CN107824194A - It is a kind of using meso-porous alumina as Hydrobon catalyst of carrier and its preparation method and application - Google Patents
It is a kind of using meso-porous alumina as Hydrobon catalyst of carrier and its preparation method and application Download PDFInfo
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- CN107824194A CN107824194A CN201711355720.XA CN201711355720A CN107824194A CN 107824194 A CN107824194 A CN 107824194A CN 201711355720 A CN201711355720 A CN 201711355720A CN 107824194 A CN107824194 A CN 107824194A
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- porous alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 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 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 14
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 claims abstract description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003294 NiMo Inorganic materials 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000003814 drug Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical class S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a kind of using meso-porous alumina as Hydrobon catalyst of carrier and its preparation method and application, the Hydrobon catalyst is using meso-porous alumina as carrier, using CoO or NiO as auxiliary agent, MoO3For active component, NiO or CoO mass fraction are 1 ~ 5%, MoO3Mass fraction be respectively 5 ~ 12%, the catalyst is designated as CoMo/Al2O3N or NiMo/Al2O3N, wherein, N=F127, P108, P123 or P4VP.Ordered mesoporous aluminium oxide is prepared using solventless method, still there is well order mesoporous after high-temperature roasting, be advantageous to active component in dipping process to be uniformly dispersed, its catalytic activity is obviously improved than similar catalyst under relatively low activity component load quantity, and has good anticoking capability.
Description
Technical field
The invention belongs to the technical field of Hydrobon catalyst, and in particular to using solventless method prepare meso-porous alumina as
Carrier, Hydrobon catalyst is prepared based on the carrier.
Background technology
Since 21st century, the increasingly raising with people's living standard and the more attention to ecological environment, it is got over
It is formulated come stricter Law on Environmental Protection.And the sulfur-containing compound in fuel oil generates oxygen sulfur compound in combustion,
It is one of the main reason for causing the environmental problems such as acid rain, haze.In face of the problem, countries in the world have also been formulated more and more strict
Sulfur content of fuel oil discharge standard.Wherein in European Union's standard of Europe V performed at present, the content of its Sulfur content in Fuel Oil must not
Higher than 10 μ g/g, and the U.S. also had been realized in the standard that Sulfur content in Fuel Oil content is less than 15 μ g/g in 2010.In China, to the greatest extent
Pipe implements the standard of state IV that sulfur content is less than 50 μ g/g in the line city of Beijing, Shanghai, Guangzhou etc. one, and will be in other national cities
City's further genralrlization, but the quality of petrol and diesel oil still far lags behind the level in World Developed Countries and area.Therefore, produce low
The sulphur even clean fuel oil without sulphur become economic development and environmental protection there is an urgent need to.
Industrially, traditional Hydrobon catalyst is typically with Al2O3For carrier, and Ni or Co are added as auxiliary agent
Mo bases or W Base Metal sulfide, although this catalyst has good hydrodesulfurization effect, in normal conditions be difficult
Break through the limit that sulfur content is less than 1000ppm.Want to reach new sulfur content standard, its reaction condition will carry out strict tune
It is whole.Therefore, developing new and effective deep hydrodesulfurizationof catalyst turns into the most effective and practical means for solving this problem.
And the research and development of deep hydrodesulfurizationof catalyst are mainly from loading method, the active higher group of screening for improving active component
Divide and find the more preferable aspect of carrier three and deploy.
