CN101543781A - Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof - Google Patents
Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof Download PDFInfo
- Publication number
- CN101543781A CN101543781A CN200910111645A CN200910111645A CN101543781A CN 101543781 A CN101543781 A CN 101543781A CN 200910111645 A CN200910111645 A CN 200910111645A CN 200910111645 A CN200910111645 A CN 200910111645A CN 101543781 A CN101543781 A CN 101543781A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- propane
- preparation
- oxidative dehydrogenation
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing propylene by oxidizing and dehydrogenating propane and a preparation method thereof, relates to a solid catalyst, and provides a catalyst for preparing propylene by oxidizing and dehydrogenating propane and a preparation method thereof. The catalyst is applicable to preparing the propylene by oxidizing and dehydrogenating the propane, and has good low-temperature catalytic activity, high selectivity and low cost. The catalyst consists of an active component and at least one additive, wherein the active component is an oxide of nickel, and the additive is an oxide alkaline-earth metal or an oxide of rare-earth metal; and the atomic ratio of the additive to the active component is between 0.2 to 1 and 0.03 to 1. The preparation method comprises the following steps: dissolving an anionic surfactant or/and a non-ionic surfactant in deionized water, and after the surfactant is dissolved, adding inorganic metal salt and a precipitating agent into the deionized water to obtain a mixed solution; placing the mixed solution into a closed container, filtering the mixed solution after hydro-thermal reaction, and washing and drying solid; and raising the temperature of the dried solid to between 300 and 500 DEG C, and baking and pelleting the solid. The yield of the propylene can reach over 15 percent.
Description
Technical field
The present invention relates to a kind of solid catalyst, especially relate to solid catalyst of a kind of meso-porous nano transition metal oxide that is used for preparing propene by oxidative dehydrogenation of propane reaction and preparation method thereof.
Background technology
Propylene is the very important petrochemical industry basic material that is only second to ethene, is widely used in producing serial important chemical products such as polypropylene, acrylonitrile, phenol, oxo alcohol, expoxy propane and acrylic acid.Along with China's rapid economy development, propylene downstream product demand increases sharply in recent years, propylene demand rapid growth, and imbalance between supply and demand is very outstanding, and the propylene import volume increases year by year.Propylene is mainly produced by ethylene vapor cracking, petroleum catalytic cracking etc. at present.China has been in rank first, but at dehydrogenating propane (PDH) and oxidative dehydrogenation of propane aspects such as (ODH) in refinery's degree of depth cat-cracker propylene enhancing technology, and certain gap is arranged on the international most advanced level.
The production process of propane catalytic dehydrogenation system propylene is subjected to the control of thermodynamical equilibrium, severe reaction conditions, and also existence causes problems such as catalyst rapid deactivation because of carbon distribution.Preparing propene by oxidative dehydrogenation of propane (ODH) is as producing a kind of new way of propylene, because of the participation of aerobic with the generation of stable product water is arranged, can overcome the restriction of thermodynamical equilibrium and carries out under lower temperature, and not have carbon distribution, and catalyst need not frequent regeneration.Thereby oxidative dehydrogenation of propane becomes one of propylene production approach a kind of likely of present comprehensive utilization oil gas and natural gas.
At present, the research of catalyst for preparing propene by oxidative dehydrogenation of propane system is quite deep.The high performance catalyst system of having reported at goal response mainly comprises vanadium-based catalyst systems and non-vanadium-based catalyst systems.The conversion of propane of V/MgO in the time of 500 ℃ is 22.5%, and this moment, the selectivity of propylene was 59.8% ([1] .M.A.Chaar, D.Patel, M.C.Kung, H.H.Kung, J.Catal.1987,105,483～497), it is carrier with mesopore molecular sieve SBA～15 that Chinese patent CN 1396146A discloses a kind of, is the loaded catalyst of active component with V, and the conversion of propane in the time of 600 ℃ is 50%, this moment, the selectivity of propylene was 72%, and yield is 36%.
Chinese patent CN 1073893A discloses a kind of fluoride of Rare-Earth Ce and composite catalyst of oxide of containing, and when reaction temperature was 500 ℃, conversion of propane was 53.4%, and this moment, the selectivity of propylene was 67.5%, and the yield of propylene is 36%.But above-mentioned catalyst all carries out under higher reaction temperature.
