CN1810370A - Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene - Google Patents
Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene Download PDFInfo
- Publication number
- CN1810370A CN1810370A CNA2005100236138A CN200510023613A CN1810370A CN 1810370 A CN1810370 A CN 1810370A CN A2005100236138 A CNA2005100236138 A CN A2005100236138A CN 200510023613 A CN200510023613 A CN 200510023613A CN 1810370 A CN1810370 A CN 1810370A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- gram
- arene
- alkyl
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to one kind of catalyst for dehydrogenating alkyl arene to prepare alkyl alkynyl arene and aims at raising the selectivity and strength of low potassium catalyst. The technological scheme of the present invention includes replacing Portland cement in the Fe-K-Ce-Mo-Mg-Ca catalyst system with aluminate cement and adding selecting modulation agent. The catalyst system may be used in industrial production to prepare alkyl alkynyl arene.
Description
Technical field
The present invention relates to a kind of catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene, particularly about being used for the catalyst of ethyl benzene dehydrogenation preparation of styrene.
Background technology
Industrial alkyl alkenyl arene mainly is to be made by alkyl aromatics catalytic dehydrogenation, and one of key of this method is to select the dehydrogenation of a kind of high activity, high selectivity, high stability.At present, industrial generally employing is to be that main active component, potassium oxide are the Fe-series catalyst of main co-catalyst with the iron oxide.As everyone knows, the Fe-series catalyst activity is higher, and the alkyl aromatics dehydrogenation reaction belongs to the macromolecular reaction that is subjected to interior DIFFUSION CONTROLLED, requires catalyst that big access opening is arranged.In catalyst development and producing, the Portland cement of taking usually to have added the binding agent effect is filled in the article shaped space, and the micropore in the blocking catalyst improves the interior diffusion of catalyst.In addition, cement can also improve the mechanical strength of catalyst.
The alkyl aromatics dehydrogenation reaction is typical base catalyzed reactions, owing to contain a large amount of weakly acidic SiO in the Portland cement that adds
2, influence selection of catalysts.Usually in catalyst, add a certain proportion of K
2Among the O and acid centre.But the potassium in the catalyst runs off and migration in course of reaction easily, and the catalyst development personnel recognize this problem gradually, and reducing potassium content at present is the main flow of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst research.
Usually there is the problem of the low and intensity difference of selectivity in low potassium catalyst.Reduce the inevitable intensity that further reduces catalyst of Portland cement content in the catalyst.Therefore, must introduce the substitute of Portland cement, the content of various auxiliary agents is adjusted accordingly, could when reducing potassium content, have higher selectivity and crush strength preferably.To this, according to relevant reported in literature up to now, people had done a lot of the trial, United States Patent (USP) 4467046 has been reported with CaO and has been replaced Portland cement, and the stability that can improve the performance of catalyst, particularly catalyst surpasses the catalyst that uses the Portland cement preparation, but the best catalyst that they obtain conversion of ethylbenzene under 620 ℃ of conditions is 76.8%, selectivity of styrene is 94%, and selectivity improves few, and does not relate to the crush strength of catalyst.Reported in the Fe-K-Ce-Mo system as disclosed Chinese patent 1253855 and to add silica gel, can make low potassium catalyst have very high activity, intensity improves nearly one times, but selection of catalysts is not high.
With regard to the scale of industrial dehydrogenation of ethylbenzene to styrene, its annual production mostly ten thousand tons to the hundreds of thousands ton, therefore, the performance of dehydrogenation is done small improvement, just can make manufacturing enterprise obtain huge economic benefit.Even selection of catalysts raising one percentage point concerning the industrial installation of a ton scale, need not changed any equipment, need not increase investment, just can increase the principal product styrene of hundreds of ton in 1 year, improve the device operating efficiency, reduce consumption of raw materials.Therefore, improve the intensity and the selectivity of hanging down the potassium catalyst is the target that the researcher makes great efforts always.
Summary of the invention
Technical problem to be solved by this invention is to exist low potassium catalyst to have all lower shortcoming of intensity and selectivity in the conventional art, and a kind of new catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene is provided.This catalyst is used for alkyl aromatics dehydrogenation reaction to have still keep higher selectivity, the characteristics of crush strength preferably when potassium content is lower.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene comprises following component by weight percentage:
(a) 60～88% Fe
2O
3
(b) 6～12% K
2O;
(c) 4～11% CeO
2
(d) 0.5～5% MoO
3
(e) 0.5～5% MgO;
(f) 0.05～5% CaO;
(g) 0.1～10% aluminate cement;
(h) 0.001～8% at least a oxide that is selected from Cu, Zn, Mn, Sn, Pb, Ge;
(i) 0.001～8% at least a oxide that is selected from Ti, V, Zr.
