CN110252321A - A method of vapor deposition preparation CoMo system Hydrobon catalyst - Google Patents
A method of vapor deposition preparation CoMo system Hydrobon catalyst Download PDFInfo
- Publication number
- CN110252321A CN110252321A CN201910655664.4A CN201910655664A CN110252321A CN 110252321 A CN110252321 A CN 110252321A CN 201910655664 A CN201910655664 A CN 201910655664A CN 110252321 A CN110252321 A CN 110252321A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- como
- carrier
- preparation
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 33
- 238000007740 vapor deposition Methods 0.000 title description 4
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 55
- 229910052593 corundum Inorganic materials 0.000 claims description 55
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 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 3
- 238000012545 processing Methods 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
- -1 Acyl cobalt Chemical compound 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000005137 deposition process Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 235000013495 cobalt Nutrition 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 229910052961 molybdenite Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000008279 sol Substances 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GHVNNFKGRJGVLD-UHFFFAOYSA-N cobalt;oxalic acid Chemical compound [Co].OC(=O)C(O)=O GHVNNFKGRJGVLD-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 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
- 238000003916 acid precipitation Methods 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
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/347—Ionic or cathodic spraying; Electric discharge
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of methods for being vapor-deposited and preparing CoMo system Hydrobon catalyst.For the problem that CoMo co-impregnation causes its dispersion uneven, poor activity.The order mesoporous Al of bigger serface is prepared first with sol-gal process2O3Carrier, then active component Mo is introduced by carrier surface using equi-volume impregnating, by vacuumizing, it is high temperature vulcanized to obtain sulphided state catalyst, and then auxiliary agent Co is re-introduced into sulphided state catalyst surface by gas phase deposition technology, the sulphided state catalyst containing more CoMoS activity phases is obtained after post-cure.CoMo/Al prepared by the present invention2O3Catalyst activity component is uniformly dispersed, and has excellent hydrodesulfurization activity and stability under auxiliary agent and the lower situation of active component content.
Description
Technical field
The invention belongs to Hydrobon catalyst technical fields, and in particular to a kind of vapor deposition preparation CoMo system adds hydrogen de-
The method of sulfur catalyst.
Background technique
As the in poor quality of fossil energy is increasingly severe, and people are also higher and higher to living standard and environmental requirement,
Therefore the Law on Environmental Protection being increasingly stringenter also is formulated in succession.Especially in fuel oil combustion oxygen sulfur compound side generated
On the one hand face, the generation of the oxysulfide are detrimental to health, be on the other hand lead to the environmental problems such as acid rain, haze main
One of reason.Based on this, stringent sulfur content of fuel oil discharge standard has all been formulated in China or even world wide.Although at me
The Shanghai of state, a line city such as Guangzhou use IV standard of state that sulfur content is lower than 50 μ g/g, but also not big in China
Area is promoted, and the quality of petrol and diesel oil still lags behind developed country.Wherein the U.S. just had reached fuel early in 2010
Sulfur content is lower than the standard of 15 μ g/g in oil.Therefore, it is raw to become health of people for the production low-sulfur even clean fuel oil without sulphur
It is living, Ecological Sustainable Development and the improved day by day most important thing of environmental resource.
So far, there is mature Hydrobon catalyst.Catalysis used in traditional hydrodesulfurization
Agent is usually with Al2O3For carrier, Ni or Co are as auxiliary agent, Mo or W as active component, and this catalyst is in normal conditions
With excellent hydrodesulfurization effect, but it is difficult to break through the limit of the sulfur content less than 1000 ppm.Therefore want to reach higher sulphur
Content discharge standard, reaction condition will carry out stringent adjustment.Therefore, new and effective deep hydrodesulfurizationof catalysis is developed
Agent becomes the most effective and practical means for solving this problem.And the research and development of deep hydrodesulfurizationof catalyst mainly from
It is unfolded in terms of the loading method, the higher component of screening activity and the better carrier three of searching that improve active component.
Currently, the CoMo Hydrobon catalyst oxide carrier studied mainly has γ-Al2O3, SiO2, TiO2, ZrO2
And its carriers such as part composite oxides.At the same time, there are also researchers by being urged to improve these support modifications
The hydrodesulfurization effect of agent.Although there are many relevant reports for selection and use aspect about carrier, it is being catalyzed
Through frequently with traditional equi-volume impregnating in the preparation of agent.And this obtained catalyst activity component dispersion of carrying method
Spend lower, the interaction between carrier and active component is weaker, is unfavorable for active promotion.Therefore herein with order mesoporous Al2O3
For carrier, highly effective hydrogenation desulphurization catalyst is prepared using vapor deposition (CVD) method, directly loads the active group easily dispersed first
Divide Mo, be vapor-deposited the active component Co for being not easy to disperse again after tentatively vulcanizing, and high dispersive is obtained after post-cure
CoMo base Hydrobon catalyst.
