CN111056955A - Method for preparing hexamethylene diamine from cyclohexene - Google Patents
Method for preparing hexamethylene diamine from cyclohexene Download PDFInfo
- Publication number
- CN111056955A CN111056955A CN201911296054.6A CN201911296054A CN111056955A CN 111056955 A CN111056955 A CN 111056955A CN 201911296054 A CN201911296054 A CN 201911296054A CN 111056955 A CN111056955 A CN 111056955A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- molecular sieve
- cyclohexene
- reaction
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing hexamethylene diamine from cyclohexene, which comprises the following steps: carrying out oxidation reaction on mixed liquor containing cyclohexene and mixed gas containing ozone under reaction condition I to obtain adipic dialdehyde, wherein the reaction condition I comprises that a supported metal oxide is used as a catalyst I; introducing the obtained hexanedial, ammonia gas and hydrogen into a reactor containing a catalyst II, and generating hexanediamine under the reaction condition II, wherein the catalyst II is an HZSM-5 molecular sieve-encapsulated metal catalyst. The method has the advantages that cyclohexene is used as a raw material, hexamethylenediamine is prepared through oxidation and amination, a highly toxic raw material adiponitrile is avoided, ozone is used as an oxidant, a heterogeneous catalyst can be used for preparing the adipaldehyde in a high-selectivity mode, a metal catalyst packaged by an HZSM-5 molecular sieve is further used, the selectivity of a target product and the stability of the catalyst are effectively improved by utilizing the confinement effect of the molecular sieve, and the route is clean and environment-friendly.
Description
Technical Field
The application relates to a method for preparing hexamethylene diamine from cyclohexene, and belongs to the field of chemical engineering.
Background
Hexamethylenediamine is an important organic chemical raw material, and can be used for preparing polyhexamethylene adipamide, also called polyamide 66(PA66) or nylon 66, by a polycondensation reaction with adipic acid. Nylon 66 can be used for injection molding, extrusion, blow molding, spray coating, cast molding, machining, welding, bonding. About 90% of the world's annual production of hexamethylenediamine is used in the production of nylon 66. The reaction with sebacic acid can produce polyhexamethylene sebacamide (PA610) product, also known as polyamide 610 or nylon 610. Nylon 610 can be made into various nylon resins, nylon fibers and engineering plastic products, and is an uncommon intermediate in synthetic materials. HDI (1, 6-hexamethylene diisocyanate) can be generated through photochemical reaction, and the HDI is a novel polyurethane plastic, can be used for producing high-grade environment-friendly coatings and is bright in color and durable. In recent years, the application field of hexamethylenediamine has been rapidly expanded. With the continuous development of the automobile industry in China, China gradually becomes the largest automobile manufacturing country in the world, under the trends of light weight, environmental protection and energy conservation, the demand of the automobile industry on nylon 66 also shows a rising trend, and nylon 66 faces a larger supply and demand gap.
The production technology of hexamethylenediamine mainly comprises an adiponitrile method, a hexanediol method and a caprolactam method. Currently, hexamethylenediamine is almost exclusively prepared by hydrogenation of adiponitrile, which is produced by processes such as adipic acid catalytic amination, acrylonitrile electrolytic dimerization and butadiene.
The production of hexamethylene diamine is mainly monopolized by some large-scale transnational companies, the total of three members of Invida, Pasteur and Oshende accounts for 74% of the global productivity, the hexamethylene diamine is in the high oligopolistic industry, and the global productivity of China Mars, ranked on the fourth place, accounts for 9%. The manufacturers capable of producing hexanediamine in China only comprise Liaoyang petrochemical company in China and Shenma group in China. In the Liaoyang petrochemical industry, adiponitrile is produced by an adipic acid ammoniation method, and production is stopped due to the problems of long process route, low product yield and the like. Domestic adiponitrile completely depends on import, the price of the adiponitrile is always high, the economic benefit and international market competitiveness of the nylon industry in China are seriously affected, and the development of the nylon 66 and related industries in China is restricted. Therefore, the development of a new technology for preparing hexamethylene diamine is a problem to be solved urgently in the field of domestic chemical industry.
CN109647419A discloses a method for preparing hexanediamine by using nickel-based catalyst loaded on alumina as active component and catalyzing adiponitrile hydrogenation in a tank reactor. US5900511 discloses a continuous adiponitrile hydrogenation process using Ni and Cr modified Raney Co catalyst to catalyze the hydrogenation of adiponitrile to produce hexamethylenediamine in a tank reactor. CN108084035A discloses a method for preparing hexanediamine by directly hydrogenating adiponitrile under the alkali-free condition, wherein an alkaline earth metal oxide or rare earth metal oxide modified aluminum trioxide supported metal nickel catalyst prepared by a coprecipitation method is used for preparing hexanediamine by hydrogenating an adiponitrile ethanol solution with a certain concentration. CN106807377A discloses a method for synthesizing hexamethylenediamine under the condition of hydrogenation by using a catalyst which takes one or more of Ni or Co main active components Fe, Cu, Ru, Re, K, Zn, B and other metals or oxides as an auxiliary agent to catalyze the ammoniation reaction of hexanediol or aminohexanol or hexanediol/aminohexanol mixture. CN104262168B discloses a method for preparing hexamethylenediamine by aminating hexanedial with nickel-based hydrogenation catalyst loaded on silica carrier.