In the technique scheme, by weight percentage, the consumption preferable range of aluminate cement is 1～6%; The consumption preferable range of the oxide of at least a by weight percentage Cu of being selected from, Zn, Mn, Sn, Pb, Ge is 0.05～5%; The consumption preferable range of the oxide of at least a by weight percentage Ti of being selected from, V, Zr is 0.05～5%; CeO by weight percentage
2The consumption preferable range be 7～11%.
The used raw material of the catalyst component that the present invention relates to is as follows:
Fe
2O
3Formed by iron oxide red and iron oxide yellow; Used K adds with sylvite or hydroxide form; Used Ce adds with oxide, hydroxide or cerium salt form; Used Mo adds with its salt or oxide form; Used Mg adds with oxide form; Used Ca adds with oxide, hydroxide or calcium salt forms; Used binding agent is an aluminate cement; Remaining element adds with its salt or oxide form.In preparation process of the present invention, except that catalyst body composition and binding agent, also should add perforating agent, perforating agent can be selected from graphite, polystyrene microsphere, carboxymethyl cellulose, and its addition is 2～6% of a total catalyst weight.
Method for preparing catalyst of the present invention is as follows:
After metal oxide, aluminate cement and the perforating agent that will add by Fe, K, Ce, Mo, Mg, Ca, the selectivity of proportioning weighing mixes, add an amount of deionized water, make the face dough of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 80～120 ℃ of dryings 4 hours, 500～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
The crush strength of catalyst is measured by the specification requirement of State Standard of the People's Republic of China GB/T 3635 regulations among the present invention.Finished catalyst after the random sampling roasting is got wherein 50 with quartering, uses QCY-602 granule strength analyzer to measure, and the crush strength of single catalyst calculates as follows:
Pi＝Fi/L
In the formula: the crush strength of single catalyst of Pi-, kilogram/millimeter;
Single catalyst anti-crushing power of Fi-, kilogram;
Single catalyst length of L-, millimeter.
The crush strength of catalyst calculates with the arithmetic mean of instantaneous value of 50 measurement results.
The catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed, for the catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene activity rating, process is summarized as follows:
Deionized water and ethylbenzene are imported preheating mixer through measuring pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 " stainless steel tube, it is interior that to load 100 milliliters, particle diameter be 3 millimeters catalyst.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene, selectivity of styrene and styrene list are received as follows and are calculated:
The styrene list is received %=conversion of ethylbenzene % * selectivity of styrene %
The present invention replaces Portland cement by adopt aluminate cement in iron-potassium-cerium-molybdenum-magnesium-calcium system, owing to reduced faintly acid SiO
2Addition, added the agent of selectivity modulation, significantly improved low potassium selection of catalysts, have the broken intensity of higher compression simultaneously, preferable water resistance has been obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 250.0 gram iron oxide reds, 140.0 gram iron oxide yellow, 70.0 gram potash, 96.0 gram cerous nitrate, 9.6 gram ammonium molybdate, 8.0 gram magnesia, 6.0 gram calcium oxide, 4.0 gram cupric oxide, 1.2 gram zinc oxide, 1.2 gram titanium oxide and 28.0 gram aluminate cements, 15.0 the gram carboxymethyl cellulose stirred in kneader 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into 3 millimeters of diameters, the particle that length is 8～10 millimeters, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, place muffle furnace then, obtained finished catalyst in 4 hours in 900 ℃ of roastings.
With 100 milliliters of catalyst reactor of packing into, normal pressure, liquid air speed 1.0 hours
-1, 620 ℃, water are than carrying out activity rating under (weight) 2.0 conditions, and measure the crush strength of catalyst, test result is listed in table 1.
[embodiment 2]
Method by embodiment 1 prepares catalyst, and different is with 280.0 gram iron oxide reds, 140.0 gram iron oxide yellows, 50.0 gram potash, 96.0 gram cerous nitrates, 9.6 gram ammonium molybdates, 8.0 gram magnesia, 10.7 gram calcium carbonate, 4.0 gram manganese oxide, 1.2 gram zinc oxide, 1.2 gram vanadic anhydrides and 13.5 gram aluminate cements, 16.0 gram carboxymethyl celluloses.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and test result is listed in table 1.
