CN1589963A - Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene - Google Patents

Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene Download PDF

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CN1589963A
CN1589963A CNA031507204A CN03150720A CN1589963A CN 1589963 A CN1589963 A CN 1589963A CN A031507204 A CNA031507204 A CN A031507204A CN 03150720 A CN03150720 A CN 03150720A CN 1589963 A CN1589963 A CN 1589963A
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catalyst
ethyl benzene
catalyzer
styrene
oxide catalyst
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CN1263541C (en
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杨诚
廖仕杰
朱敏
缪长喜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

An oxide catalyst for preparing styrene from ethylbenzene by dehydrogenation features that at least one of Ce(OH)4, Ce2(C2O4)3, and Ce3(CO3)3 is introduced to the Fe-K-Ce-Mo system for higher activity and selectivity.

Description

The oxide catalyst of ethyl benzene dehydrogenation preparation of styrene
Technical field
The present invention relates to a kind of oxide catalyst of ethyl benzene dehydrogenation preparation of styrene.
Background technology
The manufacturing of industrial alkenyl arene realizes by alkyl aromatics dehydrogenation.Catalyst system therefor basic composition is Primary Catalysts, promotor and pore-creating agent, toughener etc.The catalyzer of patent report can be divided into two big classes.One class is the Fe-K series catalysts that contains Cr, as laid-open U.S. Patents 4467046,4684619, European patent 0195252A2, though such activity of such catalysts and stability are better, but owing to more or less there is the oxide compound of Cr in forming, thereby can cause certain environmental pollution in Preparation of Catalyst, operation and the spent catalyst treating processes, eliminated gradually.Another kind of is the Fe-K-Ce-Mo series of succeeding in developing the beginning of the eighties, as laid-open U.S. Patents 5190906,4804799, world patent 09839278A1, this type of catalyzer substitutes Cr with Ce, Mo, make catalyzer keep on the basis of original stability, active also have by a relatively large margin raising than the former, adopted by countries in the world production of styrene producer, its main existing problems are that selectivity of styrene is not high, by-product benzene content is more, brings difficulty for principal product output and later separation step.Therefore, seek a kind of catalyzer of production alkenyl arene of highly selective, improve the yield of principal product alkenyl arene, be the very interested problems of people always.
Summary of the invention
Subject matter to be solved by this invention is to have activity of such catalysts, poor selectivity in the conventional art, can not effectively reduce the problem of by product in the production process, and a kind of oxide catalyst of new ethyl benzene dehydrogenation preparation of styrene is provided.This catalyzer has higher activity and selectivity, can effectively reduce the characteristics that by product generates in the reaction process.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oxide catalyst of ethyl benzene dehydrogenation preparation of styrene contains following active constituent by weight percentage:
A) 48～80% Fe 2O 3
B) 3～30% K 2O;
C) 0.5～7% MoO 3
D) 3～15% CeO 2
Be binding agent with kaolin, diatomite or cement in the catalyzer, the consumption of binding agent is 0.1～10% of a catalyst weight;
CeO wherein 2Presoma be selected from Ce (OH) 4, Ce 2(C 2O 4) 3Or Ce 2(CO 3) 3In at least a, the particle size of presoma is 0.5～20 micron.
The particle size preferable range of presoma is 1～8 micron in the technique scheme, and the catalyzer preferred version is also to contain alkaline earth metal oxide in the active constituent by weight percentage, and its consumption is 0.05～8%; The alkaline earth metal oxide preferred version is a magnesium oxide.
Method for preparing catalyst of the present invention is as follows: will be by behind Fe, the K of proportioning weighing, Ce, Mo, other active constituent that need add, tackiness agent, the perforating agent uniform mixing, add an amount of deionized water, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, in 60～120 ℃ of dryings 4 hours, 400～1000 ℃ of following roastings 4 hours, just can obtain finished catalyst then.
Fe is with Fe among the present invention 2O 3Form add; Potassium adds with potassium salt form; Molybdenum adds with its salt or oxide compound; Other active constituent that need add adds with the form of oxide compound or its salt; Perforating agent is selected from graphite, polystyrene microsphere or carboxymethyl cellulose, and its consumption is 0.5～4% of the preceding raw material gross weight of catalyzer roasting.
Among the present invention, the catalyzer that makes as stated above carries out activity rating in the isotherm formula fixed bed, and for the ethyl benzene dehydrogenation preparation of styrene activity rating, the summary process is as follows:
