CN114632539A - Catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and preparation method and application thereof - Google Patents

Catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and preparation method and application thereof Download PDF

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CN114632539A
CN114632539A CN202011493724.6A CN202011493724A CN114632539A CN 114632539 A CN114632539 A CN 114632539A CN 202011493724 A CN202011493724 A CN 202011493724A CN 114632539 A CN114632539 A CN 114632539A
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catalyst
ethanol
acetonitrile
dehydrogenation
transition metal
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CN114632539B (en
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张晓敏
许磊
袁扬扬
李沛东
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The application discloses a catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation, and a preparation method and application thereof, wherein the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation comprises a transition metal element M and a ZSM-5 molecular sieve; the transition metal element M is doped into the framework of the ZSM-5 molecular sieve; the transition metal element M is at least one selected from titanium, vanadium, manganese, iron, cobalt, nickel and copper. The catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation can be used for the reaction of preparing acetonitrile by ethanol ammoniation dehydrogenation, effectively improves the conversion rate of ethanol and the selectivity of acetonitrile, and has better industrial application prospect.

Description

Catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and preparation method and application thereof
Technical Field
The application relates to a catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation, a preparation method and application thereof, belonging to the technical field of chemical engineering.
Background
Acetonitrile is not only an excellent solvent, but also a very important fine chemical organic intermediate, and has important application in the fields of pharmacy, pesticides, organic synthesis and petrochemical industry. At present, most of acetonitrile worldwide is extracted from a byproduct for producing acrylonitrile, the yield is only 1% -2% of the yield of the acrylonitrile, the demand of the acetonitrile is continuously increased along with the continuous development of development technology of acetonitrile downstream products, and the market has presented a trend of short supply and short demand. Therefore, the development of a new technique for directly synthesizing acetonitrile is urgent.
Acetonitrile can be synthesized by chemical methods such as carbon monoxide amination hydrogenation, lower hydrocarbon ammoxidation or reaction with a cyanide compound, acetaldoxime dehydration, acetaldehyde ammoniation dehydration, ethanol ammoniation dehydrogenation or oxidation, acetic acid ammoniation dehydration and the like. Compared with various processes for synthesizing acetonitrile, the direct ethanol ammoniation method has the advantages of simple process, low energy consumption, high atom utilization rate, high acetonitrile selectivity, low operation cost and no corrosion to equipment, and is a process route with the greatest industrial prospect. The development of an efficient ammoniation dehydrogenation catalyst is the key for completing the technology of synthesizing acetonitrile by ammoniating ethanol. In the reaction process, the performance of the catalyst determines the conversion rate of ethanol and the yield of acetonitrile, and the traditional catalyst is mainly a copper catalyst loaded by active alumina. However, activated alumina-supported Cu-based catalysts tend to deactivate, are less stable and tend to require higher ammonia/alcohol ratios in ethanol dehydroamination reactions to achieve higher acetonitrile selectivity. The excessively high ammonia-alcohol ratio aggravates the inactivation of the catalyst and increases the energy consumption for ammonia gas recycling. Therefore, the development of a novel efficient catalyst solves the problems of poor catalyst stability and high ammonia-alcohol ratio in the reaction process of the existing catalyst system, and the exploration of the industrial application of the catalyst in the ethanol ammoniation synthesis of acetonitrile still has very important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and a preparation method and application thereof.
According to a first aspect of the application, an acetonitrile catalyst prepared by ethanol ammoniation dehydrogenation is provided, and the acetonitrile catalyst prepared by ethanol ammoniation dehydrogenation comprises a transition metal element M and a ZSM-5 molecular sieve;
the transition metal element M is doped into the framework of the ZSM-5 molecular sieve;
the transition metal element M is at least one selected from titanium, vanadium, manganese, iron, cobalt, nickel and copper.
Optionally, the mass content of the transition metal element M in the catalyst for preparing acetonitrile by ethanol ammoniation and dehydrogenation is 0.5-10%.
Optionally, the upper limit of the mass content of the transition metal element M in the catalyst for preparing acetonitrile by ethanol ammonification and dehydrogenation is independently selected from 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, and the lower limit is independently selected from 0.5%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%.
