CN1047097C - Dehydrogenation catalyst for prodn. of alkylalkenyl aromatic hydrocarbon - Google Patents
Dehydrogenation catalyst for prodn. of alkylalkenyl aromatic hydrocarbon Download PDFInfo
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- CN1047097C CN1047097C CN 95111761 CN95111761A CN1047097C CN 1047097 C CN1047097 C CN 1047097C CN 95111761 CN95111761 CN 95111761 CN 95111761 A CN95111761 A CN 95111761A CN 1047097 C CN1047097 C CN 1047097C
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Abstract
The present invention relates to a dehydrogenation catalyst used for producing alkane-base arene. In the composition, a plurality of kinds of metal oxide and silica sol are added in an iron-potassium-chromium system, wherein the addition of silica sol is 0.5 to 8% (weight) measured by silicon dioxide, and elements in the added metal oxide are selected from at least one kind or several kinds in an IB-VIIIB group and an IIIA-VA group. The prepared catalyst is suitable for low water ratio (the water ratio is smaller than 1.0) and has higher activity and selectivety. The present invention can be applied to the dehydrogenation production of alkyl arene.
Description
The present invention relates to a kind of dehydrogenation that is used for alkylaromatic hydrocarbon, this catalyst can be used for ethyl benzene dehydrogenation preparation of styrene, diethylbenzene dehydrogenation system divinylbenzene, also can be used for methyl-ethyl benzene dehydrogenation system methyl styrene.
As everyone knows, common industrial production alkenyl arene is to be made by alkyl aromatics catalytic dehydrogenation, yet one of key of this production method is to select a kind of low water ratio dehydrogenation efficiently.According to relevant documents and materials, divide with the main composition of catalyst, can be divided into two big classes: first kind catalyst is to be main component by iron-potassium-chromium, adds other elements again.Be characterized in throwing that material-water ratio (water vapour and ethylbenzene than) is low, selectivity is not high, conversion ratio is also low; The second class catalyst is to be main component with iron-potassium-cerium-molybdenum, adds other elements again.Increase than the former as disclosed catalyst selectivity, conversion ratio among the disclosed Chinese patent ZL91109968.9.Catalyst water ratio is 1.3～2.0 (weight ratios).
With the scale of industrial dehydrogenation of ethylbenzene to styrene, its annual production mostly be ten thousand tons to the hundreds of thousands ton, therefore, dehydrogenation is done small improvement on performance, just can make manufacturing enterprise obtain huge benefits.Even the yield of catalyst increases one percentage point or two percentage points, concerning the commercial plant of a ton scale, need not change any equipment, need not increase investment, just can increase hundreds of tons product in 1 year, and improve device operation efficiency, reduce consumption of raw materials.For this reason, in the catalyst while of seeking to be applicable to low water ratio, improving the conversion ratio and the selectivity of catalyst, is the research topic that people pay close attention to always.
The purpose of this invention is to provide a kind of dehydrogenation that is used for alkylaromatic hydrocarbon, it has higher activity, selectivity and styrene yield than the dehydrogenation of present industrial use, have simultaneously stronger again from power of regeneration, be suitable for using under than (water than less than 1.0) condition at low water, we have invented a kind of new catalyst that is suitable for production of styrene.
Dehydrogenation provided by the invention is to serve as main the composition with iron-potassium-chromium, added multiple metal oxide, its metallic element can be selected for use in alkaline-earth metal, I B-VIII B family and the III A-V A family from the periodic table of elements, adds Ludox, pore-foaming agent and adhesive again.
Specifically, dehydrogenation of the present invention, comprising component is (percentage by weight): Fe
2O
340～90%, K
2O 5～30%, MgO 0.001～5%, Cr
2O
31.0～15%, Ludox is 0.5～8% (with SiO
2The amount meter), and 0.001～5% at least a oxide that is selected from Cu, Zn, Sc, Ti, W, Mn, Ni, Pd, Al, P, Bi, B, Sn, Pb, Na, Si element, all the other are pore-foaming agent and binding agent.
The above-mentioned described dehydrogenation that is used to produce alkyl alkenyl arene, the preferable range of MgO is 0.5～4% (weight), the preferable range of the oxide of at least a Cu of being selected from, Zn, Sc, Ti, W, Mn, Ni, Pd, Al, P, Bi, B, Sn, Pb, Na element is 0.002～2% (weight), Cr
2O
3Preferable range be 3～6% (weight), Ludox is with SiO
2Weight meter preferable range be 1.0～3%.The addition of pore-foaming agent is 1～2%, and wherein used iron adds with the form of iron oxide, and iron oxide is made through oxidation by acidic ferrous salt, and used potassium adds with the carbonate form of potassium, and chromium adds with the chromate form.
