CN112516981B - Preparation method of low-titanium-load titanium-silicon material for diesel desulfurization and method for testing number of surface catalytic active sites of low-titanium-load titanium-silicon material - Google Patents
Preparation method of low-titanium-load titanium-silicon material for diesel desulfurization and method for testing number of surface catalytic active sites of low-titanium-load titanium-silicon material Download PDFInfo
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- CN112516981B CN112516981B CN202011381302.XA CN202011381302A CN112516981B CN 112516981 B CN112516981 B CN 112516981B CN 202011381302 A CN202011381302 A CN 202011381302A CN 112516981 B CN112516981 B CN 112516981B
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- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 62
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000012360 testing method Methods 0.000 title abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 63
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 61
- 238000011068 loading method Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 239000002283 diesel fuel Substances 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 36
- 239000000523 sample Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000012286 potassium permanganate Substances 0.000 claims description 24
- 238000004448 titration Methods 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 18
- 229910002027 silica gel Inorganic materials 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004440 column chromatography Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012086 standard solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000011410 subtraction method Methods 0.000 claims description 2
- 238000004809 thin layer chromatography Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 230000031700 light absorption Effects 0.000 claims 1
- 238000000691 measurement method Methods 0.000 claims 1
- 238000013508 migration Methods 0.000 claims 1
- 230000005012 migration Effects 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000004408 titanium dioxide Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000010998 test method Methods 0.000 abstract description 2
- 238000011002 quantification Methods 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 28
- 229910021642 ultra pure water Inorganic materials 0.000 description 21
- 239000012498 ultrapure water Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- RWCMHQZUYWBVAE-UHFFFAOYSA-N OS(=O)(=O)S(=O)(=O)S(O)(=O)=O Chemical class OS(=O)(=O)S(=O)(=O)S(O)(=O)=O RWCMHQZUYWBVAE-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- -1 small molecule sulfides Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
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- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention provides a preparation method of a low-titanium-loading titanium-silicon material for diesel oil desulfurization and a method for testing the number of surface catalytic active sites of the material. The preparation method of the titanium-silicon material with low titanium loading can ensure that the titanium-silicon material has very good diesel oil oxidation-adsorption desulfurization performance at lower titanium loading. The low titanium loading refers to loading of titanium dioxide at a weight fraction of titanium of 0.1% to 1.5%. The method for testing the number of the surface catalytic active sites can quantitatively test the number of the surface catalytic active sites of the catalyst, and can also be used as a test method for other similar titanium dioxide catalysts. The titanium-silicon material with low titanium loading for diesel oxidation adsorption has higher TOF value and higher atom economy in the diesel desulfurization process; the provided method for testing the number of the surface catalytic active sites has the advantages of accurate quantification and good repeatability.
Description
Technical Field
The invention relates to the field of diesel oil desulfurization, in particular to a preparation method of a low-titanium-loading titanium-silicon material for diesel oil oxidation adsorption desulfurization, and provides a method for testing the number of surface catalytic active sites.
Background
Sulfur dioxide is a major pollutant in the air and controlling sulfur dioxide emissions has become a common consensus throughout the world. Sulfur dioxide is primarily produced from the combustion of fossil fuels containing sulfides. It is recognized throughout the world that sulfur dioxide air pollution is more effectively remediated from the source, i.e., the sulfur compounds contained therein are removed during the fossil fuel refinery stage, than is the case with the retreatment of sulfur dioxide pollution following combustion of the fuel, since the collection of these emitted tail gases is relatively much more difficult to dispose of. Therefore, relevant laws and regulations and fuel standards are set by governments of various countries, and oil refining enterprises are guided to produce clean fuel oil with lower and lower sulfur content (the sulfur content of the automotive diesel oil is less than 10 ppm). At the same time the fuel cell industry and the special clean fuel requirements are expanding the demand for ultra clean fuels (sulphur content <1 ppm).
