CN115337957A - Molybdenum-containing mesoporous alumina molecular sieve, and preparation method and application thereof - Google Patents
Molybdenum-containing mesoporous alumina molecular sieve, and preparation method and application thereof Download PDFInfo
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- CN115337957A CN115337957A CN202110525242.2A CN202110525242A CN115337957A CN 115337957 A CN115337957 A CN 115337957A CN 202110525242 A CN202110525242 A CN 202110525242A CN 115337957 A CN115337957 A CN 115337957A
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- molybdenum
- molecular sieve
- mesoporous alumina
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 121
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 105
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000011733 molybdenum Substances 0.000 title claims abstract description 105
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 33
- 238000002441 X-ray diffraction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 18
- 229910039444 MoC Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000001228 spectrum Methods 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 8
- 238000009825 accumulation Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 21
- 238000003763 carbonization Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- HMYHPPPXNHYVOQ-UHFFFAOYSA-N octane;thiophene Chemical compound C=1C=CSC=1.CCCCCCCC HMYHPPPXNHYVOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—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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- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/12—Surface area
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- 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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Abstract
The invention discloses a molybdenum-containing mesoporous alumina molecular sieve, a preparation method and application thereof. Based on the weight of the molybdenum-containing mesoporous alumina molecular sieve, the content of molybdenum is 10 to 35 weight percent, preferably 20 to 25 weight percent; the specific surface area of the molybdenum-containing mesoporous alumina molecular sieve is 250-450 m 2 Per g, pore volume of 0.20-0.35 cm 3 (ii) in terms of/g. According to the invention, molybdenum is successfully introduced into the mesoporous alumina molecular sieve in one step by a one-step gel method, the interaction between alumina and molybdenum particles is enhanced by using an auxiliary agent, the molybdenum is uniformly dispersed on the alumina, the accumulation of the molybdenum on the alumina is avoided, the increase of the particle size is inhibited, and the molybdenum with high dispersion degree can be obtained at a lower temperature by combining the regulation and control of preparation conditionsAnd the molybdenum-containing mesoporous alumina molecular sieve has high specific surface area. The molybdenum-containing mesoporous alumina molecular sieve is particularly suitable for serving as a catalytic material for hydrodesulfurization of sulfur-containing hydrocarbons.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to an aluminum oxide material, a preparation method thereof and application thereof in a hydrodesulfurization process.
Background
The molecular sieve not only has good physical properties and structural characteristics, but also has good hydrothermal stability and chemical properties. It has high adsorption capacity, high selectivity and high temperature resistance, has the functions of molecular sieving, adsorption, ion exchange and catalysis, and may be used widely in petrochemical industry and organic chemical industry. Molecular sieves can be classified into both natural zeolites and synthetic zeolites. Natural zeolites are mostly formed by the reaction of volcanic tuff and tuff sedimentary rocks in marine or lake phase environments. More than 1000 kinds of zeolite ores are found, and clinoptilolite, mordenite, erionite, chabazite and the like are more common. The method is mainly distributed in countries such as America, japan, french and the like, china also finds a large number of mordenite and clinoptilolite ore beds, and Japan is the country with the largest natural zeolite exploitation amount. Since natural zeolites are resource-constrained, synthetic zeolites have been used in large quantities since the 50's of the 20 th century. Molecular sieves are used in the chemical industry as solid adsorbents, the substances adsorbed by them can be desorbed and the molecular sieves can be regenerated after use. It can also be used for drying, purifying, separating and recovering gas and liquid. Since the beginning of the 20 th century, 60 s, used as cracking catalysts in the petroleum refining industry, a variety of molecular sieve catalysts suitable for different catalytic processes have now been developed.
In recent years, non-silicon mesoporous materials such as alumina and titanium dioxide have become hot research in the fields of heterogeneous catalysis, environmental protection, clean energy and the like, wherein the alumina is widely applied to petrochemical industry such as hydrocracking, hydrodesulfurization, fine chemical industry, organic synthesis and the like as a cheap catalyst or a catalyst carrier.
