CN102040465A - Method for preparing styrene by dehydrogenation of ethylbenzene - Google Patents

Method for preparing styrene by dehydrogenation of ethylbenzene Download PDF

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CN102040465A
CN102040465A CN2009102016304A CN200910201630A CN102040465A CN 102040465 A CN102040465 A CN 102040465A CN 2009102016304 A CN2009102016304 A CN 2009102016304A CN 200910201630 A CN200910201630 A CN 200910201630A CN 102040465 A CN102040465 A CN 102040465A
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ethylbenzene
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styrene
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CN102040465B (en
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危春玲
缪长喜
陈铜
宋磊
朱敏
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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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Abstract

The invention relates to a method for preparing styrene by dehydrogenation of ethylbenzene, and mainly solves the technical problem existing in the prior art that the mechanical strength of low potassium catalyst is low without the addition of common calcium silicate cements such that the stability decreases. According to the invention, ethylbenzene is adopted as a raw material, and styrene is prepared by contacting the raw material with a catalyst in a weight ratio of water vapor to ethylbenzene of 1.0-3.0 at normal pressure, a temperature of 580-640 DEG C, and a liquid space velocity of 0.5-2.0 h<-1>, wherein the catalyst used is the iron-potassium-cerium-molybdenum-magnesium catalyst and the mixture of cerium oxalate and cerium carbonate is adopted as a raw material for cerium source. The technical scheme solves the technical problem well and is applicable to the industrial production of preparing styrene by dehydrogenation of ethylbenzene.

