CN100413581C - Catalyst for preparing cinnamene through ethyl benzene dehydrogenation - Google Patents
Catalyst for preparing cinnamene through ethyl benzene dehydrogenation Download PDFInfo
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- CN100413581C CN100413581C CNB2005100287801A CN200510028780A CN100413581C CN 100413581 C CN100413581 C CN 100413581C CN B2005100287801 A CNB2005100287801 A CN B2005100287801A CN 200510028780 A CN200510028780 A CN 200510028780A CN 100413581 C CN100413581 C CN 100413581C
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- catalyst
- oxide
- styrene
- ethyl benzene
- noble metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A catalyst for dehydrogenating ethylbenzene to prepare styrene with low energy consumption and high low-temp performance is prepared from noble metal or its oxide, the oxide of transition metal, chromium oxide and aluminum oxide.
Description
Technical field
The present invention relates to a kind of catalyst of ethyl benzene dehydrogenation preparation of styrene.
Background technology
Styrene is important Organic Chemicals, is widely used in to produce plastics, resin and synthetic rubber.It is the fourth-largest ethylene derivative product that is only second to PE, PVC, EO, and the output of styrene series resin is only second to PE, PVC and comes in third in synthetic resin.At present, world's styrene yearly productive capacity reaches 2,200 ten thousand tons, and the domestic production ability is also about 900,000 tons/year.
At present, the styrene more than 90% adopts the ethylbenzene catalytic dehydrogenation method to produce in the world.Adopt water vapour as the dehydrogenation medium in the production process, as U.S. Pat P6177602,5689023 and Chinese patent CN01802428.9, the effect of CN98116743.8 report water vapour is: (1) makes reaction raw materials be heated to required temperature; (2) additional heat is in order to avoid owing to endothermic heat of reaction is lowered the temperature; (3) reduce the ethylbenzene dividing potential drop, increase equilibrium conversion; (4) with catalyst on the coke generation water gas reaction separated out, to keep catalyst activity.Yet the use of a large amount of water vapours has occupied one bigger in the production of styrene cost in the current technology, and one ton of required energy consumption of styrene of every production is about 6.3 * 10
9KJ (kilojoule) also needs 5.4 * 10 even consider the latent heat recovery
9More than the kJ (kilojoule).Recently, people such as the Park Sang Yon of Korea S chemical research institute have reported among the USP6034032 in 500～700 ℃ temperature range, at (Fe (II)) at Japan Patent JP11165069A2 and U.S. Pat P6037511
x(Fe (III))
yO
z/ S and 5%Fe
3O
4On/ZSM-5 the catalyst, use CO
2Carry out ethylbenzene mild oxidation dehydrogenation preparation of styrene as diluent, can obtain 48% styrene, but he and fail to develop high performance catalyst.
Summary of the invention
Technical problem to be solved by this invention is the big or employing CO of available technology adopting steam diluter energy consumption
2The problem of catalyst poor performance at low temperatures when making diluent provides a kind of catalyst of new ethyl benzene dehydrogenation preparation of styrene.This catalyst is used for ethylbenzene dehydrogenation reaction, adopts CO
2When making diluent, it is low to have an energy consumption of reaction, catalyst low-temperature catalytic activity height, the advantage that the product selectivity of styrene is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst of ethyl benzene dehydrogenation preparation of styrene, form by following component by weight percentage:
A) noble metal or its oxide 0.01～1.5%;
B) transition metal oxide except that Cr and noble metal 1～15%;
C) Cr
2O
310～30% but do not comprise 10%;
d)Al
2O
3 55～88％。
The noble metal preferred version is selected from Pd, Pt or its mixture in the technique scheme; Transition metal oxide preferred version except that Cr and noble metal is selected from the oxide of Ce, oxide or its mixture of Mo.The content preferable range of noble metal or its oxide is 0.1～1.0% by weight percentage, and more preferably scope is 0.2～0.8%; Transition metal oxide content preferable range except that Cr and noble metal is 5～15%; Cr
2O
3The content preferable range be 15～25%; Al
2O
3The content preferable range be 60～80%.
Preparation of catalysts method of the present invention is as follows: at first with the compound solution of the precious metal element of aequum, transition metal element compound solution, the salting liquid of chromium, impregnated on the aluminium oxide with equi-volume impregnating, kneaded and formed, drying is 1～10 hour under 80～150 ℃ of conditions, and roasting got required catalyst in 0.5～12 hour under 450～650 ℃ of conditions then.
The raw material that uses in the catalyst of the present invention is as follows: the raw material of Pd is selected from palladium acid or its salt; The raw material of Pt is selected from chloroplatinic acid or its salt; The raw material of Mo is selected from ammonium molybdate; The raw material of Ce is selected from cerous nitrate; The raw material of Cr is selected from chromic nitrate; The raw material of Al is selected from aluminium oxide.
Catalyst of the present invention is owing to adopt Cr
2O
3And Al
2O
3Form catalyst system and catalyzing, carrying transition metal oxide and noble metal or its oxide are formed catalyst simultaneously, are used for the ethylbenzene catalytic dehydrogenation reaction, with CO
2Do under the condition of diluent, the inventor finds that unexpectedly this catalyst is under 500 ℃ of reaction temperatures, condition of normal pressure, and conversion of ethylbenzene can reach 74.6%, and cinnamic selectivity can reach more than 98%, simultaneously owing to adopt CO
2Make diluent and under 500 ℃ of temperature, react, can save a large amount of energy consumptions, obtained better technical effect.