CN109894125A discloses a supported sulfidic Co-Mo/gamma-A 2 O 3 A preparation method and application of a bimetallic catalyst. The catalyst is prepared by the following steps: using a liquid-transfering gun to suck a proper amount of deionized water, and dripping the deionized water into gamma-A with unit mass 2 O 3 In the above, the vector gamma-A was measured 2 O 3 Water absorption capacity of(ii) a Subsequently, the volume per water absorption of the carrier is measured and a certain amount of (NH) is added 4 ) 6 Mo 7 O 24 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 O, completely dissolving; slowly adding the dissolved solution into the carrier gamma-A with unit mass 2 O 3 Standing for 12 hours; then drying and roasting to obtain the oxidation state Co-Mo/gamma-A 2 O 3 A bimetallic catalyst; finally, the oxidation state catalyst is vulcanized to obtain the vulcanization state catalyst which is easy to prepare, good in utilization performance and high in catalytic activity and is used for catalytic removal of heteroatoms in coal-related model compounds, namely dibenzyl ether, furan, thiophene and quinoline. The catalyst adopts an impregnation method to load molybdenum, the load capacity of the catalyst is limited, and the catalyst has a large influence on the pore structure of the carrier, so that the improvement of the performance of the catalyst is influenced.
The traditional alumina material has wider pore size distribution and is not beneficial to shape-selective catalytic reaction, so that the synthesized mesoporous alumina molecular sieve has larger specific surface area and narrower pore size distribution and has important significance and wide application prospect. The synthesis method of the mesoporous alumina molecular sieve mainly comprises a hydrothermal method, a template method and a sol-gel method. For example, CN1958450A discloses a method for synthesizing a mesoporous alumina molecular sieve. The synthesis method comprises the steps of taking organic aluminum as an aluminum source, taking linear chain carboxylic acid containing 12 to 18 carbon atoms as a template agent, taking alcohol as a solvent and taking water as a catalyst, synthesizing a precursor by adopting an anion template method at room temperature, filtering, washing with ethanol, drying, and preparing the mesoporous alumina molecular sieve by adopting a temperature programming roasting method. However, the research on the mesoporous alumina molecular sieve is still in an immature stage, and how to prepare the catalytic material suitable for hydrodesulfurization is still to be further deeply researched.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a molybdenum-containing mesoporous alumina molecular sieve and a preparation method and application thereof. The molybdenum-containing mesoporous alumina molecular sieve is a mesoporous alumina molecular sieve material with high molybdenum dispersity, high specific surface area and good pore size distribution, and is particularly suitable for serving as a hydrodesulfurization catalytic material.
Hair brushIn a first aspect, a molybdenum-containing mesoporous alumina molecular sieve is provided, wherein the molybdenum content is 10wt% to 35wt% based on the weight of the molybdenum-containing mesoporous alumina molecular sieve; the specific surface area of the molybdenum-containing mesoporous alumina molecular sieve is 250-450 m 2 Per gram, pore volume of 0.20-0.35 cm 3 /g。
Further, the molybdenum-containing mesoporous alumina molecular sieve preferably contains 20wt% to 25wt% of molybdenum based on the weight of the molybdenum-containing mesoporous alumina molecular sieve.
Further, the molybdenum in the molybdenum-containing mesoporous alumina molecular sieve exists in a form of molybdenum oxide.
Furthermore, in the molybdenum-containing mesoporous alumina molecular sieve, the mesoporous diameter is 2.0-4.0 nm, preferably 2.5-4.0 nm.
Further, moO is not found in the XRD spectrogram of the molybdenum-containing mesoporous alumina molecular sieve 3 Characteristic peak.
Further, in the molybdenum-containing mesoporous alumina molecular sieve, moO 3 The grain size of the crystal grains is 2.0 to 4.5nm, preferably 2.5 to 4.5nm.
The second aspect of the present invention provides a method for preparing a molybdenum-containing mesoporous alumina molecular sieve, comprising:
(1) Mixing an aluminum source, a molybdenum source and water to prepare a solution A;
(2) Slowly adding an auxiliary agent into the solution A obtained in the step (1) to obtain gel B;
(3) And aging, drying and thermally treating the gel B to obtain the molybdenum-containing mesoporous alumina molecular sieve.
