CN113893880A - Preparation method and application of MIL-125(Ti) catalyst - Google Patents
Preparation method and application of MIL-125(Ti) catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 132
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000243 solution Substances 0.000 claims abstract description 51
- 239000012046 mixed solvent Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 150000007524 organic acids Chemical class 0.000 claims abstract description 23
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 17
- 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 abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 24
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- 239000005711 Benzoic acid Substances 0.000 claims description 11
- 235000010233 benzoic acid Nutrition 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims 1
- 150000003577 thiophenes Chemical class 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 50
- 238000006477 desulfuration reaction Methods 0.000 abstract description 16
- 230000023556 desulfurization Effects 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 25
- 239000003921 oil Substances 0.000 description 25
- 229910052717 sulfur Inorganic materials 0.000 description 25
- 239000011593 sulfur Substances 0.000 description 25
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 238000005070 sampling Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012377 drug delivery Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a preparation method and application of an MIL-125(Ti) catalyst, which comprises the following steps: mixing the N, N-dimethylformamide solution and the methanol solution to obtain a mixed solvent; dissolving an organic ligand in the mixed solvent, and uniformly stirring to obtain a mixed solution; adding tetrabutyl titanate and organic acid into the mixed solution, ultrasonically moving the mixed solution into a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment, and carrying out centrifugal separation to obtain a crystallization product; and (3) cleaning the obtained crystallized product, and drying in vacuum to obtain the MIL-125(Ti) catalyst. The MIL-125(Ti) catalyst can realize one-step synthesis, can effectively control the crystal size of the catalyst through the addition amount of organic acid, and can catalyze and oxidize thiophene sulfides at room temperature to realize more efficient desulfurization; the catalyst of the invention has simple preparation method and good application prospect in the aspect of oil product desulfurization.
Description
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of an MIL-125(Ti) catalyst and application thereof in removing thiophene sulfides by catalytic oxidation.
Background
In recent decades, with the rapid development of industrialization in China, the demand of people for fuel oil is gradually increased. However, the burning of fuel oil will cause SO in the airXThe concentration of (c) is increased. Recent studies have shown that changes in the concentration of airborne sulfur compounds can cause different environmental hazards and can also affect human health. Along with the gradual improvement of environmental protection laws at home and abroad, the standards of various countries on the content of sulfide in fuel oil are increasingly strict, and the fuel oil desulfurization industry in China is seriously examined in the face of the increasingly strict emission standard of the content of sulfur in the fuel oil.
The metal organic framework material has ultra-high specific surface area and abundant pore structure, so that the metal organic framework material has remarkable advantages in the aspect of adsorbing and removing sulfides in oil products, and in addition, the metal of the MOFs material also has abundant active sites, and can be combined with the sulfides, so that the MOFs has better adsorption and desulfurization capacity, and is generally concerned in the last ten years.
The metal organic framework is composed of various organic connectors and metal ions or clusters, forms a porous three-dimensional network with large pore volume and high internal surface area, is an excellent crystalline material, and has adjustable structural topology and flexible pore characteristics. The inherently large surface area, tunable pores and tunable physicochemical properties enable them to exhibit a variety of potential applications such as gas adsorption and separation, drug delivery and catalysis. Control of crystal size and morphology is an important topic as they have a significant impact on performance in various applications.
Yang et al showed a simple method to synthesize Ni (II) doped MOF-5 with size and morphology control and to detect differences in gas adsorption. Huskens et al developed a PEG-assisted method for the one-step synthesis of size-controlled MIL-88, which has potential applications in drug delivery. Tian et al studied the effect of crystal size on the wobbling effect and adsorption induced structural transformation of ZIF-8.
However, in the prior art, there are few reports on the method for regulating and controlling the size of the MIL-125(Ti) catalyst in terms of crystal size.
Disclosure of Invention
The invention provides a preparation method of an MIL-125(Ti) catalyst, which can be synthesized in one step, and the prepared MIL-125(Ti) catalyst has controllable crystal size and can be applied to catalytic oxidation for removing thiophene sulfides.
To achieve the above object, the present invention provides a method for preparing MIL-125(Ti) catalyst, comprising the steps of:
step (1): mixing the N, N-dimethylformamide solution and the methanol solution to obtain a mixed solvent;
step (2): dissolving an organic ligand in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
and (3): adding tetrabutyl titanate and organic acid into the mixed solution obtained in the step (2), performing ultrasonic treatment, moving the mixture into a polytetrafluoroethylene crystallization kettle, performing hydrothermal treatment, and performing centrifugal separation to obtain a crystallization product;
and (4): and (4) cleaning the crystallized product obtained in the step (3), and drying in vacuum to obtain the MIL-125(Ti) catalyst.