At present, the CoMo Hydrobon catalysts oxide carrier studied mainly has γ-Al2O3, SiO2, TiO2, ZrO2
With the carrier such as MgO.At the same time, also there are some researchers by the way that these support modifications are improved with the hydrodesulfurization of catalyst
Effect.Chinese patent literature CN103157518A discloses a kind of mesoporous magnesia and its load C oMo sulfide prepares hydrogenation and taken off
The preparation method of sulfur catalyst.The mesoporous magnesia is to use hydro-thermal method, using inorganic magnesium salt and surfactant by old
Change, filter, drying and be prepared by roasting, using infusion process load C oMo active components, obtained catalyst has excellent desulfurization
Activity.Chinese patent literature CN106076355A discloses a kind of preparation method of Hydrobon catalyst.The catalyst with
AlOOH and TiO2Compound be carrier, support NiO, MoO3And WO3For active component, one kind is prepared for by Complete Liquid-phast process
The slurried catalyst that reactivity is high, stability is good.Although above-mentioned catalyst has good desulfurization performance and stability,
The carbon distribution of catalyst surface, which reacts, in high-temperature reaction process causes desulphurizing activated and stability reduction, and both catalyst
Specific surface area is little, and its active component dispersion effect is general in dipping process.Therefore set forth herein a kind of aluminum oxide of preparing
Method, using solventless method green syt ordered mesoporous aluminium oxide, alumina support is just obtained after drying, roasting.
The content of the invention
The technical problems to be solved by the invention are the hydrodesulfurization in normal conditions of existing Hydrobon catalyst
Activity is low, and the problem of easy coking.And then a kind of method that solventless method prepares ordered mesoporous aluminium oxide is provided, further bear
Carry auxiliary agent CoO, NiO and active component MoO3To prepare Hydrobon catalyst.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of solventless method prepares meso-porous alumina, mixes, grinds with surfactant by organic silicon source, burin-in process obtains
Alumina precursor, it is carrier to be then dried in air atmosphere and obtain meso-porous alumina with high-temperature roasting, with CoO or
NiO is auxiliary agent, MoO3For active component, NiO or CoO mass fraction are 1 ~ 5%, MoO3Mass fraction be respectively 5 ~ 12%, should
Catalyst is designated as CoMo/Al2O3- N or NiMo/Al2O3- N, wherein, N=F127, P108, P123 or P4VP.
Described non-solvent preparation, the source of its organo-aluminium is in aluminium isopropoxide, aluminium ethide, aluminium triformate and propionic acid aluminium
One or more.For its surfactant in addition to F127, it is surfactant that F108, P123 and P4VP, which is also respectively adopted,.
Described solventless method prepare meso-porous alumina burin-in process temperature be 100 ~ 180 DEG C, ageing time be 12 ~
48h.Aging terminates that processing is dried after cooling, and drying temperature is 80 ~ 120 DEG C, and drying time is 12 ~ 36h.High-temperature roasting
Temperature is 500 ~ 800 DEG C, and roasting time is 4 ~ 12h.Then Co (NO are used3)2·6H2O or Ni (NO3)2·6H2O and (NH4)6Mo7O24·4H2O mixed solution is loaded using equi-volume impregnating, and oxygen is obtained after being then calcined 2 ~ 4h at 450 ~ 600 DEG C
Change state Hydrobon catalyst.
The preparation method of described Hydrobon catalyst comprises the following steps：
（1）The synthesis of alumina support：A certain amount of organic aluminium salt and surfactant are mixed, are then ground to certain mesh
Number.Well mixed medicine is transferred in polytetrafluoroethyllining lining kettle afterwards, then adds a certain amount of hydrochloric acid solution.Treat
Hydrochloric acid solution is added for a period of time afterwards by polytetrafluoroethyllining lining kettle, at high temperature burin-in process certain time, takes out water heating kettle
After cooling, obtained meso-porous alumina presoma is placed in inside baking oven after drying a period of time, then is placed in Muffle furnace
Row high-temperature roasting obtains mesoporous alumina carrier.Obtained mesoporous alumina carrier is designated as Al2O3- N (N=F127, P108,
P123 or P4VP).