Further, the molybdenum in the molybdenum-containing mesoporous alumina molecular sieve obtained in the step (3) exists in the form of molybdenum oxide.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, in the step (1), preferably, the aluminum source and the molybdenum source are respectively dissolved in water and then mixed to obtain the solution a.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, in the step (1), the aluminum source is an inorganic salt containing aluminum, and may be specifically one or more selected from aluminum nitrate, aluminum sulfate and aluminum chloride, and preferably is aluminum nitrate.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, in the step (1), the molybdenum source is one or more of ammonium dimolybdate, ammonium tetramolybdate and ammonium heptamolybdate, and preferably ammonium heptamolybdate.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, the water is deionized water.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, in the step (1), the molybdenum source is calculated as Mo, and the aluminum source is calculated as Al 2 O 3 The weight ratio of the water to the water is 10-35: 65 to 90:40 to 60, preferably 20 to 30: 70-80: 45 to 55.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, the auxiliary agent in the step (2) is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate, and preferably ammonium carbonate. The concentration of the auxiliary agent is 0.5 to 3.0mol/L, preferably 0.7 to 2.5mol/L, and more preferably 1.0 to 2.0mol/L.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, in the step (2), the slow addition manner of the auxiliary agent is to control the flow rate of the auxiliary agent to be 0.05 to 3.0mL/min, preferably 0.08 to 2.5mL/min, and more preferably 1.0 to 2.0mL/min, relative to 50 to 70mL of the solution a. The pH value of the gel B is adjusted and controlled to be 4.0-9.0 by the addition amount of the auxiliary agent, preferably 4.5-8.0, and more preferably 5.0-7.0. The slow addition of the auxiliary agent can be specifically carried out in a dropwise manner.
Further, in the above method for preparing a molybdenum-containing mesoporous alumina molecular sieve, when the auxiliary is added in step (2), the temperature of the solution A is controlled to be 40 to 90 ℃ (specifically, but not limited to, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃), preferably 45 to 80 ℃, and more preferably 50 to 70 ℃.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, the aging treatment conditions in the step (3) are as follows: the aging temperature is 25-60 ℃, preferably 30-55 ℃, and further preferably 35-45 ℃; the aging time is 12 to 36 hours, preferably 15 to 30 hours, and more preferably 20 to 25 hours.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, the drying conditions in the step (3) are as follows: the drying temperature is 90-150 ℃, preferably 100-140 ℃, and further preferably 110-130 ℃; the drying time is 12 to 24 hours, preferably 14 to 22 hours, and more preferably 16 to 20 hours.
Further, in the preparation method of the molybdenum-containing mesoporous alumina molecular sieve, the heat treatment conditions in the step (3) are as follows: the heat treatment temperature is 400-750 ℃, preferably 450-700 ℃, and more preferably 500-650 ℃; the heat treatment time is 3 to 16 hours, preferably 5 to 14 hours, and more preferably 8 to 12 hours. The heat treatment is performed in an oxygen-containing atmosphere (such as an air atmosphere). The heat treatment equipment preferably adopts a muffle furnace.
The third aspect of the invention provides a catalytic material for hydrodesulfurization, wherein the catalytic material for hydrodesulfurization comprises the molybdenum-containing mesoporous alumina molecular sieve or the molybdenum-containing mesoporous alumina molecular sieve obtained by the preparation method.
In a fourth aspect, the present invention provides a hydrodesulfurization catalyst comprising: the mesoporous alumina molecular sieve containing molybdenum carbide takes the weight of the mesoporous alumina molecular sieve containing molybdenum carbide as a reference, and the content of molybdenum is 10 to 35 weight percent, preferably 20 to 25 weight percent; the specific surface area of the mesoporous alumina molecular sieve containing molybdenum carbide is 180-400 m 2 Per gram, pore volume of 0.18-0.40 cm 3 /g。
Furthermore, the mesoporous aperture of the mesoporous alumina molecular sieve containing molybdenum carbide is 2.0-4.0 nm.
Further, no molybdenum carbide diffraction peak is found in the XRD spectrogram of the mesoporous alumina molecular sieve containing molybdenum carbide.
Further, the grain size of the molybdenum carbide-containing crystal grains is 2.0 to 4.5nm.
Further, the mesoporous alumina molecular sieve containing molybdenum carbide is obtained by carbonizing the mesoporous alumina molecular sieve containing molybdenum. Concretely, the molybdenum-containing mesoporous alumina molecular sieve obtained in the step (3) is carbonized and passivatedObtaining molybdenum carbide (Mo) 2 C) The mesoporous alumina molecular sieve.
