CN112044465B - Hydrodeoxygenation quality-improving catalyst for oil products and preparation method and application thereof - Google Patents
Hydrodeoxygenation quality-improving catalyst for oil products and preparation method and application thereof Download PDFInfo
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- CN112044465B CN112044465B CN202010939351.4A CN202010939351A CN112044465B CN 112044465 B CN112044465 B CN 112044465B CN 202010939351 A CN202010939351 A CN 202010939351A CN 112044465 B CN112044465 B CN 112044465B
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- catalyst
- hydrodeoxygenation
- oil
- quality
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 248
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 12
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 11
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 7
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 50
- 238000001035 drying Methods 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012684 catalyst carrier precursor Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 description 22
- 238000005984 hydrogenation reaction Methods 0.000 description 17
- 239000002283 diesel fuel Substances 0.000 description 15
- 230000006872 improvement Effects 0.000 description 14
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- 239000001257 hydrogen Substances 0.000 description 13
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000010779 crude oil Substances 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000000969 carrier Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 8
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- 150000001875 compounds Chemical class 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- 229920005610 lignin Polymers 0.000 description 7
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical group [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical group [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910003296 Ni-Mo Inorganic materials 0.000 description 6
- 229910003294 NiMo Inorganic materials 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- -1 small-molecule carboxylic acid compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
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- 235000013311 vegetables Nutrition 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C—CHEMISTRY; METALLURGY
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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
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- 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
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- 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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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a hydrodeoxygenation quality-improving catalyst for oil products and a preparation method and application thereof. The hydrodeoxygenation quality-improving catalyst for the oil product comprises a catalyst carrier, and an active component and an auxiliary agent which are loaded on the catalyst carrier; wherein the active component comprises ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide; the catalyst carrier comprises gamma-alumina, zeolite and active carbon; the auxiliary agent comprises phosphorus oxide; in the active component, the mol ratio of ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide is (0.2-1): (10-28): (2-10). The hydrodeoxygenation quality-improving catalyst for oil products provided by the invention has the characteristics of high activity and conversion rate of low-temperature hydrodeoxygenation, good selectivity, capability of being recycled for a plurality of times, good stability, strong coking resistance, good hydrothermal stability, good acid resistance and water resistance, simple preparation method and wide application prospect.
Description
Technical Field
The invention relates to the technical field of oil product refining, in particular to an oil product hydrodeoxygenation quality-improving catalyst, a preparation method and application thereof.
Background
With the rapid development of economy, petroleum resources are increasingly scarce, and people are increasingly concerned about environmental problems. How to effectively utilize biomass renewable resources to crack into bio-crude oil at high temperature and further upgrade green fuel oil has become a research subject of great attention. The method is a need for reducing and eliminating environmental pollution from the source, has very wide application prospect, and accords with the trend of clean development of clean fuel oil.
The bio-oil produced by biomass high-temperature pyrolysis has complex composition, contains almost all types of oxygen-containing organic compounds such as phenol, furan, ketone, aldehyde, alcohol, ether, acid, ester and the like besides a large amount of water, has total oxygen content as high as 50%, obviously reduces the quality of the oil, has the defects of low combustion heat value, poor stability, high viscosity, low volatility, corrosiveness and the like, and cannot be widely used as high-grade energy sources directly. If the bio-oil is used as an alternative energy source for diesel or gasoline, it must be deoxygenated and refined. Develop the high-efficiency catalytic hydrodeoxygenation catalyst with industrial application value and prospect, and have important economic and strategic significance for upgrading and modifying biological oil.
In particular, the large amount of water in the bio-crude causes the bio-oil to be difficult to ignite, reducing the heat of combustion. The small molecular organic acid has stronger corrosiveness and can reduce the service life of the internal combustion engine. Unsaturated compounds such as aldehyde and ketone are compounds with higher reactivity in biological oil, and are easy to generate polymerization reaction or other chemical reaction to generate water and macromolecular compounds, so that the kinematic viscosity of the biomass oil is increased, and layering phenomenon occurs. The lignin oligomer in the bio-oil is about 20-30wt% and is a macromolecule, the lignin oligomer is difficult to volatilize at the temperature of more than 100 ℃, the lignin oligomer can not be fully combusted in the combustion process of the bio-oil, and the lignin oligomer is easy to produce carbon deposition phenomenon to block an internal combustion engine. However, lignin oligomers have a relatively high calorific value, and if the lignin oligomers are simply separated from the bio-oil, the calorific value of combustion of the bio-oil is significantly reduced. From the analysis of the chemical composition of biological oils, the instability of biological oils and the difficulties present in refining are mainly due to the three types of components in biological oils, namely: unsaturated compounds such as aldehydes and ketones with high activity, small-molecule carboxylic acid compounds with high corrosiveness, and macromolecular compounds (lignin oligomers).
The existing biological crude oil upgrading modes mainly comprise catalytic hydrogenation, catalytic pyrolysis, catalytic esterification with solvent addition, emulsification and the like. Among them, catalytic hydrodeoxygenation is one of the most studied ways of upgrading biological oils. The catalytic hydrogenation is to hydrogenate the biological oil under the conditions of medium and high pressure (7-20 MPa), hydrogen and hydrogen-supplying solvent, thereby reducing the oxygen content, improving the energy density and the catalyst is the core. Although catalytic hydrofining of biological oils has been studied in a great deal and many important results have been achieved, the catalytic hydrogenation effect is not very ideal due to the complex components of biological oils and poor thermal stability. After upgrading, the bio-oil produced fuel oil has low yield and produces a considerable amount of carbon deposit, and the coke substances are easy to deposit on the surface of the catalyst and cover the active sites of the catalyst, so that the catalyst is deactivated. And the coke substances generated in the process are easy to block the reaction device, so that the catalytic hydrogenation process is difficult to carry out.
In bio-oil upgrading, the catalysts employed often suffer from problems such as rapid catalyst deactivation, catalyst coking. The problems greatly prevent the refining development of the biological oil, and if the catalytic hydrogenation catalyst with high activity, high selectivity, convenient operation and long service life can be designed, the catalytic hydrogenation catalyst plays an important role in reducing energy consumption, improving fuel oil yield, improving oil product quality, preventing environmental pollution and the like, and further can promote the green sustainable development of biomass energy and effectively relieve the current situation of energy shortage.
