CN102775262A - Method for preparation of olefin through light alkane dehydrogenation - Google Patents
Method for preparation of olefin through light alkane dehydrogenation Download PDFInfo
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- CN102775262A CN102775262A CN2011101246077A CN201110124607A CN102775262A CN 102775262 A CN102775262 A CN 102775262A CN 2011101246077 A CN2011101246077 A CN 2011101246077A CN 201110124607 A CN201110124607 A CN 201110124607A CN 102775262 A CN102775262 A CN 102775262A
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Abstract
The invention relates to a method for synthesis of olefin through light alkane dehydrogenation. A catalyst used by the method is prepared according to the following method of: 1) making one or more of Ga, Sn or Pb steep into a carrier, and conducting drying and roasting to obtain a carrier; 2) then using a solution containing one or more of Pt, Pd, Ir, Ru, Rh, Os or Re to steep the carrier obtained in 1), and carrying out drying and roasting to obtain a carrier; and 3) co-steeping the carrier prepared in 2) with a mixed solution containing a rare earth metal element and an alkali metal ion, performing drying and roasting, maintaining the drying process at a temperature of 50-150DEG C for 1-10 hours, and maintaining the roasting process at a temperature of 400-800DEG C for 1-10 hours. And after the step 1) and the step 2), a water vapor treatment is respectively carried out for 1-8 hours at a temperature of 500-700DEG C. Through the co-steeping process of the rare earth metal element and the alkali metal ion, the anti-carbon deposition ability of the catalyst can be substantially improved, and the service life of the catalyst can be prolonged.
Description
Technical field
The present invention relates to the method that a kind of dehydrogenating low-carbon alkane prepares alkene, this catalyzer is used for C
2-8The dehydrogenation reaction of alkane more preferably is used for C
3-4The dehydrogenation reaction of alkane.
Background technology
Two major oil companies of China all have the refinery of ten-million-ton scale at present, and the catalytic pyrolysis of these ten-million-ton scale refinerys attaches product a large amount of ethane, propane and C
4-8Alkane.Therefore, how rationally utilizing these resources, improve the economy of commercial run to greatest extent, is the important scientific research task that current urgent need solves.And manufacturing olefin by low-carbon alkane dehydrogenation is a feasible operational path.Be about to ethane, propane and C
4-8Alkene and hydrogen are produced in the alkane catalytic dehydrogenation.Progressively substitute thermal process reactor comprehensively, improve olefin production process economy property with catalytic process.
Obtaining alkene behind the dehydrating alkanes is an important catalysis commercial run, and its dehydrogenation product is an important industrial chemicals of making a lot of chemical (like plastics, rubber, gasoline, washing composition etc.).For example, the propylene that is obtained by dehydrogenating propane is the important source material of synthetic Vestolen PP 7052, vinyl cyanide and propylene oxide, and the iso-butylene that dehydrogenation of isobutane obtains can synthesizing polyisobutylene, synthetic glass, MTBE (MTBE) etc.But with the propylene is example, obtains propylene from cracking technology merely and can not satisfy the demand of market to propylene, and the production technique that exploitation enlarges the propylene source becomes focus in recent years.Therefore select appropriate catalyst for use, under the temperature relatively low, carry out low-carbon alkanes (the preferred C of hydro condition than thermal cracking processes
2-8Alkane, more preferably C
3-4Alkane) catalytic dehydrogenation system alkene has important economic implications.
Alkane dehydrogenating catalyst, wherein important one type be that to include platinum group be main active ingredient, add all kinds auxiliary agent, the high performance catalyst that utilizes advanced technology to process.Like USP 4,353,815 is Pt-Re-Mn/Al
2O
3Catalyzer is used for dehydrogenation of isobutane; USP 4,420, and 649 is Pt-Ru-Re/Al
2O
3Catalyzer is used for dehydrogenation of isobutane; EP 98,622 is Pt-Sn-Cs/Al
2O
3Catalyzer is used for dehydrogenation of isobutane; USP 4,914, and 075 is Pt-Sn-Cs/Al
2O
3Catalyzer is used for dehydrogenating propane; EP 562,906 is Pt-Sn-K/Al
2O
3Catalyzer, moving-burden bed reactor are used for dehydrogenation of isobutane (C
2-C
20).USP 4,506, and 032 is Pt-Sn-K-Cl/Al
2O
3Catalyzer contains the Sn alumina carrier and uses H
2PtCl
6Aqueous solution dipping through drying, dechlorination, roasting, floods KNO then
3, dry, roasting, and in the time of 525 ℃, through water-bath certain density HCl solution is passed through catalyzer with air, make catalyzer contain a certain amount of Cl element after the roasting, the catalyzer that makes is used for ethane and dehydrogenation of isobutane.USP 4,595, and 673 is Pt-Sn-K-Li-Cl/Al
2O
3Catalyzer contains the Sn alumina carrier and uses H
2PtCl
6And LiNO
3Soak altogether,, flood KNO then through dry, roasting
3, dry again, roasting makes, and this catalyzer is used for dehydrogenation of long-chain alkane.
