CN100418937C - Method for producing diethylbenzene through dehydrogenation of diethyl benzene - Google Patents
Method for producing diethylbenzene through dehydrogenation of diethyl benzene Download PDFInfo
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- CN100418937C CN100418937C CNB2005100287765A CN200510028776A CN100418937C CN 100418937 C CN100418937 C CN 100418937C CN B2005100287765 A CNB2005100287765 A CN B2005100287765A CN 200510028776 A CN200510028776 A CN 200510028776A CN 100418937 C CN100418937 C CN 100418937C
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- diethylbenzene
- dehydrogenation
- gram
- catalyzer
- diethyl benzene
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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
Abstract
This invention relates to a method for preparing divinylbenzene by diethylbenzene dehydrogenation. The method uses Fe-K-Ce-Mo catalyst system, and keeps high catalytic selectivity and anti-carbon deposition ability by adjusting the ratio of the above elements as well as adding multiple rare earth compounds. The method has a high divinylbenzene yield, and can be used for divinylbenzene industrial manufacture.
Description
Technical field
The present invention relates to a kind of method of producing diethylbenzene through dehydrogenation of diethyl benzene.
Background technology
The catalyzer that is used for many ethylbenzene dehydrogenations is mostly used the catalyzer of ethyl benzene dehydrogenation preparation of styrene, and main component is generally Fe-K-Ce/Cr, as patent ZL95111761.0, ZL98110739.7, ZL99113572.5.ZL95111761.0 discloses a kind of dehydrogenation catalyst that is used to produce alkyl alkenyl arene, and its composition is to have added multiple metal oxide and silicon sol in iron-potassium-chromium system.The catalyzer that makes can be applicable to ethyl benzene dehydrogenation preparation of styrene, also can be used for diethylbenzene dehydrogenation system divinylbenzene.When this catalyzer was used for ethyl benzene dehydrogenation preparation of styrene, under 600 ℃ of conditions, it was 73.9% that the vinylbenzene list is received, and conversion of ethylbenzene is 78.3%, and selectivity of styrene is 94.4%.But the catalyst activity data when this patent and unexposed diethylbenzene dehydrogenation, and this catalyzer used chromium cpd, and environment is brought pollution.ZL98110739.7 discloses a kind of Alkylarylhydrocarbondehydrogenating dehydrogenating catalyst, by in the Fe-K-Ce-Mo system, adding vanadium and titanium component, and potassium content in the control catalyst (in oxide compound) is below 15%, make catalyzer under 620 ℃ of conditions of temperature of reaction, have advantages of high catalytic activity and vinylbenzene yield, it is 74.18% that the vinylbenzene list is received, conversion of ethylbenzene is 78.37%, and selectivity of styrene is 94.65%.ZL99113572.5 discloses a kind of alkyl aromatics catalytic dehydrogenation catalyst, by in the Fe-K-Ce-Mo-Zr system, adopt low potassium (5～15 weight %), add calcium oxide and na oxide and multiple metal oxide, it is 74.3% that the catalyzer that obtains vinylbenzene list in the time of 620 ℃ is received, conversion of ethylbenzene is 78.2%, and selectivity of styrene is 95.0%.The disclosed catalyzer of ZL98110739.7 and ZL99113572.5 also can be used for diethylbenzene dehydrogenation system divinylbenzene, but does not report the activity data of diethylbenzene dehydrogenation system divinylbenzene.In actual applications, this type of catalyst selectivity is low, and the catalyzer life cycle is short, and in use also must frequently activate, and the throughput of device is lower, and material consumption and energy consumption are all higher.
Summary of the invention
Technical problem to be solved by this invention is that chromium provides a kind of method of new producing diethylbenzene through dehydrogenation of diethyl benzene to the pollution and the low problem of diethylbenzene dehydrogenation product yield of environment in the catalyzer that exists in the conventional art.Use method of the present invention to have to obtain the advantage of catalytic activity and selectivity preferably and used catalyzer environmentally safe.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing diethylbenzene through dehydrogenation of diethyl benzene is a raw material with the diethylbenzene, is 550～650 ℃ in temperature of reaction, and reaction pressure is 30KPa～normal pressure, air speed 0.05～0.3 hour
-1, water/diethylbenzene weight ratio is under 2.0～5.0: 1 condition, and raw material contacts with catalyzer and generates divinylbenzene, and wherein used catalyzer comprises following component by weight percentage:
a)60～90％Fe
2O
3；
b)5～13％K
2O；
c)4～10％Ce
2O
3；
d)0.1～5％MoO
3；
e)0.1～3％Pr
2O
3；
F) 0.001～10% at least a oxide compound that is selected from IIA family, IIIA family, IVA family or transition element.
