CN104815689A - HPPO catalyst production process - Google Patents
HPPO catalyst production process Download PDFInfo
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- CN104815689A CN104815689A CN201510115277.3A CN201510115277A CN104815689A CN 104815689 A CN104815689 A CN 104815689A CN 201510115277 A CN201510115277 A CN 201510115277A CN 104815689 A CN104815689 A CN 104815689A
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- hppo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000002425 crystallisation Methods 0.000 claims abstract description 28
- 230000008025 crystallization Effects 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000001994 activation Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 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
- 238000010792 warming Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003020 moisturizing effect Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 230000002977 hyperthermial effect Effects 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006735 epoxidation reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 abstract 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- -1 4-propyl bromide Chemical compound 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention relates to an HPPO catalyst production process. The raw materials include tetraethyl orthosilicate, tetrabutyl titanate, tetrapropylammonium hydroxide (TPAOH), tetrapropylammonium bromide (TPABr), isopropanol and the like. The equipment includes a crystallization reactor, a storage tank, a filtering device, a heat exchanger, a pump, an air compressor and the like. The production process consists of gelatinizing, aging, crystallization, alkali treatment, acid activation, separation, drying, roasting and other procedures. In the reaction of catalyzing propylene epoxidation with the HPPO catalyst prepared by the production process to prepare epoxypropane, pollution-free low concentration hydrogen peroxide can be adopted as the oxidizing agent, and the problems of complex process and environmental pollution in the traditional process can be avoided. The production process has the advantages of energy saving, economical efficiency, environmental friendliness and the like that are incomparable by the traditional system.
Description
Technical field
The present invention relates to catalyst preparing production field, the technological process of especially a kind of HPPO Catalyst Production.
Background technology
HPPO method is the new technology that hydrogen peroxide catalyzed epoxidation propylene produces expoxy propane, only produces expoxy propane and water in production process.Compared with traditional Synthesis of Propylene Oxide, HPPO technical process is simple, process unit floor space is little, and required auxiliary facility is also less, and investment and cost can reduce 25%, discharge of wastewater can reduce 70%-80%, energy consumption can reduce 35%, and product yield is high simultaneously, no coupling product, pollution-free, belong to cleaning procedure.
Produce in expoxy propane process in HPPO method, the selection of catalyst is even more important, and has domesticly carried out developmental research to the selection of this method catalyst in recent years, achieves good effect with tungsten-containing catalyst and phosphoric acid heteropolyacid salt catalyst.TS-1 HTS is introduced by transition metal titanium to have a kind of novel titanosilicate with excellent clean catalytic oxidization performance formed in the framework of molecular sieve of MFI structure, identical with the skeleton structure of ZSM-5 molecular sieve.TS-1 molecular sieve not only has the catalysed oxidn of titanium, but also the shape of selecting with MFI molecular sieve acts on and excellent stability.
TS-1 molecular sieve is prepared in propylene oxide reaction at catalytic epoxidation of propone, free of contamination low concentration hydrogen peroxide can be adopted as oxidant, avoid the problem of traditional handicraft process complexity and contaminated environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of traditional system, and there is good reaction selectivity, there is good prospects for commercial application.
Summary of the invention
Main purpose of the present invention is to provide the technological process of a kind of HPPO Catalyst Production, comprises the operations such as plastic, ageing, crystallization, alkali treatment, acid activation, separation, drying, roasting.The HPPO catalyst adopting this technique to prepare is prepared in propylene oxide reaction at catalytic epoxidation of propone, free of contamination low concentration hydrogen peroxide can be adopted as oxidant, avoid the problem of traditional handicraft process complexity and contaminated environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of traditional system, and there is good reaction selectivity, there is good prospects for commercial application.
According to the technological process of HPPO Catalyst Production, its raw material comprises ethyl orthosilicate, butyl titanate, TPAOH, 4-propyl bromide, isopropyl alcohol etc.; Equipment comprises crystallization device, storage tank, filter plant, heat exchanger, pump, air compressor machine etc.Its technological process of production comprises the operations such as plastic, ageing, crystallization, alkali treatment, acid activation, separation, drying, roasting.
