CN105692649A - Preparation method of TS-1 titanium-silicon molecular sieve - Google Patents
Preparation method of TS-1 titanium-silicon molecular sieve Download PDFInfo
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- CN105692649A CN105692649A CN201610056547.2A CN201610056547A CN105692649A CN 105692649 A CN105692649 A CN 105692649A CN 201610056547 A CN201610056547 A CN 201610056547A CN 105692649 A CN105692649 A CN 105692649A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 25
- 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 25
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000003756 stirring Methods 0.000 claims abstract description 41
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 5
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005287 template synthesis Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 grade Chemical compound 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 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
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a preparation method of a TS-1 titanium-silicon molecular sieve. The preparation method of the TS-1 titanium-silicon molecular sieve comprises the following steps: putting a tetrapropylammonium hydroxide aqueous solution into a reaction kettle, stirring at a certain rotation speed, adding organic amine into the reaction kettle, and closing a kettle cover; then adding a mixed solution of an organic silicon source and fatty alcohol into the reaction kettle, and stirring for a certain time; finally adding a mixed solution of the organic silicon source and fatty acid into the reaction kettle, and continuing to stir for a certain time; subsequently increasing the temperature of the mixed solution to remove excess ethyl alcohol; increasing the temperature to the reaction temperature after ending, reacting for a certain time and then reducing the temperature to the room temperature; washing the obtained reaction solution, then drying and roasting the reaction solution to obtain the titanium-silicon molecular sieve. The preparation method of the TS-1 titanium-silicon molecular sieve is capable of actively controlling the particle size of the TS-1 titanium-silicon molecular sieve according to the reaction requirements to obtain the molecular sieve with excellent properties.
Description
Technical field
The invention belongs to petrochemical industry catalysis technical field, the preparation method being specifically related to a kind of TS-1 HTS。
Background technology
TS-1 HTS is that transition metal titanium is introduced a kind of novel titanosilicate with excellent selective paraffin oxidation catalytic performance formed in the framework of molecular sieve with MFI structure。It not only has the catalysed oxidn of titanium, and has the shape effect of selecting of MFI and excellent stability, has excellent oxidisability and specific selectivity, can be widely applied in the organic oxidation reactions such as benzene, phenol, alcohols, ethers。Current cyclohexanone oxamidinating and epoxidation of propylene etc. have been carried out industrialized production, in addition the green catalysis system of TS-1 HTS and hydrogen peroxide composition, it is to avoid the problem of complex process and contaminated environment, it may have good prospects for commercial application。
1981, USP4410501 make public for the first time TS-1 with become method, through development and the research of 40 years, the Hydrothermal Synthesis of current TS-1 has formed two kinds of systems, one is to adopt TPAOH (TPAOH) to do template synthesis of titanium silicon molecular sieve, is called that classical formalism, another kind are to adopt cheap 4-propyl bromide to be template synthesis TS-1, it is called cheap system, in addition with multiple methods such as isomorphous substitution。But being because Ti-O key relatively Si-O bond distance, it is relatively difficult that titanium atom enters skeleton, the TS-1 of therefore current synthetic method synthesis can produce extra-framework titanium, and TS-1 is had a negative impact。First extra-framework titanium itself does not have catalytic oxidation activity but can cause a large amount of decomposition of hydrogen peroxide, thus causes the reduction of TS-1 catalytic performance；Secondly, the content of extra-framework titanium is unmanageable, and this causes that the activity stability of HTS is poor, so constrains the commercial Application of TS-1。In order to extra-framework titanium being reduced the performance to promote molecular sieve, a lot of researchs modified for TS-1 at present。In recent years, Mater.Chem.andPhy., 2011,125 (1-2): 286, Chem.Lett., 2010,39 (4): 330, J.Mater.Chem., 2010,20 (45): 10193, Micro.Meso.Mater., 2008,112 (1-3): 450 conducting in-depth research about hollow molecular sieve such as grade, it has also become the study hotspot in the fields such as chemistry and new material science。It is shown that modified can the generation in TS-1 of inorganic base or organic base, is conducive to the diffusion of reactant and product at hole。Patent CN99126289.1 adopts this thinking that TS-1 molecular screen primary powder is processed, and obtains catalytic inner with mesoporous hollow molecular sieve。