In the technique scheme, the preferable range of temperature of reaction is 600～630 ℃, and the preferable range of reaction pressure is 50KPa～normal pressure, and the preferable range of air speed is 0.1～0.2 hour
-1, the preferable range of water/diethylbenzene mass ratio is 3.0～4.0: 1, the oxide compound consumption of praseodymium is with Pr by weight percentage
2O
3The meter preferable range is 0.5～2%, and the oxide compound preferable range of at least a by weight percentage IIA of being selected from family, IIIA family, IVA family or transition element is 0.5～2.5%.
Method for preparing catalyst of the present invention is as follows:
Press compound, the pore-creating agent of other metal of proportioning weighing Fe, K, Ce, Pr, Mo and selection, dry powder blend adds an amount of deionized water, and wet feed is kneaded into the face dough that is fit to extrusion.It is 3 millimeters that extrusion, pelletizing become diameter, and bar length is the particle of 5 millimeter.In aged at room temperature 2～10 hours, 80～120 ℃ of dryings 4 hours, 800～1000 ℃ of roastings 2 hours can obtain the catalyzer finished product.Wherein, raw material Fe
2O
3Form with red iron oxide and/or iron oxide yellow adds K
2O adds with salt of wormwood, Ce
2O
3And Pr
2O
3Form with nitrate adds MoO
3Add with the form of ammonium molybdate, pore-creating agent is selected from least a in carboxymethyl cellulose, graphite, the polystyrene microsphere etc., and the consumption of pore-creating agent is 0.1～4% of a catalyst weight.
Activity rating of catalyst carries out in the isothermal fixed-bed reactor among the present invention, and reactor is that internal diameter is 25 millimeters a stainless steel tube, loads 100 milliliters of catalyzer, and dehydrogenation liquid records many ethylbenzene and many Ethenylbenzenes content for stratographic analysis.Calculating formula is as follows:
The boiling test method of catalyzer is as follows among the present invention: is one group with 100 catalyst samples with 10, is divided into 10 groups and tests.In the water that 10 catalyst samples inputs are boiled, continue to boil 30 minutes after, cooled off 30 minutes.Observe the integrity degree of granules of catalyst in the water, record disruptive granule number.Repeated test 10 times, crack-free are qualified.
The cold water test method of catalyzer is as follows among the present invention: is one group with 100 catalyst samples with 10, is divided into 10 groups and tests.10 catalyst samples are dropped in the cold water, left standstill 30 minutes.Observe the integrity degree of granules of catalyst in the water, record disruptive granule number.Repeated test 10 times, crack-free are qualified.
Because the present invention has adopted the ratio of adjusting Fe, K, elements such as Ce, Mo, simultaneously be incorporated into technical scheme in the Fe-K-Ce-Mo catalyst system with cerous nitrate and the suitable blending ratio of praseodymium nitrate, make catalyzer keep higher selectivity and anti-carbon deposition ability, obtained better technical effect.
The invention will be further elaborated below by embodiment and comparative example.
Embodiment
[embodiment 1]
185 gram red iron oxides, 120 gram iron oxide yellow, 65 gram salt of wormwood, 60 gram cerous nitrates, 20 gram praseodymium nitrates, 9.5 gram ammonium molybdates, 30 gram caoxalates, 2.1 gram vanadium oxides, 2 gram manganese oxide, 2.3 gram stannic oxide, 0.4 gram boron oxide, 10 gram carboxymethyl celluloses are mixed, add 140 gram deionized waters, wet feed is kneaded into the face dough that is fit to extrusion, extrusion, pelletizing, in aged at room temperature 10 hours, put into baking oven, in 80 ℃ of dryings 6 hours, place stoving oven, made the catalyzer finished product in 2 hours in 800 ℃ of roastings.With 100 milliliters of catalyzer assessing reactor of packing into, 620 ℃ of temperature of reaction, water/diethylbenzene weight ratio is 2.0: 1, pressure 50KPa, and air speed was carried out catalytically active assessment under the condition in 0.05 hour-1, and measured boiling test qualification rate and cold water test qualification rate.Test result: diethylbenzene transformation efficiency 80.6%, toluylene selectivity 52.1%, ethyl styrene selectivity 34.7%, boiling test is qualified, and cold water test is qualified.