（2）The preparation of catalyst：Prepare certain density Co (NO3)2·6H2O or Ni (NO3)2·6H2O and (NH4)6
Mo7O24·4H2O mixed solution.The solution is impregnated into by Al using equi-volume impregnating2O3On-N, Muffle furnace is placed in afterwards
In, then by roasting obtain oxidized catalyst CoMo/Al2O3- N or NiMo/Al2O3-N。
Using：Described catalyst is used for thiophene and dibenzothiophenes hydrodesulfurization reaction under normal pressure, is needed oxygen before reaction
The catalyst for changing state carries out vulcanizing treatment, and curing temperature is 250 ~ 350oC, cure time are 2 ~ 4h, reaction temperature 350oC。
Step（1）Described in organic aluminium salt be aluminium isopropoxide, aluminium ethide, aluminium triformate and one kind or several in propionic acid aluminium
Kind.
Step（1）Described in surfactant be F127, F108, P123 or P4VP.
Step（1）Described in burin-in process temperature be 100 ~ 180 DEG C, ageing time is 12 ~ 48h.Aging terminates to treat cold
But drying process is first carried out after, drying temperature is 80 ~ 120 DEG C, and drying time is 12 ~ 36h, then carries out high-temperature roasting processing, roasting
It is 500 ~ 800 DEG C to burn temperature, and roasting time is 2 ~ 12h.
Step（2）Described in prepare catalyst sintering temperature be 450 ~ 650 DEG C, roasting time is 2 ~ 4 h.
Step（2）Described in infusion process use equi-volume impregnating, the process entirely impregnated is carried out at normal temperatures and pressures,
After roasting in obtained catalyst, NiO or CoO mass fraction are 1 ~ 5%, MoO3Mass fraction be respectively 5 ~ 12%.
The present invention's is particularly advantageous in that：
(1) present invention prepares ordered mesoporous aluminium oxide, is synthesized using solventless method, should compared with conventional hydrothermal and coprecipitation
Its preparation technology of method is simple, and waste water will not be produced in preparation process, while its structure-controllable, easily operated, can be extensive
Production, has broad application prospects.
(2) catalyst carrier of the invention is ordered mesoporous aluminium oxide, is still had after high-temperature roasting with good
Sequence is mesoporous, while can adjust the soda acid property of carrier surface by adding different aluminium salts and template, has in dipping process
It is uniformly dispersed beneficial to active component, good interaction is formed between carrier and active component.Born in relatively low active component
Its catalytic activity is obviously improved than similar catalyst under carrying capacity, and has good anticoking capability.
Brief description of the drawings
Fig. 1 is sulphided state catalyst A and catalyst E transmission electron microscope picture, wherein（A）、（B）For sulphided state catalyst E's
Transmission electron microscope picture,（C）、（D）For sulphided state catalyst A transmission electron microscope picture.
Embodiment
The present invention is expanded on further with reference to embodiments, but protection scope of the present invention is not limited to following embodiments.For
The experimental implementation and its experimental result of the present invention is further illustrated, the embodiment that this part combines invention is retouched in more detail
State.
Embodiment 1
（1）The synthesis of alumina support：The medicine mixing of 2.04g aluminium isopropoxides and 1g F127 surfactants is weighed respectively, so
After be ground to 100 mesh.Well mixed medicine is transferred in polytetrafluoroethyllining lining kettle afterwards, then adds 0.5ml's
Hydrochloric acid solution.Hydrochloric acid solution to be added is for a period of time afterwards by polytetrafluoroethyllining lining kettle, 150oC keeps 24h, takes out water heating kettle
After cooling, obtained meso-porous alumina presoma is placed in inside baking oven 100oC dries 12h, then is placed in Muffle furnace
550oC high-temperature roastings 4h obtains alumina support.Obtained mesoporous alumina carrier is designated as Al2O3- F127.The ratio of the carrier
Surface area is 296 m2/g。
（2）The preparation of catalyst：Prepare certain density Co (NO3)2·6H2O and (NH4)6 Mo7O24·4H2O mixing
Solution.The solution is impregnated into by Al using equi-volume impregnating2O3On-F127, it is placed in afterwards in Muffle furnace, then by 450 DEG C of roastings
4h is burnt, obtains catalyst CoMo/Al2O3- F127, remember that wherein CoO is 3wt%, MoO by mass fraction in catalyst3For 9wt%.
