CN1981928A - Low-water ratio alkyl aromatics dehydrogenation catalyst - Google Patents

Low-water ratio alkyl aromatics dehydrogenation catalyst Download PDF

Info

Publication number
CN1981928A
CN1981928A CNA200510111473XA CN200510111473A CN1981928A CN 1981928 A CN1981928 A CN 1981928A CN A200510111473X A CNA200510111473X A CN A200510111473XA CN 200510111473 A CN200510111473 A CN 200510111473A CN 1981928 A CN1981928 A CN 1981928A
Authority
CN
China
Prior art keywords
catalyst
gram
oxide
low
water ratio
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
Application number
CNA200510111473XA
Other languages
Chinese (zh)
Other versions
CN100453174C (en
Inventor
宋磊
缪长喜
邬时海
徐永繁
甘明华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CNB200510111473XA priority Critical patent/CN100453174C/en
Publication of CN1981928A publication Critical patent/CN1981928A/en
Application granted granted Critical
Publication of CN100453174C publication Critical patent/CN100453174C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A catalyst for dehydrogenating the alkyl arylhydrocarbon in the condition of low water ratio to obtain alkylenyl arylhydrocarbon is prepared through adding the assistant preventing educing out of carbon and selectivity modifier to the Fe-K-Ce-Mo-Mg system. It has high strength, stability and selectivity.