Summary of the invention
It is an object of the invention to be directed to existing tradition CoMo/Al prepared by infusion process2O3Hydrodesulphurizatiocatalyst catalyst activity group
It is unevenly distributed, the low problem of catalytic performance.The present invention provides one kind with mesoporous Al2O3For the CoMo system hydrodesulfurization of carrier
Catalyst.The present invention is the load of two steps, first loads easily dispersible active component MoO using infusion process3, gas is used after vulcanization again
Phase sedimentation introduces auxiliary agent CoO, obtains the CoMo/Al of high dispersive by post-cure2O3Hydrobon catalyst.
To achieve the above object, the present invention adopts the following technical scheme:
One kind is with mesoporous Al2O3For the CoMo system Hydrobon catalyst of carrier, with mesoporous Al2O3For carrier, CoO is auxiliary agent,
MoO3For active component, wherein CoO is calculated as 0.5 ~ 3%, MoO by the mass fraction of Co33 ~ 8% are calculated as by the mass fraction of Mo, this is urged
Agent is denoted as CoMo/Al2O3。
One kind is with mesoporous Al2O3For the preparation method of the CoMo system Hydrobon catalyst of carrier, comprising the following steps:
(1) mesoporous Al2O3The preparation of carrier: at room temperature, the P123 of certain mass being dissolved in the hydrochloric acid solution of dehydrated alcohol,
It adjusts after pH is 5 ~ 6 and obtains solution A；At the same time, a certain amount of isopropanol is added in solution A and forms solution B and persistently stirs
It mixes；Then the acetic acid of certain mass and organic aluminium salt are slowly added into solution B in the case where being stirred continuously, adjust solution
A period of time is vigorously stirred with 500 ~ 800 r/min again after pH to neutrality；By solution, aging is obtained at room temperature after stirring
Colloidal sol continues drying and obtains xerogel, obtains high specific surface area and mesoporous Al after high-temperature roasting is cooling2O3Carrier；
(2) CoMo/Al2O3The preparation of catalyst: the certain density (NH of configuration4)6 Mo7O24·4H2O solution, using isometric
Infusion process is loaded to the mesoporous Al of step (1) preparation2O3On carrier, Mo/Al is obtained after dry2O3Catalyst；By Mo/Al2O3
Catalyst is placed in vulcanization plant, and system is evacuated to 10-3Primary vulcanization processing, room to be down to are carried out to the catalyst after Pa
Co salt is loaded to by sulphided state Mo/Al using vapour deposition process (CVD) at normal temperatures and pressures after temperature2O3And then catalyst carries out
Post-cure processing is to get CoMo system Hydrobon catalyst CoMo/Al2O3Catalyst.
Wherein P123 mass as described in step (1) is 1 ~ 2 g, and dehydrated alcohol dosage is 15 mL, and concentrated hydrochloric acid dosage is 1
~ 2 mL, the dosage of isopropanol are 5 mL, and the dosage of acetic acid is 1.5 mmol, and the dosage of organic aluminium salt is 0.01 mol.
Wherein organic aluminium salt as described in step (1) is one of aluminium isopropoxide, aluminium triformate and propionic acid aluminium.
Wherein drying temperature as described in step (1) is 60 ~ 100 DEG C, and maturing temperature is 800 ~ 1000 DEG C.
Wherein (NH described in step (2)4)6 Mo7O24·4H2The concentration of O solution is 0.025 mol/L.
Wherein Co salt described in step (2) is three carbonyl nitrosyl radical cobalts, one in cobalt oxalate or acetylacetone cobalt
Kind.
The above method prepares resulting CoMo/Al2O3Hydrobon catalyst is applied to thiophene and dibenzothiophenes under normal pressure
Hydrodesulfurization reaction.
Of the invention is particularly advantageous in that:
1. Al prepared by the present invention2O3Carrier has bigger serface and good order mesoporous, is on the one hand conducive to active group
Point dispersion, be on the other hand conducive to the mass transfer of reactant with separate, the raising of final promotion hydrodesulfurization activity.
2. the active component Mo that the present invention is readily able to dispersion first is carried on carrier surface and carries out vulcanizing treatment, then
Auxiliary agent Co is introduced and vulcanized using vapour deposition process, this method is conducive to the generation and dispersion of active phase CoMoS phase, thus
Promote the raising of catalytic activity.
