CN104549220A - Catalyst for dehydrogenating light alkane - Google Patents
Catalyst for dehydrogenating light alkane Download PDFInfo
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- CN104549220A CN104549220A CN201310512165.2A CN201310512165A CN104549220A CN 104549220 A CN104549220 A CN 104549220A CN 201310512165 A CN201310512165 A CN 201310512165A CN 104549220 A CN104549220 A CN 104549220A
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Abstract
The invention relates to a catalyst for dehydrogenating light alkane in order to mainly solve the problem of relatively-low activity of a dehydrogenating catalyst prepared in the prior art. The problem is better solved through the technical scheme that the catalyst for dehydrogenating light alkane comprises the following components in parts by weight: 1-30 parts of a Cr element or an oxide of the Cr element (a), 0.1-5 parts of alkali metal oxides or alkaline earth metal oxides (b), 0.001-1 part of the group VA elements selected from a periodic table of elements or oxides of the group VA elements (c), 0.001-1 part of the group IIIA elements selected from the periodic table of elements or oxides of the group IIIA elements (d), and 54-99 parts of Al2O3 or SiO2 (e). The catalyst can be used for industrial production of light olefin prepared by dehydrogenating light alkane.
Description
Technical field
The present invention relates to a kind of catalyzer for dehydrogenating low-carbon alkane.
Background technology
The low-carbon alkene such as propylene and iso-butylene is one of most important organic raw material of petrochemical industry, wherein propylene is mainly for the production of polypropylene, vinyl cyanide, propylene oxide etc., iso-butylene is mainly used in isoprene-isobutylene rubber, polyisobutene etc., particularly along with environmental requirement improves, in oil product, additive MTBE consumption increases very fast, directly cause iso-butylene to occur larger demand gap, therefore need a large amount of propylene of import, iso-butylene etc. to meet domestic needs.Current propylene and iso-butylene are mainly derived from ethene coproduction and refinery's by-product, along with the realization of the technological processs such as the development of Coal Chemical Industry, particularly MTO, MTP, except obtaining low-carbon alkene, also the low-carbon alkanes that by-product is more, simultaneously along with the exploitation of shale gas, will have more low-carbon alkanes to generate.Therefore how low-carbon alkanes being converted into low-carbon alkene and becoming Coal Chemical Industry, petrochemical complex development focal point, is also the focus of future market demand.Dehydrogenating low-carbon alkane technique can be divided into oxydehydrogenation and direct dehydrogenation two type, oxidative dehydrogenation process releases heat, reaction is not by equilibrium-limited, transformation efficiency is higher, but selectivity is low, if select pure oxygen to do its operating process of oxygenant there is larger danger, direct dehydrogenation is therefore selected to become the focus of people's concern.Dehydrogenating low-carbon alkane reaction is by the restriction of thermodynamics of reactions balance, it is a strong endothermic reaction, just comparatively ideal olefin yields must can be obtained under low pressure, hot conditions, and too high temperature of reaction will make alkane cracking react and deep dehydrogenation aggravation, easily to be 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 problems such as selectivity is lower, therefore, need the dehydrogenation catalyst that processability is excellent, improve alkane conversion and olefine selective.
Study more to relevant propane or the corresponding alkene of catalytic dehydrogenation of isobutane system abroad, define following several main De-hydrogen Technology: the FBD technique etc. of the STAR technique of the Oleflex technique of UOP, the Catofin technique of Lummus, Uhde, the PDH technique of Linde, Snamprogetti-Yarsintez cooperative development, existing more than 20 cover propane or dehydrogenation of isobutane device are running in the world so far, add and domesticly building and planning to build device, 30 cover dehydrating alkanes devices will be reached.In these industrialized units, applying maximum is Oleflex technology and Catofin technology, both catalyzer 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 reactor, carries out warm air and burns carbon cycle regeneration.With the oxygenant of the precious metal elements such as Pt for main active ingredient, utilize modern technique to add various auxiliary agent, use aluminum oxide or aluminate etc. to do carrier preparation, catalyzer has better activity, the preparation method of catalyzer waits document at home and abroad also to have more open, as US Pat. 3,488402; 5,132,484 etc.Cr system non-precious metal catalyst, the elements such as basic metal that adopt carry out modification more, do carrier prepare with aluminum oxide.In recent years, about there are more bibliographical information and patent application in dehydrating alkanes Cr series catalysts aspect, CN86104061A discloses a kind of method preparing C3 ~ C5 paraffin hydrocarbon dehydrogenation catalyst, utilize the compound oxide impregnation alumina supporter containing Cr and K, use silicon-containing compound solution impregnation after dry, finally carry out drying and roasting.The method shortcoming prepares high-content active metal component catalyzer to have larger difficulty, and active ingredient loading is subject to certain restrictions, and it is not very strong that catalyzer holds charcoal ability, and inactivation is fast.CN1668555A discloses a kind of composite oxide catalysts, and containing chromic oxide, Lithium Oxide 98min, sodium oxide and aluminum oxide etc., preparation method is pickling process.Similar patent also has CN 100406415, CN 1086150 etc., and when for dehydrogenating low-carbon alkane, transformation efficiency and selectivity are all not satisfactory.