The removal of sulfide from fuel oil is a very important link in the petroleum refining industry, and the sulfide is usually converted into hydrogen sulfide by a catalytic hydrogenation method to achieve the purpose of desulfurization. Catalytic hydrogenation is very effective for most small molecule sulfides, such as: thiols, thioethers, dithioethers, and the like. But for large thiophene sulfides, such as: dibenzothiophene and its alkyl derivatives, exhibit poor hydrogenation performance. Hydrogenolysis of catalytic hydrogenation generally requires high pressures (2-10MPa of H) at high temperatures (300-2) Lower running costs are therefore required. In order to reduce energy consumption and running cost, a non-hydrogenation deep desulfurization technology capable of running at normal temperature and low pressure is a new requirement.
The adsorption desulfurization is used as a supplementary means of hydrodesulfurization, can selectively remove a small amount of dibenzothiophene and derivatives thereof which are difficult to remove in the hydrodesulfurization, and has the advantages of low operation temperature and normal pressure. In the process of adsorption desulfurization, the design of the adsorbent is the most critical, and reported adsorbents comprise: pi complex adsorbent, reduced metal, active carbon, boron nitride, active alumina, metal organic framework material, etc. However, since adsorption desulfurization mainly depends on the weak adsorption force of sulfide and adsorbent, the biggest problem faced by adsorption desulfurization is the competitive adsorption of other polycyclic aromatic hydrocarbons (>10 wt%) in the oil, which usually results in the decrease of the adsorption performance of the adsorbent or the change of other components in the oil after adsorption.
The oxidative desulfurization solution is widely researched in the field of diesel desulfurization, and can treat oil products with higher sulfur content compared with adsorption desulfurization, and the treatment conditions are normal temperature and normal pressure. Oxidative desulfurization uses hydrogen peroxide or organic peroxide as an oxidant to convert sulfides into sulfoxides or sulfosulfones, and then uses an adsorption or extraction method to remove the compounds. However, the catalytic oxidation-extraction methods reported at present have the problems of slow speed of catalytic oxidation due to two-phase mass transfer on one hand, and complex operation and oil component loss in the extraction process on the other hand, so that the method still faces the problems of high operation cost and the like.
Therefore, the development of a diesel oil deep desulfurization method and an adsorbent which can be operated at normal temperature and normal pressure, can solve the problem that the DBT and derivatives thereof are difficult to remove in hydrodesulfurization, and simultaneously can meet the requirements of lower operation cost and reduce the loss of oil components in the desulfurization process is urgently needed.
Disclosure of Invention
Based on the facts, the invention mainly aims to provide a preparation method of a titanium-silicon material with low titanium loading for diesel oxidation adsorption desulfurization and a method for measuring the number of surface catalytic active sites thereof. The invention provides a preparation method of a low-titanium-loading titanium-silicon material for diesel oxidation adsorption desulfurization, which has the following specific technical scheme:
the titanium-silicon material with low titanium loading for diesel oxidation adsorption desulfurization has the titanium content of 0.1-1.5%, the TOF value of the material on sulfide in diesel is very high, and the concentration of the sulfide in the applied diesel is in a certain range, so that the content of the titanium loaded on a carrier can play a role in carrying out catalytic oxidation-adsorption desulfurization performance of the loaded titanium dioxide and saving the preparation cost of the material.
The preparation method comprises the following steps:
step 1: pre-treating the carrier, and calcining the activated carrier at high temperature;
step 2: dispersing the carrier in a solvent, adding a solution of an organic titanium source, and uniformly mixing;
and step 3: and (3) carrying out rotary evaporation on the mixed solution to obtain solid powder, thoroughly drying, then carrying out high-temperature calcination, and cooling to obtain the titanium-silicon material with low titanium loading.
Preferably, the carrier in the titanium-silicon material in the step 1 comprises more than one of column chromatography silica gel, thin-layer chromatography silica gel, gas phase silica gel, artificial synthetic or natural zeolite molecular sieve; the zeolite molecular sieve comprises a synthetic or natural zeolite molecular sieve; the temperature of the high-temperature calcination is 200-550 ℃.
