CN116332194A - Titanium-silicon molecular sieve, preparation method thereof and phenol hydroxylation method - Google Patents
Titanium-silicon molecular sieve, preparation method thereof and phenol hydroxylation method Download PDFInfo
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- CN116332194A CN116332194A CN202111579941.1A CN202111579941A CN116332194A CN 116332194 A CN116332194 A CN 116332194A CN 202111579941 A CN202111579941 A CN 202111579941A CN 116332194 A CN116332194 A CN 116332194A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 75
- 238000000034 method Methods 0.000 title claims abstract description 45
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 21
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000010936 titanium Substances 0.000 claims abstract description 70
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 69
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 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 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 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
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- -1 aliphatic alcohol amine Chemical class 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-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
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000000640 hydroxylating effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000002444 silanisation Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000006884 silylation reaction Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to the field of phenol hydroxylation catalytic reaction, in particular to a titanium-silicon molecular sieve, a preparation method thereof and a phenol hydroxylation method, wherein the method comprises the following steps: (1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol; (2) Adding a silanization reagent into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture. When the titanium silicasol precursor is treated by a specific silanization reagent and the prepared titanium silicasol molecular sieve is applied to catalyzing phenol hydroxylation reaction, the titanium silicasol molecular sieve has high phenol hydroxylation activity, the phenol conversion rate is obviously improved to be more than 20%, the catechol selectivity is improved to be more than 40%, and the hydroquinone selectivity is improved to be more than 40%.
Description
Technical Field
The invention relates to the field of phenol hydroxylation catalytic reaction, in particular to a titanium-silicon molecular sieve, a preparation method thereof and a phenol hydroxylation method.
Background
In the industrial production process, heterogeneous catalysts are highly valued by scientific researchers because of the advantages of recycling, easy separation and the like, and molecular sieves are also widely developed and applied as typical representatives of heterogeneous catalysts. The heteroatom molecular sieve refers to a molecular sieve which is formed by substituting silicon atoms in the all-silicon molecular sieve with specific metal atoms, enters a molecular sieve framework, and forms a catalytic active center and has a regular topological structure. In 1983, titanium silicalite (TS-1) was first synthesized by Taramasso et al and was considered as a milestone in the field of molecular sieve catalysis. Subsequently, a variety of heteroatom (e.g., tin, iron, gallium, zirconium, vanadium, etc.) molecular sieve materials have been prepared. In an oxygen-containing hydrocarbon environmentally friendly conversion reaction, the heteroatom molecular sieve exhibits an incomparable advantage over conventional methods. Particularly, the titanium-silicon molecular sieve has the advantages of mild reaction conditions, high atomic utilization rate, environment-friendly and pollution-free process and the like in the hydrocarbon selective oxidation reaction with hydrogen peroxide as an oxidant, has great industrial application prospect, and is always the focus of researchers.
At present, ti-containing heteroatom molecular sieves represented by TS-1 molecular sieves are successfully applied to industrial production processes such as propylene liquid phase epoxidation, cyclohexanone ammoxidation and the like. However, the titanium-silicon molecular sieve TS-1 has a ten-membered ring channel with an MFI structure, the aperture is about 0.55nm, and the diffusion and mass transfer of macromolecular hydrocarbons are possibly limited, so that the application of the titanium-silicon molecular sieve TS-1 is also restricted. Therefore, the mass transfer diffusion property of the TS-1 molecular sieve is improved, and the property of catalyzing macromolecular reactants is improved. In recent years, the synthesis of a hierarchical porous titanium-silicon molecular sieve with both micropores and mesoporous channels becomes a research focus, and the hierarchical porous titanium-silicon molecular sieve not only has sufficient skeleton Ti atoms, but also can effectively promote the intra-crystal diffusion and mass transfer effects of reaction molecules. Heretofore, there are numerous methods for preparing hierarchical pore titanium silicalite molecular sieves, such as alkali dissolution, hard/soft templating agent, silylation agent layering, and the like. Wherein, the silylation reagent layering method is an effective method for preparing the hierarchical porous titanium-silicon molecular sieve.