Catalyst for dehydrogenation of low-carbon paraffin obtains greater advance at present, but still it is not high to there is transformation efficiency, or the problem that in the higher situation of transformation efficiency, olefine selective is lower.P, as non-metallic element, adds in catalyzer and can change catalyst surface characteristic, particularly characteristic electron; Ga, as the Main Group Metal Elements appraised at the current rate always, adds in catalyzer and can change catalyst surface characteristic, and characteristic of particularly appraising at the current rate contributes to active ingredient Cr in reaction, therefore has better application prospect, not yet has 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) 1 ~ 30 part of Cr element or its oxide compound;
B) 0.1 ~ 5 part of alkalimetal oxide or alkaline earth metal oxide;
C) 0.001 ~ 1 part is selected from the periodic table of elements the Vth A race element or its oxide compound;
D) 0.001 ~ 1 part is selected from periodic table of elements group IIIA element or its oxide compound;
E) 54 ~ 99 parts of Al
2o
3or SiO
2.
In technique scheme, with weight parts, the preferable range of chromium or its oxide compound number is 5 ~ 20 parts; The preferable range of alkalimetal oxide or alkaline earth metal oxide number 0.5 ~ 2 part; Be selected from the periodic table of elements the Vth A race element or its oxide compound number is 0.01 ~ 0.5 part; Be selected from the preferable range 0.01 ~ 0.5 part of periodic table of elements group IIIA element or its oxide compound number; Be selected from periodic table of elements group IIIA element and be preferably Ga; Be selected from the periodic table of elements the Vth A race element and be preferably P; Al
2o
3for γ type, δ type and θ type Al
2o
3in one or both; With molar ratio computing Components of Catalysts a: the preferable range of components b is for 0.1 ~ 10:1; Component a: the preferable range of amount of component b is 1 ~ 100:1; The preferable range of component a: component d is 1 ~ 50:1.
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 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 Al
2o
3carrier I;
B) by carrier I and aequum containing the solubility solution of Cr, alkali metal containing oxide compound or alkaline earth metal oxide solubility solution, containing be selected from the periodic table of elements the Vth A race element solubility solution, be mixed into mixture I containing the solubility solution being selected from periodic table of elements group IIIA 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 ~
Liquid 0 ~ 3800 DEG C of roasting 0.5 ~ 12 hour, obtains required catalyst for dehydrogenation of low-carbon paraffin.
In technique scheme, inorganic ammonia or inorganic ammonium salt preferred version are selected from ammoniacal liquor, volatile salt or bicarbonate of ammonia, 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 dipping time preferable range is 1 ~ 3 hour, and catalyzer maturing temperature preferable range is 400 ~ 6
Liquid 0 ~ 366600 DEG C, roasting time preferable range is 4 ~ 8 hours.
The content of Components of Catalysts is measured by X ray fluorescence spectrometer (XRF).After sample compression molding, at ZSX-100e 4580 type XRF(Rigaku) the upper characteristic spectral line intensity measuring atom, thus obtain the content of component in sample.
Catalyzer obtained as stated above carries out activity rating in isotherm formula fixed-bed reactor, and for dehydrogenating low-carbon alkane producing light olefins system appraisal, summary process is as follows:
Low-carbon alkanes, for propane, by unstripped gas by mass flowmeter 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 preset temperature, the internal diameter of reactor is the stainless steel sleeve pipe of Ф 9mm-Ф 6mm, long 400mm.Reacted gas, by after drainer, enters its composition of gas chromatographic analysis.