In the step 1, the carrier is subjected to calcination pretreatment, organic matters or other volatile impurities adsorbed on the surface of the carrier can be removed, and defect sites on the surface of the carrier are exposed.
And 3, calcining the dried sample at high temperature in the step 3 to promote the formation of titanium dioxide, wherein the supported organic titanium source cannot be completely converted into oxide due to too low temperature, and the dispersion degree of metal oxide is poor due to too high temperature, so that the quality of the titanium-silicon material is influenced
Preferably, in the step 2, the mass ratio of the carrier to the solvent is: 1-5: 15-20.
Preferably, in step 2, the solvent includes one or more of absolute ethyl alcohol, acetonitrile, methanol, ethyl acetate, petroleum ether and cyclohexane.
Preferably, the organic titanium source is added in the step 2 in an amount that the Ti wt% on the surface of the finally obtained material is 0.1-1.5%.
Preferably, in the step 2, the organic titanium source includes one or more of tetrabutyl titanate, isopropyl titanate, and tetraethyl titanate.
Preferably, in the step 3, the calcination temperature is 350-550 ℃, and the calcination time is 3-10 hours.
The preparation method of the low-titanium-loading-amount titanium-silicon material can obtain the material with the titanium content of 0.1-1.5% for diesel oil oxidation adsorption desulfurization, and compared with other materials with higher titanium content, the material has a higher TOF value in the desulfurization process, and the total oxidation desulfurization effect is excellent. The preparation method of the invention can reduce the use of titanium and the production cost of the desulfurization material.
The invention also provides a method for testing the number of the catalytic active sites on the surface of the low-titanium-loading titanium-silicon material for diesel oil oxidative desulfurization. The principle of the testing method is as follows: hydrogen peroxide is used as a probe molecule, which can generate a coordination effect with titanium with catalytic activity on the surface of a titanium-silicon material, and then potassium permanganate standard solution is used for titrating the hydrogen peroxide absorbed by coordination, so that the amount of the titanium with catalytic activity on the surface of the material is calculated according to the volume of the potassium permanganate standard solution consumed by titration.
The method for testing the number of the catalytic active sites on the surface of the titanium-silicon material comprises the following specific steps:
and 4, washing the obtained filter cake with deionized water, transferring the filter cake to a conical flask, and adding a sulfuric acid solution.
And 5, titrating by using a potassium permanganate standard solution, wherein the light red color in the solution does not disappear within 30s of the titration end point.
And 6, calculating the number of the catalytic active sites in the material:
m is the mass of the weighed sample, V is the volume of the potassium permanganate solution for titration, and C is the concentration of the potassium permanganate standard solution.
The material is fully dried before testing in step 1 and weighed using a subtractive method to prevent the surface adsorption of water from affecting the accuracy of the weighing and reproducibility of the test.
Preferably, the adding amount of the deionized water in the step 2 is as follows by mass ratio: 20-40 parts of material: 1
Preferably, the adding amount of the hydrogen peroxide in the step 2 is excessive, and is calculated according to 4-6 times of the theoretical loading amount of titanium of the titanium-silicon material. The purpose of adding excessive titanium is to ensure that the titanium on the surface of the material is fully contacted with hydrogen peroxide so as to coordinate the titanium with catalytic activity with the hydrogen peroxide.
Preferably, the deionized water is used for washing the filter cake in the step 3, the principle of a small amount of washing is observed, and the total usage amount is as follows according to the mass ratio of water: 60-120 parts of materials: 1. the step aims to remove the hydrogen peroxide physically adsorbed on the surface of the material and prevent the hydrogen peroxide from influencing the subsequent titration. The result is higher when the number of washing is small or the amount of water used is too small, and the result is lower when the number of washing is too large or the amount of water used is too large, and part of hydrogen peroxide is decomposed.
Preferably, the sulfuric acid solution in step 4 is added in an amount such that the hydrogen ion concentration in the solution before and after titration is in the range of 0.5M to 1M, and the 3M sulfuric acid solution is added in an amount of 5 to 10mL/g of the titanium silicalite material. The aim of this is to control the acidity of the solution, making the end point of the titration more stable and the test more reproducible.
