CN109046318A - A kind of calcium promotes the preparation method of molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst - Google Patents
A kind of calcium promotes the preparation method of molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 49
- 230000023556 desulfurization Effects 0.000 title claims abstract description 46
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 239000011575 calcium Substances 0.000 title claims abstract description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 25
- 239000011733 molybdenum Substances 0.000 title claims abstract description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 23
- 239000004411 aluminium Substances 0.000 title claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 53
- 239000003921 oil Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 238000004088 simulation Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 70
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- -1 sulphur compound Chemical class 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J23/002—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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of calcium, and the preparation method of molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst to be promoted to be denoted as solution A, solution B and solution C respectively the specific steps of which are as follows: silicon source, molybdenum source and calcium source are first dissolved in deionized water respectively；Then template is added in the mixed solution of deionized water, ethyl alcohol and ammonium hydroxide, is denoted as mixed liquor D；Successively solution A, B and C are added separately in solution D again, stirred evenly, then aging, be filtered, washed, be dried in vacuo；It is finally calcined in inert gas and dry air respectively, obtains catalyst.Catalyst produced by the present invention has biggish specific surface area, can be in relatively mild (55 DEG C of lower reaction temperature, environmentally protective H2O2As under oxidant, normal pressure) catalytic condition under carry out deep desulfuration, desulfurization degree is up to 100%.Directly the oil product met the requirements can be can be obtained by being simply centrifugated catalyst after oxidation sweetening, it is easy to operate, it is economic and environment-friendly.
Description
Technical field
Promote the preparation method of molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst the present invention relates to a kind of calcium and utilizes catalysis
Agent belongs to petroleum catalyst for catalytic oxidation field to the method for diesel oil or gasoline catalyzing oxidation sweetening.
Background technique
The haze problem in China was increasingly sharpened in recent years, thus atmosphere polluting problem is also more and more of interest by everybody, wherein
Vehicle exhaust is one of important origin cause of formation of atmosphere pollution.With economic development, automobile increasing number, the tail gas discharged is also therewith
Increase, various sulfide can be generated after the sulfur-bearing flammability in fuel oil, these sulfide not only result in building and steel
The corrosion of product also results in environmental pollution, destroys the ecosystem.Thus the research of exploitation oil product ultra-deep desulfurization has very heavy
The meaning wanted.
In general, hydrodesulfurization (HDS) is to remove the most important technology of sulphur compound from fuel oil in petroleum refining industry.However,
HDS process usually requires harsh reaction condition, including high temperature, high pressure and a large amount of hydrogen of consumption.HDS is in removal mercaptan, vulcanization
Efficiency is higher in terms of object, disulphide and some thiophenes, but is difficult to remove sulphur compound difficult to degrade, such as dibenzo
Thiophene (DBT).In order to solve these problems in hydrodesulfurization, oxidation sweetening (ODS) adsorbs desulfurization, alkylating desulfurization,
Biological desulphurization etc. is widely studied.Wherein, ODS in a mild condition is considered as a kind of very promising ultra-deep desulfurization
Method, because its desulfuration efficiency height and the low more economy of operating cost, increasingly become research hotspot.The oxide of molybdenum is because of it
Price is inexpensive, and raw material is easy to get, and has preferable desulfurization effect in oxidation sweetening, is often adopted as the activated centre of ODS.
Jos é is reported in Mo/Al2O3-H2O2Under system, the sulfur content of diesel oil can be down to 10ppm from about 320ppm.Wang Xuesong etc. uses
Equi-volume impregnating prepares the Mo/SiO of different loads amount2Catalyst is with oil-soluble cumyl hydroperoxide (CHP)
Oxidant, modified catalysts can DBT in exhaustive oxidation simulation oil, and then polarity sulfone compound is removed after extracting.
