CN1589964A - Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation - Google Patents

Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation Download PDF

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CN1589964A
CN1589964A CNA031507212A CN03150721A CN1589964A CN 1589964 A CN1589964 A CN 1589964A CN A031507212 A CNA031507212 A CN A031507212A CN 03150721 A CN03150721 A CN 03150721A CN 1589964 A CN1589964 A CN 1589964A
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catalyzer
catalyst
oxide
styrene
dehydrogenation
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CNA031507212A
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Chinese (zh)
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CN1263542C (en
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廖仕杰
杨诚
朱敏
缪长喜
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

An oxide catalyst for preparing styrene from ethylbenzen by dehydrogenation features that at least one of FeCl3, Fe2(SO4)3, Fe2(C2O4)3 and Fe2(CO3)3 is introduced to the Fe-K-Ce-Mo system for higher activity and selectivity.

Description

The oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene

Technical field

The present invention relates to a kind of catalyzer that is used for dehydrogenating alkyl arene in preparing alkyl alkenyl arene, particularly about being used for the 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 alkenyl arene of highly selective and produce catalyzer, 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 exist activity of such catalysts, selectivity not good in the conventional art, can not effectively reduce the problem that by product generates in the reaction process, and a kind of new oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene is provided.This catalyzer has can improve catalyst activity, selectivity, keeps the characteristics of better stability simultaneously.

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 that is used for ethyl benzene dehydrogenation preparation of styrene comprises 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;

Fe wherein 2O 3Presoma be selected from FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3In at least a.

Fe in the technique scheme 2O 3The presoma preferred version for being selected from Fe 2(C 2O 4) 3Preferred version is for also containing alkaline earth metal oxide in the catalyst activity component by weight percentage, and its consumption is 0.05~8%; The alkaline earth metal oxide preferred version is a magnesium oxide.

Catalyzer provided by the invention is with Fe 2O 3, K 2O, CeO 2, MoO 3Be main body, added metal oxide simultaneously from alkaline-earth metal, IB-VIII family and IIIA-VIA family as auxiliary agent (they can be selected for use) and binding agent, perforating agent.Fe in the patent in the past 2O 3Main iron oxide yellow and iron oxide red or both mixing use of adopting industrial production, Fe of the present invention 2O 3Be to be prepared from the precursor that contains ferric oxide.

Specifically, dehydrogenation catalyst of the present invention comprises and consists of (weight percent): Fe 2O 348~80%, K 2O 3~30%, Ce 2O 33~15%, MoO 30.5~7%.Wherein Fe is with Fe 2O 3Form add preparation Fe 2O 3Used salt be to be selected from FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3In at least a composition, potassium adds with potassium salt form; Used cerium adds with oxide compound, oxyhydroxide or cerium salt; Mo adds with its salt or oxide compound; Oxides additive MgO adds with oxide form; The consumption of perforating agent is 1~4% of the preceding raw material gross weight of catalyzer roasting, can be selected from graphite, polystyrene microsphere or carboxymethyl cellulose; All the other are binding agent, available cement.

Preparation of catalysts method of the present invention is as follows: will be by behind Fe, the K of proportioning weighing, Ce, Mo, oxides additive, 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.

The catalyzer that makes as stated above carries out activity rating in the isotherm formula fixed bed, 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:

The preparation method of ferric oxide is as follows: under the room temperature, choose a certain amount of FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3One or more, add the HNO of requirement 3Dissolve, filter, the solution after filtering is placed spent the night, add the NaOH solution of reaction needed amount, control solution pH value is 9~10, filters siccative is air-dry, carries out roasting 1~3 hour under 200~500 ℃, and cool to room temperature promptly obtains ferric oxide.

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).

Pass through among the present invention to adopt in iron-potassium-cerium-molybdenum catalyst system, change the precursor material source of iron, 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, product vinylbenzene has higher selectivity and yield, and has stability preferably.The same catalyzer of forming is formed, and transformation efficiency is the highest to be improved closely 3%, and selectivity is the highest to improve 3%, has obtained better technical effect.

The composition of catalyzer among the present invention is not subjected to the restriction of open scope, adds other active constituent, and activity of such catalysts, selectivity can further improve.

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.

The invention will be further elaborated below by embodiment.

Embodiment

[embodiment 1]

With 620.2 gram FeCl 3Preparation method according to above-mentioned ferric oxide prepares ferric oxide, 59.6 gram salt of wormwood, 30.2 gram cerium oxide, 23.2 gram molybdenum oxides, 15.1 gram magnesium oxide and cement, carboxymethyl cellulose stirred in kneading machine 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.Its charging capacity situation sees Table 1, and the weight percent composition of gained catalyzer sees Table 5, and the catalyzer dehydrogenation sees Table 7.

