CN101091915B - Catalyst of ethyl benzene dehydrogenation - Google Patents

Catalyst of ethyl benzene dehydrogenation Download PDF

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CN101091915B
CN101091915B CN200610027903A CN200610027903A CN101091915B CN 101091915 B CN101091915 B CN 101091915B CN 200610027903 A CN200610027903 A CN 200610027903A CN 200610027903 A CN200610027903 A CN 200610027903A CN 101091915 B CN101091915 B CN 101091915B
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styrene
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ethyl benzene
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CN101091915A (en
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范勤
陈铜
倪军平
缪长喜
毛连生
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst of ethyl benzene dehydrogenation, mainly the technical question of inducing the catalyst stability drop by the amiable of the high potassium content ethyl benzene dehydrogenation catalyst and anti-squash strength of the low potassium content catalyst. In the Fe-K-Ce-W catalyst system, the invention adjusts MgO and CaO proportion suitably to keep the high activeness and selective of the low potassium content catalyst and simultaneity has the high anti-squash strength solves the technical question preferably; the catalyst prepared can be used in the industrial production of the ethyl benzene dehydrogenation preparation styrene.

Description

The catalyst of ethylbenzene dehydrogenation
Technical field
The present invention relates to a kind of catalyst of ethylbenzene dehydrogenation.
Background technology
At present, the catalyst of industrial alkyl aromatics dehydrogenation mostly is the Fe-K-Ce-Mo series catalysts, and as ZL91109968.9, ZL95113340.3, this type of catalyst activity and selectivity are higher, but in the component as the K of co-catalyst 20 content is quite high.As ZL91109968.9 is a kind of dehydrogenation that is used for alkylaromatic hydrocarbon, its composition is in iron-potassium-cerium-molybdenum system, added multiple metal oxide, the catalyst that makes is under 620 ℃ of conditions, it is 71.9% that the styrene list is received, conversion of ethylbenzene is 74.4%, and selectivity of styrene is 96.6%, but in catalyst component K 20 content is up to about 30%, because the strong absorptive of potassium, when catalyst placed air, the easy adsorption moisture of the catalyst of high potassium content reduced the anti-crushing power of catalyst granules, 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 caused the decline of catalyst stability, influence catalyst service life.ZL95113340.3 is a kind of dehydrogenation that is used to produce unsaturated aromatic hydrocarbon, its composition is in iron-potassium-molybdenum-magnesium-thulium system, added multiple metal oxide, wherein, thulium contains two kinds combination at least in catalyst, and the catalyst that makes is under 620 ℃ of conditions, it is 74.90% that the styrene list is received, conversion of ethylbenzene is 78.35%, and selectivity of styrene is 95.60%, but equally also is high potassium content catalyst.In above-mentioned catalyst, reduce potassium content simply and can cause the anti-crushing power of catalyst obviously to descend, catalytic activity is also had adverse influence, in catalyst, merely increase binding agent anti-crushing power is significantly improved.
Summary of the invention
Technical problem to be solved by this invention is the easily suction and cause catalyst stability to descend and the low problem of low potassium content catalyst anti-crushing power of high in the past potassium content dehydrogenation, and a kind of catalyst of new ethylbenzene dehydrogenation is provided.It is low that this catalyst has a potassium content, is used for ethylbenzene dehydrogenation reaction, and catalyst is keeping high activity and optionally also having the advantage of higher anti-crushing power simultaneously.
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 catalyst of ethylbenzene dehydrogenation comprises following component by weight percentage:
a)50～90％Fe 2O 3；
b)5～10％K 2O；
c)4～10％Ce 2O 3；
d)0.1～5％WO 3；
e)0.1～15％CaO；
f)0.1～15％MgO；
Wherein the weight ratio of MgO: CaO is 1～5: 1.
In the technique scheme, the preferable range of CaO is 0.5～10% by weight percentage, the preferable range of MgO is that the more preferably scope of 0.5～10%.CaO is 1～8% by weight percentage by weight percentage, the more preferably scope of MgO is that the weight ratio preferable range of 1～8%.MgO: CaO is 2～3: 1 by weight percentage, and the preferred version of catalyst is for also containing 0.01～10% oxide that is selected from transition metal zirconium and nickel in the catalyst by weight percentage.
Method for preparing catalyst of the present invention is as follows:
By proportioning weighing Fe, K, Ce, W, Ca, the compound of Mg and other required transition metal oxide, pore-foaming agent, 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 1～8 hour, 600～1000 ℃ of roastings 1～10 hour can obtain the catalyst finished product.Wherein, raw material Fe 2O 3Form with iron oxide red and/or iron oxide yellow adds K 2O adds Ce with the form of potash 2O 3Form with cerous nitrate adds WO 3Form with ammonium tungstate adds, and CaO adds with the form of calcium oxide and/or calcium carbonate/calcium oxalate/calcium acetate, and MgO adds with magnesian form, and the consumption of pore-foaming agent is 0.1～4% of a catalyst weight.
The activity of such catalysts evaluation is carried out in the isothermal fixed bed reactors among the present invention, and reactor is that internal diameter is 25 millimeters a stainless steel tube, loads 100 milliliters of catalyst, and dehydrogenation liquid records ethylbenzene and styrene-content for chromatography.Calculating formula is as follows:
Figure G2006100279034D00021