[embodiment 3]
Method by embodiment 1 prepares catalyst, and different is with 160.0 gram iron oxide reds, 90.0 gram iron oxide yellows, 58.0 gram potash, 75.0 gram cerium oxalates, 7.8 gram ammonium molybdates, 7.0 gram magnesia, 7.0 gram calcium oxide, 4.0 gram tin oxide, 1.2 gram zinc oxide, 1.2 gram zirconias and 5.0 gram aluminate cements, 12.0 gram carboxymethyl celluloses.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and test result is listed in table 1.
[embodiment 4]
Method by embodiment 1 prepares catalyst, and different is with 300.0 gram iron oxide reds, 130.0 gram iron oxide yellows, 80.0 gram potash, 100.0 gram cerium oxalates, 9.2 gram ammonium molybdates, 8.0 gram magnesia, 6.0 gram calcium oxide, 4.0 gram cupric oxide, 1.2 gram zinc oxide, 1.2 gram zirconias and 19.4 gram aluminate cements, 18.0 gram carboxymethyl celluloses.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and test result is listed in table 1.
[embodiment 5]
Method by embodiment 1 prepares catalyst, and different is with 330.0 gram iron oxide reds, 160.0 gram iron oxide yellows, 60.0 gram potash, 110.0 gram cerium oxalates, 9.2 gram ammonium molybdates, 10.0 gram magnesia, 4.0 gram calcium oxide, 4.0 gram cupric oxide, 1.2 gram manganese oxide, 1.2 gram vanadic anhydrides and 40.0 gram aluminate cements, 18.0 gram carboxymethyl celluloses.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and test result is listed in table 1.
The percentage by weight of gained catalyst is composed as follows:
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Fe 2O 3 K 2O CeO 2 MoO 3 CaO MgO CuO ZnO TiO 2 MnO 2 SnO 2 V 2O 5 ZrO 2Aluminate cement | 71.69 9.55 7.50 1.57 1.20 1.60 0.80 0.24 0.24 - - - - 5.61 | 77.34 6.82 7.49 1.57 1.20 1.60 - 0.24 - 0.80 - 0.24 - 2.7 | 68.07 11.72 10.79 1.89 2.08 2.08 - 0.36 - - 1.19 - 0.36 1.48 | 72.64 8.58 8.73 1.35 1.08 1.44 0.72 0.22 - - - - 0.22 3.5 | 73.56 6.66 8.70 1.22 0.65 1.63 0.65 - - 0.20 - 0.20 - 6.52 |
[comparative example 1]
Method by embodiment 1 prepares catalyst, and different is with 250.0 gram iron oxide reds, 140.0 gram iron oxide yellows, 70.0 gram potash, 77.2 gram cerium oxalates, 9.6 gram ammonium molybdates, 8.0 gram magnesia, 6.0 gram calcium oxide, 4.0 gram cupric oxide, 1.2 gram zinc oxide, 1.2 gram titanium oxide and 28.0 gram Portland cements, 15.0 gram carboxymethyl celluloses.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and test result is listed in table 1.
[comparative example 2]
Method by embodiment 1 prepares catalyst, and different is with 280.0 gram iron oxide reds, 140.0 gram iron oxide yellows, 50.0 gram potash, 96.0 gram cerous nitrates, 9.6 gram ammonium molybdates, 8.0 gram magnesia, 10.7 gram calcium carbonate, 4.0 gram manganese oxide, 1.2 gram cupric oxide and 13.5 gram Portland cements, 15.0 gram carboxymethyl celluloses.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and the test result of living is listed in table 1.
[comparative example 3]
Method by embodiment 3 prepares catalyst, and different is not add aluminate cement, adds 5.0 gram Portland cements.
Appreciation condition and crush strength assay method by embodiment 1 carry out activity rating and strength detection, and test result is listed in table 1.
The percentage by weight of gained catalyst is composed as follows:
| Form | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Fe 2O 3 K 2O CeO 2 MoO 3 CaO MgO CuO ZnO TiO 2 MnO 2 SnO 2 ZrO 2Portland cement | 71.69 9.55 7.50 1.57 1.20 1.60 0.80 0.24 0.24 - - - 5.61 | 77.53 6.83 7.51 1.57 1.20 1.61 0.24 - - 0.80 - - 2.71 | 68.07 11.72 10.79 1.89 2.08 2.08 - 0.36 - - 1.19 0.36 1.48 |
The contrast of table 1 catalyst performance
| Catalyst | Intensity, kilogram/millimeter | Conversion ratio, % | Selectivity, % | Single receipts, % |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 comparative example 2 comparative examples 3 | 2.73 2.58 2.46 2.63 2.72 2.35 2.11 1.69 | 77.2 77.4 77.2 77.3 76.8 77.1 76.9 77.0 | 96.2 95.7 95.5 95.8 95.6 94.6 94.1 94.9 | 74.27 74.07 73.73 74.05 73.42 72.94 72.36 73.07 |
Above embodiment explanation, in iron-potassium-cerium-molybdenum-magnesium-calcium system, adopt aluminate cement to replace Portland cement, add the agent of selectivity modulation, not only significantly improved low potassium selection of catalysts, improved crush strength simultaneously, the alkyl alkenyl arene selectivity has been up to 96.2%, and the catalyst crush strength has been up to 2.73 kilograms/millimeter, can be used in the industrial production of dehydrogenating alkyl arene in preparing alkyl alkenyl arene.
