CN1400052A - Dehydrogenation catalyst for preparing styrene - Google Patents

Dehydrogenation catalyst for preparing styrene Download PDF

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CN1400052A
CN1400052A CN 01126342 CN01126342A CN1400052A CN 1400052 A CN1400052 A CN 1400052A CN 01126342 CN01126342 CN 01126342 CN 01126342 A CN01126342 A CN 01126342A CN 1400052 A CN1400052 A CN 1400052A
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catalyst
cerium
dehydrogenation
oxide
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CN1151880C (en
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缪长喜
单明
毛连生
杨城
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a dehydrogenation catalyst for preparing phenylethylene, and is mainly aimed at solving the problems of that under the condition of low potassium content, at the same time of retaining high catalyst activity and selectivity, the mechanical strength of catalyst is low and the service life of catalyst is affected in the previous technology. Said invention adopts the technical scheme of introducing the raw material of cerium in the form of cerium oxalate into the iron-potassium-cerium-molybdenum catalytic system so as to better solve the above-mentioned problems. Said invention can be used in industrial production of phenylethylene.

Description

Be used to prepare cinnamic dehydrogenation
Technical field
The present invention relates to a kind of cinnamic dehydrogenation that is used to prepare.
Background technology
As everyone knows, industrially normally make alkyl alkenyl arene by alkyl aromatics catalytic dehydrogenation, selecting a kind of dehydrogenation efficiently is one of key technology of this method.The catalyst of patent report divides two classes.One class is a Fe-K-Cr series, as laid-open U.S. Patents US4467046, European patent EP 0296285A1, German patent DE 2815874A1.Though such activity of such catalysts and stability are better, because catalyst itself contains the chromated oxide not too friendly to environment, be very limited on the commercial Application, eliminated gradually.Another kind of is Fe-K-Ce-Mo series, and this type of catalyst has substituted Cr with Ce, Mo, and activity of such catalysts and stability have by a relatively large margin raising than the former.Find in the research that the source of Ce is very big to the performance impact of catalyst in the catalyst preparation process.As laid-open U.S. Patents US5376613, US5171914, world patent WO09839278A1, U.S. Pat 48804799 adopts cerous carbonate, cerium oxide or the cerous nitrate cerium source as dehydrogenation respectively.Though do not mention relevant catalyst mechanical strength and stability data in these documents, but according to evidence, such catalyst is particularly under the low potassium content condition, the bad mechanical strength that in long-term operation, has catalyst, for example crush strength is low, rate of wear is high, influences the service life of catalyst.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist in the document when potassium content is low in the catalyst keeping high activity, optionally simultaneously, the mechanical strength of catalyst is not high enough, influence the catalyst defective in service life, a kind of new cinnamic dehydrogenation that is used to prepare is provided.This catalyst has under the low situation of potassium content, is keeping high activity, optionally can keep simultaneously the characteristics of high mechanical properties.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind ofly be used to prepare cinnamic dehydrogenation, comprise following active constituent: Fe by weight percentage 2O 3: 40～85%, K 2O: 10～40%, MoO 3Or WO 3: 0.5～5%, Ce 2O 3: 3～10%, wherein the raw material of cerium oxide is introduced with the form of cerium oxalate.