Further, the carbonization is carried out in the presence of a carbonization atmosphere, wherein the carbonization atmosphere comprises a carbonization gas and hydrogen, and the carbonization gas can be one or more selected from C1-C4 alkanes, preferably methane and/or ethane; the volume ratio of the carbonized gas to the hydrogen is 1:2 to 5. The carbonization temperature is 550-750 ℃, and the carbonization time is 3-8 h. The carbonization treatment process adopts a temperature programming mode, and further preferably comprises two-stage temperature rise, wherein the temperature rise of the first stage is up to 250-350 ℃, and the temperature rise rate of the first stage is controlled at 4-6 ℃/min; the second stage is heated to the carbonization temperature, the temperature raising rate of the second stage is generally controlled to be 0.5-2 ℃/min, and the first stage is preferably higher than the second stage by 3-5 ℃/min.
Further, the passivation is carried out under the condition of a passivation atmosphere, the passivation atmosphere is a mixed gas of inert gas and oxygen, wherein the inert gas is selected from one or more of nitrogen, argon and the like. The concentration of oxygen in the passivating atmosphere may be 0.5-1 v%. The passivation temperature is 15-40 ℃, and the passivation time is 4-8 h.
The hydrodesulfurization catalyst can be used in the hydrodesulfurization process of sulfur-containing hydrocarbons, such as gasoline hydrodesulfurization, diesel hydrodesulfurization and the like.
Compared with the prior art, the invention has the following advantages:
1. the molybdenum-containing mesoporous alumina molecular sieve of the invention has a mesoporous alumina molecular sieve material with high molybdenum dispersity, high specific surface area and good pore size distribution, and is particularly suitable for serving as a catalytic material for hydrodesulfurization.
2. According to the invention, molybdenum is successfully introduced into the mesoporous alumina molecular sieve in one step by a one-step gel method, so that the molybdenum-containing mesoporous alumina molecular sieve is prepared, and the preparation steps are simplified.
3. The preparation method of the molybdenum-containing mesoporous alumina molecular sieve enhances the interaction between alumina and molybdenum particles by using the auxiliary agent, and molybdenum is uniformly dispersed on alumina, thereby avoiding the accumulation of molybdenum on alumina, inhibiting the increase of particle size, and being combined with the regulation and control of preparation conditions, the molybdenum-containing mesoporous alumina molecular sieve with high molybdenum dispersity and high specific surface area can be obtained at lower temperature.
4. The molybdenum-containing mesoporous alumina molecular sieve is a mesoporous catalytic material with special catalytic performance, can be used as a hydrodesulfurization catalytic material, and can show good activity and selectivity.
Drawings
FIG. 1 is an XRD pattern of a molybdenum-containing mesoporous alumina molecular sieve sample prepared according to examples 1-7 of the present invention;
FIG. 2 is an XRD pattern of a sample of a molybdenum containing mesoporous alumina molecular sieve prepared according to comparative examples 1-3 of the present invention;
FIG. 3 is a nitrogen adsorption-desorption isotherm curve and a pore size distribution diagram of a molybdenum-containing mesoporous alumina molecular sieve sample prepared in example 1 of the present invention;
FIG. 4 is a TEM image of a molybdenum-containing mesoporous alumina molecular sieve sample prepared in example 2 of the present invention;
FIG. 5 is an XRD pattern of a sample of the catalyst obtained in examples 8 and 9 of the present invention and comparative example 4;
FIG. 6 is an SEM photograph of a catalyst sample obtained in example 8 of the present invention;
FIG. 7 is a TEM image of a catalyst sample obtained in example 8 of the present invention;
FIG. 8 is a graph showing the evaluation results of catalysts obtained in examples 8 and 9 of the present invention and comparative example 4.
Detailed Description
In order to further illustrate the present invention, the following detailed description of the molybdenum-containing mesoporous alumina molecular sieve and the preparation method thereof are provided with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the invention, the specific surface area, the pore volume and the pore diameter are measured by adopting a low-temperature liquid nitrogen adsorption method on a Micromeritics ASAP2020 physical adsorption instrument, wherein the specific surface area is measured by adopting a BET method, the pore volume is measured by adopting a single-point adsorption total pore volume method, and the pore diameter is measured by adopting a BJH method.
