CN112439449A - Preparation method of titanium-silicon molecular sieve catalyst for improving tetravalent titanium content in framework structure and catalyst thereof - Google Patents
Preparation method of titanium-silicon molecular sieve catalyst for improving tetravalent titanium content in framework structure and catalyst thereof Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000010936 titanium Substances 0.000 title claims abstract description 52
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 50
- 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 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims description 4
- 150000007524 organic acids Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002178 crystalline material Substances 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 101
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 6
- -1 titanium halide Chemical class 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 32
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 description 46
- 229910052906 cristobalite Inorganic materials 0.000 description 46
- 229910052682 stishovite Inorganic materials 0.000 description 46
- 229910052905 tridymite Inorganic materials 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 42
- 239000000243 solution Substances 0.000 description 31
- 238000010521 absorption reaction Methods 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 10
- 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 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 229960004106 citric acid Drugs 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229960002303 citric acid monohydrate Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Abstract
The invention discloses a titanium silicalite molecular sieve catalyst and a preparation method thereof, wherein the framework structure of the titanium silicalite molecular sieve catalyst has higher tetravalent titanium content, and the titanium silicalite molecular sieve catalyst mainly solves the problems of low tetravalent titanium content, and high hexavalent titanium and non-framework titanium dioxide content in the titanium silicalite molecular sieve framework in the prior art. The invention adopts the technical scheme of adding organic acid in the synthesis process of the molecular sieve intermediate crystalline material, better solves the problem and can be used in the industrial production of preparing epoxy chloropropane by allyl chloride epoxidation.
Description
Technical Field
The invention belongs to the technical field of molecular sieve catalysts, and relates to a preparation method of a titanium silicalite molecular sieve catalyst for improving the content of tetravalent titanium in a framework structure and the catalyst.
Background
TS-1 is a titanium silicalite molecular sieve with MFI structure, demonstrated in H2O2In the presence of the catalyst, a series of organic matters can be subjected to selective oxidation reactions, such as olefin epoxidation, cyclohexanone ammoxidation, phenol hydroxylation and the like. The above reactions have the advantages of mild conditions, relatively simple process, and most importantly, the method is environment-friendly and meets the requirements of catalysts of atom economic reaction and green chemical industry.
The synthetic method of TS-1 is relatively mature, and mainly adopts a hydrothermal synthesis method. One of the most classical methods is to add a templating agent, such as tetrapropylammonium hydroxide, to a silicon source and then drop-add a titanium source, such as tetraethyl titanate. After the mixture is stirred for a period of time, alcohol is removed and water is supplemented at the temperature of 80-90 ℃. Crystallizing at 170 deg.C under stirring for 10 days. Another method is to hydrolyze tetraethyl titanate, cool to 5 ℃, and add H2O2After stirring at 5 ℃ for 2 hours until the solution became clear, tetrapropylammonium hydroxide was added, followed by a source of silicon. Aging the mixed solution overnight, heating and stirring at 80-90 deg.C for 6 hr to remove alcohol, and crystallizing at 170 deg.C in a crystallization kettle.
Later, an improved synthesis method of the TS-1 molecular sieve is to change tetraethyl titanate into tetrabutyl titanate, so that the hydrolysis rate matching degree of silicate and titanate is increased, and the content of non-framework titanium can be reduced. The use of tetrapropylammonium bromide in place of tetrapropylammonium hydroxide, in part or in whole, can reduce the amount of expensive organoamine templating agent. Organic silicon and titanate are replaced by inorganic silicon and inorganic titanium, so that the source of synthetic raw materials of the TS-1 molecular sieve is expanded and enriched, and the cost is further reduced. In addition, the crystallization time was also proved to be shortened to within 3 days.
To reduce the content of TS-1 non-framework titanium, the test was carried out on the synthesis gelAdding F into glue-And incorporating some ammonium salts such as (NH)4)2CO3Ammonium acetate, urea, triethylamine and the like. These measures improve the catalytic performance of the molecular sieve only to a certain extent.
In addition, acetic acid, nitric acid, hydrochloric acid and the like are used for pre-hydrolyzing tetraethyl orthosilicate before gelling, so that the hydrolysis rate of tetraethyl orthosilicate can be matched with that of tetrabutyl titanate better. However, experiments prove that the method can not reduce the content of non-framework titanium and has limited influence on the catalytic performance of the molecular sieve.
