CN118059948B - A method for preparing a molybdenum-based catalyst and its application - Google Patents
A method for preparing a molybdenum-based catalyst and its application Download PDFInfo
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- CN118059948B CN118059948B CN202410210652.1A CN202410210652A CN118059948B CN 118059948 B CN118059948 B CN 118059948B CN 202410210652 A CN202410210652 A CN 202410210652A CN 118059948 B CN118059948 B CN 118059948B
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- molybdenum
- acid diethanolamide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 59
- 239000011733 molybdenum Substances 0.000 title claims abstract description 58
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000010779 crude oil Substances 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 150000004668 long chain fatty acids Chemical class 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000005580 one pot reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 claims description 3
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229940031957 lauric acid diethanolamide Drugs 0.000 claims description 3
- XGZOMURMPLSSKQ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO XGZOMURMPLSSKQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 2
- GZZPOFFXKUVNSW-UHFFFAOYSA-N Dodecenoic acid Natural products OC(=O)CCCCCCCCCC=C GZZPOFFXKUVNSW-UHFFFAOYSA-N 0.000 claims description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005643 Pelargonic acid Substances 0.000 claims description 2
- 229920001800 Shellac Polymers 0.000 claims description 2
- AHANXAKGNAKFSK-PDBXOOCHSA-N all-cis-icosa-11,14,17-trienoic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCCCC(O)=O AHANXAKGNAKFSK-PDBXOOCHSA-N 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- PRHHYVQTPBEDFE-UHFFFAOYSA-N eicosatrienoic acid Natural products CCCCCC=CCC=CCCCCC=CCCCC(O)=O PRHHYVQTPBEDFE-UHFFFAOYSA-N 0.000 claims description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- BPXGKRUSMCVZAF-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)decanamide Chemical compound CCCCCCCCCC(=O)N(CCO)CCO BPXGKRUSMCVZAF-UHFFFAOYSA-N 0.000 claims description 2
- UWDGKUMOFQTNHC-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO UWDGKUMOFQTNHC-UHFFFAOYSA-N 0.000 claims description 2
- VJESJEJNMGVQLZ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)N(CCO)CCO VJESJEJNMGVQLZ-UHFFFAOYSA-N 0.000 claims description 2
- SKDZEPBJPGSFHS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)N(CCO)CCO SKDZEPBJPGSFHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004208 shellac Substances 0.000 claims description 2
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims description 2
- 229940113147 shellac Drugs 0.000 claims description 2
- 235000013874 shellac Nutrition 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 19
- 239000003921 oil Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000000571 coke Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 5
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- -1 VIB metals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a molybdenum-based catalyst, wherein a molybdenum source, long-chain fatty acid amide, an organic solvent and a vulcanizing agent are taken for one-pot reaction to obtain a molybdenum-based precursor mixed solution; and separating the molybdenum-based precursor mixed solution to obtain the oil-soluble molybdenum-based catalyst. The preparation method of the molybdenum-based catalyst provided by the invention has the advantages of simple and reliable flow, low requirements on temperature and equipment and simple operation. When the catalyst is used, no additional vulcanizing agent is needed, the catalyst can be used for in-situ self-vulcanizing active components in a slurry bed reactor, active metals are ultra-high dispersed in raw oil, the catalyst has good hydrogenation performance and coke inhibition performance, is suitable for the hydrogenation upgrading of raw oil slurry beds with various qualities, can provide high-quality raw materials for the process of directly preparing chemicals from crude oil, and has very wide application prospects.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a molybdenum-based catalyst.
Background
The main product of the traditional crude oil processing process flow is mainly finished oil. In the future, the market demand of the automobile fuel oil is further reduced under the influence of the development of new energy automobiles with hydrogen energy and electric energy, and the consumption demands of olefin and aromatic hydrocarbon of synthetic monomers of various materials are continuously increased. The traditional oil refining process is mainly characterized in that crude oil is cut into light and heavy fraction sections through atmospheric and vacuum pressure, light distillate oil is directly subjected to steam cracking, reforming, aromatization and other devices to produce olefine aromatic hydrocarbon, and heavy distillate oil is subjected to fixed bed hydrocracking, slurry bed (suspension bed) hydrocracking and other devices to be light and then maximized to produce olefine aromatic hydrocarbon. The process scheme has long overall flow, high comprehensive energy consumption and large overall device investment, and is unfavorable for structural transformation of the traditional stock refinery. Two typical techniques, steam cracking and catalytic cracking, are currently established. However, the cracking furnace has the defects of severe process operation and poor adaptability to raw materials due to high catalyst severity, and the direct one-step chemical preparation cannot be realized for crude oil with high metal content, high density, wide distillation range and high heavy component content. Therefore, the crude oil is subjected to hydrogenation upgrading through a slurry bed, the metal content and the sulfur and nitrogen content are reduced, the asphaltene content is reduced, and the light oil proportion is improved, so that an effective raw material can be provided for preparing chemicals by a crude oil one-step method, and the significance is great.