Description

Low-water ratio alkyl aromatics dehydrogenation catalyst
Technical field
The present invention relates to a kind of low-water ratio alkyl aromatics dehydrogenation catalyst, particularly about being used for the catalyst of low water than ethylbenzene dehydrogenation under the condition.
Background technology
At present, industrial alkyl alkenyl arene mainly is to be made by alkyl aromatics catalytic dehydrogenation, and what generally adopt is to be that main active component, potassium oxide are the Fe-series catalyst of main co-catalyst with the iron oxide.The alkyl aromatics dehydrogenation reaction is typical base catalyzed reactions, is generally the adding of raising catalyst strength and contains faintly acid SiO 2Portland cement, acidulous material causes catalyst to analyse charcoal easily.It is generally accepted that potash is the most effective anti-carbon deposit auxiliary agent, the reaction speed of charcoal and water vapour forms hundred times of ground increases along with adding a small amount of alkali-metal salt of weak acid.But potassium belongs to lighter alkali metal, washes away down at high-temperature water vapor, and potassium runs off and migration easily, influence catalyst from power of regeneration and stability, reducing potassium content at present is the main flow that Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst is developed.
Adopting low water is one of energy-saving and cost-reducing important measures of styrene device than operation.But reduce the water vapour consumption, reduce potassium content, destroyed and analysed charcoal reaction and the balance that disappears between the charcoal reaction, the catalyst surface carbon deposit increases, the sharply decline of the stability of catalyst.Therefore must manage to seek anti-analyse the charcoal auxiliary agent strengthen catalyst at low water than the carbon removal ability under the condition, improve the selection of catalysts inhibition simultaneously and analyse charcoal.
To this, according to relevant reported in literature up to now, people had done a lot of the trial.After European patent 0177832 has been reported the magnesia that adds 1.8～5.4% (weight) in catalyst, be lower than under 2.0 (weight) than (water/ethylbenzene) at water and show the advantages of excellent stability energy, but the potassium content of this catalyst is higher.Reported in the Fe-K-Cr system as disclosed Chinese patent 1145277 and to add multiple metal oxide and Ludox, the catalyst that makes is suitable for low water than operation down, but this catalyst contains contaminated environment, the oxide of the Cr that has been eliminated.
Along with the maximization of industrial dehydrogenation of ethylbenzene to styrene unit scale, energy-conservationly seem more and more important.Therefore, the service condition of dehydrogenation is done small improvement, need not change any equipment, need not increase investment, just can make manufacturing enterprise obtain huge economic benefit.Therefore, develop and a kind ofly be suitable for low water than the catalyst that moves under the condition, the implement device long-term operation is the very interested problem of researcher always.
Summary of the invention
Technical problem to be solved by this invention be the low potassium catalyst strength that exists in the conventional art low, in the problem of low water than stability under the condition and poor selectivity, a kind of new low-water ratio alkyl aromatics dehydrogenation catalyst is provided.This catalyst be used for that alkyl aromatics dehydrogenation system alkyl alkenyl arene reaction has crush strength preferably and at low water than good stability under the condition, characteristics that selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of low-water ratio alkyl aromatics dehydrogenation catalyst comprises following component by weight percentage:
(a) 70～85% Fe 2O 3
(b) 7～12% K 2O;
(c) 6～11% CeO 2
(d) 0.5～5% MoO 3
(e) 0.5～5% MgO;
(f) 0.5～5% SrO;
(g) 0.001～5% at least a oxide that is selected from Co, Ni, Cu, Mn, Sn, Pb or Ge;
(h) 0.001～5% at least a oxide that is selected from W, Hf or Nb;
Wherein do not add portland cement in the catalyst preparation process.
In the technique scheme, Fe 2O 3Preferred version is made up of iron oxide red and iron oxide yellow, and weight ratio is Fe 2O 3: Fe 2O 3H 2O=0.5～5: 1.By weight percentage, the oxide consumption preferable range of at least a Co of being selected from, Ni, Cu, Mn, Sn, Pb or Ge is 0.05～5%.By weight percentage, the oxide consumption preferable range of at least a W of being selected from, Hf or Nb is 0.05～5%.
The used raw material of the catalyst component that the present invention relates to is as follows:
Fe 2O 3Be made up of iron oxide red and iron oxide yellow, its proportioning is Fe 2O 3: Fe 2O 3H 2O=0.5～5: 1; 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 Sr adds with oxide, hydroxide or strontium salt form; Do not add portland cement in the catalyst preparation process as binding agent; Remaining element adds with its salt or oxide form.In preparation process of the present invention, except that the catalyst body composition, 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 that will add by Fe, K, Ce, Mo, Mg, Sr, the selectivity of proportioning weighing and perforating agent mix, the deionized water that adds aequum, make the face dough of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 5～10 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/T3635 regulation 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 Pi-single catalyst, kilogram/millimeter;
Fi-single catalyst anti-crushing power, kilogram;
L-single catalyst length, 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 calculate as follows:
Figure A20051011147300051
The present invention adds the anti-technical scheme of analysing charcoal auxiliary agent, the agent of selectivity modulation, not adding portland cement by adopting in iron-potassium-cerium-molybdenum-magnesium-strontium system, solved preferably low potassium catalyst strength low, in the problem of low water than poor stability under the condition and poor selectivity, obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
280.0 gram iron oxide reds, 100.0 gram iron oxide yellows, 70.0 gram potash, 76.0 gram cerous nitrates, 8.6 gram ammonium molybdates, 6.0 gram magnesia, 2.9 gram tungstic acids, 4.0 gram strontium oxide strontias, 4.0 gram cupric oxide, 1.2 gram manganese oxide and 17.0 gram carboxymethyl celluloses were stirred in kneader 1 hour, add deionized water, mix and stir half an hour again, take out extrusion, be extruded into the particle of 3 millimeters of diameters, 5～10 millimeters of length, 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) 1.7 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, 65.0 gram cerium oxalates, 6.6 gram ammonium molybdates, 8.0 gram magnesia, 12.1 gram strontium carbonates, 6.0 gram niobium oxide, 1.2 gram manganese oxide and 19.0 gram carboxymethyl celluloses.
Appreciation condition and strength detection method by embodiment 1 are carried 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 240.0 gram iron oxide reds, 90.0 gram iron oxide yellows, 58.0 gram potash, 60.0 gram cerous carbonates, 7.6 gram ammonium molybdates, 7.0 gram magnesia, 17.6 gram strontium hydroxides, 6.0 gram cupric oxide, 2.6 gram hafnium oxide and 16.0 gram carboxymethyl celluloses.
Appreciation condition and strength detection method by embodiment 1 are carried 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 290.0 gram iron oxide reds, 130.0 gram iron oxide yellows, 68.0 gram potash, 150.0 gram cerous nitrates, 10.8 gram ammonium molybdates, 12.0 gram magnesia, 24.0 gram strontium oxide strontias, 9.0 gram niobium oxide, 3.6 gram nickel oxide and 20.0 gram carboxymethyl celluloses.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
The weight percent of gained catalyst is composed as follows:
Form Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Fe 2O 3 K 2O CeO 2 MoO 3 MgO SrO CuO MnO 2 WO 3 Nb 2O 5 Ni 2O 3 HfO 2 77.42 10.49 6.52 1.54 1.32 0.88 0.88 0.26 0.69 - - - 82.67 7.28 6.74 0.63 0.60 1.39 - 0.26 - 0.43 - - 72.80 9.42 9.01 1.48 1.67 3.58 1.43 - - - - 0.62 70.48 8.43 10.65 1.60 2.18 4.37 - - - 1.64 0.66 -
[comparative example 1]
Method by embodiment 2 prepares catalyst, and different is not add strontium carbonate.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[comparative example 2]
Method by embodiment 3 prepares catalyst, and different is to add 29.25 gram strontium hydroxides.
Appreciation condition and strength detection method by embodiment 1 are carried 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 cupric oxide and hafnium oxide.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[comparative example 4]
Method by embodiment 4 prepares catalyst, and different is to add 2 gram strontium oxide strontias.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
[comparative example 5]
Press each catalyst of method system of embodiment 4, different is to add 22 gram Portland cements and 22.0 gram carboxymethyl celluloses.
Appreciation condition and strength detection method by embodiment 1 are carried out activity rating and strength detection, and test result is listed in table 1.
The weight percent of gained catalyst is composed as follows:
Form Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Fe 2O 3 K 2O CeO 2 MoO 3 MgO SrO CuO MnO 2 Nb 2O 5 Ni 2O 3 HfO 2Portland cement 83.83 7.39 6.84 0.64 0.61 - - 0.26 0.43 - - - 71.11 9.20 8.80 1.44 1.63 5.82 1.40 - - - 0.61 - 74.33 9.61 9.20 1.51 1.70 3.65 - - - - - - 73.42 8.88 10.99 1.67 2.27 0.38 - - 1.71 0.68 - - 67.77 8.10 10.24 1.54 2.10 4.20 - - 1.57 0.63 - 3.85
The contrast of table 1 catalyst performance
Catalyst Intensity kilogram/millimeter Water is than (weight) Reaction time
100 hours 500 hours
Conversion ratio % Selectivity % Conversion ratio % Selectivity %
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 2.46 2.58 2.75 2.63 1.65 2.72 2.11 1.87 2.71 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 76.1 76.2 76.4 75.7 76.1 75.1 76.1 75.9 75.2 95.2 95.3 95.3 95.2 95.1 94.9 94.2 94.9 94.0 75.1 75.1 75.5 74.8 73.7 74.0 74.7 73.8 70.1 95.2 95.1 95.2 95.0 95.2 94.8 94.3 95.0 93.9
Above embodiment explanation, in iron-potassium-cerium-molybdenum-magnesium system, adopt and add anti-analyse charcoal auxiliary agent, the agent of selectivity modulation, cast out Portland cement, not only significantly improved low potassium catalyst at low water than stability under the condition and selectivity, and improved crush strength, can be used in the low industrial production of water than dehydrogenating alkyl arene in preparing alkyl alkenyl arene under the condition, is a kind of energy-saving catalyst.

