CN1398674A - Composite Ti-Si catalyst and its in-situ forming prepn process - Google Patents
Composite Ti-Si catalyst and its in-situ forming prepn process Download PDFInfo
- Publication number
- CN1398674A CN1398674A CN 02126775 CN02126775A CN1398674A CN 1398674 A CN1398674 A CN 1398674A CN 02126775 CN02126775 CN 02126775 CN 02126775 A CN02126775 A CN 02126775A CN 1398674 A CN1398674 A CN 1398674A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- composite
- inorganic oxide
- preparation
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 229910004339 Ti-Si Inorganic materials 0.000 title claims abstract description 47
- 229910010978 Ti—Si Inorganic materials 0.000 title claims abstract description 47
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000001788 irregular Effects 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 9
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- -1 amine compound Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000035800 maturation Effects 0.000 claims description 2
- 239000012452 mother liquor Substances 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
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000010952 in-situ formation Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 40
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000011324 bead Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000006735 epoxidation reaction Methods 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A composite Ti-Si catalyst consists of MFI structure Ti-Si molecular sieve 1.0-80.0 wt% and inorganic oxide 20.0-99.0 wt%. It is prepared by the in-situ forming process, that is, inorganic oxide is introduced into Ti-Si molecular sieve hydrothermal synthesis system comprising Si source, Ti source, template agent, alkali and distilled water so that Ti-Si molecular sieve grows in the in-situ formation of inorganic oxide. The obtained composite Ti-Si catalyst is spherical or irregular particle, and may be used directly in fixed bed, mobile bed or catalytic rectifying reactor for the catalytic oxidation between propylene and hydrogen peroxide to product epoxy propane.
Description
Technical field the present invention relates to a kind of composite Ti-Si catalyst and preparation method thereof.
Background technology U.S. Pat P 4,410,501 had once disclosed HTS of MFI structure and preparation method thereof, it is to be template agent and alkali source with TPAOH (abbreviation TPAOH), is the silicon source with tetraalkyl esters of silicon acis or Ludox, and hydrolyzable titanium compound is the titanium source, they are mixed by certain molar ratio, mixture in autoclave, under 130 ℃-200 ℃, hydrothermal crystallizing 6-30 days.
The HTS of MFI structure, in a series of catalytic oxidation systems with hydrogen peroxide as oxidant, has superior catalytic performance, it can be applicable in the reactions such as alkene epoxidation, ammoxidation of cyclohexanone, aromatic hydrocarbons hydroxylating, saturated hydrocarbons oxidation, oxidation of alcohols, has the reaction selectivity height, the reaction condition gentleness, characteristics such as technology is simple and safe, and is environmentally friendly.
It is oxidant that another piece U.S. Pat P 4,833,260 has introduced with the hydrogen peroxide, and HTS is the olefin epoxidation process of catalyst.Reaction temperature is 0-150 ℃, and pressure is 1-100atm, and preferred solvent is methyl alcohol, the tert-butyl alcohol, acetone.With rare hydrogen peroxide is oxidant, and alkene epoxidations such as ethene, propylene, chloropropene, 2-butylene, 1-octene have all obtained result preferably.But wherein used HTS is powdery or simple compressing tablet, can not be used for industrial continuous device.
Usually the synthetic HTS that obtains of hydro-thermal is the fine powder of grain size between 0.1-5 μ m, be difficult to separate with reaction medium, can not satisfy the requirement of commercial plant to aspects such as catalyst strength, life-span, shapes, therefore, the forming process of HTS is an indispensable step of its industrial applications.
Consider that from the commercial Application angle EP 0200260 has studied the moulding problem of titanium-silicon molecular sieve catalyst.At TS-1 crystal periphery oligomerisation SiO
2, spray shaping has been made the high strength microballoon about average grain 20 μ m then.In batch reactor, carry out propylene ring oxidation reaction, H
2O
2Conversion ratio reach 97%, expoxy propane (PO) selectivity reaches 92%.Successive reaction in fixed bed reactors, stable after 40 hours, through running in 400 hours, H
2O
2Conversion ratio is stabilized in 60%, and the PO selectivity is 93%.A large amount of TPAOH that use in this catalyst preparation process, cost is higher, and its activity can not satisfy industrial requirements.
