.1% in Equation 5 represents the mass fraction of C 5 -asphaltene in the VR reactant.
초중질유의 분해 반응을 통해 제조되는 경질유는 액상 생성물에 포함되어 있으며, 상기 액상 생성물은 끓는점이 약 35 ~ 130 ℃인 경질 나프타(Naphtha), 끓는점이 약 130 ~ 220 ℃인 중질 나프타 및 이를 제외한 경질유 및 중질유 생성물을 포함한다. 고상 생성물은 주로 코크(coke)를 의미한다. 따라서, 반응물인 초중질유로부터 고상 및 기상 생성물을 제외한 액상 생성물의 수득률을 계산함으로써 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 (NiMoWS)분산형 촉매를 사용함에 따른 경질유의 제조 방법의 유용성을 판단할 수 있다.The light oil produced through the decomposition of super heavy oil is contained in the liquid product, and the liquid product includes light naphtha having a boiling point of about 35 to 130 ° C., heavy naphtha having a boiling point of about 130 to 220 ° C., and light oil except for this. And heavy oil products. Solid product means mainly coke. Therefore, a process for preparing light oil by using a sulfided nickel-molybdenum-tungsten (NiMoWS) dispersed catalyst without a carrier by calculating the yield of liquid products except solid and gaseous products from the reactant ultra heavy oil. The usefulness of can be judged.
모의 증류 (ASTM 방법 D-7169)를 사용하여 액체 생성물의 질량 분율을 측정 하였다. 가스 크로마토 그래피 분석 (Perkin-Elmer, Clarus 600)을 사용하여 각 분획의 중량%를 측정하였다.Simulated distillation (ASTM method D-7169) was used to determine the mass fraction of the liquid product. Gas chromatographic analysis (Perkin-Elmer, Clarus 600) was used to determine the weight percent of each fraction.
황 오염물의 함량을 원소 분석 (FISONS Instruments, 1108 CHNS-O)으로 측정 하였다. 밀도 측정기 (Anton Paar, DMA 35) 및 ASTM 방법 D-287을 사용하여 액체 생성물의 API 중력 값을 측정하였다.The content of sulfur contaminants was determined by elemental analysis (FISONS Instruments, 1108 CHNS-O). The API gravity value of the liquid product was measured using a density meter (Anton Paar, DMA 35) and ASTM method D-287.
결과 및 고찰Results and Discussion
촉매의 특성Characteristics of the catalyst
도 2는 분산된 NMWS (x) 샘플의 HRTEM 이미지를 도시한 것이다. 모든 샘플은 스택(stack)과 곡률(curvature)이 있는 MoS2 및 WS2 층의 일반적인 구조를 나타내었다. MoS2와 WS2의 굴곡 형태는 더 많은 활성 부위를 가짐으로써 수소화 활성을 선호한다는 것이 보고된바 있다(C. Yin, Y. Wang, S. Xue, H. Liu, H. Li, C. Liu, Influence of sulfidation conditions on morphology and hydrotreating performance of unsupported Ni-Mo-W catalysts, Fuel, 175 (2016) 13-19.). 도 2의 라멜라 구조는 0.61 내지 0.65 nm 사이의 층간 간격 및 각각 3 및 9와 같은 적층 수를 가짐을 확인하였다.2 shows an HRTEM image of a distributed NMWS (x) sample. All samples showed the general structure of MoS 2 and WS 2 layers with stacks and curvatures. It has been reported that the bent forms of MoS 2 and WS 2 favor hydrogenation activity by having more active sites (C. Yin, Y. Wang, S. Xue, H. Liu, H. Li, C. Liu). , Influence of sulfidation conditions on morphology and hydrotreating performance of unsupported Ni-Mo-W catalysts, Fuel, 175 (2016) 13-19.). The lamellar structure of FIG. 2 was found to have an interlayer spacing between 0.61 and 0.65 nm and a stacking number such as 3 and 9, respectively.