CN108726528A discloses a hierarchical pore titanium-silicon molecular sieve, a preparation method thereof and a method for olefin epoxidation, and mesoporous pore channels with a certain proportion can be introduced into the titanium-silicon molecular sieve through treatment of a silylating agent, but the catalytic oxidation performance of the molecular sieve needs to be further improved.
Disclosure of Invention
The invention aims to improve the catalytic oxidation performance of a titanium-silicon molecular sieve in a phenol hydroxylation reaction, and provides the titanium-silicon molecular sieve, a preparation method thereof and a phenol hydroxylation method.
To achieve the above object, a first aspect of the present invention provides a method for preparing a titanium silicalite molecular sieve, the method comprising:
(1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Each independently selected from C 1 -C 6 Is a hydrocarbon group.
In a second aspect, the invention provides a titanium silicalite molecular sieve prepared according to the method of the first aspect.
In a third aspect the present invention provides a process for hydroxylation of phenol, the process comprising: and (2) contacting phenol with a catalyst and hydrogen peroxide for reaction, wherein the catalyst comprises the titanium silicalite molecular sieve in the second aspect.
According to the technical scheme, the titanium silicasol precursor is treated by the specific silanization reagent, so that the prepared titanium silicasol molecular sieve has high phenol hydroxylation activity when being applied to catalyzing phenol hydroxylation reaction, the phenol conversion rate is remarkably improved to be more than 20%, the catechol selectivity is improved to be more than 40%, and the hydroquinone selectivity is improved to be more than 40%.
Drawings
FIG. 1 is an XRD spectrum of a titanium silicalite molecular sieve obtained in example 1 of the present invention;
FIG. 2 is a UV-Vis spectrum of the titanium silicalite molecular sieve obtained in example 1 of the present invention;
FIG. 3 is a TEM image of the titanium silicalite molecular sieve obtained in example 1 of the present invention;
fig. 4 is an XRD spectrum of the titanium silicalite molecular sieve obtained in comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a process for preparing a titanium silicalite molecular sieve, the process comprising:
(1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Each independently selected from C 1 -C 6 Alkyl of (2)。
In the invention, C 1 -C 6 The alkyl group of (a) means an alkyl group having 1 to 6 carbon atoms in total, and may be, for example, one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl.
In some preferred embodiments of the invention i is an integer from 1 to 5, which may be 1, 2, 3, 4 or 5, for example.
In some preferred embodiments of the invention, R 1 、R 2 And R is 3 Each independently selected from C 1 -C 3 Alkyl group of said C 1 -C 3 The alkyl group of (a) may be methyl, ethyl, n-propyl or isopropyl, preferably R 1 、R 2 And R is 3 Each independently selected from methyl, ethyl or n-propyl. In the present invention, R 1 、R 2 And R is 3 May be the same or different, and R is preferably selected from 1 、R 2 And R is 3 All the same.
According to the invention, a specific silylation reagent (a compound shown in a formula (I)) is added into the titanium silicasol, and the titanium silicalite molecular sieve obtained by crystallization has a richer micropore structure through electrostatic acting force among sulfhydryl groups in a plurality of silylation reagents; in the phenol hydroxylation reaction process, the mass transfer diffusion between the reactant molecules and the product molecules in and between the crystals is facilitated, so that the reaction effect is effectively improved.
According to the invention, too high an amount of the silylating agent (the compound represented by the formula (I)) may result in poor crystallization performance of the titanium silicasol and imperfect molecular sieve framework structure; the use level of the silylation reagent (the compound shown in the formula (I)) is too low, so that the internal surface area of the obtained titanium-silicon molecular sieve can be reduced, mass transfer is influenced, and the activity of catalyzing phenol hydroxylation reaction is further influenced; according to the present invention, preferably, in the step (1), the silicon source is formed of SiO 2 The molar ratio of the silicon source to the compound represented by formula (I) is 1: (0.01-0.3), preferably 1: (0.01-0.2); more preferably 1: (0.05-0.1).