Description

The method of ethyl benzene dehydrogenation preparation of styrene
Technical field
The present invention relates to a kind of method that is used for ethyl benzene dehydrogenation preparation of styrene.
Background technology
Vinylbenzene is a kind of important intermediate that can be used to prepare plastics and rubber, is widely used in to produce polystyrene, acrylonitrile-styrene-divinyl (ABS), styrene-acrylonitrile (SAN) and styrene butadiene rubbers (SBR).Vinylbenzene more than 85% adopts the ethylbenzene dehydrogenation production technique in the world at present, and what this technology generally adopted is to be that main active component, potassium oxide are the Fe-series catalyst of main promotor with the ferric oxide.
At present, the ethyl benzene dehydrogenation preparation of styrene Technology is quite ripe, is not changing any equipment, does not increase under the situation of investment will realize increasing production and improying productivity, and it is one of crucial that catalyzer becomes.Early stage catalyzer is the Fe-K-Cr system, as laid-open U.S. Patents 4467046 and European patent 0296285A1.Though such activity of such catalysts and stability are better, because catalyzer contains the oxide compound of Cr, environment caused certain pollution, eliminated gradually.Develop into the catalyzer of Fe-K-Ce-Mo-Mg series afterwards, as disclosed EP502510, WO9710898, CN1233604 and CN1470325.The adding of Ce can significantly improve activity of such catalysts, and especially the catalysts influence to high potassium content is remarkable.When but the catalyzer of high potassium content was placed in the air, the easy adsorption moisture of catalyzer made the anti-crushing power of catalyzer low, is easy to efflorescence.And, in dehydrogenation reaction process, potassium can be little by little to the granule interior migration, or easily washed away, thereby cause catalyst stability to descend, influence catalyzer work-ing life, therefore, research at present concentrates on mostly hangs down on the potassium catalyzer.Find in the research that the source of Ce is very big to the performance impact of catalyzer in the catalyst preparation process in low potassium catalyzer, according to relevant reported in literature up to now, the scientific research personnel had done a lot of the trial.As laid-open U.S. Patents 5376613 and 5171914 employing cerous carbonates are the cerium source of catalyzer, it is the cerium source that Chinese patent 1298856A adopts cerous nitrate and Sedemesis, it is the cerium source that Chinese patent 1233604 and 1470325 adopts cerous nitrate, and its characteristics relatively pay close attention to the influence of Ce source to catalyst activity, and have all added the physical strength that common Calucium Silicate powder cement guarantees catalyzer in the catalyzer.These documents all do not relate under the situation that does not add cement, change the influence of cerium source to catalyzer physical strength and catalyst life.For this reason, seek appropriate C e source and prepare high mechanical strength and long-life low potassium catalyzer, realize that cinnamic increasing production and improying productivity is the target that the researchist makes great efforts.It is raw material that cerium of the present invention adopts the mixture of Sedemesis and cerous carbonate, and joins in the catalyst component with suitable blending ratio, and the catalyzer that makes is used for ethyl benzene dehydrogenation preparation of styrene technology, can achieve the above object fully.
Summary of the invention
Technical problem to be solved by this invention is in the ethyl benzene dehydrogenation preparation of styrene method, uses low potassium catalyzer (K 2O is less than 16%) time, not adding under the situation of common Calucium Silicate powder cement, the catalyzer physical strength is not high enough, thereby causes the problem of stability decreases, and a kind of method of new ethyl benzene dehydrogenation preparation of styrene is provided.This method can make catalyzer keep greater activity and optionally also have higher physical strength simultaneously, and have the advantage of stability preferably under low potassium situation.
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 method that is used for ethyl benzene dehydrogenation preparation of styrene is a raw material with ethylbenzene, is normal pressure in reaction pressure, and temperature is that 580～640 ℃, liquid air speed are 0.5～2.0 hour -1, water vapour/ethylbenzene weight ratio is that raw material contacts with catalyzer under 1.0～3.0 the condition, reaction of styrene, used catalyzer comprises following composition by weight percentage:
(a) 65～82% Fe 2O 3
(b) 6～13% K 2O;
(c) 8～14% CeO 2
(d) 0.5～5% Mo 2O 3
(e) 0.5～5% MgO;
Wherein the raw material sources of cerium oxide are in Sedemesis and cerous carbonate in the catalyzer, and in cerium oxide, Sedemesis: the weight ratio of cerous carbonate is 2～20: 1.
In the technique scheme, the ratio of catalyst system therefor mesoxalic acid cerium and cerous carbonate, in cerium oxide, Sedemesis: the weight ratio preferable range of cerous carbonate is 8～15: 1, more preferably scope is 10～13: 1.
The used raw material of the catalyst component that the present invention relates to is as follows:
Fe 2O 3Formed by red iron oxide and iron oxide yellow; Used K adds with sylvite or hydroxide form; Used Ce adds with the form of Sedemesis and cerous carbonate mixture; Used Mo adds with its salt or oxide form; Used Mg adds with its salt or oxide form.In preparation process of the present invention, perforating agent is a kind of of methylcellulose gum, carboxymethyl cellulose or polystyrene microsphere, and its add-on is 1～6% of a total catalyst weight.
Method for preparing catalyst of the present invention is as follows:
After will mixing by the compound of Fe, the K of proportioning weighing, Ce, Mo, Mg and perforating agent, add an amount of deionized water, 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 catalyzer 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:
Respectively through volume pump input preheating mixer, preheating enters reactor after being mixed into gaseous state with reaction raw materials, 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 of catalyzer.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 B2009102016304D0000031
Figure B2009102016304D0000032
The raw material of above-mentioned reaction is deionized water and ethylbenzene, and reaction conditions is a normal pressure, and temperature range is that 580～640 ℃, liquid air speed are 0.5～2.0 hour -1, water vapour/ethylbenzene (weight ratio) is 1.0～3.0.
The physical strength of catalyzer is measured by the technical requirements of standard HG/T2782-1996 regulation among the present invention, uses DL-II type intelligence granule strength instrument.5 millimeters of specimen lengths are one group with 40 and test that the arithmetical av of getting its measurement result is final mechanical strength value, are the unit of physical strength with newton (N).
The present invention is by in iron-potassium-cerium-molybdenum-magnesium system, it is raw material that cerium adopts the mixture of Sedemesis and cerous carbonate, and join in the catalyst component with suitable blending ratio, because these two kinds of cerium sources all belong to basic materials, do not add ordinary Portland cement in the catalyzer simultaneously, improved the alkalescence of system, stable and disperseed activity of such catalysts mutually, thereby make low potassium catalyzer keep greater activity and optionally also have higher physical strength simultaneously, use catalyzer of the present invention, normal pressure, liquid air speed 1.0 hours -1, under 620 ℃, water vapour/ethylbenzene (weight ratio) 2.0 conditions, be used for the reaction of ethyl benzene dehydrogenation preparation of styrene, its transformation efficiency can reach 77.2%, selectivity can reach 94.6%, the intensity of catalyzer reaches 135N, and stability was obtained better technical effect greater than 500 hours.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
212.0 gram red iron oxides, 80.0 gram iron oxide yellow, 60.0 gram salt of wormwood, 88.0 gram Sedemesiss, 7.2 gram cerous carbonates, 10.0 gram ammonium molybdates, 9.6 gram magnesium oxide and 20.5 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, placed muffle furnace then, obtained finished catalyst in 4 hours in 850 ℃ of roastings.
Catalyzer is carried out physical strength measure, test result is listed in table 1.
With 100 milliliters of catalyzer reactor of packing into, normal pressure, liquid air speed 1.0 hours -1, 620 ℃, water vapour/ethylbenzene (weight ratio) are to carry out activity rating under 2.0 conditions, test result is listed in table 1.
[embodiment 2]
Method by embodiment 1 prepares catalyzer, and different is 212.0 gram red iron oxides, 183.0 gram iron oxide yellow, 52.0 gram salt of wormwood, 82.0 gram Sedemesiss, 9.5 gram cerous carbonates, 5.1 gram ammonium molybdates, 6.5 gram magnesium oxide, 8.0 gram lime carbonate and 18.1 gram carboxymethyl celluloses.
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
[embodiment 3]
Method by embodiment 1 prepares catalyzer, and different is with 282.0 gram red iron oxides, 103.5 gram iron oxide yellow, 75.0 gram salt of wormwood, 72.0 gram Sedemesiss, 15.0 gram cerous carbonates, 10.5 gram ammonium molybdates, 6.0 gram magnesium oxide and 20.0 gram methylcellulose gum
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
[embodiment 4]
Method by embodiment 1 prepares catalyzer, and different is with 130.0 gram red iron oxides, 145.0 gram iron oxide yellow, 60.0 gram salt of wormwood, 75.0 gram Sedemesiss, 26.0 gram cerous carbonates, 15.0 gram ammonium molybdates, 5.0 gram magnesium oxide, 10.8 gram lime carbonate and 14.5 gram carboxymethyl celluloses.
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
[embodiment 5]
Method by embodiment 1 prepares catalyzer, and different is to restrain salt of wormwood, 80.3 gram Sedemesiss, 5.5 gram cerous carbonates, 16.8 gram ammonium molybdates, 18.6 gram magnesium oxide, reach 15.3 gram polystyrene microspheres with 240.0 gram red iron oxides, 98.0 gram iron oxide yellow, 60.0.
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
[embodiment 6]
Method by embodiment 1 prepares catalyzer, and different is with 190.0 gram red iron oxides, 135.0 gram iron oxide yellow, 78.0 gram salt of wormwood, 100.0 gram Sedemesiss, 5.5 gram cerous carbonates, 6.3 gram ammonium molybdates, 11.6 gram magnesium oxide, 5.0 gram lime carbonate and 20.3 gram carboxymethyl celluloses.
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
The weight percent of gained catalyzer is composed as follows:
Figure B2009102016304D0000051
[comparative example 1]
Method by embodiment 1 prepares catalyzer, and different is, and the cerium source all adopts Sedemesis is 95.2 grams.
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
[comparative example 2]
Method by embodiment 1 prepares catalyzer, and different is, and the cerium source all adopts cerous nitrate is 118.4 grams.
Appreciation condition by embodiment 1 carries out activity rating and physical strength mensuration, and test result is listed in table 1.
The contrast of table 1 catalyst performance
Figure B2009102016304D0000052
[embodiment 7]
Getting the catalyzer of embodiment 1 method preparation, is raw material with ethylbenzene, and with 100 milliliters of catalyzer reactor of packing into, under normal pressure, temperature is that 620 ℃, liquid air speed are 1.0 hours -1, water vapour/ethylbenzene (weight ratio) is that raw material contacts with catalyzer under 2.0 the condition, reaction of styrene, reaction result is listed in table 2.
[embodiment 8]
Temperature of reaction is adjusted into 580 ℃, and all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 9]
Temperature of reaction is adjusted into 600 ℃, and all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 10]
Temperature of reaction is adjusted into 640 ℃, and all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 11]
The liquid air speed is become 0.5 hour -1, all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 12]
The liquid air speed is become 1.5 hours -1, all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 13]
The liquid air speed is become 2.0 hours -1, all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 14]
Change water into 1.0 than (weight), all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 15]
Change water into 1.5 than (weight), all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 16]
Change water into 2.5 than (weight), all the other are with embodiment 7, and reaction result is listed in table 2.
[embodiment 17]
Change water into 3.0 than (weight), all the other are with embodiment 7, and reaction result is listed in table 2.
The reaction result of table 2 catalyzer
Figure B2009102016304D0000071