분산된 NMWS (x) 샘플의 XRD 패턴을 도 3에 나타내었다. 준비된 모든 시료는 이황화 텅스텐 (PDF # 08-0237), 이황화 몰리브덴 (PDF # 37-1492) 및 황화 니켈 (PDF # 44-1418)에 해당하는 회절 피크를 나타내었다. 2θ=14.3°에서 피크(002)의 강도는 c 방향으로 적층된 2차원 WS2/MoS2 슬라브(slabs)의 특성을 나타낸다. 또한, Ni3S2의 회절 피크도 모든 샘플에서 명확하게 구별할 수 있었다.The XRD pattern of the dispersed NMWS (x) samples is shown in FIG. 3. All prepared samples showed diffraction peaks corresponding to tungsten disulfide (PDF # 08-0237), molybdenum disulfide (PDF # 37-1492) and nickel sulfide (PDF # 44-1418). The intensity of the peak 002 at 2θ = 14.3 ° indicates the properties of two-dimensional WS 2 / MoS 2 slabs stacked in the c direction. In addition, the diffraction peaks of Ni 3 S 2 were also clearly distinguishable in all the samples.
도 4는 분산된 NMWS (x) 샘플의 TEM-EDX 원소 매핑을 나타낸다. 이를 통해 Ni, Mo, W 및 S 등 모든 구성 원소가 샘플 내에 균일하게 분포되어 있음을 확인하였다.4 shows TEM-EDX elemental mapping of dispersed NMWS (x) samples. This confirmed that all constituent elements such as Ni, Mo, W and S are uniformly distributed in the sample.
수소의 탈착량을 평가하기 위해 H2-TPD를 적용하였고, 분산된 NMWS (x) 샘플의 H2-TPD 결과를 도 7에 나타내었다. 수소 탈착 속도(H2-TPD)는 분산된 NMWS (x) 샘플의 실행 시간과 온도의 함수로서 샘플 탈착량에 대해 정규화되었다. 기록된 TPD 패턴은 복잡하고 몇 가지 최대값을 나타내었으며 이를 통해 금속 황화물 촉매에 약하고 강하게 결합된 다양한 형태의 수소가 나타났다. 분산된 NMWS (x) 샘플의 탈착 프로파일은 온도 범위에 따라 약 (-300 ℃), 중간 (300-500 ℃) 또는 강한 (500 ℃)로 표시되었다. 탈착된 수소의 양은 표 3에 요약 된 바와 같이 적분에 의해 추정하였다. 측정 결과, NMWS(1.5)로부터 탈착된 H2의 총량은 NMS보다 높은 측정값을 나타낸 NWS보다 약 4.2 배 더 높은 것으로 확인되었다. 이를 통해 텅스텐과 몰리브덴을 함께 사용하면 수소 탈착 능력이 크게 향상됨을 확인하였다.H 2 -TPD was applied to evaluate the desorption amount of hydrogen, and the H 2 -TPD results of the dispersed NMWS (x) samples are shown in FIG. 7. Hydrogen desorption rate (H2-TPD) was normalized to sample desorption amount as a function of run time and temperature of dispersed NMWS (x) samples. The recorded TPD pattern was complex and showed some maximum values, resulting in various forms of hydrogen that were weakly and strongly bound to the metal sulfide catalyst. Desorption profiles of the dispersed NMWS (x) samples were expressed as about (-300 ° C.), medium (300-500 ° C.) or strong (500 ° C.) depending on the temperature range. The amount of desorbed hydrogen was estimated by integration as summarized in Table 3. As a result of the measurement, the total amount of H 2 desorbed from the NMWS (1.5) was found to be about 4.2 times higher than the NWS showing a higher value than the NMS. It was confirmed that the use of tungsten and molybdenum together greatly improved the hydrogen desorption capacity.