Claims (5)
1, a kind of catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene comprises following component by weight percentage:
(a) 60～88% Fe
2O
3
(b) 6～12% K
2O;
(c) 4～11% CeO
2
(d) 0.5～5% MoO
3
(e) 0.5～5% MgO;
(f) 0.05～5% CaO;
(g) 0.1～10% aluminate cement;
(h) 0.001～8% at least a oxide that is selected from Cu, Zn, Mn, Sn, Pb, Ge;
(i) 0.001～8% at least a oxide that is selected from Ti, V, Zr.
2,, it is characterized in that the consumption of aluminate cement is 1～6% by weight percentage according to the described catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene of claim 1.
3, according to the described catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene of claim 1, the consumption that it is characterized in that the oxide of at least a by weight percentage Cu of being selected from, Zn, Mn, Sn, Pb, Ge is 0.05～5%.
4, according to the described catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene of claim 1, the consumption that it is characterized in that the oxide of at least a by weight percentage Ti of being selected from, V, Zr is 0.05～5%.
5, according to the described catalyst that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene of claim 1, it is characterized in that CeO by weight percentage
2Consumption be 7～11%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100236138A CN100384532C (en) | 2005-01-26 | 2005-01-26 | Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100236138A CN100384532C (en) | 2005-01-26 | 2005-01-26 | Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1810370A true CN1810370A (en) | 2006-08-02 |
| CN100384532C CN100384532C (en) | 2008-04-30 |
Family
ID=36843568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100236138A Active CN100384532C (en) | 2005-01-26 | 2005-01-26 | Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100384532C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422735B (en) * | 2007-11-01 | 2010-12-15 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
| CN101279268B (en) * | 2007-04-04 | 2011-05-18 | 中国石油化工股份有限公司 | Energy-saving alkyl aromatics dehydrogenation catalyst |
| CN104105544A (en) * | 2011-12-22 | 2014-10-15 | 巴斯夫欧洲公司 | Catalyst for dehydrogenating hydrocarbons |
| CN105056966A (en) * | 2015-08-25 | 2015-11-18 | 营口市风光化工有限公司 | Catalyst for preparing styrene through ethylbenzene dehydrogenation |
| CN106582691A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low-water-to-ethylbenzene-ratio ethylbenzene dehydrogenation catalyst and preparation method therefor |
| CN106582674A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low rare earth catalyst for ethylbenzene dehydrogenation |
| CN107790150A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Produce the catalyst of alkyl alkenyl arene |
| CN109569639A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
| WO2020078303A1 (en) * | 2018-10-16 | 2020-04-23 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon and preparation method therefor |
| CN113388376A (en) * | 2021-06-22 | 2021-09-14 | 东营俊林新材料有限公司 | Alkane dehydrogenation heating auxiliary agent, and preparation method and application thereof |
| CN115475624A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Alkyl aromatic dehydrogenation catalyst and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095399C (en) * | 1998-02-20 | 2002-12-04 | 中国科学院大连化学物理研究所 | Alkyl aromatic hydrocarbon dehydrogenation catalyst and preparation thereof |
| CN1076633C (en) * | 1998-03-30 | 2001-12-26 | 中国石油化工总公司 | Low-temperature alkyl arene dehydrogenating catalyst |
-
2005
- 2005-01-26 CN CNB2005100236138A patent/CN100384532C/en active Active
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279268B (en) * | 2007-04-04 | 2011-05-18 | 中国石油化工股份有限公司 | Energy-saving alkyl aromatics dehydrogenation catalyst |
| CN101422735B (en) * | 2007-11-01 | 2010-12-15 | 中国石油天然气股份有限公司 | Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof |
| CN104105544A (en) * | 2011-12-22 | 2014-10-15 | 巴斯夫欧洲公司 | Catalyst for dehydrogenating hydrocarbons |
| CN107298634B (en) * | 2011-12-22 | 2021-06-01 | 巴斯夫欧洲公司 | Catalyst for dehydrogenation of hydrocarbons |