Compared with the prior art, the invention has the advantages that:
the oxidation-adsorption coupling desulfurization technology used by the invention can realize low operation cost of removing sulfide from diesel oil at normal temperature and normal pressure;
the method has the advantages that the titanium-silicon material with low titanium loading is used for converting sulfides in the diesel oil, the conversion rate is high, the atom economy is better, and the material production cost is low;
the titanium-silicon material used by the invention can realize regeneration after diesel oil desulfurization and can be recycled.
Drawings
FIG. 1 is a comparison of DBT TOF values in simulated oil for low titanium loading titanium-silicon materials and literature materials;
FIG. 2 shows the results of the surface catalytic activity test of low titanium-loading titanium-silicon materials.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto.
Preparing a titanium-silicon material with low titanium loading: roasting the carrier for a certain time before use, then weighing a certain mass of the calcined carrier in a round-bottom flask, adding excessive solvent, and fully stirring and dispersing the solution by using a magnetic stirrer. An appropriate amount of organic titanium source is measured and dissolved in an appropriate amount of cyclohexane, a constant pressure dropping funnel is used for dropwise adding the organic titanium source into the dispersed carrier dispersion liquid, and the mixed solution is continuously stirred for 2 hours after the dropwise adding. Transferring the stirred solution to a rotary evaporator, performing rotary evaporation to remove the solvent, and continuously drying the powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining at high temperature. And cooling to obtain the titanium-silicon material with low titanium loading.
Testing of the catalytic activity site on the surface of the titanium-silicon material with low titanium loading: roasting a sample to be detected for a period of time, then transferring the sample to a weighing bottle, weighing the sample to be detected with a certain mass by using a decrement method, recording the weighed mass m, dispersing the sample by using a certain amount of ultrapure water, adding a proper amount of hydrogen peroxide solution, performing suction filtration to remove the liquid of the mixed solution after magnetic stirring for a period of time, washing a filter cake for multiple times by using the ultrapure water, performing suction filtration, transferring solid powder to a titration bottle, dispersing by using the ultrapure water, acidifying by using sulfuric acid, then titrating to an end point by using a potassium permanganate standard solution, and recording the volume V of the used potassium permanganate solution.
Example 1
(1) Preparing a titanium silicon material:
calcining and activating column chromatography silica gel at 400 ℃ for 4h, weighing 5g of calcined column chromatography silica gel, placing into a round-bottom flask, adding 90mL of absolute ethanol, stirring uniformly with a magneton, and performing ultrasound for 5 min. Adding 2mL of cyclohexane into a constant-pressure dropping funnel, adding 0.218mL of tetrabutyl titanate, uniformly mixing, dropwise adding the carrier dispersion liquid, and continuously stirring the mixed solution for 2 hours after dropwise adding. Transferring the stirred solution to a rotary evaporator to remove the solvent by rotary evaporation, and continuously drying the rotary evaporated powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining the powder for 3 hours at the high temperature of 350 ℃ to obtain the titanium-silicon material.
(2) Testing the catalytic activity sites on the surface of the titanium silicon material:
the sample to be tested is roasted for 4h at 200 ℃ and then transferred to a weighing bottle, 1g of the sample is accurately weighed by using a subtractive method, and the mass m is recorded. The weighed sample was dispersed with 30mL of ultrapure water, 100uL of a hydrogen peroxide solution was added, the mixture was magnetically stirred for 1min, then the liquid portion of the mixed solution was removed by suction filtration, the filter cake was washed 4 times with 100mL of ultrapure water, the filter cake was transferred to a conical flask after washing, 50mL of ultrapure water was added and dispersed, and 7mL of a 3M sulfuric acid solution was added and acidified. Titration was performed using a 1mM potassium permanganate standard solution and the volume V of potassium permanganate solution used at the end of the titration was recorded. And calculating to obtain the number of the catalytic active sites.