The aim of the biological oil hydrodeoxygenation technology is to produce high-quality green gasoline and diesel components and to increase the oil yield as much as possible, and the core of the technology is a catalyst. The existing biological oil hydrogenation catalyst mainly has the following problems: first, the catalyst used is mainly a commercial catalyst in the petrochemical industry. Compared to petroleum, biocrude has its own unique composition and properties. The biological crude oil has complex composition, contains a large amount of water, also contains polyunsaturated oxygen-containing compounds, has high viscosity, high density and high viscosity density, inevitably has coking phenomenon under a typical catalytic hydrogenation environment (370-420 ℃), leads to equipment coking, deactivates a catalyst and has a continuous reaction time of less than 3 days. Secondly, the prior art scheme is mainly to carry out simple review on the active components and the carrier components of the catalyst, most of the active components and the carrier of the bio-oil hydrodeoxygenation catalyst are single-function, the active components and the carrier are rarely compounded, and the specific preparation method of the catalyst suitable for low-temperature hydrodeoxygenation of the bio-oil is rarely searched.
Therefore, the development of the special catalyst with strong coking resistance, high low-temperature deoxidization activity and good hydrothermal stability, which is suitable for the low-temperature hydrogenation of biological crude oil, is an urgent need for the research and industrial development of biological oil hydrogenation.
Disclosure of Invention
In order to solve the problems of single activity of hydrodeoxygenation and upgrading of the existing oil product, low activity, poor stability, easy deactivation and coking and the like of a carrier catalyst, one of the purposes of the invention is to provide an oil product hydrodeoxygenation and upgrading catalyst, the other purpose of the invention is to provide a preparation method of the oil product hydrodeoxygenation and upgrading catalyst, and the third purpose of the invention is to provide application of the oil product hydrodeoxygenation and upgrading catalyst.
The inventive concept of the present invention is as follows: the catalyst is compounded with composite carrier capable of regulating acid-base and mesoporous-macroporous distribution and raising low temperature hydrodeoxygenation conversion rate and selectivity, multifunctional active component capable of raising coking resistance, low temperature deoxidation conversion rate and selectivity, and assistant capable of raising hydrothermal stability, water resistance, acid resistance and fast deactivation. The invention fully utilizes the advantages of the respective components of the catalyst and avoids the respective defects, thereby obtaining the hydrodeoxygenation catalyst with high low-temperature deoxidation activity, good selectivity, strong coking resistance, good hydrothermal stability and good acid and water resistance, and the purposes of effectively improving the product quality and yield of the hydrodeoxygenation quality of the oil product can be realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an oil hydrodeoxygenation quality-improving catalyst, which comprises a catalyst carrier, and an active component and an auxiliary agent which are loaded on the catalyst carrier; wherein the active component comprises ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide; the catalyst carrier comprises gamma-alumina, zeolite and active carbon; the auxiliary agent comprises phosphorus oxide; in the active component, the mol ratio of ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide is (0.2-1): (10-28): (2-10).
The components of the hydrodeoxygenation quality-improving catalyst for the oil product provided by the invention comprise a multifunctional active component, a composite carrier and an auxiliary agent. The components are described in detail below.
The active components of the hydrodeoxygenation quality-improving catalyst for oil products are compounded by a small amount of noble metal Ru oxide, conventional metal oxide Mo oxide, ni oxide or Co oxide. Noble metal Ru has the advantages of mild hydrogenation reaction conditions, good low-temperature activity, high reaction rate, high selectivity, good stability, strong carbon deposition resistance, strong particulate matter poisoning and the like, but the noble metal Ru catalyst also has the defects of being very sensitive to sulfur, nitrogen organic compounds, hydrogen sulfide and the like, easy to cause poisoning and deactivation, high in price, high in cost and unfavorable for industrialization. The non-noble metal or oxide with synergistic effect with active component Ru is found to be taken as a cocatalyst, and the catalyst is added into Ru catalyst, so that the content of Ru catalyst can be reduced, the catalytic hydrogenation performance of Ru catalyst can be improved, and the industrial application cost can be reduced.
The present inventors have found through a great deal of research and experimentation that: the hydrogenation of unsaturated aldehyde, ketone, acid, ester and other components in biological oil by a small amount of noble metal Ru oxide and non-noble metal hydrogenation active components Mo oxide, ni oxide or Co oxide at 180-400 ℃ has a synergistic promotion effect, ru can be rapidly activated to dissociate hydrogen, and the formation of coordination unsaturated NiMo or CoMo active center is promoted by overflow hydrogen, meanwhile, the granularity of Ru oxide is finer than that of Mo oxide, ni oxide or Co oxide, the content is less, the specific surface is large, and the number of active centers is more. The structure of a small amount of Ru adjustable catalyst is introduced into the NiMo or CoMo catalyst, the reduction temperature of the NiMo or CoMo catalyst is reduced by 50-150 ℃, the dispersion of the NiMo or CoMo active components is promoted, the grain size of metal is reduced, and the bimetallic Ru-Ni-Mo of the catalyst has synergistic effect, so that the catalytic activity can be improved. Meanwhile, the synergistic effect between Ru-Ni-Mo or Ru-Co-Mo can inhibit sintering of NiMo or CoMo crystal grains, reduce carbon deposit of the catalyst, and further improve the stability of the catalyst. Compared with single hydrogenation active component noble metal Ru or conventional hydrogenation component NiMo or CoMo, the multifunctional active component Ru-Ni-Mo or Ru-Co-Mo can generate more active center numbers in a low-temperature hydrogenation environment, so that the catalyst has the characteristics of higher low-temperature hydrodeoxygenation upgrading activity, selectivity, water resistance and acid resistance, hydrothermal stability and difficult rapid deactivation, the content of noble metal Ru is reduced, the utilization rate of noble metal Ru is improved, the cost can be reduced, and the catalyst is very beneficial to industrial realization.
The composite carrier of the hydrodeoxygenation quality-improving catalyst for oil products is formed by compounding gamma-alumina, zeolite and active carbon. The composite carrier of the present invention is obtained based on the following studies and knowledge of the inventors: gamma-alumina is an active alumina, and although gamma-alumina has the advantages of large specific surface area, good mechanical properties, good stability, low cost and the like, the gamma-alumina is mainly used as a carrier to provide the defects of weak acidity of L acid, relatively small influence on active components, low mechanical strength, weak acidity and the like. The molecular sieve has high specific surface area, regular and ordered holes, large specific surface area and high acid strength, especially B acid, is a relatively ideal catalyst carrier suitable for reaction cracking of macromolecules, is beneficial to the contact of biological oil raw materials with acid sites and active parts in more holes and is more beneficial to the diffusion and discharge of products, but the molecular sieve of the types such as Y, HY, USY and the like has the defects of high price, strong acidity and easy deactivation. The active carbon can be used as a carrier for reaming, the interaction with active metals Ru, niMo or CoMo is reduced, the dispersity of active components can be increased, the specific surface area of the catalyst is increased, and the active carbon is reduced and activated at a lower temperature to generate more active species, but has the defect of low strength. Therefore, the invention not only can keep the advantages of the carrier and realize complementary advantages by adopting the composite carrier formed by compounding the gamma-alumina, the zeolite and the active carbon, but also can avoid respective defects, can play a role in enlarging pores, can increase the dispersity of active components, regulate and control different pore structures, increase the specific surface area of the catalyst and the like, can complement the advantages of long and short, cooperatively play a role, improve the overall performance of the carrier, improve the structure of an active phase of the catalyst, regulate and control the L and B acid strength of the catalyst, and improve the hydrodeoxygenation reaction rate, selectivity and stability of the catalyst surface.