The major advantage of precious metals pt catalyzer is active high, and selectivity is better.But catalyzer is comparatively responsive to impurity, and inactivation is very fast, and regeneration is frequent, and the labor energy has also brought huge pressure to environment.
Summary of the invention
The method that the purpose of this invention is to provide the synthetic alkene of a kind of dehydrogenating low-carbon alkane.The supported metal catalyst that this method is used has longer catalyzer work-ing life than known catalyzer to above-mentioned reaction.
Catalyzer provided by the invention by weight 100% by among Pt, Pd, Ir, Ru, Rh, Os or the Re one or more, wherein is best with Pt, and weight is 0.01～5%, is preferably 0.01～2%; With among Ga, Sn or the Pb one or more, wherein be best with Sn, weight is 0.01～10%, is preferably 0.2～3%; With among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc or the Y one or more, weight is 0.01～10%, is preferably 0.2～5%; With among Li, Na, K, Rb, Cs or the Fr one or more, be the best wherein with Li or K, weight is 0.01～10%, is preferably 0.1～5%; With carrier be silicon-dioxide, molecular sieve, magnesium-aluminium spinel or aluminum oxide, surplus.
Preparation of catalysts method provided by the present invention is that the solubility soln using dipping technique as each component of catalyzer is supported on the carrier, it is characterized in that steeping process press the order carry out:
1) one or more components among Ga, Sn or the Pb is impregnated on the carrier, makes carrier through dry and roasting;
2) again with containing one or more solution impregnation 1 among Pt, Pd, Ir, Ru, Rh, Os or the Re) carrier, make carrier through dry and roasting;
3) 2) on the carrier that makes, dipping contains the mixing solutions of above-mentioned thulium and alkalimetal ion altogether, through drying and roasting.
Dipping solution in the above-mentioned preparation process, the nitrate salt of available each metallic element, muriatic solution.Drying under 50～150 ℃, was carried out 1～10 hour usually, and roasting process carried out 1～10 hour under 400～800 ℃.
In the Preparation of catalysts method, for improving activity of such catalysts, in step 1) and 2) after, also can use water vapor respectively and handle, the steam-treated time is 1～8 hour, treatment temp is 500～700 ℃.
Catalyzer of the present invention is being used for low-carbon alkanes (preferred C
2-8Alkane, more preferably C
3-4Alkane) before the dehydrogenation reaction, reduce, make platinum family transition element be reduced into metallic state as active ingredient with hydrogen.Reduction temperature is 300～600 ℃, and the time is 1～5 hour, promptly can be used for catalyzed reaction through the catalyzer after the reduction.The condition of its catalyzed reaction is: temperature of reaction: 500～700 ℃; Reaction pressure: normal pressure～1MPa; Liquid air speed: 0.1～10h
-1
The present invention prepares catalyzer through the common steeping process of alkali metal and REE; Prepared catalyzer has good carbon accumulation resisting ability; Therefore the stability that has good catalysis dehydrogenating low-carbon alkane reaction, and this preparation method is simple, has the prospect of Application and Development.
Give to explain further for technology of the present invention through embodiment below.
Embodiment
Following embodiment is used for the present invention is specified.As not having specified otherwise, percentage compositions all among following Comparative Examples and the embodiment are weight percentage.
Method described in the following embodiment if no special instructions, is ordinary method.
Embodiment 1.
Catalyst A consists of 0.375%Pt, 0.5%Sn, and 1.4%K and 0.6%Sm are supported on γ-Al
2O
3On.The preparation method is following:
(1) 0.5%Sn/Al
2O
3Preparation
A certain amount of carrier places the dipping bottle, with preparing the SnCl that is equivalent to 0.5%Sn content
2Hydrochloric acid soln (quite alumina carrier weight 2%) steeping fluid put into carrier fast, kept 4 hours, and constantly shake; Make dipping evenly, incline then and flood surplus liquid, taking-up is dried; Respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then bubbling air (SV=5000h in tube furnace
-1), in 550 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control through 70 ℃, with steam-treated 4 hours.