From the literature and the technology which are available at present, the raw material adiponitrile in the industrialized adiponitrile hydrogenation preparation route of the hexamethylenediamine is high in toxicity, dependent on import and high in price. The development of a new green hexamethylenediamine preparation process is of great significance. Therefore, the development of a catalyst with good catalyst activity and target product selectivity is the key for realizing a green new process of the hexamethylene diamine.
Disclosure of Invention
According to one aspect of the application, the method for preparing hexanediamine from cyclohexene is provided, the hexanediamine is prepared by oxidizing and aminating cyclohexene serving as a raw material, a highly toxic raw material adiponitrile is avoided, ozone serving as an oxidant is adopted, a heterogeneous catalyst can be used for preparing hexanediamine in a high selectivity manner, a metal catalyst packaged by an HZSM-5 molecular sieve is further adopted, the selectivity of a target product and the stability of the catalyst are effectively improved by utilizing the confinement effect of the molecular sieve, and the route is clean and environment-friendly.
A method for preparing hexamethylene diamine from cyclohexene comprises the following steps:
(a) carrying out oxidation reaction on mixed liquor containing cyclohexene and mixed gas containing ozone under reaction condition I to obtain adipic dialdehyde, wherein the reaction condition I comprises that a supported metal oxide is used as a catalyst I;
alternatively, adipic dialdehyde is obtained by distillation under reduced pressure after the oxidation reaction is completed.
(b) Introducing the obtained hexanedial, ammonia gas and hydrogen into a reactor containing a catalyst II, and generating hexanediamine under the reaction condition II, wherein the catalyst II is an HZSM-5 molecular sieve-encapsulated metal catalyst.
Optionally, the molar ratio of the ester auxiliary agent to the cyclohexene is (0.05-0.5): 1, preferably (0.05 to 0.30): 1, more preferably 0.10: 1.
In another embodiment, the carrier in the catalyst I is at least one of mesoporous molecular sieve, mesoporous alumina and mesoporous silica; the mesoporous molecular sieve is selected from at least one of MCM-41 or SBA-15; the metal oxide in the catalyst I consists of W oxide and Mo oxide; the mass loading amount of the metal W is 0.5-5.0%, and the mass loading amount of the metal Mo is 0.02-2.0%.
Preferably, the mass loading amount of the metal W is 2-3%, and the mass loading amount of the metal Mo is 1-2%.
Alternatively, the upper limit of the mass loading of the metal W may be selected from 5.0%, 4.0%, 3.0%, 2.0% or 1.0%, and the lower limit may be selected from 4.0%, 3.0%, 2.0%, 1.0% or 0.5%; the upper limit of the mass loading of the metal Mo can be selected from 2.0%, 1.5%, 1.0%, 0.5% or 0.1%, and the lower limit can be selected from 1.5%, 1.0%, 0.5%, 0.1% or 0.02%.
Optionally, the mixed solution further contains an ester auxiliary agent; the ester auxiliary agent comprises at least one of methyl pyruvate, methyl trifluoropyruvate, methyl acetylacetonate and methyl acetoacetate; methyl pyruvate is preferred.
By adding methyl pyruvate, cyclohexene forms a stable intermediate transition state in the reaction process, the cyclohexene is prevented from being excessively oxidized to generate acid, and the selectivity of the hexanedial is effectively improved.
The mixed solution containing cyclohexene in the step (a) also comprises an organic solvent;
the organic solvent is at least one selected from acetonitrile, dichloromethane and acetone.
In this particular example, the preparation of the catalyst I comprises:
soaking a metal salt solution into the carrier by adopting an isometric soaking method, and drying and roasting to obtain a catalyst I;
the metal salt in the metal salt solution is ammonium tungstate and ammonium molybdate;
optionally, the drying conditions specifically include:
the drying temperature is 90-110 ℃; the drying time is 10-14 h;
the conditions for calcination include:
the roasting temperature is 480-520 ℃; the roasting time is 3-5 h.
Optionally, the mixed solution containing cyclohexene in step (a) further comprises an organic solvent;
the organic solvent is at least one selected from acetonitrile, dichloromethane and acetone.
Optionally, the reaction conditions I further include:
the reaction temperature is-70-50 ℃;
the reaction time is 0.5-2 h.
Optionally, the mass ratio of the catalyst to the cyclohexene is (0.05-0.40): 1, preferably (0.05-0.20): 1.
Optionally, the molar ratio of the ozone to the cyclohexene is 0.40-3.00.