Compared with single carriers such as alumina or Y, HY mesoporous molecular sieve, active carbon and the like, the composite carrier has proper binding force with active component metal, can not be excessively strong or weak, inhibits the sintering and deactivation of noble metal Ru, can better improve the dispersibility of multifunctional active component Ru-Ni-Mo or Ru-Co-Mo, has higher catalytic activity and stability in low-temperature hydrodeoxygenation quality improvement, can better serve as multifunctional active component Ru-Ni-Mo or Ru-Co-Mo skeleton, can provide proper L and B acid active center and acid strength, can better improve the utilization rate of the multifunctional active component, and improves the stability and toxicity resistance of the catalyst. Proved by experimental study: the zeolite and active carbon modified gamma-alumina carrier supported catalyst has moderate acidity, is not easy to coke, can obviously improve the low-temperature hydrodeoxygenation activity, selectivity and stability of the catalyst, has no obvious coking deactivation phenomenon at the reaction time of 250 hours, and has a great amount of coking deactivation only in a few hours, and the service life of the catalyst is short.
The auxiliary agent of the hydrodeoxygenation quality-improving catalyst for the oil product is phosphorus oxide, so that the low-temperature hydrodeoxygenation activity, stability and service life of the catalyst are improved. The inventor finds through research and experiments that: the phosphorus oxide can improve the dispersity of the hydrogenation component Ru-Ni-Mo or Ru-Co-Mo active metal on the surface of the catalyst, improve the pore structure, increase the active sites of the catalyst, regulate and control the distribution of mesopores and macropores, thereby realizing complementary advantages, avoiding respective defects, ensuring uniform granularity, improving pore volume, pore diameter and specific surface area, obviously improving the hydrodeoxygenation activity of the catalyst, promoting the dispersion of the metal component on the surface of the carrier and improving the structure of the active phase of the catalyst.
Preferably, the active component in the hydrodeoxygenation quality-improving catalyst for oil products is selected from ruthenium oxide, molybdenum oxide and nickel oxide, or ruthenium oxide, molybdenum oxide and cobalt oxide, or ruthenium oxide, molybdenum oxide, nickel oxide and cobalt oxide.
Preferably, in the hydrodeoxygenation quality-improving catalyst for oil products, the molar ratio of ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide is (0.3-0.7): (12-20): (4-8); further preferably, the molar ratio of ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide is (0.4 to 0.6): (14-17): (5-6).
Preferably, in the active component of the hydrodeoxygenation quality-improving catalyst for oil products, the ruthenium oxide is RuO 2 。
Preferably, in the active component of the hydrodeoxygenation quality-improving catalyst for oil products, molybdenum oxide is MoO 3 。
Preferably, in the active component of the hydrodeoxygenation quality-improving catalyst for oil products, the nickel oxide is NiO.
Preferably, in the active component of the hydrodeoxygenation quality-improving catalyst for oil products, the cobalt oxide is CoO.
Preferably, in the hydrodeoxygenation quality-improving catalyst for oil products, the active component accounts for 13-25% of the mass of the hydrodeoxygenation quality-improving catalyst for oil products; further preferably, the active component accounts for 18 to 25 percent of the mass of the hydrodeoxygenation quality-improving catalyst for oil products.
Preferably, in the hydrodeoxygenation quality-improving catalyst for oil products, the catalyst carrier accounts for 70-85% of the mass of the hydrodeoxygenation quality-improving catalyst for oil products; further preferably, the catalyst carrier accounts for 73-80% of the mass of the hydrodeoxygenation quality-improving catalyst for oil products.
Preferably, in the hydrodeoxygenation quality-improving catalyst for oil products, the auxiliary agent accounts for 0.5-6% of the mass of the hydrodeoxygenation quality-improving catalyst for oil products; further preferably, the auxiliary agent accounts for 0.7-3% of the mass of the oil hydrodeoxygenation quality-improving catalyst.
In the hydrodeoxygenation quality-improving catalyst for oil products, the sum of the mass of active components, catalyst carriers and auxiliary agents is 100%.
Preferably, in the catalyst carrier of the hydrodeoxygenation quality-improving catalyst for oil products, the mass ratio of gamma-alumina, zeolite and active carbon is (75-85): (13-25): (1-8); further preferably, the mass ratio of the gamma-alumina, zeolite to activated carbon is (77-83): (14-22): (2-7); still more preferably, the mass ratio of gamma-alumina, zeolite to activated carbon is (80-82): (14-16): (4-5).
Preferably, in the catalyst carrier of the hydrodeoxygenation quality-improving catalyst for oil products, the zeolite is at least one selected from Y-type zeolite, HY-type zeolite and USY-type zeolite.
Preferably, in the catalyst carrier of the hydrodeoxygenation quality-improving catalyst for oil products, the activated carbon is mesoporous activated carbon.
Preferably, in the auxiliary agent of the hydrodeoxygenation quality-improving catalyst for oil products, the phosphorus oxide is P 2 O 5 。P 2 O 5 Can interact with activated alumina to generate AlPO on the surface of the catalyst 4 The number of strong acid centers is reduced, and the number of medium strong acid centers is increased, so that the carbon deposition resistance of the catalyst is enhanced, and the hydrothermal stability of the catalyst is improved.
Preferably, the bulk density of the hydrodeoxygenation quality-improving catalyst for oil products is 0.65 g/mL-0.80 g/mL; it is further preferred that the bulk density of the hydrodeoxygenation upgrading catalyst for oil products is between 0.70g/mL and 0.71g/mL.