Detailed description of the invention
Fig. 1 is Al in embodiment 22O3The transmission electron microscope picture of carrier；
Fig. 2 is the In-situ Infrared figure of embodiment 2 and the preparation gained catalyst of comparative example 1.A: embodiment 2；B: comparative example 1.
Fig. 3 is the transmission electron microscope picture of embodiment 3 and the preparation gained catalyst of comparative example 1.A: embodiment 3；B: comparative example 1.
Specific embodiment
The present invention is further explained with reference to embodiments, but protection scope of the present invention is not limited to following embodiments.For
Further illustrate experimental implementation and its experimental result of the invention, this part combines the embodiment of invention to be retouched in more detail
It states.
Embodiment 1
One kind is with mesoporous Al2O3For the preparation method of the CoMo system Hydrobon catalyst of carrier, comprising the following steps:
(1) mesoporous Al2O3The preparation of carrier: at room temperature, 1.00 g P123 are dissolved in 15 mL dehydrated alcohols and 1.00 mL
In the mixed liquor of concentrated hydrochloric acid, pH is adjusted as 5 and obtains solution A.At the same time, solution A is added in 5 mL isopropanols and forms solution B simultaneously
30 min are persistently stirred, are then slowly added to 1.5 mmol acetic acid and 0.01 mol aluminium isopropoxide in the case where being stirred continuously
In solution B, adjusting pH value to 7, then carry out being vigorously stirred 5 h with 500r/min.By above-mentioned solution, 12 h of aging is obtained at room temperature
To colloidal sol, then places it in 60 °C of progress solvents in baking oven and volatilize to obtain xerogel, then xerogel is placed in Muffle furnace
In 400 °C of 4 h of heat preservation are raised to the rate of 1 °C/min, 800 °C of 1 h of roasting are then raised to the rate of 10 °C/min,
Obtain high specific surface area and mesoporous Al2O3Carrier.The mesoporous Al of gained2O3Specific surface be 287 m2/ g, average pore size are 7.9 nm.
(2) CoMo/Al2O3The preparation of catalyst: configuration concentration is the (NH of 0.025 mol/L4)6 Mo7O24·4H2O is molten
Liquid uses equi-volume impregnating by active component MoO after weighing the molybdenum solution of 9.5 mL3Load to Al prepared by 2g2O3Carrier
On, oxidation state Mo/Al is obtained after 150 DEG C of 2 h of drying2O3Catalyst.By above-mentioned Mo/Al2O3Catalyst is placed in vulcanization plant,
System is evacuated to 10-310%H is passed through under the conditions of 350 DEG C after Pa2S/H2(30ml/min) vulcanizes 2 h, is then switched to Ar
The system is down to room temperature.And then using vapour deposition process (CVD) by three carbonyl nitrosyl radical cobalt liquors (0.1 mol/L,
2.25 mL) Mo/Al of the pulse injection to after vulcanizing2O3On, later at 350 DEG C 2 h of revulcanization to get arrive CoMo/
Al2O3Catalyst is denoted as catalyst A, and the mass fraction that wherein mass fraction of Co is 1.3%, Mo is 8.0%.
Embodiment 2
One kind is with mesoporous Al2O3For the preparation method of the CoMo system Hydrobon catalyst of carrier, comprising the following steps:
(1) mesoporous Al2O3The synthesis of carrier: at room temperature, 2.00 g P123 are dissolved in 15 mL dehydrated alcohols and 1.00mL
In the mixed liquor of concentrated hydrochloric acid, pH is adjusted as 6 and obtains solution A.At the same time, solution A is added in 5 mL isopropanols and forms solution B simultaneously
30 min are persistently stirred, are then slowly added to 1.5 mmol acetic acid and 0.01 mol propionic acid aluminium in the case where being stirred continuously molten
In liquid B, adjusting pH value is 7, then carries out being vigorously stirred 5 h with 800r/min.By above-mentioned solution, 12 h of aging is obtained at room temperature
To colloidal sol, then places it in 70 °C of progress solvents in baking oven and volatilize to obtain xerogel, xerogel is placed in Muffle furnace
400 °C of 4 h of heat preservation are raised to the rate of 1 °C/min, 900 °C of 2 h of roasting are then raised to the rate of 10 °C/min, are obtained
High specific surface area and mesoporous Al2O3Carrier.The mesoporous Al of gained2O3The specific surface of carrier is 249 m2/ g, average pore size are 7.5 nm.
