CN102553632B - A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof and application - Google Patents
A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof and application Download PDFInfo
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Abstract
A kind of catalyst for dehydrogenation of low-carbon paraffin, comprise the molecular sieve with MFI structure and be carried on the active component following with the molecular sieve of the butt MFI structure content that is benchmark on molecular sieve: group VIII metal 0.01 ~ 5.0 quality %, IVA race metal 0.01 ~ 5.0 quality %, IA race metal 0.8 ~ 5.0 quality %, phosphorus 0.3 ~ 5.0 quality %.This method for preparing catalyst is simple, reacts for dehydrogenating low-carbon alkane.Under the condition of high temperature, low pressure, carbon deposit is low, can the single pass life of extending catalyst.
Description
Technical field
The present invention is a kind of alkane dehydrogenating catalyst and preparation method thereof and application, specifically, is a kind of catalyst for dehydrogenation of low-carbon paraffin containing group VIII metal active component and preparation method thereof and application.
Background technology
In recent years, along with the raising of refinery's level of crude oil processing and increasing substantially of ethene production capacity, the output of catalytic cracking and preparing ethylene by steam cracking process by-product low-carbon alkanes increases sharply, and the utilization ratio of China to low-carbon alkanes is lower at present, major part uses as domestic fuel, causes the waste of resource.Along with China's expanding economy, the demand as the low-carbon alkene such as propylene, butylene of important industrial chemicals constantly increases.Therefore, utilize low-carbon alkanes resource produce propylene, butylene product dehydrogenating low-carbon alkane technology there is good application prospect.
Dehydrogenating low-carbon alkane technique can be divided into oxidative dehydrogenation and direct dehydrogenation two kinds.Oxidative dehydrogenation process needs to use the oxidants such as oxygen usually, and this not only increases the danger of technique, and easily causes the deep oxidation of olefin product, reduces the yield of alkene.Direct dehydrogenation process does not need to use oxidant, low-carbon alkanes highly selective can be converted into corresponding alkene, conversion per pass can reach more than 35% usually, the selective of olefin product reaches more than 90%, the a large amount of hydrogen of by-product simultaneously, above-mentioned advantage makes direct dehydrogenation technique more and more be paid close attention to.
The important class that to take Pt as the catalyst of active component be in direct dehydrogenation catalyst.Because dehydrogenating low-carbon alkane reaction is the strong endothermic reaction that molecular number increases, and be subject to the restriction of thermodynamical equilibrium, reaction needed is carried out under the harsh conditions of high temperature, low pressure, and this makes Pt catalyst carbon deposit speed fast, and the regeneration period is short.In order to reduce the deactivation rate of Pt based dehydrogenation catalyst, people have carried out a large amount of research work, and one of them important research direction is the screening of novel carriers material.Molecular sieve has good stability, abundant pore passage structure and higher specific area usually, holds charcoal ability strong, is therefore widely used as the carrier of Pt based dehydrogenation catalyst.
CN95193967.X discloses a kind of dehydrogenation, and this catalyst is containing the platinum group metal of 0.01% ~ 5.0% weight of having an appointment, the zinc of about 0.02% ~ 10.0% weight and contain L zeolite and alkali-metal carrier component.
CN01804051.9 discloses a kind of hydrocarbon dehydrogenation, and in this catalyst carrier, load has platinum group metal component, containing zinc component with containing magnesium component, carrier comprises ZSM or has the crystalline borosilicate of ZSM structure, and hydrocarbon molecule is containing 2 ~ 20 carbon atoms.
CN200610086006.0 discloses a kind of catalyst for low-carbon alkanes catalytic dehydrogenation and the method for the catalytic dehydrogenation of paraffin for preparing propylene that is catalyst with it.This catalyst is carrier with molecular sieve, take platinum group metal as active component, with IVA race metallic element and alkaline element for auxiliary agent, with resistant to elevated temperatures inorganic oxide for coupler.Described low-carbon alkanes contains 2 ~ 8 carbon atoms, and molecular sieve is ZSM-5.
CN200710023431.X discloses a kind of with the catalyst of the skeleton preparing propylene by dehydrogenating propane that is carrier containing the ZSM-5 molecular sieve of Sn.Sn in molecular sieve carrier skeleton is the part of catalyst promoter, and all right load of Sn, on ZSM-5 molecular sieve, plays promoter effect jointly; Active component is one or more elements in platinum, palladium, iridium, rhodium, osmium or rhenium, and alkalinous metal auxiliary agent is one or more of IA race and IIA race element.