Preferably, the specific surface area of the hydrodeoxygenation quality-improving catalyst for oil products is 120m 2 /g～200m 2 /g; it is further preferred that the specific surface area of the hydrodeoxygenation upgrading catalyst for oil products is 140m 2 /g～160m 2 /g; still further preferred, the specific surface area of the hydrodeoxygenation upgrading catalyst for oil products is 145m 2 /g～154m 2 /g。
Preferably, the pore volume of the hydrodeoxygenation quality-improving catalyst for oil products is 0.5 mL/g-1.2 mL/g; further preferably, the pore volume of the hydrodeoxygenation upgrading catalyst for oil products is 0.56 mL/g-0.62 mL/g.
The second aspect of the invention provides a preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, which comprises the following steps:
1) Preparing a catalyst carrier: mixing gamma-alumina, zeolite and active carbon to obtain a mixture, processing and forming the mixture to obtain a catalyst carrier precursor, and then drying and roasting to obtain a catalyst carrier;
2) Preparing a catalyst: mixing a ruthenium source, a molybdenum source, a nickel source and/or a cobalt source with water, and then mixing with a phosphorus source to obtain a mixed solution; and (3) immersing the catalyst carrier in the mixed solution, drying and roasting to obtain the hydrodeoxygenation quality-improving catalyst for the oil product.
Preferably, in the mixture of the step 1) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the mass ratio of gamma-alumina, zeolite and active carbon is (75-85): (13-25): (1-8); further preferably, in the mixture of step 1), the mass ratio of gamma-alumina, zeolite to activated carbon is (77-83): (14-22): (2-7); still more preferably, in the mixture of step 1), the mass ratio of gamma-alumina, zeolite to activated carbon is (80 to 82): (14-16): (4-5).
Preferably, in the step 1) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the mixture is ground to below 200 meshes.
Preferably, in the step 1) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the catalyst carrier precursor obtained by processing and shaping the mixture is specifically: mixing the mixture with sesbania powder, adding acid, kneading, and extrusion to obtain catalyst carrier precursor. Further preferably, the sesbania powder accounts for 1-3% of the mixture; the mass ratio of the acid to the mixture is (1-2): 1, a step of; the acid is selected from nitric acid or hydrochloric acid solution with the concentration of 6-15%; the kneading time is 40-80 minutes; still more preferably, the sesbania powder accounts for 1-2% of the mass of the mixture; the mass ratio of the acid to the mixture is (1.4-1.6): 1, a step of; the acid is selected from nitric acid solution with the concentration of 8-12%; the kneading time is 50 minutes to 70 minutes.
Preferably, in the step 1) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the drying comprises primary drying and secondary drying, and specifically, the primary drying is performed first and then the secondary drying is performed. Wherein, the primary drying is carried out for 4 to 6 hours at the temperature of 40 to 60 ℃; the secondary drying is carried out at 100-120 ℃ for 12-24 hours. Further preferably, in step 1), the primary drying is carried out at 40 to 60 ℃ for 5 hours; the secondary drying is carried out at 100-105 ℃ for 24 hours.
Preferably, in the step 1) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the roasting is specifically as follows: heating to 400-800 ℃ at 2-5 ℃/min, and roasting for 4-8 hours in a protective atmosphere; further preferably, the calcination is specifically: heating to 550-650 deg.c at 3-4 deg.c/min and roasting in protecting atmosphere for 5-7 hr. The protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere.
Preferably, in the step 2) of the preparation method of the oil hydrodeoxygenation quality-improving catalyst, the temperature at which the ruthenium source, the molybdenum source, the nickel source and/or the cobalt source are mixed with water is 25-60 ℃.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the mixing time with the phosphorus source is 0.5-2 hours.
Preferably, in the step 2) of the preparation method of the oil hydrodeoxygenation quality-improving catalyst, the ruthenium source is ruthenium nitrate.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the molybdenum source is molybdenum nitrate.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the nickel source is nickel nitrate.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the cobalt source is cobalt nitrate.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the phosphorus source is phosphoric acid. Phosphoric acid may provide a component of the adjuvant.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the soaking time is 4-8 hours; more preferably, the time for immersion is 5 to 7 hours.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the drying comprises primary drying and secondary drying, and specifically, the primary drying is performed first and then the secondary drying is performed. Wherein, the primary drying is carried out for 2 to 4 hours at the temperature of 40 to 60 ℃; the secondary drying is carried out for 4 to 12 hours at the temperature of 100 to 120 ℃. Further preferably, in step 2), the primary drying is carried out at 40 to 60 ℃ for 4 hours; the secondary drying is carried out at 100-105 ℃ for 6 hours.
Preferably, in the step 2) of the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products, the roasting is specifically as follows: heating to 400-800 ℃ at 2-5 ℃/min, and roasting for 6-8 hours in a protective atmosphere; further preferably, the calcination is specifically: heating to 550-650 deg.c at 3-4 deg.c/min and roasting in protecting atmosphere for 5-7 hr. The protective atmosphere is preferably a nitrogen atmosphere or an argon atmosphere.
The third aspect of the invention provides application of the hydrodeoxygenation quality-improving catalyst for oil products.
The application of the hydrodeoxygenation quality-improving catalyst in the hydrodeoxygenation quality-improving reaction of oil products.
The application of the hydrodeoxygenation quality-improving catalyst for the oil products provided by the invention is not limited to a hydrodeoxygenation conversion process, hydrofining or pretreatment, and the catalyst can be used for a hydrotreating process, a hydrocracking process and the like.
Preferably, in use, the oil is an oil comprising an oxygen-containing organic compound. The oxygen-containing organic compounds include, for example, phenols, furans, ketones, aldehydes, alcohols, ethers, acids or esters. Further preferably, the oil product comprises at least one of bio-oil and high acid crude oil. In particular, the bio-oil may be selected from the following: each distillation range section of various biological crude oils, including the full distillation range; cracking tar at high temperature, wherein each distillation range section comprises a full distillation range; each distillation range section of the vegetable bio-oil comprises a full distillation range; a mixture of any light distillation range of various biological crude oils and diesel oil and heavy oil components in petroleum refining. The hydrodeoxygenation quality-improving catalyst for the oil products can be applied to hydrodeoxygenation quality-improving treatment of biological oil, high-acid crude oil or a mixture containing the oil products.
Preferably, in the application, the reaction temperature of the hydrodeoxygenation upgrading reaction is 180-400 ℃; further preferably, the reaction temperature of the hydrodeoxygenation upgrading reaction is 200-360 ℃; still more preferably, the reaction temperature of the hydrodeoxygenation upgrading reaction is 300 ℃ to 350 ℃.
Preferably, in application, the particle size of the hydrodeoxygenation quality-improving catalyst for oil products is 400-600 meshes.