According to the preparation method of the MIL-125(Ti) catalyst, in the step (1), the volume ratio of N, N-dimethylformamide to methanol in a mixed solvent is 8-10.
According to the preparation method of the MIL-125(Ti) catalyst, in the step (2), the adding amount of the organic ligand is 2.0-3.0 g.
According to the preparation method of the MIL-125(Ti) catalyst, in the step (3), the addition amount of tetrabutyl titanate is 1.0-1.1 ml, and the addition amount of organic acid is 0-0.3 g.
According to the preparation method of the MIL-125(Ti) catalyst, in the step (3), the ultrasonic time is 10-15 min.
According to the preparation method of the MIL-125(Ti) catalyst, in the step (3), the hydrothermal treatment temperature is 120-180 ℃, and the time is 24-48 hours.
According to the preparation method of the MIL-125(Ti) catalyst, in the step (4), a crystallized product is respectively washed by N, N-dimethylformamide and methanol, the washing frequency is 2-3 times, the vacuum drying temperature is 50-80 ℃, and the drying time is 12-24 hours.
According to the preparation method of the MIL-125(Ti) catalyst, the organic ligand is terephthalic acid.
According to the preparation method of the MIL-125(Ti) catalyst, the organic acid is at least one of glacial acetic acid (HAc), Benzoic Acid (BA) and thioglycollic acid (HS), and the addition amount is 0-0.3 g.
The invention also provides an application of the MIL-125(Ti) catalyst prepared by the preparation method of the MIL-125(Ti) catalyst in catalytic oxidation of thiophene sulfides, wherein the MIL-125(Ti) catalyst, the thiophene sulfides and n-octane are placed in a reactor, an oxidant and an extracting agent are added, the reactor is placed in a heat collection type constant temperature heating magnetic stirrer for water bath heating, and sulfoxide or sulfone oxidation products are finally obtained, wherein the reaction temperature is 40 ℃, and the reaction time is 30-60 min.
In the application of the invention, the thiophene sulfide is at least one of thiophene, Benzothiophene (BT), Dibenzothiophene (DBT), 4, 6-dimethyldibenzothiophene (4,6-DMDBT) and other thiophene with alkyl side chain.
According to the application of the method, the oxidant is at least one of hydrogen peroxide, tert-butyl hydroperoxide and cumyl hydroperoxide, and the extracting agent is at least one of anhydrous methanol, acetonitrile, dimethyl sulfoxide and sulfolane.
The invention can also be detailed as follows:
the preparation method of the MIL-125(Ti) catalyst provided by the invention comprises the following steps:
(1) weighing 35-40 mL of N, N-dimethylformamide solution and 4-8 mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing a certain amount of organic ligand, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing a certain amount of tetrabutyl titanate, weighing organic acids with different masses into the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 10-15 min, transferring the solution into a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment at 120-180 ℃ for 24-48 h, and carrying out centrifugal separation to obtain a crystallization product;
(4) and (4) respectively washing the crystallized product obtained in the step (3) with N, N-dimethylformamide and methanol for 2-3 times, and placing the product at 50-80 ℃ for vacuum drying for 12-24 hours, wherein the size of the crystal can be controlled by using an MIL-125(Ti) catalyst.
Preferably, the organic ligand in step (1) is terephthalic acid, and the added organic acids include, but are not limited to, glacial acetic acid (HAc), Benzoic Acid (BA) and thioglycolic acid (HS).
Preferably, the amount of the organic acid added in step (1) is controlled to be 0 to 0.3 g.
The method for preparing the MIL-125(Ti) catalyst with controllable size to catalyze and oxidize the thiophene sulfides comprises the following steps:
putting MIL-125(Ti) catalyst, thiophene sulfide and normal octane into a reactor, adding an oxidant and an extracting agent, putting the reactor into a heat collection type constant temperature heating magnetic stirrer for water bath heating, wherein the reaction temperature is 40 ℃, the interval sampling time is 10min, the reaction time is 60min, the oxidation product is sulfoxide or sulfone, and analyzing by using High Performance Liquid Chromatography (HPLC).
Preferably, the thiophene sulfide is one or more of thiophene, Benzothiophene (BT), Dibenzothiophene (DBT), 4, 6-dimethyldibenzothiophene (4,6-DMDBT) and other thiophene with alkyl side chain.