In the technique scheme, Fe 2O 3By Fe 2O 3And Fe 2O 3H 2O forms, and proportioning is Fe by weight 2O 3: Fe 2O 3H 2O is 0.2～5: 1.Also comprise alkaline earth oxide by weight percentage in the catalyst activity component, its consumption is 0.005～6%, and alkaline-earth metal can be selected from metals such as calcium, magnesium, barium.K by weight percentage 2The amount preferable range of O is 10～18%.
The used raw material of catalyst component of the present invention is as follows:
Fe 2O 3Formed by iron oxide red and iron oxide yellow;
K 2O adds with potassium salt form, for example carbonate or nitrate etc.;
Ce 2O 3Introduce with the cerium oxalate form;
MoO 3Or WO 3Salt or oxide form with it are introduced;
Alkaline earth oxide is introduced with its oxide, carbonate or nitrate form.
Also contain perforating agent in the catalyst, its consumption is 1～4% of a catalyst weight, can from graphite, polystyrene microsphere, carboxymethyl cellulose etc., choose, for further improving catalyst activity and selectivity, also can add other useful co-catalyst, other binding agent in addition, binding agent can be used cement.
Method for preparing catalyst of the present invention:
After will evenly mixing by Fe, K, Mo (W), Ce, co-catalyst, adhesive, the perforating agent of proportioning weighing, 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 50～120 ℃ of dryings 1～10 hour, 400～1000 ℃ of following roastings 1～8 hour, just can obtain finished catalyst then.
The catalyst 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 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 and selectivity of styrene calculate as follows:
Figure A0112634200042
The evaluating catalyst condition is as follows: reaction pressure is that normal pressure, 1.0 liters of ethylbenzene of liquid air speed/rise catalyst hour, 620 ℃ of reaction temperatures, water are than (water/ethylbenzene) 2.0 (weight ratio).Evaluation result sees Table 1.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, Alpha-Methyl ethylbenzene dehydrogenation generate styrene, divinylbenzene and AMS.
At iron-potassium-cerium-molybdenum is in the dehydrogenation of catalyst system and catalyzing, and iron oxide is main active constituent; Potassium oxide is important accelerative activator, links to each other closely with the mechanical strength of catalyst again simultaneously, and potassium content is high more, and mechanical strength is higher relatively; Cerium oxide is an accelerative activator, again can double as catalysis stabilizing agent, so the raw material sources of cerium are very big to the catalyst performance influence.The present invention confirms that through test the increase of basic materials potash helps improving intensity, and the alkaline matter that adds other type in requiring the catalyst system and catalyzing of low potassium content helps improving the catalyst mechanical strength.The inventor is by changing raw material cerium source in technical scheme, introduce this strong base weak acid material of cerium oxalate, under low potassium content (about 13%) condition, when keeping catalytic activity and selectivity all to increase, the mechanical strength example crush strength of its catalyst has improved more than 3%, rate of wear has reduced more than 40%, has obtained better technical effect.
Below by embodiment the present invention is further described.
The specific embodiment [embodiment 1～3]