In some preferred embodiments of the invention, the silicon source is in the form of SiO 2 Calculated by N when the alkaline template agent contains nitrogen element, and calculated by OH when the alkaline template agent does not contain nitrogen element - The molar ratio of the silicon source to the alkaline template to the water is 1: (0.05-0.4): (5-40); preferably 1: (0.1-0.3): (5-25).
According to the present invention, preferably, the silicon source is at least one selected from the group consisting of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, white carbon black, and silica sol.
According to the present invention, preferably, the basic template is at least one selected from the group consisting of quaternary ammonium base, aliphatic amine and aliphatic alcohol amine, preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
In some preferred embodiments of the invention, the silicon source is in the form of SiO 2 The titanium source is calculated as TiO 2 The molar ratio of the silicon source to the titanium source is 1: (0.001-0.04), preferably 1: (0.005-0.025).
According to the present invention, preferably, the titanium source is selected from an organic titanium source and/or an inorganic titanium source; further preferably, the titanium source is selected from at least one of titanium tetrachloride, titanium sulfate, titanium nitrate, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
In a preferred embodiment of the present invention, step (1) further comprises: mixing a silicon source, an alkaline template agent and water, stirring for 0.1-2h at room temperature, adding a titanium source in the stirring process, and stirring for 0.5-6h to obtain the titanium silicasol. Preferably, the second stirring time is 0.5 to 3 hours, more preferably 1 to 3 hours.
According to the present invention, preferably, step (1) further comprises: alcohol is removed after the mixing; alcohol removal can remove alcohol generated by hydrolysis of a silicon source and a titanium source, in the invention, the alcohol generated in a system is preferably removed by adopting an azeotropic distillation mode, and meanwhile, water lost by azeotropic distillation is supplemented in the alcohol removal process, so that the proportion of each substance in the titanium silicasol is ensured to meet the requirements; preferably, the alcohol expelling conditions include: the temperature is 30-100 ℃ and the time is 2-10h; more preferably: the temperature is 40-90 ℃ and the time is 4-10h.
According to the present invention, in order to enable the silylating agent (the compound represented by formula (I)) to be uniformly dispersed in the titanium silicasol, the step (1) preferably further comprises: the compound shown in the formula (I) is added into the titanium silicasol for third stirring for 0.1-24h, preferably for 0.5-10h, and more preferably for 3-5h.
In the invention, the nucleation and growth process of the molecular sieve can be controlled by rapid temperature rise, so as to obtain molecular sieve particles with smaller size; according to the present invention, preferably, in step (2), the conditions for hydrothermal crystallization include: heating the mixture to 50-200 ℃ within 0.1-1h, and then carrying out hydrothermal crystallization for 10-100h at 50-200 ℃; preferably, the hydrothermal crystallization is carried out at the temperature of 100-200 ℃ for 10-80 hours; further preferably, the heating time is 0.1 to 0.5h; more preferably, the conditions for hydrothermal crystallization include: the temperature is 120-200 ℃ and the time is 20-70h; under the above preferred conditions, the specific surface area and pore volume of the molecular sieve can be balanced; molecular sieves having a specific surface area and pore volume are prepared.
The pressure of the hydrothermal crystallization is not particularly limited, and may be the autogenous pressure of the crystallization system.
According to the present invention, preferably, the method further comprises: washing, filtering and drying a product obtained by hydrothermal crystallization; wherein the washing, filtering and drying processes may be known to those skilled in the art, respectively. Illustratively, the temperature of the washing may be 20-50 ℃, the solvent for washing may be water, and the amount of the solvent for washing is 1-20 times the mass of the crystallized product; the drying conditions may be: the temperature is 40-150 ℃ and the time is 0.5-24h.
In some preferred embodiments of the invention, the firing conditions include: the temperature is 400-800 ℃ and the time is 1-15h; preferably 500-600deg.C for 4-10 hr.
In a second aspect, the invention provides a titanium silicalite molecular sieve prepared according to the method of the first aspect.
