CN104437515A - Low-carbon alkane dehydrogenation catalyst and use method thereof - Google Patents

Low-carbon alkane dehydrogenation catalyst and use method thereof Download PDF

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Publication number
CN104437515A
CN104437515A CN201310435313.5A CN201310435313A CN104437515A CN 104437515 A CN104437515 A CN 104437515A CN 201310435313 A CN201310435313 A CN 201310435313A CN 104437515 A CN104437515 A CN 104437515A
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catalyst
low
oxide
grams
dehydrogenation
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吴省
缪长喜
刘瑞丹
姜冬宇
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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

The invention relates to a low-carbon alkane dehydrogenation catalyst and a use method thereof, and the low-carbon alkane dehydrogenation catalyst is mainly used for solving the problem of low activity of a dehydrogenation catalyst prepared in the prior art. In order to better solve the problem, the technical scheme adopted by the invention is as follows: the low-carbon alkane dehydrogenation catalyst provided by the invention comprises the following components in parts by weight: a) 1-30 parts of Cr element or an oxide thereof; b) 0.1-5 parts of K element or an oxide thereof; c) 0.1-10 parts of Cu element or an oxide thereof; d) 0.001-1 part of P element or an oxide thereof; e) 0-5 parts of Ca element or an oxide thereof; f) 0-5 parts of Fe element or an oxide thereof; g) 44-99 parts of Al2O3. The low-carbon alkane dehydrogenation catalyst can be used in the industrial production of low-carbon alkane dehydrogenation for preparing low-carbon olefin.