Open the strong equal MoO prepared with sol-gel method3-CeO2-SiO2Composite oxides are catalyst, using CHP as oxidant, mild
Oxidation sweetening is carried out to the toluene solution of DBT under condition (40 DEG C, normal pressure), as the result is shown: can to DBT removal efficiency in simulation oil product
To reach 90% or more.Li Xiang etc. uses Molybdenum-dioxide-boxidative oxidative desulfurization catalyst, in fixed bed reactors, with mass fraction
The toluene solution of 0.2% dibenzothiophenes is substrate, carries out continuous oxidation desulphurization reaction, the removing of DBT by oxidant of CHP
Rate is close to 100%.Azam etc. passes through the MoO for preparing different molybdenum load capacity3/Al2O3Catalyst is catalyzed using ultrasonic wave added
Oxidation sweetening, the DBT more than 95% are oxidized after 6 ultrasonic wave addeds recycle.Shen etc. utilizes the modified MoO of Wo3/Al2O3's
15% (MoO3–WO3)/Al2O3Catalyst can realize the conversion higher than 99.2% at lower reaction temperature (≤338K)
Rate.
In ODS, nonpolar organic sulfur compound is oxidized the homology sulfone that agent is oxidized to them under catalyst, then passes through essence
It evaporates, extracts, absorption or the removing of other separating steps.It is needed in the process using a large amount of extractant, such as volatile, flammable,
It is toxic and be not easily recycled to the organic solvents such as dimethyl sulfoxide, sulfolane, tetraethylene glycol, diethylene glycol (DEG) or expensive ionic liquid
Body etc.；Time-consuming for the materials such as adsorbent such as zeolite, active carbon, porous material, clay, consumes energy the disadvantages of high；Distillation operation process
The disadvantages of complexity, high production cost.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of novel calcium to promote the catalysis of molybdenum aluminium composite oxide
The preparation method of oxidation-desulfurizing catalyst, it is another object of the present invention to be urged using the catalyst of above-mentioned preparation bavin Water Oil Or Gas
Change the method for oxidation sweetening.By-product after the reaction was completed can be adsorbed on catalyst by the present invention completely, and then pass through letter
Single separation of solid and liquid can directly obtain the oil product met the requirements, easy to operate, economic and environment-friendly.
The technical solution of the present invention is as follows: a kind of calcium promotes the preparation method of molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst,
The specific steps of which are as follows:
1) silicon source, molybdenum source and calcium source are dissolved in deionized water respectively, are denoted as solution A, solution B and solution C respectively；
2) template is added in the mixed solution of deionized water, ethyl alcohol and ammonium hydroxide, is denoted as mixed liquor D；
3) successively solution A, B and C are added separately in solution D, and then stirred evenly, then aging at room temperature；
4) after being separated by filtration, deionized water washing, vacuum drying；
5) it is warming up in inert gas and dry air at 500-600 DEG C respectively and respectively calcines 5-7h, obtained calcium and promote molybdenum aluminium multiple
Close oxide catalyst oxidation-desulfurizing catalyst.
It is preferred that the concentration of Al is 4-5mol/L in above-mentioned solution A；The concentration of Mo is 0.72-0.76mol/L in solution B；Solution C
The concentration of middle Ca is 0.025-0.06mol/L.
Preferred steps 2) in deionized water, ethyl alcohol and ammonium hydroxide volume ratio be (15-25): (5-15): 1；Template in mixed liquor D
Concentration be 0.0004-0.0006mol/L.
It is preferred that the template is the one or more of P123, F127 or CTAB.
Preferred steps 3) in solution A, B and C be added separately to solution D control Mo:Ca:Al component molar ratio be (0.15-
0.18): (0.005-0.015): 1；The volume ratio of solution A, the total volume of B and C and D is 1:(12-13).
It is preferred that the calcium presoma is the one or more of calcium nitrate, calcium chloride or calcium carbonate；The molybdenum presoma is molybdenum
The one or more of sour ammonium, phosphomolybdic acid or molybdenum chloride；The aluminium presoma is one kind of aluminium chloride, aluminum nitrate or aluminium isopropoxide
Or it is several.
Preferred steps 3) in mixing time 1-2h；Ageing time 4-6h.It is preferred that the vacuum drying temperature 100-110
DEG C, dry time 20-24h.It is preferred that the inert gas is one or more of nitrogen, argon gas or helium.
