CN1296134C - Composite titanium-silicon catalyst and its preparation and use - Google Patents
Composite titanium-silicon catalyst and its preparation and use Download PDFInfo
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- CN1296134C CN1296134C CNB2003101208687A CN200310120868A CN1296134C CN 1296134 C CN1296134 C CN 1296134C CN B2003101208687 A CNB2003101208687 A CN B2003101208687A CN 200310120868 A CN200310120868 A CN 200310120868A CN 1296134 C CN1296134 C CN 1296134C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- 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 20
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 alicyclic ketone Chemical class 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 46
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 40
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000033444 hydroxylation Effects 0.000 abstract 1
- 238000005805 hydroxylation reaction Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical class [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006146 oximation reaction Methods 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- UJBOOUHRTQVGRU-UHFFFAOYSA-N 3-methylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1 UJBOOUHRTQVGRU-UHFFFAOYSA-N 0.000 description 2
- 241001502050 Acis Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 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
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- GPRUGHZJEFRSRF-UHFFFAOYSA-N [O].N.C1(CCCCC1)=O Chemical compound [O].N.C1(CCCCC1)=O GPRUGHZJEFRSRF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001125 extrusion 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
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a composite titanium-silicon catalyst, a preparation method and the application of the catalyst, which provides a composite titanium-silicon catalyst which can be used for alicyclic ketone ammoxidation, alkene epoxidation and aromatic hydrocarbon hydroxylation. The catalyst powder contains 5.0 to 90.0 wt% of titanium-silicon molecular sieve in an MFI structure and 10.0 to 95.0 wt% of graphite. The catalyst is prepared by introducing powdery graphite in a titanium-silicon molecular sieve hydrothermal synthesis system which is composed of a silicon source, a titanium source, a template agent, alkali and distilled water. The obtained composite titanium-silicon catalyst can be used in reaction devices of batch stills or slurry beds.
Description
Technical field the present invention relates to a kind of alicyclic ketone ammoxidation, alkene epoxidation, hydroxylated composite Ti-Si catalyst of aromatic hydrocarbons of can be used for.
Background technology U.S. Pat P 4,410,501 had once disclosed HTS (TS-1) 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, with 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.
U.S. Pat P 4,833, and 260 to have introduced with the hydrogen peroxide be oxidant, and the TS-1 molecular sieve 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.
J Catal, 1996,161:570 has reported alicyclic ketone and H
2O
2, NH
3Oximation reaction.On the TS-1 molecular sieve catalyst, the active order of alicyclic ketone is: cycloheptanone＞cyclopentanone＞cyclohexanone＞cyclooctanone, cyclohexanone＞2-methyl cyclohexanone=3-methyl cyclohexanone＞2,6-dimethylcyclohexanon.Use is during greater than the TS-1 molecular sieve catalyst of 1.5 μ m, the extending influence significantly of cyclohexanone and oxime thereof; When TS-1 crystal grain during less than 0.3 μ m, oximation reaction is active irrelevant with diffusion, and by the activated centre quantity decision in the TS-1 framework of molecular sieve.
The little crystal grain TS-1 of alicyclic ketone oximation reaction molecular sieve has greater activity, but little crystal grain TS-1 molecular sieve preparation cost height, and separates with the reaction medium difficulty, and carrier disperses, moulding so need to add in commercial Application.German patent DE 4240698 has disclosed activated carbon supported HTS and has been used for the corresponding oxime of alicyclic ketone prepared by ammoxidation, and reaction temperature is 20～120 ℃, NH
3/ ketone=1.2～2.5, hydrogen peroxide/ketone=0.8～1.2, active and selectivity is higher than unsupported HTS.But activated carbon supported HTS can not adopt under the conventional air/oxygen roasting mode to regenerate.
U.S. Pat P 2002/0058840 has introduced HTS and Al
2O
3Adopt the method for extrusion or compressing tablet to carry out moulding, HTS/Al
2O
3=0.1～10: 1, make composite Ti-Si catalyst, be used for the corresponding oxime of alicyclic ketone prepared by ammoxidation of 7～20 carbon atoms.
USP 5,637, and 715 have disclosed in-situ crystallization HTS formation composite Ti-Si catalyst on MFI or MEL structure Si-Al molecular sieve, are used for reactions such as ammoxidation of cyclohexanone.
Do not see so far to have the powdered graphite of inertia is introduced HTS hydro-thermal synthetic system, make composite Ti-Si catalyst, be used for alicyclic ketone ammoxidation, alkene epoxidation, the hydroxylated report of aromatic hydrocarbons.
Summary of the invention the purpose of this invention is to provide a kind ofly to be made up of MFI structure titanium silicon molecular sieve and graphite, is used for the composite Ti-Si catalyst and the preparation thereof of reactions such as alicyclic ketone ammoxidation, alkene epoxidation.
Technical solution of the present invention is, a kind of composite Ti-Si catalyst, the powder of being made up of the graphite of 5.0～90.0% MFI structure titanium silicon molecular sieve and 10.0～95.0% by weight percentage.Prioritization scheme is: this compound titanium silicon molecular sieve is the powder that the graphite of 50～90.0% MFI structure titanium silicon molecular sieve and 10.0～50% is formed by weight percentage.