Claims (4)

1, a kind of low-water ratio alkyl aromatics dehydrogenation catalyst comprises following component by weight percentage:
(a) 70～85% Fe 2O 3
(b) 7～12% K 2O;
(c) 6～11% CeO 2
(d) 0.5～5% MoO 3
(e) 0.5～5% MgO;
(f) 0.5～5% SrO;
(g) 0.001～5% at least a oxide that is selected from Co, Ni, Cu, Mn, Sn, Pb or Ge;
(h) 0.001～5% at least a oxide that is selected from W, Hf or Nb;
Wherein do not add portland cement in the catalyst preparation process.
2, according to the described low-water ratio alkyl aromatics dehydrogenation catalyst of claim 1, it is characterized in that Fe 2O 3By Fe 2O 3And Fe 2O 3H 2O forms, and weight ratio is Fe 2O 3: Fe 2O 3H 2O=0.5～5: 1.
According to the described low-water ratio alkyl aromatics dehydrogenation catalyst of claim 1, it is characterized in that by weight percentage that 3, the oxide consumption of at least a Co of being selected from, Ni, Cu, Mn, Sn, Pb or Ge is 0.05～5%.
According to the described low-water ratio alkyl aromatics dehydrogenation catalyst of claim 1, it is characterized in that by weight percentage that 4, the oxide consumption of at least a W of being selected from, Hf or Nb is 0.05～5%.
CNB200510111473XA 2005-12-14 2005-12-14 Low-water ratio alkyl aromatics dehydrogenation catalyst Active CN100453174C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200510111473XA CN100453174C (en) 2005-12-14 2005-12-14 Low-water ratio alkyl aromatics dehydrogenation catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200510111473XA CN100453174C (en) 2005-12-14 2005-12-14 Low-water ratio alkyl aromatics dehydrogenation catalyst

Publications (2)