The methods have the problems that the synthesis steps are complicated, solvents such as isopropanol in gel need to be removed by heating, and the titanium silicalite molecular sieve synthesized by the methods has low tetravalent titanium content in a framework and high hexavalent titanium and non-framework titanium dioxide content.
Disclosure of Invention
The invention aims to solve the problem of low tetravalent titanium content in the framework of the titanium silicalite molecular sieve. The titanium silicalite molecular sieve framework has the characteristics of high content of tetravalent titanium in the titanium silicalite molecular sieve framework and low content of hexavalent titanium and non-framework titanium dioxide, and is applied to industrial production of epoxy chloropropane prepared by epoxidation of allyl chloride, and the catalytic performance is stable.
The first aspect of the invention provides a preparation method of a titanium silicalite molecular sieve catalyst, which comprises a step of synthesizing an intermediate crystalline material and a step of roasting, wherein the step of synthesizing the intermediate crystalline material comprises a step of adding organic acid.
According to some embodiments of the invention, the organic acid contains at least two carboxyl groups.
It has been found that the effectiveness of the use of organic acids may be due to the chelation of the multiple carboxyl groups contained in the organic acid, slowing the rate of hydrolysis of the titanium species in alkaline environments. Thereby reducing the generation of species such as anatase and rutile, which are considered to decompose hydrogen peroxide and reduce the selectivity of the allyl chloride epoxidation reaction.
According to some embodiments of the invention, the method comprises the steps of:
s1 intermediate crystalline material synthesis: mixing an aqueous solution of an organic amine template agent with an organic acid, a titanium source and a silicon source to obtain a reaction mixture; crystallizing the reaction mixture, filtering, washing and drying to obtain an intermediate crystalline material;
s2 roasting: and (4) roasting the intermediate crystalline material obtained in the step S1 to obtain the titanium-silicon molecular sieve.
According to some embodiments of the present invention, the intermediate crystalline material is synthesized by crystallization at a crystallization temperature of 130 ℃ and 200 ℃ for 12-100 hours.
According to some embodiments of the present invention, the intermediate crystalline material is synthesized by crystallization at a crystallization temperature of 160 ℃ and 180 ℃ for 24-72 hours.
According to some embodiments of the present invention, the calcination is at 400-600 ℃ for 3-10 hours.
According to some embodiments of the invention, the TiO in the titanium source2SiO in silicon source2Organic amine template agent, organic acid and H2The molar ratio of O is (0.02-0.1): 1: (0.16-0.35): (0.007-0.06): (10-20).
According to some embodiments of the invention, the titanium source is selected from at least one of a tetraalkyl titanate and a titanium halide.
According to some embodiments of the invention, the silicon source is selected from at least one of silica sol, solid silica, silica gel and silicate ester.
According to some embodiments of the invention, the organic amine templating agent is selected from at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ethylenediamine, hexamethylenediamine, cyclohexylamine, and n-butylamine.
According to some embodiments of the invention, the organic acid is selected from at least one of oxalic acid, citric acid, tartaric acid, adipic acid and ethylenediaminetetraacetic acid.
The second aspect of the invention provides a titanium silicalite molecular sieve catalyst prepared according to the preparation method of the first aspect.
According to some embodiments of the invention, the titanium silicalite molecular sieve has uv-vis absorption spectra data as follows:
the third aspect of the invention provides a titanium silicalite catalyst prepared by the preparation method of the first aspect or the application of the titanium silicalite catalyst of the second aspect.
According to some embodiments of the invention, the application is in H2O2The organic matter under participation is selected to be oxidized.
According to some embodiments of the invention, the H2O2The organic matter selective oxidation reaction under participation is one or more of olefin epoxidation, cyclohexanone ammoxidation and phenol hydroxylation.
