CN1173961C - Catalyst for olefine epoxidation - Google Patents
Catalyst for olefine epoxidation Download PDFInfo
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- CN1173961C CN1173961C CNB011322004A CN01132200A CN1173961C CN 1173961 C CN1173961 C CN 1173961C CN B011322004 A CNB011322004 A CN B011322004A CN 01132200 A CN01132200 A CN 01132200A CN 1173961 C CN1173961 C CN 1173961C
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- Prior art keywords
- catalyst
- hts
- sio
- catalyzer
- epoxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 150000003818 basic metals Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 12
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229960003511 macrogol Drugs 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst used for olefine epoxidation. The present invention mainly overcomes the disadvantage that because the particle diameter of a titanium silicon molecular sieve which is synthesized in the past is too small, the industrial application is difficult. The present invention leads a catalyst to have a size which is suitable for industrial application by leading a titanium silicon molecular sieve which is synthesized in a hydrothermal method to be loaded on an alumina supporter. Alkali metal components or/and alkaline earth oxide components are added into the catalyst, which leads the catalyst to have high activity and selectivity, and leads the catalyst to be used in industrial production.
Description
Technical field
The present invention relates to be used for the catalyzer of alkene epoxidation, particularly about the catalyzer of epoxidation of propylene.
Background technology
HTS has very high catalytic activity and selectivity to the low-carbon (LC) oxidation operation.With the hydrogen peroxide is oxygenant, is under 40～100 ℃ of conditions in temperature, but the reactions such as ammonia oxidation of the hydroxylation of the partial oxidation of the epoxidation of catalyzed alkene, alkane, aromatic hydrocarbon and phenol and pimelinketone.The synthetic method of HTS generally is to be the titanium source with tetraethyl titanate or tetrabutyl titanate, and tetraethyl orthosilicate is the silicon source, is template with TPAOH (TPAOH) or TBAH (TBAOH), utilizes hydrothermal method synthetic.Wherein the mol ratio of reaction mass is SiO
2/ TiO
2＞30; TPAOH or TBAOH/SiO
2=0.3～0.6.It is the method for the synthetic TS-1 HTS of template with TPAOH that U.S. Pat 04410501 has been introduced.Utilize aforesaid method to synthesize its complicated operating process of TS-1, long reaction time (6～30 days), and be difficult to avoid the tetraethyl titanate hydrolysis and be polymerized to non-body phase anatase.Yet with hydrothermal method synthetic HTS since its crystal grain less than 1 micron, thereby catalyzer is difficult to separate and reclaims.In fact particle diameter less than 5 microns pressed powder be extremely be difficult to from solution isolating.In order to address this problem, U.S. Pat 4701428 had once been reported the method by the HTS of spray drying method for preparation carrierization, yet its particle diameter of catalyzer with this method preparation only is about 20 microns, slurry bed reactor can only be used for, still bed bioreactor can not be used for fixing on a large scale.
Summary of the invention
Technical problem to be solved by this invention is to overcome HTS in the past because too for a short time being difficult to of particle diameter adapts to the shortcoming that industrial production requires, and a kind of new catalyzer that is used for alkene epoxidation is provided.It is big that this catalyzer has a particle diameter, can be suitable for fixed-bed reactor and use, and has advantages of high catalytic activity and characteristics optionally simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer that is used for alkene epoxidation comprises following component by weight percentage:
A) 10～50% alumina supporter;
B) 40～80% HTS, HTS general formula are xTiO
2(1-x) SiO
2, x=0.0005～0.04, wherein x is a mol ratio, x=Ti/ (Si+Ti);
C) 5～40% basic metal or alkaline earth metal oxide or its mixture.
In the technique scheme, the alumina supporter preferred version is α-Al
2O
3Or γ-Al
2O
3The weight ratio preferred version of alumina supporter and basic metal or alkaline earth metal oxide or its mixture is 0.5～6, and more preferably scheme is 3～5.The basic metal preferred version is for being selected from potassium or sodium, and the alkaline-earth metal preferred version is for being selected from calcium or magnesium.The amount preferable range of HTS is 60～80% by weight percentage.
The preparation process of HTS of the present invention is as follows: with trivalent titanium compound, tetraethyl titanate or tetrabutyl titanate is the titanium source, with tetraethyl orthosilicate or silicon sol is the silicon source, quaternary ammonium hydroxide, quaternary ammonium salt are or/and organic amine is a template, by the hydrothermal method synthesis of titanium silicon molecular sieve.The mol ratio of each material is in the molecular sieve precursor: SiO
2/ TiO
2Be 20～200; OH
-/ SiO
2Be 0.03～0.6; H
2O/SiO
2Be 60～100; Template/SiO
2Be 0.2～0.50, above-mentioned reaction mixture is warming up to 70～90 ℃ earlier also to be continued to stir 0.5～5 hour, and crystallization is after 1～3 day under 120～200 ℃ of temperature then, and collection, fractional crystallization product from reaction mixture wash then and dry.Behind the calcination crystallized product certain hour, get HTS in air, the sieve particle diameter is about 10 microns.