USP 5,756, and 778 have disclosed the composite catalyst that the in-situ crystallization HTS is formed on MFI or MEL structure Si-Al molecular sieve.But Si-Al molecular sieve can be introduced strong acid center in composite catalyst, promote expoxy propane that propylene ring oxidation reaction generates further with solvent generation side reaction.
USP 5,736, and 479 have disclosed the composite catalyst of being made up of the HTS of metal oxide and in-situ crystallization generation on metal oxide.Metal oxide is meant TiO
2, SiO
2, ZrO
2, Al
2O
3Or their mixture.HTS accounts for the 1-90% (weight) of composite catalyst in the catalyst.This Preparation of catalysts method is: in the presence of template agent TPAOH, the mixture in titanium source and silicon source is deposited on the metal oxide, or fully flood the metal oxide of deposition of silica with titanium compound, 150-200 ℃, self-generated pressure reaction 48-240 hour down in autoclave again.But used metal oxide is the fine powder of≤32 μ m, and the composite catalyst of HTS in-situ crystallization generation thereon still is a powdery, needs further moulding, just can be used for industrial reactor.
Do not see so far to have inorganic oxide is introduced HTS hydro-thermal synthetic system, make HTS growth in situ on inorganic oxide, make composite Ti-Si catalyst, be directly used in the report of fixed bed, moving bed or catalytic distillation reaction unit.
The objective of the invention is to provide on the basis of existing technology a kind of and form, be used for the composite catalyst of propylene ring oxidation reaction, and the preparation method of this composite catalyst is provided by MFI structure titanium silicon molecular sieve and inorganic oxide.
Summary of the invention composite Ti-Si catalyst of the present invention is formed spherical or irregular particle by the MFI structure titanium silicon molecular sieve of 1.0-80.0% (weight) and the inorganic oxide of 20.0-99.0% (weight).
The formation of HTS needs silicon source, titanium source, template agent, alkali and distilled water.
It is (R that the silicon source is selected from silica gel, Ludox, white carbon black or general formula
1O)
4The organosilicon acid esters of Si, R in the formula
1Alkyl for 1-4 carbon atom.
The titanium source is organic titanate or inorganic titanium salt.The general formula of organic titanate is (R
2O)
4Ti, R in the formula
2Alkyl for 1-4 carbon atom; Inorganic titanium salt is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4
The template agent is selected from tetraalkyl ammonium bromide (TRABr) or its corresponding quaternary ammonium base (TRAOH), and wherein alkyl R is selected from ethyl, propyl group, butyl.
Alkali is ammoniacal liquor or organic amine, and organic amine is that general formula is R
m 3[NH
(3-m)]
nFat amine compound, R wherein
3Alkyl for 1-6 carbon atom; M=1-3, n=1 or 2, fat amine compound are selected from a kind of in ethamine, n-propylamine, n-butylamine, ethylenediamine, hexamethylene diamine, diethylamine, triethylamine, tripropyl amine (TPA) or the tri-n-butylamine.
Inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2O
3, Na
2O, CaO, K
2O, PbO or compound in them or mixture.Inorganic oxide is spherical or the irregular particle shape, and particle grain size is 0.1-20mm.
The in-situ forming preparation process of composite Ti-Si catalyst, be that inorganic oxide is incorporated into the silicon source: the titanium source: template agent: alkali: distilled water=1: 0 001-0.2: 0.03-0.5: 0.1-5: in the HTS hydro-thermal synthetic system that the 10-200 mol ratio is formed, before the normal crystallization, can be at 0-100 ℃ of following low temperature maturation 1-5 days, make the MFI structure titanium silicon molecular sieve separate out nucleus and growth in situ in inorganic oxide surface, the normal crystallization temperature is 120-200 ℃, crystallization time is 1-10 days, then composite is separated with mother liquor, drying, roasting is made.The composite catalyst that makes is again through 1-5 formed in situ, to increase the load capacity of MFI structure titanium silicon molecular sieve.