The invention has the beneficial effects that:
the invention adopts the technical proposal of adding organic acid in the synthesis process of the molecular sieve intermediate crystalline material, so that the organic acid and titanium metal ions in the sol generate complexation, thereby further reducing the hydrolysis rate of titanate. Titanium ions can enter crystal lattices to be condensed with silicon-oxygen bonds, and the titanium ions are prevented from being condensed with each other to form non-skeleton titanium dioxide. The inventor finds that in the ultraviolet-visible light absorption spectrum data of the molecular sieve prepared by the method, the absorption intensity of the wavelength of 220nm is greater than that of a sample without organic acid added in the synthesis process of the intermediate crystalline material, and the absorption intensities of the wavelengths of 260 nm and 330nm are less than that of the sample without the organic acid added. The titanium silicalite molecular sieve with higher tetravalent titanium content in the skeleton structure of the catalyst is adopted as the catalyst, so that the reaction performance of preparing epoxy chloropropane by epoxidation of allyl chloride is more stable, and a good technical effect is obtained.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD diffraction pattern of a titanium silicalite molecular sieve prepared in example 1;
FIG. 2 is a graph of UV-visible absorption intensity of the Ti-Si molecular sieve prepared in example 1.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the present invention is not limited to the examples.
[ example 1 ]
0.28g citric acid monohydrate was added to 24.98g 25% tetrapropylammonium hydroxide and 15.88g H2The O solution was stirred for 0.5 hour to dissolve it. 2.18g of tetrabutyltitanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 40g of tetraethyl orthosilicate was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a 100ml kettle reactor with a teflon liner and crystallized at 170 ℃ for 24 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 2 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝30
citric acid/SiO2＝0.0075
TPAOH/SiO2＝0.16
H2O/SiO2＝10
The UV-VIS absorption data of the calcined sample are shown in Table 1.
TABLE 1
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 22.55 | 4.45 | 0.21 |
1g of the molecular sieve synthesized in example 1 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 32.79 percent, the selectivity of the ECH (calculated by the allyl chloride) is 97.49 percent, and the H content is2O2Conversion 92.65%, H2O2The effective utilization rate is 97.70%.
[ example 2 ]
0.70g of oxalic acid was added to 24.98g of tetrapropylammonium hydroxide, 1.02g of tetrapropylammonium bromide and 33.18g of H2The O solution was stirred for 0.5 hour to dissolve it. 6.54g of tetrabutyltitanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 38.46g of 30% silica sol was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a 100ml kettle reactor with a teflon liner and crystallized at 172 ℃ for 48 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 2 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝10
oxalic acid/SiO2＝0.007
TPAOH/SiO2＝0.16
TPABr/SiO2＝0.02
H2O/SiO2＝15
The UV-VIS absorption data of the calcined sample are shown in Table 2.
TABLE 2
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 30.15 | 14.67 | 0.87 |
1g of the molecular sieve synthesized in example 2 was taken and charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 11.21 percent, the selectivity of the ECH (calculated by the allyl chloride) is 93.80 percent, and the reaction is carried out in H2O2Conversion 60.65%, H2O2The effective utilization rate is 48.16%.
[ example 3 ]
0.57g tartaric acid was added to 7.67g 25% tetrapropylammonium bromide, 5.80g 35% tetraethylammonium hydroxide, and 62.31g H2The O solution was stirred for 0.5 hour to dissolve it. 4.36g of tetraethyl titanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hours. 11.53g of solid silica was added dropwise to the above clear solution, and stirred at room temperature for 1 hour. The resulting gum was transferred to a kettle reactor and crystallized at 165 ℃ for 72 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 4 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. Reaction ofThe material ratio (mol ratio) of the materials is as follows:
SiO2/TiO2＝15
tartaric acid/SiO2＝0.02
TPABr/SiO2＝0.15
TEAOH/SiO2＝0.20
H2O/SiO2＝18
The UV-VIS absorption data of the calcined sample are shown in Table 3.
TABLE 3
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 27.33 | 13.42 | 0.64 |
1g of the molecular sieve synthesized in example 3 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 16.12 percent, the selectivity of the ECH (calculated by the allyl chloride) is 94.24 percent, and the H content is2O2Conversion 70.32%, H2O2The effective utilization rate is 61.00 percent.