Description

Catalyst for dehydrogenation of low-carbon paraffin and using method thereof
Technical field
The present invention relates to a kind of for catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof.
Background technology
Low-carbon alkene is often referred to the alkene that carbon number is less than or equal to 4, it is very important Organic Chemicals, especially ethene, propylene, butylene etc., be considered to the basic material of modern petrochemical, in order to produce polyethylene, polypropylene, acrylonitrile, oxirane, expoxy propane, butanols, isopropylbenzene etc.Wherein propylene consumption is only second to ethene etc., in recent years global propylene consumption figure with average annual 4.8% speed increase, exceed the amplification of the propone output same period.China's propylene demand is quite large, and relies on import for a long time, it is predicted that during 12, China needs import 5,000,000 tons of propylene every year.And along with the development of rubber industry, particularly along with environmental requirement, the demand of MTBE increases very fast, the demand of isobutene also significantly increases, much larger than output amplification.The production of low-carbon alkene mainly adopts ethene coproduction and catalytic pyrolysis (cracking such as naphtha, light diesel fuel) by-product, due to day by day lacking and the conventional restriction obtaining propylene, isobutene means of Global Oil resource, development new technologies substitute conventional olefin production method and seem very important.Utilize abundance, to prepare low-carbon alkene be one of most promising method to cheap dehydrogenating low-carbon alkane.Dehydrogenating low-carbon alkane is a strong endothermic reaction, only under low pressure, hot conditions, just can obtain comparatively ideal olefin yields, and react under hot conditions be easily polymerized, cyclisation, the side reaction such as charing, make the quick carbon distribution of catalyst surface, inactivation, catalyst performance is caused to be deteriorated, the selective problem such as lower, therefore, need the dehydrogenation that processability is excellent, improve alkane conversion and olefine selective.
At present about independent propane or the corresponding alkene of catalytic dehydrogenation of isobutane system are studied more, and existing more than 20 cover propane or dehydrogenation of isobutane device are running in the world, main De-hydrogen Technology has the Oleflex technique of UOP, the Catofin technique of Lummus, the STAR technique of Uhde, the PDH technique of Linde, the FBD technique etc. of Snamprogetti-Yarsintez cooperative development, what wherein industrialized unit was maximum is Oleflex technology and Catofin technology, both catalyst of application are Pt system and Cr series catalysts respectively, dehydrogenating technology is substantially identical, different just dehydrogenation and catalyst regeneration part, Oleflex technique uses moving-burden bed reactor, external regeneration, Catofin adopts fixed bed reactors, carries out hot-air and burns carbon cycle regeneration.In recent years, about there are more bibliographical information and patent application in dehydrating alkanes Cr series catalysts aspect, CN 1086150C, have studied a kind of catalyst iso-butane being converted into isobutene, active component is wherein CrPt, auxiliary agent is alkali metal, alkaline-earth metal and transition metal, and load is on aluminium oxide or alumina globule; This catalyst is 65.1% to the maximum conversion of iso-butane, selective isobutene 93.2%.CN 101940922 take chromium as active component, and alkali metal is cocatalyst component, is that carrier has prepared alkane dehydrogenating catalyst containing Cr aluminium oxide, and when reacting 10 minutes, propane maximum conversion is 57.8%, Propylene Selectivity 91.5%.CN 100406415 relates to the dehydrogenation catalyst complex containing aluminium oxide, chromium oxide, lithia and sodium oxide molybdena.
Catalyst for dehydrogenation of low-carbon paraffin obtains greater advance at present, but still it is not high to there is conversion ratio, or the problem that in the higher situation of conversion ratio, olefine selective is lower.P, as nonmetalloid always, adds in catalyst and can change catalyst surface characteristic, particularly characteristic electron, can improve catalyst surface Acidity of Aikalinity simultaneously, therefore have better application prospect, not yet have relevant report at present.
Summary of the invention
One of technical problem to be solved by this invention is the active lower problem of catalyst for dehydrogenation of low-carbon paraffin in prior art, provide a kind of newly for catalyst for dehydrogenation of low-carbon paraffin.The technical problem to be solved in the present invention two, is to provide a kind of method for preparing catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of for catalyst for dehydrogenation of low-carbon paraffin, with weight parts, comprises following component:
A) the Cr element of 1 ~ 30 part or its oxide;
B) K element of 0.1 ~ 5 part or its oxide;
C) the Cu element of 0.1 ~ 10 part or its oxide;
D) 0.001 ~ 1 part P element or its oxide;
E) the Ca element of 0 ~ 5 part or its oxide;
F) 0 ~ 5 part of Fe element or its oxide;
G) Al of 44 ~ 99 parts 2o 3carrier.
In technique scheme, with catalyst for dehydrogenation of low-carbon paraffin weight parts, the preferable range of Cr or its oxide number is 5 ~ 20 parts; The number of K or its oxide is 0.5 ~ 2 part; The number of Cu or its oxide is 1 ~ 3 part; P element or its oxide number are 0.01 ~ 0.5 part; The number of Ca element or its oxide is 0.01 ~ 1 part; The number of Fe element or its oxide is 0.01 ~ 1 part; Al 2o 3for γ type, δ type and θ type Al 2o 3in one or both.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of be used for catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, comprises the following steps:
A) by nanometer Al 2o 3carrier compressing tablet, screening, choose 40 ~ 60 mesh sieves divide after carrier calcination process 0.5 ~ 12 hour under 400 ~ 600 DEG C of conditions, obtain nanometer Al 2o 3carrier I;
B) carrier I and aequum are mixed into mixture I containing the solubility solution of Cr, the solubility solution containing K, the solubility solution containing Ca, the solubility solution containing Cu, the solubility solution containing P element, with inorganic ammonia or inorganic ammonium salt solution under temperature is 10 ~ 80 DEG C of conditions, the pH value regulating mixture I is 1 ~ 7, obtains mixture II;
C) under temperature is 10 ~ 100 DEG C of conditions, said mixture II is flooded 0.5 ~ 8 hour, then carry out filtering, dry, 300 ~ 800 DEG C of roastings 0.5 ~ 12 hour, obtain required catalyst for dehydrogenation of low-carbon paraffin.
In technique scheme, inorganic ammonia or inorganic ammonium salt preferred version are selected from ammoniacal liquor, ammonium carbonate or carbonic hydroammonium, and the pH value preferable range of solution is 1 ~ 7, and more preferably scope is 1 ~ 3; Dipping temperature preferable range is 50 ~ 80 DEG C, and dip time preferable range is 1 ~ 3 hour, and catalyst sintering temperature preferable range is 400 ~ 600 DEG C, and roasting time preferable range is 4 ~ 8 hours.
The using method of catalyst is: reaction raw materials is propane or iso-butane, and reaction condition is: reaction pressure is 0 ~ 1MPa, temperature is 500 ~ 650 DEG C, mass space velocity is 0.1 ~ 10h -1, the catalyst exposure in reaction raw materials and technique scheme is obtained by reacting propylene or isobutene.
Catalyst obtained as stated above carries out activity rating in isotherm formula fixed bed reactors, and for dehydrogenating low-carbon alkane producing light olefins system appraisal, summary process is as follows:
Low-carbon alkanes, for propane, by unstrpped gas by mass flowmenter adjust flux, enter pre-add hot-zone to mix, then enter reaction zone, the pre-add hot-zone of reactor and reaction zone all adopt electric-heating-wire-heating, make it to reach predetermined temperature, the internal diameter of reactor is the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, is about 400mm.Reacted gas, by after drainer, enters its composition of gas chromatographic analysis.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows: it is (catalyst bed layer height 17mm) in the isothermal reactor of Ф 9mm-Ф 6mm that the catalyst of about 0.5 gram is loaded internal diameter, and reaction pressure is normal pressure, gas space velocity 600 hours -1, reaction temperature 560 DEG C.
Conversion of propane and Propylene Selectivity calculate as follows:
In dehydrogenating low-carbon alkane process, simple Cr 2o 3/ Al 2o 3catalyst surface acidity is comparatively strong, the easy carbon distribution of catalyst surface and deactivation rate is accelerated.For slowing down catalysqt deactivation speed, improve catalyst performance by adding other auxiliary agent, also can reduce reaction temperature alleviates catalyst surface carbon distribution simultaneously.As the Al with stronger surface acidity 2o 3material, adding of alkali and alkaline earth metal ions element can reduce its surface acidity, the dispersion of Cr element on carrier can be improved adding of transition metal Cu and nonmetalloid P etc. simultaneously, or impel the formation of more active sites Cr, thus improve Cr series catalysts carbon accumulation resisting ability, improve catalyst performance.Above-mentioned appreciation condition is adopted to be used for by catalyst of the present invention in dehydrogenating low-carbon alkane reaction, its Activity evaluation shows, this catalyst has higher alkane conversion, comparatively can reach 60% under low reaction temperatures, there is higher olefine selective simultaneously, be greater than 90%, achieve good technique effect.
Below by embodiment, the present invention is further elaborated.
 