Additionally, also there is material impact in its life-span by the size of TS-1 HTS itself, particle diameter too conference increases the desorption difficulty of product, causes molecular sieve pore passage to block, in turn results in the inactivation of molecular sieve。Therefore, its size that controls of the influence factor targeted that study TS-1 HTS particle diameter has important meaning。
Summary of the invention
In view of this, it is contemplated that the preparation method proposing a kind of TS-1 HTS, it is achieved that controlledization of HTS particle diameter, and then by changing particle diameter, the molecular sieve of catalysis good activity is obtained。
For reaching above-mentioned purpose, the technical scheme is that and be achieved in that:
The preparation method of a kind of TS-1 HTS, comprises the steps:
1) putting in reactor by the TPAOH aqueous solution that mass fraction is 5-20%, rotating speed is under the stirring of 50-300r/min, adds in reactor by organic amine mixed liquor with the speed of 10-50ml/min, continues stirring 10-300min after having added；Preferably, the mass fraction of TPAOH aqueous solution is 8-14%, stirs under rotating speed 100-150r/min, and described organic amine mixed liquor, with the speed of 20-30ml/min, continues stirring 60-100min after having added；
2) mixed liquor of organosilicon source and fatty alcohol is added in reactor with the speed of 10-50ml/min, at 15～25 DEG C, after having added, continue stirring 10-300min；Preferably, add reactor with the speed of 20-30ml/min, at 20 DEG C, stir 60-100min；
3) mixed liquor of organic titanium source and fatty acid is added in reactor with the speed of 1-5ml/min, at 15～25 DEG C, after having added, continue stirring 10-300min；Preferably, at 20 DEG C, 60-100min is stirred；
4) by step 3) mixed liquor prepared is warming up to 40-100 DEG C with the speed of 1-15 DEG C/min, and open vacuum condensing system, maintain 1-10h, to remove unnecessary ethanol；Preferably, it is warming up to 50-80 DEG C with the speed of 5-8 DEG C/min, opens vacuum condensing system, maintain 2-4h；
5) except the mass fraction of ethanol contained in mixed liquor after alcohol is 2-20%；After terminating except alcohol, above-mentioned mixed liquor is warming up to 70-190 DEG C with the speed of 1-15 DEG C/min, reacts 10-120h, be down to room temperature；Preferably, the mass fraction of contained ethanol is 5-10%, is warming up to 150-180 DEG C with the speed of 5-8 DEG C/min, reacts 30-70h；
6) gained reactant liquor with deionized water wash to the pH of filtrate be 7-11；
7) dried, at 500-650 DEG C, roasting 2-12h, obtains titanium-silicon molecular sieve catalyst；Preferably, 6-10h is bakeed。
Preferably, described organic amine is the one in triethylamine, Tri-n-Propylamine, n-butylamine, di-n-propylamine, n-propylamine。
Preferably, described organosilicon source is the one in tetraethyl orthosilicate, Ludox, Silicon chloride.。
Preferably, described fatty alcohol is the one in methanol, ethanol, propanol, the tert-butyl alcohol。
Preferably, described organic titanium source is the one in butyl titanate, titanium tetrachloride。
Preferably, described fatty acid is the one in formic acid, glacial acetic acid。
Preferably, the mol ratio of described organosilicon source and fatty alcohol is 1:(2-10)；Preferably, for 1:(4-6)。
Preferably, described organosilicon source is (3-10) with the mol ratio of TPAOH: 1；Preferably, (4-6): 1。
Preferably, described organic titanium source is (2-10) with the mol ratio of fatty acid: 1；Preferably, for (4-6): 1。
Preferably, described organic titanium source is 1:(10-100 with the mol ratio in organosilicon source)；Preferably, 1:(20-30)。
Present invention also offers HTS prepared by the preparation method of TS-1 HTS as above application in synthesizing cyclohexane 1 ketoxime。
Relative to prior art, the preparation method of TS-1 HTS of the present invention, have the advantage that
1, present invention achieves TS-1 HTS size tunable；By regulating organic formwork agent and organosilicon source mol ratio, controlling HTS particle diameter except conditions such as alcohol amount, crystallization temperatures；The TS-1 HTS of preparation utilizes the mean diameter that Malvern ParticleSizer records to be 200-550nm；Wider range。