[ example 4 ]
0.34g of adipic acid was added to 20.30g of 25% tetrapropylammonium hydroxide, 6.91g of 25% tetramethylammonium hydroxide and 26.31g of H2The O solution was stirred for 0.5 hour to dissolve it. 3.27g of tetraethyl titanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hours. 11.53g of silica gel was added dropwise to the above clear solution, and stirred at room temperature for 1 hour. The resulting gum was transferred to a 100ml kettle reactor with a teflon liner and crystallized at 162 ℃ for 72 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 2 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝20
adipic acid/SiO2＝0.012
TPAOH/SiO2＝0.13
TMAOH/SiO2＝0.18
H2O/SiO2＝12
The UV-VIS absorption data of the calcined sample are shown in Table 4.
TABLE 4
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 27.10 | 12.68 | 0.51 |
1g of the molecular sieve synthesized in example 4 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 17.92 percent, the selectivity of the ECH (calculated by the allyl chloride) is 94.23 percent, and the reaction is carried out in H2O2Conversion 58.20%, H2O2The effective utilization rate is 81.55%.
[ example 5 ]
5.61g of ethylenediaminetetraacetic acid was added to 20.30g of 25% tetrapropylammonium hydroxide, 3.57g of hexamethylenediamine and 36.70g of H2The O solution was stirred for 0.5 hour to dissolve it. 2.62g of tetrabutyltitanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 28.84g of 40% silica sol was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a 100ml kettle reactor with a teflon liner and crystallized at 175 ℃ for 24 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 2 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝25
ethylene diamine tetraacetic acid/SiO2＝0.01
TPAOH/SiO2＝0.13
hexamethylenediamine/SiO2＝0.16
H2O/SiO2＝15
The UV-VIS absorption data of the calcined sample are shown in Table 5.
TABLE 5
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 27.36 | 11.91 | 0.49 |
1g of the molecular sieve synthesized in example 5 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 24.61 percent, the selectivity of the ECH (calculated by the allyl chloride) is 96.70 percent, and the H content is2O2Conversion 88.79%, H2O2The effective utilization rate is 75.57%.
[ example 6 ]
1.84g of citric acid monohydrate was added to 7.16g of tetrapropylammonium bromide, 1.82g of n-butylamine and 62.31g of H2The O solution was stirred for 0.5 hour to dissolve it. 1.87g of tetrabutyltitanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 40g of tetraethyl orthosilicate was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a kettle reactor and crystallized at 180 ℃ for 24 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 4 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝35
citric acid/SiO2＝0.05
TPABr/SiO2＝0.14
n-butylamine/SiO2＝0.13
H2O/SiO2＝18
The UV-VIS absorption data of the calcined sample are shown in Table 6.
TABLE 6
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 13.70 | 2.40 | 0.18 |
1g of the molecular sieve synthesized in example 6 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 25.97 percent, the selectivity of the ECH (calculated by the allyl chloride) is 96.81 percent, and the reaction is carried out in H2O2Conversion 85.60%, H2O2The effective utilization rate is 82.64%.
[ example 7 ]
1.03g of oxalic acid was added to 20.30g of 25% tetrapropylammonium hydroxide, 1.84g of ethylenediamine and 54.01g of H2The O solution was stirred for 0.5 hour to dissolve it. 4.93g of a 15% hydrochloric acid solution of titanium trichloride was added dropwise to the above solution, and dissolved by stirring at room temperature for 0.5 hour. 40g of tetraethyl orthosilicate was added dropwise to the above purple-black clear solution, and stirred at room temperature for 1 hour. The resulting purple-black gum was transferred to a kettle reactor and crystallized at 170 ℃ for 72 hours. The product is filtered, dried and roasted for 2 hours at 550 ℃ in a muffle furnace to obtain moleculesAnd (5) screening the product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝40
oxalic acid/SiO2＝0.06
TPAOH/SiO2＝0.13
Ethylene diamine/SiO2＝0.16
H2O/SiO2＝20
The UV-VIS absorption data of the calcined sample are shown in Table 7.
TABLE 7
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 11.22 | 0.77 | 0.012 |
1g of the molecular sieve synthesized in example 7 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 29.22 percent, the selectivity of the ECH (calculated by the allyl chloride) is 97.40 percent, and the reaction is carried out in H2O2Conversion 92.63%, H2O2The effective utilization rate is 87.13%.