CN200710020064.8 discloses a kind of catalyst for preparing propylene by dehydrogenating propane, this catalyst take refractory oxides as carrier, take platinum group metal as major catalyst, with IVA race metal, rare earth element for auxiliary agent, take halogen as modifier, with resistant to elevated temperatures inorganic oxide for binding agent is shaping.This catalyst has higher conversion of propane, Propylene Selectivity and reaction stability under the condition of high temperature, low pressure.
CN200810155908.4 discloses a kind of catalyst for preparing propylene with propane dehydrogenation and preparation method thereof, this catalyst contains the molecular sieve of rare earth element for carrier with skeleton, take platinum group metal as major catalyst, with IVA race metal, IA race or IIA race metal for auxiliary agent, take halogen as modifier, with resistant to elevated temperatures inorganic oxide for binding agent is shaping, described molecular sieve is one or more in A, X, Y, ZSM-5, MCM, SBA.
CN200910091226.6 discloses a kind of Catalysts and its preparation method for manufacturing olefin by low-carbon alkane dehydrogenation and application, this catalyst take aluminium silicophosphate molecular sieve as carrier, with VIII or group vib element for active component, with IVA race element for auxiliary agent, wherein active component accounts for the percentage by weight of catalyst is 0.001% ~ 20%, and the percentage by weight that auxiliary agent accounts for catalyst is 0.001% ~ 20%.
Summary of the invention
The object of this invention is to provide a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, this catalyst has higher reactivity worth and high appearance charcoal ability, can one way service life of extending catalyst.
Another object of the present invention is to provide the application of described catalyst in dehydrogenating low-carbon alkane producing light olefins.
Catalyst for dehydrogenation of low-carbon paraffin provided by the invention, comprises the molecular sieve with MFI structure and is carried on the active component following with the molecular sieve of the butt MFI structure content that is benchmark on molecular sieve:
Group VIII metal 0.01 ~ 5.0 quality %,
IVA race metal 0.01 ~ 5.0 quality %,
IA race metal 0.5 ~ 5.0 quality %,
Phosphorus 0.3 ~ 5.0 quality %.
The molecular sieve phosphorus of MFI structure and IA race metal are carried out modification by the present invention, and load IVA race's metal and group VIII metal, catalyst is made to have stronger appearance charcoal ability, improve the activity of catalyst, selective and coking resistivity simultaneously, catalyst coke deposit rate under the dehydrogenating low-carbon alkane condition of high temperature, low pressure is declined, extends the single pass life of catalyst.
Detailed description of the invention
The present invention's phosphorus-containing compound dipping has the molecular sieve of MFI structure, introduces IVA race metal, group VIII metal and IA race metal and obtains catalyst.The phosphorus introduced in molecular sieve and IA race metal interaction, make the activity of catalyst and selectivity of light olefin increase, and the coke deposit rate of catalyst is significantly reduced, and extends the single pass life of catalyst.
The preferred each active component content of catalyst of the present invention is as follows:
Group VIII metal 0.05 ~ 2.0 quality %,
IVA race metal 0.05 ~ 2.0 quality %,
IA race metal 0.5 ~ 3.0 quality %,
Phosphorus 0.3 ~ 3.5 quality %.
Wherein IA race tenor more preferably 0.8 ~ 2.5 quality %, phosphorus content is 0.3 ~ 1.0 quality % more preferably.
The preferred platinum of described group VIII metal or palladium, more preferably platinum, the preferred tin of IVA race metal or germanium, more preferably tin, the described preferred sodium of IA race metal or potassium, or sodium and potassium.IA race metal in catalyst of the present invention does not comprise the IA race metal of the molecular sieve cation-bit of MFI structure, as the sodium in the molecular sieve of sodium form MFI structure.
The described preferred Hydrogen of the molecular sieve with MFI structure or ZSM-5, ZSM-11 or ZSM-12 of sodium form, more preferably ZSM-5, ZSM-11 or ZSM-12 of sodium form.
The silica/alumina molar ratio of described ZSM-5 is 20 ~ 300, preferably 30 ~ 200.
