CN115716837A - Quaternary ammonium salt template agent, preparation method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve - Google Patents
Quaternary ammonium salt template agent, preparation method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve Download PDFInfo
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- CN115716837A CN115716837A CN202211322608.7A CN202211322608A CN115716837A CN 115716837 A CN115716837 A CN 115716837A CN 202211322608 A CN202211322608 A CN 202211322608A CN 115716837 A CN115716837 A CN 115716837A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 11
- 239000010936 titanium Substances 0.000 title abstract description 11
- 229910052719 titanium Inorganic materials 0.000 title abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 12
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 56
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 26
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- AJOKVQJMBRBMQR-UHFFFAOYSA-N BrC1=CC=C[S+]1[S+]1C=CC=C1 Chemical class BrC1=CC=C[S+]1[S+]1C=CC=C1 AJOKVQJMBRBMQR-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 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
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- -1 silicate ester Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 70
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 229930192474 thiophene Natural products 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 5
- XQJNXCHDODCAJF-UHFFFAOYSA-N 2-bromo-3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1Br XQJNXCHDODCAJF-UHFFFAOYSA-N 0.000 description 4
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000011 acetone peroxide Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a quaternary ammonium salt template agent, a preparation method of a titanium silicalite molecular sieve and application thereof. The template agent is obtained by taking bithiophene as a raw material and reacting with bromine and N, N-dimethyl benzylamine in sequence, and the titanium silicalite molecular sieve catalyst is obtained by mixing the template agent with a titanium source and a silicon source, crystallizing in a crystallization kettle, filtering, washing and drying. The TS-1 catalyst synthesized by the new template agent has larger inner pore channels of the catalyst, is more favorable for generating hydroquinone with larger molecular volume, can improve the selectivity of the hydroquinone when being applied to the phenol hydroxylation reaction under the same reaction condition, and has higher economic value.
Description
Technical Field
The invention relates to the field of catalyst preparation, and particularly relates to a quaternary ammonium salt template, a preparation method of a titanium silicalite molecular sieve and application of the titanium silicalite molecular sieve.
Background
Catechol and hydroquinone are two important fine chemicals and have wide application in industry, catechol can be used for synthesizing various daily chemical and medical intermediates, and hydroquinone is mainly used as a polymerization inhibitor, a coating, a rubber anti-aging agent and the like. Most of catechol and hydroquinone sold in the market at present are jointly produced by hydroxylation reaction of phenol and hydrogen peroxide, and the process has the characteristics of short flow, mild reaction conditions, less three wastes and the like, conforms to the characteristics of green chemical industry and has larger development prospect.
The hydroxylation process using hydrogen peroxide as an oxidant and phenol as a raw material mainly comprises a UBE method, a Rhone-Poulenc method, a Brichima method, an Enichem method and the like, wherein the Japanese UBE method uses sulfuric acid as a catalyst, adopts 60wt% of hydrogen peroxide and ketone to generate ketone peroxide as the oxidant, oxidizes phenol to generate benzenediol, and the content of the pyrocatechol/hydroquinone in the product is 1.5. Rhone Poulenc process using HClO 4 /H 3 PO 4 As a catalyst, 70wt% of hydrogen peroxide and phenol are used as raw materials to produce the benzenediol, the selectivity of the benzenediol is about 85% -90%, the catechol/hydroquinone in the product is 1.4, and the conversion per pass of the phenol in the process is low and is only 5%. The Brichima method adopts an iron catalyst, which can promote the decomposition of hydrogen peroxide and has higher safety risk; an Italy Enichem process replaces a Brichima process, is a mainstream production process at present, and takes a titanium silicalite molecular sieve (TS-1) as a catalyst, 27.5 percent of hydrogen peroxide and phenol are adopted to react to generate the benzenediol, the reaction condition is mild, the selectivity of the benzenediol is more than 90 percent, and the pyrocatechol/hydroquinone in the product is 1.4.