[embodiment 2]
With 100 milliliters of catalyzer of embodiment 1 catalyzer assessing reactor of packing into, 580 ℃ of temperature of reaction, water/diethylbenzene weight ratio is 4.5: 1, pressure 30KPa, air speed 0.1 hour
-1Carry out catalytically active assessment under the condition, and measure boiling test qualification rate and cold water test qualification rate.Test result: diethylbenzene transformation efficiency 80.9%, toluylene selectivity 52.0%, ethyl styrene selectivity 34.1%, boiling test is qualified, and cold water test is qualified.
[embodiment 3]
With 100 milliliters of catalyzer of embodiment 1 catalyzer assessing reactor of packing into, 640 ℃ of temperature of reaction, water/diethylbenzene weight ratio is 3.0: 1, normal pressure, air speed 0.3 hour
-1Carry out catalytically active assessment under the condition, and measure boiling test qualification rate and cold water test qualification rate.Test result: diethylbenzene transformation efficiency 80.6%, toluylene selectivity 52.3%, ethyl styrene selectivity 34.3%, boiling test is qualified, and cold water test is qualified.
[embodiment 4]
185 gram red iron oxides, 120 gram iron oxide yellow, 65 gram salt of wormwood, 50 gram cerous nitrates, 30 gram praseodymium nitrates, 9.5 gram ammonium molybdates, 30 gram caoxalates, 2.1 gram vanadium oxides, 0.4 gram boron oxide, 10 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: diethylbenzene transformation efficiency 80.1%, toluylene selectivity 52.6%, ethyl styrene selectivity 35.6%, boiling test is qualified, and cold water test is qualified.
[embodiment 5]
With 100 milliliters of catalyzer of embodiment 4 catalyzer assessing reactor of packing into, 580 ℃ of temperature of reaction, water/diethylbenzene weight ratio is 4.5: 1, pressure 30 KPa, air speed 0.1 hour
-1Carry out catalytically active assessment under the condition, and measure boiling test qualification rate and cold water test qualification rate.Test result: diethylbenzene transformation efficiency 79.8%, toluylene selectivity 52.9%, ethyl styrene selectivity 35.1%, boiling test is qualified, and cold water test is qualified.
[embodiment 6]
With 100 milliliters of catalyzer of embodiment 4 catalyzer assessing reactor of packing into, 640 ℃ of temperature of reaction, water/diethylbenzene weight ratio is 3.0: 1, normal pressure, air speed 0.3 hour
-1Carry out catalytically active assessment under the condition, and measure boiling test qualification rate and cold water test qualification rate.Test result: diethylbenzene transformation efficiency 80.5%, toluylene selectivity 52.0%, ethyl styrene selectivity 35.3%, boiling test is qualified, and cold water test is qualified.
[comparative example 1]
185 gram red iron oxides, 120 gram iron oxide yellow, 65 gram salt of wormwood, 80 gram cerous nitrates, 9.5 gram ammonium molybdates, 30 gram caoxalates, 2.1 gram vanadium oxides, 2 gram manganese oxide, 2.3 gram stannic oxide, 0.4 gram boron oxide, 10 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: diethylbenzene transformation efficiency 75.3%, divinylbenzene selectivity 50.1%, ethyl styrene selectivity 36.4%, boiling test is qualified, and cold water test is qualified.
More than each embodiment explanation, among the present invention, be incorporated in the Fe-K-Ce-Mo catalyst system with cerous nitrate and the suitable blending ratio of praseodymium nitrate, make catalyzer have catalytic activity and selectivity preferably.
[embodiment 7～9]
Method by embodiment 1 is carried out Preparation of Catalyst and test, and the catalyst activity appreciation condition is 630 ℃ of temperature of reaction, and water/diethylbenzene weight ratio is 3.5: 1, normal pressure, air speed 0.1 hour
-1, its result such as table 1.