(2) CoMo/Al2O3The preparation of catalyst: configuration concentration is the (NH of 0.025 mol/L4)6 Mo7O24·4H2O is molten
Liquid uses equi-volume impregnating by active component MoO after weighing the molybdenum solution of 3.56 mL3Load to Al prepared by 2 g2O3Carrier
On, oxidation state Mo/Al is obtained after 150 DEG C of 2 h of drying2O3Catalyst.By above-mentioned Mo/Al2O3Catalyst is placed in vulcanization plant,
System is evacuated to 10-310%H is passed through under the conditions of 350 DEG C after Pa2S/H2(30ml/min) vulcanizes 2 h, is then switched to Ar
The system is down to room temperature.And then use vapour deposition process (CVD) by oxalic acid cobalt liquor (0.05 mol/L, 1.7 mL) pulse
Mo/Al after being injected to vulcanization2O3On, later at 350 DEG C 2 h of revulcanization to get arrive CoMo/Al2O3Catalyst is denoted as
Catalyst B, the mass fraction that wherein mass fraction of Co is 0.5%, Mo is 3%.
Embodiment 3
One kind is with mesoporous Al2O3For the preparation method of the CoMo system Hydrobon catalyst of carrier, comprising the following steps:
(1) mesoporous Al2O3The synthesis of carrier: at room temperature, 1.00 g P123 are dissolved in 15 mL dehydrated alcohols and 1.00mL
In concentrated hydrochloric acid mixed liquor, pH is adjusted as 5.5 and obtains solution A.At the same time, solution A is added in 5 mL isopropanols and forms new soln B
And continue to stir 30 min, then 1.5 mmol acetic acid and 0.01 mol aluminium triformate are slowly added in the case where being stirred continuously
In the solution, adjusting pH value is 7, then carries out being vigorously stirred 5 h with 600r/min.By above-mentioned solution, aging 12h is obtained at room temperature
To colloidal sol, then places it in 80 °C of progress solvents in baking oven and volatilize to obtain xerogel, xerogel is placed in Muffle furnace
400 °C of 4 h of heat preservation are raised to the rate of 1 °C/min, 1000 °C of 1 h of roasting are then raised to the rate of 10 °C/min,
Obtain high specific surface area and mesoporous Al2O3Carrier.The mesoporous Al of gained2O3The specific surface of carrier is 221 m2/ g, average pore size 6.8
nm。
(2) CoMo/Al2O3The preparation of catalyst: configuration concentration is the (NH of 0.025 mol/L4)6 Mo7O24·4H2O is molten
Liquid uses equi-volume impregnating by active component MoO after weighing the molybdenum solution of 7 mL3Load to Al prepared by 2 g2O3On carrier,
Oxidation state Mo/Al is obtained after 150 DEG C of 2 h of drying2O3Catalyst.By above-mentioned Mo/Al2O3Catalyst is placed in vulcanization plant, is
System is evacuated to 10-310%H is passed through under the conditions of 350 DEG C after Pa2S/H2(30ml/min) vulcanizes 2 h, and being then switched to Ar will
The system is down to room temperature.And then use vapour deposition process (CVD) by acetylacetone,2,4-pentanedione cobalt liquor (0.15 mol/L, 3.38 mL)
Pulse injection to sulphided state Mo/Al2O3On, later at 350 DEG C 2 h of revulcanization to get arrive CoMo/Al2O3Catalysis
Agent is denoted as catalyst C, and the mass fraction that wherein mass fraction of Co is 3%, Mo is 5.9%.
Embodiment 4
One kind is with mesoporous Al2O3For the preparation method of the CoMo system Hydrobon catalyst of carrier, comprising the following steps:
(1) mesoporous Al2O3The synthesis of carrier: at room temperature, 1.50 g P123 are dissolved in 15 mL dehydrated alcohols and 1.50 mL
Concentrated hydrochloric acid mixed liquor in, adjusting pH is 5 to obtain solution A.At the same time, solution A is added in 5 mL isopropanols and forms solution B
And continue to stir 30 min, it is then in the case where being stirred continuously that 1.5 mmol acetic acid and 0.01 mol aluminium isopropoxide are slow
It is added in the solution, adjusting pH value is 7, then carries out being vigorously stirred 5 h with 700r/min.By above-mentioned solution aging 12 at room temperature
H obtains colloidal sol, then places it in 100 °C of progress solvents in baking oven and volatilizees to obtain xerogel, xerogel is placed in horse
300 °C of 4 h of heat preservation are not raised to the rate of 1 °C/min in furnace, 800 °C of roastings 3 are then raised to the rate of 10 °C/min
H obtains high specific surface area and mesoporous Al2O3Carrier.The mesoporous Al of gained2O3The specific surface of carrier is 314 m2/ g, average pore size 8.5
nm。
(2) preparation of catalyst: configuration concentration is the (NH of 0.025 mol/L4)6 Mo7O24·4H2O solution weighs 8 mL
Molybdenum solution after using equi-volume impregnating by active component MoO3Load to Al prepared by 2 g2O3On carrier, 150 DEG C of dryings
Oxidation state Mo/Al can be obtained after 2h2O3Catalyst.By above-mentioned Mo/Al2O3Catalyst is placed in vulcanization plant, and system is evacuated to
10-310%H is passed through under the conditions of 350 DEG C after Pa2S/H2(30ml/min) vulcanizes 2h, is then switched to Ar for the system and is down to room
Temperature.And then (0.15 mol/L, the 2.10 mL) pulse of three carbonyl nitrosyl radical cobalt liquors is infused using vapour deposition process (CVD)
Mo/Al after being incident upon vulcanization2O3On, later at 350 DEG C 2 h of revulcanization to get arrive CoMo/Al2O3Catalyst is denoted as
Catalyst D, the mass fraction that wherein mass fraction of Co is 1.9%, Mo is 6.7%.