Detailed description of the invention
[embodiment 1]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.0014 gram of phosphoric acid, join in the deionized water of 100 milliliters, add 87.4999 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.By propane gas by mass flowmenter adjust flux, enter pre-add hot-zone and mix, then enter reaction zone, the pre-add hot-zone of reactor and reaction zone all adopt electric-heating-wire-heating, make it to reach predetermined temperature, the internal diameter of reactor is the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, is about 400mm.Reacted gas, by after drainer, enters its composition of gas chromatographic analysis.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows: loaded by 0.5 gram of catalyst (catalyst bed layer height 17mm) in above-mentioned isothermal fixed bed reactors, reaction pressure is normal pressure, mass space velocity 1.5 hours -1, reaction temperature 560 DEG C.It the results are shown in Table 1.
 
[embodiment 2]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 1.4 grams of phosphoric acid, join in the deionized water of 100 milliliters, add 85.5 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 3]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.014 gram of phosphoric acid, join in the deionized water of 100 milliliters, then add 87.499 grams of alumina supports, ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then flood in 80 DEG C of water-baths after 1 hour, take out sample and filter, drying 8 hours in 120 DEG C of baking ovens, again sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 4]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.7 gram of phosphoric acid, join in the deionized water of 100 milliliters, add 86.5 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 5]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.028 gram of phosphoric acid, join in the deionized water of 100 milliliters, add 87.498 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 7, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 6]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.7 gram of phosphoric acid, 1.47 grams of calcium nitrate, join in the deionized water of 100 milliliters, then add 86.0 grams of alumina supports, ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then flood in 80 DEG C of water-baths after 1 hour, take out sample and filter, drying 8 hours in 120 DEG C of baking ovens, again sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 7]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.7 gram of phosphoric acid, 2.53 grams of ferric nitrates, join in the deionized water of 100 milliliters, then add 86.0 grams of alumina supports, ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then flood in 80 DEG C of water-baths after 1 hour, take out sample and filter, drying 8 hours in 120 DEG C of baking ovens, again sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 8]
Weigh 52.65 grams of chromic nitrates, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.7 gram of phosphoric acid, 1.47 grams of calcium nitrate, 2.53 grams of ferric nitrates, join in the deionized water of 100 milliliters, add 85.5 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 9]
Weigh 5.27 grams of chromic nitrates, 0.22 gram of potassium nitrate, 30.4 grams of copper nitrates, 0.07 gram of phosphoric acid, 25.3 grams of ferric nitrates, join in the deionized water of 100 milliliters, then add 83.8 grams of alumina supports, ammoniacal liquor with 2.5 % by weight regulates solution ph to 3, then flood in 80 DEG C of water-baths after 1 hour, take out sample and filter, drying 8 hours in 120 DEG C of baking ovens, again sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 10]
Weigh 157.95 grams of chromic nitrates, 10.75 grams of potassium nitrate, 3.04 grams of copper nitrates, 0.07 gram of phosphoric acid, 14.7 grams of calcium nitrate, join in the deionized water of 100 milliliters, then add 58.9 grams of alumina supports, ammoniacal liquor with 2.5 % by weight regulates solution ph to 7, then flood in 50 DEG C of water-baths after 1 hour, take out sample and filter, drying 8 hours in 120 DEG C of baking ovens, again sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 11]
Weigh 105.3 grams of chromic nitrates, 4.3 grams of potassium nitrate, 30.4 grams of copper nitrates, 0.7 gram of phosphoric acid, 2.94 grams of calcium nitrate, 0.05 gram of ferric nitrate, join in the deionized water of 100 milliliters, add 72 grams of alumina supports again, the hydrochloric acid solution with 2.5 % by weight regulates solution ph to 1, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 12]
Weigh 26.33 grams of chromic nitrates, 1.23 grams of potassium nitrate, 3.04 grams of copper nitrates, 0.0007 gram of phosphoric acid, 0.03 gram of calcium nitrate, 25.3 grams of ferric nitrates, join in the deionized water of 100 milliliters, add 93.4 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 3, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[embodiment 13]
Weigh 157.95 grams of chromic nitrates, 10.75 grams of potassium nitrate, 30.4 grams of copper nitrates, 0.007 gram of phosphoric acid, 14.7 grams of calcium nitrate, 25.3 grams of ferric nitrates, join in the deionized water of 100 milliliters, add 44 grams of alumina supports again, the ammoniacal liquor with 2.5 % by weight regulates solution ph to 3, then floods after 1 hour in 80 DEG C of water-baths, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
 