The slurry bed hydrogenation is that a small amount of catalyst is dispersed in the raw material in the form of solid powder or liquid, the raw material and hydrogen are heated to the reaction temperature and then pass through the reactor from bottom to top in the form of gas, liquid and solid three-phase slurry, and the catalyst has the advantages of strong raw material adaptability, simple flow, high conversion rate and the like.
The key to the development of slurry bed hydrocracking technology is the sustainable progress of high quality hydrogenation catalysts, wherein oil soluble catalysts can be effectively dissolved in heavy raw materials, show excellent hydrogenation effect and effectively inhibit coking, and are ideal catalysts. Chinese patent CN201610804914.2 discloses that an active metal precursor is prepared by precipitation of a soluble salt of Mo or W at 40-100 ℃ and an oil soluble catalyst is prepared by reaction with a C6-C20 organic acid. Chinese patent CN201410216485.8 discloses that the oil-soluble catalyst is prepared by reacting reduced metal with organic amine. Chinese patent CN202010553349.3 metalloate and surfactant are mixed homogeneously and ground to obtain mixture, and the suspension bed hydrogenation catalyst is obtained. U.S. patent 4125455 discloses hydrogenation applications using a metal salt composed of group VIB metals (molybdenum, tungsten, chromium) of C7-C32 fatty acids as catalyst, which adds 590ppm molybdenum octoate as catalyst, and has better hydrogenation effect at 430 ℃ and 13.7 MPa. Most of the catalysts have complex synthetic routes and need to be vulcanized independently, so that the hydrogenation efficiency of the slurry bed crude oil is reduced and the equipment investment is increased.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a molybdenum-based catalyst, the preparation method has simple and reliable flow, low requirements on temperature and equipment, simple operation, capability of in-situ self-vulcanizing active components in a slurry bed reactor, ultrahigh dispersion of active metals in raw oil, good hydrogenation performance and coke inhibition performance, and suitability for hydrogenation and upgrading of crude oil slurry beds with various qualities.
In order to achieve the aim, the invention provides the following technical scheme that the preparation method of the molybdenum-based catalyst comprises the following steps:
S1, taking a molybdenum source, long-chain fatty acid amide, an organic solvent and a vulcanizing agent to react in a one-pot method to obtain a molybdenum-based precursor mixed solution;
s2, separating the molybdenum-based precursor mixed solution to obtain the oil-soluble molybdenum-based catalyst.
Preferably, in the step S1, a molybdenum source, long-chain fatty acid amide, an organic solvent and a vulcanizing agent are added into a reaction kettle together, stirring and heating are carried out for 6-12 hours at a temperature of 85-150 ℃, in the step S2, the solution obtained in the step S1 is cooled, stood and layered, and the water phase is removed, so that the oil-soluble molybdenum-based catalyst with dispersed organic solvent is prepared.
Preferably, the molybdenum source in the step S1 is any one or a combination of a plurality of molybdenum trioxide, ammonium heptamolybdate, ammonium tetramolybdate, molybdic acid, molybdenum acetylacetonate and molybdenum hexacarbonyl.
Preferably, the long-chain fatty acid amide in step S1 is any one or more of palmitic acid diethanolamide, lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, behenic acid diethanolamide, arachic acid diethanolamide, pelargonic acid diethanolamide, capric acid diethanolamide, myristic acid diethanolamide, lignoceric acid diethanolamide, cerotic acid diethanolamide, shellac acid diethanolamide, dodecenoic acid diethanolamide, eicosatrienoic acid diethanolamide, erucic acid diethanolamide.
Preferably, the organic solvent in the step S1 is any one or more of toluene, petroleum ether, xylene, DMF and n-butanol.
Preferably, the vulcanizing agent in the step S1 is one or more of ammonium sulfide, sodium hydrosulfide, sodium polysulfide and thioacetamide.
Preferably, the molar ratio of the molybdenum source, the long-chain fatty acid amide, the organic solvent and the vulcanizing agent is 1:0.6-1:5-10:4-10.