Table 1 embodiment 1

Raw material FeCl 3K 2CO 3Cement carboxymethyl cellulose MgO MoO 3CeO 2

Charging capacity (gram) 620.2 59.6 60.4 25.7 15.1 23.2 30.2

[embodiment 2~4]

The preparation method of embodiment 2,3,4 is the preparation precursor difference of ferric oxide with embodiment 1, and wherein embodiment is with FeCl 3Be precursor, embodiment 2 is with Fe 2(C 2O 4) 3Be precursor, embodiment 3 is with Fe 2(SO 4) 3Be precursor, embodiment 4 is with Fe 2(CO 3) 3Be precursor.The charging capacity situation of embodiment 2 sees Table 2, and the weight percent composition of gained catalyzer sees Table 5, and the catalyzer dehydrogenation sees Table 7, and the steadiness of catalyzer sees Table 8.The embodiment 3 and 4 the situation that feeds intake see Table 3 and table 4 respectively, and the weight percent of gained catalyzer is formed and seen Table 5, and the catalyzer dehydrogenation sees Table 7.

Table 2 embodiment 2

Raw material Fe 2(C 2O 4) 3K 2CO 3Cement carboxymethyl cellulose MgO MoO 3CeO 2

Charging capacity (gram) 721.9 59.6 60.4 25.7 15.1 23.2 30.2

Table 3 embodiment 3

Raw material Fe 2(SO 4) 3K 2CO 3Cement carboxymethyl cellulose MgO MoO 3CeO 2

Charging capacity (gram) 768.0 59.6 60.4 25.7 15.1 23.2 30.2

Table 4 embodiment 4

Raw material Fe 2(CO 3) 3K 2CO 3Cement carboxymethyl cellulose MgO MoO 3CeO 2

Charging capacity (gram) 560.4 59.6 60.4 25.7 15.1 23.2 30.2

The weight percent of table 5 gained catalyst activity component is composed as follows

Form embodiment 1 embodiment 2 embodiment 3 embodiment 4

Fe 2O 3 72.2 72.2 72.2 72.2

K 2O 11.0 11.0 11.0 11.0

MgO 3.6 3.6 3.6 3.6

MoO 3 6.0 6.0 6.0 6.0

CeO 2 7.2 7.2 7.2 7.2

[comparative example 1~3]

The method for preparing catalyst of comparative example is with embodiment 1, and comparative example 1 all adopts red iron oxides, comparative example 2 usefulness be iron oxide yellow, 3 of comparative examples are that red iron oxide, iron oxide yellow respectively account for half, concrete charging capacity is:

Table 6

Charging capacity, gram

Raw material

Comparative example 1 comparative example 2 comparative examples 3

Fe 2O 3·H 2O 341.8 170.9

Fe 2O 3 307.2 153.6

K 2CO 3 59.6 59.6 59.6

Cement 60.4 60.4 60.4

Carboxymethyl cellulose 25.7 25.7 25.7

MgO 15.1 15.1 15.1

MoO 3 23.2 23.2 23.2

CeO 2 30.2 30.2 30.2

The composition of gained catalyzer is identical with embodiment 1~4.

All by aforesaid reaction conditions and device examination, appraisal result is as follows for the catalyzer of above-mentioned gained:

Table 7 catalyzer dehydrogenation

The single % that receives of catalyzer transformation efficiency % selectivity %

Embodiment 1 72.6 95.6 69.4

Embodiment 2 74.7 95.5 70.6

Embodiment 3 71.6 95.5 68.4

Embodiment 4 72.5 95.6 69.3

Comparative example 1 69.2 94.3 65.3

Comparative example 2 68.6 92.3 63.3

Comparative example 3 70.3 94.3 66.3

The stability result of table 8 embodiment 2 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

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)

74.6 95.6 74.4 95.5 74.5 94.4 74.4 95.5 74.3 95.3 74.4 95.7

Wherein 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 Fe 2O 3Precursor, prepare Fe 2O 3, made dehydrogenation catalyst had both had high activity, selectivity, and good stability is arranged again.

Claims (4)

1, a kind of oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene comprises 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;
Fe wherein 2O 3Presoma be selected from FeCl 3, Fe 2(SO 4) 3, Fe 2(C 2O 4) 3Or Fe 2(CO 3) 3In at least a.
2, according to the described oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that Fe 2O 3Presoma be selected from Fe 2(C 2O 4) 3
3, according to the described oxide catalyst that is used for 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 described oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 3.
CNB031507212A 2003-09-03 2003-09-03 Oxide catalyst for preparing phenylethylene by ethylbenzene dehydrogenation CN1263542C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104888817A (en) * 2015-05-27 2015-09-09 廖仕杰 Low-water-ratio ethylbenzene dehydrogenation catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104888817A (en) * 2015-05-27 2015-09-09 廖仕杰 Low-water-ratio ethylbenzene dehydrogenation catalyst

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