Chinese patent CN 1557546A discloses the nano-composite catalyst of a kind of Ce of containing, Ni, and when reaction temperature was 300 ℃, conversion of propane was 52%, the propylene selectivity is 31.7%, propene yield is 16.5%, though the reaction temperature of this catalyst is lower, its selectivity is very low.Therefore the catalyst of seeking to have high catalytic performance under mild reaction conditions is one of research focus of this reaction at present.
Summary of the invention
The objective of the invention is to exist reaction temperature than problems such as height, provide a kind of and be applicable to preparing propene by oxidative dehydrogenation of propane, have the good low-temperature catalytic activity, than high selectivity and lower-cost catalyst for preparing propene by oxidative dehydrogenation of propane and preparation method thereof at existing solid catalyst.
Catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention is made up of a kind of active component and at least a interpolation component, and described active component is the oxide of nickel, and described interpolation component is selected from the oxide of alkaline-earth metal or rare earth metal; The atomic ratio that adds component and active component is 0.2: 1～0.03: 1, preferably 0.15: 1～0.05: 1.
The preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane of the present invention comprises following steps:
1) with anion surfactant or/and non-ionic surface active agent is dissolved in the deionized water, after the dissolving, add inorganic metal salt and precipitating reagent, mixed solution;
2) above-mentioned mixed solution is placed closed container, after the hydro-thermal reaction, filter, washing, oven dry;
3) solid after the above-mentioned oven dry is warmed up to 300～500 ℃, roasting, granulation gets catalyst for preparing propene by oxidative dehydrogenation of propane.
In step 1), described dissolving is preferably in 30～60 ℃ of stirred in water bath dissolvings; Described anion surfactant can be a lauryl sodium sulfate (SDS) etc., and described non-ionic surface active agent can be triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (EO
20PO
70EO
20, P123) etc.; Described inorganic metal salt can be an inorganic nickel, preferably is selected from Nickel dichloride hexahydrate, Nickelous nitrate hexahydrate, six hydration nickel sulfate or four hydration nickel acetates etc.; Described precipitating reagent can be itrogenous organic substance, and itrogenous organic substance is preferably urea etc.; In molar ratio, SDS: P123 can be 1: (1～25), preferably 1: (15～20); In molar ratio, the nickel ion in the described inorganic nickel: SDS can be (50～2): 1, preferably (5～2.75): 1; In molar ratio, the nickel ion in the described inorganic nickel: urea can be 1: (5～30), preferably 1: (10～20); In molar ratio, nickel ion and deionized water can be 1: (100～500), preferably 1: (250～300).
In step 2) in, the temperature of described hydro-thermal reaction is preferably 70～120 ℃, and the time of hydro-thermal reaction is preferably 10～20h; Described washing can be adopted the deionized water washing, and the temperature of described oven dry is preferably 40～100 ℃.
In step 3), the speed of intensification is preferably 1 ℃/min, and the time of roasting is preferably 3～6h.
The performance of described catalyst for preparing propene by oxidative dehydrogenation of propane can be tested with the following method:
Evaluating catalyst carries out in atmospheric fixed bed reactor, and wherein reactor (200mm * 6mm) controlled through the program temperature controller by thermocouple by reaction bed temperature.The mole of reactor feed gas consists of C
3H
8: O
2: He is 1.2: 1: 1.2, and air speed (GHSV) is 10000mlh
～1G
～1, reaction temperature is preferably 250～450 ℃ at 200～600 ℃.Product quantitatively detects by online twin columns gas-chromatography.
The present invention has overcome existing solid catalyst and has existed reaction temperature than problems such as height, not only provide a kind of and be applicable to preparing propene by oxidative dehydrogenation of propane, had the good low-temperature catalytic activity, than high selectivity and lower-cost catalyst for preparing propene by oxidative dehydrogenation of propane, and its preparation method is simple, the catalytic reaction desired reaction temperature is low, can be used for preparing propene by oxidative dehydrogenation of propane in the range of reaction temperature of broad.
The specific embodiment
Embodiment 1
The lauryl sodium sulfate (SDS) of getting 11.6g joins in the 22.6ml deionized water, after 40 ℃ of stirred in water bath dissolvings, adds the Nickelous nitrate hexahydrate of 36g urea and 5.816g, stirs to clarify, and obtains clear solution.With in 80 ℃ of baking ovens, behind the reaction 20h, taking out and filter in the above-mentioned solution adding closed container, spend the night in 60 ℃ of oven dry after the deionized water washing with 1L.Above-mentioned precursor is raised to 300 ℃ of roasting 4h with the heating rate of 1 ℃/min, and aftershaping to be lowered the temperature is 40～80 order particles.The catalyst of preparation is used for the reaction of preparing propene by oxidative dehydrogenation of propane, and reaction condition is that reaction gas is formed C
3H
8: O
2: He=1.2: 1: 1.2, air speed 10000mlh
～1G
～1, catalyst amount 0.1g.When reaction temperature was 450 ℃, conversion of propane was 26.0%,, the propylene selectivity is 50.2%, propene yield is 13.1%.