In isotherm formula fixed-bed reactor, evaluating catalyst condition is as follows: it is (catalyst bed layer height is about 17mm) in the isothermal reactor of Ф 9mm-Ф 6mm that the catalyzer of about 0.5 gram is loaded internal diameter, and reaction pressure is normal pressure, gas space velocity 600 hours
-1, temperature of reaction 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 catalyst deactivation speed, improve catalyst performance by adding other auxiliary agent, also can reduce temperature of reaction alleviates catalyst surface carbon distribution simultaneously.As the Al with stronger surface acidity
2o
3material, adding of alkali metal can reduce its surface acidity, simultaneously can improve catalyst surface characteristic electron adding of the 3rd main group element Ga that appraises at the current rate of non-metallic element P and having etc., Cr element is better disperseed on carrier, or impel the formation of more active sites Cr, thus it is active to improve Cr series catalysts, improve catalyst performance.Above-mentioned appreciation condition is adopted to be used for by catalyzer of the present invention in dehydrogenating low-carbon alkane reaction, its Activity evaluation shows, this catalyzer 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.
Embodiment
[embodiment 1]
Weigh 52.65 grams of chromium nitrates, 2.15 grams of saltpetre, 0.07 gram of phosphoric acid, 0.0027 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 88.899 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.By propane gas by mass flowmeter 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 preset 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 reactor, evaluating catalyst condition is as follows: loaded by 0.5 gram of catalyzer (catalyst bed layer height 17mm) in above-mentioned isothermal fixed-bed reactor, reaction pressure is normal pressure, gas space velocity 600 hours
-1, temperature of reaction 560 DEG C.It the results are shown in Table 1.
[embodiment 2]
Weigh 52.65 grams of chromium nitrates, 2.15 grams of saltpetre, 0.07 gram of phosphoric acid, 2.7 grams of gallium nitrates, join in the deionized water of 100 milliliters, add 86.5 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 3]
Weigh 52.65 grams of chromium nitrates, 2.15 grams of saltpetre, 0.07 gram of phosphoric acid, 0.027 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 87.499 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 4]
Weigh 52.65 grams of chromium nitrates, 2.15 grams of saltpetre, 0.07 gram of phosphoric acid, 1.35 grams of gallium nitrates, join in the deionized water of 100 milliliters, add 87 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 5]
Weigh 52.65 grams of chromium nitrates, 2.74 grams of SODIUMNITRATE, 0.07 gram of phosphoric acid, 0.0545 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 87.498 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 6]
Weigh 52.65 grams of chromium nitrates, 4.61 grams of lithium nitrates, 0.07 gram of phosphoric acid, 2.7 grams of gallium nitrates, join in the deionized water of 100 milliliters, add 87 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 7 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 7]
Weigh 52.65 grams of chromium nitrates, 1.05 grams of rubidium nitrates, 0.07 gram of phosphoric acid, 2.7 grams of gallium nitrates, 0.01 part of nitrocalcite, joins in the deionized water of 100 milliliters, then adds 87 grams of alumina supporters, by the ammoniacal liquor regulator solution pH value to 1 of 2.5%, 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 retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 8]
Weigh 52.65 grams of chromium nitrates, 2.15 grams of saltpetre, 0.007 gram of phosphoric acid, 0.27 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 88.89 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 5 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.The catalyzer of preparation is loaded in fixed-bed reactor, under 550 DEG C of conditions, carries out activity rating, the results are shown in Table 1.
[embodiment 9]
Weigh 5.27 grams of chromium nitrates, 0.215 gram of saltpetre, 0.07 gram of phosphoric acid, 0.27 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 98.7 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3 of 2.5%, then flood in 80 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 10]
Weigh 157.95 grams of chromium nitrates, 10.75 grams of saltpetre, 0.7 gram of phosphoric acid, 0.27 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 63.9 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 50 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 11]
Weigh 105.3 grams of chromium nitrates, 4.3 grams of saltpetre, 0.21 gram of phosphoric acid, 0.27 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 75.6 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 50 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[embodiment 12]
Weigh 26.33 grams of chromium nitrates, 1.23 grams of saltpetre, 0.007 gram of phosphoric acid, 0.27 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 89.99 grams of alumina supporters again, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, then flood in 50 DEG C of water-baths after 1 hour, take out sample to filter, in 120 DEG C of baking ovens dry 8 hours, then sample is put into retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[comparative example 1]
Weigh 52.65 grams of chromium nitrates, 2.15 gram saltpetre, 1.35 grams of gallium nitrates, join in the deionized water of 100 milliliters, then add 88.5 grams of alumina supporters, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, 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 retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
[comparative example 2]
Weigh 52.65 grams of chromium nitrates, 2.15 gram saltpetre, 0.07 gram of phosphoric acid, joins in the deionized water of 100 milliliters, then adds 88.9 grams of alumina supporters, by the ammoniacal liquor regulator solution pH value to 3.5 of 2.5%, 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 retort furnace roasting 4 hours under 550 DEG C of conditions, obtain required catalyzer.Examination condition, with embodiment 1, the results are shown in Table 1.