In the present invention, XRD analysis was performed on a Rigaku D/MAX-2200 type powder X-ray diffractometer using a graphite monochromator, cu Kalpha rays, a tube voltage of 40 kV, a tube current of 40 mA, and a scanning speed of 2 o ·min -1 The scanning range 2 theta is 10-90 degrees. Among them, standard MoO 3 The characteristic peaks correspond to positions 2 θ = 12.7 °, 23.3 °,25.8 °, 27.2 °, 34.1 °,35.4 °, 45.7 °,46.6 °,54.7 ° (JCPDS card No. 05-0508) as follows.
In the present invention, the measurement was carried out by a Transmission Electron Microscope (TEM) of JEM-2100, manufactured by Nippon electronics Co. The grain size of the molybdenum oxide is obtained by counting 20 TEM pictures (grain number is more than 200).
In the present invention, a Scanning Electron Microscope (SEM) was obtained by a model-type SEM of Nova Nano SEM 450 from FEI, USA.
Example 1
19.14g of Al (NO) 3 ) 3 ·9H 2 O was dissolved in 50mL of deionized water to give solution A1, and 2.57g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O in 10mL of deionized water, stirring and dissolving to obtain a solution A2; mixing the solution A1 and the solution A2 to obtain a solution A, then placing the solution A in a 40 ℃ water bath kettle to stir to uniformly mix the solution A, heating the mixed solution to 40 ℃, adding 3mol/L ammonia water solution into the mixed aqueous solution at the speed of 0.05mL/min under the stirring condition through a peristaltic pump until a gel is formed, and stopping titration to obtain the gel after the pH =4 is measured; then aging the formed gel for 36h at 25 ℃, and then drying in an oven at 150 ℃ for 12h to obtain xerogel; and finally, roasting the obtained xerogel in a muffle furnace at 400 ℃ for 16h to obtain a molybdenum-containing mesoporous alumina molecular sieve sample, wherein the XRD (X-ray diffraction) pattern of the molecular sieve sample is shown in figure 1, the nitrogen adsorption and desorption isothermal curve and the pore size distribution diagram of the molecular sieve sample are shown in figure 3, and the specific properties of the sample are shown in table 1.
Example 2
7.89g AlCl 3 Dissolved in 40mL of deionized water to give solution A1, and 1.72g (NH) 4 ) 2 Mo 4 O 13 ·2H 2 Dissolving O in 10mL of deionized water, stirring and dissolving to obtain a solution A2; mixing the solution A1 and the solution A2 to obtain a solution A, then placing the solution A in a water bath kettle at 60 ℃ to be stirred to be uniformly mixed, heating the mixed solution to 60 ℃, and then stirring 1.5mol/L (NH) by a peristaltic pump under the condition of stirring 4 ) 2 CO 3 Adding the solution into the mixed aqueous solution at a speed of 1mL/min until the pH =6 is measured when a gel is formed, and stopping titration to obtain the gel; then aging the formed gel at 40 ℃ for 24h, and then drying in an oven at 120 ℃ for 18h to obtain dry gel; and finally, roasting the obtained xerogel in a muffle furnace at 550 ℃ for 9h to obtain a molybdenum-containing mesoporous alumina molecular sieve sample, wherein an XRD (X-ray diffraction) pattern of the molecular sieve sample is shown in figure 1, a TEM (transmission electron microscope) representation pattern of the molecular sieve sample is shown in figure 4, and the specific properties of the sample are shown in table 1.
Example 3
24.37g of Al 2 (SO 4 ) 3 Dissolved in 30mL of deionized water to give solution A1, 0.71g (NH) 4 ) 2 Mo 2 O 7 Dissolving in 10mL of deionized water, stirring and dissolving to obtain a solution A2; mixing the solution A1 and the solution A2 to obtain a solution A, then placing the solution A in a 90 ℃ water bath kettle to stir for uniform mixing, heating the mixed solution to 90 ℃, and then stirring 0.5mol/L NH by a peristaltic pump under the stirring condition 4 HCO 3 Adding the solution into the mixed aqueous solution at the speed of 3mL/min until the formed gel is detected to have pH =9, and stopping titration to obtain the gel; then aging the formed gel at 60 ℃ for 12h, and then drying in a 90 ℃ oven for 24h to obtain dry gel; and finally, roasting the obtained xerogel in a muffle furnace at 700 ℃ for 3h to obtain a molybdenum-containing mesoporous alumina molecular sieve sample, wherein an XRD (X-ray diffraction) pattern of the molecular sieve sample is shown in figure 1, and the specific properties of the sample are shown in Table 1.