Comparative example 1
(1) Al2O3The synthesis of carrier: with embodiment 1
(2) preparation of catalyst: compound concentration is 0.05 mol/LCo (NO3)2·6H2O and 0.025mol/L (NH4)6
Mo7O24·4H2The mixed solution of O.Using equi-volume impregnating, by 8 mL, the solution is impregnated into 2 g Al of gained2O3On, after pass through
CoMo/Al is obtained after crossing standing, drying2O3The catalyst is placed in vulcanization plant by catalyst, and system is evacuated to 10-3 After Pa
10%H is passed through under the conditions of 350 DEG C2S/H2(30 ml/min) vulcanizes 2 h, is then switched to Ar for the system and is down to room temperature, remembers
For catalyst E, the mass fraction that wherein mass fraction of Co is 2.3%, Mo is 6.7%.
Comparative example 2
(1) Al2O3Carrier: with business Al2O3(traditional Chinese medicines, specific surface area are about 250 m2/ g) it is carrier.
(2) configuration concentration is the (NH of 0.025 mol/L4)6 Mo7O24·4H2O solution is adopted after weighing the molybdenum solution of 6 mL
With equi-volume impregnating by active component MoO3Load to 2 g business Al2O3On, oxidation state Mo/ is obtained after 150 DEG C of dry 2h
Al2O3Catalyst.By above-mentioned Mo/Al2O3It is placed in vulcanization plant, system is evacuated to 10-3It is passed through under the conditions of 350 DEG C after Pa
10%H2S/H2(30ml/min) vulcanizes 2 h, is then switched to Ar for the system and is down to room temperature.And then vapour deposition process is used
(CVD) Mo/A by three carbonyl nitrosyl radical cobalt liquors (0.015 mol/L, 1.80 mL) pulse injection to after vulcanizing2O3On,
Later at 350 DEG C revulcanization 2h to get arrive CoMo/Al2O3Catalyst is denoted as catalyst F, and wherein the mass fraction of Co is
The mass fraction of 1.6%, Mo are 5.0%.
The activity rating of the catalyst of above-mentioned case preparation is produced by Beijing Xin Hangdun petrochemical industry Science and Technology Ltd.
(MRT-6113) is carried out on microscale experiment reaction unit, 500 DEG C of system design pressure, system design temperature: 8 MPa, reactor
10 mm of internal diameter, microprocessor pump drive range 0.001-1sccm, mass flowmenter range: 0-200sccm；By Shimadzu Corporation's production
Product analysis is carried out on GC-MS.
Application Example
Using thiophene or 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) content be 3 wt% n-heptane solution as model chemical combination
Raw material.Rhohene desulfiirization reaction: being packed into 2 g catalyst into hydrodesulfurization unit, normal pressure, and 350 DEG C, hydrogen flowing quantity 150
ml min-1.Then pure hydrogen passes through the chemical industry saturator containing organic sulfur at 18 DEG C of constant temperature.After reaction, using GC or
Sulfur content carries out analysis survey in RPP-5000SN type sulphur blood urea/nitrogen analyzer (Taizhou Zhonghuan Analyzer Instrument Co., Ltd.) analysis product
Examination.
Interpretation of result
The thiophene of 1 catalyst of table and the Activity Results of dibenzothiophenes Hydrobon catalyst
Table 1 is the evaluation index of the Hydrobon catalyst in embodiment 1-4 and comparative example 1,2 using the method for the present invention preparation.