According to a second aspect of the present application, there is provided a preparation method of the above catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation, the method comprising:
(1) carrying out hydrothermal crystallization on a mixture containing a structure directing agent, water, a silicon source, an aluminum source, a hydroxide of an alkali metal ion M' and a transition metal element M source at the temperature of 130-200 ℃ for 2-10 days;
(2) after crystallization is finished, washing, drying and roasting are carried out in sequence to obtain the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation;
in the mixture, the molar ratio of each substance is as follows:
SiO2：Al2O3：M’2O：H2o: transition metal element M oxide: structure directing agent 1: 0.001-0.1: 0.002-1: 50: 0.001-0.5: 0.05-5.
Optionally, the upper temperature limit of the hydrothermal crystallization is independently selected from 200 ℃, 190 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, and the lower temperature limit is independently selected from 130 ℃, 190 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃.
Alternatively, the upper limit of the hydrothermal crystallization time is independently selected from 10 days, 8 days, 6 days, 4 days, 3 days, and the lower limit is independently selected from 2 days, 8 days, 6 days, 4 days, 3 days.
Optionally, the silicon source is selected from one of ethyl orthosilicate, white carbon black, silica sol and sodium silicate;
the aluminum source is selected from one of aluminum sulfate, aluminum nitrate, sodium metaaluminate, aluminum isopropoxide and aluminum sol;
the hydroxide of the alkali metal ion M' is selected from sodium hydroxide;
the structure directing agent is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
Optionally, the method comprises: mixing raw materials required for preparing the transition metal doped ZSM-5 molecular sieve, a silicon source, an aluminum source, an alkali source, a transition metal salt, a structure directing agent and water, wherein the molar ratio of oxides is as follows: 1SiO2：0.001-0.1Al2O3:0.002-1Na2O:50H2O:0.001-0.5MOX0.05 to 5SDA, and performing hydrothermal crystallization for 2 to 10 days at the temperature of 130 ℃ and 200 ℃; and washing, drying and roasting by using deionized water after crystallization is finished, wherein the SDA is a structure directing agent.
Optionally, the source of transition metal element M is selected from at least one of transition metal element M salts.
Optionally, the roasting conditions are: the temperature is 300-600 ℃; the time is 3-10 h.
Optionally, the method further comprises the steps of:
(3) and in a hydrogen-containing atmosphere, reducing the roasted material to obtain the catalyst for preparing the acetonitrile by the ethanol ammoniation dehydrogenation.
Optionally, the reducing conditions are: the temperature is 200-500 ℃; the time is 0.5-5 h.
According to a third aspect of the present application, there is provided a process for the preparation of acetonitrile, the process comprising: reacting materials containing ethanol and ammonia gas in the presence of a catalyst to obtain acetonitrile;
the catalyst is selected from any one of the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation and the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation prepared by the method.
Optionally, the molar ratio of ethanol to ammonia in the feed is 1: 1.5 to 5.
Optionally, the reaction conditions are: the temperature is 200 ℃ and 450 ℃; the pressure is 0.2-5.0 Mpa; the mass space velocity of the ethanol is 0.2-2h-1。
Alternatively, the upper limit of the reaction temperature is independently selected from 450 ℃, 400 ℃, 350 ℃, 300 ℃, 250 ℃, and independently selected from 200 ℃, 400 ℃, 350 ℃, 300 ℃, 250 ℃.
Alternatively, the upper limit of the reaction pressure is independently selected from 5MPa, 4MPa, 3MPa, 2MPa, 1MPa, 0.5MPa, and the lower limit is independently selected from 0.2MPa, 4MPa, 3MPa, 2MPa, 1MPa, 0.5 MPa.
The catalyst is used for the reaction of preparing acetonitrile by ethanol ammoniation dehydrogenation, and the specific reaction process comprises the following steps: the catalyst is filled in a fixed bed reactor and H is used before reaction2And N2Reducing the formed mixed gas; then raw materials of ethanol and ammonia gas are respectively introduced into a fixed bed reactor to react, and the molar ratio of ethanol to ammonia is 1/1.5-5; the reaction temperature is 200-450 ℃; the pressure of the reactor is 0.2-5.0 Mpa; the mass space velocity of the ethanol is 0.2-2h-1. The catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation is a transition metal doped ZSM-5 molecular sieve.