[ example 8 ]
0.86g tartaric acid was added to 20.30g 25% tetrapropylammonium hydroxide, 2.85g cyclohexylamine and 47.08g H2The O solution was stirred for 0.5 hour to dissolve it. 1.45g of tetrabutyltitanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 40g of tetraethyl orthosilicate was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a kettle reactor and crystallized at 175 ℃ for 48 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 2 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝45
tartaric acid/SiO2＝0.03
TPAOH/SiO2＝0.13
cyclohexylamine/SiO2＝0.15
H2O/SiO2＝18
The UV-VIS absorption data of the calcined sample are shown in Table 8.
TABLE 8
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 10.01 | 0.64 | 0.0028 |
1g of the molecular sieve synthesized in example 8 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 30.58 percent, the selectivity of the ECH (calculated by the allyl chloride) is 96.88 percent, and the H content is2O2Conversion 88.02%, H2O2The effective utilization rate is 93.57%.
[ example 9 ]
1.10g of citric acid monohydrate was added to 20.30g of 25% tetrapropylammonium hydroxide, 2.10g of n-butylamine and 54.01g of H2The O solution was stirred for 0.5 hour to dissolve it. 1.31g of tetrabutyltitanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 40g of tetraethyl orthosilicate was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a kettle reactor and crystallized at 178 ℃ for 72 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 3 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product. The material ratio (mol ratio) of the reactants is as follows:
SiO2/TiO2＝50
citric acid/SiO2＝0.03
TPAOH/SiO2＝0.13
n-butylamine/SiO2＝0.15
H2O/SiO2＝20
The UV-VIS absorption data of the calcined sample are shown in Table 9.
TABLE 9
| UV-visible wavelength (10)-9Rice) | 220 | 260 | 330 |
| Absorption peak intensity (I/I)0) | 10.04 | 0.64 | 0.002 |
1g of the molecular sieve synthesized in example 9 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 27.60 percent, the selectivity of the ECH (calculated by the allyl chloride) is 96.91 percent, and the H content is H2O2Conversion 83.30%, H2O2The effective utilization rate is 89.20%.
Examples 10 to 12
The material formulation when synthesizing the intermediate crystalline material is shown in table 10. The organic amine template species and other experimental conditions were the same as in example 1.
| Examples | Organic acid species | TiO2：SiO2: organic amine template agent: organic acid: h2O (molar ratio) |
| 10 | Citric acid | 30：1：0.16：0.006：10 |
| 11 | Citric acid | 30：1：0.16：0.02：10 |
| 12 | Citric acid | 30：1：0.16：0.04：10 |
| 13 | Citric acid | 30：1：0.16：0.065：10 |
The UV-VIS absorption data of the calcined sample are shown in Table 11.
TABLE 11
1g of the molecular sieve synthesized in example 10-12 was taken and charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. Stirring and reacting in water bath at 40 ℃ for 1 hour, wherein the conversion rate of allyl chloride is 30.05 percent, 31.00 percent and 32.13 percent, the ECH selectivity is 95.24 percent, 96.66 percent and 93.51 percent (calculated by allyl chloride), and the H content is2O2Conversion 89.27%, 92.30%, 88.29%, H2O2Effective utilization rates are 92.28%, 93.84% and 90.64%. Example 13 gave an amorphous product, which could not be evaluated for reaction.
Examples 14 to 17
The material formulation when synthesizing the intermediate crystalline material is shown in table 12. The organic amine templating agent species and other experimental conditions were the same as in example 7.
TABLE 12
| Examples | Organic acid species | TiO2：SiO2: organic amine template agent: organic acid: h2O (molar ratio) |
| 14 | Oxalic acid | 40：1：0.29：0.006：20 |
| 15 | Oxalic acid | 40：1：0.29：0.02：20 |
| 16 | Oxalic acid | 40：1：0.29：0.04：20 |
| 17 | Oxalic acid | 40：1：0.29：0.07：20 |
The UV-VIS absorption data of the calcined sample are shown in Table 13.