As it can be seen from table 1 Hydrobon catalyst (sample A-D) of the present invention has high desulphurizing activated, wherein catalyst A
Thiophene conversion ratio under normal pressure at 350 DEG C is up to 96.4%, and the conversion ratio of dibenzothiophenes conversion ratio is also up to 91.9%.Add hydrogen
It is desulphurizing activated to be apparently higher than catalyst E that traditional infusion process is prepared and with business Al2O3The catalyst F obtained for carrier.Its
At 350 DEG C, the conversion ratio of thiophene and dibenzothiophenes is respectively 75.6% and 69.3% under middle catalyst F normal pressure.By connecting
It can be seen that after the dibenzothiophenes hydrodesulfurization stability test of continuous 40 h, in embodiment 1-4 under the conversion ratio of dibenzothiophenes
That drops is unobvious.Especially embodiment 4, conversion ratio is reduced only by 1.6% after 40 h test, and comparative example 1 and 2 is same
Under conditions of have dropped 8.7% and 15% respectively.Illustrate that the catalyst of invention preparation is with good stability.
Fig. 1 is 2 intermediary hole Al of embodiment2O3The transmission electron microscope picture of carrier.It is observed from fig. 1 that orderly Jie arranged in parallel
The two-dimentional hexagonal hole road in hole duct and high-sequential illustrates prepared mesoporous Al2O3Carrier has typical case after high-temperature roasting
Six side's symmetric form ordered mesopore structure of two dimension.
Fig. 2 is embodiment 2 (A) and the In-situ Infrared figure of comparative example 1 (B) preparation gained catalyst.It uses as seen from Figure 2
Its surface after over cure catalyst B prepared by the method for the present invention forms more CoMoS activity phases, and is significantly more than
MoS2Active phase.And the surface catalyst E for using traditional infusion process to be prepared is then to form more MoS2Active phase.It is many
Well known, CoMoS activity mutually has higher hydrodesulfurization activity, therefore catalyst prepared by the present invention is with superior
Hydrodesulfurization activity.
Fig. 3 is the transmission electron microscope picture of embodiment 3 and the preparation gained catalyst of comparative example 1, the catalyst as can be seen from Figure 3 vulcanized
C and catalyst E analyzes to investigate different carriers to MoS by high-resolution-ration transmission electric-lens (HRTEM)2The length and stacking number of lamella
Influence.As shown in (A) of fig. 3, it is evident that find out catalyst surface have the less number of plies and short length MoS2Piece.From
(B) its MoS in catalyst E is found out in2The lamella number of plies has rising, and length increases.And MoS2The drop of the stacking number of plies and length
It is low to be conducive to expose more active site Mo position, especially reduction of the stacking number of plies at position and S and promote middle layer MoS2
Exposure, and then be conducive to active raising.Therefore catalyst prepared by the present invention has excellent hydrodesulfurization activity.
Obviously, above-described embodiment be used for the purpose of clearly demonstrating situation and for example, be not to embodiment into
Restriction is gone.It therefore, can be can also make on the basis of examples detailed above for those of ordinary skill in the art
Other various forms of variations.Here it illustrates, but is thus drawn apparent one by one without to all embodiments
Variation or change still in the protection scope of the invention within.
Claims (8)
1. one kind is with mesoporous Al2O3For the CoMo system Hydrobon catalyst of carrier, it is characterised in that: the CoMo system plus hydrogen are de-
Sulfur catalyst is with mesoporous Al2O3For carrier, using CoO as auxiliary agent, MoO3For active component, wherein CoO is calculated as by the mass fraction of Co
0.5 ~ 3%, MoO33 ~ 8% are calculated as by the mass fraction of Mo, which is denoted as CoMo/Al2O3。
2. one kind as described in claim 1 is with mesoporous Al2O3For the preparation method of the CoMo system Hydrobon catalyst of carrier,
It is characterized by comprising the following steps:
(1) mesoporous Al2O3The preparation of carrier: at room temperature, the P123 of certain mass being dissolved in the hydrochloric acid solution of dehydrated alcohol,
It adjusts after pH is 5 ~ 6 and obtains solution A；At the same time, a certain amount of isopropanol is added in solution A and forms solution B and persistently stirs
It mixes, then a certain amount of acetic acid and organic aluminium salt is slowly added into solution B in the case where being stirred continuously, adjust pH value of solution
A period of time is vigorously stirred with 500 ~ 800 r/min again after to neutrality；By above-mentioned solution, aging is obtained at room temperature after stirring
To colloidal sol, continues drying and obtain xerogel, obtain high specific surface area and mesoporous Al after high-temperature roasting is cooling2O3Carrier；
(2) CoMo/Al2O3The preparation of catalyst: the certain density (NH of configuration4)6 Mo7O24·4H2O solution, using isometric leaching
Stain method is loaded to mesoporous Al2O3On carrier, Mo/Al can be obtained after dry2O3Catalyst；By Mo/Al2O3Catalyst is placed in vulcanization
Device, system are evacuated to 10-3Vulcanizing treatment is carried out to the catalyst after Pa, wait be cooled to room temperature at normal temperatures and pressures using gas
Co salt is loaded to sulphided state Mo/Al by phase sedimentation2O3And then catalyst carries out post-cure processing to get CoMo system plus hydrogen
Desulphurization catalyst CoMo/Al2O3。
3. preparation method according to claim 2, which is characterized in that P123 mass as described in step (1) is 1 ~ 2 g,
Dehydrated alcohol dosage is 15 mL, and concentrated hydrochloric acid dosage is 1 ~ 2 mL, and the dosage of isopropanol is 5 mL, and the dosage of acetic acid is 1.5
Mmol, the dosage of organic aluminium salt are 0.01 mol.