Composite Ti-Si catalyst profile provided by the invention is spherical or irregular particle, can directly use in fixed bed, moving bed or catalytic distillation propylene ring oxidation reaction device.
Composite Ti-Si catalyst of the present invention can be under common process conditions, be used for reactions such as alkene epoxidation, styrene oxidation, ammoxidation of cyclohexanone, aromatic hydrocarbons hydroxylating, saturated hydrocarbons oxidation, oxidation of alcohols, be particularly useful for the hydrogen peroxide is in the propylene ring oxidation reaction of oxidant, reaction temperature is 0-100 ℃, pressure 1-50atm, methyl alcohol is solvent, propylene/H
2O
2=1-10: 1.
Composite Ti-Si catalyst catalytic epoxidation of propone reaction in fixed-bed reactor of adopting the formed in situ method to make, the running reaction result saw Table 1 in 47 hours:
The table 1 composite catalyst catalytic epoxidation of propone reaction result time (hour) H
2O
2Conversion ratio (%) expoxy propane selectivity propylene glycol monomethyl ether selectivity
(%) (%) 8 91.4 82.9 15.2 23 95.9 88.3 11.1 26 94.4 82.5 16.5 29 94.8 80.8 18.1 32 93.8 84.1 14.8 35 94.8 86.1 13.6 47 92.7 89.2 10.8 mean values 94.0 84.8 14.3
The reaction condition of table 1 data: 55 ℃ of temperature, pressure 3.0Mpa, C
3H
6/ H
2O
2Mol ratio 4.17, solvent methanol, H
2O
20.85mol/l,
Propylene weight air speed 0.10h
-1
By table 1 as seen, in 47 hours, H
2O
2Conversion ratio remains on more than 90%, and expoxy propane selectivity mean value reaches 84.8% (accessory substance is propylene glycol monomethyl ether and the propane diols that expoxy propane further forms with solvent reaction).Show that composite catalyst provided by the invention is being in the propylene ring oxidation reaction of oxidant with the hydrogen peroxide, has higher activity and epoxidation selectivity.
Effect of the present invention: adopt the formed in situ legal system to be equipped with composite Ti-Si catalyst, the HTS hydro-thermal is synthetic, HTS moulding is integrated in a step to be carried out, and the gained catalyst can directly use in fixed bed, moving bed or catalytic distillation reaction unit.
The specific embodiment
Embodiment 1
Get the 1.2ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g 4-propyl bromide (TPABr), stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the silicon ball of 6.0308g particle diameter 3mm,,,, obtain the 5.7020g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.Because the silicon ball is partly dissolved in the HTS hydro-thermal synthetic system of high-temperature alkaline, the silicon ball of composite Ti-Si catalyst quality before than moulding lacks 5.45% (weight).
Embodiment 2
Get the 1.2ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the silicon ball of 5.9039g particle diameter 1mm,,,, obtain the 4.7701g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.Because the silicon ball is partly dissolved in the HTS hydro-thermal synthetic system of high-temperature alkaline, the silicon ball of composite Ti-Si catalyst quality before than moulding lacks 19.2% (weight).
Embodiment 3
Get the 1.2ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 6.3182g particle diameter 0.9mm,,,, obtain the 6.5820g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 4.2% (weight).
Embodiment 4
Get the 12ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 20ml deionized water of 23.2g 30% (weight) mixed with 3.2g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 7ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 6.1228g particle diameter 1.8mm,,,, obtain the 6.3838g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 4.3% (weight).
Embodiment 5
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 6.0020g particle diameter 0.9mm,,,, obtain the 6.1586g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours through conventional method filtration, washing, drying at 170 ℃ of heating crystallization 4-9 days.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 2.6% (weight).
Embodiment 6
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the alumina silicate bead of 5.9934g particle diameter 0.9mm, 25 ℃ of ageings 2 days, then at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying,, obtain the 6.1676g composite Ti-Si catalyst in 540 ℃ of roastings 5 hours.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 2.9% (weight).