The invention also provides an application of the molybdenum-based catalyst, which is prepared by adopting the preparation method, and the molybdenum-based catalyst is used for hydrotreating in a crude oil slurry bed before crude oil is subjected to atmospheric and vacuum distillation or before the crude oil enters a device for directly preparing chemicals.
Preferably, the catalyst addition amount is 50-1200 ppm, the reaction temperature is 330-460 ℃, the reaction pressure is 5-20 MPa, the liquid hourly space velocity is 0.2-1.5 h -1, and the volume ratio of hydrogen to raw materials is 300-1500.
Preferably, the crude oil is one or more of paraffin-based crude oil, intermediate-based crude oil and cycloalkyl crude oil.
Compared with the prior art, the invention provides a preparation method and application of a preparation method of a molybdenum-based catalyst, and the preparation method has the following beneficial effects:
the invention adopts a one-pot reaction of molybdenum source, long-chain fatty acid amide, organic solvent and vulcanizing agent to obtain molybdenum-based precursor mixed solution, and the oil-soluble molybdenum-based catalyst with dispersed organic solvent is directly prepared by liquid separation. The preparation method has simple and reliable flow, low requirements on temperature and equipment and simple operation. When the catalyst is used, no additional vulcanizing agent is needed, the catalyst can be used for in-situ self-vulcanizing active components in a slurry bed reactor, active metals are ultra-high dispersed in raw oil, the catalyst has good hydrogenation performance and coke inhibition performance, is suitable for the hydrogenation upgrading of raw oil slurry beds with various qualities, can provide high-quality raw materials for the process of directly preparing chemicals from crude oil, and has very wide application prospects.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
The experimental methods in the embodiment of the application are conventional methods unless otherwise specified. The test materials used in the examples, unless otherwise specified, were purchased from conventional reagent stores.
Example 1
30G of molybdenum oxide is weighed, 100ml of water is added, 30g of oleic acid diethanolamide, 120g of toluene and 70g of thioacetamide are weighed, sequentially added into the solution, and the temperature is raised to 145 ℃ and the mixture is stirred for reaction for 3 hours. And centrifuging the obtained solution, separating the solution to obtain an oil phase, and obtaining the oil-soluble molybdenum-based catalyst which is named M-1.
Example 2
30G of ammonium heptamolybdate is weighed, 80ml of water is added, 30g of diethanolamide palmitate, 150g of toluene and 80g of sodium sulfide are weighed, sequentially added into the solution, and the temperature is raised to 130 ℃ and the mixture is stirred for reaction for 4 hours. And centrifuging the obtained solution, separating the solution to obtain an oil phase, and obtaining the oil-soluble molybdenum-based catalyst which is named M-2.
Example 3
30G of molybdenum oxide was weighed, 100ml of water was added, 30g of lauric acid diethanolamide, 150g of toluene, 70g of sodium hydrosulfide were weighed, and then the mixture was added to the above solution in sequence, and the temperature was raised to 150℃and the reaction was stirred for 3 hours. And centrifuging the obtained solution, separating the solution to obtain an oil phase, and obtaining the oil-soluble molybdenum-based catalyst which is named M-3.
Example 4
30G of ammonium heptamolybdate is weighed, 100ml of water is added, 30g of stearic acid diethanolamide, 160g of petroleum ether and 70g of thioacetamide are sequentially added into the solution, and the temperature is raised to 150 ℃ and the mixture is stirred for reaction for 3 hours. And centrifuging the obtained solution, separating the solution to obtain an oil phase, and obtaining the oil-soluble molybdenum-based catalyst which is named M-4.
Comparative example 1
Comparative example 1 commercial molybdenum octoate catalyst purchased
The oil-soluble Mo catalyst can be used for slurry bed hydrocracking processes of various crude oils, and the use method comprises the steps of directly adding the oil-soluble Mo-based catalyst into the crude oil, performing self-vulcanization in a heating process to generate active metal molybdenum sulfide, wherein the active metal molybdenum sulfide has excellent hydrogenation activity, the catalyst addition amount is 50-1200 ppm (calculated by metal Mo), the reaction temperature is 330-460 ℃, the reaction pressure is 5-20 MPa, the liquid hourly space velocity is 0.2-1.5 h -1, and the volume ratio of hydrogen to raw materials is 300-1500.