Examples 4 to 7
The steps are the same as example 2 except for changing the amount of the molybdenum salt to prepare the molybdenum-containing mesoporous alumina molecular sieve samples with the molybdenum contents of 15wt%,18wt%,20wt% and 30wt%, respectively, wherein the XRD patterns of the molecular sieve samples are shown in fig. 1, and the specific properties of the samples are shown in table 1.
Comparative example 1
The same as example 1 except that no auxiliary agent was used and no ammonia was added in comparative example 1. The XRD pattern of the molecular sieve sample is shown in fig. 2, and the specific properties of the sample are shown in table 1.
Comparative example 2
The same as example 2 except that no auxiliary agent was used and no ammonium carbonate was added in comparative example 1. The XRD pattern of the molecular sieve sample is shown in fig. 2, and the specific properties of the sample are shown in table 1.
Comparative example 3
The same as example 3, except that no adjuvant was used and no ammonium bicarbonate was added in comparative example 1. The XRD pattern of the molecular sieve sample is shown in fig. 2, and the specific properties of the sample are shown in table 1.
TABLE 1 Properties of samples of molybdenum-containing mesoporous alumina molecular sieves obtained in each of examples and comparative examples
| Mo content (wt%) | Specific surface area (m) 2 /g） | Pore volume (cm) 3 /g） | Mesoporous aperture (nm) | MoO 3 Average grain size (nm) | |
| Example 1 | 35 | 369.1 | 0.29 | 3.0 | 3.5 |
| Example 2 | 25 | 442.6 | 0.34 | 3.3 | 3.2 |
| Example 3 | 10 | 263.7 | 0.27 | 2.6 | 4.3 |
| Example 4 | 15 | 301.3 | 0.30 | 2.9 | 2.8 |
| Example 5 | 18 | 329.8 | 0.28 | 3.1 | 2.9 |
| Example 6 | 20 | 344.1 | 0.29 | 3.2 | 3.0 |
| Example 7 | 30 | 360.4 | 0.32 | 3.2 | 3.3 |
| Comparative example 1 | 35 | 121.7 | 0.20 | 2.1 | 5.7 |
| Comparative example 2 | 25 | 180.4 | 0.23 | 2.3 | 6.4 |
| Comparative example 3 | 10 | 92.6 | 0.19 | 2.0 | 7.3 |
The properties of the molecular sieve samples prepared in examples 1-7 and comparative examples 1-3 are shown in table 1. As can be seen from Table 1, the molecular sieve samples (examples 1-7) prepared by the one-step gel method using ammonia, ammonium carbonate or ammonium bicarbonate as an auxiliary agent had large specific surface areas (250-450 m) 2 Per g), good pore volume and pore size distribution without assistanceThe specific surface area, pore volume and pore diameter of the molecular sieve samples prepared by the agent (comparative examples 1-3) are all obviously reduced.
The XRD patterns of the molecular sieve samples prepared in examples 1-7 are shown in fig. 1. As can be seen from FIG. 1, the molecular sieve sample prepared by the one-step gel method by using the auxiliary agent has only alumina diffraction peak and no obvious MoO under the condition of high Mo loading (10-35wt%) 3 Diffraction peaks show that the molecular sieve sample prepared by the method has better molybdenum dispersibility in an alumina carrier even under the condition of high loading and smaller molybdenum particles.
The XRD patterns of the molecular sieve samples prepared in comparative examples 1-3 are shown in fig. 2. As can be seen from FIG. 2, the molecular sieve prepared without the addition of the auxiliary agent has obvious MoO by XRD 3 Diffraction peaks, which indicate that molybdenum has poor dispersibility in alumina carrier and larger molybdenum particles.
The nitrogen adsorption desorption isotherm and pore size distribution of the molecular sieve sample prepared in example 1 are shown in fig. 3. As can be seen from fig. 3 (a), the nitrogen adsorption-desorption isotherm curve of the molybdenum-containing mesoporous alumina molecular sieve is an H1-type hysteresis loop, and shows the characteristics of a significant mesoporous material; as can be seen from fig. 3 (b), the molybdenum-containing mesoporous alumina molecular sieve has a narrow pore size distribution and a uniform pore size.
