CN104549220B - Catalyst for dehydrogenating low-carbon alkane - Google Patents
Catalyst for dehydrogenating low-carbon alkane Download PDFInfo
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- CN104549220B CN104549220B CN201310512165.2A CN201310512165A CN104549220B CN 104549220 B CN104549220 B CN 104549220B CN 201310512165 A CN201310512165 A CN 201310512165A CN 104549220 B CN104549220 B CN 104549220B
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Abstract
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane, mainly solves the problems, such as that dehydrogenation activity prepared by prior art is relatively low.The present invention is used for catalyst for dehydrogenation of low-carbon paraffin by using one kind, in terms of parts by weight, including following components：a）1~30 part of Cr element or its oxide；b）0.1~5 part of alkali metal oxide or alkaline earth oxide；c）0.001~1 part is selected from the A races element of the periodic table of elements the Vth or its oxide；d）0.001~1 part is selected from periodic table of elements group IIIA element or its oxide；e）54~99 parts of Al2O3Or SiO2Technical scheme, preferably solve the problem, prepared available for dehydrogenating low-carbon alkane in low-carbon alkene industrial production.
Description
Technical field
The present invention relates to a kind of catalyst for dehydrogenating low-carbon alkane.
Background technology
The low-carbon alkene such as propylene and isobutene is one of most important Organic Ingredients of petrochemical industry, and wherein propylene is main
For producing polypropylene, acrylonitrile, expoxy propane etc., isobutene is mainly used in butyl rubber, polyisobutene etc., in particular with
Environmental requirement improves, and the increase of additive MTBE dosages is very fast in oil product, directly results in isobutene and larger demand gap occurs, therefore
The a large amount of propylene of import, isobutene etc. is needed to meet domestic demand.Propylene and isobutene are mainly derived from ethene coproduction and refining at present
Factory's by-product, it is also secondary in addition to obtaining low-carbon alkene with the realization of the technical process such as the development of coal chemical industry, particularly MTO, MTP
More low-carbon alkanes are produced, while with the exploitation of shale gas, there will be more low-carbon alkanes to generate.Therefore how by lower alkanes
Hydrocarbon is converted into low-carbon alkene as coal chemical industry, petrochemical industry development focal point, and the focus of future market demand.Lower alkanes
Hydrocarbon dehydrogenating technology can be divided into oxidative dehydrogenation and direct dehydrogenation two types, and oxidative dehydrogenation process releases heat, and reaction is not balanced
Limitation, conversion ratio is higher, but selectivity is low, if doing oxidant its operating process from pure oxygen has larger danger, therefore
Selection direct dehydrogenation turns into focus of concern.Dehydrogenating low-carbon alkane reaction is limited by thermodynamics of reactions balance, is one
Strong endothermic reaction, comparatively ideal olefin yields must can be just obtained under low pressure, hot conditions, and too high reaction temperature will make alkane
Hydrocarbon pyrolysis reaction and deep dehydrogenation aggravation, easily occur the side reactions such as polymerization, cyclisation, charing, make the quick carbon distribution of catalyst surface, mistake
It is living, cause catalyst performance to be deteriorated, the problems such as selectivity is relatively low, therefore, it is necessary to the excellent dehydrogenation of processability, is improved
Alkane conversion and olefine selective.
It is external more to relevant propane or the corresponding alkene research of catalytic dehydrogenation of isobutane system, form following several main de-
Hydrogen technology：UOP Oleflex techniques, Lummus Catofin techniques, Uhde STAR techniques, Linde PDH techniques,
FBD techniques of Snamprogetti-Yarsintez cooperative development etc., have more than 20 set propane or different in the world so far
Butane dehydrogenation device is being run, plus the country build with proposed device, be up to 30 sets of dehydrating alkanes devices.In these industrialization
In device, using it is most be Oleflex technologies and Catofin technologies, the catalyst that both apply is Pt systems and Cr systems respectively
Catalyst, dehydrogenating technology are substantially the same, and different simply dehydrogenation and catalyst regenerating section, Oleflex techniques use moving bed
Reactor, external regeneration；Catofin uses fixed bed reactors, carries out hot-air and burns carbon cycle regeneration.With the noble metals such as Pt member
Element is the oxidant of main active component, adds various auxiliary agents using advanced technology, carrier system is done using aluminum oxide or aluminate etc.