The described a kind of composite Ti-Si catalyst of preparation claim 1, adopt the preparation of formed in situ method, be about to powdered graphite and introduce the HTS hydro-thermal synthetic system of forming by silicon source, titanium source, template agent, alkali and distilled water, make HTS growth in situ on powdered graphite, then composite is separated with mother liquor, drying, roasting are made.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in the alicyclic ketone ammoxidation reaction.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in the ammoxidation of cyclohexanone reaction, and ammoxidation of cyclohexanone reaction response temperature is 60～100 ℃, presses the mol ratio, NH
3/ cyclohexanone=1.0～3.0, hydrogen peroxide/cyclohexanone=0.90～1.20, the tert-butyl alcohol, water, acetone or its mixture are solvent, normal pressure.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in alkene epoxidation, and epoxidation reaction temperature is 0～100 ℃, pressure 1～50atm, methyl alcohol, ethanol, acetone or its mixture are solvent, alkene/H
2O
2=1～10: 1.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in epoxidation of propylene and the 1-butylene epoxidation reaction.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst also can be used for reactions such as aromatic hydrocarbons hydroxylating, oxidation of alcohols under common process conditions.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can use in batch still or slurry-bed reaction device.
The synthetic method that adopts U.S. Pat P 4,410,501 to disclose of HTS hydro-thermal is carried out.With TPAOH is template agent and alkali source, 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, with mixture in autoclave, under 130 ℃～200 ℃, hydrothermal crystallizing 6～30 days.
The graphite that the present invention introduces in HTS hydro-thermal synthetic system is inertia, and it does not dissolve under strong alkaline condition, can not hinder the HTS crystallization or change the synthetic batching of HTS and form; And Al under the same conditions
2O
3Powder can hinder the HTS crystallization, causes HTS degree of crystallinity to descend; SiO
2Powder is solvable in strong basicity HTS synthetic system, can change the synthetic batching of HTS and form, and causes the decline of gained HTS Ti content, reactivity to reduce.
The graphite that the present invention introduces in HTS hydro-thermal synthetic system is chemically neutral, can not introduce the acid site that promotes side reaction in HTS, the alkali center; Graphite has good heat endurance, can be not destroyed in composite Ti-Si catalyst high-temperature roasting activation or regenerative process.Simultaneously, the graphite carrier that adds in the HTS hydro-thermal is synthetic has played peptizaiton to TS-1 molecular sieve active component, can improve TS-1 molecular sieve utilization rate, reduces TS-1 molecular sieve active component consumption in the reaction.Add and to help that the synthetic back of HTS is separated with mother liquor behind the graphite powder and catalytic reaction finishes separating of rear catalyst and reaction medium.
HTS hydro-thermal synthesis material mixes with powdered graphite, carries out hydro-thermal and synthesize under stirring condition, and is owing to HTS evenly mixes with powdered graphite, better than hydro-thermal synthetic effect under the quiescent conditions.
Effect of the present invention is, the composite Ti-Si catalyst that provides is used for reactivity height such as alicyclic ketone ammoxidation, alkene epoxidation, and selectivity is good, and it is easily separated that reaction finishes the back, Heat stability is good during high-temperature roasting.
The specific embodiment
Comparative Examples 1
This Comparative Examples is to prepare the MFI structure titanium silicon molecular sieve according to the method that embodiment among the USP 4,410,501 1 discloses.
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain product TS-1, and its relative crystallinity is decided to be 100%.
Embodiment 1
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, add Al again
2O
3Powder 11.9g was 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/Al of the heavy % of TS-150
2O
3Product, its relative crystallinity are 36.7%.
Embodiment 2
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, add SiO again
2Powder 11.9g was 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/SiO of the heavy % of TS-150
2Product, its relative crystallinity are 113.6%.
Embodiment 3
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, add powdered graphite 11.9g again, 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/ graphite products of the heavy % of TS-150, and its relative crystallinity is 85.6%.
Comparative Examples 2
The catalytic performance of MFI structure titanium silicon molecular sieve in cyclohexanone ammonia oxygen oxidation reaction that the method that the explanation of this Comparative Examples discloses according to embodiment among the USP 4,410,501 1 prepares.
In 100mL chuck there-necked flask, add 0.3g MFI structure titanium silicon molecular sieve, the 9ml tert-butyl alcohol and 3ml cyclohexanone, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 98.8%; Cyclohexanone oxime selectivity 99.1%.
Embodiment 4
In 100mL chuck there-necked flask, add the TS-1/SiO that contains the heavy % of TS-150 that 0.6g embodiment 2 makes
2Composite Ti-Si catalyst, the 9ml tert-butyl alcohol and 3ml cyclohexanone, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 71.0%; Cyclohexanone oxime selectivity 99.4%.
Embodiment 5
In 100mL chuck there-necked flask, add the TS-1/ graphite composite Ti-Si catalyst, the 9ml tert-butyl alcohol and the 3ml cyclohexanone that contain TS-1 50 heavy % that 0.6g embodiment 3 makes, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 99.1%; Cyclohexanone oxime selectivity 99.3%.