TEM characterization of the molecular sieve samples prepared in example 2 is shown in figure 4. As can be seen from FIG. 4, the molybdenum-containing mesoporous alumina molecular sieve has fine and highly dispersed particles, and the average particle size is about 3nm, which is consistent with the XRD result.
Example 8
The molybdenum-containing mesoporous alumina molecular sieve sample obtained in the example 2 is placed in CH 4 And H 2 Of (CH) 4 :H 2 Volume ratio of = 1/4), heating to 300 ℃ at a heating rate of 5 ℃/min, adjusting the temperature to be increased from 300 ℃ to 600 ℃ at a heating rate of 1 ℃/min, and carbonizing for 5h; cooling to room temperature (20 ℃) after the carbonization process, 1v% of 2 /N 2 Passivating in the atmosphere for 6h to obtain a highly dispersed molybdenum carbide catalyst loaded by mesoporous alumina molecular sieves, wherein the properties of the catalyst are shown in Table 2, and the XRD pattern of a catalyst sample is shown in FIG. 5; SEM characterization of the prepared catalyst is shown in FIG. 6The TEM characterization of the catalyst is shown in FIG. 7.
Example 9
The only difference from example 8 is that: the molybdenum-containing mesoporous alumina molecular sieve sample obtained in example 2 was replaced with the molybdenum-containing mesoporous alumina molecular sieve sample obtained in example 3, and a catalyst was prepared.
Comparative example 4
The difference from example 8 is only that: and replacing the molybdenum-containing mesoporous alumina molecular sieve sample obtained in the example 2 with the molybdenum-containing mesoporous alumina molecular sieve sample obtained in the comparative example 2 to obtain the catalyst.
TABLE 2 Properties of catalysts obtained in examples and comparative examples
| Specific surface area (m) 2 /g） | Pore volume (cm) 3 /g） | Mesoporous aperture (nm) | Mo 3 C average grain diameter (nm) | |
| Example 8 | 218.4 | 0.23 | 3.3 | 2.7 |
| Example 9 | 191.3 | 0.20 | 2.5 | 4.1 |
| Comparative example 4 | 123.1 | 0.21 | 2.2 | 5.8 |
Evaluation test
Using 1wt% thiophene-octane solution as a simulation raw material, and carrying out the same reaction conditions (280 ℃,3MPa, liquid hourly volume space velocity of 4 h) in a micro-reactor -1 The volume ratio of hydrogen to oil is 600: 1) The catalysts obtained in example 8, example 9 and comparative example 4 were subjected to reaction evaluation, and the conversion of thiophene, that is, the removal of S, was obtained from the results of gas chromatography analysis. The specific experimental results are shown in FIG. 8.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that various changes, modifications, substitutions and alterations to the embodiments described herein may be made by those skilled in the art without departing from the principles of the invention, and such improvements and modifications should also be considered within the scope of the invention.
Claims (17)
1. A molybdenum-containing mesoporous alumina molecular sieve, based on the weight of the molybdenum-containing mesoporous alumina molecular sieve, the molybdenum content is 10wt% -35 wt%, preferably 20wt% -25 wt%; the specific surface area of the molybdenum-containing mesoporous alumina molecular sieve is 250-450 m 2 Per g, pore volume of 0.20-0.35 cm 3 /g。
2. The molecular sieve of claim 1, wherein the molybdenum in the molybdenum-containing mesoporous alumina molecular sieve exists in the form of molybdenum oxide, and MoO is not found in an XRD (X-ray diffraction) spectrum 3 Diffraction peaks.
3. The molecular sieve of claim 1, wherein the mesoporous alumina molecular sieve containing molybdenum has a mesoporous diameter of 2.0-4.0 nm, preferably 2.5-4.0 nm.
4. The molecular sieve of any one of claims 1 to 3, wherein MoO is present in the molybdenum-containing mesoporous alumina molecular sieve 3 The grain size of the crystal grains is 2.0 to 4.5nm, preferably 2.5 to 4.5nm.
5. A process for preparing the molecular sieve of any of claims 1 to 4, comprising:
(1) Mixing an aluminum source, a molybdenum source and water to prepare a solution A;
(2) Slowly adding an auxiliary agent into the solution A obtained in the step (1) to obtain gel B;
(3) And aging, drying and thermally treating the gel B to obtain the molybdenum-containing mesoporous alumina molecular sieve.