212.4 gram iron oxide reds, 157.7 gram iron oxide yellows, 160.1 gram potash, 22.1 gram ammonium molybdates, 41.1 cerium oxalates that restrain and cement, carboxymethyl cellulose were 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 catalyst in 4 hours in 900 ℃ of roastings.The preparation method of embodiment 2,3 is with embodiment 1, and just the addition of cerium oxalate is different or with WO 3Substituted MoO 3And a spot of MgO, CaO have been introduced.
The Preparation of Catalyst inventory is:
Raw material Inventory, gram
Embodiment 1 Embodiment 2 Embodiment 3
?Fe 2O 3?Fe 2O 3·H 2O ?K 2CO 3?(NH 4) 6Mo 7O 24·4H 2O ?WO 3MgO CaO cement carboxymethyl cellulose Ce 2(C 2O 4) 3·9H 2O ????212.4 ????157.7 ????160.1 ????22.1 ????- ????- ????- ????25.0 ????10.0 ????41.1 ????194.5 ????216.6 ????97.7 ????17.2 ????- ????- ????0.5 ????25.0 ????15.0 ????61.6 ????227.8 ????136.4 ????113.1 ????- ????13.8 ????11.0 ????19.0 ????25.0 ????15.0 ????82.1
Gained catalyst composed as follows:
Form Embodiment 1 Embodiment 2 Embodiment 3
????Fe 2O 3????K 2O ????MoO 3????WO 3????MgO ????CaO ????Ce 2O 3 ????70.8 ????21.8 ????3.6 ????- ????- ????- ????4.0 ????77.8 ????13.3 ????2.8 ????- ????- ????0.1 ????6.0 ????68.2 ????15.4 ????- ????2.4 ????2.2 ????3.8 ????8.0
[comparative example 1～3]
The method for preparing catalyst of comparative example is with embodiment 1, and what comparative example 1 adopted is cerous nitrate, comparative example 2,3 usefulness be respectively cerium oxide and cerous carbonate, concrete inventory is:
Raw material Inventory
Comparative example 1 Comparative example 2 Comparative example 3
?Fe 2O 3?Fe 2O 3·H 2O ?K 2CO 3?MoO 3?WO 3MgO CaO cement carboxymethyl cellulose Ce 2(NO 3) 3·6H 2O ?Ce 2O 3?Ce 2(CO 3) 3·5H 2O ????233.1 ????173.1 ????99.9 ????16.6 ????- ????- ????- ????25.0 ????20.0 ????75.8 ????- ????- ????180.3 ????200.7 ????119.7 ????19.6 ????- ????- ????15.0 ????25.0 ????20.0 ????- ????27.0 ????- ????207.6 ????154.1 ????112.3 ????- ????14.0 ????20.0 ????10.0 ????25.0 ????20.0 ????- ????- ????53.3
Gained catalyst composed as follows:
Form Comparative example 1 Comparative example 2 Comparative example 3
????Fe 2O 3????K 2O ????MoO 3????WO 3????MgO ????CaO ????Ce 2O 3 ????77.7 ????13.6 ????2.7 ????- ????- ????- ????6.0 ????72.1 ????16.3 ????3.2 ????- ????- ????3.0 ????5.4 ????69.2 ????15.3 ????- ????2.8 ????4.0 ????2.0 ????6.7
[embodiment 4]
With embodiment 1～3, the catalyst that comparative example 1～3 makes is 1, and " check and rate in the stainless steel isotherm formula fixed bed reactors; wherein reaction pressure is a normal pressure; the liquid air speed is 1.0 liters of ethylbenzene/rise catalyst hour; reaction temperature is 620 ℃, and water is than (water/ethylbenzene) 2.0 (weight ratio), and evaluation result sees Table 1; above-mentioned catalyst is carried out crush strength and rate of wear is measured, measurement result sees Table 2.
The contrast of table 1 catalyst performance
Catalyst Conversion ratio % Selectivity % Single % that receives
Embodiment 1 embodiment 2 embodiment 3 comparative examples 1 comparative example 2 comparative examples 3 ????77.8 ????78.4 ????78.2 ????76.2 ????72.8 ????71.3 ????95.0 ????95.2 ????95.1 ????94.4 ????93.7 ????93.4 ????73.9 ????74.6 ????74.4 ????71.9 ????68.2 ????66.6
Table 2 catalyst crush strength and rate of wear
Catalyst The crush strength Newton/millimeter Rate of wear %
Embodiment 1 embodiment 2 embodiment 3 comparative examples 1 comparative example 2 comparative examples 3 ????24.6 ????25.3 ????24.8 ????23.1 ????18.3 ????17.7 ????0.43 ????0.41 ????0.47 ????0.59 ????0.69 ????0.74
From implementation, catalyst of the present invention, in Fe-K-Ce-Mo (W) system, introduce cerium oxide with cerium oxalate as the cerium source, made dehydrogenation had both had high activity, selectivity, good crush strength and abrasion resistance are arranged again, are a kind of styrene dehydrogenations of suitable long period industrial operation.