It is designated as catalyst A.
Embodiment 2
（1）The synthesis of alumina support：The medicine mixing of 3.12g aluminium ethides and 1.6g F108 surfactants is weighed respectively, so
After be ground to 100 mesh numbers.Well mixed medicine is transferred in polytetrafluoroethyllining lining kettle afterwards, then adds 1.5ml
Hydrochloric acid solution.Hydrochloric acid solution to be added is for a period of time afterwards by polytetrafluoroethyllining lining kettle, 120oC keeps 24h, takes out hydro-thermal
After cooling, obtained meso-porous alumina presoma is placed in inside baking oven 80 for kettleoC dries 12h, then is placed in Muffle furnace
500oC high-temperature roastings 3h obtains alumina support.Obtained mesoporous alumina carrier is designated as Al2O3- F108.The ratio of the carrier
Surface area is 283 m2/g。
（2）The preparation of catalyst：Prepare certain density Ni (NO3)2·6H2O and (NH4)6 Mo7O24·4H2O mixing
Solution.The solution is impregnated into by Al using equi-volume impregnating2O3On-F108, it is placed in afterwards in Muffle furnace, then by 500 DEG C of roastings
3h is burnt, obtains catalyst n iMo/Al2O3- F108, remember that wherein NiO is 5wt%, MoO by mass fraction in catalyst3For
11wt%.It is designated as catalyst B.
Embodiment 3
（1）The synthesis of alumina support：The medicine mixing of 4.24g aluminium triformates and 2g P4VP surfactants is weighed respectively, then
It is ground to 100 mesh.Well mixed medicine is transferred in polytetrafluoroethyllining lining kettle afterwards, then adds 1ml hydrochloric acid
Solution.Hydrochloric acid solution to be added is for a period of time afterwards by polytetrafluoroethyllining lining kettle, 150oC keeps 36h, and taking-up water heating kettle is treated cold
But after, obtained meso-porous alumina presoma is placed in inside baking oven 120oC dries 12h, then is placed in Muffle furnace 600oC
High-temperature roasting 4h obtains alumina support.Obtained mesoporous alumina carrier is designated as Al2O3- P4VP.The ratio surface of the carrier
Product is 231 m2/g。
（2）The preparation of catalyst：Prepare certain density Co (NO3)2·6H2O and (NH4)6 Mo7O24·4H2O mixing
Solution.The solution is impregnated into by Al using equi-volume impregnating2O3On-P4VP, it is placed in afterwards in Muffle furnace, then by 550 DEG C of roastings
3h is burnt, obtains catalyst CoMo/Al2O3- P4VP, wherein CoO is 5wt%, MoO in catalyst as mass fraction3For 9wt%.
It is designated as catalyst C.
Embodiment 4
（1）The synthesis of alumina support：The medicine mixing of 3.26g aluminium isopropoxides and 2.4g P123 surfactants is weighed respectively,
Then 100 mesh are ground to.Well mixed medicine is transferred in polytetrafluoroethyllining lining kettle afterwards, then adds 2ml's
Hydrochloric acid solution.Hydrochloric acid solution to be added is for a period of time afterwards by polytetrafluoroethyllining lining kettle, 130oC keeps 48h, takes out water heating kettle
After cooling, obtained meso-porous alumina presoma is placed in inside baking oven 100oC dries 12h, then is placed in Muffle furnace
500oC high-temperature roastings 2h obtains alumina support.Obtained mesoporous alumina carrier is designated as Al2O3- P123.The ratio of the carrier
Surface area is 261m2/g。
（2）The preparation of catalyst：Prepare certain density Ni (NO3)2·6H2O and (NH4)6 Mo7O24·4H2O mixing
Solution.The solution is impregnated into by Al using equi-volume impregnating2O3On-P123, it is placed in afterwards in Muffle furnace, then by 650 DEG C of roastings
2h is burnt, obtains catalyst n iMo/Al2O3- P123, wherein NiO is 3wt%, MoO in catalyst as mass fraction3For
11wt%.It is designated as catalyst D.