4. preparation method according to claim 2, which is characterized in that organic aluminium salt as described in step (1) is isopropanol
One of aluminium, aluminium triformate and propionic acid aluminium.
5. preparation method according to claim 2, which is characterized in that drying temperature as described in step (1) is 60 ~ 100
DEG C, maturing temperature is 800 ~ 1000 DEG C.
6. preparation method according to claim 2, which is characterized in that (NH described in step (2)4)6 Mo7O24·4H2O is molten
The concentration of liquid is 0.025 mol/L.
7. preparation method according to claim 2, which is characterized in that Co salt described in step (2) is three carbonyl nitrous
Acyl cobalt, one of cobalt oxalate or acetylacetone cobalt.
8. one kind as described in claim 1 is with mesoporous Al2O3It is special for the application of the CoMo system Hydrobon catalyst of carrier
Sign is: the catalyst is used for thiophene and dibenzothiophenes hydrodesulfurization under normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910655664.4A CN110252321A (en) | 2019-07-19 | 2019-07-19 | A method of vapor deposition preparation CoMo system Hydrobon catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910655664.4A CN110252321A (en) | 2019-07-19 | 2019-07-19 | A method of vapor deposition preparation CoMo system Hydrobon catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110252321A true CN110252321A (en) | 2019-09-20 |
Family
ID=67927266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910655664.4A Pending CN110252321A (en) | 2019-07-19 | 2019-07-19 | A method of vapor deposition preparation CoMo system Hydrobon catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110252321A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021078282A1 (en) * | 2019-10-25 | 2021-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst, manufacturing method therefor and use thereof |
| CN114433134A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-strength alumina-based hydrogenation catalyst, and preparation method and application thereof |
| 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 |
| CN115337957A (en) * | 2021-05-14 | 2022-11-15 | 中国石油化工股份有限公司 | Molybdenum-containing mesoporous alumina molecular sieve, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872073A (en) * | 1995-10-08 | 1999-02-16 | The United States Of America As Represented By The United States Department Of Energy | Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith |
| CN102614856A (en) * | 2012-04-20 | 2012-08-01 | 北京化工大学 | Preparation method and application of mesoporous alumina-supported metal catalyst |
| CN103252229A (en) * | 2013-05-12 | 2013-08-21 | 大连理工大学 | Molybdenum-dioxide-based oxidative desulfurization catalyst |
| US20150182952A1 (en) * | 2013-12-18 | 2015-07-02 | Lorena ALVAREZ CONTRERAS | OBTENTION OF LOW LOADING CATALYSTS FOR DEEP HYDROCARBONS HYDRODESULFURIZATION BASED OF CoMoS, WITH NiMoS HYDRODENITROGENANT ADDITIVE, SUPPORTED ON THREE-DIMENSIONAL NANOSTRUCTURED MESOPOROUS MATERIALS |
| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
| CN107824194A (en) * | 2017-12-16 | 2018-03-23 | 福州大学 | It is a kind of using meso-porous alumina as Hydrobon catalyst of carrier and its preparation method and application |
| CN109289876A (en) * | 2018-11-23 | 2019-02-01 | 中国石油大学(北京) | A kind of deep desulfurization catalyst and its preparation method and application |
-
2019
- 2019-07-19 CN CN201910655664.4A patent/CN110252321A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5872073A (en) * | 1995-10-08 | 1999-02-16 | The United States Of America As Represented By The United States Department Of Energy | Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith |
| CN102614856A (en) * | 2012-04-20 | 2012-08-01 | 北京化工大学 | Preparation method and application of mesoporous alumina-supported metal catalyst |
| CN103252229A (en) * | 2013-05-12 | 2013-08-21 | 大连理工大学 | Molybdenum-dioxide-based oxidative desulfurization catalyst |
| US20150182952A1 (en) * | 2013-12-18 | 2015-07-02 | Lorena ALVAREZ CONTRERAS | OBTENTION OF LOW LOADING CATALYSTS FOR DEEP HYDROCARBONS HYDRODESULFURIZATION BASED OF CoMoS, WITH NiMoS HYDRODENITROGENANT ADDITIVE, SUPPORTED ON THREE-DIMENSIONAL NANOSTRUCTURED MESOPOROUS MATERIALS |
| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
| CN107824194A (en) * | 2017-12-16 | 2018-03-23 | 福州大学 | It is a kind of using meso-porous alumina as Hydrobon catalyst of carrier and its preparation method and application |
| CN109289876A (en) * | 2018-11-23 | 2019-02-01 | 中国石油大学(北京) | A kind of deep desulfurization catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| YASUAKI OKAMOTO ET AL.: "A model catalyst approach to the effects of the support on Co–Mo hydrodesulfurization catalysts", 《CATALYSIS TODAY》 * |
| YASUAKI OKAMOTO ET AL.: "Structure of the Active Sites of Co-Mo Hydrodesulfurization Catalysts as Studied by Magnetic Susceptibility Measurement and NO Adsorption", 《J. PHYS. CHEM. B》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021078282A1 (en) * | 2019-10-25 | 2021-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst, manufacturing method therefor and use thereof |
| EP4035770A4 (en) * | 2019-10-25 | 2023-03-29 | China Petroleum & Chemical Corporation | Hydrogenation catalyst, manufacturing method therefor and use thereof |
| CN114433134A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-strength alumina-based hydrogenation catalyst, and preparation method and application thereof |
| CN114433134B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | High-strength alumina-based hydrogenation catalyst, and preparation method and application thereof |
| 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 |
| CN114570392B (en) * | 2020-12-02 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN115337957A (en) * | 2021-05-14 | 2022-11-15 | 中国石油化工股份有限公司 | Molybdenum-containing mesoporous alumina molecular sieve, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110252321A (en) | A method of vapor deposition preparation CoMo system Hydrobon catalyst | |
| CN102151582B (en) | Preparation method of hydrodesulfurization catalyst for high-nitrogen low-quality gasoline and diesel | |
| CN107824194A (en) | It is a kind of using meso-porous alumina as Hydrobon catalyst of carrier and its preparation method and application | |
| CN104368344A (en) | Cobalt-base Fischer-Tropsch synthesis catalyst and preparation method and application thereof | |
| CN107899619A (en) | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof | |
| CN104437578B (en) | Hydrodesulfurization catalyst, preparation method and applications thereof | |
| CN108273485A (en) | It is a kind of using order mesoporous Ti-Si composite oxide as Hydrobon catalyst of carrier and preparation method thereof | |
| CN107537476A (en) | Dehydrogenation, preparation method and its usage | |
| CN108654700A (en) | Three peak pore size distribution Hydrodemetalation catalysts of one kind and preparation method thereof | |
| CN112717946A (en) | Spent lubricating oil hydrogenation regeneration catalyst and preparation method thereof | |
| CN107537587A (en) | The processing method of catalyst | |
| CN1133726C (en) | Hydrocatalyst arrier and its preparing process | |
| CN101590416A (en) | Molybdenum-nickel hydrogenation catalyst and preparation method thereof | |
| CN110465306A (en) | A kind of preparation method of active isomer phase hydrogenation catalyst | |
| CN103725312B (en) | A kind of catalysis conversion method reducing rich benzoline component benzene content | |
| CN109092320A (en) | A kind of alumina support and preparation method | |
| CN1221313C (en) | Petroleum fraction hydrofining catalyst and preparing method thereof | |
| CN1766052A (en) | Distillate oil hydrogenation catalyst and its preparation method | |
| CN108816240A (en) | It is a kind of using titanium oxide as the Hydrobon catalyst of carrier | |
| CN116621163B (en) | Synthesis method of carbon nano tube | |
| CN104437571A (en) | Hydrodesulfurization catalyst, preparation method and application thereof | |
| CN106622358A (en) | Composite support hydrodesulfurization catalyst | |
| CN1301794C (en) | Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process | |
| CN114570392B (en) | Hydrodesulfurization catalyst and preparation method thereof | |
| CN117654647A (en) | Out-of-device presulfiding method of coke oven gas hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190920 |