The preparation method of catalyst provided by the invention, comprises the steps:
(1) will have the aqueous impregnation of the molecular sieve phosphorus-containing compound of MFI structure, dry roasting obtains the molecular sieve of P Modification,
(2) flooded by the compound solution of the molecular sieve of P Modification containing IVA race metal, then dry, roasting, obtains the metal-modified molecular sieve of phosphorus and IVA race,
(3) flooded by the compound solution of the metal-modified molecular sieve of phosphorus and IVA race containing group VIII metal, drying, roasting obtain catalyst precarsor,
(4) compound solution of catalyst precarsor containing IA race metal is flooded, after drying, roasting, carry out steam treatment, after reduction, obtain catalyst.
Said method (1) step is the preparation of the molecular sieve of P Modification, the preferred Hydrogen of the molecular sieve with MFI structure described in (1) step or ZSM-5, ZSM-11 or ZSM-12 of sodium form.
P Modification phosphorus-containing compound used is selected from phosphoric acid, metaphosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.Gu liquid/mass ratio during dipping is 0.5 ~ 1.5: 1, suitable dipping temperature is 20 ~ 200 DEG C, preferably 25 ~ 100 DEG C.
Described method (2) step is in the molecular sieve through P Modification, introduce IVA race metal, preferred Sn or Ge, the chloride of preferred Sn or Ge of compound containing IVA race metal that the molecular sieve of dipping P Modification is used or nitrate.During dipping, the mass ratio of maceration extract and modified molecular screen is 0.5 ~ 1.5: 1, preferably 0.8 ~ 1.2: 1.
Described method (3) step for introduce group VIII metal in modified molecular screen carrier, and preferred Pt or Pd, described contains the preferred chloroplatinic acid of group VIII metal compound, ammonium chloroplatinate, tri-chlorination platinum, platinum tetrachloride hydrate or palladium bichloride.During dipping, the mass ratio of maceration extract and modified molecular screen is 0.5 ~ 1.5: 1, preferably 0.8 ~ 1.2: 1.
Described method (4) step is introducing IA race metal, preferred K or Na of IA race metal, the chloride of preferred K or Na of compound containing IA race metal used or nitrate, preferred potassium nitrate, potassium chloride, sodium nitrate or sodium chloride.During dipping, the mass ratio of maceration extract and impregnated molecular sieve is 0.5 ~ 1.5: 1, preferably 0.6 ~ 1.2: 1.
During said method respectively walks, the dipping temperature that dipping introduces each active component is 20 ~ 200 DEG C, preferably 25 ~ 100 DEG C.After dipping introduces each active component, comparatively suitable baking temperature is 80 ~ 140 DEG C, and preferably 100 ~ 120 DEG C, drying time is 5 ~ 30 hours, preferably 8 ~ 24 hours.Suitable sintering temperature is 500 ~ 650 DEG C, and preferably 550 ~ 600 DEG C, roasting time is 1 ~ 10 hour, preferably 3 ~ 5 hours.
(4) need by steam treatment after the molecular sieve drying after step dipping, roasting, the temperature of described steam treatment is 400 ~ 700 DEG C, preferably 450 ~ 600 DEG C.The steam treatment time is 0.5 ~ 8 hour, preferably 2 ~ 6 hours.Catalyst reduction temperature is 400 ~ 700 DEG C, preferably 450 ~ 600 DEG C, and the recovery time is 1 ~ 8 hour, preferably 2 ~ 6 hours, the preferred hydrogen of reducing gas.
The method using catalyst of the present invention to carry out dehydrogenating low-carbon alkane is included in 400 ~ 700 DEG C, 0.05 ~ 2.0MPa, hydrogen/hydrocarbon mol ratio be make low-carbon alkanes and catalyst exposure of the present invention react under the condition of 0.25 ~ 20.0.
Described dehydrogenating low-carbon alkane reaction temperature preferably 500 ~ 650 DEG C, reaction pressure is 0.1 ~ 1.0MPa preferably, hydrogen/hydrocarbon mol ratio preferably 0.5 ~ 10.0 during reaction.During reaction, low-carbon alkanes feedstock quality air speed is 0.1 ~ 20.0hr
-1, preferably 0.5 ~ 5.0hr
-1.Described low-carbon alkanes is C
3~ C
5alkane, comprise propane, iso-butane, normal butane or pentane.