Preferably, the oxidant is one or more of hydrogen peroxide, tert-butyl hydroperoxide or cumene hydroperoxide, and the extractant is one or more of anhydrous methanol, acetonitrile, dimethyl sulfoxide and sulfolane.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method is simple, can realize one-step synthesis of the MIL-125(Ti) catalyst, can effectively control the crystal size of the catalyst through the addition amount of the organic acid, and can reduce the crystal size of the catalyst and increase the specific surface area of the catalyst so as to improve the activity of the catalyst.
(2) The MIL-125(Ti) catalyst prepared by the invention can realize catalytic oxidation of thiophene sulfides at room temperature, high-efficiency desulfurization is realized, and the desulfurization rate can reach 99% within 30 min.
Drawings
FIG. 1 is an SEM image of MIL-125(Ti) catalysts prepared in examples 1-4 of the present invention;
FIG. 2 is a normal distribution plot of crystal size for the MIL-125(Ti) catalyst prepared in example 1 of the present invention;
FIG. 3 is a crystal size normal distribution plot of the MIL-125(Ti) catalyst prepared in example 2 of the present invention;
FIG. 4 is a crystal size normal distribution plot of the MIL-125(Ti) catalyst prepared in example 3 of the present invention;
FIG. 5 is a normal distribution plot of crystal size for the MIL-125(Ti) catalyst prepared in example 4 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples describing preferred embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention and is not intended to limit the scope of the claims.
Examples 1 to 10 are examples of the MIL-125(Ti) catalyst of the present invention, and examples 11 to 14 are examples of the MIL-125(Ti) catalyst of the present invention in a method for catalytically oxidizing thiophene sulfides.
Example 1
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) measuring 1mL of tetrabutyl titanate in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallization product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 2
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.1g of glacial acetic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 3
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.2g of glacial acetic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 4
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.3g of glacial acetic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Table 1 below shows the specific surface area properties of the MIL-125(Ti) catalysts prepared in examples 1 to 4. Example 1 no organic acid was added to control the crystal grain size of the catalyst during the preparation of the catalyst, and examples 2 to 4 were organic acids added in amounts of 0.1g, 0.2g and 0.3g, respectively, and the results of table 1 show that: the specific surface area of the catalyst tends to increase and then decrease as the amount of the organic acid added increases.
TABLE 1
Fig. 1 is a Scanning Electron Microscope (SEM) image of the MIL-125(Ti) catalysts prepared in examples 1 to 4, and it can be seen from fig. 1 that the crystal grains of the prepared MIL-125(Ti) catalysts are all "cakes", the crystal grains are uniformly distributed, but the crystal sizes are different, which shows that the addition amount of the organic acid has a regulating effect on the crystal size of the catalyst, and the crystal size of the catalyst can be regulated by changing the use amount of the organic acid.
FIG. 2 is a normal distribution plot of crystal size for the MIL-125(Ti) catalyst prepared in example 1 of the present invention, further microscopically analyzing the size of the catalyst particles. It can be seen from FIG. 2 that the crystal size of the catalyst conforms to the normal distribution, and the average size of the catalyst is 0.95. + -. 0.005. mu.m. Similarly, it can be seen from FIG. 3 that the average size of the catalyst prepared in example 2 was 0.83. + -. 0.003. mu.m, from FIG. 4 that the average size of the catalyst prepared in example 3 was 0.70. + -. 0.008. mu.m, and from FIG. 5 that the average size of the catalyst prepared in example 4 was 095. + -. 0.0018. mu.m. The crystal size of the MIL-125(Ti) catalyst tends to decrease and then increase along with the increase of the addition amount of the organic acid, and the change of the crystal size of the catalyst directly influences the change of the specific surface area of the catalyst corresponding to the table 1, which further indicates that the crystal size of the catalyst can be regulated and controlled by different addition amounts of the organic acid, so that the specific surface area of the catalyst is influenced.
Example 5
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.1g of benzoic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 6
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.2g of benzoic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 7
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.3g of benzoic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
The following table 2 is a table of specific surface area properties of catalysts prepared in examples 5 to 7 by adding different amounts of benzoic acid, and it can be seen from table 2 that the specific surface area of the catalyst shows a rule that the specific surface area increases first and then decreases as the amount of benzoic acid increases compared with the catalyst prepared in example 1 without adding organic acid for regulation.