Example 2
(1) Preparing a titanium silicon material:
calcining and activating column chromatography silica gel at 400 ℃ for 4h, weighing 10g of calcined column chromatography silica gel, placing in a round-bottom flask, adding 180mL of acetonitrile, uniformly stirring by using a magneton, and performing ultrasound for 5 min. 3mL of cyclohexane and 0.634mL of isopropyl titanate are added into a constant-pressure dropping funnel, the mixture is uniformly mixed and then is dropwise added into the carrier dispersion, and the mixed solution is continuously stirred for 2 hours after the dropwise addition. Transferring the stirred solution to a rotary evaporator to remove the solvent by rotary evaporation, and continuously drying the rotary evaporated powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining at the high temperature of 400 ℃ for 4h to obtain the titanium-silicon material.
(2) Testing the catalytic activity sites on the surface of the titanium silicon material:
the sample to be tested was calcined at 200 ℃ for 4h, then transferred to a weighing bottle, and 0.78g of the sample was accurately weighed using the subtractive method, and the mass m was recorded. Dispersing the weighed sample with 30mL of ultrapure water, adding 110uL of hydrogen peroxide solution, performing magnetic stirring for 1min, performing suction filtration to remove the liquid part of the mixed solution, washing the filter cake by using 100mL of ultrapure water for 4 times, transferring the filter cake after washing into a conical flask, adding 50mL of ultrapure water for dispersing, and adding 7mL of 3M sulfuric acid solution for acidification. Titration was performed using a 1mM potassium permanganate standard solution and the volume V of potassium permanganate solution used at the end of the titration was recorded. And calculating to obtain the number of the catalytic active sites.
Example 3
(1) Preparing a titanium silicon material:
calcining and activating column chromatography silica gel at 400 ℃ for 4h, weighing 5g of calcined column chromatography silica gel, placing in a round-bottom flask, adding 100mL of methanol, uniformly stirring with a magneton, and performing ultrasound for 5 min. 4mL of cyclohexane is added into a constant pressure dropping funnel, 0.337mL of tetraethyl titanate is added, the mixture is uniformly mixed and then is dropwise added into the carrier dispersion liquid, and the mixed solution is continuously stirred for 2 hours after the dropwise addition. Transferring the stirred solution to a rotary evaporator to remove the solvent by rotary evaporation, and continuously drying the rotary evaporated powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining at the high temperature of 450 ℃ for 5 hours to obtain the titanium-silicon material.
(2) Testing the catalytic activity sites on the surface of the titanium silicon material:
the sample to be tested was calcined at 200 ℃ for 4h, then transferred to a weighing bottle, and 0.65g of the sample was accurately weighed using the subtractive method, and the mass m was recorded. Dispersing the weighed sample with 30mL of ultrapure water, adding 120uL of hydrogen peroxide solution, magnetically stirring for 1min, removing the liquid part of the mixed solution by suction filtration, washing the filter cake by using 100mL of ultrapure water for 4 times, transferring the filter cake after washing into a conical flask, adding 50mL of ultrapure water for dispersing, and then adding 8mL of 3M sulfuric acid solution for acidification. Titration was performed using a 1mM potassium permanganate standard solution and the volume V of potassium permanganate solution used at the end of the titration was recorded. And calculating to obtain the number of the catalytic active sites.
Example 4
(1) Preparing a titanium silicon material:
calcining and activating column chromatography silica gel at 400 ℃ for 4h, weighing 10g of calcined column chromatography silica gel, placing in a round-bottom flask, adding 180mL of ethyl acetate, stirring uniformly with a magneton, and performing ultrasound for 5 min. 5mL of cyclohexane and 1.49mL of tetrabutyl titanate are added into a constant-pressure dropping funnel, the mixture is uniformly mixed and then is dropwise added into the carrier dispersion liquid, and the mixed solution is continuously stirred for 2 hours after the dropwise addition. Transferring the stirred solution to a rotary evaporator to remove the solvent by rotary evaporation, and continuously drying the rotary evaporated powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining for 6 hours at a high temperature of 500 ℃ to obtain the titanium-silicon material.