2, after the HTS loading catalyst that prepared by the present invention, in synthesizing cyclohexane 1 ketoxime, the selectivity of Ketohexamethylene conversion ratio and Ketohexamethylene is higher。
Detailed description of the invention
The present invention is described in detail below in conjunction with embodiment。
Embodiment 1
Putting in reactor by the TPAOH aqueous solution that 1kg mass fraction is 8%, rotating speed is under the stirring of 100r/min, adds in reactor by 10g triethylamine with the speed of 20ml/min, continues stirring 60min after having added。Then adding in reactor with the speed of 20ml/min after Silicon chloride. and methanol being mixed with 1:4, wherein Silicon chloride. is 4:1 with the mol ratio of TPAOH, continues stirring 60min after having added at 20 DEG C。Adding in reactor with the speed of 1ml/min after finally being mixed with 4:1 with formic acid by titanium tetrachloride, wherein titanium tetrachloride is 1:20 with the mol ratio of Silicon chloride., continues stirring 60min after having added at 20 DEG C。
The mixed liquor above-mentioned preparation completed is warming up to 50 DEG C with the speed of 5 DEG C/min, opens vacuum condensing system, maintains 2h, to remove unnecessary ethanol。Except the mass fraction of ethanol contained in mixed liquor after alcohol is 5%。After terminating except alcohol, above-mentioned mixed liquor is warming up to 150 DEG C with the speed of 5 DEG C/min, reacts 30h, be down to room temperature。Gained reactant liquor is with the pH=7 of deionized water wash to filtrate。After drying, at 500 DEG C, roasting 6h, obtains titanium-silicon molecular sieve catalyst。
Embodiment 2
Putting in reactor by the TPAOH aqueous solution that 1kg mass fraction is 14%, rotating speed is under the stirring of 150r/min, adds in reactor by 100g di-n-propylamine with the speed of 30ml/min, continues stirring 100min after having added。Then adding in reactor with the speed of 30ml/min after Ludox and ethanol being mixed with 1:6, wherein Ludox is 6:1 with the mol ratio of TPAOH, continues stirring 100min after having added at 20 DEG C。Adding in reactor with the speed of 5ml/min after finally being mixed with 6:1 with glacial acetic acid by butyl titanate, wherein butyl titanate is 1:30 with the mol ratio of Ludox, continues stirring 100min after having added at 20 DEG C。
The mixed liquor above-mentioned preparation completed is warming up to 80 DEG C with the speed of 8 DEG C/min, opens vacuum condensing system, maintains 4h, to remove unnecessary ethanol。Except the mass fraction of ethanol contained in mixed liquor after alcohol is 10%。After terminating except alcohol, above-mentioned mixed liquor is warming up to 180 DEG C with the speed of 8 DEG C/min, reacts 70h, be down to room temperature。Gained reactant liquor is with the pH=11 of deionized water wash to filtrate。After drying, at 650 DEG C, roasting 10h, obtains titanium-silicon molecular sieve catalyst。
Embodiment 3
Putting in reactor by the TPAOH aqueous solution that 1kg mass fraction is 10%, rotating speed is under the stirring of 120r/min, adds in reactor by 50g n-butylamine with the speed of 25ml/min, continues stirring 80min after having added。Then adding in reactor with the speed of 25ml/min after silester and ethanol being mixed with 1:5, wherein silester is 5:1 with the mol ratio of TPAOH, continues stirring 80min after having added at 20 DEG C。Adding in reactor with the speed of 3ml/min after finally being mixed with 5:1 with glacial acetic acid by butyl titanate, wherein butyl titanate is 1:25 with the mol ratio of silester, continues stirring 80min after having added at 20 DEG C。
The mixed liquor above-mentioned preparation completed is warming up to 60 DEG C with the speed of 6 DEG C/min, opens vacuum condensing system, maintains 3h, to remove unnecessary ethanol。Except the mass fraction of ethanol contained in mixed liquor after alcohol is 10%。After terminating except alcohol, above-mentioned mixed liquor is warming up to 170 DEG C with the speed of 8 DEG C/min, reacts 40h, be down to room temperature。Gained reactant liquor is with the pH=8 of deionized water wash to filtrate。After drying, at 550 DEG C, roasting 8h, obtains titanium-silicon molecular sieve catalyst。
Embodiment 4
Putting in reactor by the TPAOH aqueous solution that 1kg mass fraction is 12%, rotating speed is under the stirring of 130r/min, adds in reactor by 50g n-butylamine with the speed of 25ml/min, continues stirring 90min after having added。Then adding in reactor with the speed of 25ml/min after silester and ethanol being mixed with 1:5, wherein silester is 5:1 with the mol ratio of TPAOH, continues stirring 90min after having added at 20 DEG C。Adding in reactor with the speed of 5ml/min after finally being mixed with 5:1 with glacial acetic acid by butyl titanate, wherein butyl titanate is 1:24 with the mol ratio of silester, continues stirring 90min after having added at 20 DEG C。
