CN1883796A - Catalysts for ethyl benzene dehydrogenation preparation of styrene - Google Patents
Catalysts for ethyl benzene dehydrogenation preparation of styrene Download PDFInfo
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- CN1883796A CN1883796A CNA2005100270139A CN200510027013A CN1883796A CN 1883796 A CN1883796 A CN 1883796A CN A2005100270139 A CNA2005100270139 A CN A2005100270139A CN 200510027013 A CN200510027013 A CN 200510027013A CN 1883796 A CN1883796 A CN 1883796A
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- styrene
- ethyl benzene
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- benzene dehydrogenation
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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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Abstract
The invention relates to a catalyst for preparing phenylethene through ethylbenzene dehydrogenation, wherein 0.1-5% of oxide compounds of at least one selected from Y, Eu, Gd, Tb, Dy and Yb are charged into the conventional Fe-K-Ce-Mo catalytic system.
Description
Technical field
The present invention relates to a kind of catalyst that is used for ethyl benzene dehydrogenation preparation of styrene.
Background technology
The industrial cinnamic overwhelming majority is to realize by the hot dehydrogenation of the direct catalysis of ethylbenzene at present.The basic composition of catalyst system therefor comprises major catalyst, co-catalyst and pore-foaming agent, reinforcing agent etc.The report of relevant catalyst generally can be divided into two big classes, and a class is the early stage Fe-K series catalysts that contains Cr, as laid-open U.S. Patents US4467046, US4684619 and European patent EP 0195252A2 etc.Though such activity of such catalysts and stability are better, owing to more or less have the oxide of Cr in forming, thereby can cause certain environmental pollution in Preparation of catalysts, operation and the dead catalyst processing procedure, eliminated gradually.Another kind of is the Fe-K-Ce-Mo series that early eighties is succeeded in developing, as laid-open U.S. Patents US5190906, US4804799, world patent W009839278A1 etc.This type of catalyst substitutes Cr with Ce, Mo, make catalyst keep on the basis of original stability, active also have raising than the former, adopted by countries in the world production of styrene producer, the subject matter that it exists is relative industrial requirements, its activity is still on the low side, and selectivity of styrene is not high yet, and by-product benzene, toluene bring difficulty for principal product output and later separation step.For this reason, seek the cinnamic high activity of a kind of production, high-selectivity catalyst, improve the cinnamic yield of principal product, be the very interested problems of people always.What Chinese patent CN115006A invented is to be principal component with Fe-K-Ce-Mo, add the catalyst of second kind of rare earth element again, improved activity of such catalysts and selectivity, also being improved of catalyst from power of regeneration, the rare earth oxide that its invention is contained is Ce, La, Pr, Nd, Sm.The present invention further expands the application of rare earth oxide as the important auxiliary agent of Fe-K-Ce-Mo catalyst series on its basis.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist catalyst activity, selectivity of styrene not high enough in the document, and the shortcoming that the styrene yield is on the low side provides a kind of new oxide catalyst that is used for ethyl benzene dehydrogenation preparation of styrene.This catalyst has can improve conversion of ethylbenzene, cinnamic selectivity height, while styrene yield height, the characteristics that catalyst stability is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for ethyl benzene dehydrogenation preparation of styrene comprises following active constituent by weight percentage:
A) 55～85% Fe
2O
3
B) 5～30% K
2O;
C) 3～10% Ce
2O
3
D) 0.5～5% MoO
3
E) 0.1～5% be selected from oxide at least a among Y, Eu, Gd, Tb, Dy, the Yb;
Fe wherein
2O
3By Fe
2O
3And Fe
2O
3H
2O forms, by weight Fe
2O
3: Fe
2O
3H
2O is 0.2～5: 1.