6. The method according to claim 5, wherein the step (1) comprises dissolving the aluminum source and the molybdenum source in water, respectively, and mixing the solution to obtain the solution A.
7. The preparation method according to claim 5, wherein the aluminum source in the step (1) is one or more selected from aluminum nitrate, aluminum sulfate and aluminum chloride;
and/or the molybdenum source is one or more of ammonium dimolybdate, ammonium tetramolybdate and ammonium heptamolybdate;
and/or the molybdenum source is calculated as Mo, and the aluminum source is calculated as Al 2 O 3 The weight ratio of the water to the water is 10-35: 65-90: 40 to 60, preferably 20 to 30: 70-80: 45 to 55.
8. The preparation method according to claim 5, wherein the auxiliary agent in step (2) is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate, preferably ammonium carbonate;
preferably, the concentration of the auxiliary agent is 0.5 to 3.0mol/L, preferably 0.7 to 2.5mol/L, and more preferably 1.0 to 2.0mol/L.
9. The preparation method according to claim 5, wherein the slow addition manner of the auxiliary agent in step (2) is to control the flow rate of the auxiliary agent to be 0.05 to 3.0mL/min, preferably 0.08 to 2.5mL/min, and more preferably 1.0 to 2.0mL/min, relative to 50 to 70mL of the solution A;
and/or, the pH value of the gel B is adjusted and controlled to be 4.0-9.0 through the adding amount of the auxiliary agent, preferably the pH value is 4.5-8.0, and further preferably the pH value is 5.0-7.0.
10. The process according to claim 5, wherein the temperature of the solution A is controlled to be 40 to 90 ℃, preferably 45 to 80 ℃, and more preferably 50 to 70 ℃ when the auxiliary is added in the step (2).
11. The production method according to claim 5, wherein the aging treatment conditions in the step (3) are as follows: the aging temperature is 25-60 ℃, preferably 30-55 ℃, and further preferably 35-45 ℃; the aging time is 12 to 36 hours, preferably 15 to 30 hours, and more preferably 20 to 25 hours;
and/or, the drying conditions are as follows: the drying temperature is 90-150 ℃, preferably 100-140 ℃, and more preferably 110-130 ℃; the drying time is 12 to 24 hours, preferably 14 to 22 hours, and more preferably 16 to 20 hours.
12. The production method according to claim 5, wherein the heat treatment conditions are as follows: the heat treatment temperature is 400-750 ℃, preferably 450-700 ℃, and more preferably 500-650 ℃; the heat treatment time is 3 to 16 hours, preferably 5 to 14 hours, and more preferably 8 to 12 hours.
13. A catalytic material for hydrodesulfurization, comprising the molybdenum-containing mesoporous alumina molecular sieve according to any one of claims 1 to 4 or the molybdenum-containing mesoporous alumina molecular sieve obtained by the preparation method according to any one of claims 5 to 12.
14. A hydrodesulfurization catalyst comprising: the mesoporous alumina molecular sieve containing molybdenum carbide takes the weight of the mesoporous alumina molecular sieve containing molybdenum carbide as a reference, and the content of molybdenum is 10 to 35 weight percent, preferably 20 to 25 weight percent; the specific surface area of the mesoporous alumina molecular sieve containing molybdenum carbide is 180-400 m 2 Per g, pore volume of 0.18-0.40 cm 3 /g。
15. The catalyst of claim 14, wherein the mesoporous alumina molecular sieve containing molybdenum carbide has an XRD spectrum without molybdenum carbide diffraction peak;
and/or the mesoporous aperture of the mesoporous alumina molecular sieve containing molybdenum carbide is 2.0-4.0 nm;
and/or the grain diameter of the crystal grain containing the molybdenum carbide is 2.0-4.5 nm.
16. The catalyst of claim 14, wherein the molybdenum-carbide mesoporous alumina molecular sieves are obtained by carbonizing the molybdenum-containing mesoporous alumina molecular sieves of any one of claims 1 to 4 or the molybdenum-containing mesoporous alumina molecular sieves obtained by the preparation method of any one of claims 5 to 12.
17. Use of a hydrodesulphurisation catalyst according to any of claims 14-16 for the hydrodesulphurisation of sulphur containing hydrocarbons.
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