Claims (3)

1. a method that is used for ethyl benzene dehydrogenation preparation of styrene is a raw material with ethylbenzene, is normal pressure in reaction pressure, and temperature is that 580～640 ℃, liquid air speed are 0.5～2.0 hour -1, water vapour/ethylbenzene weight ratio is that raw material contacts with catalyzer under 1.0～3.0 the condition, reaction of styrene, used catalyzer comprises following composition by weight percentage:
(a) 65～82% Fe 2O 3
(b) 6～13% K 2O;
(c) 8～14% CeO 2
(d) 0.5～5% Mo 2O 3
(e) 0.5～5% MgO;
Wherein the raw material sources of cerium oxide are in Sedemesis and cerous carbonate in the catalyzer, and in cerium oxide, Sedemesis: the weight ratio of cerous carbonate is 2～20: 1.
2. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that in cerium oxide Sedemesis: the weight ratio of cerous carbonate is 8～15: 1.
3. according to the described method that is used for ethyl benzene dehydrogenation preparation of styrene of claim 2, it is characterized in that in cerium oxide Sedemesis: the weight ratio of cerous carbonate is 10～13: 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103537291A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Catalyst for preparing styrene through ethylbenzene dehydrogenation and preparation method of catalyst
CN103537292A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Dehydrogenation catalyst used for preparing styrene
CN103664496A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for preparing styrene employing ethylbenzene dehydrogenation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101992092B (en) * 2009-08-31 2013-06-05 中国石油化工股份有限公司 Catalyst for preparing styrene by dehydrogenizing ethylbenzene and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103537291A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Catalyst for preparing styrene through ethylbenzene dehydrogenation and preparation method of catalyst
CN103537292A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Dehydrogenation catalyst used for preparing styrene
CN103537292B (en) * 2012-07-12 2015-09-09 中国石油化工股份有限公司 For the preparation of cinnamic dehydrogenation
CN103537291B (en) * 2012-07-12 2016-09-07 中国石油化工股份有限公司 Catalyst of ethyl benzene dehydrogenation preparation of styrene and preparation method thereof
CN103664496A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for preparing styrene employing ethylbenzene dehydrogenation

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