The mixed liquor above-mentioned preparation completed is warming up to 70 DEG C with the speed of 7 DEG C/min, opens vacuum condensing system, maintains 3h, to remove unnecessary ethanol。Except the mass fraction of ethanol contained in mixed liquor after alcohol is 8%。After terminating except alcohol, above-mentioned mixed liquor is warming up to 170 DEG C with the speed of 8 DEG C/min, reacts 40h, be down to room temperature。Gained reactant liquor is with the pH=8 of deionized water wash to filtrate。After drying, at 550 DEG C, roasting 8h, obtains titanium-silicon molecular sieve catalyst。
Embodiment 5
Putting in reactor by the TPAOH aqueous solution that 1kg mass fraction is 13%, rotating speed is under the stirring of 120r/min, adds in reactor by 50g n-butylamine with the speed of 25ml/min, continues stirring 90min after having added。Then adding in reactor with the speed of 25ml/min after silester and ethanol being mixed with 1:5, wherein silester is 5:1 with the mol ratio of TPAOH, continues stirring 100min after having added at 20 DEG C。Adding in reactor with the speed of 4ml/min after finally being mixed with 5:1 with glacial acetic acid by butyl titanate, wherein butyl titanate is 1:28 with the mol ratio of silester, continues stirring 70min after having added at 20 DEG C。
The mixed liquor above-mentioned preparation completed is warming up to 70 DEG C with the speed of 158 DEG C/min, opens vacuum condensing system, maintains 3h, to remove unnecessary ethanol。Except the mass fraction of ethanol contained in mixed liquor after alcohol is 8%。After terminating except alcohol, above-mentioned mixed liquor is warming up to 170 DEG C with the speed of 8 DEG C/min, reacts 40h, be down to room temperature。Gained reactant liquor is with the pH=8 of deionized water wash to filtrate。After drying, at 550 DEG C, roasting 7h, obtains titanium-silicon molecular sieve catalyst。
Embodiment 6
Putting in reactor by the TPAOH aqueous solution that 1kg mass fraction is 8%, rotating speed is under the stirring of 100r/min, adds in reactor by 50g n-butylamine with the speed of 20ml/min, continues stirring 100min after having added。Then adding in reactor with the speed of 20ml/min after silester and ethanol being mixed with 1:5, wherein silester is 4:1 with the mol ratio of TPAOH, continues stirring 70min after having added at 20 DEG C。Adding in reactor with the speed of 5ml/min after finally being mixed with 5:1 with glacial acetic acid by butyl titanate, wherein butyl titanate is 1:30 with the mol ratio of silester, continues stirring 100min after having added at 20 DEG C。
The mixed liquor above-mentioned preparation completed is warming up to 80 DEG C with the speed of 15 DEG C/min, opens vacuum condensing system, maintains 3h, to remove unnecessary ethanol。Except the mass fraction of ethanol contained in mixed liquor after alcohol is 8%。After terminating except alcohol, above-mentioned mixed liquor is warming up to 170 DEG C with the speed of 8 DEG C/min, reacts 40h, be down to room temperature。Gained reactant liquor is with the pH=8 of deionized water wash to filtrate。After drying, at 550 DEG C, roasting 9h, obtains titanium-silicon molecular sieve catalyst。
The evaluation methodology of TS-1 HTS is as follows:
Cyclohexanone oxamidinating reaction carries out on the continuous slurry-bed reaction device of normal pressure, wherein molecular sieve completes with the ceramic membrane adopting aperture to be 100nm that separates of liquid reaction mixture, loaded catalyst is 100g, raw material cyclohexanone, hydrogen peroxide, ammonia mix with certain proportion, solvent is made with the tert-butyl alcohol, reaction temperature is 70～90 DEG C, every 2h samples, use gas chromatographic analysis product, obtain the conversion ratio of Ketohexamethylene and the selectivity of Ketohexamethylene, when low conversion rate judges that catalyst is as inactivation in 90% time。The molecular sieve of embodiment 1～embodiment 6 preparation carries out the evaluation of performance under identical conditions, and result is as shown in the table:
The different embodiment prepared catalyst cyclohexanone oxamidinating evaluation result of table 1
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention。
Claims (10)
1. the preparation method of a TS-1 HTS, it is characterised in that: comprise the steps:
1) putting in reactor by the TPAOH aqueous solution that mass fraction is 5-20%, rotating speed is under the stirring of 50-300r/min, adds in reactor by organic amine mixed liquor with the speed of 10-50ml/min, continues stirring 10-300min after having added；Preferably, the mass fraction of TPAOH aqueous solution is 8-14%, stirs under rotating speed 100-150r/min, and described organic amine mixed liquor, with the speed of 20-30ml/min, continues stirring 60-100min after having added；
2) mixed liquor of organosilicon source and fatty alcohol is added in reactor with the speed of 10-50ml/min, at 15～25 DEG C, after having added, continue stirring 10-300min；Preferably, add reactor with the speed of 20-30ml/min, at 20 DEG C, stir 60-100min；
3) mixed liquor of organic titanium source and fatty acid is added in reactor with the speed of 1-5ml/min, at 15～25 DEG C, after having added, continue stirring 10-300min；Preferably, at 20 DEG C, 60-100min is stirred；
4) by step 3) mixed liquor prepared is warming up to 40-100 DEG C with the speed of 1-15 DEG C/min, and open vacuum condensing system, maintain 1-10h, to remove unnecessary ethanol；Preferably, it is warming up to 50-80 DEG C with the speed of 5-8 DEG C/min, opens vacuum condensing system, maintain 2-4h；
5) except the mass fraction of ethanol contained in mixed liquor after alcohol is 2-20%；After terminating except alcohol, above-mentioned mixed liquor is warming up to 70-190 DEG C with the speed of 1-15 DEG C/min, reacts 10-120h, be down to room temperature；Preferably, the mass fraction of contained ethanol is 5-10%, is warming up to 150-180 DEG C with the speed of 5-8 DEG C/min, reacts 30-70h；
6) gained reactant liquor with deionized water wash to the pH of filtrate be 7-11；
7) dried, at 500-650 DEG C, roasting 2-12h, obtains titanium-silicon molecular sieve catalyst；Preferably, 6-10h is bakeed。
2. the preparation method of TS-1 HTS according to claim 1, it is characterised in that: described organic amine is the one in triethylamine, Tri-n-Propylamine, n-butylamine, di-n-propylamine, n-propylamine。
3. the preparation method of TS-1 HTS according to claim 1, it is characterised in that: described organosilicon source is the one in tetraethyl orthosilicate, Ludox, Silicon chloride.。
4. the preparation method of TS-1 HTS according to claim 1, it is characterised in that: described fatty alcohol is the one in methanol, ethanol, propanol, the tert-butyl alcohol。
5. the preparation method of TS-1 HTS according to claim 1, it is characterised in that: described organic titanium source is the one in butyl titanate, titanium tetrachloride。
6. the preparation method of TS-1 HTS according to claim 1, it is characterised in that: described fatty acid is the one in formic acid, glacial acetic acid。
7. the preparation method of the TS-1 HTS according to any one of claim 1～6, it is characterised in that: the mol ratio of described organosilicon source and fatty alcohol is 1:(4-6)；Preferably, for 1:5；The mol ratio of described organosilicon source and TPAOH is (3-10): 1；Preferably, for (4-6): 1。
8. the preparation method of the TS-1 HTS according to any one of claim 1～6, it is characterised in that: the mol ratio of described organic titanium source and fatty acid is (4-6): 1；Preferably, for 5:1。
9. the preparation method of the TS-1 HTS according to any one of claim 1～6, it is characterised in that: the mol ratio in described organic titanium source and organosilicon source is 1:(10-100)；Preferably, for 1:(20-30)。
10. the HTS that prepared by the preparation method of the TS-1 HTS described in any one of claim 1～9 application in synthesizing cyclohexane 1 ketoxime。
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| CN109721066A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
| CN109721064A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
| CN110668463A (en) * | 2019-11-06 | 2020-01-10 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
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| CN104528759A (en) * | 2014-12-22 | 2015-04-22 | 中国天辰工程有限公司 | Preparation method of TS-1 titanium silicalite molecular sieve |
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| CN103787360A (en) * | 2013-12-26 | 2014-05-14 | 中国天辰工程有限公司 | Preparation method of full-process TS-1 titanium-silicate mesoporous molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109721066A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
| CN109721064A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method |
| CN109721064B (en) * | 2017-10-31 | 2020-10-27 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN109721066B (en) * | 2017-10-31 | 2021-02-09 | 中国石油化工股份有限公司 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
| CN110668463A (en) * | 2019-11-06 | 2020-01-10 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
| CN110668463B (en) * | 2019-11-06 | 2021-04-02 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
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