Alternatively, the transition metal element M in the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation in the present application may exist in the form of oxide, or may exist in the form of simple substance, and if the catalyst is not subjected to a reduction process during the preparation of the catalyst, the reduction process during the preparation of acetonitrile is also feasible.
The beneficial effects that this application can produce include:
the catalyst is used for the reaction of preparing acetonitrile by ethanol ammoniation dehydrogenation, and effectively improves the conversion rate of ethanol and the selectivity of acetonitrile, so the catalyst has better industrial application prospect.
Detailed Description
The invention will be further described with reference to specific examples, but it should be understood that the invention is not limited thereto.
Example 1
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker, stirring, then slowly dropwise adding 20.83g of tetraethoxysilane into the beaker, and uniformly stirring at room temperature; 0.75g of aluminum nitrate, 0.2g of nickel nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, stirred uniformly at room temperature and then added dropwise into the mixed solution and stirred continuously until uniform. Then will be combinedPouring the liquid into a polytetrafluoroethylene inner container, sealing in a stainless steel kettle, and crystallizing at 180 deg.C for 2 days. And (3) quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for multiple times, drying, and roasting at 300 ℃ for 10 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: SiO 22:0.01Al2O3:0.05Na2O:50H2O:0.01NiO2:0.25SDA。
Example 2
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker, stirring, then slowly dropwise adding 20.83g of tetraethoxysilane into the beaker, and uniformly stirring at room temperature; 0.75g of aluminum nitrate, 0.5g of copper nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, stirred uniformly at room temperature and then added dropwise to the mixed solution and stirred continuously until uniform. Then the synthetic liquid is poured into a polytetrafluoroethylene inner container, sealed in a stainless steel kettle and crystallized for 2 days at 180 ℃. And (3) quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for multiple times, drying, and roasting at 400 ℃ for 8 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: SiO 22:0.01Al2O3:0.05Na2O:50H2O:0.01CuO:0.25SDA。
Example 3
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker, stirring, then slowly dropwise adding 20.83g of tetraethoxysilane into the beaker, and uniformly stirring at room temperature; 0.75g of aluminum nitrate, 0.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, and the mixture is stirred uniformly at room temperature and then is dripped into the mixed solution to be continuously stirred uniformly. Then the synthetic liquid is poured into a polytetrafluoroethylene inner container, sealed in a stainless steel kettle and crystallized for 2 days at 180 ℃. And (3) quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for multiple times, drying, and roasting at 500 ℃ for 7 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: SiO 22:0.01Al2O3:0.05Na2O:50H2O:0.01CoO:0.25SDA。
Example 4
20.35g of aqueous tetrapropylammonium hydroxide solution (25% strength by weight) and 45g ofPouring the ionized water into a beaker, stirring, slowly and dropwise adding 20.83g of tetraethoxysilane into the beaker, and uniformly stirring at room temperature; 0.75g of aluminum nitrate, 0.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, stirred uniformly at room temperature and then added dropwise into the mixed solution and stirred continuously until uniform. Then the synthetic solution is poured into a polytetrafluoroethylene inner container, sealed in a stainless steel kettle and crystallized for 2 days at 180 ℃. And (3) quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for multiple times, drying, and roasting at 600 ℃ for 6 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: SiO 22:0.033Al2O3:0.05Na2O:50H2O:0.01CoO:0.25SDA。
Example 5
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker, stirring, then slowly dropwise adding 20.83g of tetraethoxysilane into the beaker, and uniformly stirring at room temperature; 0.75g of aluminum nitrate, 2.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, stirred uniformly at room temperature and then added dropwise into the mixed solution and stirred continuously until uniform. Then the synthetic solution is poured into a polytetrafluoroethylene inner container, sealed in a stainless steel kettle and crystallized for 2 days at 180 ℃. And (3) quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for multiple times, drying, and roasting at 450 ℃ for 7.5 hours to obtain the catalyst. The molar composition of the synthesized catalyst is as follows: SiO 22:0.033Al2O3:0.05Na2O:50H2O:0.02CoO:0.25SDA。