Publication Number Publication Date
CN1981928A true CN1981928A (en) 2007-06-20
CN100453174C CN100453174C (en) 2009-01-21

Family

ID=38164940

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200510111473XA Active CN100453174C (en) 2005-12-14 2005-12-14 Low-water ratio alkyl aromatics dehydrogenation catalyst

Country Status (1)

Country Link
CN (1) CN100453174C (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582693A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Low temperature alkyl arene dehydrogenation catalyst and preparation method thereof
CN106582697A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Low rare earth catalyst for dehydrogenation of alkyl aromatics
CN106582681A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Low steam-to-oil ratio ethylbenzene dehydrogenation catalyst
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
CN111054362A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for producing divinylbenzene and preparation method thereof
EP4219004A4 (en) * 2020-10-14 2024-04-03 China Petroleum & Chemical Corporation Iron-potassium-cerium-based composite oxide catalyst, and preparation and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04277030A (en) * 1991-03-05 1992-10-02 Nissan Gaadoraa Shokubai Kk Ethylbenzene dehydrogenation catalyst
CN1028495C (en) * 1991-10-30 1995-05-24 中国石油化工总公司 Deoxidized catalyst for alkyl hydrocarbon
CN1084229C (en) * 1998-11-18 2002-05-08 中国石油化工集团公司 Alkyl aromatics dehydrogenation catalyst
CN1204098C (en) * 2002-03-13 2005-06-01 中国石油化工股份有限公司 Oxide catalyst for ethylbenzene dehydrogenation to prepare styrene
CN1290615C (en) * 2003-09-03 2006-12-20 中国石油化工股份有限公司 Alkyl aromatics dehydrogen catalyst

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582693A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Low temperature alkyl arene dehydrogenation catalyst and preparation method thereof
CN106582697A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Low rare earth catalyst for dehydrogenation of alkyl aromatics
CN106582681A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Low steam-to-oil ratio ethylbenzene dehydrogenation catalyst
CN106582693B (en) * 2015-10-16 2019-11-08 中国石油化工股份有限公司 Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof
CN106582681B (en) * 2015-10-16 2019-12-10 中国石油化工股份有限公司 catalyst for low-water-ratio 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
CN111054362A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Catalyst for producing divinylbenzene and preparation method thereof
EP4219004A4 (en) * 2020-10-14 2024-04-03 China Petroleum & Chemical Corporation Iron-potassium-cerium-based composite oxide catalyst, and preparation and application thereof

Also Published As

Publication number Publication date
CN100453174C (en) 2009-01-21

Similar Documents

Publication Publication Date Title
CN100384532C (en) Catalyst for dehydrogenating alkyl arene in preparing alkyl alkenyl arene
CN103769152B (en) The catalyst for phenylethylene dehydrogenation of the low water ratio of high activity, preparation method and application thereof
CN100453174C (en) Low-water ratio alkyl aromatics dehydrogenation catalyst
CN102040466A (en) Method for preparing styrene through ethylbenzene dehydrogenation
CN103769151B (en) High activity ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof
CN102371160A (en) Low-temperature ethyl benzene dehydrogenation catalyst
CN101992094B (en) Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof
CN102371161B (en) Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof
CN101993336B (en) Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition
CN100391604C (en) Dehydrogenating catalyst for preparing styrene
CN101279266B (en) Energy-saving catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene
CN106582693B (en) Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof
CN100490971C (en) Oxide catalyst for dehydrogenating ethyl benzene to prepare styrene
CN101279267B (en) Energy-saving catalyst for phenylethylene dehydrogenation
CN101623642B (en) Ethylbenzene dehydrogenation catalyst with low water ratio
CN101279269B (en) Low water ratio catalyst for preparing phenylethylene from dehydrogenation of phenylethane
CN103537292A (en) Dehydrogenation catalyst used for preparing styrene
CN103028418A (en) High-activity low-water ratio ethylbenzene dehydrogenation catalyst and preparation method
CN109569638A (en) Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof
CN100358632C (en) Alkyl arene dehydrogenating catalyst
CN106582827A (en) High activity and low water ratio ethylbenzene dehydrogenation catalyst
CN102000587B (en) Catalyst for methyl ethylbenzene dehydrogenation to prepare alpha methyl styrene
CN102372592B (en) Method for preparing styrene by dehydrogenating ethylbenzene
CN102040463B (en) Method for preparing styrene by ethylbenzene dehydrogenation
CN100391605C (en) Dehydrogenating catalyst for preparing alkyl alkenyl arene

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