TABLE 2
| Catalyst and process for preparing same | Specific surface area (m)2/g) |
| Example 1 | 933.6 |
| Example 5 | 1156.2 |
| Example 6 | 1285.5 |
| Example 7 | 1067.3 |
Example 8
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.1g of thioglycollic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 9
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.2g of thioglycollic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
Example 10
(1) Measuring 36mL of N, N-dimethylformamide solution and 4mL of methanol solution in a beaker, and mixing to obtain a mixed solvent;
(2) weighing 2.0g of terephthalic acid, dissolving in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
(3) weighing 1mL of tetrabutyl titanate, weighing 0.3g of thioglycollic acid in the mixed solution obtained in the step (2), carrying out ultrasonic treatment for 15min, transferring the solution to a polytetrafluoroethylene crystallization kettle, carrying out hydrothermal treatment for 48h at 150 ℃, and carrying out centrifugal separation to obtain a crystallized product;
(4) and (4) respectively washing the crystal product obtained in the step (3) with N, N-dimethylformamide and methanol for 3 times, and placing the crystal product at 70 ℃ for vacuum drying for 12 hours to obtain the corresponding catalyst.
TABLE 3
| Catalyst and process for preparing same | Specific surface area (m)2/g) |
| Example 1 | 933.6 |
| Example 8 | 996.2 |
| Example 9 | 1075.3 |
| Example 10 | 967.3 |
Table 3 shows the specific surface area properties of the catalysts prepared in examples 8 to 10 with different amounts of thioglycolic acid, and it can be seen from table 3 that the specific surface area of the catalyst increases first and then decreases with the increase of the amount of thioglycolic acid compared to the catalyst prepared in example 1 without organic acid regulation.
Example 11
0.1g of the catalyst prepared in example 1 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of BT model oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 1 was weighed into a 50mL round-bottomed flask, 15mL (with a sulfur content of 320ppmw) of DBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 1 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of 4,6-DMDBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. After the reaction, the catalyst was recovered by filtration and separation, and the sulfur content in the oil phase was measured by High Performance Liquid Chromatography (HPLC), and the desulfurization effect was as shown in table 4.
TABLE 4 desulfurization effect of thiophene sulfide catalyzed by catalyst prepared in example 1
Example 12
0.1g of the catalyst prepared in example 2 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of BT model oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 2 was weighed into a 50mL round-bottomed flask, 15mL (with a sulfur content of 320ppmw) of DBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 deg.C, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 2 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of 4,6-DMDBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. After the reaction was completed, the catalyst was recovered by filtration and separation, and the sulfur content in the oil phase was measured by High Performance Liquid Chromatography (HPLC), and the desulfurization rate was as shown in table 5.
TABLE 5 desulfurization effect of thiophene sulfide catalyzed by catalyst prepared in example 2
Example 13
0.1g of the catalyst prepared in example 3 was weighed into a 50mL round bottom flask and 15mL (sulfur content: 15 mL) was added320ppmw) of BT model oil and 10mL of anhydrous methanol solution, after warming to 40 ℃ 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 3 was weighed into a 50mL round-bottomed flask, 15mL (with a sulfur content of 320ppmw) of DBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 deg.C, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 3 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of 4,6-DMDBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. After the reaction was completed, the catalyst was recovered by filtration and separation, and the sulfur content in the oil phase was measured by High Performance Liquid Chromatography (HPLC), and the desulfurization rate was as shown in table 6.
TABLE 6 desulfurization effect of thiophene sulfide catalyzed oxidation by the catalyst prepared in example 3
Example 14
0.1g of the catalyst prepared in example 4 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of BT model oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. Filtering, separating and recovering the catalyst after the reaction is finished, and performing High Performance Liquid Chromatography (HPLC)And (4) measuring the sulfur content of the oil phase.
0.1g of the catalyst prepared in example 4 was weighed into a 50mL round-bottomed flask, 15mL (with a sulfur content of 320ppmw) of DBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 deg.C, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. And after the reaction is finished, filtering, separating and recovering the catalyst, and measuring the sulfur content of the oil phase by using a High Performance Liquid Chromatography (HPLC).
0.1g of the catalyst prepared in example 4 was weighed into a 50mL round-bottomed flask, 15mL (320 ppmw sulfur content) of 4,6-DMDBT simulated oil and 10mL of anhydrous methanol solution were added, and after warming to 40 ℃, 43. mu. L H was added2O2As the oxidant, the sampling interval was 10min, and the reaction time was 60 min. After the reaction was completed, the catalyst was recovered by filtration and separation, and the sulfur content in the oil phase was measured by High Performance Liquid Chromatography (HPLC), and the desulfurization rate was as shown in table 7.