Preferably, the UV-Vis characteristic peak of the titanium silicalite molecular sieve is located between 210 and 230nm; the micropore volume is 0.34-0.37cm 3 /g; the inner surface area is 430-480m 2 /g。
In the present invention, the internal surface area means the specific surface area of the internal pore structure contained in the molecular sieve.
In a third aspect the present invention provides a process for hydroxylation of phenol, the process comprising: and (2) contacting phenol with a catalyst and hydrogen peroxide for reaction, wherein the catalyst comprises the titanium silicalite molecular sieve in the second aspect.
According to the present invention, preferably, the conditions for hydroxylation of phenol include: the temperature is 30-120 ℃, and the mole ratio of phenol to hydrogen peroxide is (2-5): 1, the weight ratio of the titanium silicon molecular sieve to the phenol is (0.01-0.1): 1.
The form of the catalyst can be selected according to actual requirements, and the catalyst can be a molecular sieve loaded on a carrier or molecular sieve powder; in the present invention, it is preferable to directly use molecular sieve powder as a catalyst.
According to a particularly preferred embodiment of the present invention, the method for preparing a titanium silicalite molecular sieve comprises:
(1) The silicon source, the alkaline template agent and water are mixed according to the mole ratio of 1: (0.1-0.3): (5-25), mixing, performing first stirring at room temperature for 0.1-2h, adding a titanium source in the stirring process, and performing second stirring for 0.5-6h to obtain a mixed system; wherein the molar ratio of the silicon source to the titanium source is 1: (0.005-0.025);
then alcohol is removed from the mixed system to obtain titanium silicasol; the alcohol expelling temperature is 40-90 ℃ and the time is 4-10h;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture; wherein the molar ratio of the silicon source to the compound represented by formula (I) is 1: (0.01-0.3), the crystallization conditions are as follows: heating the mixture to 120-200 ℃ within 0.1-0.5h, and then carrying out hydrothermal crystallization for 20-70h at 120-200 ℃;
wherein i is an integer of 1 to 5; r is R 1 、R 2 And R is 3 Are all the same; r is R 1 、R 2 And R is 3 Selected from ethyl or propyl.
The present invention will be described in detail by examples. In the examples below, room temperature is 25.+ -. 5 ℃.
In the following examples and comparative examples, X-ray diffraction (XRD) pattern measurement of the samples was performed on a Siemens D5005 type X-ray diffractometer with a source of Cu ka, a tube voltage of 40kV, a tube current of 40mA, a scanning speed of 0.5 °/min, and a scanning range of 2θ=5 ° -35 °;
the ultraviolet-visible spectrum diagram (UV-Vis) of the sample is obtained by testing an Agilent Cary 300 ultraviolet spectrophotometer, the wavelength interval is 3nm, and the scanning range is 190-800nm;
a Transmission Electron Microscope (TEM) characterization was obtained using a JEOL JEM-2100 assay;
the internal surface area was measured as the static N of the sample using an ASAP2405J static nitrogen adsorber from Micromeritics at liquid nitrogen temperature (77.4K) 2 After the absorption and desorption curve, P/P 0 Adsorption curves in the range of 0.05-0.35 are subjected to BET fitting;
the pore volume was measured according to the method described in RIPP 151-90 in petrochemical analysis method (first edition, published by science Press 1990, 9) written by Yang Cuiding et al.
In the following examples, the chemical structural formulas of the silylating agents employed are shown in table 1, wherein compound 1, compound 2 and compound 3 are all commercially available.