Comparative example 1
The preparation of catalyst：Prepare certain density Co (NO3)2·6H2O and (NH4)6 Mo7O24·4H2O mixed solution.Adopt
The solution is impregnated into business Al with equi-volume impregnating2O3（Traditional Chinese medicines, specific surface area 250m2/g）On, afterwards by standing, doing
It is placed in after dry in Muffle furnace, then catalyst CoMo/Al is obtained by roasting2O3,In catalyst as mass fraction, wherein CoO is
5wt%, MoO3For 9wt%.It is designated as catalyst E.
Comparative example 2
（1）The synthesis of alumina support：2.04g aluminum nitrates and 1g natrium carbonicum calcinatums are weighed respectively, are then placed in above-mentioned medicine
It is stirred, moves on to mixed solution in polytetrafluoroethyllining lining kettle after 30min to be mixed, 150 in 250ml beakeroC is protected
24h is held, water heating kettle is taken out after cooling, solution will be obtained and centrifuged to pH=7, then by the sample after centrifugation 100oC is done
Dry 12h, then be placed in Muffle furnace 550oC high-temperature roastings 4h obtains alumina support.Obtained mesoporous alumina carrier is remembered
For Al2O3- HT.The specific surface area of the carrier is 138 m2/g。
（2）The preparation of catalyst：Prepare certain density Co (NO3)2·6H2O and (NH4)6 Mo7O24·4H2O mixing
Solution.The solution is impregnated into by Al using equi-volume impregnating2O3On-HT, it is placed in Muffle furnace, then is obtained by roasting afterwards
Catalyst CoMo/Al2O3- HT, wherein CoO is 3wt%, MoO in catalyst as mass fraction3For 10wt%.It is designated as catalyst
F。
The activity rating of catalyst prepared by above-mentioned case is produced by Beijing Xin Hangdun petrochemical industry Science and Technology Ltd.
(MRT-6113,500 DEG C of system design pressure, system design temperature are carried out on microscale experiment reaction unit：8MPa, in reactor
Footpath 10mm, microprocessor pump drive range 0.001-1sccm, mass flowmenter range：0-200sccm) and by Shimadzu Corporation produce
GC-MS on carry out product analysis.Using thiophene or 4,6- dimethyl Dibenzothiophenes (4,6-DMDBT) content as 3 wt% just
N-heptane solution is model compound raw material.Rhohene desulfiirization reacts：Load 2 g catalyst into hydrodesulfurization unit, first 350
DEG C, with gaseous mixture 10%H2S/H2(50 ml/min) vulcanizes 2 h to oxidized catalyst presoma.Switch after the completion of reduction anti-
Should, reaction condition is：Normal pressure, 350 DEG C, hydrogen flowing quantity is 150 ml min-1.Then pure hydrogen passes through containing at 18 DEG C of constant temperature
The chemical industry saturator of organic sulfur.After reaction terminates, using GC or RPP-5000SN type sulphur blood urea/nitrogen analyzers（Taizhou City middle ring analyzer
Device Co., Ltd）Sulfur content carries out analysis test in analysis product.
The thiophene of the catalyst of table 1 and the evaluation index of dibenzothiophenes Hydrobon catalyst
Table 1 is the evaluation index of the Hydrobon catalyst prepared in embodiment 1-4 and comparative example 1,2 using the inventive method.