According to the market conditions, the price of the hydroquinone is far higher than that of the catechol, and the application range of the hydroquinone is wider. In order to improve the yield of hydroquinone in the product, patent CN111085265a uses silicon oxide or aluminum oxide as a binder to extrude or spray the binder into a strip, uses iron as a first modified component, uses lanthanum and phosphorus as second modified components to synthesize a modified titanium-silicon molecular sieve, and transports the modified titanium-silicon molecular sieveWhen the catalyst is used in phenol hydroxylation reaction, the ratio of catechol to hydroquinone in the product is about 0.5, but metals such as lanthanum and the like are used in the process, so the price is high, and the cost is increased. Patent CN108484366A provides a method for preparing hydroquinone by hydroxylation of phenol under visible light catalysis, which takes soluble carbon nitride and iron salt as catalysts under the irradiation of visible light to ensure that phenol and H are reacted 2 O 2 Selective hydroxylation reaction is carried out to obtain the hydroquinone product. The process only generates hydroquinone directionally, and does not generate catechol byproduct, but the process is a photocatalytic reaction, has low reaction efficiency and is difficult to be applied industrially.
At present, the O/hydroquinone prepared by phenol and hydrogen peroxide mainly adopts TS-1 as a catalyst, and the TS-1 sold in the market at present basically adopts tetrapropylammonium hydroxide (TPAOH) as a template agent. Because the molecular volume of TPAOH is not large, most of the channels of the TS-1 molecular sieve synthesized by TPAOH are 0.4-0.5nm, the molecular sieve has smaller internal channels and is subjected to steric hindrance effect, the less the generation amount of hydroquinone is, and the higher the catechol/hydroquinone ratio is. In order to improve the selectivity of hydroquinone, the invention provides a novel quaternary ammonium salt template agent, a preparation method of a titanium-silicon molecular sieve and application thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a quaternary ammonium salt template and a titanium-silicon molecular sieve, so that the quaternary ammonium salt template has a relatively larger pore channel structure, the obtained molecular sieve is more beneficial to phenol hydroxylation reaction, and the hydroquinone prepared by adopting the silicon-titanium molecular sieve as a catalyst has high selectivity.
In order to achieve the technical purpose, the invention provides a quaternary ammonium salt template, which has the following structure:
in the formula, R 1 、R 2 Represents hydrogen or an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl or isobutyl.
Further, the preparation method of the template agent comprises the following steps:
(1) Dropwise adding bromine into the bithiophene derivative, and reacting to generate a 2-bromo-bithiophene derivative;
(2) The 2-bromo-bithiophene derivative reacts with N, N-dimethyl benzylamine to generate bithiophene-benzyl quaternary ammonium salt.
The reaction scheme is schematically as follows:
preferably, the structural formula of the bithiophene derivative is:
in the formula R 1 And R 2 Each represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
The reaction of step (1) of the present invention is carried out in a solvent A, wherein the solvent A is one or more of acetone, water, DMF, dimethylacetamide, tetrahydrofuran and toluene, and preferably acetone or DMF.
In the step (1) of the present invention, the weight ratio of the bithiophene derivative to the solvent A is 1 (1-10), preferably 1 (5-8).
In the step (1) of the present invention, the mass ratio of the bithiophene derivative to the bromine is 1 (0.3 to 1), preferably 1 (0.5 to 0.7).
The reaction condition in the step (1) of the invention is normal pressure.
In the step (1), the initial reaction stage, namely the bromine dripping stage, is carried out at the temperature of-100 to-50 ℃, preferably at the reaction temperature of-78 ℃, an acetone bath can be adopted, and the temperature is slowly increased to 30 to 80 ℃ after the bromine reagent is dripped, preferably at the temperature of 50 to 60 ℃ for continuous reaction.
The dropping time of the step (1) is 0.2-2 h, preferably 0.5-1h; the reaction is continued for 3 to 10 hours, preferably 5 to 8 hours, after the dropwise addition.
In the step (1) of the invention, the crude product is purified by adopting a column chromatography, a separation medium is silica gel with 30-50 meshes, the adopted eluent comprises one or more of normal hexane, ethyl acetate, dichloromethane, chloroform and the like, and the preferable eluent is a mixture of normal hexane and chloroform.
Step (2) of the present invention may be performed in a solvent B, wherein the solvent B comprises one or more of methanol, ethanol, propanol, water and acetone, and preferably the solvent B is ethanol or acetone.
In the step (2) of the present invention, the mass ratio of the 2-bromo-bithiophene derivative to the solvent B is 1: (3-12), preferably 1 (4-10).
In the step (2), the mass ratio of the N, N-dimethyl benzylamine to the 2-bromo-bithiophene derivative is (1-8): 1, preferably (3 to 6): 1.
the reaction time in the step (2) of the invention is 5 to 20 hours, preferably 8 to 12 hours.
The reaction temperature in the step (2) is 30-100 ℃, and the preferable reaction temperature is 50-80 ℃.