Table 1*
* component concentration is measured by XRF and obtains
[embodiment 13 ~ 16]
The catalyzer 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 conditions and evaluation result are in table 2.
Table 2
Claims (10)
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 compound;
B) 0.1 ~ 5 part of alkalimetal oxide or alkaline earth metal oxide;
C) 0.001 ~ 1 part is selected from the periodic table of elements the Vth A race element or its oxide compound;
D) 0.001 ~ 1 part is selected from periodic table of elements group IIIA element or its oxide compound;
E) 54 ~ 99 parts of Al
2o
3or SiO
2.
2. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that in low-carbon alkanes catalyst weight number, the number of chromium or its oxide compound is 5 ~ 20 parts.
3. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that in low-carbon alkanes catalyst weight number, the number of alkalimetal oxide or alkaline earth metal oxide is 0.5 ~ 2 part.
4., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that the number being selected from the periodic table of elements the Vth A race element or its oxide compound with low-carbon alkanes catalyst weight number is 0.01 ~ 0.5 part.
5. according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that in low-carbon alkanes catalyst weight number, the number being selected from periodic table of elements group IIIA element or its oxide compound is 0.01 ~ 0.5 part.
6., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with molar ratio computing Components of Catalysts a: components b is for 0.1 ~ 10:1.
7., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with molar ratio computing Components of Catalysts a: amount of component b is for 1 ~ 100:1.
8., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with molar ratio computing Components of Catalysts a: component d for 1 ~ 50:1.
9., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that Al
2o
3for γ, δ and θ type Al
2o
3in one or both.
10. catalyzer described in any one of claim 1 ~ 8 is used for dehydrogenating low-carbon alkane reaction, reaction raw materials is propane or Trimethylmethane, and reaction conditions 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 iso-butylene.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106582773A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for production of isobutene by dehydrogenation of isobutane |
| CN106964392A (en) * | 2016-01-13 | 2017-07-21 | 中国石油化工股份有限公司 | Oxidative dehydrogenation of propane catalyst and application thereof |
| CN110563537A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | method for preparing propylene by propane dehydrogenation |
| CN110560043A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for producing propylene by propane dehydrogenation |
| CN110560041A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | catalyst for producing propylene by propane dehydrogenation |
| CN110560039A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | propane dehydrogenation catalyst and preparation method thereof |
| CN110560060A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for propane dehydrogenation and preparation method |
| CN110560042A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN112705198A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Dehydrogenation catalyst, preparation method and application thereof |
| CN112717919A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing isobutene by dehydrogenating isobutane |
| CN113058586A (en) * | 2021-03-31 | 2021-07-02 | 四川大学 | Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof |
| CN114425322A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Supported propane dehydrogenation catalyst and preparation method thereof |
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| CN110560060A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for propane dehydrogenation and preparation method |
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| CN110563537B (en) * | 2018-06-05 | 2022-07-08 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN110560043B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Method for producing propylene by propane dehydrogenation |
| CN110563537A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | method for preparing propylene by propane dehydrogenation |
| CN110560043A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for producing propylene by propane dehydrogenation |
| CN110560039B (en) * | 2018-06-05 | 2021-09-03 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst and preparation method thereof |
| CN110560041A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | catalyst for producing propylene by propane dehydrogenation |
| CN112717919A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for producing isobutene by dehydrogenating isobutane |
| CN112705198A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Dehydrogenation catalyst, preparation method and application thereof |
| CN114425322A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Supported propane dehydrogenation catalyst and preparation method thereof |
| CN114425322B (en) * | 2020-10-15 | 2024-03-26 | 中国石油化工股份有限公司 | Supported propane dehydrogenation catalyst and preparation method thereof |
| CN113058586A (en) * | 2021-03-31 | 2021-07-02 | 四川大学 | Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof |
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