Embodiment 2
Preparation of Catalyst is with reference to embodiment 1, and the Nickelous nitrate hexahydrate of the 5.816g in the first step is changed to the Nickel dichloride hexahydrate of 4.754g, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 25.8%,, the propylene selectivity is 51.3%, propene yield is 13.2%.
Embodiment 3
Preparation of Catalyst is with reference to embodiment 2.The examination condition is with embodiment 1, and when reaction temperature was 600 ℃, conversion of propane was 21.7%,, the propylene selectivity is 31.2%, propene yield is 6.8%.
Embodiment 4
Preparation of Catalyst is raised to 450 ℃ of roasting 4h with reference to embodiment 2 with sintering temperature, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 22.3%,, the propylene selectivity is 51.1%, propene yield is 11.4%.
Embodiment 5
Get the lauryl sodium sulfate (SDS) of 2.163g and the P123 of 2.32g, join in the 100ml deionized water, in 40 ℃ of stirred in water bath.Add the Nickel dichloride hexahydrate of 18g urea and 4.754g after waiting to dissolve simultaneously, stir to clarify.With in 80 ℃ of baking ovens, behind the reaction 20h, taking out and filter in the above-mentioned solution adding closed container, spend the night in 60 ℃ of oven dry after the deionized water washing with 1L.Above-mentioned precursor is raised to 300 ℃ of roasting 4h with the heating rate of 1 ℃/min, and aftershaping to be lowered the temperature is 40～80 order particles.The examination condition is with embodiment 1, and when reaction temperature was 250 ℃, conversion of propane was 19.8%,, the propylene selectivity is 40.7%, propene yield is 8.1%.
Embodiment 6
Preparation of Catalyst is with reference to embodiment 5.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 24.6%,, the propylene selectivity is 49.1%, propene yield is 12.1%.
Embodiment 7
Preparation of Catalyst is raised to 380 ℃ of roasting 4h with reference to embodiment 5 with sintering temperature, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 26.2%,, the propylene selectivity is 47.9%, propene yield is 12.5%.
Embodiment 8
Preparation of Catalyst is with reference to embodiment 5, and the Nickel dichloride hexahydrate of the 4.754g in the first step is changed to the Nickelous nitrate hexahydrate of 5.816g, will be kept to reaction 12h by 80 ℃ of reaction 20h in closed container, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 25.0%,, the propylene selectivity is 49.5%, propene yield is 12.4%.
Embodiment 9
Preparation of Catalyst is with reference to embodiment 5, and the Nickel dichloride hexahydrate of the 4.754g in the first step is changed to the six hydration nickel acetates of 4.974g, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 24.2%,, the propylene selectivity is 50.6%, propene yield is 12.2%.
Embodiment 10
Preparation of Catalyst is with reference to embodiment 1, and the Nickelous nitrate hexahydrate of the 5.816g in the first step is changed to the Nickel dichloride hexahydrate of 4.754g and the six nitric hydrate ceriums of 0.52g, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 27.8%,, the propylene selectivity is 54.3%, propene yield is 15.1%.
Embodiment 11
Preparation of Catalyst is with reference to embodiment 1, and the Nickelous nitrate hexahydrate of the 5.816g in the first step is changed to the Nickel dichloride hexahydrate of 4.754g and the hydrated magnesium chloride of 0.407g, and all the other conditions are identical.The examination condition is with embodiment 1, and when reaction temperature was 450 ℃, conversion of propane was 24.6%,, the propylene selectivity is 51.4%, propene yield is 12.7%.
Reference examples 1
With the Nickelous nitrate hexahydrate of 5g in baking oven at 110 ℃ of dry 4h, with behind the solid abrasive of gained in 380 ℃ of calcining 4h, programming rate is 2 ℃/min.With above-mentioned shaping of catalyst is 40～80 order particles.The catalyst of preparation is used for the reaction of preparing propene by oxidative dehydrogenation of propane, and reaction condition is that reaction gas is formed C
3H
8: O
2: He=1.2: 1: 1.2, air speed 10000mlh
～1G
～1, catalyst amount 0.1g.When reaction temperature was 350 ℃, conversion of propane was 14.8%,, the propylene selectivity is 24.1%, propene yield is 3.6%.