The invention relates to a preparation method of a silicon-titanium molecular sieve, which adopts quaternary ammonium salt as a template agent.
Preferably, the preparation method of the silicon-titanium molecular sieve comprises the following steps: dissolving a template agent, titanate and solid alkali in water, adding silicate ester, aging for 3-5h, heating the mixed solution to 100-180 ℃ for hydrothermal crystallization, and finally filtering, washing and drying to obtain the silicon-titanium molecular sieve.
Preferably, the silicate, the template, the titanate and the solid alkali are added in the following mass ratio: 1: (0.1-0.2): (0.02-0.03): (0.15-0.4).
Preferably, the solid base is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
Preferably, the silicate is selected from one or more of ethyl orthosilicate, tetramethyl silicate, propyl orthosilicate and butyl orthosilicate.
Preferably, the titanate is selected from one or more of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate.
The invention also provides application of the silicon-titanium molecular sieve in phenol hydroxylation reaction.
The invention relates to a method for hydroxylation reaction of phenol, which comprises the step of reacting phenol and hydrogen peroxide under the catalysis of a silicon-titanium molecular sieve.
The reaction temperature of the phenol hydroxylation reaction is 40-60 ℃, the pressure is 10-100Kpa, and the reaction temperature of phenol: hydrogen peroxide molar ratio = (1-5): 1, solvent, phenol: the mass ratio of the solvent is 1: (2-4).
The adding amount of the silicon-titanium molecular sieve accounts for 1-5% of the total mass of the phenol, the hydrogen peroxide and the solvent, and the reaction time is 1-3h.
The phenol hydroxylation reaction of the present invention may be carried out in reactors known in the art including, but not limited to, batch tank reactors, tubular reactors, CSTR reactors, and the like.
The method has the following beneficial effects:
the method takes bithiophene as a raw material to synthesize a novel bithiophene-benzyl quaternary ammonium salt compound, takes the bithiophene as a template agent to synthesize a titanium-silicon molecular sieve catalyst together with a silicon source and a titanium source, and applies the obtained catalyst to a phenol hydroxylation reaction. The novel template has larger molecular volume, can effectively etch the inner pore passage of the molecular sieve, increases the inner space of the molecular sieve, and is beneficial to the entrance of hydroquinone with larger volume, thereby improving the selectivity of the hydroquinone, increasing the content of the hydroquinone in the product and greatly improving the economic value.
Drawings
FIG. 1 is a TEM image (50 nm) of a silicon titanium molecular sieve prepared in example 1.
FIG. 2 is a TEM image (50 nm) of a silicon titanium molecular sieve prepared in comparative example 1.
The specific implementation mode is as follows:
the method according to the invention will be further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
The performance of the catalyst can be measured by the conversion rate of phenol and the selectivity of target products catechol and hydroquinone, and the content of phenol, catechol and hydroquinone in the system is calibrated by an Agilent liquid chromatography instrument and an external standard method.
600 million ultra-low temperature nuclear magnetic resonance spectrometer manufacturers: BRUKER; the model is as follows: AV-HD-600X
The raw material sources are as follows: thiophene [3,2-B ] bithiophene, CAS:251-41-2, 3-hexyl-thiophene [3,2-B ] bithiophene, beijing largevich technologies ltd, CAS:880088-89-1, nakai science ltd, su zhou
Example 1
Into a three-necked glass bottle, 28g of thiophene [3,2-B ] was added]Adding bithiophene and 150g acetone dropwise into the reaction system at-78 ℃ within 0.5h, raising the temperature to 35 ℃ after the dropwise addition, continuing the reaction for 7h, and separating and purifying to obtain 2-bromo-thiophene [3,2-B]And thiophene. 20g of 2-bromo-thiophene [3,2-B is taken]Dissolving the bithiophene in 80g of ethanol, adding 60g of N, N-dimethyl benzylamine into the ethanol solution at one time, heating to 80 ℃, reacting for 8 hours, and separating and purifying to obtain the bithiophene-benzyl quaternary ammonium salt. The nuclear magnetic results were as follows: 1 H NMR(600MHz，CDCl 3 )：δ2.27(6H),4.32(2H),6.01(1H),6.96(1H),7.20(1H),7.23(2H),7.26(1H),7.33(2H)。
20g of bithiophene-benzyl quaternary ammonium salt, 2g of tetrabutyl titanate, 15g of sodium hydroxide and 100g of water are added into a 250ml reaction kettle and stirred for 20min until the components are completely dissolved. Then 100g of ethyl silicate is slowly added, after the dropwise addition, the temperature is raised to 160 ℃, and the aging is continued for 5 hours. Finally transferring the reaction liquid into a crystallization kettle, maintaining the constant temperature of 150 ℃, crystallizing for 100 hours, filtering, washing and drying to obtain TS-1, and measuring the BET to 359.6m 2 /g。
The obtained TS-1 is used in a phenol hydroxylation reaction, and the ratio of phenol: hydrogen peroxide molar ratio =3:1, the mass ratio of phenol to acetone is 1:2, the reaction pressure is 50KPa, the added silicon-titanium molecular sieve TS-1 prepared in the embodiment accounts for 3 percent of the total mass of phenol, hydrogen peroxide and acetone, the reaction is carried out for 3 hours at the temperature of 80 ℃, the conversion rate of hydrogen peroxide is more than 99.5 percent, the yield of the product (catechol + hydroquinone) is 95.2 percent, and the hydroquinone/catechol is 4.8.