(2) 0.375%Pt～0.5%Sn/Al
2O
3Preparation
With 0.5%Sn/Al
2O
3Place the dipping bottle, with configuring the H that is equivalent to 0.375%Pt content
2PtCl
6Hydrochloric acid soln (quite alumina carrier weight 2%) steeping fluid put into carrier fast, kept 4 hours, and constantly shake; Make dipping evenly, incline then and flood surplus liquid, taking-up is dried; Respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, then bubbling air (SV=5000h in tube furnace
-1), in 500 ℃ of calcination process 4 hours; Then air is switched the water bath with thermostatic control through 70 ℃, with steam-treated 4 hours.
(3)0.375％Pt～0.5％Sn～1.4％K～0.6％Sm/Al
2O
3
The KNO that will be equivalent to 1.4%K content
3Solution and the Sm (NO that is equivalent to 0.6%Sm content
3)
3Behind the solution uniform mixing, be impregnated into Pt-Sn/Al altogether
2O
3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.
Obtain catalyzer 0.375%Pt～0.5%Sn～1.4%K～0.6%Sm/Al through aforesaid method
2O
3, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer is as shown in table 1:
Table 1. dehydrogenation of isobutane reactivity worth
Reaction conditions: 625 ℃ of temperature of reaction, LHSV=9h
-1, H
2/ Trimethylmethane (mol/mol)=1, the reaction pressure normal pressure.
Embodiment 2.
Catalyst B consists of 0.5%Pt, 0.5%Sn, and 1.4%K and 0.6%La are supported on the ZSM-5.The preparation method replaces γ-Al with embodiment 1 with ZSM-5
2O
3, with La (NO
3)
3Replace Sm (NO
3)
3, and Pt content becomes 0.5%.
Obtain catalyzer 0.5%Pt～0.5%Sn～1.4%K～0.6%La/ZSM-5 through aforesaid method, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer is as shown in table 2:
Table 2. dehydrogenating propane reactivity worth
Reaction conditions: 650 ℃ of temperature of reaction, LHSV=6h
-1, H
2/ propane (mol/mol)=1, the reaction pressure normal pressure.
Embodiment 3.
Catalyzer C consists of 0.375%Pt, 1.0%Sn, and 1.4%Li and 0.6%Ce are supported on γ-Al
2O
3On.The preparation method is with embodiment 1, with LiNO
3Replace KNO
3, with Ce (NO
3)
3Replace Sm (NO
3)
3, Sn content is become 1.0%.
Obtain catalyzer 0.375%Pt～1.0%Sn～1.4%Li～0.6%Ce/Al through aforesaid method
2O
3, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer is as shown in table 3:
Table 3. normal butane dehydrogenation reaction performance
Reaction conditions: 610 ℃ of temperature of reaction, LHSV=6h
-1, H
2/ normal butane (mol/mol)=1, the reaction pressure normal pressure.
Catalyst A shows stability preferably, and it is carried out the one way life experiment, and experimental result is as shown in table 4.
Table 4. catalyzer is to normal butane/dehydrogenation of isobutane reaction experiment result
Reaction conditions: 590 ℃ of temperature of reaction, LHSV=3h
-1, H
2/ C
4(mol/mol)=2, reaction pressure 0.05MPa
(gauge pressure)
Comparative Examples 1.
Catalyzer D consists of 0.375%Pt, 0.5%Sn, and 1.4%K and 0.6%Sm are supported on γ-Al
2O
3On.The preparation method is following:
Preceding two one step preparation methods obtain 0.375%Pt～0.5%Sn/Al with embodiment 1
2O
3
(3) 0.375%Pt～0.5%Sn～1.4%K/Al
2O
3Preparation
The KNO that will be equivalent to 1.4%K content
3Solution is dipped in Pt-Sn/Al
2O
3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.
(4) 0.375%Pt～0.5%Sn～1.4%K～0.6%Sm/Al
2O
3Preparation
Sm (the NO that will be equivalent to 0.6%Ls content
3)
3Solution is dipped in Pt-Sn-K/Al
2O
3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.
Obtain catalyzer 0.375%Pt～0.5%Sn～1.4%K～0.6%Sm/Al through aforesaid method
2O
3, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer is as shown in table 5:
The dehydrogenation of isobutane reactivity worth of table 5. catalyzer D and A
Reaction conditions: 625 ℃ of temperature of reaction, LHSV=9h
-1, H
2/ Trimethylmethane (mol/mol)=1, the reaction pressure normal pressure.