또한, 본 발명에 따른 NMWS (x) 샘플의 수소 탈착 총량은 NMWS (0.2) <NMWS (0.6) <NMWS (3.6) <NMWS (1.5)의 순서로 나타났다. 특히, 수소 (약 500 ℃ 미만)의 약한 및 중간 결합의 양은 NMWS (1.5)에서 총 탈착 된 수소의 약 72%를 차지하는 것으로 나타났다. 이는 다른 NMWS (x) 샘플에 비해 수소의 약 결합 및 중간 결합의 탈착량과 비율에 중요한 이점을 제공한다. 또한, Mo 및 W가 수소 탈착에 미치는 이 상승효과는 수소 첨가 분해 반응 성능에 긍정적인 영향을 줄 것으로 기대되었다.In addition, the total amount of hydrogen desorption of NMWS (x) samples according to the present invention was shown in the order of NMWS (0.2) <NMWS (0.6) <NMWS (3.6) <NMWS (1.5). In particular, the amount of weak and moderate bonds of hydrogen (below about 500 ° C.) was found to account for about 72% of the total desorbed hydrogen in NMWS (1.5). This provides a significant advantage in the amount and ratio of desorption of weak and intermediate bonds of hydrogen over other NMWS (x) samples. In addition, this synergistic effect of Mo and W on hydrogen desorption was expected to have a positive effect on the hydrocracking reaction performance.
분산된 Distributed NMWSNMWS (x) 촉매의 활성 (x) activity of the catalyst
도 8의 (a)는 고형물 (코크스), 액체 및 가스 생성물의 질량 분율을 나타내며, 액체 생성물은 가상 증류(Simulated distillation, SIMDIS) 분석(Y.G. Hur, M.-S. Kim, D.-W. Lee, S. Kim, H.-J. Eom, G. Jeong, M.-H. No, N.S. Nho, K.-Y. Lee, Hydrocracking of vacuum residue into lighter fuel oils using nanosheet-structured WS2 catalyst, Fuel, 137 (2014) 237-244.)에 의해 잔사유(residue)(525 ℃), 가스오일(gas oil) (343-525 ℃ ), 중질유(middle distillate) (177-343 ℃) 및 나프타(naphtha) (-177 ℃)로 끓는점에 따라 분류하였다. 촉매가 VR의 수소 첨가 분해에 사용되지 않은 경우, 액체 질량 분율은 단지 56.2 중량% 이고, 기체 및 고체의 촉매는 17.8 및 26.0 중량% 이다. 그러나 분산된 NMWS (x) 촉매를 사용하면 액체 질량 분율이 증가하고 고체 분율은 감소한다. 분산된 NMS 촉매 및 분산된 NWS 촉매를 적용할 때, 액체 질량 분율은 각각 53.8 및 56.5 중량% 였고, NMWS (0.2), NMWS (0.6), NMWS (1.5) 및 NMWS (3.6)가 각각 사용되었을 때 59.5, 61.7, 64.9 및 60.5 중량%로 증가함을 확인하였다.Figure 8 (a) shows the mass fraction of solids (coke), liquid and gas products, the liquid product is simulated distillation (SIMDIS) analysis (YG Hur, M.-S. Kim, D.-W. Lee, S. Kim, H.-J. Eom, G. Jeong, M.-H.No, NS Nho, K.-Y. Lee, Hydrocracking of vacuum residue into lighter fuel oils using nanosheet-structured WS2 catalyst, Fuel , 137 (2014) 237-244.), Residues (525 ° C.), gas oil (343-525 ° C.), middle distillate (177-343 ° C.) and naphtha. (-177 ° C) was classified according to the boiling point. If the catalyst is not used for hydrocracking of VR, the liquid mass fraction is only 56.2% by weight and the catalysts of gases and solids are 17.8 and 26.0% by weight. However, using a dispersed NMWS (x) catalyst increases the liquid mass fraction and decreases the solid fraction. When applying the dispersed NMS catalyst and the dispersed NWS catalyst, the liquid mass fractions were 53.8 and 56.5 wt%, respectively, when NMWS (0.2), NMWS (0.6), NMWS (1.5) and NMWS (3.6) were used, respectively. It was found to increase to 59.5, 61.7, 64.9 and 60.5 wt%.