Catalyst of the present invention is applicable to fluid bed, moving bed or fixed bed reactors, and wherein fixed bed reactors can use two or more parallel connection, so that be fixed a handover operation, carries out continuous seepage.
Below by example, the present invention is described, but the present invention is not limited to this.
Example 1
(1) ZSM-5 molecular sieve of P Modification is prepared
Get the silica alumina ratio (SiO of 60.0g
2/ Al
2o
3mol ratio) be 111 sodium form ZSM-5 molecular sieve (molecular sieve contents on dry basis 95 quality %), join in the phosphate aqueous solution of the phosphorous 0.60 quality % of 60.0g (quality relative to butt ZSM-5), 25 DEG C are stirred dipping 10 hours, 120 DEG C of dryings 12 hours, in 550 DEG C, roasting 4 hours under the condition of gas/agent volume ratio 700 in dry air, obtain the ZSM-5 molecular sieve of P Modification.
(2) ZSM-5 molecular sieve of phosphorus and tin modification is prepared
Get the ZSM-5 molecular sieve of P Modification prepared by 45.0g (1) step, join 63.0g containing in the butter of tin aqueous solution of Sn 0.30 quality % (quality relative to butt ZSM-5), 60 DEG C are stirred dipping 2 hours, 100 DEG C of dryings 12 hours, in 550 DEG C, roasting 4 hours under the condition of gas/agent volume ratio 500 in dry air, obtain the ZSM-5 molecular sieve of phosphorus and tin modification.
(3) Kaolinite Preparation of Catalyst precursor
Get the ZSM-5 molecular sieve of phosphorus prepared by 40.0g (2) step and tin modification, join 60.0g containing in the chloroplatinic acid aqueous solution of Pt 0.30 quality % (quality relative to butt ZSM-5), 40 DEG C are stirred dipping 5 hours, 120 DEG C of dryings 12 hours, in 500 DEG C, roasting 4 hours under the condition of gas/agent volume ratio 700 in dry air, obtain catalyst precarsor.
(4) Kaolinite Preparation of Catalyst
Get catalyst precarsor prepared by 38.0g (3) step, join 30.4g containing in the Alkitrate of K 1.00 quality % (quality relative to butt ZSM-5), 30 DEG C flood 4 hours, 60 DEG C of dryings 3 hours, 120 DEG C of dryings 10 hours, in 500 DEG C, roasting 5 hours under the condition of gas/agent volume ratio 700 in dry air, 4 hours are processed again in 500 DEG C of water vapours, then in hydrogen in 550 DEG C, reduction 4 hours under the condition of gas/agent volume ratio 300, obtain catalyst A, its composition is in table 1.
Example 2
By the method Kaolinite Preparation of Catalyst of example 1, unlike use in (1) step silica alumina ratio be 111 Hydrogen ZSM-5 molecular sieve replace sodium form ZSM-5 molecular sieve, the composition of obtained catalyst B is in table 1.
Example 3 ~ 5
By the method Kaolinite Preparation of Catalyst of example 1, unlike using the sodium form ZSM-5 molecular sieve of Different Silicon aluminum ratio to carry out modification in (1) step, obtained catalyst C ~ E, the sodium form ZSM-5 molecular sieve that each example is used and obtained catalyst composition are in table 1.
Example 6
By the method Kaolinite Preparation of Catalyst of example 1, flood unlike in the ammonium dibasic phosphate aqueous solution in (1) step, 60.0g NaZSM-5 molecular sieve being joined the phosphorous 1.50 quality % of 72.0g (quality relative to butt ZSM-5), the ZSM-5 carrier of P Modification is obtained after drying, roasting, again by the method Kaolinite Preparation of Catalyst of (2), (3), (4) step, the composition of obtained catalyst F is in table 1.
Example 7
By the method Kaolinite Preparation of Catalyst of example 1, flood unlike in the ammonium hydrogen phosphate aqueous solution in (1) step, 60.0g NaZSM-5 molecular sieve being joined the phosphorous 3.00 quality % of 90.0g (quality relative to butt ZSM-5), the ZSM-5 carrier of P Modification is obtained after drying, roasting, then press the method Kaolinite Preparation of Catalyst G of example (2), (3), (4) step, its composition is in table 1.