Figure G2006100279034D00022
The styrene list is received (%)=conversion of ethylbenzene (%) * selectivity of styrene (%)
The boiling test method of testing of catalyst 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 catalyst granules in the water, the granule number that record breaks.Retest 10 times, crack-free are qualified.
The cold water test method of testing of catalyst 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 catalyst granules in the water, the granule number that record breaks.Retest 10 times, crack-free are qualified.
The anti-crushing power of catalyst is measured by the specification requirement of standard HG/T 2782-1996 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 arithmetic mean of instantaneous value of getting its measurement result is final anti-crushing power value, is the resistance to crusing unit of force with newton (N).
Because the present invention has adopted in the Fe-K-Ce-W catalyst system, suitably regulate the technical scheme of the ratio of MgO and CaO, thereby make the low potassium content catalyst keeping higher activity and optionally also having the broken power of higher compression simultaneously, obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstate, 44.8 gram calcium oxide, 20.8 gram calcium oxalate, 38.2 calcium acetate, 66.2 gram magnesia, 1.6 gram manganese oxide, 1.4 gram zirconia, 1.2 gram nickel oxide, 18 gram carboxymethyl celluloses mix, add 160 gram deionized waters, wet feed is mediated to 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 roaster, made the catalyst finished product in 2 hours in 800 ℃ of roastings. with 100 milliliters of catalyst assessing reactor of packing into, 620 ℃ of reaction temperatures, water is than carrying out catalytically active assessment under 2.0 conditions, and the anti-crushing power of mensuration catalyst, the boiling test qualification rate, the cold water test qualification rate. test result: conversion of ethylbenzene 77.5%, selectivity of styrene 95.2%, the styrene list receives 73.8%, anti-crushing power 123N, boiling test is qualified, cold water test is qualified.
[embodiment 2]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 16.4 gram ammonium tungstates, 5.6 gram calcium carbonate, 15.6 gram magnesia, 1.2 gram manganese oxide, 1.6 gram zirconias, 1 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 78.3%, selectivity of styrene 95.1%, the styrene list receives 74.5%, anti-crushing power 124N, boiling test is qualified, cold water test is qualified.
[embodiment 3]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstates, 12.4 gram calcium carbonate, 18.2 calcium acetates, 50.6 gram magnesia, 1 gram manganese oxide, 1.2 gram zirconias, 1.4 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 78.1%, selectivity of styrene 95.1%, the styrene list receives 74.3%, anti-crushing power 122N, boiling test is qualified, cold water test is qualified.
[embodiment 4]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstates, 26.2 gram calcium oxide, 30.2 gram calcium oxalates, 10.2 calcium carbonate, 46.2 gram magnesia, 2.2 gram manganese oxide, 1.2 gram zirconias, 1.4 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 78.9%, selectivity of styrene 95.2%, the styrene list receives 75.1%, anti-crushing power 120N, boiling test is qualified, cold water test is qualified.
[embodiment 5]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstates, 8.8 gram calcium oxide, 18.4 gram calcium oxalates, 20.8 calcium acetates, 41.3 gram magnesia, 1.6 gram manganese oxide, 1 gram zirconia, 1.2 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 78.7%, selectivity of styrene 95.3%, the styrene list receives 75.0%, anti-crushing power 123N, boiling test is qualified, cold water test is qualified.
[embodiment 6]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 16.8 gram ammonium tungstates, 12.3 gram calcium oxalates, 4.8 gram magnesia, 2.2 gram manganese oxide, 1 gram zirconia, 1.4 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 77.8%, selectivity of styrene 95.1%, the styrene list receives 74.0%, anti-crushing power 120N, boiling test is qualified, cold water test is qualified.
[embodiment 7]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstates, 13.1 gram calcium oxide, 38.2 gram magnesia, 1.6 gram manganese oxide, 1.2 gram zirconias, 1.2 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 78.8%, selectivity of styrene 95.3%, the styrene list receives 75.1%, anti-crushing power 125N, boiling test is qualified, cold water test is qualified.
[comparative example 1]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstates, 38.7 gram calcium oxide, 4.5 gram magnesia, 1.6 gram manganese oxide, 1 gram zirconia, 1.2 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, method by embodiment 1 is prepared and measures. test result: conversion of ethylbenzene 75.9%, selectivity of styrene 95.3%, the styrene list receives 72.3%, anti-crushing power 85N, boiling test is defective, cold water test is defective.
[comparative example 2]
230 gram iron oxide reds, 170 gram iron oxide yellows, 56 gram potash, 76 gram cerous nitrates, 13.6 gram ammonium tungstates, 4.1 gram calcium oxide, 48.9 gram magnesia, 1.6 gram manganese oxide, 1 gram zirconia, 1.2 gram nickel oxide, 18 gram carboxymethyl celluloses are mixed, be prepared and measure by the method for embodiment 1.Test result: conversion of ethylbenzene 75.9%, selectivity of styrene 95.3%, the styrene list receives 72.3%, anti-crushing power 85N, boiling test is defective, cold water test is defective.
More than each embodiment explanation, among the present invention, the ratio of suitably regulating MgO and CaO is incorporated in the catalyst component, makes the low potassium content catalyst keep higher activity and optionally also have the broken power of higher compression simultaneously.