Deionized water and ethylbenzene are imported preheating mixer through volume pump respectively, and preheating enters reactor after being mixed into gaseous state, and reactor adopts the nichrome wire heating, makes it to reach preset temperature.Reactor inside diameter is 1 " stainless steel tube, interiorly load 100 milliliters, particle diameter is 3 millimeters a catalyzer.Analyzing it with gas chromatograph by the reactant of reactor outflow behind water condensation forms.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
Figure A0315072000041
The evaluating catalyst condition is as follows: reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyzer hour, 620 ℃ of temperature of reaction, water are than (water/ethylbenzene) 2.0 (weight ratio).Evaluation result sees Table 1.
The stability result of catalyzer sees Table 2.
Dehydrogenation catalyst of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene dehydrogenation generate vinylbenzene, divinylbenzene and alpha-methyl styrene.
Pass through among the present invention to adopt in iron-potassium-cerium-molybdenum system, change the precursor material source of cerium, and the size of control granular precursor size, the inventor is surprised to find that when catalyzer that this technical scheme makes is used for ethyl benzene dehydrogenation preparation of styrene, catalyzer has higher activity, and product vinylbenzene has higher selectivity and yield, and same catalyzer is formed transformation efficiency can improve nearly 2%, selectivity can improve more than 3%, has obtained better technical effect.The composition of catalyzer of the present invention is not subjected to the restriction of open scope, adds other active constituent, and activity of such catalysts, selectivity will be further improved.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 307.2 the gram common ferric oxide, 59.6 the gram salt of wormwood, 53.7 the gram granular sizes be 4 microns cerous carbonate, 23.2 the gram molybdenum oxides, 15.1 the gram magnesium oxide and 60.4 the gram cement, 25.7 the gram carboxymethyl celluloses in kneading machine, stirred 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, 8～10 millimeters of length, put into baking oven, 80 ℃ were dried by the fire 2 hours, 120 ℃ were dried by the fire 2 hours, placed muffle furnace then, made catalyzer in 4 hours in 900 ℃ of roastings.
The examination condition of catalyzer as mentioned above, its appraisal result sees Table 1, its catalyst weight percentage composition sees Table 2.
[embodiment 2～9]
The preparation method of embodiment 2～9, the composition of catalyzer are with embodiment 1, and just the oxidation precursor is different with granular size, and wherein embodiment 2 and 3 is that its granular size of precursor is respectively 8 and 16 microns with sour cerium, and embodiment 4,5 and 6 is with 48.5 gram Ce (OH) 4For its granular size of precursor is respectively 4,8,16 microns, embodiment 7,8 and 9 is with 127.3 gram Ce 2(C 2O 4) 3For its granular size of precursor is respectively 4,8,16 microns, the examination condition of catalyzer as mentioned above, its appraisal result sees Table 1, its catalyst weight percentage composition sees Table 2, wherein the catalyst stability data of embodiment 7 see Table 3.
[comparative example 1～9]
The method for preparing catalyst of comparative example 1～9, charging capacity, composition are distinguished identical with embodiment 1～9, wherein comparative example 1,2 and 3 is that its size of precursor is respectively 25,35,40 microns with the cerous carbonate, and comparative example 4～6 is with Ce (OH) 4For its granular size of precursor is respectively 25,35,40 microns, comparative example 7～9 is with Ce 2(C 2O 4) 3For its granular size of precursor is respectively 25,35,40 microns, the examination condition of catalyzer as mentioned above, its appraisal result sees Table 1, its catalyst weight percentage composition sees Table 2.
The contrast of table 1 catalyzer dehydrogenation
The single % that receives of catalyzer transformation efficiency % selectivity %
Embodiment 1 70.2 95.6 67.1
Embodiment 2 71.0 95.1 67.5
Embodiment 3 70.5 94.3 66.4
Embodiment 4 70.2 95.1 66.7
Embodiment 5 70.5 94.8 66.8
Embodiment 6 70.5 94.2 66.4
Embodiment 7 73.5 95.2 69.9
Embodiment 8 72.6 95.1 69.0
Embodiment 9 72.5 94.0 68.1
Comparative example 1 68.3 92.2 62.9
Comparative example 2 67.5 91.3 61.6
Comparative example 3 68.3 90.3 61.6
Comparative example 4 67.2 91.5 61.4
Comparative example 5 66.5 92.1 61.2
Comparative example 6 66.7 90.3 60.2
Comparative example 7 67.8 90.2 61.1
Comparative example 8 68.2 90.4 61.6
Comparative example 9 67.8 91.5 62.0
The weight percent of table 2 catalyst activity component is formed
Form embodiment 1～9 (%) comparative example 1～9 (%)
Fe 2O 3 75.0 75.0
K 2O 5.8 5.8
MgO 3.7 3.7
MoO 3 5.6 5.6
CeO 2 9.9 9.9
The stability of table 3 embodiment 7 catalyzer
Reaction times
50 hours 100 hours 200 hours 300 hours 400 hours 500 hours
Con Sel Con Sel Con Sel Con Sel Con Sel Con Sel
(％) (％) (％) (％) (％) (％) (％) (％) (％) (％) (％) (％)
72.6 95.1 73.4 950 73.5 95.0 73.4 95.5 73.3 95.3 73.4 95.1
Con is a conversion of ethylbenzene, and Sel is a selectivity of styrene.
From implementation, catalyzer of the present invention, its essentially consist is with Fe 2O 3, K 2O, CeO 2, MoO 3, MgO is main component, suitably selects CeO 3Precursor and the made dehydrogenation catalyst of particulate size thereof both had high activity, selectivity, good stability is arranged again.