In the technique scheme, Fe by weight
2O
3: Fe
2O
3H
2The preferable range of O is 0.5～4: 1.Being selected from oxide consumption preferable range at least a among Y, Eu, Gd, Tb, Dy, the Yb by weight percentage is 0.1～3%, and more preferably scope is 0.5～2%.Preferred version is that active constituent also comprises 0.05～8% alkaline earth oxide by weight percentage, and alkaline earth oxide is selected from magnesia, calcium oxide or its mixture.Also contain 1～10% binding agent cement by weight percentage in the catalyst.
The used raw material of catalyst component of the present invention is as follows:
Fe
2O
3Be made up of iron oxide red and iron oxide yellow, potassium adds with the form of sylvite, and cerium adds with oxide, hydroxide or metallic salt form, is selected from salt or the oxide form adding of the rare-earth oxide of Y, Eu, Gd, Tb, Dy, Yb with it.Other component adds with the form of its oxide, hydroxide or its salt.
Also can comprise perforating agent in the Preparation of Catalyst of the present invention, its consumption is 1～4% of a catalyst weight, can choose from graphite, polystyrene microsphere, carboxymethyl cellulose etc.Also have binding agent in addition, generally use cement, its consumption counts 1～10% with catalyst weight percentage.
Method for preparing catalyst of the present invention is as follows:
After will evenly mixing by Fe, K, Ce, Mo and other co-catalyst component that need add, adhesive, the perforating agent of proportioning weighing, add proper amount of deionized water, make the paste of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 5～10 millimeters particle, in 40～150 ℃ of dryings 1～10 hour, 400～1000 ℃ of following roastings 1～8 hour, just can obtain finished catalyst then.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully by ethylbenzene, diethylbenzene, methyl-ethyl benzene and make styrene, divinylbenzene and methyl styrene.
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:
With ethylbenzene and deionized water preheating in the measuring pump input mixer respectively, enter reactor with gaseous form, 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 3.0 millimeters catalyst.Analyzing it with gas chromatograph by the dehydrogenation product of reactor outflow behind water condensation forms.
The evaluating catalyst condition is as follows in the isotherm formula fixed bed reactors: with 100 milliliters, particle diameter is that 3 millimeters catalyst is put into internal diameter 1 " isothermal reactor, reaction pressure is normal pressure, liquid air speed 1.0 hours
-1, 620 ℃ of reaction temperatures, water be than (water/ethylbenzene) (weight) 2.0.
Conversion of ethylbenzene and selectivity of styrene calculate as follows:
The styrene list is received (%)=conversion of ethylbenzene (%) * selectivity of styrene (%)
The main side reaction of ethylbenzene dehydrogenation is to generate toluene and benzene.Prove after deliberation: when reaction was in stable state, carbon distribution form that catalyst surface is suitable and amount were the important assurances that catalyst has good catalytic performance, and too much carbon distribution and out of season carbon distribution form can cause catalysqt deactivation, side reaction to increase.Therefore reduce excessive carbon distribution, the modified catalyst surface can guarantee the high activity and the high selectivity of catalyst.Add proper proportion and be selected from rare earth oxide at least a among Y, Eu, Gd, Tb, Dy, the Yb, can improve the specific area of catalyst on the one hand, and the decentralization of active constituent, suppressed excessive carbon distribution simultaneously, improve activity of such catalysts, modified catalyst surface effectively makes it help suitable carbon distribution form and generates on the other hand, thereby the side reaction degree is reduced, improved cinnamic selectivity of purpose product and yield.Its conversion ratio generally improves more than 2%, and selectivity generally can improve more than 1%, thereby causes purpose product styrene yield to be greatly improved.Confirm that through test such Fe-K-Ce-Mo-Mg catalyst system and catalyzing has good catalytic stability, has obtained better technical effect in addition.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
90.5 iron oxide reds, 190.5 gram iron oxide yellows, 50.6 gram potash, 90.5 gram nitric acid persimmons, 10.3 gram ammonium molybdates, 10.4 gram magnesia and cement, carboxymethyl cellulose and an amount of rare earth oxide (seeing Table 1) were stirred 1 hour in kneading machine, 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, 40～80 ℃ were dried by the fire 1～6 hour, place muffle furnace then, made catalyst in 2～6 hours in 500～1000 ℃ of roastings.The preparation method of embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 just adds the different rare earth oxide of 2.5 grams with embodiment 1.The method for preparing catalyst of comparative example is with embodiment 1, but do not add any rare earth oxide.