Embodiment 6
In 100mL chuck there-necked flask, add the TS-1/ graphite composite Ti-Si catalyst, the 9ml tert-butyl alcohol and the 3ml cyclohexanone that contain TS-1 50 heavy % that 0.45g embodiment 3 makes, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 96.4%; Cyclohexanone oxime selectivity 99.2%.
Embodiment 7
Get the 220ml TPAOH and be dissolved in the 440ml distilled water, under 0～5 ℃, slowly splash in the 253ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 7.48ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 550ml deionized water.Above-mentioned reactant mixture is moved in the 2L high pressure stirred tank, add powdered graphite 65.5g again, 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/ graphite products of the heavy % of TS-150.
Embodiment 8
In 100mL chuck there-necked flask, add the TS-1/ graphite composite Ti-Si catalyst, the 9ml tert-butyl alcohol and the 3ml cyclohexanone that contain TS-1 50 heavy % that 0.45g embodiment 7 makes, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 99.3%; Cyclohexanone oxime selectivity 99.5%.
Embodiment 9
In the 0.4L stainless steel cauldron, the hydrogen peroxide of the TS-1/ graphite composite Ti-Si catalyst that contains TS-1 50 heavy % that adding 0.6g embodiment 7 makes, 31.6ml methyl alcohol and 2.0ml 30 heavy %.Feed propylene, 0.4MPa keep-ups pressure.Magnetic agitation, water bath with thermostatic control temperature control, 60 ℃ of reaction 1.5h.Reaction finishes back sampling, iodimetric analysis H
2O
2Concentration.With Shanghai analytical instrument factory 1102 type gas chromatograph analytical reactions products, quartzy capillary chromatograph, fixer are PEG-20M, column length 40m.Reaction result hydrogen peroxide conversion ratio 97.4%, expoxy propane selectivity 89.2%.
Embodiment 10
In the 0.4L stainless steel cauldron, the hydrogen peroxide of the TS-1/ graphite composite Ti-Si catalyst that contains TS-1 50 heavy % that adding 0.5g embodiment 7 makes, 31.6ml methyl alcohol and 2.0ml 30 heavy %.Feed the 1-butylene, 0.25MPa keep-ups pressure.Magnetic agitation, water bath with thermostatic control temperature control, 60 ℃ of reaction 1.5h.Reaction finishes back sampling, iodimetric analysis H
2O
2Concentration.With Shanghai analytical instrument factory 1102 type gas chromatograph analytical reactions products, quartzy capillary chromatograph, fixer are PEG-20M, column length 40m.Reaction result hydrogen peroxide conversion ratio 92.1%, epoxy butane selectivity 93.3%.
Claims (6)
1. a composite Ti-Si catalyst is characterized in that, this catalyst adopts the preparation of formed in situ method, by weight percentage the powder of being made up of the graphite of 50～90.0% MFI structure titanium silicon molecular sieve and 10.0～50%.
2. the method for preparing the described a kind of composite Ti-Si catalyst of claim 1, it is characterized in that, adopt the preparation of formed in situ method, be about to powdered graphite and introduce the HTS hydro-thermal synthetic system of forming by silicon source, titanium source, template agent, alkali and distilled water, make HTS growth in situ on powdered graphite, then composite is separated with mother liquor, drying, roasting are made.
3. the purposes of the composite Ti-Si catalyst that a kind of composite Ti-Si catalyst according to claim 1 or the described preparation method of claim 2 obtain is characterized in that composite Ti-Si catalyst is used for the alicyclic ketone ammoxidation reaction.
4. the purposes of a kind of composite Ti-Si catalyst according to claim 3 is characterized in that, composite Ti-Si catalyst is used for the ammoxidation of cyclohexanone reaction, and ammoxidation of cyclohexanone reaction response temperature is 60～100 ℃, presses the mol ratio, NH
3/ cyclohexanone=1.0～3.0, hydrogen peroxide/cyclohexanone=0.90～1.20, the tert-butyl alcohol, water, acetone or its mixture are solvent, normal pressure.
5. the purposes of the composite Ti-Si catalyst that a kind of composite Ti-Si catalyst according to claim 1 or the described preparation method of claim 2 obtain, it is characterized in that, composite Ti-Si catalyst is used for alkene epoxidation, epoxidation reaction temperature is 0～100 ℃, pressure 1～50atm, methyl alcohol, ethanol, acetone or its mixture are solvent, alkene/H
2O
2Mol ratio is 1～10: 1.
6. the purposes of a kind of composite Ti-Si catalyst according to claim 5 is characterized in that, composite Ti-Si catalyst is used for epoxidation of propylene and 1-butylene epoxidation reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284213B1 (en) * | 1998-08-05 | 2001-09-04 | Enichem S.P.A. | Catalyst, process for the production of hydrogen peroxide and its use in oxidation processes |
| CN1418876A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284213B1 (en) * | 1998-08-05 | 2001-09-04 | Enichem S.P.A. | Catalyst, process for the production of hydrogen peroxide and its use in oxidation processes |
| CN1418876A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
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