Comparative Examples 2
Catalyzer E consists of 0.5%Pt, 0.5%Sn, and 0.6%La and 1.4%K are supported on the ZSM-5.The preparation method is following:
Preceding two one step preparation methods obtain 0.5%Pt～0.5%Sn/ZSM-5 with embodiment 2.
(3) preparation of 0.5%Pt～0.5%Sn～0.6%La/ZSM-5
La (the NO that will be equivalent to 0.6%La content
3)
3Solution is dipped on the Pt-Sn/ZSM-5, and after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, takes out to be cooled to room temperature.
(4) preparation of 0.5%Pt～0.5%Sn～1.4%K～0.6%La/ZSM-5
The KNO that will be equivalent to 1.4%K content
3Solution is dipped on the Pt-Sn-La/ZSM-5, and after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, takes out to be cooled to room temperature.
Obtain catalyzer 0.5%Pt～0.5%Sn～1.4%K～0.6%La/ZSM-5 through aforesaid method, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer is as shown in table 6:
The dehydrogenating propane reactivity worth of table 6. catalyzer E and B
Reaction conditions: 650 ℃ of temperature of reaction, LHSV=6h
-1, H
2/ propane (mol/mol)=1, the reaction pressure normal pressure.
Comparative Examples 3.
Catalyzer F consists of 0.375%Pt, 1.0%Sn, and 1.4%Li and 0.6%Ce are supported on γ-Al
2O
3On.The preparation method is following:
Preceding two one step preparation methods obtain 0.375%Pt～1.0%Sn/Al with embodiment 3
2O
3
(3) 0.375%Pt～1.0%Sn～0.6%Ce/Al
2O
3Preparation
Ce (the NO that will be equivalent to 0.6%Ce content
3)
3Solution is dipped in Pt-Sn/Al
2O
3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.
(4) preparation of 0.375%Pt～1.0%Sn～1.4%Li～0.6%Ce/ZSM-5
The LiNO that will be equivalent to 1.4%Li content
3Solution is dipped in Pt-Sn-Ce/Al
2O
3On, after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.
Obtain catalyzer 0.375%Pt～1.0%Sn～1.4%Li～0.6%Ce/Al through aforesaid method
2O
3, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer is as shown in table 7:
The normal butane dehydrogenation reaction performance of table 7. catalyzer F and C
Reaction conditions: 610 ℃ of temperature of reaction, LHSV=6h
-1, H
2/ normal butane (mol/mol)=1, the reaction pressure normal pressure.
Comparative Examples 4.
The main composition of catalyzer G is identical with catalyst A, but does not soak Sm (NO
3)
3
Obtain catalyzer 0.375%Pt～0.5%Sn～1.4%K/Al through aforesaid method
2O
3, can know that through ultimate analysis its actual charge capacity conforms to the theoretical negative carrying capacity.
The reactivity worth of this catalyzer dehydrogenation of isobutane reaction is more as shown in table 8:
The dehydrogenation of isobutane reactivity worth of table 8. catalyzer G and A
Reaction conditions: 625 ℃ of temperature of reaction, LHSV=9h
-1, H
2/ Trimethylmethane (mol/mol)=1, the reaction pressure normal pressure.
Can find out from the comparison of above embodiment and Comparative Examples; The modification of independent dipping rare earth metal is for the not significantly effect of raising of catalyst stability; But adopt method provided by the invention,, can obviously improve the carbon accumulation resisting ability of catalyzer through thulium and alkali-metal steeping process altogether; Prolong catalyzer work-ing life, have the prospect of industrial application.
Claims (3)
1. a dehydrogenating low-carbon alkane prepares the method for alkene, and low-carbon alkanes is C
2-8Alkane is characterized in that:
Reaction conditions is: temperature of reaction: 500～700 ℃; Reaction pressure: normal pressure～1MPa; Liquid air speed: 0.1～10h
-1
Catalyzer by weight 100%, by among Pt, Pd, Ir, Ru, Rh, Os or the Re one or more, weight is 0.01～5%; With among Ga, Sn or the Pb one or more, weight is 0.01～10%; With among La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc or the Y one or more, weight is 0.01～10%; With among Li, Na, K, Rb, Cs or the Fr one or more, weight is 0.01～10%; With balance carriers be silicon-dioxide, molecular sieve, magnesium-aluminium spinel or aluminum oxide;
The Preparation of catalysts method is that the solubility solution as each component of catalyzer is supported on the carrier with dipping:
1) one or more components among Ga, Sn or the Pb is impregnated on the carrier, makes carrier through dry and roasting;
2) again with containing one or more solution impregnation 1 among Pt, Pd, Ir, Ru, Rh, Os or the Re) carrier, make carrier through dry and roasting;
3) 2) on the carrier that makes, dipping contains the mixing solutions of above-mentioned thulium and alkalimetal ion altogether, through drying and roasting.