The Fe-K-Mo-Ce-Mg Preparation of Catalyst inventory that the different rare earth oxides of table 1 promote
| Raw material | Inventory (gram) | ||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example | |
| Iron oxide red iron oxide yellow potash cerous nitrate ammonium molybdate magnesia cement carboxymethyl cellulose rare earth oxide* | 90.1 190.5 50.6 90.8 10.3 10.4 15 10 Y | 130.3 152.6 60.3 70.3 15.1 8.4 25 8 Eu | 100.1 183.1 55.9 75.4 17.4 11.2 23 9 Gd | 123.7 167.5 65.6 60.7 8.3 20.1 19 5 Tb | 170.3 112.5 68.2 69.8 11.2 13.6 19 8 Dy | 190.1 95.5 70.8 65.8 9.8 16.5 17 4 Yb | 140.0 145.3 60.6 71.2 13.3 12.3 21 7 - |
*: rare earth element adds with its salt or oxide form, and its inventory that is converted into corresponding oxide is 2.5 grams.
[embodiment 7～10]
Method for preparing catalyst is with embodiment 1, and concrete inventory is:
The Fe-K-Mo-Ce-Mg Preparation of Catalyst inventory that table 2 different content rare earth oxide promotes
| Raw material | Inventory (gram) | ||||
| Embodiment 7 | Embodiment 8 | Embodiment 3 | Embodiment 9 | Embodiment 10 | |
| Iron oxide red iron oxide yellow potash cerous nitrate ammonium molybdate magnesia cement carboxymethyl cellulose Gd2O 3 | 139.1 142.3 59.6 80.2 20.1 15.4 28 9 1.5 | 90.1 190.5 51.7 70.8 10.3 6.4 20 9 2.0 | 100.1 183.1 55.9 75.4 17.4 11.2 23 9 2.5 | 90.1 190.5 48.6 68.8 15.3 9.8 15 9 3.0 | 90.1 190.5 46.3 65.2 13.8 7.4 17 9 6.0 |
The ethyl benzene dehydrogenation preparation of styrene performance of embodiment, comparative example catalyst:
Table 3 catalyst ethylbenzene dehydrogenation performance relatively
*
| Catalyst | Inventory | ||
| Conversion of ethylbenzene (%) | Selectivity of styrene (%) | The styrene list is received (%) | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 comparative examples | 77.3 77.5 77.6 76.9 77.3 77.5 76.9 75.2 77.7 77.5 76.5 | 91.4 91.3 95.0 94.8 94.9 94.7 95.0 94.7 94.6 94.4 94.2 | 70.6 70.8 73.7 72.9 73.4 73.4 73.0 71.2 73.5 73.2 72.0 |
*: catalyst performance is 200 hours a mean value after the stable reaction.
From the embodiment explanation, catalyst of the present invention, on the basis of Fe-K-Ce-Mo-Mg basic composition, introduce the rare earth oxide of proper proportion, made dehydrogenation had both had high activity, selectivity, having suitable stability simultaneously, is a kind of new and effective ethylbenzene dehydrogenation oxide catalyst.
Claims (7)
1, a kind of catalyst that is used for ethyl benzene dehydrogenation preparation of styrene comprises following active constituent by weight percentage:
A) 55～85% Fe
2O
3
B) 5～30% K
2O;
C) 3～10% Ce
2O
3
D) 0.5～5% MoO
3
E) 0.1～5% be selected from oxide at least a among Y, Eu, Gd, Tb, Dy, the Yb;
Fe wherein
2O
3By Fe
2O
3And Fe
2O
3H
2O forms, by weight Fe
2O
3: Fe
2O
3H
2O is 0.2～5: 1.
2, according to the described catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that Fe by weight
2O
3: Fe
2O
3H
2O is 0.5～4: 1.