The appreciation condition of gained catalyst of the present invention is that temperature is controlled at 500 ℃, and reaction pressure is a normal pressure, and the mol ratio of carbon dioxide and ethylbenzene maintains 20: 1, the flow velocity of ethylbenzene be 0.42 mM/hour.Product is directly by online gas chromatographic analysis.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
0.1 gram weight percentage is consisted of 0.4%Pd/5%CeO
2/ 20%Cr
2O
3/ 74.6%Al
2O
3Catalyst, in the stainless steel reactor of 5 millimeters of the diameters of packing into, temperature programming to 500 ℃, 20 ℃/minute of heating rates, catalyst is at N
2Preliminary treatment is 2 hours under the atmosphere, and ethylbenzene is through the gasification of saturated vapor generator, then with CO
2Mix the formation unstripped gas and enter catalyst bed reaction.Be reflected at 500 ℃ and carry out, pressure is normal pressure, CO
2With the mol ratio of ethylbenzene be 20: 1, the ethylbenzene flow be 0.42 mM/hour, its catalyst is formed and dehydrogenation is listed in table 1 and table 2 respectively.
[embodiment 2～8]
Just change the kind and the weight percent content of noble metal in the catalyst composition by each step of embodiment 1, the kind of transition metal oxide and weight content, the weight content of chromium oxide and the weight content of aluminium oxide, the weight percent of gained catalyst is formed, the dehydrogenation under the carbon dioxide atmosphere and stability see Table 1 respectively, table 2, table 3.
The weight percent of table 1 catalyst is formed
The dehydrogenation of table 2 catalyst under carbon dioxide atmosphere
| Conversion ratio % | Selectivity % | |
| Embodiment 1 | 74.6 | 98.6 |
| Embodiment 2 | 69.9 | 99.1 |
| Embodiment 3 | 70.4 | 98.8 |
| Embodiment 4 | 74.2 | 98.0 |
| Embodiment 5 | 73.1 | 98.8 |
| Embodiment 6 | 74.1 | 98.9 |
| Embodiment 7 | 74.4 | 98.6 |
| Embodiment 8 | 74.5 | 98.7 |
The stability of table 3 embodiment 1 catalyst
| Reaction time, hour | Conversion ratio | Selectivity |
| 50 | 74.6 | 98.6 |
| 100 | 74.4 | 98.6 |
| 200 | 74.3 | 98.7 |
| 300 | 74.2 | 98.8 |
| 400 | 74.0 | 98.0 |
Claims (5)
1. the catalyst of an ethyl benzene dehydrogenation preparation of styrene, form by following component by weight percentage:
A) noble metal or its oxide 0.01～1.5%;
B) transition metal oxide except that Cr and noble metal 1～15%;
C) Cr
2O
310～30% but do not comprise 10%;
d)Al
2O
3 55～88％。
2. according to the catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that noble metal is selected from Pd, Pt or its mixture.
3. according to the catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that the transition metal oxide except that Cr and noble metal is selected from oxide or its mixture of the oxide of Ce, Mo.
4. according to the catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that the content of noble metal by weight percentage or its oxide is 0.1～1.0%; Transition metal oxide content except that Cr and noble metal is 5～15%; Cr
2O
3Content be 15～25%; Al
2O
3Content be 60～80%.
5. according to the catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 4, it is characterized in that the content of noble metal by weight percentage or its oxide is 0.2～0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100287801A CN100413581C (en) | 2005-08-15 | 2005-08-15 | Catalyst for preparing cinnamene through ethyl benzene dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100287801A CN100413581C (en) | 2005-08-15 | 2005-08-15 | Catalyst for preparing cinnamene through ethyl benzene dehydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1915495A CN1915495A (en) | 2007-02-21 |
| CN100413581C true CN100413581C (en) | 2008-08-27 |
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ID=37736645
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100287801A Active CN100413581C (en) | 2005-08-15 | 2005-08-15 | Catalyst for preparing cinnamene through ethyl benzene dehydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100413581C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717928A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for preparing butylene by dehydrogenating n-butane |
| CN116803498B (en) * | 2023-06-13 | 2024-02-13 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4939973B1 (en) * | 1970-02-25 | 1974-10-30 | ||
| AU5876973A (en) * | 1972-08-04 | 1975-02-06 | Engelhard Minerals & Chemicals Corporation | Product and process |
| EP0094684A2 (en) * | 1982-05-19 | 1983-11-23 | Phillips Petroleum Company | Impregnating a noble metal on the surface of a refractory catalyst support |
-
2005
- 2005-08-15 CN CNB2005100287801A patent/CN100413581C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4939973B1 (en) * | 1970-02-25 | 1974-10-30 | ||
| AU5876973A (en) * | 1972-08-04 | 1975-02-06 | Engelhard Minerals & Chemicals Corporation | Product and process |
| EP0094684A2 (en) * | 1982-05-19 | 1983-11-23 | Phillips Petroleum Company | Impregnating a noble metal on the surface of a refractory catalyst support |
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| Publication number | Publication date |
|---|---|
| CN1915495A (en) | 2007-02-21 |
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