Embodiment 7
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the composite Ti-Si catalyst that 6.1586g embodiment 5 makes, at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours, obtain the 6.2848g composite Ti-Si catalyst.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 4.7% (weight).
Embodiment 8
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the composite Ti-Si catalyst that 6.2848g embodiment 7 makes, at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours, obtain the 6.3890g composite Ti-Si catalyst.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 6.4% (weight).
Embodiment 9
Get the 0.6ml butyl titanate, under 0-5 ℃, slowly splash in the 28ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 28ml deionized water of 11.6g 30% (weight) mixed with 1.6g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 3.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, add the composite Ti-Si catalyst that 6.3890g embodiment 8 makes, at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours, obtain the 6.4834g composite Ti-Si catalyst.The alumina silicate bead of composite Ti-Si catalyst quality before than moulding increases by 8.0% (weight).
Embodiment 10
Get the 3.8ml butyl titanate, under 0-5 ℃, slowly splash in the 180ml deionized water, drip off the back and stir 30min, get A solution.In another container, Ludox (Haiyang Chemical Plant, Qingdao's product), the 210ml deionized water of 72.4g 30% (weight) mixed with 10.0g TPABr, stir 30min, B solution.A solution is added in the B solution, stir 30min.Add the 21.5ml n-butylamine again, stir 60min.Above-mentioned reactant mixture is packed in the autoclave, and adding the 9.0020g granularity is the 0.9-1.25mm ceramic bead, 25 ℃ of ageings 2 days, then at 170 ℃ of heating crystallization 4-9 days, through conventional method filtration, washing, drying, in 540 ℃ of roastings 5 hours.Resultant composite is carried out formed in situ once more, obtain the 9.4742g composite Ti-Si catalyst at last.The ceramic bead of composite Ti-Si catalyst quality before than moulding increases by 5.2% (weight).
Embodiment 11
The present embodiment explanation is by the catalytic performance of composite Ti-Si catalyst in propylene ring oxidation reaction of the embodiment of the invention 10 preparations.
8.0g is packed in the pressurization static bed reactor of stainless steel by the composite Ti-Si catalyst of the embodiment of the invention 10 preparation, and maintenances system pressure is 3.0Mpa, and reaction temperature is 55 ℃, unlatching H
2O
2Methanol solution and the inlet valve of propylene, react.H
2O
2Concentration is 0.85mol/l in methanol solution.C
3H
6/ H
2O
2(mol ratio)=4.17.The propylene weight air speed is 0.10h
-1Timing sample analysis from the material receiving tube in cryostat.Iodimetric analysis H
2O
2Concentration.With day island proper Tianjin GC-8A of company type gas chromatograph analytical reactions product.React 47 hours the results are shown in Table 1.
Claims (7)
1, a kind of composite Ti-Si catalyst of being made by silicon source, titanium source, template agent, alkali, distilled water and inorganic oxide reaction is characterized in that this catalyst forms spherical or irregular particle by the MFI structure titanium silicon molecular sieve of 1.0-80.0% (weight) and the inorganic oxide of 20.0-99.0% (weight).
2,, it is characterized in that inorganic oxide is selected from TiO according to the described composite Ti-Si catalyst of claim 1
2, SiO
2, ZrO
2, Al
2O
3, Na
2O, CaO, K
2O, PbO or compound in them or mixture, inorganic oxide are spherical or the irregular particle shape, and particle diameter is 0.1-20mm.
3, a kind of preparation method with the described composite Ti-Si catalyst of claim 1, it is characterized in that this in-situ forming preparation process is that inorganic oxide is incorporated into the silicon source: titanium source: template agent: alkali: the mol ratio of distilled water is 1: in the MFI structure titanium silicon molecular sieve hydro-thermal synthetic system that 0.001-0.2: 0.03-0.5: 0.1-5: 10-200 forms, before the normal crystallization, can be at 0-100 ℃ of following low temperature maturation 1-5 days, make the MFI structure titanium silicon molecular sieve separate out nucleus and growth in situ in inorganic oxide surface, again at 120-200 ℃ of normal crystallization 1-10 days, then composite is separated with mother liquor, drying, roasting is made; The composite catalyst that makes is again through 1-5 formed in situ.