Example 8
(1) ZSM-5 molecular sieve of P Modification is prepared
Get the sodium form ZSM-5 molecular sieve (molecular sieve contents on dry basis 95 quality %) that 65.0g silica alumina ratio is 111, join in the ammonium dibasic phosphate aqueous solution of the phosphorous 0.60 quality % of 80.0g (quality relative to butt ZSM-5), 80 DEG C are stirred dipping 4 hours, 120 DEG C of dryings 8 hours, in 550 DEG C, roasting 4 hours under the condition of gas/agent volume ratio 500 in dry air, obtain the ZSM-5 molecular sieve of P Modification.
(2) ZSM-5 molecular sieve of phosphorus and tin modification is prepared
Get the ZSM-5 carrier of P Modification prepared by 50.0g (1) step, join 68.0g containing in the butter of tin aqueous solution of Sn 0.50 quality % (quality relative to butt ZSM-5), 30 DEG C are stirred dipping 2 hours, 120 DEG C of dryings 12 hours, in 550 DEG C, roasting 4 hours under the condition of gas/agent volume ratio 500 in dry air, obtain the ZSM-5 molecular sieve of phosphorus and tin modification.
(3) Kaolinite Preparation of Catalyst precursor
Get the ZSM-5 molecular sieve of phosphorus prepared by 48.0g (2) step and tin modification, join 60.0g containing in the chloroplatinic acid aqueous solution of Pt 0.50 quality % (quality relative to butt ZSM-5), 25 DEG C are stirred dipping 4 hours, 120 DEG C of dryings 12 hours, in 500 DEG C, roasting 4 hours under the condition of gas/agent volume ratio 600 in dry air, obtain catalyst precarsor.
(4) Kaolinite Preparation of Catalyst
Get catalyst precarsor prepared by 40.0g (3) step, join 32.0g containing in the sodium-chloride water solution of Na 0.90 quality % (quality relative to butt ZSM-5), 28 DEG C flood 4 hours, 60 DEG C of dryings 3 hours, 120 DEG C of dryings 12 hours, in 500 DEG C, roasting 5 hours under the condition of gas/agent volume ratio 700 in dry air, 4 hours are processed again in 500 DEG C of water vapours, last in hydrogen in 550 DEG C, under the condition of gas/agent volume ratio 400 reduction within 4 hours, obtain catalyst H, its composition is in table 1.
Comparative example 1
Get the silica alumina ratio (SiO of 45.0g
2/ Al
2o
3mol ratio) be 111 sodium form ZSM-5 molecular sieve (molecular sieve contents on dry basis 95 quality %), by the method Kaolinite Preparation of Catalyst I of example 1 (2) ~ (4) step, its composition in table 1.
Comparative example 2
Get the Hydrogen ZSM-5 molecular sieve that 60.0g silica alumina ratio is 111, by the method Kaolinite Preparation of Catalyst of example 1 (1) ~ (3) step, and by catalyst precarsor obtained after roasting for (3) step, 4 hours are processed in 500 DEG C of water vapours, last in hydrogen in 550 DEG C, reduction 4 hours under the condition of gas/agent volume ratio 400, the composition of the catalyst J obtained is in table 1.
Comparative example 3
Get the sodium form ZSM-5 molecular sieve that 50.0g silica alumina ratio is 111, by the method Kaolinite Preparation of Catalyst K of example 8 (2) ~ (4) step, its composition is in table 1.
Example 9
The dehydrogenation of isobutane reactivity worth of this case expedition catalyst.
Be reaction raw materials with iso-butane, micro-reactor is evaluated catalyst of the present invention and comparative catalyst, and appreciation condition is: 580 DEG C, 0.15MPa, feedstock quality air speed 3.0hr
-1, hydrogen/hydrocarbon mol ratio 1: 1,10 hours reaction time, evaluation result is in table 2.
As shown in Table 2, catalyst of the present invention, than comparative catalyst, has higher catalytic activity and selective isobutene.
Example 10
The dehydrogenating propane reactivity worth of this case expedition catalyst.
Take propane as reaction raw materials, 10 milliliters of fixed bed devices are evaluated catalyst H and comparative catalyst K, and appreciation condition is: 590 DEG C, 0.1MPa, feedstock quality air speed be 3.5hr
-1, hydrogen/hydrocarbon mol ratio 1: 1,500 hours reaction time, the coke content of evaluation result and post catalyst reaction is in table 3.