TABLE 7 desulfurization effect of thiophene sulfide catalyzed oxidation by the catalyst prepared in example 4
In conclusion, the catalyst prepared in example 1 has no organic acid added to regulate the crystal size, the crystal size is the largest, and the specific surface area is the smallest; in examples 2 to 4, different amounts of organic acid are added to control the crystal size, and the crystal size of the corresponding catalyst is smaller than that of the catalyst prepared in example 1, and the specific surface area is larger than that of the catalyst prepared in example 1, wherein the crystal size of the catalyst prepared in example 3 is the smallest, and the specific surface area is the largest. These physical properties directly affect their desulfurization activity for the catalytic oxidation of thiophene sulfides. Comparing tables 4, 5, 6 and 7, it was found that the catalyst of example 1 had the lowest catalytic activity and that after 60 minutes of reaction, the removal rates of BT, DBT and 4,6-DMDBT reached 83%, 99% and 49%, respectively. The catalyst prepared in example 3 has the highest catalytic activity, and after reacting for 30 minutes, the removal rates of BT, DBT and 4,6-DMDBT respectively reach 85%, 99% and 49%. The invention can synthesize the MIL-125(Ti) catalyst with controllable crystal size in one step, and the specific surface area is improved by regulating and controlling the crystal size, thereby regulating and controlling the desulfurization performance of the catalytic oxidation thiophene sulfide.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (12)
1. A preparation method of MIL-125(Ti) catalyst is characterized by comprising the following steps:
step (1): mixing the N, N-dimethylformamide solution and the methanol solution to obtain a mixed solvent;
step (2): dissolving an organic ligand in the mixed solvent in the step (1), and uniformly stirring to obtain a mixed solution;
and (3): adding tetrabutyl titanate and organic acid into the mixed solution obtained in the step (2), performing ultrasonic treatment, moving the mixture into a polytetrafluoroethylene crystallization kettle, performing hydrothermal treatment, and performing centrifugal separation to obtain a crystallization product;
and (4): and (4) cleaning the crystallized product obtained in the step (3), and drying in vacuum to obtain the MIL-125(Ti) catalyst.
2. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein the volume ratio of N, N-dimethylformamide to methanol in the mixed solvent in the step (1) is 8 to 10.
3. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein the organic ligand is added in an amount of 2.0 to 3.0g in the step (2).
4. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein the tetrabutyl titanate is added in an amount of 1.0 to 1.1ml and the organic acid is added in an amount of 0 to 0.3g in the step (3).
5. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein the sonication time in the step (3) is 10 to 15 min.
6. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein the hydrothermal treatment temperature is 120-180 ℃ and the hydrothermal treatment time is 24-48 h in the step (3).
7. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein in the step (4), the crystallized product is washed with N, N-dimethylformamide and methanol respectively, the number of washing times is 2-3, the vacuum drying temperature is 50-80 ℃, and the drying time is 12-24 hours.
8. The method of preparing a MIL-125(Ti) catalyst according to claim 1, wherein the organic ligand is terephthalic acid.
9. The method for preparing the MIL-125(Ti) catalyst according to claim 1, wherein the organic acid is at least one of glacial acetic acid (HAc), Benzoic Acid (BA), and thioglycolic acid (HS), and is added in an amount of 0 to 0.3 g.
10. The application of the MIL-125(Ti) catalyst prepared by the preparation method of the MIL-125(Ti) catalyst according to any one of claims 1-9 in catalytic oxidation of thiophene sulfides is characterized in that the MIL-125(Ti) catalyst, the thiophene sulfides and n-octane are placed in a reactor, an oxidant and an extracting agent are added, the reactor is placed in a heat collection type constant-temperature heating magnetic stirrer to be heated in a water bath, and finally sulfoxide or sulfone oxidation products are obtained, wherein the reaction temperature is 40 ℃ and the reaction time is 30-60 min.
11. The use according to claim 10, wherein the thiophene sulfide is at least one of thiophene, Benzothiophene (BT), Dibenzothiophene (DBT), 4, 6-dimethyldibenzothiophene (4,6-DMDBT), and other thiophenes with alkyl side chains.
12. The use of claim 10, wherein the oxidizing agent is at least one of hydrogen peroxide, t-butyl hydroperoxide, and cumene hydroperoxide, and the extractant is at least one of anhydrous methanol, acetonitrile, dimethyl sulfoxide, and sulfolane.
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