Example 6
Pouring 20.35g of tetrapropylammonium hydroxide aqueous solution (with the concentration of 25 wt%) and 45g of deionized water into a beaker, stirring, then slowly dropwise adding 20.83g of tetraethoxysilane into the beaker, and uniformly stirring at room temperature; 0.75g of aluminum nitrate, 2.5g of cobalt nitrate and 0.5g of NaOH are dissolved in 5g of deionized water, stirred uniformly at room temperature and then added dropwise into the mixed solution and stirred continuously until uniform. Then the synthetic solution is poured into a polytetrafluoroethylene inner container, sealed in a stainless steel kettle and crystallized for 2 days at the temperature of 200 ℃. And (3) quenching the synthesis kettle, centrifugally washing the synthesized molecular sieve for multiple times, drying, and roasting at 500 ℃ for 7 hours to obtain the catalyst. Of the synthesized catalystsThe molar composition is as follows: SiO 22:0.033Al2O3:0.05Na2O:50H2O:0.05CoO:0.25SDA。
Comparative example 1
Adding 9g of copper nitrate into 50mL of water, heating to 60 ℃, and stirring until the copper nitrate is completely dissolved to obtain a mixed solution; adding 10g of alumina microspheres into the prepared copper nitrate mixed solution by adopting an impregnation method, and excessively impregnating for 4 hours under the condition of water bath at 60 ℃; drying the impregnated alumina microspheres at room temperature for 12h, then drying at 110 ℃ for 24h, and then roasting at 550 ℃ for 8h to obtain the catalyst.
Example 7
The catalysts prepared in the above examples 1-6 and comparative example 1 were used in the reaction for preparing acetonitrile by ammonification dehydrogenation of ethanol. The specific implementation process is as follows: tabletting a catalyst, then crushing the catalyst into 20-40-mesh particles, weighing 1g of the catalyst particles, and placing the catalyst particles in a fixed bed reactor, wherein the inner diameter of the fixed bed reactor is 10mm, and both ends of the fixed bed reactor are filled with quartz sand; the catalyst is used for reaction with H with the flow rate of 50mL/min2Reducing with mixed gas composed of nitrogen with flow rate of 100mL/min at 400 deg.C for 2h, and then adding ethanol at mass space velocity of 1h-1The flow rate of ammonia gas was 200mL/min, and the reactor was previously pumped. Ethanol and ammonia gas are introduced into a fixed bed reactor for catalytic reaction to obtain a reaction product, and the reaction product is analyzed by Agilent 7890A gas chromatography, and the result is shown in Table 1 below.
Ethanol conversion rate ═ amount of ethanol converted by reaction (mol)/amount of ethanol fed (mol) × 100%
The acetonitrile selectivity is the amount of ethanol converted to acetonitrile in the reaction (mol)/the amount of ethanol converted in the reaction (mol) × 100%.
Table 1 properties of the catalysts prepared in examples 1 to 6 and comparative example 1.
Catalyst and process for preparing same Conversion rate of ethanol Selectivity to acetonitrile
Example 1 92.8％ 96.0％
Example 2 96.1％ 95.8％
Example 3 95.2％ 97.1％
Example 4 93.4％ 98.0％
Example 5 93.6％ 97.5％
Example 6 94.1％ 97.8％
Comparative example 1 70.5％ 85.6％
As can be seen from table 1, the catalysts prepared in examples 1 to 6 of the present invention have a conversion rate of ethanol of 90% or more and a selectivity of acetonitrile of 95% or more, indicating that the catalysts have excellent catalytic activity. Comparing comparative example 1 with the examples, it can be seen that the transition metal doped ZSM-5 molecular sieve has excellent catalytic performance, and the excellent performance mainly comes from strong acid centers of the ZSM-5 molecular sieve and highly uniformly distributed transition metal active centers on the surface.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation is characterized by comprising a transition metal element M and a ZSM-5 molecular sieve;
the transition metal element M is doped into the framework of the ZSM-5 molecular sieve;
the transition metal element M is at least one selected from titanium, vanadium, manganese, iron, cobalt, nickel and copper.