(2) Testing the catalytic activity sites on the surface of the titanium silicon material:
the sample to be tested was calcined at 200 ℃ for 4h, then transferred to a weighing bottle, and 0.55g of the sample was accurately weighed using the subtractive method, and the mass m was recorded. Dispersing the weighed sample with 30mL of ultrapure water, adding 125uL of hydrogen peroxide solution, performing magnetic stirring for 1min, performing suction filtration to remove the liquid part of the mixed solution, washing the filter cake by using 100mL of ultrapure water for 4 times, transferring the filter cake after washing into a conical flask, adding 50mL of ultrapure water for dispersing, and adding 8mL of 3M sulfuric acid solution for acidification. Titration was performed using a 1mM potassium permanganate standard solution and the volume V of potassium permanganate solution used at the end of the titration was recorded. And calculating to obtain the number of the catalytic active sites.
Example 5
(1) Preparing a titanium silicon material:
calcining and activating column chromatography silica gel at 400 ℃ for 4h, weighing 5g of calcined column chromatography silica gel, placing in a round-bottom flask, adding 100mL of petroleum ether, stirring uniformly with a magneton, and performing ultrasound for 5 min. 6mL of cyclohexane and 0.957mL of isopropyl titanate are added into a constant-pressure dropping funnel, the mixture is uniformly mixed and then is dropwise added into the carrier dispersion liquid, and the mixed solution is continuously stirred for 2 hours after the dropwise addition. Transferring the stirred solution to a rotary evaporator to remove the solvent by rotary evaporation, and continuously drying the rotary evaporated powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining at the high temperature of 500 ℃ for 8h to obtain the titanium-silicon material.
(2) Testing the catalytic activity sites on the surface of the titanium silicon material:
the sample to be tested was calcined at 200 ℃ for 4h, then transferred to a weighing bottle, 0.5g of the sample was accurately weighed using the subtractive method, and the mass m was recorded. Dispersing the weighed sample with 30mL of ultrapure water, adding 130uL of hydrogen peroxide solution, performing magnetic stirring for 1min, performing suction filtration to remove the liquid part of the mixed solution, washing the filter cake by using 100mL of ultrapure water for 4 times, transferring the filter cake after washing into a conical flask, adding 50mL of ultrapure water for dispersing, and adding 9mL of 3M sulfuric acid solution for acidification. Titration was performed using a 1mM potassium permanganate standard solution and the volume V of potassium permanganate solution used at the end of the titration was recorded. And calculating to obtain the number of the catalytic active sites.
Example 6
(1) Preparing a titanium silicon material:
calcining and activating column chromatography silica gel at 400 ℃ for 4h, weighing 10g of calcined column chromatography silica gel, placing in a round-bottom flask, adding 180mL of cyclohexane, uniformly stirring with a magneton, and performing ultrasound for 5 min. 6mL of cyclohexane and 1.07mL of tetrabutyl titanate are added into a constant-pressure dropping funnel, the mixture is uniformly mixed and then is dropwise added into the carrier dispersion liquid, and the mixed solution is continuously stirred for 2 hours after the dropwise addition. Transferring the stirred solution to a rotary evaporator to remove the solvent by rotary evaporation, and continuously drying the rotary evaporated powder in an electric heating constant-temperature air blast drying oven for 5 hours. And finally transferring the dried powder into a crucible, and calcining at 550 ℃ for 10 hours to obtain the titanium-silicon material.
(2) Testing the catalytic activity sites on the surface of the titanium silicon material:
the sample to be tested was calcined at 200 ℃ for 4h, then transferred to a weighing bottle, and 0.45g of the sample was accurately weighed using the subtractive method, and the mass m was recorded. Dispersing the weighed sample with 30mL of ultrapure water, adding 140uL of hydrogen peroxide solution, performing magnetic stirring for 1min, performing suction filtration to remove the liquid part of the mixed solution, washing the filter cake by using 100mL of ultrapure water for 4 times, transferring the filter cake after washing into a conical flask, adding 50mL of ultrapure water for dispersing, and adding 9mL of 3M sulfuric acid solution for acidification. Titration was performed using a 1mM potassium permanganate standard solution and the volume V of potassium permanganate solution used at the end of the titration was recorded. And calculating to obtain the number of the catalytic active sites.