Example 2
Into a three-necked glass bottle, 30g of thiophene [3,2-B ] was charged]And 270g of water, at-100 ℃,dropwise adding 24g of bromine into the reaction system within 1.8h, raising the temperature to 70 ℃ after the dropwise adding is finished, continuing the reaction for 4h, and separating and purifying to obtain 2-bromo-thiophene [3,2-B]And thiophene. 25g of 2-bromo-thiophene [3,2-B is taken]Dissolving the bithiophene in 250g of acetone, adding 180g of N, N-dimethyl benzylamine into the solution at one time, heating to 50 ℃, reacting for 12 hours, and separating and purifying to obtain the bithiophene-benzyl quaternary ammonium salt. The nuclear magnetic results were as follows: : 1 H NMR(600MHz，CDCl 3 )：δ2.27(6H),4.32(2H),6.01(1H),6.96(1H),7.20(1H),7.23(2H),7.26(1H),7.33(2H)。
20g of bithiophene-benzyl quaternary ammonium salt, 4g of tetrabutyl titanate, 30g of sodium hydroxide and 150g of water are added into a 250ml reaction kettle and stirred for 20min until the bithiophene-benzyl quaternary ammonium salt, the tetrabutyl titanate, the sodium hydroxide and the water are completely dissolved. Then 200g of methyl silicate is slowly added, after the dripping is finished, the temperature is raised to 150 ℃, and the aging is continued for 4h. Finally transferring the reaction liquid to a crystallization kettle, maintaining the constant temperature of 150 ℃, crystallizing for 100h, filtering, washing and drying to obtain TS-1, and measuring BET to 366.7m 2 /g。
The resulting TS-1 was used in a phenol hydroxylation reaction with phenol: hydrogen peroxide molar ratio =3:1, the mass ratio of phenol to acetone is 1:2, the reaction pressure is 50KPa, the added silicon-titanium molecular sieve TS-1 prepared in the embodiment accounts for 3 percent of the total mass of phenol, hydrogen peroxide and acetone, the reaction is carried out for 3 hours at the temperature of 80 ℃, the conversion rate of hydrogen peroxide is more than 99.5 percent, the yield of the product (catechol + hydroquinone) is 94.8 percent, and the hydroquinone/catechol is 4.6.
Example 3
Into a three-necked glass bottle, 30g of 3-hexylthiophene [3,2-B was charged]Adding bithiophene and 140g tetrahydrofuran, dropwise adding 10g bromine into the reaction system for 1h at-60 ℃, raising the temperature to 50 ℃ after dropwise adding, continuing to react for 9h, and separating and purifying to obtain 2-bromo-3-hexylthiophene [3,2-B]And thiophene. 25g of 2-bromo-3-hexyl-thiophene [3,2-B is taken]Dissolving the bithiophene in 100g of methanol, adding 125g of N, N-dimethyl benzylamine into the solution at one time, heating to 65 ℃ for reaction for 16h, and separating and purifying to obtain the bithiophene-benzyl quaternary ammonium salt. The nuclear magnetic results are as follows 1 H NMR(600MHz，CDCl 3 )：δ0.88(3H),1.29(4H)，1.31(2H),1.59(2H)2.27(6H),2.60(2H),4.32(2H),6.96(1H),7.20(1H),7.23(2H),7.26(1H),7.33(2H)。
20g of bithiophene are takenBenzyl quaternary ammonium salt, 3.2g tetrapropyl titanate, 30g sodium hydroxide and 150g water were added to a 250ml reaction vessel and stirred for 20min until completely dissolved. Then slowly adding 150g of butyl silicate, after the dripping is finished, raising the temperature to 150 ℃ and continuing aging for 4h. Finally transferring the reaction liquid to a crystallization kettle, maintaining the constant temperature of 150 ℃, crystallizing for 100h, filtering, washing and drying to obtain TS-1, and measuring BET to 378.4m 2 /g。
The obtained TS-1 is used in a phenol hydroxylation reaction, and the ratio of phenol: hydrogen peroxide molar ratio =3:1, the mass ratio of phenol to acetone is 1:2, the reaction pressure is 50KPa. The silicon-titanium molecular sieve TS-1 prepared in the embodiment is added to account for 2% of the total mass of phenol, hydrogen peroxide and acetone, the reaction is carried out for 3h at the temperature of 80 ℃, the conversion rate of hydrogen peroxide is more than 99.5%, the yield of products (catechol and hydroquinone) is 93.4%, and the content of hydroquinone/catechol is 4.9.