Method for preparing catalyst of the present invention:
After will mixing by Fe, K, Mg, B family element, A family element, silicon melten gel, binding agent, the pore-foaming agent of proportioning weighing, add an amount of deionized water, make the face dough of toughness, suitable extrusion, becoming diameter through extrusion, pelletizing is 3 millimeters, long 8～10 millimeters particle, then, 400～800 ℃ of following roastings 2～4 hours, just can obtain finished catalyst.
Dehydrogenation of the present invention under certain process conditions, can be applicable to fully that ethylbenzene, diethylbenzene, methyl-ethyl benzene dehydrogenation generate styrene, divinylbenzene and methyl styrene.
The catalyst that makes as stated above carries out activity rating in the isotherm formula fixed bed.The activity rating of catalyst for preparing phenylethylene from dehydrogenation of ethylbenzene, 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.Reactor adopts the heating wire heating, makes it to reach predetermined temperature.Reactor inside diameter is 1 stainless steel tube, and interior 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:
Ethylbenzene concentration (%wt) before ethylbenzene concentration (%wt) reaction back ethylbenzene concentration (%wt)/reaction before the conversion of ethylbenzene %=reaction.
Ethylbenzene concentration (%wt) before concentration of styrene (%wt)/reaction that selectivity of styrene %=generates-reaction back ethylbenzene concentration (%wt).
Further describe the present invention with embodiment below
[embodiment 1]
550 gram iron oxide, 54 gram potash, 70 gram potassium chromates, 20 gram Ludox (are contained SiO
227%), 9 gram magnesia, 0.9 gram cupric oxide, 35 gram cement, 4.1 gram pore-foaming agents stirred in pinching machine 2～4 hours.Take out extrusion, be extruded into 3 millimeters of diameters, long 8～10 millimeters particle.Place roaster then, made catalyst in 2～4 hours in 450～650 ℃ of roastings.With 100 milliliters, particle diameter be 3 millimeters catalyst to put into internal diameter be 1 isothermal reactor, carry out activity rating.Appreciation condition is that reaction pressure is 600 ℃ of normal pressure, reaction temperatures, and water is than (water/ethylbenzene) 0.9 (weight ratio), and evaluation result: conversion of ethylbenzene 76.5%, selectivity of styrene 94.30%, styrene yield are 72.14%.
[embodiment 2]
235 gram iron oxide, 97 gram potash, 50 gram potassium chromates, 80 gram Ludox (are contained SiO
227%), 6 the gram magnesia, 0.8 the gram cobalt nitrate, 0.5 the gram cupric oxide, 0.1 the gram lead oxide, 16 the gram cement, 6 the gram pore-foaming agents, make catalyst by embodiment 1 method, estimate by the appreciation condition of embodiment 1.Evaluation result: conversion of ethylbenzene 77.3%, selectivity of styrene 94.35%, styrene yield are 72.9 3%.
[embodiment 3]
340 gram iron oxide, 80 gram potash, 25 gram potassium chromates, 40 gram Ludox (contain SiO
227%), 10 gram magnesia, 20 gram bismuth nitrates, 0.9 gram cupric oxide, 26 gram cement, 8 gram pore-foaming agents, make catalyst by embodiment 1 method, pressing the similarity condition of embodiment 1 estimates active, evaluation result: conversion of ethylbenzene 77.21%, selectivity of styrene 93.98%, styrene yield are 72.56%.
[embodiment 4]
550 gram iron oxide, 100 gram potash, 8 gram magnesia, 9 gram nickel oxide, 0.9 gram cupric oxide, 0.1 gram boron oxide, 0.9 gram titanium oxide, 0.1 gram tin oxide, 0.1 gram tungsten oxide, 22 gram cement, 50 gram potassium chromates, 60 gram Ludox (contain SiO
227%), 9 the gram pore-foaming agents, make catalyst by embodiment 1 method, estimate by the appreciation condition of embodiment 1, different is that reaction temperature is 585 ℃, water is than 0.85 (weight ratio).Evaluation result: conversion of ethylbenzene 70.81%, selectivity of styrene 93.93%, styrene yield are 66.51%.