Watch 13
1g of the molecular sieves synthesized in examples 14 to 16 was charged into a 100-pot reactor, and 10ml of 30% H was sequentially added2O240ml of acetone and 25ml of allyl chloride. The reaction is carried out in a water bath at 40 ℃ for 1 hour under stirring, the conversion rate of the allyl chloride is 32.68 percent, 34.91 percent and 32.74 percent respectively, and the ECH selectivity is 95.24 percent, 96.66 percent and 93.51 percent respectively (calculated by the allyl chloride)2O2Conversion 90.55%, 93.74%, 92.57%, H2O2Effective utilization rates are 94.92%, 95.17% and 93.52%. Example 17 gave an amorphous product, which was not evaluated for reaction.
[ COMPARATIVE EXAMPLES 1 to 9 ]
During the synthesis of the intermediate crystalline material, no organic acid is added, and the mixture ratio of other materials is the same as that of example 1. 24.98g of 25% tetrapropylammonium hydroxide and 15.88g of H were taken2O and 2.18g of tetrabutyl titanate was added dropwise to the above solution, and stirred at room temperature for 0.5 hour. 40g of tetraethyl orthosilicate was added dropwise to the clear solution and stirred at room temperature for 1 hour. The resulting gum was transferred to a 100ml kettle reactor with a teflon liner and crystallized at 170 ℃ for 24 hours. And (3) carrying out suction filtration and drying on the product, and roasting the product for 2 hours at 550 ℃ in a muffle furnace to obtain a molecular sieve product.
Comparative examples 2-9 intermediate crystalline materials were synthesized without the addition of organic acid and in the same proportions as in examples 2-9.
Comparative examples 1-9 the uv-vis absorption intensity data for the fired samples are shown in table 14.
TABLE 14
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A preparation method of a titanium silicalite molecular sieve catalyst for improving the content of tetravalent titanium in a framework structure comprises a step of synthesizing an intermediate crystalline material and a step of roasting, wherein the step of synthesizing the intermediate crystalline material comprises a step of adding organic acid, and preferably, the organic acid contains at least two carboxyl groups.
2. The method of claim 1, comprising the steps of:
s1 intermediate crystalline material synthesis: mixing an aqueous solution of an organic amine template agent with an organic acid, a titanium source and a silicon source to obtain a reaction mixture; crystallizing the reaction mixture, filtering, washing and drying to obtain an intermediate crystalline material; preferably, the intermediate crystalline material is crystallized at a crystallization temperature of 130 ℃ and 200 ℃ for 12-100 hours, and further preferably crystallized at a crystallization temperature of 160 ℃ and 180 ℃ for 24-72 hours;
s2 roasting: roasting the intermediate crystalline material obtained in the step S1 to obtain a titanium-silicon molecular sieve; preferably, the calcination is at 400-600 ℃ for 3-10 hours.
3. A method according to claim 1 or 2, characterized in that TiO in the titanium source2SiO in silicon source2Organic amine template agent, organic acid and H2The molar ratio of O is (0.02-0.1): 1: (0.16-0.35): (0.007-0.06): (10-20).
4. The method of any one of claims 1 to 3, wherein the titanium source is selected from at least one of a tetraalkyl titanate and a titanium halide.
5. The method of any one of claims 1 to 4, wherein the silicon source is selected from at least one of silica sol, solid silica, silica gel and silicate ester.
6. The method of any of claims 1-5, wherein the organic amine templating agent is selected from at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, ethylenediamine, hexamethylenediamine, cyclohexylamine, and n-butylamine.
7. The method of any one of claims 1 to 6, wherein the organic acid is at least one selected from the group consisting of oxalic acid, citric acid, tartaric acid, adipic acid, and ethylenediaminetetraacetic acid.
8. A titanium silicalite catalyst prepared according to the method of any one of claims 1 to 7.
9. The catalyst of claim 8, wherein the titanium silicalite molecular sieve has uv-vis absorption spectrum data of:
10. use of a titanium silicalite catalyst prepared according to the process of any one of claims 1 to 7 or of the titanium silicalite catalyst of claim 8, preferably in H2O2The organic matter under participation is applied to selective oxidation reaction; further preferably, said H2O2The organic matter selective oxidation reaction under participation is one or more of olefin epoxidation, cyclohexanone ammoxidation and phenol hydroxylation.
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