The present invention also provides promote molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst to bavin using above-mentioned prepared calcium
The method of Water Oil Or Gas catalytic oxidation desulfurization, the specific steps of which are as follows: using sulfur-bearing simulation oil as raw material, in oxidant and catalyst
In the presence of, catalytic oxidation desulfurization reaction is carried out, centrifuged product simulation oil after reaction；Wherein the oxidant is peroxidating
Hydrogen；Reaction condition are as follows: reaction time 8-10min, 55-60 DEG C of reaction temperature, hydrogen peroxide and simulation oil volume ratio are 0.18-
0.22%, catalyst amount is the 0.5-0.75% for simulating oil quality.
Its concrete operations are as follows: weigh the simulation oil (the normal octane solution of dibenzothiophenes) of a certain amount of sulfur-bearing 450ppm, be added with
Oil quality is than the catalyst for 0.5-0.75%, in 55-60 DEG C of water bath with thermostatic control, after stirring a period of time, and dropwise addition and mould
Intend oil volume than the hydrogen peroxide for 0.18-0.22%.After reacting 8-10min, after being centrifugated catalyst, high performance liquid chromatography
Total sulfur content in instrument analysis mode oil product.
The utility model has the advantages that
1, the calcium of technical solution provided by the invention preparation promote molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst have compared with
Big specific surface area (188.68m2·g-1, it is better than literature value 151.09m2·g-1)。
2, catalyst provided by the invention can be in relatively mild (55 DEG C of lower reaction temperature, environmentally protective H2O2As
Under oxidant, normal pressure) catalytic condition under carry out deep desulfuration, desulfurization degree is up to 100%.
3, it can directly can be obtained by being simply centrifugated catalyst after oxidation sweetening in technical solution provided by the invention
The oil product met the requirements, it is easy to operate, it is economic and environment-friendly.
Detailed description of the invention
Fig. 1 is the XRD diagram that calcium promotes molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst A；
Fig. 2 is that calcium promotes molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst A nitrogen adsorption desorption curve (left side) and pore-size distribution
Scheme on (right side).
Specific embodiment
3.17g aluminium chloride, 0.67g ammonium molybdate and 0.056g calcium nitrate: being dissolved in deionized water by embodiment 1 respectively first, note
Do containing Al be 4.75mol/L solution A, containing Mo be 0.76mol/L solution B and containing Ca be 0.047mol/L solution C.It will
0.38g template F127 is added to deionized water, ethyl alcohol and ammonium hydroxide (V (deionized water): V (ethyl alcohol): V (ammonium hydroxide)=20:10:
1) in mixed solution D, wherein template is 0.0005mol/L.And then successively add the solution A prepared in advance, solution B and
Solution C (volume ratio of A, B, C and D are 1:12.4), and 1.5h is stirred at 1000rpm, aged at room temperature 5h, filtering, deionization
Water washing, 105 DEG C of vacuum drying are for 24 hours.Finally, calcining 6h respectively at 540 DEG C in nitrogen and air atmosphere, calcium promotion is obtained
Molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst A (0.02Ca/0.334MoO3/Al2O3), XRD diagram is as shown in Figure 1；Its
Nitrogen adsorption desorption curve is as shown in Fig. 2 left figure, and pore-size distribution is as shown in Fig. 2 right figure.