Standby, catalyst has preferably activity, and at home and abroad document also has more disclosure for preparation method of catalyst etc., such as US Pat. 3,
488402；5,132,484 etc..Cr systems non-precious metal catalyst, it is modified using elements such as alkali metal, is carried with aluminum oxide more
Body is prepared.In recent years, about having more document report and patent application in terms of dehydrating alkanes Cr series catalysts,
CN86104061A discloses a kind of method for preparing C3~C5 paraffin hydrocarbon dehydrogenation catalysts, is impregnated using the compound containing Cr and K
Alumina support, impregnated after drying with silicon-containing compound solution, roasting is finally dried.This method shortcoming is to prepare high content
Active metal component catalyst has larger difficulty, and active component loading is subject to certain restrictions, and catalyst, which holds charcoal ability, is not
Very strong, inactivation is fast.CN1668555A discloses a kind of composite oxide catalysts, contains chromium oxide, lithia, sodium oxide molybdena and oxygen
Change aluminium etc., preparation method is infusion process.Similar patent also has CN 100406415, CN 1086150 etc., when for lower alkanes
During hydrocarbon dehydrogenation, conversion ratio and selectivity are all not satisfactory.
Catalyst for dehydrogenation of low-carbon paraffin has been achieved with greater advance at present, but it is not high to still suffer from conversion ratio, or conversion ratio
The problem of olefine selective is relatively low in the case of higher.For P as nonmetalloid, catalyst surface spy can be changed by adding in catalyst
Property, particularly characteristic electron；For Ga as the Main Group Metal Elements to appraise at the current rate always, catalyst surface spy can be changed by adding in catalyst
Property, characteristic of particularly appraising at the current rate contributes to active component Cr in reaction, therefore has preferable application prospect, and there has been no correlation at present to report
Road.
The content of the invention
One of technical problems to be solved by the invention are that catalyst for dehydrogenation of low-carbon paraffin activity is relatively low in the prior art
Problem, there is provided a kind of new to be used for catalyst for dehydrogenation of low-carbon paraffin.The second technical problem to be solved by the present invention, it is to provide one kind
With solving one of technical problem corresponding method for preparing catalyst.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for dehydrogenating low-carbon alkane
Catalyst, in terms of parts by weight, including following components：
a）1~30 part of Cr element or its oxide；
b）0.1~5 part of alkali metal oxide or alkaline earth oxide；
c）0.001~1 part is selected from the A races element of the periodic table of elements the Vth or its oxide；
d）0.001~1 part is selected from periodic table of elements group IIIA element or its oxide；
e）54~99 parts of Al2O3Or SiO2。
In above-mentioned technical proposal, in terms of parts by weight, the preferred scope of chromium or its oxide number is 5~20 parts；Alkali gold
Belong to 0.5~2 part of the preferred scope of oxide or alkaline earth oxide number；Selected from the A races element of the periodic table of elements the Vth or its
Oxide number is 0.01~0.5 part；Preferred scope 0.01 selected from periodic table of elements group IIIA element or its oxide number
~0.5 part；It is preferably Ga selected from periodic table of elements group IIIA element；It is preferably P selected from the A races element of the periodic table of elements the Vth；
Al2O3For γ types, δ types and θ types Al2O3One or both of；With molar ratio computing Components of Catalysts a：Component b preferred model
Enclose for 0.1 ~ 10：1；Component a：Component c preferred scope is 1 ~ 100：1；Component a：Component d preferred scope is 1 ~ 50：1.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is used for dehydrogenating low-carbon alkane
Catalyst and preparation method thereof, comprise the following steps：
a）By Al2O3Carrier tabletting, screening, choose the carrier after 40~60 mesh sieves point and be calcined under the conditions of 400~600 DEG C
Processing 0.5~12 hour, obtains Al2O3Carrier I；
b）By carrier I and soluble solution of the aequum containing Cr, alkali metal containing oxide or alkaline earth oxide can
Soluble solution, containing the soluble solution selected from the A races element of the periodic table of elements the Vth, containing selected from periodic table of elements group IIIA element
Soluble solution mixing resulting mixture I, with inorganic ammonia or inorganic ammonium salt solution under the conditions of temperature is 10~80 DEG C, regulation is mixed
Compound I pH value is 1~7, obtains mixture II；
c）Said mixture II is impregnated 0.5~8 hour under the conditions of being 10~100 DEG C in temperature, then is filtered, done
It is dry, 300~
0 ~ 3800 DEG C of liquid is calcined 0.5~12 hour, obtains required catalyst for dehydrogenation of low-carbon paraffin.