Preferably, in the application, the hydrogen pressure of the hydrodeoxygenation upgrading reaction is 6MPa to 10MPa; more preferably, the hydrogen pressure of the hydrodeoxygenation upgrading reaction is 8MPa to 10MPa.
Preferably, in the application, the reaction time of hydrodeoxygenation upgrading reaction is 2-6 hours; it is further preferred that the hydrodeoxygenation upgrading reaction takes 3 to 4 hours.
Preferably, in the application, the mass ratio of the hydrodeoxygenation quality-improving catalyst to the biological oil is 1: (4-6).
Preferably, in application, the volume ratio of hydrogen to bio-oil is (600-1200): 1, a step of; further preferably, the volume ratio of hydrogen to bio-oil is (700-800): 1.
preferably, in the application, the hydrodeoxygenation quality-improving catalyst for oil products is presulfided by carbon disulfide before use; the presulfiding temperature is 280-320 ℃, and the presulfiding time is 10-15 hours.
Preferably, in the application, the hydrodeoxygenation upgrading reaction of the oil is that of biological oil.
Preferably, the hydrodeoxygenation quality-improving catalyst for oil products is applied to hydrodeoxygenation quality-improving reaction of biological oil, and the biological oil is subjected to hydrodeoxygenation reaction to obtain the quality-improved biological oil; distilling the upgraded biological oil at normal pressure to obtain gasoline fraction and diesel fraction; wherein the fraction with the distillation temperature less than or equal to 190 ℃ is gasoline, and the fraction with the distillation temperature of 190-360 ℃ is diesel.
In the application of the present invention, the reactor for hydrodeoxygenation upgrading reaction is not particularly limited, and those skilled in the art can select according to actual needs, such as a fixed bed reactor, a batch reactor or an ultrasonic reactor, and a fluidized bed or a slurry bed.
The beneficial effects of the invention are as follows:
compared with the existing catalyst with single active component and carrier, the hydrodeoxygenation quality-improving catalyst for oil products provided by the invention has the characteristics of high activity and conversion rate of low-temperature hydrodeoxygenation, good selectivity, capability of being recycled for a plurality of times, good stability, strong coking resistance, good hydrothermal stability, good acid resistance and water resistance, simple preparation method and wide application prospect.
The catalyst is prepared by adopting an impregnation method, the prepared composite catalyst carries out hydrodeoxygenation quality improvement on the biological oil, the biological oil deoxidization rate is high, the heat value is obviously improved, the pH value is greatly increased to be neutral, the density is greatly reduced, the color is brown and clear, the quality improvement effect is obvious, and the product quality and the yield are effectively improved. The diesel oil fraction after hydrodeoxygenation quality improvement has high cetane number, and can be used as a green diesel oil blending component. The catalyst of the invention has the total reaction time of more than 250 hours after 3-4 times of multiple condition cycles, almost no change in catalyst activity and no obvious coking phenomenon of the catalyst.
Drawings
FIG. 1 is a schematic illustration of a preparation flow of a catalyst support according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a catalyst preparation flow according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples are all commercially available from conventional sources or may be obtained by methods known in the art unless otherwise specified. Unless otherwise indicated, assays or testing methods are routine in the art.
Catalyst preparation example 1
Referring to the schematic of the catalyst carrier preparation flow chart of fig. 1 and the schematic of the catalyst preparation flow chart of fig. 2, the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products of this example is as follows:
(1) Preparation of the catalyst support: mixing the active gamma-alumina powder, Y-type zeolite and mesoporous active carbon in the required proportion to obtain the mixture. In the mixture, the active gamma-alumina, the Y-zeolite and the mesoporous activated carbon respectively account for 80 percent, 16 percent, the mass of the mixture,4%. And then the mixture is ground to below 200 meshes and stirred uniformly. Then adding sesbania powder accounting for 1.5 percent of the total mass of the mixture into the mixture, then adding nitric acid solution accounting for 1.5 times of the mass of the mixture and 10 percent of the mixture, kneading for 60 minutes, repeatedly extruding for a plurality of times on an extruder, and extruding and molding to obtain the molded carrier. Drying the molded carrier at 40-45deg.C for 5 hr, drying at 105deg.C for 24 hr, and heating to 600deg.C at a rate of 4deg.C/min under N 2 Roasting for 6 hours in atmosphere to obtain the finished catalyst carrier.
(2) Preparation of the catalyst: adding ruthenium nitrate, molybdenum nitrate and nickel nitrate according to the required proportion into distilled water respectively, stirring uniformly at the temperature of 40 ℃, then adding phosphoric acid, and stirring continuously for 1 hour to obtain a mixed solution. In the mixed solution, the mol ratio of ruthenium nitrate, molybdenum nitrate and nickel nitrate is 0.5:17:6. Immersing the catalyst carrier in the mixed solution for 6 hr, drying at 40-45 deg.C for 4 hr, drying at 105 deg.C for 6 hr, heating to 600 deg.C at 4 deg.C/min, and adding N 2 Roasting for 6 hours in atmosphere to obtain the hydrodeoxygenation quality-improving catalyst (A1 catalyst) for the oil product.
The composition and morphology of the A1 catalyst were analyzed by SEM, ICP-AES, FT-IR, XRD, TEM, etc., and the results are shown in Table 1. The A1 catalyst prepared in this example has a bulk density of 0.70g/mL and a specific surface area of 145m 2 Per gram, pore volume was 0.62mL/g.
Catalyst preparation example 2
Referring to the schematic of the catalyst carrier preparation flow chart of fig. 1 and the schematic of the catalyst preparation flow chart of fig. 2, the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products of this example is as follows:
(1) Preparation of the catalyst support: mixing the active gamma-alumina powder, HY-type zeolite and mesoporous activated carbon according to a required proportion to obtain a mixture. In the mixture, the active gamma-alumina, the HY-type zeolite and the mesoporous activated carbon respectively account for 82 percent, 14 percent and 4 percent of the mass of the mixture. Wherein, the mesoporous activated carbon is used as a pore-expanding agent. And then the mixture is ground to below 200 meshes and stirred uniformly. Then adding sesbania accounting for 1.5 percent of the total mass of the mixtureAdding 1.5 times of 10% nitric acid solution into the powder, kneading for 60 minutes, repeatedly extruding for several times on an extruder, and extruding to obtain the molded carrier. Drying the molded carrier at 60deg.C for 5 hours, then at 105deg.C for 24 hours, and then raising the temperature to 600deg.C at a rate of 4deg.C/min under N 2 Roasting for 6 hours in atmosphere to obtain the finished catalyst carrier.