Brief Introduction of Process:
(1) plastic: by distilled water, ethyl orthosilicate and TPABr with mol ratio (150 ~ 200): (5 ~ 10): 1 joins in crystallization device, adjusts pH to be 9 ~ 11 with ethanol ammonium, at room temperature stirs 0.5 ~ 2h, by H
2o
2solution, butyl titanate, isopropyl alcohol are with mol ratio (1 ~ 6): 1: after (20 ~ 30) mix, slowly join in above-mentioned crystallization device, wherein the mol ratio of butyl titanate and ethyl orthosilicate is 1: (30 ~ 70), stirring at room temperature 0.5 ~ 2h, be warming up to 60 ~ 90 DEG C except alcohol, suitable moisturizing in process, altogether except alcohol 2 ~ 5h, obtains colloidal sol.
(2) ageing: add a small amount of TS-1 molecular sieve crystal seed in above-mentioned colloidal sol, room temperature lower seal ageing 2 ~ 24h.
(3) crystallization: be warming up to 120 ~ 200 DEG C of crystallization 12 ~ 150h after ageing, after filtration, washing, after 110 ~ 150 DEG C of dryings in 350 ~ 800 DEG C of roasting 3 ~ 10h, obtain TS-1 molecular screen primary powder.
(4) alkali treatment: by water, TPAOH and TS-1 molecular screen primary powder by weight (5 ~ 50): (0.5 ~ 5): 1 joins in crystallization device successively, stirring at room temperature 0.5 ~ 5h, be warming up to 120 ~ 200 DEG C of crystallization 12 ~ 150h under sealing, after filtration, washing, obtain the TS-1 molecular sieve after alkali treatment after 110 ~ 150 DEG C of dryings.
(5) acid activation: by H
2sO
4solution (0.25M), H
2o
2tS-1 molecular sieve after solution, alkali treatment is with weight ratio (10 ~ 30): (0.5 ~ 5): 1 joins in the tank diameter of band heating successively, be warming up to process 1 ~ 6h, after filtration, washing, after 110 ~ 150 DEG C of dryings in 350 ~ 800 DEG C of roasting 3 ~ 10h, obtain HPPO catalyst.
Compared with prior art add H in plastic process
2o
2form complex compound with titanium, prevent the hydrolytic precipitation of butyl titanate, protection butyl titanate; suppress the hydrolysis of butyl titanate; add isopropyl alcohol and suppress the hydrolysis of butyl titanate, the hydrolysis rate making the hydrolysis rate of butyl titanate and ethyl orthosilicate quite, is formed with great role to TS-1 molecular sieve.The step that the present invention in turn introduces acid treatment activation after alkali treatment secondary crystallization effective selectivity can remove extra-framework titanium in molecular sieve, and modified catalysts activity is improved significantly, and hydrogen peroxide can assist the extra-framework titanium removed in molecular sieve.
The HPPO catalyst adopting this technological process of production to prepare is prepared in propylene oxide reaction at catalytic epoxidation of propone, free of contamination low concentration hydrogen peroxide can be adopted as oxidant, avoid the problem of traditional handicraft process complexity and contaminated environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of traditional system, and there is good reaction selectivity, there is good prospects for commercial application.
Detailed description of the invention
Embodiment 1
(1) 205kg distilled water, 129kg ethyl orthosilicate, 19.26kg ethanol ammonium and 17.20kgTPABr are joined stirring at room temperature 30min in crystallization device successively, add 8.26kg H
2o
2, stir 5min, 4.6kg butyl titanate be dissolved in after 18.2kg isopropyl alcohol mixes, slowly join in above-mentioned crystallization device (about 30min adds), stirring at room temperature 1h, be warming up to 80 DEG C except alcohol, every 30min moisturizing, to liquid level before alcohol, altogether except alcohol 3h, obtains colloidal sol.
(2) in above-mentioned colloidal sol, 1.65kg TS-1 molecular sieve crystal seed is added, room temperature lower seal ageing 24h.
(3) be warming up to 175 DEG C of crystallization 72h after ageing, after filtration, washing and 120 DEG C of dryings, obtain TS-1 molecular screen primary powder after 550 DEG C of roasting 6h.
(4) by part by weight be 11.5: 1.5: 1 water, TPAOH and TS-1 molecular screen primary powder join in the crystallization device of stirring successively, stirring at room temperature 2h, be warming up to 175 DEG C of crystallization 48h under sealing, after filtration, obtain the TS-1 molecular sieve after alkali treatment after washing and 120 DEG C of dryings.