In above-mentioned technical proposal, inorganic ammonia or inorganic ammonium salt preferred scheme are selected from ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate, molten
The pH value preferred scope of liquid is 1~7, and more preferably scope is 1~3；Dipping temperature preferred scope is 50~80 DEG C, and dip time is excellent
It is 1~3 hour to select scope, and catalyst sintering temperature preferred scope is 400~6
0 ~ 366600 DEG C of liquid, roasting time preferred scope are 4~8 hours.
The content of Components of Catalysts is by X ray fluorescence spectrometers（XRF）Measure.After sample compression molding, in ZSX-
The type XRF of 100e 4580（Rigaku）The characteristic spectral line intensity of upper measure atom, so as to obtain the content of component in sample.
Obtained catalyst carries out activity rating in isotherm formula fixed bed reactors as stated above, and low-carbon alkanes are taken off
For hydrogen producing light olefins system appraisal, summary process is as follows：
Low-carbon alkanes, by taking propane as an example, unstrpped gas is adjusted into flow by mass flowmenter, carried out into pre-add hot-zone
Mixing, subsequently into reaction zone, the pre-add hot-zone of reactor and reaction zone use electric-heating-wire-heating, make up to pre- constant temperature
Degree, the internal diameter of reactor are Ф 9mm-Ф 6mm stainless steel sleeve pipe, long 400mm.After reacted gas is by drainer, enter
Entering gas chromatographic analysis, it is formed.
Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors：0.5 gram or so of catalyst is loaded into internal diameter is
In Ф 9mm-Ф 6mm isothermal reactor（Catalyst bed layer height about 17mm）, reaction pressure is normal pressure, and gas space velocity 600 is small
When-1, 560 DEG C of reaction temperature.
Conversion of propane and Propylene Selectivity calculate as follows：
During dehydrogenating low-carbon alkane, simple Cr2O3/Al2O3Catalyst surface acidity is stronger, and catalyst surface is easily long-pending
Carbon and accelerate deactivation rate.To slow down catalyst inactivation speed, catalyst performance can be improved by adding other auxiliary agents, simultaneously
Also reaction temperature can be reduced and mitigate catalyst surface carbon distribution.As the Al with stronger surface acidity2O3For material, alkali metal
The addition of element can reduce its surface acidity, while nonmetalloid P and the addition with the 3rd major element Ga to appraise at the current rate etc.
Catalyst surface characteristic electron can be improved, Cr elements is preferably disperseed on carrier, or promotes more active sites Cr's
Formed, so as to improve Cr series catalysts activity, improve catalyst performance.The catalyst of the present invention is used using above-mentioned appreciation condition
In dehydrogenating low-carbon alkane reaction, its Activity evaluation shows, the catalyst has higher alkane conversion, compared with low reaction
At a temperature of up to 60%, while there is higher olefine selective, more than 90%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 0.07 gram of phosphoric acid, 0.0027 gram of gallium nitrate, are added to 100 millis
In the deionized water risen, 88.899 grams of alumina supports are added, solution ph is adjusted to 3.5, Ran Hou with 2.5% ammoniacal liquor
After being impregnated 1 hour in 80 DEG C of water-baths, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into horse
Not it is calcined 4 hours under the conditions of 550 DEG C in stove, obtains required catalyst.Propane gas is adjusted by mass flowmenter and flowed
Amount, is mixed, subsequently into reaction zone, the pre-add hot-zone of reactor and reaction zone are added using heating wire into pre-add hot-zone
Heat, predetermined temperature is made up to, the internal diameter of reactor is Ф 9mm-Ф 6mm stainless steel sleeve pipe, is about 400mm.It is reacted
After gas is by drainer, into its composition of gas chromatographic analysis.
Evaluating catalyst condition is as follows in isotherm formula fixed bed reactors：0.5 gram of catalyst is loaded into above-mentioned isothermal to fix
In bed reactor（Catalyst bed layer height 17mm）, reaction pressure is normal pressure, gas space velocity 600 hours-1, 560 DEG C of reaction temperature.
It the results are shown in Table 1.
【Embodiment 2】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 0.07 gram of phosphoric acid, 2.7 grams of gallium nitrates, are added to 100 milliliters
In deionized water, 86.5 grams of alumina supports are added, solution ph are adjusted to 3.5 with 2.5% ammoniacal liquor, then in 80 DEG C of water
After being impregnated 1 hour in bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
It is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 3】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 0.07 gram of phosphoric acid, 0.027 gram of gallium nitrate, are added to 100 milliliters
Deionized water in, add 87.499 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3.5, then 80
After being impregnated 1 hour in DEG C water-bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle
It is calcined 4 hours under the conditions of 550 DEG C in stove, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 4】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 0.07 gram of phosphoric acid, 1.35 grams of gallium nitrates, are added to 100 milliliters
Deionized water in, add 87 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3.5, then in 80 DEG C of water
After being impregnated 1 hour in bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
It is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 5】
52.65 grams of chromic nitrates are weighed, 2.74 grams of sodium nitrate, 0.07 gram of phosphoric acid, 0.0545 gram of gallium nitrate, are added to 100 millis
In the deionized water risen, 87.498 grams of alumina supports are added, solution ph is adjusted to 3.5, Ran Hou with 2.5% ammoniacal liquor
After being impregnated 1 hour in 80 DEG C of water-baths, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into horse
Not it is calcined 4 hours under the conditions of 550 DEG C in stove, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 6】
52.65 grams of chromic nitrates are weighed, 4.61 grams of lithium nitrates, 0.07 gram of phosphoric acid, 2.7 grams of gallium nitrates, are added to 100 milliliters
In deionized water, 87 grams of alumina supports are added, solution ph are adjusted to 7 with 2.5% ammoniacal liquor, then in 80 DEG C of water-baths
Dipping takes out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace 550 after 1 hour
It is calcined 4 hours under the conditions of DEG C, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 7】
52.65 grams of chromic nitrates are weighed, 1.05 grams of rubidium nitrates, 0.07 gram of phosphoric acid, 2.7 grams of gallium nitrates, 0.01 part of calcium nitrate, are added
Enter into 100 milliliters of deionized water, add 87 grams of alumina supports, adjust solution ph to 1 with 2.5% ammoniacal liquor, then
After being impregnated 1 hour in 80 DEG C of water-baths, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into
It is calcined 4 hours under the conditions of 550 DEG C in Muffle furnace, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 8】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 0.007 gram of phosphoric acid, 0.27 gram of gallium nitrate, are added to 100 milliliters
Deionized water in, add 88.89 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 5, then in 80 DEG C of water
After being impregnated 1 hour in bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
It is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.The catalyst of preparation is fitted into fixed bed reactors,
Activity rating is carried out under the conditions of 550 DEG C, the results are shown in Table 1.
【Embodiment 9】
5.27 grams of chromic nitrates are weighed, 0.215 gram of potassium nitrate, 0.07 gram of phosphoric acid, 0.27 gram of gallium nitrate, are added to 100 milliliters
Deionized water in, add 98.7 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3, then in 80 DEG C of water
After being impregnated 1 hour in bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
It is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 10】
157.95 grams of chromic nitrates are weighed, 10.75 grams of potassium nitrate, 0.7 gram of phosphoric acid, 0.27 gram of gallium nitrate, are added to 100 milliliters
Deionized water in, add 63.9 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3.5, then at 50 DEG C
After being impregnated 1 hour in water-bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
In be calcined 4 hours under the conditions of 550 DEG C, obtain required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 11】
105.3 grams of chromic nitrates are weighed, 4.3 grams of potassium nitrate, 0.21 gram of phosphoric acid, 0.27 gram of gallium nitrate, are added to 100 milliliters
In deionized water, 75.6 grams of alumina supports are added, solution ph are adjusted to 3.5 with 2.5% ammoniacal liquor, then in 50 DEG C of water
After being impregnated 1 hour in bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
It is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Embodiment 12】
26.33 grams of chromic nitrates are weighed, 1.23 grams of potassium nitrate, 0.007 gram of phosphoric acid, 0.27 gram of gallium nitrate, are added to 100 milliliters
Deionized water in, add 89.99 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3.5, then at 50 DEG C
After being impregnated 1 hour in water-bath, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace
In be calcined 4 hours under the conditions of 550 DEG C, obtain required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Comparative example 1】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 1.35 grams of gallium nitrates, are added to 100 milliliters of deionized water
In, 88.5 grams of alumina supports are added, solution ph is adjusted to 3.5 with 2.5% ammoniacal liquor, then impregnates 1 in 80 DEG C of water-baths
After hour, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace in 550 DEG C of bars
It is calcined 4 hours under part, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
【Comparative example 2】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 0.07 gram of phosphoric acid, are added in 100 milliliters of deionized water,
88.9 grams of alumina supports are added, adjust solution ph to 3.5 with 2.5% ammoniacal liquor, then dipping 1 is small in 80 DEG C of water-baths
Shi Hou, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace in 550 DEG C of conditions
Lower roasting 4 hours, obtains required catalyst.Examination condition the results are shown in Table 1 with embodiment 1.
Table 1*
* constituent content is determined to obtain by XRF
【Embodiment 13~16】
The catalyst that embodiment 1 is prepared is used for dehydrogenating low-carbon alkane, and reaction raw materials are propane, and reaction raw materials are one
Under fixed condition propylene is obtained with catalyst haptoreaction；Reaction condition and evaluation result are shown in Table 2.
Table 2
Claims (10)
1. one kind is used for low-carbon alkanes direct dehydrogenation catalyst, in terms of catalyst weight number, including following components：
A) 1~30 part of Cr element or its oxide；
B) 0.1~5 part of alkali metal oxide or alkaline earth oxide；
C) 0.001~1 part is selected from the A races element of the periodic table of elements the Vth or its oxide；
D) 0.001~1 part is selected from periodic table of elements group IIIA element or its oxide；
E) 54~99 parts of Al2O3Or SiO2；Vth A races element is P, and the group IIIA element is Ga.
2. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
The number of number meter, chromium or its oxide is 5~20 parts.
3. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
The number of number meter, alkali metal oxide or alkaline earth oxide is 0.5~2 part.
4. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
Number meter, the number selected from the A races element of the periodic table of elements the Vth or its oxide are 0.01~0.5 part.
5. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with low-carbon alkanes catalyst weight
Number meter, the number selected from periodic table of elements group IIIA element or its oxide are 0.01~0.5 part.
6. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with group in molar ratio computing catalyst
Divide a：Component b is 0.1~10：1.
7. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with group in molar ratio computing catalyst
Divide a：Component c is 1~100：1.
8. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with group in molar ratio computing catalyst
Divide a：Component d is 1~50：1.
9. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that Al2O3For γ, δ and θ type Al2O3In
One or two.
10. any one of claim 1~8 catalyst is reacted for dehydrogenating low-carbon alkane, reaction raw materials are propane or different
Butane, reaction condition are：Reaction pressure be 0~1MPa and be not 0MPa, temperature be 500~650 DEG C, mass space velocity be 0.1~
10h-1；Reaction raw materials obtain propylene or isobutene with the catalyst haptoreaction.
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| CN106582773B (en) * | 2015-10-16 | 2019-04-12 | 中国石油化工股份有限公司 | The catalyst of dehydrogenation of isobutane production isobutene |
| CN106964392B (en) * | 2016-01-13 | 2021-08-03 | 中国石油化工股份有限公司 | Propane oxidative dehydrogenation catalyst and application thereof |
| CN110560042B (en) * | 2018-06-05 | 2021-10-01 | 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 |
| CN110560041B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for producing propylene by propane dehydrogenation |
| CN110560060B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for propane dehydrogenation and preparation method |
| 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 |
| 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 |
| 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 |
| 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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| US3488402A (en) * | 1967-05-18 | 1970-01-06 | Sinclair Research Inc | Dehydrogenation of hydrocarbons using dehydrogenation-oxidation catalyst system |
| CN1086150C (en) * | 1996-12-24 | 2002-06-12 | 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 |
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