Preparation of catalysts process of the present invention is as follows:
The crystallization product that obtains through said process is mixed with aluminum oxide, basic metal or alkaline earth metal oxide or its mixture and suitable quantity of water or nitric acid by weight percentage, after stirring, extrusion or compression molding, after 500～600 ℃ of roastings, be ground into required granularity, promptly make required catalyzer.
Among the present invention since with HTS as catalyst activity component, with aluminum oxide as carrier mix, extrusion or compression molding, the particle diameter of catalyzer can be regulated as required, to meet the needs that the commercial fixed bed reactor is used, after making propylene ring oxidation reaction, avoided the catalyst separating problem.Because after having added alumina catalyst support in the catalyzer, reduced the effective active component of every gram catalyzer, activity of such catalysts can be descended to some extent, after in catalyzer, adding basic metal or alkaline earth metal oxide and composition thereof, activity of such catalysts and selectivity are improved.40 ℃ of temperature of reaction, carry out the epoxidation reaction of propylene and hydrogen peroxide under the reaction pressure 0.4MPa condition, its hydrogen peroxide transformation efficiency can reach 93.5%, and the selectivity of propylene oxide can reach 96.9%, has obtained effect preferably.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
After in the positive tetraethyl orthosilicate of 204 grams, adding TEAOH, the TBAOH and tetrabutyl titanate of requirement, under agitation slowly be heated to 85 ℃, and kept 3 hours.Change over to again in the stainless autoclave that is lined with PTFE and carry out crystallization, 175 ℃ of crystallization temperatures, crystallization time 3 days.The relative molar content of each component in the precursor wherein:
SiO
2/ TiO
2=50, (TEAOH+TBAOH)/SiO
2=0.25, TEA/TBA=1, H
2O/SiO
2After=45 crystallization finished, water cooled off fast, and isolates crystallized product; After 120 ℃ of dryings,, get titanium-silicon molecular sieve TS-1 550 ℃ of calcinations 6 hours.
The 35 gram titanium-silicon molecular sieve TS-1s that obtain by said process and 15 gram hydrated aluminum oxides, 10 restrain magnesium nitrates and an amount of rare nitric acid mixes, extruded moulding then, and catalyst size is 2 * 2 millimeters.
[embodiment 2]
The preparation method of HTS is with embodiment 1 operation.
The 35 gram titanium-silicon molecular sieve TS-1s that obtain by said process and 15 gram hydrated aluminum oxides, 10 gram magnesium nitrates, 5 restrain Macrogol 2000s 0 and an amount of rare nitric acid mixes, extruded moulding then, and catalyst size is 2 * 2 millimeters.
[embodiment 3]
The preparation method of HTS is with embodiment 1 operation.But the relative molar content of component is in the raw material:
SiO
2/TiO
2＝80，TPAOH/SiO
2＝0.25，H
2O/SiO
2＝40
The 35 gram titanium-silicon molecular sieve TS-1s that obtain by said process and 15 gram hydrated aluminum oxides, 11 gram nitrocalcite, 8 restrain Macrogol 4000s and an amount of rare nitric acid mixes, extruded moulding then, and catalyst size is 2 * 2 millimeters.
[embodiment 4]
The preparation method of HTS is with embodiment 1 operation.But the relative molar content of component is in the raw material:
SiO
2/TiO
2＝40，(TEAOH+TBAOH)/SiO
2＝0.25，TEA/TBA＝0.2，H
2O/SiO
2＝60
The 35 gram titanium-silicon molecular sieve TS-1s that obtain by said process and 15 gram hydrated aluminum oxides, 10 gram magnesium nitrates, 10 restrain Walsroder MC 20000Ss and an amount of rare nitric acid mixes, extruded moulding then, and catalyst size is 2 * 2 millimeters.
[embodiment 5]
Component is with embodiment 1 operation in the preparation method of HTS and the raw material.
The 40 gram titanium-silicon molecular sieve TS-1s that obtain by said process and 10 gram Alpha-aluminas, 3.6 gram yellow soda ash, 12 restrain polyvinyl alcohol and an amount of rare nitric acid mixes, extruded moulding then, and catalyst size is 2 * 2 millimeters.
[embodiment 6]
With embodiment 1 operation.The relative molar content of component is in the raw material:
SiO
2/TiO
2＝30，TPAOH/SiO
2＝0.29，H
2O/SiO
2＝50
The 35 gram titanium-silicon molecular sieve TS-1s that obtain by said process and 35 gram hydrated aluminum oxides, 8.2 gram sodium bicarbonates, 12 restrain polyethylene oxides and an amount of rare nitric acid mixes, extruded moulding then, and catalyst size is 2 * 2 millimeters.