Determination of desulfurization performance of titanium-silicon material on fuel oil
112.5mg of titanium silicon material is weighed and placed in a round-bottom flask, 30mL of simulated oil (200 ppm-S-dodecane dibenzothiophene solution) is added to make the mass ratio of the oil agent be 200:1, and then 25.5 μ L of cumene hydroperoxide is added to make the molar ratio of oxygen to sulfur in the system be 2: 1, at room temperature (30 ℃). The concentration change of DBT (dibenzothiophene) in the reaction process is measured by using high performance liquid chromatography, and the total sulfur concentration change in a system in the reaction process is measured by using a TS-3000 total sulfur tester. The conversion of DBT is calculated as: conversion (DBT) — (1-measured DBT concentration/original DBT concentration) × 100%, TOF (conversion frequency) calculation formula of material to DBT is: TOF DBT concentration change amount system volume/catalyst moles/conversion time.
The invention provides a preparation method of a low-titanium-loading titanium-silicon material and a method for testing the number of surface catalytic active sites of the material, wherein the specific surface area, the titanium loading, the simulated oil desulfurization performance and the number of the surface catalytic active sites are characterized as follows:
(1) specific surface area and titanium loading
The series of titanium silicalite materials prepared in accordance with the present invention were tested for specific surface area using Micromeritics model ASAP2460 and pore distribution, and the actual loading of titanium in the series was measured using Agilent 720ES for ICPOES measurements. The results of both are shown in Table 1. The specific surface area of the carrier is not greatly influenced by the load of the titanium, the specific surface area of the loaded material is only slightly reduced, the actual load amount and the calculated amount of the titanium deviate, and the whole body is smaller.
TABLE 1 variation of specific surface area of material and titanium content
(2) Material simulating oil desulfurizing performance
The simulated oil desulfurization performance of the material under the static reaction condition is tested and compared with the titanium silicon material reported in the literature, and the result is shown in figure 1. The titanium silicalite materials with low titanium loading in the simulated oil are shown in fig. 1 to have higher TOF values for DBT than the titanium silicalite materials (RXL) in the literature, and the TOF values are gradually reduced with the increase of the loading. This indicates that the catalytic activity per unit of titanium is higher in the low titanium loading titanium silicalite.
(3) Material surface catalytic activity site test
Hydrogen peroxide is used as a probe molecule, the hydrogen peroxide can generate coordination with unsaturated titanium coordinated on the surface of the material (the unsaturated titanium coordinated has catalytic oxidation activity), the hydrogen peroxide can stably react with the material, and the content of the hydrogen peroxide can be quantitatively measured through potassium permanganate chemical titration so as to indirectly know the number of catalytic activity sites on the surface of the material. The testing method provides a new idea for the quantity characterization of the catalytic active sites on the surface of the titanium-silicon material. The change rule of the catalytic activity site quantity of the surface of the titanium-silicon material with low titanium content measured by the test method is shown in figure 2, and the test data is shown in table 2. The titration result shows that, at low load, the catalytic activity site is in a direct proportion relation with the increase of the load, and a straight line which almost passes through the origin is obtained by fitting; and when the loading capacity is higher, the slope of the catalytic activity site is reduced along with the increase of the loading capacity, and the catalytic activity site is in a linear increasing trend after fitting. The two lines intersect at 1.56% of Ti by weight. This shows that under the condition of low load, the titanium dioxide dispersion degree on the surface of the titanium silicon material is higher, the catalytic activity is higher (22%), and the catalytic activity position is linearly increased along with the load. However, as the loading is further increased, although the total amount of the catalytically active sites still increases, the rate of increase is much lower than at relatively low loadings, the proportion of the catalytically active sites decreases to 6%, and the loading of this transition is 1.56%.