(2) Preparation of the catalyst: adding ruthenium nitrate, molybdenum nitrate and cobalt nitrate according to the required proportion into distilled water respectively, stirring uniformly at the temperature of 40 ℃, then adding phosphoric acid, and stirring continuously for 1 hour to obtain a mixed solution. In the mixed solution, the mol ratio of ruthenium nitrate, molybdenum nitrate and cobalt nitrate is 0.5:14:5.5. Immersing the finished catalyst carrier obtained in the first step in the mixed solution, saturating for 6 hours, drying at 60 ℃ for 4 hours, drying at 105 ℃ for 6 hours, heating to 600 ℃ at a heating rate of 4 ℃/min, and adding N 2 Roasting for 6 hours in atmosphere to obtain the hydrodeoxygenation quality-improving catalyst (A2 catalyst) for oil products.
The composition and morphology of the A2 catalyst were analyzed by SEM, ICP-AES, FT-IR, XRD, TEM, etc., and the results are shown in Table 1. The A2 catalyst prepared in this example has a bulk density of 0.71g/mL and a specific surface area of 152m 2 Per gram, pore volume was 0.58mL/g.
Catalyst preparation example 3
Referring to the schematic of the catalyst carrier preparation flow chart of fig. 1 and the schematic of the catalyst preparation flow chart of fig. 2, the preparation method of the hydrodeoxygenation quality-improving catalyst for oil products of this example is as follows:
(1) Preparation of the catalyst support: mixing active gamma-alumina powder, USY zeolite and mesoporous active carbon in the required proportion to obtain the mixture. In the mixture, the active gamma-alumina, USY zeolite and mesoporous activated carbon respectively account for 80%, 15% and 5% of the mass of the mixture. And then the mixture is ground to below 200 meshes and stirred uniformly. Then adding sesbania powder accounting for 1.5 percent of the total mass of the mixture into the mixture, then adding nitric acid solution accounting for 1.5 times of the mass of the mixture and 10 percent of the mixture, kneading for 60 minutes, repeatedly extruding for a plurality of times on an extruder, and extruding and molding to obtain the molded carrier. Drying the molded carrier at 40deg.CDrying for 5 hours, then drying at 105 ℃ for 24 hours, then raising the temperature to 600 ℃ at a heating rate of 4 ℃/min, and finally adding the mixture into N 2 Roasting for 6 hours in atmosphere to obtain the finished catalyst carrier.
(2) Preparation of the catalyst: adding ruthenium nitrate, molybdenum nitrate and nickel nitrate according to the required proportion into distilled water respectively, stirring uniformly at the temperature of 40 ℃, then adding phosphoric acid, and stirring continuously for 1 hour to obtain a mixed solution. In the mixed solution, the mol ratio of ruthenium nitrate, molybdenum nitrate and nickel nitrate is 0.5:15:5.5. Immersing the finished catalyst carrier obtained in the first step in the mixed solution, saturating for 6 hours, drying at 40 ℃ for 4 hours, drying at 105 ℃ for 6 hours, heating to 600 ℃ at a heating rate of 4 ℃/min, and adding N 2 Roasting for 6 hours in atmosphere to obtain the hydrodeoxygenation quality-improving catalyst (A3 catalyst) for oil products.
The composition and morphology of the A3 catalyst were analyzed by SEM, ICP-AES, FT-IR, XRD, TEM, etc., and the results are shown in Table 1. The A3 catalyst prepared in this example has a bulk density of 0.70g/mL and a specific surface area of 154m 2 Per gram, pore volume was 0.56mL/g.
Table 1 shows the compositions and properties of the A1 to A3 catalysts prepared in examples 1 to 3.
TABLE 1 catalyst composition and Properties
The catalyst prepared in examples 1-3 was used for low temperature hydrodeoxygenation upgrading application tests on bio-oil. The low-temperature hydrodeoxygenation and upgrading are carried out by taking biological crude oil (application example 1), biological crude oil doped modified diesel oil (application example 2), biological crude oil and an oxygen-containing model compound (application example 3) as raw materials respectively, and the deoxidization and upgrading effects of the catalyst are evaluated. The raw material conditions and the operation conditions of the application test application examples 1 to 3 can be seen in Table 2.
Table 2 raw materials and operating conditions for the application test
Catalyst application example 1
The biological oil is subjected to low-temperature hydrodeoxygenation and upgrading by using the catalyst A1 prepared in the example 1, and the deoxidation and upgrading effects of the catalyst are evaluated. Referring now to Table 2, the test methods for the present application are described as follows:
taking a commercial pyrolysis bio-oil as a raw material B1, the density of the bio-oil is as follows: 1.15g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Mass water content: 20% of a base; viscosity at 30 ℃): 58.2 mPa.s; color: brown black; pH value: 3.2; oxygen content: 47.3%; heating value: 17.5MJ/kg; cetane number: 25.
in a 1000mL intermittent high-pressure hydrogenation reaction kettle, CS is firstly used 2 The A1 catalyst was presulfided at a sulfiding temperature of 300℃for a sulfiding time of 12 hours. The catalyst with 400 meshes obtained by screening after vulcanization and the bio-oil after filtration and dehydration are added into a batch type high-pressure reaction kettle together, and the operation conditions are as follows: hydrogen pressure is 8.0-10.0MPa, the mass ratio of catalyst to bio-oil is 1:5, the reaction time is 3-4 hours, the hydrogen to bio-oil ratio (volume ratio) is (700-800): 1, the reaction temperature is 320-350 ℃.
After the biological oil is distilled under normal pressure after hydrogenation and quality improvement, the biological oil is cut into gasoline (the temperature is less than or equal to 190 ℃) and diesel (the temperature is 190-360 ℃) fractions according to the distillation temperature.
The catalytic hydrodeoxygenation quality improvement effect of the bio-oil is as follows: diesel fraction after upgrading, density: 0.88-0.91g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Mass water content: 1.2-3.3%; viscosity at 30 ℃): 33.6-42.3 mPas; color: dark brown yellow; pH value: 6.7-6.8; oxygen content: 3.2-5.0%; heating value: 35.5-36.8MJ/kg; cetane number: 48-53. The test results show that: the deoxidation rate of the biological oil is 89-93%, the calorific value is improved by 103-110%, the acid value is greatly improved, the biological oil almost reaches neutrality, the quality improving effect is obvious, and the diesel oil fraction after quality improvement can be used as a green diesel oil blending component.
The comparison of the effects of the bio-oil of this application example before and after hydrodeoxygenation and upgrading is shown in Table 3.