4.08g aluminium isopropoxide, 0.55g phosphomolybdic acid and 0.033g calcium chloride: being dissolved in deionized water by embodiment 2 respectively first,
It is denoted as the solution A for being 4mol/L containing Al, the solution B for being 0.72mol/L containing Mo and is 0.06mol/L solution C containing Ca.By 0.14g
Template P123 is added to deionized water, ethyl alcohol and ammonium hydroxide (V (deionized water): V (ethyl alcohol): V (ammonium hydroxide)=15:15:1) it is mixed
It closes in solution D, wherein template is 0.0004mol/L.And then successively add the solution A prepared in advance, solution B and solution C
(volume ratio of A, B, C and D are 1:13), and 2h is stirred at 1000rpm, aged at room temperature 4h, filtering, deionized water washing, 100
DEG C vacuum drying 22h.Finally, calcining 5h respectively at 500 DEG C in argon gas and air atmosphere, obtains calcium and promote molybdenum aluminium composite oxygen
Compound catalytic oxidation desulfurization catalyst B (0.03Ca/0.360MoO3/Al2O3)。
9.38g aluminum nitrate, 1.02g molybdenum chloride and 0.013g calcium carbonate: being dissolved in deionized water by embodiment 3 respectively first, note
Do containing Al be 5mol/L solution A, containing Mo be 0.75mol/L solution B and containing Ca be 0.025mol/L solution C.By 0.014g
Template CTAB is added to deionized water, ethyl alcohol and ammonium hydroxide (V (deionized water): V (ethyl alcohol): V (ammonium hydroxide)=25:5:1) it is mixed
It closes in solution D, wherein template is 0.0006mol/L.And then successively add the solution A prepared in advance, solution B and solution C
(volume ratio of A, B, C and D are 1:12), and 1h is stirred at 1000rpm, aged at room temperature 6h, filtering, deionized water washing, 110
DEG C vacuum drying 20h.Finally, calcining 7h respectively at 600 DEG C in helium and air atmosphere, obtains calcium and promote molybdenum aluminium composite oxygen
Compound catalytic oxidation desulfurization catalyst C (0.01Ca/0.3MoO3/Al2O3)。
Embodiment 4-18:
It is the simulation oil that 100mL sulfur content is 450ppm in oxidation sweetening experiment condition using A, B, C sample as catalyst, reaction
Temperature is 55 DEG C, reaction time 8min, V (H2O2)/V (simulation oil) is 0.20%, and investigating catalyst amount is simulation oil quality
0.14%, 0.28%, 0.42%, 0.56% and 0.72% influence pair desulfurization degree, experimental result is shown in Table 1.
Influence of 1 catalyst amount of table to desulfurization effect
As it can be seen that the increase desulfurization degree with catalyst amount is gradually increased, when catalyst A, B dosage is simulation oil quality 0.56%
Desulfurization degree reaches 100.0%, then gradually tends to be steady；Desulfurization degree reaches when catalyst C dosage is simulation oil quality 0.72%
100.0%.Therefore, during catalytic oxidation, catalyst amount is that the 0.56-0.72% of simulation oil quality is suitable for.
Embodiment 19-33:
It is the simulation oil that 100mL sulfur content is 450ppm in oxidation sweetening experiment condition using A, B, C sample as catalyst, reaction
Temperature is 55 DEG C, reaction time 8min, and catalyst amount is simulate oil quality 0.56%, investigates V (H2O2)/V (simulation oil)
Influence when being 0.1%, 0.2%, 0.3%, 0.4% and 0.5% to desulfurization degree, experimental result are shown in Table 2.
Table 2V (H2O2Influence of the)/V (simulation oil) to desulfurization effect
As it can be seen that catalyst A, B and C are in V (H as the increase desulfurization of hydrogen peroxide use takes the lead in subtracting after increasing2O2)/V (simulation oil)
Desulfurization degree is respectively 100.0%, 100.0% and 95.3% when being 0.2, is then successively decreased, because of excessive H2O2Mo is caused to urge
The side reaction of change simultaneously generates excessive H2O.On the one hand, side reaction occupies leading and increases H2O2Consumption.On the other hand, one
The hydrophilic catalyst of certainty ratio is transferred to water phase, to reduce the drop that the catalyst of dispersion in the oil results in desulfurization degree
It is low.Therefore, during catalytic oxidation, V (H2O2It is suitable for when)/V (simulation oil) is 0.2.
Embodiment 34-48:
It is the simulation oil that 100mL sulfur content is 450ppm in oxidation sweetening experiment condition using A, B, C sample as catalyst, reaction
Time is 8min, and catalyst amount is 0.56%, the V (H for simulating oil quality2O2)/V (simulation oil) is 0.20%, investigates reaction temperature
Influence when degree is 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C and 60 DEG C to desulfurization degree, experimental result are shown in Table 3.
Influence of 3 temperature of table to desulfurization effect
As it can be seen that desulfurization takes the lead in as the temperature rises, increasing is then gradually steady, and catalyst A, B desulfurization degree when temperature is 55 DEG C reach
To 100.0%；Catalyst C desulfurization degree at 55 DEG C of temperature reaches 95.3%.Therefore, during catalytic oxidation, temperature is
It is suitable at 55-60 DEG C.