TABLE 2 Ti-SiO2Chemical titration result a of catalytically active titanium on the surface of the material
The concentration of a potassium permanganate standard solution is as follows: 0.968mmol/L
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a low-titanium-loading titanium-silicon material for diesel oil desulfurization is characterized by comprising the following steps:
step 1: pre-treating the carrier, and calcining the activated carrier at high temperature;
step 2: dispersing the carrier obtained in the step 1 in a solvent, adding a solution of an organic titanium source, and uniformly mixing;
and step 3: performing rotary evaporation on the mixed solution to obtain solid powder, completely drying, then calcining at high temperature, and cooling to obtain a titanium-silicon material with low titanium loading;
in the step 1, the carrier comprises more than one of column chromatography silica gel, thin-layer chromatography silica gel, gas phase silica gel, zeolite molecular sieve and clay; the zeolite molecular sieve comprises a synthetic or natural zeolite molecular sieve; in the step 1, the temperature of the high-temperature calcination is 200-550 ℃;
the organic titanium source is used in an amount such that the mass fraction of titanium in the titanium-silicon material obtained by final calcination is 0.1-1.5%.
2. The method of claim 1 for producing a low titanium loading titanium silicalite material for diesel fuel desulfurization, wherein in step 2, the solvent comprises: more than one of acetonitrile, methanol, ethanol, n-hexane, cyclohexane, ethyl acetate, petroleum ether, acetone and chloroform; the mass ratio of the carrier to the solvent is 1-5: 15-20.
3. The method of preparing a low titanium loading titanium silicalite material for diesel fuel desulfurization as claimed in claim 1 wherein in step 2, the source of organic titanium comprises: more than one of isopropyl titanate, tetraethyl titanate, tetrabutyl titanate and titanium tetrachloride.
4. The method for preparing a low titanium loading titanium silicalite material for desulfurization of diesel oil as claimed in claim 1, wherein in step 3, the temperature of the high temperature calcination is 300-550 ℃, and the calcination time is 3-10 hours.
5. The method for measuring the catalytic activity site on the surface of the titanium-silicon material with low titanium loading for oxidative adsorption desulfurization of diesel oil, which is prepared by the preparation method according to any one of claims 1 to 4, is characterized in that hydrogen peroxide is used as a probe molecule, and the hydrogen peroxide and titanium atoms with catalytic activity on the surface generate a reaction condition that the ratio of 1: 1, after coordination, the titanium-silicon material generates visible light absorption due to the charge migration effect of hydrogen peroxide and titanium, and is yellow, and the coordination condition is judged according to the phenomenon.
6. The method for measuring the catalytic activity site on the surface of the titanium-silicon material with low titanium loading for oxidative adsorption desulfurization of diesel oil according to claim 5, wherein the hydrogen peroxide adsorbed on the surface of the material is titrated under acidic conditions by using a potassium permanganate standard solution, and the volume of the consumed potassium permanganate solution is used for quantitative calculation.
7. The method for measuring the surface catalytic activity site of the titanium-silicon material with low titanium loading for diesel oil oxidative adsorption desulfurization according to claim 5, which is characterized by comprising the following steps:
step 1, weighing a dried titanium-silicon material by using a subtraction method;
step 2, adding deionized water to disperse, adding hydrogen peroxide, and stirring;
step 3, removing water in the mixed solution by suction filtration, and washing the filter cake for 3 times by using deionized water;
step 4, washing the obtained filter cake with deionized water, transferring the filter cake to a conical flask, and adding a sulfuric acid solution;
and 5, titrating by using a potassium permanganate standard solution, wherein the light red color in the solution does not disappear within 30s of the titration end point.
8. The measurement method according to claim 7, wherein in the step 2, the addition amount of the hydrogen peroxide is 4 to 6 times of the molar amount of the titanium atoms of the titrated titanium-silicon material.
9. The method according to claim 7, wherein in step 4, the sulfuric acid is added in an amount such that the hydrogen ion concentration in the solution before and after the reaction is between 0.5M and 1M.
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