TABLE 3 comparison of the effects of the catalyst application example 1 before and after hydrodeoxygenation and upgrading of biological oils
The catalyst of the example has little change in catalyst activity after 4 or more condition cycles and the total reaction time reaches 250 hours, and no obvious coking phenomenon of the catalyst is found. Compared with single active components such as Ru, niMo or CoMo, single carriers such as gamma alumina and Y-type molecular sieve carrier catalysts, XRD, TEM and TGA find that single active component carrier catalysts such as Ru/gamma-alumina, ni-Mo/HY zeolite and the like react for coking deactivation for 4-12 hours, and the service life of the catalyst is short.
Catalyst application example 2
The biological oil is subjected to low-temperature hydrodeoxygenation and upgrading by using the catalyst A2 prepared in the example 2, and the deoxidation and upgrading effects of the catalyst are evaluated. Referring now to Table 2, the test methods for the present application are described as follows:
taking the mixture of a certain high-temperature pyrolysis biological oil (B2) +modified diesel oil (C1) as a raw material, the density of the mixture is as an example: 1.20g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Mass water content: 18%; viscosity at 30 ℃): 55.2 mPa.s; color: brown black; pH value: 3.0; oxygen content: 46.5%; heating value: 18.1MJ/kg; cetane number: 28.
the mass ratio of the biological oil B2 to the modified diesel oil C1 is 0.75:0.25. the modified diesel oil has the following properties and density: 0.89g/cm 3 Mass water content: 0.1%; viscosity at 30 ℃): 45.2 mPa.s; color: brown yellow; pH value: 7.0; oxygen content: 0.1%; heating value: 39.5MJ/kg.
In a 1000mL intermittent high-pressure hydrogenation reaction kettle, CS is firstly used 2 The A2 catalyst was presulfided at a sulfiding temperature of 300℃for a sulfiding time of 12 hours. The vulcanized catalyst with 600 meshes and the bio-oil are added into an intermittent high-pressure reaction kettle, and the operation conditions are as follows: hydrogen pressure is 8.0-10.0MPa, and mass ratio of catalyst to bio-oil is 1:5, the reaction time is 3-4 hours, and the hydrogen/bio-oil ratio (volume ratio) is (700-800): 1 reaction temperature320-350℃。
After the biological oil is distilled under normal pressure after hydrogenation and quality improvement, the biological oil is cut into gasoline (the temperature is less than or equal to 190 ℃) and diesel (the temperature is 190-360 ℃) fractions according to the distillation temperature.
The catalytic hydrodeoxygenation quality improvement effect of the bio-oil is as follows: bio-oil density after upgrading: 0.87-0.90g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Mass water content: 1.0-2.0%; viscosity at 30 ℃): 28.2-33.6 mPa.s; color: dark brown yellow; pH value: 6.8-7.0; oxygen content: 1.0-1.2%; heating value: 38.8-39.0MJ/kg; cetane number: 46-51. The test results show that: the deoxidizing rate of the biological oil is 97.4-97.8%, the calorific value is improved by 114-115%, the quality improving effect is remarkable, and after the quality is further improved, the diesel oil fraction reaches the standard of green diesel oil blending components.
The comparison of the effects of the bio-oil of this application example before and after hydrodeoxygenation and upgrading is shown in Table 4.
Table 4 catalyst application example 2 comparison of effects before and after hydrodeoxygenation and upgrading of bio-oil
| Index (I) | Pyrolysis of bio-oil B2 | B2 diesel fraction after hydrodeoxygenation |
| Density g/cm 3 | 1.2 | 0.87-0.90 |
| Water content/wt% | 18 | 1.0-2.0 |
| Viscosity at 30 ℃ per mPa.s | 55.2 | 28.2-33.6 |
| Color of | Brown black | Deep brown yellow |
| pH value of | 3 | 6.8-7.0 |
| Oxygen content/wt% | 46.5 | 1.0-1.2 |
| Heating value MJ/kg | 18.1 | 38.8-39.0 |
| Bio-oil deoxygenation rate/% | 97.4-97.8 | |
| Heating value increase/% | 114-115 | |
| Cetane number | 28 | 46-51 |
The catalyst of the example has little change in catalyst activity after 4 or more condition cycles and the total reaction time reaches 280 hours, and no obvious coking phenomenon of the catalyst is found. Compared with the catalysts of single active components such as Ru, niMo or CoMo, single carriers such as gamma alumina and Y-type molecular sieve carriers, XRD, TEM and TGA are used for finding that the catalysts of single active component carriers such as Ru/gamma-alumina, ni-Mo/HY zeolite and the like are subjected to reaction coking deactivation for 6-12 hours, and the service life of the catalysts is very short.
Catalyst application example 3
The biological oil is subjected to low-temperature hydrodeoxygenation and upgrading by using the catalyst A3 prepared in the example 3, and the deoxidation and upgrading effects of the catalyst are evaluated. Referring now to Table 2, the test methods for the present application are described as follows:
taking a certain high-temperature cracking biological oil (B3) +model compound (C2) as a raw material, the density of the biological oil is as follows: 1.10g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Mass water content: 20% of a base; viscosity at 30 ℃): 52.2 mPa.s; color: brown black; pH value: 2.9; oxygen content: 45.5%; heating value: 18.3MJ/kg; cetane number: 27.
the mass ratio of the biological oil B3 to the model compound C2 is 3:1, the model compound (C2) is o-methoxyphenol, phenol and acetic acid, and the mass ratio of the o-methoxyphenol to the phenol to the acetic acid is 1:1:1.
In a 1000mL intermittent high-pressure hydrogenation reaction kettle, CS is firstly used 2 The A3 catalyst was presulfided at a sulfiding temperature of 300℃for a sulfiding time of 12 hours. The vulcanized catalyst with 600 meshes and the bio-oil are added into an intermittent high-pressure reaction kettle, and the operation conditions are as follows: hydrogen pressure is 8.0-10.0MPa, and mass ratio of catalyst to bio-oil is 1:5, the reaction time is 3-4 hours, the hydrogen/bio-oil ratio (volume ratio) (700-800): 1, the reaction temperature is 300-350 ℃.
After the biological oil is distilled under normal pressure after hydrogenation and quality improvement, the biological oil is cut into gasoline (the temperature is less than or equal to 190 ℃) and diesel (the temperature is 190-360 ℃) fractions according to the distillation temperature.