Claims (4)

1, a kind ofly is used to prepare cinnamic dehydrogenation, comprises following active constituent: Fe by weight percentage 2O 3: 40～85%, K 2O: 10～40%, MoO 3Or WO 3: 0.5～5%, Ce 2O 3: 3～10%, it is characterized in that the raw material of cerium oxide is introduced with the form of cerium oxalate.
2, be used to prepare cinnamic dehydrogenation according to claim 1 is described, it is characterized in that Fe 2O 3By Fe 2O 3And Fe 2O 3H 2O forms, and proportioning is Fe by weight 2O 3: Fe 2O 3H 2O is 0.2～5: 1.
3, be used to prepare cinnamic dehydrogenation according to claim 1 is described, it is characterized in that also comprising alkaline earth oxide in the catalyst activity component by weight percentage, its consumption is 0.005～6%.
4, be used to prepare cinnamic dehydrogenation according to claim 1 is described, it is characterized in that K by weight percentage 2The amount of O is 10～18%.
CNB011263423A 2001-07-27 2001-07-27 Dehydrogenation catalyst for preparing styrene Expired - Lifetime CN1151880C (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100368083C (en) * 2004-10-29 2008-02-13 中国石油化工股份有限公司 Catalyst for preparing cinnamene by dehydrogenation of ethylbenzene
CN101602003B (en) * 2008-06-12 2011-07-20 中国石油化工股份有限公司 Oxide catalyst for preparing styrene by ethylbenzene dehydrogenation
CN101733113B (en) * 2008-11-18 2012-05-30 中国石油天然气股份有限公司 Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof
CN101940931B (en) * 2009-07-06 2012-09-05 中国石油化工股份有限公司 Method for preparing ethylbenzene dehydrogenation catalyst
CN102040463B (en) * 2009-10-13 2012-10-10 中国石油化工股份有限公司 Method for preparing styrene by ethylbenzene dehydrogenation
CN101992094B (en) * 2009-08-31 2012-10-10 中国石油化工股份有限公司 Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof
CN102040466B (en) * 2009-10-13 2012-10-10 中国石油化工股份有限公司 Method for preparing styrene through ethylbenzene dehydrogenation
CN102040467B (en) * 2009-10-13 2012-11-14 中国石油化工股份有限公司 Method for producing styrene by ethylbenzene dehydrogenation
CN102039204B (en) * 2009-10-13 2012-11-14 中国石油化工股份有限公司 Method for preparing styrene catalyst by ethyl benzene dehydrogenation
CN102039193B (en) * 2009-10-13 2013-03-06 中国石油化工股份有限公司 Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof
CN103030521A (en) * 2011-09-29 2013-04-10 中国石油化工股份有限公司 Method for preparing styrene through ethylbenzene dehydrogenation
CN103028414A (en) * 2011-09-29 2013-04-10 中国石油化工股份有限公司 Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparing method thereof
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
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

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100368083C (en) * 2004-10-29 2008-02-13 中国石油化工股份有限公司 Catalyst for preparing cinnamene by dehydrogenation of ethylbenzene
CN101602003B (en) * 2008-06-12 2011-07-20 中国石油化工股份有限公司 Oxide catalyst for preparing styrene by ethylbenzene dehydrogenation
CN101733113B (en) * 2008-11-18 2012-05-30 中国石油天然气股份有限公司 Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof
CN101940931B (en) * 2009-07-06 2012-09-05 中国石油化工股份有限公司 Method for preparing ethylbenzene dehydrogenation catalyst
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
CN101992094B (en) * 2009-08-31 2012-10-10 中国石油化工股份有限公司 Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof
CN102040466B (en) * 2009-10-13 2012-10-10 中国石油化工股份有限公司 Method for preparing styrene through ethylbenzene dehydrogenation
CN102040467B (en) * 2009-10-13 2012-11-14 中国石油化工股份有限公司 Method for producing styrene by ethylbenzene dehydrogenation
CN102039204B (en) * 2009-10-13 2012-11-14 中国石油化工股份有限公司 Method for preparing styrene catalyst by ethyl benzene dehydrogenation
CN102039193B (en) * 2009-10-13 2013-03-06 中国石油化工股份有限公司 Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparation method thereof
CN102040463B (en) * 2009-10-13 2012-10-10 中国石油化工股份有限公司 Method for preparing styrene by ethylbenzene dehydrogenation
CN103030521A (en) * 2011-09-29 2013-04-10 中国石油化工股份有限公司 Method for preparing styrene through ethylbenzene dehydrogenation
CN103028414A (en) * 2011-09-29 2013-04-10 中国石油化工股份有限公司 Catalyst for preparing styrene by ethylbenzene dehydrogenation and preparing method thereof
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

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