Reference examples 2
The Nickelous nitrate hexahydrate solution (1mol/L) of 20ml dropwise is added drop-wise in the citric acid solution (1mol/L) of 20ml, the pH value of regulator solution system is about 1, extremely do in 70 ℃ of stirred in water bath, transfer in the baking oven in 110 ℃ of dry 24h, with behind the solid abrasive of gained in 380 ℃ the calcining 4h, programming rate is 2 ℃/min.With above-mentioned shaping of catalyst is 40～80 order particles.The examination condition is with reference examples 1, and when reaction temperature was 350 ℃, conversion of propane was 18.2%,, the propylene selectivity is 37.8%, propene yield is 6.9%.
Claims (10)
1. catalyst for preparing propene by oxidative dehydrogenation of propane is characterized in that being made up of a kind of active component and at least a interpolation component, and described active component is the oxide of nickel, and described interpolation component is selected from the oxide of alkaline-earth metal or rare earth metal; The atomic ratio that adds component and active component is 0.2: 1～0.03: 1.
2. catalyst for preparing propene by oxidative dehydrogenation of propane as claimed in claim 1, the atomic ratio that it is characterized in that adding component and active component is 0.15: 1～0.05: 1.
3. the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane according to claim 1 is characterized in that comprising following steps:
1) with anion surfactant or/and non-ionic surface active agent is dissolved in the deionized water, after the dissolving, add inorganic metal salt and precipitating reagent, mixed solution;
2) mixed solution is placed closed container, after the hydro-thermal reaction, filter, washing, oven dry;
3) solid after will drying is warmed up to 300～500 ℃, roasting, granulation, catalyst for preparing propene by oxidative dehydrogenation of propane.
4. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 1), describedly be dissolved in 30～60 ℃ of stirred in water bath dissolvings.
5. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 1) described anion surfactant is a lauryl sodium sulfate; Described non-ionic surface active agent is the triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.
6. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 1) described inorganic metal salt is an inorganic nickel, inorganic nickel is selected from Nickel dichloride hexahydrate, Nickelous nitrate hexahydrate, six hydration nickel sulfate or four hydration nickel acetates.
7. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 1) described precipitating reagent is an itrogenous organic substance.
8. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 1), in molar ratio, lauryl sodium sulfate: the triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene is 1: 1～25, nickel ion in the described inorganic nickel: lauryl sodium sulfate is 50～2: 1, nickel ion in the described inorganic nickel: urea is 1: 5～30, and nickel ion and deionized water are 1: 100～500.
9. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 2) in, the temperature of described hydro-thermal reaction is 70～120 ℃, the time of hydro-thermal reaction is 10～20h; The temperature of described oven dry is 40～100 ℃.
10. as the preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane as described in the claim 3, it is characterized in that in step 3) the speed of intensification is 1 ℃/min, the time of roasting is 3～6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101116451A CN101543781B (en) | 2009-05-04 | 2009-05-04 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101116451A CN101543781B (en) | 2009-05-04 | 2009-05-04 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101543781A true CN101543781A (en) | 2009-09-30 |
| CN101543781B CN101543781B (en) | 2013-06-05 |
Family
ID=41191310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101116451A Expired - Fee Related CN101543781B (en) | 2009-05-04 | 2009-05-04 | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101543781B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294251A (en) * | 2011-06-02 | 2011-12-28 | 厦门大学 | Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
| CN102887550A (en) * | 2012-10-09 | 2013-01-23 | 四川大学 | Method for producing mesoporous nickel oxide |
| CN104888818A (en) * | 2015-06-26 | 2015-09-09 | 王敏 | Catalyst for preparation of propylene by propane dehydrogenation and preparing method thereof |
| CN105593169A (en) * | 2013-09-30 | 2016-05-18 | 富士胶片株式会社 | Production method for metal oxide particles, metal oxide powder, and magnetic recording medium |
| CN106944088A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN114522703A (en) * | 2022-02-23 | 2022-05-24 | 浙江浙能技术研究院有限公司 | Preparation method and application of NiO-X catalyst based on anionic surface modification |