TABLE 1
Example 1
(1) Tetraethyl silicate, tetrapropylammonium hydroxide and water are stirred and mixed at room temperature and stirredAdding tetrabutyl titanate in the process, and carrying out second stirring for 2 hours to obtain a mixed system; wherein, the tetraethyl silicate is prepared by SiO 2 Tetrapropylammonium hydroxide in N, tetrabutyltitanate in TiO 2 The molar ratio of tetraethyl silicate, tetrapropylammonium hydroxide, water and tetrabutyl titanate is 1:0.2:20:0.015;
then alcohol expelling is carried out on the mixed system at 70 ℃ for 6 hours to obtain titanium silicasol;
(2) Adding the compound (1) into the titanium silicasol, and carrying out third stirring at room temperature for 5 hours to obtain a mixture, wherein the molar ratio of the compound 1 to the tetraethyl silicate is 0.1:1;
(3) Heating the mixture to 160 ℃ for 0.5h, and performing hydrothermal crystallization for 72h at 160 ℃ to obtain a crystallized product;
sequentially leaching the crystallized product with water, filtering, and drying at 120 ℃ for 2 hours;
roasting the dried product at 550 ℃ for 6 hours to obtain a titanium-silicon molecular sieve;
the XRD spectrum of the titanium silicalite molecular sieve obtained in the embodiment is shown in figure 1, the UV-Vis spectrum is shown in figure 2, the TEM spectrum is shown in figure 3, and the physical parameters are shown in table 3; as can be seen from fig. 1, the titanium-silicon molecular sieve prepared in this embodiment has an MFI structure and good crystallinity; the peak at 220nm in FIG. 2 belongs to the characteristic peak of four-coordinated titanium atoms, which shows that the titanium-silicon molecular sieve prepared in the embodiment has skeleton titanium active center; as can be seen from FIG. 3, the particle size of the titanium silicalite molecular sieve prepared in this example was about 250nm.
Examples 2 to 20
Titanium silicalite molecular sieves were prepared according to the procedure of example 1, the proportions and synthesis conditions of which are shown in Table 2, and the physical properties of the molecular sieves prepared are shown in Table 3.
Comparative example 1
The titanium-silicon molecular sieve is prepared according to the method for preparing the titanium-silicon micro-mesoporous molecular sieve composite material disclosed in Zeolite, 1992, vol.12, pages 943-950, and the specific method is as follows:
22.5g of tetraethyl silicate, 7g of tetrapropylammonium hydroxide and 59.8g of deionized water were mixed well and hydrolyzed at 60℃for 1h. Then, a solution of 1.1g of tetrabutyl titanate and 5g of isopropyl alcohol was slowly dropped into the above solution under vigorous stirring, and the mixture was stirred at 75℃for 3 hours to give a clear and transparent colloid. And transferring the colloid into a stainless steel closed reaction kettle, and crystallizing at the constant temperature of 170 ℃ for 72 hours to obtain the conventional TS-1 molecular sieve. The XRD analysis spectrum is shown in FIG. 4.
Comparative examples 2 to 6
Titanium silicalite molecular sieves were prepared according to the procedure of example 1, the proportions and synthesis conditions of which are shown in Table 2, and the physical properties of the molecular sieves prepared are shown in Table 3.
Comparative example 7
A titanium silicalite molecular sieve was prepared as in example 1, except that the silylating agent was methyltriethoxysilane (Compound 4), the raw material ratios and synthesis conditions are shown in Table 2, and the physical properties of the molecular sieve prepared are shown in Table 3.
Comparative example 8
A titanium silicalite molecular sieve was prepared as in example 1, except that the silylating agent was N- (2-aminoethyl) -3-aminopropyl trimethoxysilane (compound 5), the raw material ratios and synthesis conditions are shown in Table 2, and the physical properties of the molecular sieve prepared are shown in Table 3.
TABLE 3 Table 3
Test case
This test example demonstrates the effect of the reaction of the inventive example samples and the comparative examples samples for the hydroxylation of phenol to produce benzenediol. The reagents used in this test example were all commercially available chemically pure reagents. The concentration of each substance after the reaction was quantitatively analyzed by gas chromatography. 6890 type gas chromatograph manufactured by Agilent company is used; the analytical chromatographic column used was an FFAP column.