Claims (7)

1. the catalyst of an ethylbenzene dehydrogenation comprises following component by weight percentage:
a)50～90％Fe 2O 3；
b)5～10％K 2O；
c)4～10％Ce 2O 3；
d)0.1～5％WO 3；
e)0.1～15％CaO；
f)0.1～15％MgO；
Wherein the weight ratio of MgO: CaO is 1～5: 1.
2. according to the catalyst of the described ethylbenzene dehydrogenation of claim 1, it is characterized in that the content of CaO is 0.5～10% by weight percentage.
3. according to the catalyst of the described ethylbenzene dehydrogenation of claim 2, it is characterized in that the content of CaO is 1～8% by weight percentage.
4. according to the catalyst of the described ethylbenzene dehydrogenation of claim 1, it is characterized in that the content of MgO is 0.5～10% by weight percentage.
5. according to the catalyst of the described ethylbenzene dehydrogenation of claim 4, it is characterized in that the content of MgO is 1～8% by weight percentage.
6. according to the catalyst of the described ethylbenzene dehydrogenation of claim 1, it is characterized in that MgO: the weight ratio of CaO is 2～3: 1.
7. according to the catalyst of the described ethylbenzene dehydrogenation of claim 1, it is characterized in that also containing in the catalyst by weight percentage 0.01～10% oxide that is selected from transition metal zirconium and nickel.
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Publication number Priority date Publication date Assignee Title
CN101992095B (en) * 2009-08-31 2012-10-10 中国石油化工股份有限公司 Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof
CN102040464B (en) * 2009-10-13 2013-01-23 中国石油化工股份有限公司 Method for preparing styrene from crude ethylbenzene by dehydrogenation
CN103539627B (en) * 2012-07-12 2015-09-09 中国石油化工股份有限公司 Manufacture cinnamic method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6551958B1 (en) * 1998-03-30 2003-04-22 Basf Aktiengesellschaft Catalyst for dehydrogenating ethyl benzene to produce styrene
CN1443735A (en) * 2002-03-13 2003-09-24 中国石油化工股份有限公司 Method for preparing alkyl aromatics dehydrogenation catalyst
CN1589963A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene
CN1589962A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Alkyl aromatics dehydrogen catalyst
CN1765495A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Catalyst for preparing cinnamene by dehydrogenation of ethylbenzene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6551958B1 (en) * 1998-03-30 2003-04-22 Basf Aktiengesellschaft Catalyst for dehydrogenating ethyl benzene to produce styrene
CN1443735A (en) * 2002-03-13 2003-09-24 中国石油化工股份有限公司 Method for preparing alkyl aromatics dehydrogenation catalyst
CN1589963A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Oxide catalyst used in ethyl benzene dehydrogen for preparing phenyl ethylene
CN1589962A (en) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 Alkyl aromatics dehydrogen catalyst
CN1765495A (en) * 2004-10-29 2006-05-03 中国石油化工股份有限公司 Catalyst for preparing cinnamene by dehydrogenation of ethylbenzene

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