As it can be seen from table 1 Hydrobon catalyst of the present invention（Sample A-D）There is higher desulphurizing activated, wherein sample A
In 350 DEG C of thiophene conversion ratio up to 94.68% under normal pressure, the conversion ratio of its dibenzothiophenes conversion ratio is also up to 86.72%.Add
Hydrogen is desulphurizing activated apparently higher than other catalyst.And the activity of the Hydrobon catalyst prepared using meso-porous alumina as carrier
Higher than using commercial oxidation aluminium as the Hydrobon catalyst prepared by carrier.It is de- in the dibenzothiophenes hydrogenation by continuous 40h
It can see after sulphur test, the unobvious that the conversion ratio of dibenzothiophenes declines in embodiment 1-4.Especially embodiment 1, pass through
Conversion ratio is reduced only by 1.38% after 40h tests, and comparative example 1 have dropped close to 7% under identical condition.Illustrate the invention system
Standby catalyst has good stability.It is not only simple and easy to get compared with meso-porous alumina prepared by conventional hydrothermal method, and
And there is larger specific surface area and good performance.
The catalyst E and catalyst A of vulcanization pass through high-resolution-ration transmission electric-lens（HRTEM）Analyze to investigate different carriers pair
MoS2The length of lamella and the influence of stacking number.Such as Fig. 1（A）With（B）It is shown, it is evident that find out catalyst surface have compared with
The MoS of the more numbers of plies and length2.From（C）With（D）In it can be seen that in catalyst A its MoS2Under the lamella number of plies has significantly
Drop, and length there has also been obvious reduction.And MoS2The reduction of the stacking number of plies and length is advantageous to expose more activity
Site Mo positions at position and S, the especially reduction of the stacking number of plies, promote intermediate layer MoS2Exposure, and then be advantageous to activity
Improve.
Obviously, above-described embodiment is not that embodiment is entered just for the sake of clearly demonstrating situation and illustrated example
Restriction is gone.Therefore, can be can also make on the basis of examples detailed above for one of ordinary skill in the field
Other various forms of changes.Here illustrate, but thus drawn apparent one by one without to all embodiments
Change or change still in the protection domain of the invention within.
Claims (8)
- A kind of 1. Hydrobon catalyst using meso-porous alumina as carrier, it is characterised in that the Hydrobon catalyst with Meso-porous alumina is carrier, using CoO or NiO as auxiliary agent, MoO3For active component, NiO or CoO mass fraction are 1 ~ 5%, MoO3 Mass fraction be respectively 5 ~ 12%, the catalyst is designated as CoMo/Al2O3- N or NiMo/Al2O3- N, wherein, N=F127, P108, P123 or P4VP.
- 2. a kind of preparation method using meso-porous alumina as the Hydrobon catalyst of carrier as claimed in claim 1, it is special Sign is, comprises the following steps：（1）The synthesis of alumina support：A certain amount of organic aluminium salt and surfactant are mixed, are then ground to certain mesh Number, is transferred in polytetrafluoroethyllining lining kettle, then adds a certain amount of hydrochloric acid solution, one section of hydrochloric acid solution to be added afterwards By polytetrafluoroethyllining lining kettle, burin-in process certain time, taking-up polytetrafluoroethyllining lining kettle are to be cooled at high temperature after time Afterwards, obtained meso-porous alumina presoma is placed in inside baking oven after drying a period of time, then is placed in Muffle furnace and carries out high temperature Roasting obtains mesoporous alumina carrier, and obtained mesoporous alumina carrier is designated as into Al2O3- N, wherein N=F127, P108, P123 Or P4VP；（2）The preparation of catalyst：Prepare certain density Co (NO3)2·6H2O or Ni (NO3)2·6H2O and (NH4)6 Mo7O24· 4H2O mixed solution, the solution is impregnated into by Al using equi-volume impregnating2O3On-N, it is placed in Muffle furnace, then passes through afterwards Roasting obtains catalyst CoMo/Al2O3- N or NiMo/Al2O3-N。
- 3. preparation method according to claim 2, it is characterised in that step（1）Described in organic aluminium salt be isopropanol One or more in aluminium, aluminium ethide, aluminium triformate and propionic acid aluminium.