4,, it is characterized in that it is (R that the used silicon source of this method is selected from silica gel, Ludox, white carbon black or general formula according to the preparation method of the described composite Ti-Si catalyst of claim 3
1O)
4The organosilicon acid esters of Si, R in the formula
1Alkyl for 1-4 carbon atom.
5,, it is characterized in that the used titanium source of this method is selected from TiCl according to the preparation method of the described composite Ti-Si catalyst of claim 3
4, TiCl
3, TiOCl
2, TiOSO
4Or general formula is (R
2O)
4The organic titanate of Ti, wherein R
2Alkyl for 1-4 carbon atom.
6, according to the preparation method of the described composite Ti-Si catalyst of claim 3, it is characterized in that the used template agent of this method is selected from tetraalkyl ammonium bromide TRABr or its corresponding quaternary ammonium base TRAOH, wherein alkyl R is selected from ethyl, propyl group, butyl.
7, according to the preparation method of the described composite Ti-Si catalyst of claim 3, it is characterized in that the used alkali of this method is ammoniacal liquor or organic amine, the general formula of organic amine is R
m 3[NH
(3-m)]
nFat amine compound, R wherein
3Be the alkyl of 1-6 carbon atom, m=1-3, n=1 or 2 one of can be selected from ethamine, n-propylamine, n-butylamine, ethylenediamine, hexamethylene diamine, diethylamine, triethylamine, tripropyl amine (TPA) or the tri-n-butylamine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB021267758A CN1140348C (en) | 2002-07-25 | 2002-07-25 | Composite Ti-Si catalyst and its in-situ forming prepn process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB021267758A CN1140348C (en) | 2002-07-25 | 2002-07-25 | Composite Ti-Si catalyst and its in-situ forming prepn process |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1398674A true CN1398674A (en) | 2003-02-26 |
CN1140348C CN1140348C (en) | 2004-03-03 |
Family
ID=4745802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB021267758A Expired - Fee Related CN1140348C (en) | 2002-07-25 | 2002-07-25 | Composite Ti-Si catalyst and its in-situ forming prepn process |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1140348C (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1330416C (en) * | 2004-01-10 | 2007-08-08 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
WO2008019586A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | An insitu synthesis method of a microsphere catalyst used for converting oxygen compound to olefine |
CN101696019B (en) * | 2009-10-26 | 2011-06-08 | 吉林大学 | Large blocked TS-1 molecular sieve with high catalytic activity and synthetic method thereof |
CN102206147A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexane |
CN102259023A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve catalyst and preparation method and use thereof |
CN102441429A (en) * | 2010-10-11 | 2012-05-09 | 中国石油化工股份有限公司 | Olefin epoxidation catalyst, preparation method, and method for epoxidation of olefin |
CN103706346A (en) * | 2013-12-27 | 2014-04-09 | 江苏晶晶新材料有限公司 | Method for improving activity of anthraquinone degradation product regeneration catalyst |
CN103896881A (en) * | 2012-12-24 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
CN110420134A (en) * | 2019-08-28 | 2019-11-08 | 广州骏朗生物科技有限公司 | A kind of sheet silica/nano TiO 2 composite material and preparation method |
CN111682372A (en) * | 2020-06-30 | 2020-09-18 | 立讯精密工业(昆山)有限公司 | Connector structure |
-
2002
- 2002-07-25 CN CNB021267758A patent/CN1140348C/en not_active Expired - Fee Related
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1330416C (en) * | 2004-01-10 | 2007-08-08 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
WO2008019586A1 (en) * | 2006-08-08 | 2008-02-21 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | An insitu synthesis method of a microsphere catalyst used for converting oxygen compound to olefine |
CN101696019B (en) * | 2009-10-26 | 2011-06-08 | 吉林大学 | Large blocked TS-1 molecular sieve with high catalytic activity and synthetic method thereof |
CN102206147A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexane |
CN102206147B (en) * | 2010-03-31 | 2013-09-04 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexane |
CN102259023B (en) * | 2010-05-27 | 2014-04-30 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve catalyst and preparation method and use thereof |
CN102259023A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Titanium silicalite molecular sieve catalyst and preparation method and use thereof |
CN102441429A (en) * | 2010-10-11 | 2012-05-09 | 中国石油化工股份有限公司 | Olefin epoxidation catalyst, preparation method, and method for epoxidation of olefin |
CN102441429B (en) * | 2010-10-11 | 2013-11-27 | 中国石油化工股份有限公司 | Olefin epoxidation catalyst, preparation method, and method for epoxidation of olefin |
CN103896881B (en) * | 2012-12-24 | 2016-09-07 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
CN103896881A (en) * | 2012-12-24 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
CN103706346B (en) * | 2013-12-27 | 2015-09-16 | 江苏晶晶新材料有限公司 | A kind of method improving activity of anthraquinone degradation product regeneration catalyst |
CN103706346A (en) * | 2013-12-27 | 2014-04-09 | 江苏晶晶新材料有限公司 | Method for improving activity of anthraquinone degradation product regeneration catalyst |
CN110420134A (en) * | 2019-08-28 | 2019-11-08 | 广州骏朗生物科技有限公司 | A kind of sheet silica/nano TiO 2 composite material and preparation method |
CN110420134B (en) * | 2019-08-28 | 2022-04-15 | 广州骏朗生物科技有限公司 | Flaky silica/nano TiO2 composite material and preparation method thereof |
CN111682372A (en) * | 2020-06-30 | 2020-09-18 | 立讯精密工业(昆山)有限公司 | Connector structure |
CN111682372B (en) * | 2020-06-30 | 2022-02-25 | 立讯精密工业(昆山)有限公司 | Connector structure |
Also Published As
Publication number | Publication date |
---|---|
CN1140348C (en) | 2004-03-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1300125C (en) | Direct epoxidation process using a mixed catalyst system | |
CN1314662C (en) | Process for producing cyclohexanone-oxime | |
CN1264831C (en) | Direct epoxidation process using carbonate modifiers | |
US6512128B2 (en) | Process using a titanium-containing silicon oxide catalyst | |
CN1114495C (en) | Process for preparing composite catalyst and its application | |
CN1140348C (en) | Composite Ti-Si catalyst and its in-situ forming prepn process | |
WO2012011124A1 (en) | Ordered mesoporous titanosilicate and the process for the preparation thereof | |
CN1241564A (en) | Epoxidation of olefing using catalyst containing titanostannosilicalites | |
CN1639143A (en) | Method for producing propylene oxide | |
PL173731B1 (en) | Oxidation catalysts | |
US20090234143A1 (en) | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst | |
CN1255393C (en) | Direct epoxidation process using a mixed catalyst system | |
CN1138039A (en) | Integrated process for epoxidation | |
US6720435B2 (en) | Oxirane production method | |
EP1252928B1 (en) | Molded catalyst, process for producing the molded catalyst, and process for producing oxirane compound | |
CN1177758C (en) | Method for the production of a titanium-containing zeolite | |
EP1588762A1 (en) | Method for producing titanium-containing silicon oxide catalyst | |
CA2438882A1 (en) | Process for producing titanium-containing silicon oxide catalyst | |
CN1089279C (en) | Synthesis of titania-silica molecular sieve | |
CN108117087B (en) | Silicon-containing molecular sieve and preparation method thereof | |
CN113083358A (en) | Ti-HMS/carbon nanofiber composite catalyst modified by magnesium-containing compound, preparation and application | |
CN1291982C (en) | Direct epoxidation process using a palladium on niobium-containing support | |
CN1286827C (en) | Epoxidation process using a supported niobium oxide catalyst | |
CN1296134C (en) | Composite titanium-silicon catalyst and its preparation and use | |
CN112717997B (en) | Preparation method of high-activity catalytic oxidation catalyst TS-1 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
DD01 | Delivery of document by public notice |
Addressee: Dalian University of Technology Document name: Notification to Pay the Fees |
|
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040303 Termination date: 20110725 |