Drying process was carried out under 50～150 ℃ 1～10 hour, and roasting process carried out under 400～800 ℃ 1～10 hour;
Step 1) and 2) after, passed through steam-treated respectively 1～8 hour, treatment temp is 500～700 ℃.
2. the method for the synthetic alkene of dehydrogenating low-carbon alkane as claimed in claim 1, it is characterized in that: each dipping solution is the nitrate salt of metallic element, muriatic solution.
3. the method for the synthetic alkene of dehydrogenating low-carbon alkane according to claim 1, it is characterized in that: Ga, Sn or Pb weight content are 0.2～3%; Pt, Pd, Ir, Ru, Rh, Os or Re weight content are 0.01～2%, and the thulium weight content is 0.2～5%, and the alkali metal weight content is 0.1～5%.
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| CN103394349A (en) * | 2013-07-26 | 2013-11-20 | 中国石油大学(华东) | Catalyst for dehydrogenation of light alkane and preparation method of catalyst |
| CN104190418A (en) * | 2014-08-19 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Catalyst for preparation of light olefins from light alkanes as well as preparation method and application of catalyst |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| WO2015025286A3 (en) * | 2013-08-21 | 2015-05-28 | Saudi Basic Industries Corporation | Selective zeolite supported catalysts for propane and butane dehydrogenation |
| CN105363496A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Low-carbon olefin catalysts made through dehydrogenation of low-carbon alkane and preparation method thereof |
| CN105363484A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Catalyst used for preparing low-carbon olefin through low-carbon alkane dehydrogenation and application thereof |
| CN105642264A (en) * | 2014-11-21 | 2016-06-08 | 中国科学院大连化学物理研究所 | Preparation method of magnesium aluminate spinel for catalyst carrier |
| CN105664903A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method of low-carbon alkane dehydrogenation catalyst carrier |
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| CN109701530A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method of preparing isobutene through dehydrogenation of iso-butane |
| CN109701533A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of catalyst of preparing isobutene through dehydrogenation of iso-butane, preparation method and application |
| CN110813288A (en) * | 2019-10-21 | 2020-02-21 | 万华化学集团股份有限公司 | Catalyst for preparing butadiene by selective hydrogenation of carbon-tetra-alkyne, preparation method and application thereof |
| WO2021128867A1 (en) * | 2019-12-26 | 2021-07-01 | 润和催化材料(浙江)有限公司 | Catalyst for preparing propylene by propane dehydrogenation, preparation method therefor, and use thereof |
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| CN105473228A (en) * | 2013-08-21 | 2016-04-06 | 沙特基础工业公司 | Selective zeolite supported catalysts for propane and butane dehydrogenation |
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| CN105363484B (en) * | 2014-08-27 | 2018-08-17 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating low-carbon alkane producing light olefins and its application |
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| CN105642264A (en) * | 2014-11-21 | 2016-06-08 | 中国科学院大连化学物理研究所 | Preparation method of magnesium aluminate spinel for catalyst carrier |
| CN105664903A (en) * | 2014-11-21 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method of low-carbon alkane dehydrogenation catalyst carrier |
| CN105642264B (en) * | 2014-11-21 | 2019-01-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of catalyst carrier magnesium aluminate spinel |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
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| CN107847908A (en) * | 2015-06-29 | 2018-03-27 | Smh有限公司 | Dehydrogenation and the method using the catalyst |
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| CN108325523A (en) * | 2018-02-02 | 2018-07-27 | 华东理工大学 | A kind of propane dehydrogenation catalyst and preparation method thereof |
| CN108325523B (en) * | 2018-02-02 | 2021-01-08 | 华东理工大学 | Propane dehydrogenation catalyst and preparation method thereof |
| CN109126788A (en) * | 2018-08-01 | 2019-01-04 | 西安凯立新材料股份有限公司 | A kind of platinum oxidation aluminium composite catalyst of dehydrating alkanes |
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| CN110813288B (en) * | 2019-10-21 | 2022-07-12 | 万华化学集团股份有限公司 | Catalyst for preparing butadiene through selective hydrogenation of C-C alkyne, and preparation method and application thereof |
| WO2021128867A1 (en) * | 2019-12-26 | 2021-07-01 | 润和催化材料(浙江)有限公司 | Catalyst for preparing propylene by propane dehydrogenation, preparation method therefor, and use thereof |
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