As shown in Table 3, catalyst of the present invention is than comparative catalyst, and have higher catalytic activity, selective and coking resistivity, catalyst single pass life is longer.
Table 1
Table 2
Table 3
Claims (12)
1. a catalyst for dehydrogenation of low-carbon paraffin, comprises the molecular sieve with MFI structure and is carried on the active component following with the molecular sieve of the butt MFI structure content that is benchmark on molecular sieve:
The described molecular sieve with MFI structure is ZSM-5, ZSM-11 or ZSM-12 of sodium form.
2. according to catalyst according to claim 1, it is characterized in that described group VIII metal is selected from platinum or palladium, IVA race metal is selected from tin or germanium.
3., according to catalyst according to claim 1, it is characterized in that described IA race metal is sodium and/or potassium.
4., according to catalyst according to claim 1, it is characterized in that the silica/alumina molar ratio of described ZSM-5 is 20 ~ 300.
5. a preparation method for catalyst described in claim 1, comprises the steps:
(1) will have the aqueous impregnation of the molecular sieve phosphorus-containing compound of MFI structure, dry roasting obtains the molecular sieve of P Modification, described in there is MFI structure molecular sieve be ZSM-5, ZSM-11 or ZSM-12 of sodium form,
(2) flooded by the compound solution of the molecular sieve of P Modification containing IVA race metal, then dry, roasting, obtains the metal-modified molecular sieve of phosphorus and IVA race,
(3) flooded by the compound solution of the metal-modified molecular sieve of phosphorus and IVA race containing group VIII metal, drying, roasting obtain catalyst precarsor,
(4) compound solution of catalyst precarsor containing IA race metal is flooded, after drying, roasting, carry out steam treatment, after reduction, obtain catalyst.
6. in accordance with the method for claim 5, it is characterized in that the phosphorus-containing compound described in (1) step is selected from phosphoric acid, metaphosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate or ammonium phosphate.
7. in accordance with the method for claim 5, it is characterized in that the compound containing IVA race metal described in (2) step is selected from chloride or the nitrate of Sn or Ge.
8. in accordance with the method for claim 5, it is characterized in that the group VIII metal compound that contains described in (3) step is selected from chloroplatinic acid, ammonium chloroplatinate, tri-chlorination platinum, platinum tetrachloride hydrate or palladium bichloride.
9. in accordance with the method for claim 5, it is characterized in that the compound containing IA race metal described in (4) step is selected from chloride or the nitrate of K or Na.
10. in accordance with the method for claim 5, it is characterized in that the temperature of the steam treatment described in (4) step is 400 ~ 700 DEG C.
11. 1 kinds of dehydrogenating low-carbon alkane methods, are included in 400 ~ 700 DEG C, 0.05 ~ 2.0MPa, hydrogen/hydrocarbon mol ratio are make low-carbon alkanes and catalyst exposure according to claim 1 react under the condition of 0.25 ~ 20.0.
12. in accordance with the method for claim 11, it is characterized in that described low-carbon alkanes feedstock quality air speed is 0.1 ~ 20.0hr
-1.
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| CN104107692B (en) * | 2013-04-16 | 2016-07-13 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN109746030B (en) * | 2017-11-03 | 2022-03-15 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation |
| CN111097457B (en) * | 2018-10-29 | 2023-01-13 | 中国石油化工股份有限公司 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN112619686B (en) * | 2019-10-09 | 2024-01-30 | 中国石油化工股份有限公司 | Supported non-noble metal dehydrogenation catalyst and preparation method and application thereof |
| CN113546651B (en) * | 2020-04-23 | 2022-11-11 | 中国科学院上海高等研究院 | Phosphorus-modified carbon-based catalyst and preparation method and application thereof |
| CN114602549B (en) * | 2022-03-28 | 2024-06-25 | 香港中文大学（深圳） | Catalyst for preparing unsaturated hydrocarbon from saturated hydrocarbon, preparation method of catalyst and method for preparing unsaturated hydrocarbon from saturated hydrocarbon |
| CN115814839B (en) * | 2022-12-27 | 2024-03-22 | 中触媒新材料股份有限公司 | Boron or phosphorus doped Silicalite-1 molecular sieve encapsulated metal catalyst and preparation method and application thereof |
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