CN104549321B - Catalyst for dehydrogenation of low-carbon paraffin and application thereof - Google Patents
Catalyst for dehydrogenation of low-carbon paraffin and application thereof Download PDFInfo
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- CN104549321B CN104549321B CN201310512212.3A CN201310512212A CN104549321B CN 104549321 B CN104549321 B CN 104549321B CN 201310512212 A CN201310512212 A CN 201310512212A CN 104549321 B CN104549321 B CN 104549321B
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Abstract
It is used for catalyst for dehydrogenation of low-carbon paraffin and application thereof the present invention relates to one kind, the problem of dehydrogenation activity that mainly prepared by solution 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 Li, Na, K, Rb element or its oxide；c）0.1~10 part of Cu, Co, Ni, Fe element or its oxide；d）0.001~1 part of Ga element or its oxide；e）54~99 parts of Al2O3Technical scheme, preferably solve the problem, prepared available for dehydrogenating low-carbon alkane in low-carbon alkene industrial production.
Description
Technical field
It is used for catalyst for dehydrogenation of low-carbon paraffin and application thereof the present invention relates to one kind.
Background technology
Low-carbon alkene, such as propylene and isobutene, are very important Organic Chemicals, and they and ethene are recognized together
To be the basis of modern petrochemical, to produce polymer, gasoline, detergent and other chemical raw materials etc..Prepare propylene and
The conventional method of isobutene is to use ethene coproduction and light oil（Naphtha, light diesel fuel）Cracking technology, but petroleum reserves is limited, third
Alkene and isobutene are limited by target product, it is difficult to extensive increase, so countries in the world are directed to exploitation and prepare propylene and isobutyl
The variation route of alkene.Wherein using the propane and iso-butane in petrochemical industry by-product or natural gas etc. as raw material, pass through direct dehydrogenation technique system
Standby corresponding propylene and isobutene method are greatly paid attention to.The mankind held to worldwide petrochemical raw material and petroleum chemicals demand in recent years
Continuous increase, as the propylene of petrochemical industry basic material, isobutene demand sustainable growth, traditional conventional method can not meet its growth
Demand, is occurred in that global in short supply.And as petroleum resources are increasingly deficient, propylene, isobutene production rely on stone from simple
Oil converts for raw material to the technology path of diversification of feedstock, particularly the skill using low-carbon alkanes as waste propylene, isobutene
Art route, it is one of most promising method to prepare low-carbon alkene using abundance, cheap dehydrogenating low-carbon alkane.It is low
Carbon alkane dehydrogenation reaction is balanced by thermodynamics of reactions to be limited, and is a strong endothermic reaction, must under low pressure, hot conditions ability
Comparatively ideal olefin yields are obtained, and too high reaction temperature will make alkane cracking reaction and deep dehydrogenation aggravation, easily occur poly-
The side reactions such as conjunction, cyclisation, charing, make the quick carbon distribution of catalyst surface, inactivation, cause catalyst performance to be deteriorated, and selectivity is relatively low
The problems such as, accordingly, it would be desirable to which the excellent dehydrogenation of processability, improves alkane conversion and olefine selective.
Relevant single propane or the corresponding alkene research of catalytic dehydrogenation of isobutane system are more at present, and have 20 in the world
Many set propane or dehydrogenation of isobutane devices are in operation, and main De-hydrogen Technology has UOP Oleflex techniques, Lummus
Catofin techniques, Uhde STAR techniques, Linde PDH techniques, the FBD of Snamprogetti-Yarsintez cooperative development
Technique etc., wherein industrialized unit at most be Oleflex technologies and Catofin technologies, the catalyst that both apply is respectively
Pt systems and Cr series catalysts, dehydrogenating technology are substantially the same, different simply dehydrogenation and catalyst regenerating section, Oleflex techniques
Use moving-burden bed reactor, external regeneration；Catofin uses fixed bed reactors, carries out hot-air and burns carbon cycle regeneration.In recent years
Come, more document report and patent application about having in terms of dehydrating alkanes Cr series catalysts, CN86104061A disclose one kind
The method for preparing C3~C5 paraffin hydrocarbon dehydrogenation catalysts, using the compound oxide impregnation alumina supporter containing Cr and K, with containing after drying
Silicon compound solution impregnates, and roasting is finally dried.This method has the disadvantage that preparing high content active metal component catalyst has
Larger difficulty, active component loading is subject to certain restrictions, and it is not very strong that catalyst, which holds charcoal ability, and inactivation is fast.
CN1668555A discloses a kind of composite oxide catalysts, containing chromium oxide, lithia, sodium oxide molybdena and aluminum oxide etc., prepares
Method is infusion process.Similar with the next item up patent, CN 100406415 is related to containing aluminum oxide, chromium oxide, lithia and oxygen
Change the dehydrogenation catalyst complex of sodium, each performance indications of catalyst are also essentially identical.CN 1086150C, have studied one kind will be different
Conversion of butane is the catalyst of isobutene, and active component therein is CrPt, and auxiliary agent is alkali metal, alkaline-earth metal and transition metal
Element, is supported on aluminum oxide or alumina globule；The catalyst is 65.1% to the maximum conversion of iso-butane, isobutene choosing
Selecting property 93.2%.CN 101940922 is using chromium as active component, and alkali metal is cocatalyst component, and aluminum oxide containing Cr is carrier system
For alkane dehydrogenating catalyst, propane maximum conversion is 57.8%, Propylene Selectivity 91.5% when reacting 10 minutes.
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.Ga is as the Main Group Metal Elements appraised at the current rate always, and adding can change in catalyst
Change catalyzer surface characteristic, characteristic of particularly appraising at the current rate contributes to active component Cr in reaction, therefore with preferable application prospect, mesh
It is preceding not yet to have relevant report.
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 new is used for catalyst for dehydrogenation of low-carbon paraffin there is provided a kind of.The second technical problem to be solved by the present invention, 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 elements or its oxide；
b）0.1~5 part of Li, Na, K, Rb element or its oxide；
c）0.1~10 part of Cu, Co, Ni, Fe element or its oxide；
d）0.001~1 part of Ga elements or its oxide；
e）54~99 parts of Al2O3Carrier.
In above-mentioned technical proposal, in terms of parts by weight, the preferred scope of chromium or its oxide number is 5~20 parts；Li、
0.5~2 part of the preferred scope of Na, K, Rb or its oxide number；The preferred scope of the number of Cu, Co, Ni, Fe or its oxide
1~3 part；0.01~0.5 part of the preferred scope of Ga elements or its oxide number；Al2O3For γ types, δ types and θ types Al2O3In
It is one or two kinds of；With Cr in molar ratio computing catalyst:K（Or Li, Na）Preferred scope be 0.1 ~ 10：1；Cr in catalyst:Cu
（Or Co, Ni, Fe）Preferred scope be 0.1 ~ 10：1.
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, comprises the following steps：
a）By Al2O3Carrier tabletting, screening, choose the carrier after 40~60 mesh sieves point and are 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, the soluble solution containing K or Li, Na, Rb etc., containing Cu or
Co, Ni, Fe etc. soluble solution, the soluble solution mixing resulting mixture I of the element containing Ga, it is molten with inorganic ammonia or inorganic ammonium salt
Liquid is under the conditions of temperature is 10~80 DEG C, and regulation mixture I pH value is 1~7, obtains mixture II；
c）Said mixture II is impregnated 0.5~8 hour under the conditions of temperature is 10~100 DEG C, 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 is 4~8 hours.
Obtained catalyst carries out activity rating in isotherm formula fixed bed reactors as stated above, de- to low-carbon alkanes
For hydrogen producing light olefins system appraisal, summary process is as follows：
Low-carbon alkanes, by taking propane as an example, adjust flow by mass flowmenter by unstrpped gas, are 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 is Ф 9mm-Ф 6mm stainless steel sleeve pipe, is about 400mm.After reacted 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 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 are calculated as follows：
During dehydrogenating low-carbon alkane, simple Cr2O3/Al2O3Catalyst surface is acid stronger, and catalyst surface is easily accumulated
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.It is used as the Al with stronger surface acidity2O3For material, alkali metal
The addition of element can reduce its surface acidity, while transition metal Cu and adding with the 4th major element Ga appraised at the current rate etc.
Enter to improve Cr elements scattered on carrier, or promote more active sites Cr formation, so as to improve the anti-product of Cr series catalysts
Carbon ability, improves catalyst performance.The catalyst of the present invention is used in dehydrogenating low-carbon alkane reaction using above-mentioned appreciation condition,
Its Activity evaluation shows that the catalyst has higher alkane conversion, compared with low reaction temperatures reachable 60%, has simultaneously
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, 4.56 grams of copper nitrates, 0.0027 gram of gallium nitrate is added to 100
In the deionized water of milliliter, 87.4999 grams of alumina supports are added, solution ph are adjusted to 3.5 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.Propane gas is adjusted by mass flowmenter
Flow, is mixed into pre-add hot-zone, subsequently into reaction zone, and the pre-add hot-zone of reactor and reaction zone use heating wire
Heating, makes up to predetermined temperature, and the internal diameter of reactor is Ф 9mm-Ф 6mm stainless steel sleeve pipe, is about 400mm.After reaction
Gas by drainer after, into gas chromatographic analysis its composition.
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, 4.56 grams of copper nitrates, 2.7 grams of gallium nitrates are added to 100 milliliters
Deionized water in, add 86.5 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3.5, then at 80 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 3】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 0.027 gram of gallium nitrate is added to 100 millis
In the deionized water risen, 87.499 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 4】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates, 1.35 grams of gallium nitrates are added to 100 millis
In the deionized water risen, 87 grams of alumina supports are added, solution ph are adjusted to 3.5 with 2.5% ammoniacal liquor, then at 80 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 5】
52.65 grams of chromic nitrates are weighed, 2.74 grams of sodium nitrate, 4.56 grams of copper nitrates, 0.0545 gram of gallium nitrate is added to 100
In the deionized water of milliliter, 87.498 grams of alumina supports are added, solution ph are adjusted to 3.5 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 6】
52.65 grams of chromic nitrates are weighed, 4.61 grams of lithium nitrates, 3.88 grams of cobalt nitrates, 2.7 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 7, then in 80 DEG C of water-baths
Middle dipping takes out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put into Muffle furnace after 1 hour
It is calcined 4 hours under the conditions of 550 DEG C, obtains required catalyst.Examination condition be the same as Example 1, the results are shown in Table 1.
【Embodiment 7】
52.65 grams of chromic nitrates of weighing, 1.05 grams of rubidium nitrates, 3.89 grams of nickel nitrates, 2.7 grams of gallium nitrates, 0.01 part of calcium nitrate,
In the deionized water for being added to 100 milliliters, 87 grams of alumina supports are added, solution ph are adjusted to 1 with 2.5% ammoniacal liquor, so
After being impregnated 1 hour in 80 DEG C of water-baths afterwards, take out sample and filtered, dried 8 hours in 120 DEG C of baking ovens, then sample is put
Enter in Muffle furnace and be calcined 4 hours under the conditions of 550 DEG C, obtain required catalyst.Examination condition be the same as Example 1, the results are shown in Table
1。
【Embodiment 8】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 5.06 grams of part ferric nitrates, 2.7 grams of gallium nitrates are added to 100 millis
In the deionized water risen, 87 grams of alumina supports are added, solution ph are adjusted to 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.The catalyst of preparation is fitted into fixed bed reactors,
Activity rating is carried out under the conditions of 550 DEG C, 1 is the results are shown in Table.
【Embodiment 9】
5.27 grams of chromic nitrates are weighed, 0.215 gram of potassium nitrate, 30.4 grams of copper nitrates, 0.27 gram of gallium nitrate is added to 100 millis
In the deionized water risen, 88.8 grams of alumina supports are added, solution ph are adjusted to 3 with 2.5% ammoniacal liquor, then at 80 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 10】
157.95 grams of chromic nitrates are weighed, 10.75 grams of potassium nitrate, 3.04 grams of copper nitrates, 0.27 gram of gallium nitrate is added to 100
In the deionized water of milliliter, 63.9 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 50 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 11】
105.3 grams of chromic nitrates are weighed, 4.3 grams of potassium nitrate, 9.12 grams of copper nitrates, 2.7 grams of gallium nitrates are added to 100 milliliters
Deionized water in, add 74 grams of alumina supports, with 2.5% ammoniacal liquor adjust solution ph to 3.5, 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 be the same as Example 1, the results are shown in Table 1.
【Embodiment 12】
26.33 grams of chromic nitrates are weighed, 1.23 grams of potassium nitrate, 3.04 grams of copper nitrates, 0.027 gram of gallium nitrate is added to 100 millis
In the deionized water risen, 88.99 grams of alumina supports are added, solution ph are adjusted to 3.5 with 2.5% ammoniacal liquor, then 50
Dipping takes out sample and filtered after 1 hour in DEG C water-bath, drying 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 be the same as Example 1, the results are shown in Table 1.
【Comparative example 1】
52.65 grams of chromic nitrates are weighed, 2.15 grams of potassium nitrate, 4.56 grams of copper nitrates are added to 100 milliliters of deionized water
In, 87.5 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 be the same as Example 1, the results are shown in Table 1.
Table 1
【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 catalyst for dehydrogenation of low-carbon paraffin, in terms of catalyst weight number, including following components：
A) 1~30 part of Cr oxide；
B) 0.1~5 part of Li oxide, Na oxide, K oxide or Rb oxide；
C) 0.1~10 part of Cu oxide, Co oxide, Ni oxide or Fe oxide；
D) 0.001~1 part of Ga oxide；
E) 54~99 parts of Al2O3；
The preparation method for catalyst for dehydrogenation of low-carbon paraffin comprises the following steps：
A) by Al2O3Carrier tabletting, screening, choose the calcination process under the conditions of 400~600 DEG C of the carrier after 40~60 mesh sieves point
0.5~12 hour, obtain Al2O3Carrier I；
B) by carrier I and soluble solution of the aequum containing Cr, the soluble solution containing K, Li, Na or Rb, containing Cu, Co, Ni or
Fe soluble solution, the soluble solution mixing resulting mixture I of the element containing Ga, with inorganic ammonia or inorganic ammonium salt solution in temperature
Under the conditions of 10~80 DEG C, regulation mixture I pH value is 1~7, obtains mixture II；
C) said mixture II is impregnated 0.5~8 hour under the conditions of temperature is 10~100 DEG C, then is filtered, dried, 300
~550 DEG C are calcined 0.5~12 hour, obtain required catalyst for dehydrogenation of low-carbon paraffin.
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
Number meter, the number of Cr 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
Number meter, Li oxide, Na oxide, the number of K oxide or Rb oxide are 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, Cu oxide, Co oxide, the number of Ni oxide or Fe oxide are 1~3 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 of Ga oxide is 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 Cr in molar ratio computing catalyst:
Li is 0.1~10:1 or Cr:Na 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 Cr in molar ratio computing catalyst:
Cu is 0.1~10:1、Cr:Co is 0.1~10:1 or Cr:Ni is 0.1~10:1.
8. it is used for catalyst for dehydrogenation of low-carbon paraffin according to claim 1, it is characterised in that with Cr in molar ratio computing catalyst:
Ga 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 is：Reaction pressure be 0~1MPa, temperature be 500~650 DEG C, mass space velocity be 0.1~10h-1；Reaction is former
Material obtains propylene or isobutene with the catalyst haptoreaction.
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| CN105457623B (en) * | 2015-12-24 | 2018-01-16 | 江苏扬子催化剂有限公司 | The industrial production process of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst |
| CN107537509B (en) * | 2016-06-29 | 2020-10-30 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of light alkane and application thereof |
| CN107537461B (en) * | 2016-06-29 | 2020-08-07 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of light alkane and application thereof |
| CN110272327B (en) * | 2019-07-02 | 2022-11-22 | 河南龙都石油化工有限公司 | Method for preparing olefin by dehydrogenating low-carbon alkane |
| CN112239387B (en) * | 2019-07-16 | 2023-03-28 | 中国石油化工股份有限公司 | Carbon deposition inhibitor |
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| 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 |
| CN102040466A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
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