- 4. preparation method according to claim 2, it is characterised in that step（1）Described in surfactant for F127, F108, P123 or P4VP.
- 5. preparation method according to claim 2, it is characterised in that step（1）Described in burin-in process temperature be 100 ~ 180 DEG C, ageing time is 12 ~ 48h；Drying temperature is 80 ~ 120 DEG C, and drying time is 12 ~ 36h；Sintering temperature is 500 ~ 800 DEG C, roasting time is 2 ~ 12h.
- 6. preparation method according to claim 2, it is characterised in that step（2）Described in prepare the roasting temperature of catalyst Spend for 450 ~ 650 DEG C, roasting time is 2 ~ 4 h.
- 7. preparation method according to claim 2, it is characterised in that step（2）Described in equi-volume impregnating, entirely The process of dipping is carried out at normal temperatures and pressures.
- 8. a kind of application using meso-porous alumina as the Hydrobon catalyst of carrier as claimed in claim 1, its feature exist In described catalyst is used for thiophene and dibenzothiophenes hydrodesulfurization reaction under normal pressure, is needed the catalysis of oxidation state before reaction Agent carries out vulcanizing treatment, and curing temperature is 250 ~ 350oC, cure time are 2 ~ 4h, reaction temperature 350oC。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816240A (en) * | 2018-05-24 | 2018-11-16 | 绍兴文理学院 | It is a kind of using titanium oxide as the Hydrobon catalyst of carrier |
| CN109046324A (en) * | 2018-06-22 | 2018-12-21 | 清华大学盐城环境工程技术研发中心 | It is a kind of using mesoporous cerium oxide as the middle low-temperature denitration catalyst and preparation method of carrier |
| CN110252321A (en) * | 2019-07-19 | 2019-09-20 | 福州大学 | A method of vapor deposition preparation CoMo system Hydrobon catalyst |
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| CN114570392A (en) * | 2020-12-02 | 2022-06-03 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614856A (en) * | 2012-04-20 | 2012-08-01 | 北京化工大学 | Preparation method and application of mesoporous alumina-supported metal catalyst |
| CN103922373A (en) * | 2014-04-14 | 2014-07-16 | 浙江大学 | Preparation method of alumina porous microsphere |
| CN105195164A (en) * | 2015-11-05 | 2015-12-30 | 中国石油化工股份有限公司 | Catalyst as well as preparation method and application thereof |
| CN106914251A (en) * | 2015-12-28 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrodesulfurization catalyst and preparation method thereof |
-
2017
- 2017-12-16 CN CN201711355720.XA patent/CN107824194A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614856A (en) * | 2012-04-20 | 2012-08-01 | 北京化工大学 | Preparation method and application of mesoporous alumina-supported metal catalyst |
| CN103922373A (en) * | 2014-04-14 | 2014-07-16 | 浙江大学 | Preparation method of alumina porous microsphere |
| CN105195164A (en) * | 2015-11-05 | 2015-12-30 | 中国石油化工股份有限公司 | Catalyst as well as preparation method and application thereof |
| CN106914251A (en) * | 2015-12-28 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrodesulfurization catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张高良: "《工业催化剂的生产》", 31 January 1988 * |
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| CN109046324B (en) * | 2018-06-22 | 2021-07-20 | 清华大学盐城环境工程技术研发中心 | Medium-low temperature denitration catalyst with mesoporous cerium oxide as carrier and preparation method thereof |
| CN111908490A (en) * | 2019-05-10 | 2020-11-10 | 中国石油天然气股份有限公司 | Horn-hole alumina and preparation method and application thereof |
| CN110252321A (en) * | 2019-07-19 | 2019-09-20 | 福州大学 | A method of vapor deposition preparation CoMo system Hydrobon catalyst |
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