[embodiment 7]
The catalyzer that above-mentioned comparative example 1 and embodiment 1～6 are made carries out propylene ring oxidation reaction respectively and investigates in caliber is 2 centimetres fixed-bed reactor, its appreciation condition is: raw material hydrogen peroxide is a solvent with the first alcohol and water, hydrogen peroxide concentration is 0.78 mol, loaded catalyst is 8 gram/kilogram hydrogen peroxide, temperature of reaction is 40 ℃, propylene pressure is 0.4 MPa, and the reaction times is 90 minutes, and its reaction result sees Table 1.
Table 1 titanium-silicon molecular sieve catalyst catalytic epoxidation of propone reaction result
| Embodiment number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hydrogen peroxide transformation efficiency % | 86.8 | 89.1 | 88.4 | 85.1 | 92.6 | 93.5 |
| Propylene oxide selectivity % | 100 | 96.4 | 95.7 | 98.5 | 95.6 | 96.9 |
Claims (7)
1, a kind of catalyzer that is used for alkene epoxidation comprises following component by weight percentage:
A) 10～50% alumina supporter;
B) 40～80% HTS, HTS general formula are xTiO
2(1-x) SiO
2, x=0.0005～0.04, wherein x is a mol ratio, x=Ti/ (Si+Ti);
C) 5～40% basic metal or alkaline earth metal oxide or its mixture.
2,, it is characterized in that alumina catalyst support is α-Al according to the described catalyzer that is used for alkene epoxidation of claim 1
2O
3Or γ-Al
2O
3
3, according to the described catalyzer that is used for alkene epoxidation of claim 1, the weight ratio that it is characterized in that alumina supporter and basic metal or alkaline earth metal oxide or its mixture is 0.5～6.
4, according to the described catalyzer that is used for alkene epoxidation of claim 3, the weight ratio that it is characterized in that alumina supporter and basic metal or alkaline earth metal oxide or its mixture is 3～5.
5,, it is characterized in that basic metal is selected from potassium or sodium according to the described catalyzer that is used for alkene epoxidation of claim 1.
6,, it is characterized in that alkaline-earth metal is selected from calcium or magnesium according to the described catalyzer that is used for alkene epoxidation of claim 1.
7,, it is characterized in that the amount of HTS is 60～80% by weight percentage according to the described catalyzer that is used for alkene epoxidation of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011322004A CN1173961C (en) | 2001-11-14 | 2001-11-14 | Catalyst for olefine epoxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011322004A CN1173961C (en) | 2001-11-14 | 2001-11-14 | Catalyst for olefine epoxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1418876A CN1418876A (en) | 2003-05-21 |
| CN1173961C true CN1173961C (en) | 2004-11-03 |
Family
ID=4671238
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011322004A Expired - Lifetime CN1173961C (en) | 2001-11-14 | 2001-11-14 | Catalyst for olefine epoxidation |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296134C (en) * | 2003-12-27 | 2007-01-24 | 大连理工大学 | Composite titanium-silicon catalyst and its preparation and use |
| CN103586069B (en) * | 2010-10-11 | 2016-06-01 | 中国石油化工股份有限公司 | For the preparation method of catalyzer and the method for epoxidation of olefins of epoxidation reaction of olefines |
| CN102476808B (en) * | 2010-11-25 | 2013-09-04 | 中国石油化工股份有限公司 | Modified titanium silicate molecular sieve material and preparation method thereof |
| CN102476975B (en) * | 2010-11-25 | 2014-04-30 | 中国石油化工股份有限公司 | Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve |
| CN103360218B (en) * | 2012-04-01 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of benzene hydroxylation reaction method |
| CN103360220B (en) * | 2012-04-01 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of method of voluminous Resorcinol |
| CN103373904B (en) * | 2012-04-27 | 2015-03-18 | 中国石油化工股份有限公司 | Synthesis method of benzenediol |
| CN103373902B (en) * | 2012-04-27 | 2015-03-18 | 中国石油化工股份有限公司 | Method for hydroxylating aromatic hydrocarbon to prepare corresponding phenol or diphenol |
| CN103418445B (en) * | 2012-05-16 | 2015-04-08 | 中国石油化工股份有限公司 | Method for increasing catalyst strength |
| CN103666544B (en) | 2012-09-21 | 2016-04-06 | 中国石油化工股份有限公司 | A kind of recapitalization generating oil hydrogenation treatment process |
| SG10201702254UA (en) | 2012-09-21 | 2017-05-30 | China Petroleum & Chem Corp | Hydrocarbon oil hydrotreating method |
| CN106334583B (en) * | 2016-07-27 | 2019-01-29 | 万华化学集团股份有限公司 | A kind of preparation method of titanium-silicon composite oxide catalyst and application thereof |
| CN110252394B (en) * | 2019-07-18 | 2022-03-25 | 北京赛诺时飞石化科技有限公司 | Catalyst for preparing propylene oxide by propylene oxidation, preparation and application thereof |
-
2001
- 2001-11-14 CN CNB011322004A patent/CN1173961C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1418876A (en) | 2003-05-21 |
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