3, according to the described catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that being selected from by weight percentage oxide consumption at least a among Y, Eu, Gd, Tb, Dy, the Yb is 0.1～3%.
4, according to the described catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 3, it is characterized in that being selected from by weight percentage oxide consumption at least a among Y, Eu, Gd, Tb, Dy, the Yb is 0.5～2%.
5, according to the described catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1, it is characterized in that active constituent also comprises 0.05～8% alkaline earth oxide by weight percentage.
6,, it is characterized in that alkaline earth oxide is selected from magnesia, calcium oxide or its mixture according to the described catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 5.
7,, it is characterized in that also containing by weight percentage in the catalyst 1～10% binding agent cement according to the described catalyst that is used for ethyl benzene dehydrogenation preparation of styrene of claim 1.
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|---|---|---|---|
| CNB2005100270139A CN100531905C (en) | 2005-06-22 | 2005-06-22 | Catalysts for ethyl benzene dehydrogenation for preparation of styrene |
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| Publication Number | Publication Date |
|---|---|
| CN1883796A true CN1883796A (en) | 2006-12-27 |
| CN100531905C CN100531905C (en) | 2009-08-26 |
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| CN102371161A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof |
| CN102371160A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Low-temperature ethyl benzene dehydrogenation catalyst |
| CN102372592A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing styrene by dehydrogenating ethylbenzene |
| CN101993336B (en) * | 2009-08-31 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition |
| CN106582688A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparation of styrene and preparation method thereof |
| 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 |
| KR20180092993A (en) * | 2015-12-11 | 2018-08-20 | 쿠라리안토 쇼쿠바이 가부시키가이샤 | Alkyl aromatic compound dehydrogenation catalyst, a process for producing the same, and a dehydrogenation process using the same |
| CN109569636A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | High activity ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof |
| CN110681389A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Low water ratio ethylbenzene dehydrogenation catalyst with low potassium content |
| CN110681392A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Low-water-ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN110681391A (en) * | 2018-07-06 | 2020-01-14 | 中国石油化工股份有限公司 | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN112237921A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Low-water-ratio high-space-velocity ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN112239392A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Low temperature alkyl aromatic dehydrogenation method |
| CN112237922A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
| CN113877596A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
| CN114452981A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Ultra-low water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof |
-
2005
- 2005-06-22 CN CNB2005100270139A patent/CN100531905C/en active Active
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| CN102372592B (en) * | 2010-08-23 | 2014-07-23 | 中国石油化工股份有限公司 | Method for preparing styrene by dehydrogenating ethylbenzene |
| CN102372592A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing styrene by dehydrogenating ethylbenzene |
| CN102371160A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Low-temperature ethyl benzene dehydrogenation catalyst |
| CN102371160B (en) * | 2010-08-23 | 2013-05-08 | 中国石油化工股份有限公司 | Low-temperature ethyl benzene dehydrogenation catalyst |
| CN102371161B (en) * | 2010-08-23 | 2013-05-08 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof |
| CN102371161A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst with low steam-to-oil ratio and preparation method thereof |
| CN106582688A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for preparation of styrene and preparation method thereof |
| 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 |
| CN106582688B (en) * | 2015-10-16 | 2019-02-19 | 中国石油化工股份有限公司 | It is used to prepare the dehydrogenation and preparation method thereof of styrene |
| KR102208674B1 (en) * | 2015-12-11 | 2021-01-27 | 쿠라리안토 쇼쿠바이 가부시키가이샤 | Alkyl aromatic compound dehydrogenation catalyst and process for preparing same, and dehydrogenation process using same |
| KR20180092993A (en) * | 2015-12-11 | 2018-08-20 | 쿠라리안토 쇼쿠바이 가부시키가이샤 | Alkyl aromatic compound dehydrogenation catalyst, a process for producing the same, and a dehydrogenation process using the same |
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| CN113877596A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Ethylbenzene dehydrogenation catalyst and preparation method and application thereof |
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