The phenol conversion and the selectivity to benzene-diol in the test examples were calculated according to the following formulas:
% phenol conversion = (moles of phenol remaining after 1-reaction/moles of phenol charged before reaction) ×100%
Benzene two phenol selectivity% = mole number after reaction/(mole number of phenol added before reaction-mole number of phenol remaining after reaction) ×100%
1.25g of each of the samples prepared in examples 1 to 20 and comparative examples 1 to 8 was added to a three-necked flask reaction vessel containing 25g of phenol and 20ml of acetone, and after the temperature had stabilized to the set value, 9.81g of hydrogen peroxide and phenol were added: hydrogen peroxide (H) 2 O 2 Calculated as) molar ratio 3:1, followed by phenol hydroxylation at 80℃and 0.1MPa (normal pressure) for 2 hours, and then sampling, and analysis of phenol conversion, catechol selectivity and hydroquinone selectivity were carried out, and the results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, the sample obtained by the invention can be used as a catalyst for phenol hydroxylation reaction, can obviously improve the conversion rate of phenol to 27%, the selectivity of catechol to 48%, and the selectivity of hydroquinone to 48%, and has better catalytic effect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method of making a titanium silicalite molecular sieve, the method comprising:
(1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Each independently selected from C 1 -C 6 Is a hydrocarbon group.
2. The method of claim 1, wherein i is an integer from 1 to 5;
preferably, R 1 、R 2 And R is 3 Each independently selected from methyl, ethyl or propyl.
3. The method of claim 1 or 2, wherein the silicon source is in SiO 2 The molar ratio of the silicon source to the compound represented by formula (I) is 1: (0.01-0.3), preferably 1: (0.01-0.2).
4. A method according to any one of claims 1-3, wherein the silicon source is in SiO 2 Calculated by N when the alkaline template agent contains nitrogen element, and calculated by OH when the alkaline template agent does not contain nitrogen element - The titanium source is calculated as TiO 2 The meter is used for measuring the number of the wires,
the molar ratio of the silicon source to the alkaline template to the water is 1: (0.05-0.4): (5-40); preferably 1: (0.1-0.3): (5-25);
preferably, the molar ratio of the silicon source to the titanium source is 1: (0.001-0.04), preferably 1: (0.005-0.025).
5. The method of any of claims 1-4, wherein the silicon source is selected from at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, white carbon black, and silica sol;
preferably, the basic template is selected from at least one of quaternary ammonium base, aliphatic amine and aliphatic alcohol amine, preferably at least one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide and tetrabutyl ammonium hydroxide;
preferably, the titanium source is selected from an organic titanium source and/or an inorganic titanium source;
preferably, the titanium source is selected from at least one of titanium tetrachloride, titanium sulfate, titanium nitrate, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
6. The method of any one of claims 1-5, wherein step (1) further comprises the step of mixing followed by alcohol expelling;
preferably, the alcohol expelling conditions include: the temperature is 30-100 ℃ and the time is 2-10h; preferably at 40-90deg.C for 4-10 hr.
7. The method according to any one of claims 1 to 6, wherein in step (2), the conditions for hydrothermal crystallization include: heating the mixture to 50-200 ℃ within 0.1-1h, and crystallizing at 50-200 ℃ for 10-100h; preferably crystallization is carried out at a temperature of 100-200 ℃ for 20-80 hours;
preferably, the roasting conditions include: the temperature is 400-800 ℃ and the time is 1-15h.
8. A titanium silicalite molecular sieve prepared according to the method of any one of claims 1-7;
preferably, the UV-vis characteristic peak of the titanium silicalite molecular sieve is located between 210 and 230nm; the micropore volume is 0.34-0.37cm 3 /g; the inner surface area is 430-480m 2 /g。
9. A method of hydroxylating phenol, the method comprising: the method is characterized in that phenol, a catalyst and hydrogen peroxide are contacted to react, and the catalyst comprises the titanium silicalite molecular sieve as claimed in claim 8.
10. The method of claim 9, wherein the conditions for phenol hydroxylation include: the temperature is 30-120 ℃, and the mole ratio of phenol to hydrogen peroxide is (2-5): 1, the weight ratio of the titanium silicon molecular sieve to the phenol is (0.01-0.1): 1.
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