| CN107298634A (en) * | 2011-12-22 | 2017-10-27 | 巴斯夫欧洲公司 | Catalyst for hydrocarbon dehydrogenation |
| CN105056966B (en) * | 2015-08-25 | 2018-09-25 | 营口风光新材料股份有限公司 | Catalyst for ethyl benzene dehydrogenation preparation of styrene |
| CN105056966A (en) * | 2015-08-25 | 2015-11-18 | 营口市风光化工有限公司 | Catalyst for preparing styrene through ethylbenzene dehydrogenation |
| CN106582691A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low-water-to-ethylbenzene-ratio ethylbenzene dehydrogenation catalyst and preparation method therefor |
| CN106582691B (en) * | 2015-10-16 | 2019-04-12 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof |
| CN106582674B (en) * | 2015-10-16 | 2019-05-14 | 中国石油化工股份有限公司 | The low rare earth catalyst of ethylbenzene dehydrogenation |
| CN106582674A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Low rare earth catalyst for ethylbenzene dehydrogenation |
| CN107790150A (en) * | 2016-09-06 | 2018-03-13 | 中国石油化工股份有限公司 | Produce the catalyst of alkyl alkenyl arene |
| CN109569639A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
| CN109569639B (en) * | 2017-09-29 | 2020-06-09 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparing styrene and preparation method thereof |
| WO2020078303A1 (en) * | 2018-10-16 | 2020-04-23 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of alkyl aromatic hydrocarbon and preparation method therefor |
| CN115475624A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Alkyl aromatic dehydrogenation catalyst and preparation method and application thereof |
| CN115475624B (en) * | 2021-06-16 | 2024-01-30 | 中国石油化工股份有限公司 | Alkyl arene dehydrogenation catalyst and preparation method and application thereof |
| CN113388376A (en) * | 2021-06-22 | 2021-09-14 | 东营俊林新材料有限公司 | Alkane dehydrogenation heating auxiliary agent, and preparation method and application thereof |
| CN113388376B (en) * | 2021-06-22 | 2022-05-06 | 东营俊林新材料有限公司 | Alkane dehydrogenation heating auxiliary agent, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100384532C (en) | 2008-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1810370A (en) | Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene | |
| CN100430133C (en) | Low-water ratio ethylbenzene dehydrogenation catalyst | |
| CN1883796A (en) | Catalysts for ethyl benzene dehydrogenation preparation of styrene | |
| CN101992092B (en) | Catalyst for preparing styrene by dehydrogenizing ethylbenzene and preparation method thereof | |
| CN1810367A (en) | Dehydrogenating catalyst for preparing styrene | |
| CN1400052A (en) | Dehydrogenation catalyst for preparing styrene | |
| CN100453174C (en) | Low-water ratio alkyl aromatics dehydrogenation catalyst | |
| CN100490971C (en) | Oxide catalyst for dehydrogenating ethyl benzene to prepare styrene | |
| CN102371161A (en) | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof | |
| CN101279269B (en) | Low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane | |
| CN103537292A (en) | Dehydrogenation catalyst used for preparing styrene | |
| CN1810366A (en) | Catalyst for dehydrogenating alkyl arene | |
| CN1136047C (en) | Alkyl aromatics catalytic dehydrogenation catalyst | |
| CN1084229C (en) | Alkyl aromatics dehydrogenation catalyst | |
| CN1810365A (en) | Alkyl arene dehydrogenating catalyst | |
| CN100460069C (en) | Production of phenylethylene catalyst by low-water ratio ethylbenzene dehydrogenation | |
| CN102000587B (en) | Catalyst for methyl ethylbenzene dehydrogenation to prepare alpha methyl styrene | |
| CN102040464B (en) | Method for preparing styrene from crude ethylbenzene by dehydrogenation | |
| CN1076633C (en) | Low-temperature alkyl arene dehydrogenating catalyst | |
| CN1181918C (en) | Catalyst for alkyl aromatics dehydrogenation | |
| CN1810369A (en) | Dehydrogenating catalyst for preparing alkyl alkenyl arene | |
| CN1290615C (en) | Alkyl aromatics dehydrogen catalyst | |
| CN1263541C (en) | Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene | |
| CN1226091C (en) | Deoxidizing catalyst for producing alkyl thiazolinyl aromatic hydrocarbon | |
| CN1302847C (en) | Dehydrogen catalyst for preparing phenyl ethylene from ethylbenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |