CN104549321A - Catalyst for dehydrogenating light alkane and application of catalyst - Google Patents
Catalyst for dehydrogenating light alkane and application of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for dehydrogenating light alkane and application of the catalyst 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 Li, Na, K and Rb elements or oxides of the Li, Na, K and Rb elements (b), 0.1-10 parts of Cu, Co, Ni and Fe elements or oxides of the Cu, Co, Ni and Fe elements (c), 0.001-1 part of a Ga element or an oxide of the Ga element (d), and 54-99 parts of Al2O3 (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 for catalyst for dehydrogenation of low-carbon paraffin and uses thereof.
Background technology
Low-carbon alkene, such as propylene and iso-butylene, be very important Organic Chemicals, they are considered to the basis of modern petrochemical together with ethene, in order to produce polymkeric substance, gasoline, washing composition and other chemical feedstocks etc.The traditional method preparing propylene and iso-butylene adopts ethene coproduction and light oil (petroleum naphtha, solar oil) cracking technology, but prospective oil is limited, propylene and iso-butylene are limited by target product, are difficult to extensive increase, so the variation route preparing propylene and iso-butylene is devoted to develop in countries in the world.Wherein with the propane in petrochemical industry by-product or Sweet natural gas etc. and Trimethylmethane for raw material, prepare corresponding propylene by direct dehydrogenation technique and iso-butylene method is subject to very big attention.The mankind continued to increase worldwide petrochemical raw material and petroleum chemicals demand in recent years, as propylene, the sustainable growth of iso-butylene demand of petrochemical industry basic material, traditional ordinary method can not meet its increased requirement, occurred global in short supply.And along with petroleum resources day by day deficient, propylene, iso-butylene produce that to rely on oil be raw material transforms to the technological line of diversification of feedstock from simple, be particularly the technological line of waste propylene, iso-butylene with low-carbon alkanes, utilize abundance, to prepare low-carbon alkene be one of most promising method to cheap dehydrogenating low-carbon alkane.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.
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 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.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 with the next item up patent, CN 100406415 relates to the dehydrogenation catalyst complex containing aluminum oxide, chromic oxide, Lithium Oxide 98min and sodium oxide, and each performance index of catalyzer are also substantially identical.CN 1086150C, have studied a kind of catalyzer Trimethylmethane being converted into iso-butylene, active ingredient is wherein CrPt, and auxiliary agent is basic metal, alkaline-earth metal and transition metal, and load is on aluminum oxide or alumina globule; This catalyzer is 65.1% to the peak rate of conversion of Trimethylmethane, selective isobutene 93.2%.CN 101940922 take chromium as active ingredient, and basic metal is cocatalyst component, is that carrier has prepared alkane dehydrogenating catalyst containing Cr aluminum oxide, and when reacting 10 minutes, propane peak rate of conversion is 57.8%, Propylene Selectivity 91.5%.
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.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) the Cr element of 1 ~ 30 part or its oxide compound;
B) Li, Na, K, Rb element of 0.1 ~ 5 part or its oxide compound;
C) Cu, Co, Ni, Fe element of 0.1 ~ 10 part or its oxide compound;
D) 0.001 ~ 1 part Ga element or its oxide compound;
E) Al of 54 ~ 99 parts
2o
3carrier.
In technique scheme, with weight parts, the preferable range of chromium or its oxide compound number is 5 ~ 20 parts; The preferable range of Li, Na, K, Rb or its oxide compound number 0.5 ~ 2 part; The preferable range of the number of Cu, Co, Ni, Fe or its oxide compound 1 ~ 3 part; The preferable range of Ga element or its oxide compound number 0.01 ~ 0.5 part; Al
2o
3for γ type, δ type and θ type Al
2o
3in one or both; With Cr:K(or Li, Na in molar ratio computing catalyzer) preferable range for 0.1 ~ 10:1; Cr:Cu(or Co, Ni, Fe in catalyzer) preferable range be 0.1 ~ 10:1.
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) carrier I and aequum contained solubility solution, the solubility solution containing K or Li, Na, Rb etc., the solubility solution containing Cu or Co, Ni, Fe etc. of Cr, be mixed into mixture I containing the solubility solution of Ga 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.
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, 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: 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 the dispersion of Cr element on carrier adding of the 4th main group element Ga that appraises at the current rate of transition metal Cu and having etc., 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 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, 4.56 grams of cupric nitrates, 0.0027 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 87.4999 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, 4.56 grams of cupric nitrates, 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, 4.56 grams of cupric nitrates, 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, 4.56 grams of cupric nitrates, 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, 4.56 grams of cupric nitrates, 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, 3.88 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 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, 3.89 grams of nickelous nitrates, 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, 5.06 grams of part iron nitrates, 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 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, 30.4 grams of cupric nitrates, 0.27 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 88.8 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, 3.04 grams of cupric nitrates, 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, 9.12 grams of cupric nitrates, 2.7 grams of gallium nitrates, join in the deionized water of 100 milliliters, add 74 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, 3.04 grams of cupric nitrates, 0.027 gram of gallium nitrate, join in the deionized water of 100 milliliters, add 88.99 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, 4.56 grams of cupric nitrates, join in the deionized water of 100 milliliters, then add 87.5 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.
Table 1
[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 Li, Na, K, Rb element or its oxide compound;
C) 0.1 ~ 10 part of Cu, Co, Ni, Fe element or its oxide compound;
D) 0.001 ~ 1 part of Ga element or its oxide compound;
E) 54 ~ 99 parts of Al
2o
3.
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 Li, Na, K, Rb or its oxide compound is 0.5 ~ 2 part.
4. 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 Cu, Co, Ni, Fe or its oxide compound is 1 ~ 3 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, Ga element or its oxide compound 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 Cr:K(or Li, Na in molar ratio computing catalyzer) for 0.1 ~ 10:1.
7., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with Cr:Cu(or Co, Ni, Fe in molar ratio computing catalyzer) for 0.1 ~ 10:1.
8., according to claim 1 for catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that with Cr:Ga in molar ratio computing catalyzer 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457623A (en) * | 2015-12-24 | 2016-04-06 | 江苏扬子催化剂有限公司 | Industrial preparation method of chrome-serial microspheric fluidized bed isobutene dehydrogenation catalyst |
| CN107537509A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst of dehydrogenating low-carbon alkane and application thereof |
| CN107537461A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The catalyst of dehydrogenating low-carbon alkane and its application |
| CN110272327A (en) * | 2019-07-02 | 2019-09-24 | 滕州京腾鑫汇新材料科技有限公司 | A kind of method of manufacturing olefin by low-carbon alkane dehydrogenation |
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| 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 |
| CN102040466B (en) * | 2009-10-13 | 2012-10-10 | 中国石油化工股份有限公司 | Method for preparing styrene through ethylbenzene dehydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457623A (en) * | 2015-12-24 | 2016-04-06 | 江苏扬子催化剂有限公司 | Industrial preparation method of chrome-serial microspheric fluidized bed isobutene dehydrogenation catalyst |
| 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 |
| CN107537509A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst of dehydrogenating low-carbon alkane and application thereof |
| CN107537461A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The catalyst of dehydrogenating low-carbon alkane and its application |
| 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 |
| 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 |
| CN110272327A (en) * | 2019-07-02 | 2019-09-24 | 滕州京腾鑫汇新材料科技有限公司 | A kind of method of manufacturing olefin by low-carbon alkane dehydrogenation |
| 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 |
| CN112239387A (en) * | 2019-07-16 | 2021-01-19 | 中国石油化工股份有限公司 | Carbon deposition inhibitor |
| 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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