Example 4
Into a three-necked glass bottle, 30g of 3-hexylthiophene [3,2-B was charged]Adding 18g of bromine into a reaction system at the temperature of minus 78 ℃ dropwise in the presence of 140g of DMF (dimethyl formamide), heating to 55 ℃ after dropwise addition, continuing to react for 6h, and separating and purifying to obtain 2-bromo-3-hexylthiophene [3,2-B)]And a thiophene. 25g of 2-bromo-3-hexyl-thiophene [3,2-B is taken]Dissolving bithiophene in 150g of water, adding 110g of N, N-dimethyl benzylamine into the solution at one time, heating to 60 ℃, reacting for 10 hours, and separating and purifying to obtain the bithiophene-benzyl quaternary ammonium salt. The nuclear magnetic results were as follows: 1 H NMR(600MHz，CDCl 3 )：δ0.88(3H),1.29(4H)，1.31(2H),1.59(2H)2.27(6H),2.60(2H),4.32(2H),6.96(1H),7.20(1H),7.23(2H),7.26(1H),7.33(2H)。
20g of bithiophene-benzyl quaternary ammonium salt, 3g of tetrapropyl titanate, 25g of sodium hydroxide and 150g of water are added into a 250ml reaction kettle and stirred for 20min until the materials are completely dissolved. Then 120g of butyl silicate is slowly added, after the dripping is finished, the temperature is raised to 150 ℃, and the aging is continued for 4 hours. Finally transferring the reaction liquid into a crystallization kettle, maintaining the constant temperature of 150 ℃, crystallizing for 100h, filtering, washing and drying to obtain TS-1, and measuring BET to 380.9m 2 /g。
The obtained TS-1 is used in a phenol hydroxylation reaction, and the ratio of phenol: hydrogen peroxide molar ratio =3:1, the mass ratio of phenol to acetone is 1:2, the reaction pressure is 50KPa. The silicon-titanium molecular sieve TS-1 prepared in the embodiment is added to account for 5% of the total mass of phenol, hydrogen peroxide and acetone, the reaction is carried out for 3 hours at the temperature of 80 ℃, the conversion rate of hydrogen peroxide is more than 99.5%, the yield of products (catechol and hydroquinone) is 91.8%, and the content of hydroquinone/catechol is 4.
Comparative example 1
20g of tetrapropylammonium hydroxide, 3.5g of tetrapropyltitanate, 25g of sodium hydroxide and 160g of water are added to a 250ml reaction kettle and stirred for 20min until complete dissolution. Then 120g of butyl silicate is slowly added, after the dripping is finished, the temperature is raised to 150 ℃, and the aging is continued for 4 hours. Finally transferring the reaction liquid to a crystallization kettle, maintaining the constant temperature of 150 ℃, crystallizing for 90 hours, filtering, washing and drying to obtain TS-1, and measuring BET to be 284.2m 2 /g。
The obtained TS-1 is used in a phenol hydroxylation reaction, and the ratio of phenol: hydrogen peroxide molar ratio =3:1, the mass ratio of phenol to acetone is 1:2, the reaction pressure is 50KPa. The added silicon-titanium molecular sieve TS-1 prepared by the comparative example accounts for 5 percent of the total mass of phenol, acetone and hydrogen peroxide, the reaction lasts for 3 hours at 80 ℃, the conversion rate of the hydrogen peroxide is more than 99.5 percent, the yield of the product (catechol + hydroquinone) is 80.3 percent, and the hydroquinone/catechol is 1.3 percent.