(5) by ratio be 15 (L): 1.5 (kg): the H of 1 (kg)
2sO
4solution (0.25M), H
2o
2tS-1 molecular sieve after solution (27.5wt%), alkali treatment join successively band heating tank diameter in stir, be warming up to 85 DEG C process 2.5h, after filtration, washing, 120 DEG C of rear 550 DEG C of roasting 6h of drying, obtain HPPO catalyst.
Comparative example 1
Adopt Ludox, titanium sulfate, TPAOH is template, and add ammoniacal liquor and regulate basicity, deionized water is in 1: 0.013-0.035: 0.025-0.2: 25-45: 15-35 ratio, wherein Si/TPA
+=0.08 and different order of addition mixing glue, with ammoniacal liquor (NH
3) regulate glue basicity, add crystal seed, and ceaselessly stir, stir after 1-5 hour, made coagulant liquid is proceeded in the special polytetrafluoroethylene (PTFE) autoclave of microwave (30ml/100ml), regulate microwave power 400W-1600W not, crystallization temperature is 160-180 DEG C, crystallization 2-30h, then taking out cooling, filter, is repeatedly neutral to filtrate with distilled water washing, and then drying (> 12 hours), 550 DEG C of high-temperature roasting 5-10 hour, obtain the former powder of titanium-silicon molecular sieve TS-1.Former for the TS-1 of above-mentioned gained powder is mixed with ammonia spirit, PH 8-13 is regulated to keep temperature 130-190 DEG C, crystallization 24-72 hour again under autogenous hydrothermal pressure, after filtration, washing, after drying, at 500-600 DEG C, roasting 5-6 hour obtains titanium-silicon molecular sieve catalyst sample.
Comparative example 2
In the first step, the TS-1 molecular screen primary powder of non-roasting: weight ratio=1 of acid compound solution: 50, the concentration of acid compound solution is 2.0mol/l, and acid compound is nitric acid;
In second step, the reactant mixture that the first step obtains reacts and obtains titanium-silicon molecular sieve catalyst sample in 20 hours at 120 DEG C.
Comparative example 3
In 2 liters of stainless steel reactors, add 400 grams of propylene, 12 grams of SiO2/TiO2 mol ratios are the titanium-silicon molecular sieve TS-1 catalyst of 50, and reaction pressure is 2.8MPa, be heated to 40 DEG C, then add 60 gram of 30 % by weight H2O2, under agitation, react and obtain titanium-silicon molecular sieve catalyst sample in 20 hours.
Test result contrast catalyst being used for HPPO is as follows:
X
h2O2: hydrogen peroxide conversion ratio;
S
pO: expoxy propane is selective;
Y
pO: expoxy propane yield;
U
h2O2: hydrogen peroxide effective rate of utilization.
Claims (5)
1. the technological process of HPPO Catalyst Production, is characterized in that, comprises the steps:
(1) plastic: distilled water, ethyl orthosilicate and TPABr are joined in crystallization device, adjusts pH to be 9 ~ 11 with ethanol ammonium, at room temperature stirs 0.5 ~ 2h, by H
2o
2solution, butyl titanate, isopropyl alcohol mix and slowly join in above-mentioned crystallization device afterwards, stirring at room temperature 0.5 ~ 2h, are warming up to 60 ~ 90 DEG C except alcohol, suitable moisturizing in process, remove alcohol 2 ~ 5h altogether, obtain colloidal sol;
(2) ageing: add a small amount of TS-1 molecular sieve crystal seed in above-mentioned colloidal sol, room temperature lower seal ageing 2 ~ 24h.
(3) crystallization: be warming up to 120 ~ 200 DEG C of crystallization 12 ~ 150h after ageing, after filtration, washing, after 110 ~ 150 DEG C of dryings in 350 ~ 800 DEG C of roasting 3 ~ 10h, obtain TS-1 molecular screen primary powder.
(4) alkali treatment: water, TPAOH and TS-1 molecular screen primary powder are joined in crystallization device successively, stirring at room temperature 0.5 ~ 5h, be warming up to 120 ~ 200 DEG C of crystallization 12 ~ 150h under sealing, after filtration, washing, obtain the TS-1 molecular sieve after alkali treatment after 110 ~ 150 DEG C of dryings.