Table 1 properties of sauter crude oil
The oil-soluble molybdenum-based catalysts (M-1, M-2, M-3, M-4) and the molybdenum octoate catalysts in example 1, example 2, example 3 and example 4 were prepared from sauter crude oil (properties shown in Table 1), and the volume space velocity of the liquid was 1h -1 at a reaction temperature of 390 ℃ and a hydrogen pressure of 7MPa, the catalyst addition amount was 200ug/g in terms of metallic molybdenum, and the volume ratio of hydrogen to the raw material was 1200. The results of the hydrogenation upgrading evaluation of the sauter crude oil under the same reaction conditions of different oil-soluble molybdenum-based catalysts are shown in table 2.
Table 2 results of experimental evaluation of hydrogenation upgrading of sauter crude oil
As can be seen from the data in Table 2, the oil-soluble molybdenum-based catalyst prepared by the invention has excellent hydrogenation performance, and can effectively reduce the asphaltene content in oil products, improve the light oil yield by 7 percent and lead the coke generation amount to be less than 0.1 weight percent under the conditions that the reaction temperature is 390 ℃, the initial hydrogen pressure is 7MPa, the catalyst dosage is 200 mug/g (calculated by metal), the liquid hourly space velocity is 1h -1 and the volume ratio of hydrogen to raw materials is 1200. Compared with a commercial molybdenum isooctanoate catalyst, the oil-soluble molybdenum-based catalyst provided by the invention has better activity, and the crude oil after hydrogenation modification can directly enter a crude oil chemical preparation process, so that the requirements of crude oil steam cracking and catalytic cracking on the severity of oil products are reduced.
The above embodiments are only for illustrating the technical solution of the present invention, but not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solution described in the above embodiments or equivalents may be substituted for some of the technical features thereof, and the modifications or substitutions may be made without departing from the spirit and scope of the technical solution as claimed in the present invention.
Claims (6)
1. A method for preparing a molybdenum-based catalyst, comprising the steps of:
S1, taking a molybdenum source, long-chain fatty acid amide, an organic solvent and a vulcanizing agent to react in a one-pot method to obtain a molybdenum-based precursor mixed solution;
s2, separating the molybdenum-based precursor mixed solution to prepare an oil-soluble molybdenum-based catalyst;
In the step S1, adding a molybdenum source, long-chain fatty acid amide, an organic solvent and a vulcanizing agent into a reaction kettle, stirring and heating for 6-12 hours at 85-150 ℃, cooling, standing and layering the solution obtained in the step S1, and removing a water phase to obtain an oil-soluble molybdenum-based catalyst with dispersed organic solvent;
The molybdenum source in the step S1 is any one or a combination of a plurality of molybdenum trioxide, ammonium heptamolybdate, ammonium tetramolybdate, molybdic acid, molybdenum acetylacetonate and molybdenum hexacarbonyl;
In the step S1, the long-chain fatty acid amide is any one or more of palmitic acid diethanolamide, lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, behenic acid diethanolamide, arachic acid diethanolamide, pelargonic acid diethanolamide, capric acid diethanolamide, myristic acid diethanolamide, cerotic acid diethanolamide, melissic acid diethanolamide, shellac diethanolamide, dodecenoic acid diethanolamide, eicosatrienoic acid diethanolamide and erucic acid diethanolamide;
The vulcanizing agent in S1 is one or more of ammonium sulfide, sodium hydrosulfide, sodium polysulfide and thioacetamide.
2. The method for preparing a molybdenum-based catalyst according to claim 1, wherein the organic solvent in the step S1 is any one or more of toluene, petroleum ether, xylene, DMF, and n-butanol.
3. The method for preparing the molybdenum-based catalyst according to claim 1, wherein the molar ratio of the molybdenum source, the long-chain fatty acid amide, the organic solvent and the vulcanizing agent is 1:0.6-1:5-10:4-10.
4. Use of a molybdenum-based catalyst, obtainable by the process according to any one of claims 1-3, characterized in that the crude oil is hydrotreated in a slurry bed of crude oil by means of a molybdenum-based catalyst before it is subjected to atmospheric and vacuum distillation or before it enters a unit for directly preparing chemicals from crude oil.
5. The use of a molybdenum-based catalyst according to claim 4, wherein the catalyst is added in an amount of 50-1200 ppm, the reaction temperature is 330-460 ℃, the reaction pressure is 5-20 MPa, the liquid hourly space velocity is 0.2-1.5 h -1, and the volume ratio of hydrogen to raw materials is 300-1500.
6. The use of a molybdenum-based catalyst according to claim 4 or 5, wherein the crude oil is one or more of paraffinic crude oil, intermediate crude oil, naphthenic crude oil.
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