Claims (10)
1. The quaternary ammonium salt template agent is characterized by having the following structure:
in the formula, R 1 、R 2 Represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
2. The method for preparing the template according to claim 1, comprising the steps of:
(1) Dropwise adding bromine into the bithiophene derivative, and reacting to generate a 2-bromo-bithiophene derivative;
(2) The 2-bromo-bithiophene derivative reacts with N, N-dimethyl benzylamine to generate bithiophene-benzyl quaternary ammonium salt.
3. The method for preparing the template according to claim 2, wherein the structural formula of the bithiophene derivative is:
in the formula R 1 And R 2 Each represents hydrogen or an alkyl group having 1 to 6 carbon atoms.
4. The method for preparing the template according to any one of claims 2 or 3, wherein the reaction of step (1) is performed in a solvent A, wherein the solvent A is one or more of acetone, water, DMF, dimethylacetamide, tetrahydrofuran, and toluene, and preferably acetone or DMF;
preferably, the weight ratio of the bithiophene derivative to the solvent A is 1 (1-10), preferably 1 (5-8);
preferably, in the step (1), the mass ratio of the bithiophene derivative to the bromine is 1 (0.3-1), preferably 1 (0.5-0.7);
preferably, the initial reaction stage in the step (1) is a bromine dripping stage, the temperature is-100 ℃ to-50 ℃, and the reaction is continued after the dripping of the bromine reagent is finished and slowly increased to 30-80 ℃, preferably 50-60 ℃;
preferably, the dropping time of the step (1) is 0.2 to 2 hours, preferably 0.5 to 1 hour; after the dropwise addition, the reaction is continued for 3 to 10 hours, preferably 5 to 8 hours;
preferably, in the step (1), the crude product is purified by column chromatography, and the eluent comprises one or more of n-hexane, ethyl acetate, dichloromethane and chloroform.
5. The method for preparing the template according to any one of claims 2-4, wherein the step (2) can be performed in a solvent B, wherein the solvent B comprises one or more of methanol, ethanol, propanol, water and acetone, and preferably the solvent B is ethanol or acetone;
preferably, in the step (2), the mass ratio of the 2-bromo-bithiophene derivative to the solvent B is 1: (3-12), preferably 1 (4-10);
preferably, in the step (2), the mass ratio of the N, N-dimethyl benzylamine to the 2-bromo-bithiophene derivative is (1-8): 1, preferably (3 to 6): 1;
preferably, the reaction time in the step (2) is 5 to 20 hours, preferably 8 to 12 hours;
preferably, the reaction temperature in the step (2) is 30-100 ℃, and preferably 50-80 ℃.
6. A method for preparing a silicon-titanium molecular sieve by using the template agent of claim 1 or the template agent prepared by the preparation method of any one of claims 2 to 5.
7. The preparation method of claim 6, wherein the template agent, titanate and solid alkali are hydrolyzed in water, then silicate ester is added into the water, after aging is carried out for 3-5h, the mixed solution is heated to 100-180 ℃ for hydrothermal crystallization, and finally, the silicon-titanium molecular sieve is obtained by filtering, washing and drying.
8. The preparation method according to claim 7, wherein the silicate, the template, the titanate and the solid base are added in a mass ratio of: 1: (0.1-0.2): (0.02-0.03): (0.15-0.4);
preferably, the silicate is selected from one or more of ethyl orthosilicate, tetramethyl silicate, propyl orthosilicate and butyl orthosilicate;
preferably, the titanate is selected from one or more of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate.
9. Use of the silicon-titanium molecular sieve prepared by the preparation method of any one of claims 6 to 8 in phenol hydroxylation reaction.
10. A phenol hydroxylation reaction method, reacting phenol and hydrogen peroxide under the catalysis of the silicon-titanium molecular sieve prepared by the preparation method of any one of claims 6-8;
preferably, the reaction temperature of the phenol hydroxylation reaction is 40-60 ℃, the pressure is 10-100Kpa, and the reaction pressure of phenol: hydrogen peroxide molar ratio = (1-5): 1, phenol: the mass ratio of the solvent is 1: (2-4);
preferably, the adding amount of the silicon-titanium molecular sieve accounts for 1-5% of the total mass of phenol, the solvent and hydrogen peroxide, and the reaction time is 1-3h.
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