(5) acid activation: by H
2sO
4solution (0.25M), H
2o
2tS-1 molecular sieve after solution, alkali treatment joins in the tank diameter of band heating successively, hyperthermic treatment 1 ~ 6h, after filtration, washing, after 110 ~ 150 DEG C of dryings in 350 ~ 800 DEG C of roasting 3 ~ 10h, obtain HPPO catalyst.
2. HPPO Catalyst Production according to claim 1 technological process, is characterized in that, in step 1, distilled water, ethyl orthosilicate and TPABr are with mol ratio (150 ~ 200): (5 ~ 10): 1 joins in crystallization device, H
2o
2solution, butyl titanate, isopropyl alcohol are with mol ratio (1 ~ 6): 1: (20 ~ 30) mix, and wherein the mol ratio of butyl titanate and ethyl orthosilicate is 1: (30 ~ 70).
3. HPPO Catalyst Production according to claim 1 technological process, is characterized in that, in step 2, the mol ratio of TS-1 molecular sieve crystal seed and ethyl orthosilicate is 1:(150 ~ 200).
4. HPPO Catalyst Production according to claim 1 technological process, is characterized in that, in step 4, water, TPAOH and TS-1 molecular screen primary powder are by weight (5 ~ 50): (0.5 ~ 5): 1 joins in crystallization device successively.
5. HPPO Catalyst Production according to claim 1 technological process, is characterized in that, H in step
2sO
4solution (0.25M), H
2o
2tS-1 molecular sieve after solution, alkali treatment is with weight ratio (10 ~ 30): (0.5 ~ 5): 1 joins in the tank diameter of band heating successively.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354875A (en) * | 1993-12-23 | 1994-10-11 | Uop | Epoxidation of olefins using a titania-supported titanosilicate |
| CN1256273A (en) * | 1998-12-09 | 2000-06-14 | 中国石油化工集团公司 | Equipment and procedure for epoxidizing propylene with hydrogen peroxide solution |
| CN1294585A (en) * | 1998-03-24 | 2001-05-09 | 索尔维公司 | Method for making oxirane |
| US6288004B1 (en) * | 1998-05-19 | 2001-09-11 | Enichem S.P.A. | Activation method of titanium silicalite |
| CN101913620A (en) * | 2010-07-20 | 2010-12-15 | 大连理工大学 | Method for quickly synthesizing small-crystallite titanium-silicon molecular sieve in cheap system |
| CN102424398A (en) * | 2011-09-08 | 2012-04-25 | 湘潭大学 | Method for rapid synthesis of titanium silicate molecular sieve |
| CN102616806A (en) * | 2012-04-20 | 2012-08-01 | 上海卓悦化工科技有限公司 | Method for preparing high-performance titanium and silicon molecular sieve |
| CN104291352A (en) * | 2014-09-30 | 2015-01-21 | 浙江大学 | Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation |
-
2015
- 2015-03-17 CN CN201510115277.3A patent/CN104815689B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354875A (en) * | 1993-12-23 | 1994-10-11 | Uop | Epoxidation of olefins using a titania-supported titanosilicate |
| CN1294585A (en) * | 1998-03-24 | 2001-05-09 | 索尔维公司 | Method for making oxirane |
| US6288004B1 (en) * | 1998-05-19 | 2001-09-11 | Enichem S.P.A. | Activation method of titanium silicalite |
| CN1256273A (en) * | 1998-12-09 | 2000-06-14 | 中国石油化工集团公司 | Equipment and procedure for epoxidizing propylene with hydrogen peroxide solution |
| CN101913620A (en) * | 2010-07-20 | 2010-12-15 | 大连理工大学 | Method for quickly synthesizing small-crystallite titanium-silicon molecular sieve in cheap system |
| CN102424398A (en) * | 2011-09-08 | 2012-04-25 | 湘潭大学 | Method for rapid synthesis of titanium silicate molecular sieve |
| CN102616806A (en) * | 2012-04-20 | 2012-08-01 | 上海卓悦化工科技有限公司 | Method for preparing high-performance titanium and silicon molecular sieve |
| CN104291352A (en) * | 2014-09-30 | 2015-01-21 | 浙江大学 | Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation |
Non-Patent Citations (1)
| Title |
|---|
| XIAOXUE WU等: "Effect of TS-1 treatment by tetrapropyl ammonium hydroxide on cyclohexanone ammoximation", 《CATALYSIS COMMUNICATIONS》 * |
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| CN104815689B (en) | 2018-03-06 |
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