도 8의 (b)는 분산된 NMWS (x) 촉매가 사용될 때의 상업용 액체 연료 생성물 (즉, 나프타, 중질유, 가스오일 등)의 수율을 나타낸다. NMWS (x) 촉매의 사용은 상업용 액체 연료 제품의 생산성을 NMWS (0.2) <NMWS (0.6) <NMWS (3.6) <NMWS (1.5)의 순서로 효과적으로 향상시켰다. FIG. 8 (b) shows the yield of commercial liquid fuel products (ie naphtha, heavy oil, gas oil, etc.) when dispersed NMWS (x) catalysts are used. The use of NMWS (x) catalyst effectively improved the productivity of commercial liquid fuel products in the order of NMWS (0.2) <NMWS (0.6) <NMWS (3.6) <NMWS (1.5).
도 9는 C5-아스팔텐 전환율 및 고체 생성물 (코크스)의 수율을 나타낸다. 수소 첨가 분해 촉매를 시험할 때, 아스팔텐은 코크스 형성의 주요 선구 물질이기 때문에 아스팔텐 전환은 중요한 활동 지수로 간주된다(F. Trejo, J. Ancheyta, Kinetics of asphaltenes conversion during hydrotreating of Maya crude, Catalysis Today, 109 (2005) 99-103.). 측정 결과, 분산된 NiMoWS (x) 촉매가 사용될 때, C5-아스팔텐 전환율이 증가하였고, 코크스 생성물의 수율은 실질적으로 감소하였다. 특히 분산된 NMWS (1.5) 촉매는 가장 낮은 코크스 형성(15.8 중량 %) 및 가장 높은 C5-아스팔텐 전환율(93.7 %)을 보임을 확인하였다.9 shows C 5 -asphaltene conversion and yield of solid product (coke). When testing hydrocracking catalysts, asphaltene conversion is considered an important activity index because asphaltene is a major precursor to coke formation (F. Trejo, J. Ancheyta, Kinetics of asphaltenes conversion during hydrotreating of Maya crude, Catalysis Today, 109 (2005) 99-103.). As a result of the measurement, when the dispersed NiMoWS (x) catalyst was used, the C 5 -asphaltene conversion increased and the yield of coke product decreased substantially. In particular, the dispersed NMWS (1.5) catalyst was found to show the lowest coke formation (15.8 wt%) and the highest C 5 -asphalten conversion (93.7%).
하기 표 4에 수소화 분해 반응 활성도와 황 함량 및 API 중력 값과 같은 액체 생성물의 품질 측정값을 측정하여 나타내었다. 측정 결과, 분산된 NMWS (1.5) 촉매가 사용될 때, 액체 생성물의 황 함량은 0.52 중량%로 상당히 감소됨을 확인하였다. 한편, API 중력 값은 액체 제품의 품질을 분류하는 데 사용되는 가장 중요한 요소인데, VR 반응물은 2.3° API 중력 값을 가졌지만, 분산된 NMWS (1.5) 촉매 하에서의 VR의 수소 첨가 분해는 API 중력을 20.4°로 증가시킴을 확인하였다. 이러한 결과는 수소 첨가 분해 생성물이 중질 원유로 분류될 수 있음을 의미한다. 황 제거 전환율과 API 중력은 분산된 NMWS (x) 촉매의 Mo/W 비율에 큰 영향을 받는 것으로 나타났으며, 구체적으로 분산된 NMWS (0.2) <NMWS (0.6) <NMWS (3.6) <NMWS (1.5) 순으로 측정되었다. 특히 NMWS (1.5) 촉매는 가장 높은 수소 탈착 능력과 금속-황 결합 에너지 (EMS)와의 상관관계로 인해 가장 높은 촉매 성능을 보임을 확인하였다.Table 4 below shows the measurement of the quality of the liquid product such as hydrocracking activity and sulfur content and API gravity value. The measurement showed that when the dispersed NMWS (1.5) catalyst was used, the sulfur content of the liquid product was significantly reduced to 0.52% by weight. On the other hand, the API gravity value is the most important factor used to classify the quality of the liquid product, while the VR reactants had a 2.3 ° API gravity value, but the hydrocracking of VR under dispersed NMWS (1.5) catalysts led to API gravity. It was confirmed that the increase to 20.4 °. This result means that hydrocracking products can be classified as heavy crude oil. Sulfur removal conversion and API gravity were found to be strongly influenced by the Mo / W ratio of the dispersed NMWS (x) catalyst, specifically the dispersed NMWS (0.2) <NMWS (0.6) <NMWS (3.6) <NMWS ( 1.5) in order. In particular, the NMWS (1.5) catalyst showed the highest catalyst performance due to the correlation between the highest hydrogen desorption capacity and the metal-sulfur bond energy (EMS).