[embodiment 5]
550 gram iron oxide, 100 gram potash, 60 gram potassium chromates, 35 gram Ludox (are contained SiO
227%), 5 gram magnesia, 2.35 gram zinc oxide, 0.1 gram palladium oxide, 0.1 gram lead oxide, 0.5 gram aluminium oxide, 0.7 gram bismuth nitrate, 0.2 gram cupric oxide, 25 gram cement, 9 gram pore-foaming agents, make catalyst by embodiment 1 method, appreciation condition by embodiment 1 is estimated, evaluation result: conversion of ethylbenzene 78.3%, selectivity of styrene 94.44%, styrene yield are 73.95%.
[embodiment 6]
Press the catalyst of embodiment 4 and form, use the appreciation condition of embodiment 1, evaluation result: conversion of ethylbenzene 78.6%, selectivity of styrene 94.82%, styrene yield are 74.53%, then, still press the appreciation condition of embodiment 1, continue logical ethylbenzene, stop supplying water steam after 20 minutes, continue to feed water vapour and react, evaluation result: conversion of ethylbenzene 78.21%, selectivity of styrene 94.39%, the styrene yield is 73.82%, it is very strong from power of regeneration to illustrate that catalyst of the present invention has.
The foregoing description explanation, by in iron-potassium-chromium system, add multiple metal oxide, pore-foaming agent, binding agent and Ludox, made dehydrogenation of the present invention has and is applicable to the performance of low water than (less than 1.0), and have higher conversion ratio and selectivity, have stronger again from power of regeneration.
Claims (5)
1. dehydrogenation that is used to produce alkyl alkenyl arene contains component and is by weight percentage: Fe
2O
340～90%, K
2O 5～30%, MgO 0.001～5% and 0.001～5% at least a oxide that is selected from Cu, Zn, Sc, Ti, W, Mn, Ni, Pd, Al, P, Bi, B, Sn, Pb, Na element, and pore-foaming agent 1～2% is characterized in that catalyst also contains Cr
2O
31～15%, Ludox is 0.5～8% with SiO
2The amount meter, all the other are binding agent.
2. according to the described dehydrogenation that is used to produce alkyl alkenyl arene of claim 1, the weight content that it is characterized in that MgO is 0.5～4%.
3. according to the described dehydrogenation that is used to produce alkyl alkenyl arene of claim 1, it is characterized in that the oxide of at least a Cu of being selected from, Zn, Sc, Ti, W, Mn, Ni, Pd, Al, P, Bi, B, Sn, Pb, Na element is 0.002～2% with weight content.
4. according to the described dehydrogenation that is used to produce alkyl alkenyl arene of claim 1, it is characterized in that Cr
2O
3Weight content be 3～6%.
5. according to the described dehydrogenation that is used to produce alkyl alkenyl arene of claim 1, it is characterized in that the Ludox weight content is 1.0～3.0% (with SiO
2The amount meter).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111761 CN1047097C (en) | 1995-09-15 | 1995-09-15 | Dehydrogenation catalyst for prodn. of alkylalkenyl aromatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111761 CN1047097C (en) | 1995-09-15 | 1995-09-15 | Dehydrogenation catalyst for prodn. of alkylalkenyl aromatic hydrocarbon |
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| Publication Number | Publication Date |
|---|---|
| CN1145277A CN1145277A (en) | 1997-03-19 |
| CN1047097C true CN1047097C (en) | 1999-12-08 |
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ID=5079010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95111761 Expired - Fee Related CN1047097C (en) | 1995-09-15 | 1995-09-15 | Dehydrogenation catalyst for prodn. of alkylalkenyl aromatic hydrocarbon |
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| Country | Link |
|---|---|
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242379B1 (en) | 1998-04-01 | 2001-06-05 | United Catalysts Inc. | Dehydrogenation catalysts |
| US6756339B1 (en) | 1998-04-01 | 2004-06-29 | Sud-Chemie Inc. | Dehydrogenation catalysts |
| CN100443170C (en) * | 2005-09-01 | 2008-12-17 | 中国石油天然气股份有限公司 | Catalyst for producing phenylethene by ethylbenzene dehydrogenation and its preparation method |
| CN101940922B (en) * | 2009-07-09 | 2012-05-23 | 中国石油化工股份有限公司 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN106000448B (en) * | 2016-05-26 | 2019-01-29 | 江苏正丹化学工业股份有限公司 | Vinyltoluene production catalyst and preparation method thereof |
| CN107973682B (en) * | 2016-10-21 | 2020-07-24 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN107970913B (en) * | 2016-10-21 | 2020-06-09 | 中国石油化工股份有限公司 | Chromium-bismuth catalyst for preparing propylene by propane dehydrogenation, preparation method and application |
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1995
- 1995-09-15 CN CN 95111761 patent/CN1047097C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1145277A (en) | 1997-03-19 |
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