| CN117820069A (en) * | 2024-03-05 | 2024-04-05 | 山东天弘化学有限公司 | Method for producing propylene from propane |
| CN117820069B (en) * | 2024-03-05 | 2024-05-10 | 山东天弘化学有限公司 | Method for producing propylene from propane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029915C (en) * | 1992-10-19 | 1995-10-04 | 厦门大学 | Catalyst for preparing propene by oxidative dehydrogenation of propane |
| WO2000048971A1 (en) * | 1999-02-22 | 2000-08-24 | Symyx Technologies, Inc. | Compositions comprising nickel and their use as catalyst in oxidative dehydrogenation of alkanes |
-
2009
- 2009-05-04 CN CN2009101116451A patent/CN101543781B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294251A (en) * | 2011-06-02 | 2011-12-28 | 厦门大学 | Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
| CN102294251B (en) * | 2011-06-02 | 2013-01-30 | 厦门大学 | Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
| CN102887550A (en) * | 2012-10-09 | 2013-01-23 | 四川大学 | Method for producing mesoporous nickel oxide |
| CN102887550B (en) * | 2012-10-09 | 2014-07-16 | 四川大学 | Method for producing mesoporous nickel oxide |
| CN105593169A (en) * | 2013-09-30 | 2016-05-18 | 富士胶片株式会社 | Production method for metal oxide particles, metal oxide powder, and magnetic recording medium |
| CN104888818A (en) * | 2015-06-26 | 2015-09-09 | 王敏 | Catalyst for preparation of propylene by propane dehydrogenation and preparing method thereof |
| CN106944088A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN106944088B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN114522703A (en) * | 2022-02-23 | 2022-05-24 | 浙江浙能技术研究院有限公司 | Preparation method and application of NiO-X catalyst based on anionic surface modification |
| CN117820069A (en) * | 2024-03-05 | 2024-04-05 | 山东天弘化学有限公司 | Method for producing propylene from propane |
| CN117820069B (en) * | 2024-03-05 | 2024-05-10 | 山东天弘化学有限公司 | Method for producing propylene from propane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101543781B (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101543781B (en) | Catalyst for preparing propylene by oxidizing and dehydrogenating propane and preparation method thereof | |
| CN103212411B (en) | High-performance catalyst for preparing olefin through dehydrogenation of light alkane and preparation method thereof | |
| CN105214657B (en) | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof | |
| CN105582977B (en) | A kind of preparation method of dehydrogenation | |
| CN102698806B (en) | A kind of catalyst without mercury synthesizing vinyl chloride for acetylene hydrochlorination | |
| CN101851160A (en) | Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst | |
| CN107185594B (en) | Preparation method of Ni-Zn-K-Ru/MOF catalyst | |
| CN103752316A (en) | Iron catalyst for preparing butadiene through n-butene oxydehydrogenation and preparation method and application of iron catalyst | |
| CN105727930A (en) | Catalyst for propylene production using propane dehydrogenation and preparation method and application of catalyst | |
| CN105582919A (en) | Catalyst used for producing olefin through low-carbon alkane dehydrogenation, and preparation method thereof | |
| CN105582929A (en) | Light alkane dehydrogenation catalyst, and preparation method and application thereof | |
| CN108821306B (en) | Preparation method of metal modified hierarchical pore HZSM-5 molecular sieve | |
| CN103551157B (en) | The preparation method of rare earth modified zinc-iron composite oxide catalysts and the application in the reaction of butylene butadiene thereof | |
| CN104107718A (en) | Catalyst used for preparing olefin by dehydrating low carbon alkane, and preparation method thereof | |
| CN107715862B (en) | Anti-carbon deposition chromium-based catalyst for preparing propylene by propane dehydrogenation, preparation method and application | |
| CN107008255B (en) | Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene | |
| CN105582923A (en) | Catalyst used for producing olefin through light alkane dehydrogenation | |
| CN101993336B (en) | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition | |
| CN103028421B (en) | Low-water ratio ethylbenzene dehydrogenation catalyst | |
| CN108067228B (en) | Propane dehydrogenation catalyst and preparation method thereof | |
| CN102233274A (en) | Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof | |
| CN104549321A (en) | Catalyst for dehydrogenating light alkane and application of catalyst | |
| CN101773848A (en) | Catalyst used for synthesizing methyl tertiary butyl ether and preparation method thereof | |
| CN103769150B (en) | The catalyst of low-water ratio ethylbenzene dehydrogenation and method thereof | |
| CN102294251B (en) | Nano-oxide catalyst for preparing propylene by oxidative dehydrogenation of propane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130605 Termination date: 20190504 |