마지막으로, 수소 첨가 분해 반응에서 분산된 NMWS (1.5) 촉매를 황화 처리된 NiMo/Al2O3 상업용 촉매와 비교하였으며, 촉매 성능의 비교 결과를 하기 표 5에 나타내었다. Finally, the NMWS (1.5) catalyst dispersed in the hydrocracking reaction was compared with the sulfided NiMo / Al 2 O 3 commercial catalyst, and the results of the catalyst performance are shown in Table 5 below.
측정 결과, 본 발명에 따른 NMWS (1.5) 분산형 촉매와 비교하여, NiMo/Al2O3 촉매는 보다 낮은 액체 생성물 수율 (59.5 중량 %)을 나타낸 반면, 가스 (23.4 중량 %) 및 고체 (17.1 중량 %) 생성물 수율은 더 높은 것으로 나타났다. 또한, NiMo/Al2O3 촉매는 C5-아스팔텐 전환, 황 전환 및 API 중력 값의 관점에서 더 낮은 촉매 성능을 가지는 것으로 나타났다. 이러한 결과를 통해 본 발명에 따른 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매가 VR의 수소 첨가 분해에서 경쟁력 있는 촉매 성능을 가짐을 확인하였다.As a result of the measurement, compared to the NMWS (1.5) dispersed catalyst according to the present invention, the NiMo / Al 2 O 3 catalyst showed a lower liquid product yield (59.5 wt%), whereas gas (23.4 wt%) and solid (17.1 Weight%) product yield was found to be higher. In addition, NiMo / Al 2 O 3 catalysts have been shown to have lower catalyst performance in terms of C 5 -asphalten conversion, sulfur conversion and API gravity values. These results confirm that the sulfided nickel-molybdenum-tungsten dispersed catalyst without the carrier according to the present invention has a competitive catalytic performance in hydrocracking of VR.