Table 1
Claims (7)
1. the method for a producing diethylbenzene through dehydrogenation of diethyl benzene is a raw material with the diethylbenzene, is 550～650 ℃ in temperature of reaction, and reaction pressure is 30KPa～normal pressure, air speed 0.05～0.3 hour
-1, water/diethylbenzene weight ratio is under 2.0～5.0: 1 condition, and raw material contacts with catalyzer and generates divinylbenzene, and wherein used catalyzer comprises following component by weight percentage:
a)60～90％Fe
2O
3；
b)5～13％K
2O；
c)4～10％Ce
2O
3；
d)0.1～5％MoO
3；
e)0.1～3％Pr
2O
3；
F) 0.001～10% at least a oxide compound that is selected from IIA family, IIIA family, IVA family or transition element.
2. according to the method for the described producing diethylbenzene through dehydrogenation of diethyl benzene of claim 1, it is characterized in that temperature of reaction is 600～630 ℃.
3. according to the method for the described producing diethylbenzene through dehydrogenation of diethyl benzene of claim 1, it is characterized in that reaction pressure is 50KPa～normal pressure.
4. according to the method for the described producing diethylbenzene through dehydrogenation of diethyl benzene of claim 1, it is characterized in that air speed is 0.1～0.2 hour
-1
5. according to the method for the described producing diethylbenzene through dehydrogenation of diethyl benzene of claim 1, it is characterized in that water/diethylbenzene weight ratio is 3.0～4.0: 1.
6. according to the method for the described producing diethylbenzene through dehydrogenation of diethyl benzene of claim 1, it is characterized in that Pr by weight percentage
2O
3Consumption be 0.5～2%.
7. according to the method for the described producing diethylbenzene through dehydrogenation of diethyl benzene of claim 1, it is characterized in that the oxide compound consumption of at least a by weight percentage IIA of being selected from family, IIIA family, IVA family or transition element is 0.5～2.5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100287765A CN100418937C (en) | 2005-08-15 | 2005-08-15 | Method for producing diethylbenzene through dehydrogenation of diethyl benzene |
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|---|---|---|---|
| CNB2005100287765A CN100418937C (en) | 2005-08-15 | 2005-08-15 | Method for producing diethylbenzene through dehydrogenation of diethyl benzene |
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| CN1915941A CN1915941A (en) | 2007-02-21 |
| CN100418937C true CN100418937C (en) | 2008-09-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107790145B (en) * | 2016-09-06 | 2023-06-06 | 中国石油化工股份有限公司 | Catalyst for preparing alkenyl arene and preparation method and application thereof |
| CN111375449B (en) * | 2020-03-26 | 2023-03-21 | 江苏大学 | Dehydrogenation catalyst and application thereof in preparation of divinylbenzene by virtue of dehydrogenation of diethylbenzene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062678A (en) * | 1991-10-30 | 1992-07-15 | 中国石油化工总公司 | The dehydrogenation that is used for alkylaromatic hydrocarbon |
| CN1150062A (en) * | 1995-11-15 | 1997-05-21 | 中国石油化工总公司 | Dehydrogenation catalyst for producing unsaturated aromatic hydrocarbon |
| CN1180687A (en) * | 1996-10-22 | 1998-05-06 | 中国石油化工总公司上海石油化工研究院 | Dehydrogenating technology for producing phenylethylene |
| CN1323767A (en) * | 2001-03-14 | 2001-11-28 | 中国石油天然气股份有限公司兰州石化分公司 | Alkyl aromatics dehydrogenating catalyst and its prepn. |
-
2005
- 2005-08-15 CN CNB2005100287765A patent/CN100418937C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062678A (en) * | 1991-10-30 | 1992-07-15 | 中国石油化工总公司 | The dehydrogenation that is used for alkylaromatic hydrocarbon |
| CN1150062A (en) * | 1995-11-15 | 1997-05-21 | 中国石油化工总公司 | Dehydrogenation catalyst for producing unsaturated aromatic hydrocarbon |
| CN1180687A (en) * | 1996-10-22 | 1998-05-06 | 中国石油化工总公司上海石油化工研究院 | Dehydrogenating technology for producing phenylethylene |
| CN1323767A (en) * | 2001-03-14 | 2001-11-28 | 中国石油天然气股份有限公司兰州石化分公司 | Alkyl aromatics dehydrogenating catalyst and its prepn. |
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| CN1915941A (en) | 2007-02-21 |
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