Claims (4)

1, a kind of oxide catalyst of ethyl benzene dehydrogenation preparation of styrene comprises following active constituent by weight percentage:
A) 48～80% Fe 2O 3
B) K of 3～3O% 2O;
C) 0.5～7% MoO 3
D) 3～15% CeO 2
Be binding agent with kaolin, diatomite or cement in the catalyzer, the consumption of binding agent is 0.1～10% of a catalyst weight;
CeO wherein 2Presoma be selected from Ce (OH) 4, Ce 2(C 2O 4) 3Or Ce 2(CO 3) 3In at least a, the particle size of presoma is 0.5～20 micron.
2, according to the oxide catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, the particle size that it is characterized in that presoma is 1～8 micron.
3, according to the oxide catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that also containing alkaline earth metal oxide in the catalyst activity component by weight percentage, its consumption is 0.05～8%.
4,, it is characterized in that alkaline earth metal oxide is a magnesium oxide according to the oxide catalyst of the described ethyl benzene dehydrogenation preparation of styrene of claim 3.
CNB031507204A 2003-09-03 2003-09-03 Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene Expired - Lifetime CN1263541C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100408167C (en) * 2005-09-07 2008-08-06 中国石油化工股份有限公司 Catalyst for ethylbenzene dehydrogenation-hydroxide reaction
CN101091915B (en) * 2006-06-21 2010-05-12 中国石油化工股份有限公司 Catalyst of ethyl benzene dehydrogenation
CN104368355A (en) * 2014-12-02 2015-02-25 厦门大学 Ethylbenzene dehydrogenation catalyst and preparation method thereof
CN104959146A (en) * 2015-05-27 2015-10-07 廖仕杰 Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100408167C (en) * 2005-09-07 2008-08-06 中国石油化工股份有限公司 Catalyst for ethylbenzene dehydrogenation-hydroxide reaction
CN101091915B (en) * 2006-06-21 2010-05-12 中国石油化工股份有限公司 Catalyst of ethyl benzene dehydrogenation
CN104368355A (en) * 2014-12-02 2015-02-25 厦门大学 Ethylbenzene dehydrogenation catalyst and preparation method thereof
CN104368355B (en) * 2014-12-02 2016-06-15 厦门大学 A kind of catalyst for phenylethylene dehydrogenation and preparation method thereof
CN104959146A (en) * 2015-05-27 2015-10-07 廖仕杰 Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio

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