2. The catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation according to claim 1, wherein the mass content of the transition metal element M in the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation is 0.5-10%.
3. The method for preparing the acetonitrile catalyst by ethanol ammoniation dehydrogenation as claimed in claim 1 or 2, which is characterized by comprising the following steps:
(1) carrying out hydrothermal crystallization on a mixture containing a structure directing agent, water, a silicon source, an aluminum source, a hydroxide of an alkali metal ion M' and a transition metal element M source at the temperature of 130-200 ℃ for 2-10 days;
(2) after crystallization is finished, washing, drying and roasting are carried out in sequence to obtain the catalyst for preparing acetonitrile by ethanol ammoniation dehydrogenation;
in the mixture, the molar ratio of each substance is as follows:
SiO2：Al2O3：M’2O：H2o: transition metal element M oxide: structure directing agent 1: 0.001-0.1: 0.002-1: 50: 0.001-0.5: 0.05-5.
4. The preparation method according to claim 3, wherein the silicon source is selected from one of ethyl orthosilicate, white carbon black, silica sol and sodium silicate;
the aluminum source is selected from one of aluminum sulfate, aluminum nitrate, sodium metaaluminate, aluminum isopropoxide and aluminum sol;
the hydroxide of the alkali metal ion M' is selected from sodium hydroxide;
the structure directing agent is at least one selected from tetraethyl ammonium hydroxide, tetrapropyl ammonium bromide and tetrapropyl ammonium chloride.
5. The production method according to claim 3, wherein the source of the transition metal element M is at least one selected from salts of the transition metal element M.
6. The method according to claim 3, wherein the firing conditions are: the temperature is 300-600 ℃; the time is 3-10 h.
7. The method of manufacturing according to claim 3, further comprising the steps of:
(3) and in a hydrogen-containing atmosphere, reducing the roasted material to obtain the catalyst for preparing the acetonitrile by the ethanol ammoniation dehydrogenation.
8. The method according to claim 7, wherein the reducing conditions are: the temperature is 200-500 ℃; the time is 0.5-5 h.
9. A method of preparing acetonitrile, the method comprising: reacting materials containing ethanol and ammonia gas in the presence of a catalyst to obtain acetonitrile;
the catalyst is any one selected from the group consisting of the catalyst for preparing acetonitrile by ethanol ammonification and dehydrogenation as described in claim 1 or 2, and the catalyst for preparing acetonitrile by ethanol ammonification and dehydrogenation as prepared by the method as described in any one of claims 3 to 8.
10. The method according to claim 9, wherein the molar ratio of ethanol to ammonia in the material is 1: 1.5 to 5;
preferably, the reaction conditions are: the temperature is 200 ℃ and 450 ℃; the pressure is 0.2-5.0 Mpa; the mass space velocity of the ethanol is 0.2-2h-1。
CN202011493724.6A 2020-12-16 2020-12-16 Catalyst for preparing acetonitrile by ammonification and dehydrogenation of ethanol, and preparation method and application thereof Active CN114632539B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108187680A (en) * 2017-12-29 2018-06-22 西安元创化工科技股份有限公司 A kind of preparation method of alcohol dehydrogenase ammonification synthesis acetonitrile catalyst
CN109675548A (en) * 2019-01-21 2019-04-26 福州大学 A kind of molecular sieve catalyst and preparation method thereof for preparing propylene by dehydrogenating propane
CN110560151A (en) * 2019-09-16 2019-12-13 延长中科（大连）能源科技股份有限公司 Molecular sieve solid acid catalyst, preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108187680A (en) * 2017-12-29 2018-06-22 西安元创化工科技股份有限公司 A kind of preparation method of alcohol dehydrogenase ammonification synthesis acetonitrile catalyst
CN109675548A (en) * 2019-01-21 2019-04-26 福州大学 A kind of molecular sieve catalyst and preparation method thereof for preparing propylene by dehydrogenating propane
CN110560151A (en) * 2019-09-16 2019-12-13 延长中科（大连）能源科技股份有限公司 Molecular sieve solid acid catalyst, preparation method and application thereof

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