[comparative example 1]
Weigh 52.65 grams of chromic nitrates, 2.15 gram potassium nitrate, 4.56 grams of copper nitrates, join in the deionized water of 100 milliliters, then add 87.5 grams of alumina supports, ammoniacal liquor with 2.5 % by weight regulates solution ph to 3.5, then flood in 80 DEG C of water-baths after 1 hour, take out sample and filter, drying 8 hours in 120 DEG C of baking ovens, again sample is put into Muffle furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyst.Examination condition, with embodiment 1, the results are shown in Table 1.
Table 1
[embodiment 14 ~ 17]
The catalyst that embodiment 1 prepares is used for dehydrogenating low-carbon alkane, and reaction raw materials is propane, and reaction raw materials is obtained by reacting propylene with catalyst exposure under certain condition; Reaction condition and evaluation result are in table 2.
Table 2

Claims (9)

1., for a catalyst for dehydrogenation of low-carbon paraffin, in catalyst weight number, comprise following component:
A) 1 ~ 30 part of Cr element or its oxide;
B) 0.1 ~ 5 part of K element or its oxide;
C) 0.1 ~ 10 part of Cu element or its oxide;
D) 0.001 ~ 1 part of P element or its oxide;
E) 0 ~ 5 part of Ca element or its oxide;
F) 0 ~ 5 part of Fe element or its oxide;
G) 44 ~ 99 parts of Al 2o 3.
2. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with catalyst for dehydrogenation of low-carbon paraffin weight parts, the number of Cr or its oxide is 5 ~ 20 parts.
3. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with catalyst for dehydrogenation of low-carbon paraffin weight parts, the number of K or its oxide is 0.5 ~ 2 part.
4. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with catalyst for dehydrogenation of low-carbon paraffin weight parts, the number of Cu or its oxide is 1 ~ 3 part.
5. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with catalyst for dehydrogenation of low-carbon paraffin weight parts, P element or its oxide number are 0.01 ~ 0.5 part.
6. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with catalyst for dehydrogenation of low-carbon paraffin weight parts, the number of Ca element or its oxide is 0.01 ~ 1 part.
7. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with catalyst for dehydrogenation of low-carbon paraffin weight parts, the number of Fe element or its oxide is 0.01 ~ 1 part.
8., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that Al 2o 3for γ type, δ type and θ type Al 2o 3in one or both.
9. catalyst described in any one of claim 1 ~ 8 is used for dehydrogenating low-carbon alkane, reaction raw materials is propane or iso-butane, and reaction condition is: reaction pressure is 0 ~ 1MPa, temperature is 500 ~ 650 DEG C, mass space velocity is 0.1 ~ 10h -1, reaction raw materials and described catalyst exposure are obtained by reacting propylene or isobutene.
CN201310435313.5A 2013-09-24 2013-09-24 Low-carbon alkane dehydrogenation catalyst and use method thereof Pending CN104437515A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108654596A (en) * 2018-04-28 2018-10-16 洛阳市科创石化科技开发有限公司 A kind of propane dehydrogenation catalyst and preparation method thereof

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CN102794167A (en) * 2012-06-15 2012-11-28 北京石油化工学院 Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method for catalyst
CN103055930A (en) * 2011-10-18 2013-04-24 中国石油化工股份有限公司 Low carbon alkane dehydrogenation catalyst and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3781223A (en) * 1971-05-06 1973-12-25 Phillips Petroleum Co Catalyst for oxidative dehydrogenation
CN1185994A (en) * 1996-12-24 1998-07-01 中国科学院兰州化学物理研究所 Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof
CN103055930A (en) * 2011-10-18 2013-04-24 中国石油化工股份有限公司 Low carbon alkane dehydrogenation catalyst and preparation method
CN102794167A (en) * 2012-06-15 2012-11-28 北京石油化工学院 Catalyst for preparing isobutene by isobutane dehydrogenation and preparation method for catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108654596A (en) * 2018-04-28 2018-10-16 洛阳市科创石化科技开发有限公司 A kind of propane dehydrogenation catalyst and preparation method thereof

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