결론conclusion
VR의 수소 첨가 분해에서 본 발명에 따른 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 활성은 반응 공정에서 촉매의 수소 탈착 정도를 결정하는 Mo/W 비율에 크게 영향을 받는다. 본 발명에 따른 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매는 모우 우수한 촉매 성능을 가짐을 확인하였으며, 특히 NMWS (1.5) 분산형 촉매는 VR의 수소 첨가 분해 (hydrocracking)에서 가장 우수한 촉매 성능을 보였으며 상업용 액체 연료 생산성이 가장 우수한 것으로 나타났다. 또한, 본 발명에 따른 촉매는 모두 높은 C5-아스팔텐 전환율과 낮은 코크스 형성 특성을 보였으며, 상업용 촉매와 비교할 때, 수소 첨가 분해 반응 및 수소화 반응에 대한 모든 지표에 대해 우수한 촉매 성능을 나타냄을 확인하였다. 특히 NMWS (1.5) 분산형 촉매를 VR (API 중력 = 2.3 °)의 수소 첨가 분해에 적용하면 무거운 원유 수준의 생성물 (API 중력 = 20.4°)이 생성되었으며, 황제거 환원 및 코크스 형성 억제에서 가장 뛰어난 성능을 가지는 것을 확인하였다.The activity of the sulfided nickel-molybdenum-tungsten dispersed catalyst according to the invention in the hydrocracking of VR is greatly influenced by the Mo / W ratio which determines the degree of hydrogen desorption of the catalyst in the reaction process. The sulfided nickel-molybdenum-tungsten dispersed catalyst according to the present invention was found to have excellent catalytic performance. In particular, the NMWS (1.5) dispersed catalyst had the best catalytic performance in hydrocracking of VR. And commercial liquid fuel productivity was the best. In addition, the catalysts according to the invention all exhibited high C 5 -asphaltene conversion and low coke formation properties, and showed excellent catalytic performance for all indicators of hydrocracking and hydrogenation compared to commercial catalysts. Confirmed. In particular, the application of NMWS (1.5) dispersing catalysts to hydrocracking at VR (API gravity = 2.3 °) produced heavy crude oil levels (API gravity = 20.4 °), the most excellent in desulfurization reduction and coke formation inhibition. It was confirmed to have a performance.
결론적으로, 본 발명에 따른 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매는 수소 첨가 분해 반응 및 수소화 반응에 대한 모든 지표에 대해 우수한 촉매 성능을 나타내었는바, 초중질유로부터 경질유를 생산하는 공정에 매우 효과적으로 적용될 수 있음을 확인하였다.In conclusion, the sulfided nickel-molybdenum-tungsten dispersion catalyst according to the present invention showed excellent catalytic performance for all the indicators for hydrocracking and hydrogenation reactions. It can be seen that it can be applied very effectively.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.The specific parts of the present invention have been described in detail above. For those skilled in the art, the specific descriptions are merely preferred embodiments, and the scope of the present invention is limited thereto. It will be clear. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (3)
(b) 상기 혼합물에 수소를 첨가하는 단계; 및
(c) 상기 수소가 첨가된 혼합물을 380 ~ 500 ℃ 에서 수소화 분해하는 단계;를 포함하고,
상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매는, 텅스텐 전구체와 몰리브데늄 전구체를 혼합하는 단계; 상기 혼합 후 암모니아 용액을 첨가하는 단계; 상기 암모니아 용액 첨가 후 니켈 전구체를 혼합하는 단계; 및 상기 니켈 전구체 혼합 후 H2S/H2 가스를 사용하여 300 ~ 500 ℃에서 황화 처리(sulfidation)하는 단계;를 통해 제조되며,
상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 몰리브데늄/텅스텐의 몰비율은 1.2 내지 1.8인 것을 특징으로 하는 경질유의 제조방법.(a) mixing a sulfided nickel-molybdenum-tungsten (NiMoWS) dispersed catalyst without the use of ultra heavy oil and a support to produce a mixture;
(b) adding hydrogen to the mixture; And
(c) hydrocracking the mixture to which the hydrogen is added at 380 to 500 ° C;
The sulfided nickel-molybdenum-tungsten dispersed catalyst that does not use the support may include: mixing a tungsten precursor and a molybdenum precursor; Adding the ammonia solution after the mixing; Mixing the nickel precursor after the ammonia solution is added; And sulfidation at 300 to 500 ° C. using H 2 S / H 2 gas after mixing the nickel precursor.
The molar ratio of molybdenum / tungsten of the sulfided nickel-molybdenum-tungsten dispersed catalyst which does not use the carrier is 1.2 to 1.8, characterized in that the light oil.
상기 담지체를 사용하지 않은 황화 처리된 니켈-몰리브데늄-텅스텐 분산형 촉매의 크기는 100 nm 내지 1 ㎛인 것을 특징으로 하는 경질유의 제조방법.The method of claim 1,
Process for producing a light oil, characterized in that the size of the sulfided nickel- molybdenum-tungsten dispersed catalyst not using the carrier is 100 nm to 1 ㎛.
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