Embodiment 49-63:
It is the simulation oil that 100mL sulfur content is 450ppm in oxidation sweetening experiment condition using A, B, C sample as catalyst, reaction
Temperature is 55 DEG C, and catalyst amount is 0.56%, the V (H for simulating oil quality2O2)/V (simulation oil) is 0.20%, when investigating reaction
Between influence to desulfurization degree when being 2,4,6,8 and 10min, experimental result is shown in Table 4.
Influence of 4 time of table to desulfurization effect
As it can be seen that the increase desulfurization degree with the reaction time is gradually increased, catalyst A, B desulfurization degree when the time is 8min reach
100.0%, then gradually tend to be steady；Catalyst C desulfurization degree in 10min reaches 100.0%.Therefore, catalytic oxidation
In the process, the time is that 8-10min is most appropriate.
Claims (10)
1. calcium promotes the preparation method of molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst, the specific steps of which are as follows:
1) silicon source, molybdenum source and calcium source are dissolved in deionized water respectively, are denoted as solution A, solution B and solution C respectively；
2) template is added in the mixed solution of deionized water, ethyl alcohol and ammonium hydroxide, is denoted as mixed liquor D；
3) successively solution A, B and C are added separately in solution D, are stirred evenly, then aging at room temperature；
4) after being separated by filtration, deionized water washing, vacuum drying；
5) it is warming up in inert gas and dry air at 500-600 DEG C respectively and respectively calcines 5-7h, obtained calcium and promote molybdenum aluminium multiple
Close oxide catalyst oxidation-desulfurizing catalyst.
2. preparation method according to claim 1, it is characterised in that the concentration of Al is 4-5mol/L in the solution A；
The concentration of Mo is 0.72-0.76mol/L in solution B；The concentration of Ca is 0.025-0.06mol/L in solution C.
3. preparation method according to claim 1, it is characterised in that deionized water, the volume of ethyl alcohol and ammonium hydroxide in step 2)
Than for (15-25): (5-15): 1；The concentration of template is 0.0004-0.0006mol/L in mixed liquor D.
4. preparation method according to claim 1, it is characterised in that the template is the one of P123, F127 or CTAB
Kind is several.
5. preparation method according to claim 1, it is characterised in that solution A, B and C are added separately to solution D in step 3)
The molar ratio for controlling Mo:Ca:Al component is (0.15-0.18): (0.005-0.015): 1；Solution A, the total volume of B and C and D
Volume ratio is 1:(12-13).
6. preparation method according to claim 1, it is characterised in that the calcium presoma is calcium nitrate, calcium chloride or carbon
The one or more of sour calcium；The molybdenum presoma is the one or more of ammonium molybdate, phosphomolybdic acid or molybdenum chloride；Before the aluminium
Drive body is the one or more of aluminium chloride, aluminum nitrate or aluminium isopropoxide.
7. preparation method according to claim 1, it is characterised in that the mixing time 1-2h in step 3)；Ageing time 4-
6h。
8. preparation method according to claim 1, it is characterised in that described 100-110 DEG C of vacuum drying temperature is done
Dry time 20-24h.
9. preparation method according to claim 1, it is characterised in that the inert gas is in nitrogen, argon gas or helium
One or more.
10. a kind of promote molybdenum aluminium composite oxide catalytic oxidation desulfurization catalyst to bavin using the calcium as prepared by claim 1
The method of Water Oil Or Gas catalytic oxidation desulfurization, the specific steps of which are as follows: using sulfur-bearing simulation oil as raw material, in oxidant and catalyst
In the presence of, catalytic oxidation desulfurization reaction is carried out, centrifuged product simulation oil after reaction；Wherein the oxidant is peroxidating
Hydrogen；Reaction condition are as follows: reaction time 8-10min, 55-60 DEG C of reaction temperature, hydrogen peroxide and simulation oil volume ratio are 0.18-
0.22%, catalyst amount is the 0.5-0.75% for simulating oil quality.
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