The catalytic hydrodeoxygenation quality improvement effect of the bio-oil is as follows: bio-oil density after upgrading: 0.88-0.91g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Mass water content: 1.0-2.5%; viscosity at 30 ℃): 30.2-35.6 mPa.s; color: brown yellow; pH value: 6.8-7.0; oxygen content: 1.8-3.8%; heating value: 35.3-37.8MJ/kg; cetane number: 47-52. The test results show that: the deoxidizing rate of the biological oil is 91.6-96%, the calorific value is improved by 92.9-106.5%, the quality improving effect is remarkable, and the diesel oil fraction can reach green after further quality improvementDiesel fuel blend composition standard.
The comparison of the effects of the bio-oil of this application example before and after hydrodeoxygenation and upgrading is shown in Table 5.
TABLE 5 comparison of the effects of the catalyst application example 3 before and after hydrodeoxygenation and upgrading of biological oils
| Index (I) | Pyrolysis of bio-oil B3 | B3 diesel fraction after hydrodeoxygenation |
| Density g/cm 3 | 1.1 | 0.88-0.91 |
| Water content/wt% | 20 | 1.0-2.5 |
| Viscosity at 30 ℃ per mPa.s | 52.2 | 30.2-35.6 |
| Color of | Brown black | Brown yellow |
| pH value of | 2.9 | 6.8-7.0 |
| Oxygen content/wt% | 45.5 | 1.8-3.8 |
| Heating value MJ/kg | 18.3 | 35.3-37.8 |
| Bio-oil deoxygenation rate/% | 91.6-96.0 | |
| Heating value increase/% | 92.9-106.5 | |
| Cetane number | 27 | 47-52 |
The catalyst of the example has little change in catalyst activity after 3 or more condition cycles and the total reaction time reaches 250 hours, and no obvious coking phenomenon of the catalyst is found. Compared with the catalysts of single active components such as Ru, niMo or CoMo, single carriers such as gamma alumina and HY type molecular sieve carriers, XRD, TEM and TGA are used for finding that the catalysts of single active component carriers such as Ru/gamma-alumina, ni-Mo/HY zeolite and the like are subjected to reaction coking deactivation for 4-12 hours, and the service life of the catalysts is very short.
From the test results, the catalyst provided by the invention is applied to hydrodeoxygenation quality improvement treatment of biological oil, the deoxidation rate of the biological oil is 89% -97.8%, the calorific value is improved by 92.9% -115%, the pH value is greatly increased, neutrality is achieved, the density is greatly reduced, the color and luster are clarified, the quality improvement effect is obvious, and the product quality and the yield are effectively improved. After the biological oil subjected to hydrogenation and quality improvement is distilled at a constant pressure, the cetane number of the obtained diesel oil fraction is 46-53, and the diesel oil fraction can be used as a green diesel oil blending component. The catalyst has little change in activity after 3-4 times of multiple condition cycles, the total reaction time reaches more than 250 hours, and no obvious coking phenomenon of the catalyst is found.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. The application of the hydrodeoxygenation quality-improving catalyst for the oil products in hydrodeoxygenation quality-improving reaction of the oil products is characterized in that: the hydrodeoxygenation quality-improving catalyst for the oil product consists of a catalyst carrier, and an active component and an auxiliary agent which are loaded on the catalyst carrier;
the active component is ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide;
the catalyst carrier is gamma-alumina, zeolite and active carbon;
the auxiliary agent is phosphorus oxide;
in the active component, the molar ratio of ruthenium oxide, molybdenum oxide, nickel oxide and/or cobalt oxide is (0.2-1): (10-28): (2-10);
the active component accounts for 13-25% of the mass of the hydrodeoxygenation quality-improving catalyst for oil products; the catalyst carrier accounts for 70% -85% of the mass of the oil hydrodeoxygenation quality-improving catalyst; the auxiliary agent accounts for 0.5-6% of the mass of the hydrodeoxygenation quality-improving catalyst for oil products;
in the catalyst carrier, the mass ratio of gamma-alumina, zeolite and active carbon is (75-85): (13-25): (1-8);
in the catalyst carrier, zeolite is selected from at least one of Y-type zeolite, HY-type zeolite and USY-type zeolite; the active carbon is mesoporous active carbon;
the phosphorus oxide is P 2 O 5 。
2. The use according to claim 1, characterized in that: the bulk density of the hydrodeoxygenation quality-improving catalyst for the oil product is 0.65 g/mL-0.80 g/mL; the specific surface area of the oil hydrodeoxygenation quality-improving catalyst is 120m 2 /g~200m 2 /g; the pore volume of the oil hydrodeoxygenation quality-improving catalyst is 0.5 mL/g-1.2 mL/g.
3. The use according to claim 1, characterized in that: the preparation method of the hydrodeoxygenation quality-improving catalyst for the oil product comprises the following steps:
1) Preparing a catalyst carrier: mixing gamma-alumina, zeolite and active carbon to obtain a mixture, processing and forming the mixture to obtain a catalyst carrier precursor, and then drying and roasting to obtain a catalyst carrier;
2) Preparing a catalyst: mixing a ruthenium source, a molybdenum source, a nickel source and/or a cobalt source with water, and then mixing with a phosphorus source to obtain a mixed solution; and (3) immersing the catalyst carrier in the mixed solution, drying and roasting to obtain the hydrodeoxygenation quality-improving catalyst for the oil product.
4. Use according to claim 1, characterized in that: the oil product is an oil product containing an oxygen-containing organic compound.
5. Use according to claim 1, characterized in that: the reaction temperature of the hydrodeoxygenation upgrading reaction is 180-400 ℃.
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| CN103977796A (en) * | 2014-05-18 | 2014-08-13 | 华东理工大学 | Catalyst used in preparation of long-chain alkane through catalytic hydrodeoxygenation of biomass |
| CN104744204A (en) * | 2015-02-04 | 2015-07-01 | 华东理工大学 | Method for preparing aromatic hydrocarbon by carrying out catalytic hydrodeoxygenation on lignin |
| CN105985216A (en) * | 2015-02-06 | 2016-10-05 | 中国科学院大连化学物理研究所 | Method for preparing napthene used for diesel oil or aviation kerosene |
| CN104841466A (en) * | 2015-04-09 | 2015-08-19 | 厦门大学 | Bio-oil-based oxygen compound hydrodeoxygenation catalyst and preparation method thereof |
| CN105132003A (en) * | 2015-08-27 | 2015-12-09 | 中国科学院青岛生物能源与过程研究所 | Preparation method for biological aircraft fuel |
| CN107303489A (en) * | 2016-04-19 | 2017-10-31 | 中国石油天然气股份有限公司 | Double bond saturation and hydrogenation deoxidation catalyst and its preparation method and application |
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