Optionally, the mixture further comprises:
at least one of oxygen, nitrogen, and inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
In a specific embodiment, the metal in the catalyst II is a noble metal, and the noble metal is at least one selected from Ru, Rh, and Pd;
the mass content of the noble metal in the catalyst is 0.1-6.0% of the total mass of the catalyst.
Optionally, the molar ratio of ammonia to adipaldehyde in step (b) is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 1-80: 1.
alternatively, the reaction conditions II comprise:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa;
preferably, the reaction temperature is 80-150 ℃; the reaction pressure is 5-10 Mpa.
Optionally, the method for obtaining the HZSM-5 molecular sieve-encapsulated metal catalyst of step (b) comprises:
and (3) carrying out in-situ crystal transformation to obtain a ZSM-5 molecular sieve for packaging metal, and then roasting and carrying out ammonium exchange to obtain the HZSM-5 molecular sieve packaging metal catalyst.
Optionally, the in-situ transcrystalizing to obtain the metal-encapsulated ZSM-5 molecular sieve comprises:
(1) placing the metal-loaded HBeta molecular sieve in a template agent solution, and impregnating and drying to obtain the metal-loaded HBeta molecular sieve adsorbed with the template agent;
optionally, the metal is a noble metal selected from at least one of Ru, Rh, and Pd; the mass content of the noble metal in the metal-loaded HBeta molecular sieve is 0.1-6.0%;
(2) crystallizing a mixture containing an alkali source, water and the metal-loaded HBeta molecular sieve adsorbed with the template in the step (1) to obtain the metal-encapsulated ZSM-5 molecular sieve.
By dipping the silicon-aluminum molecular sieve loaded with noble metal into the template solution and drying, the template existing in the molecular sieve can effectively slow down the dissolution of the molecular sieve, so that the dissolution speed and the crystallization speed are more coordinated, and compared with the method of directly adding the template into the crystallization liquid, the method can obtain higher yield, ensure that the transition metal is uniformly dispersed in the pore canal of the molecular sieve, avoid the transition metal from being separated, and ensure the content of the transition metal. Not only ensures that the metal is uniformly dispersed in the molecular sieve pore canal, but also avoids the metal from being separated, and ensures the metal content.
Optionally, the templating agent is selected from TPAOH, TPABr, or ethanol.
In the embodiment of the invention, the template is not limited to the above, and any template with the same or similar functions can be selected.
Optionally, the template agent and SiO contained in the HBeta molecular sieve loaded with noble metal2The molar ratio of (A) to (B) is 0.10 to 0.40.
Optionally, the impregnation conditions in step (1) include:
the dipping temperature is 20-30 ℃;
the dipping time is 1-3 h.
Optionally, the drying conditions in step (1) comprise:
the drying time is 30-100 ℃;
the drying time is 12-16 h.
Optionally, the mass loading of the metal in the metal-loaded HBeta molecular sieve in the step (1) is 5.0-50.0%, preferably 5-30%. The loading amount in the embodiment of the invention is based on the total mass of the catalyst.
Optionally, the alkali source in step (2) is sodium hydroxide;
SiO in the metal-loaded HBeta molecules adsorbed with the template agent2The mass ratio of the alkali source to the water is 1 (0.05-0.50) to 2-40.
Alternatively, the upper limit of the mass ratio of the metal-loaded HBeta molecular sieve adsorbed with the template to the alkali source can be selected from 1:0.06, 1:0.07, 1:0.072, 1:0.074, 1:0.075, 1:0.08 or 1:0.083, and the lower limit can be selected from 1:0.07, 1:0.072, 1:0.074, 1:0.075, 1:0.08, 1:0.083 or 1: 0.2.
Optionally, the crystallization conditions in step (2) include:
the crystallization temperature is 80-200 ℃;
the crystallization time is 2-10 h.
Optionally, in the step (1), a metal salt precursor solution is impregnated on the HBeta molecular sieve by an isometric impregnation method, and the HBeta molecular sieve loaded with the metal is obtained after drying and roasting in a reducing atmosphere;
the metal salt is at least one selected from acetate, oxalate, nitrate, sulfate and chloride of metal.
Optionally, the ammonium exchange specifically includes the following steps:
adopting solution containing ammonium ions to carry out ion exchange on the ZSM-5 molecular sieve for encapsulating the metal, and then roasting.
Optionally, the ion exchange conditions comprise:
the concentration of ammonium ions in the solution containing ammonium ions is 0.2-1 mol/L;
the solid-liquid weight ratio is 0.1-0.5: 1;
the temperature of the solution containing ammonium ions is 60-80 ℃;
the exchange time is 1-12 h.
Optionally, the calcination conditions after ion exchange include:
the roasting temperature is 400-600 ℃;
the roasting time is 3-6 h.
Optionally, the ion exchange is repeated 1-3 times.
In a specific embodiment, a method for preparing hexamethylenediamine from cyclohexene comprises:
(1) oxidizing cyclohexene to prepare hexanedial: cyclohexene, a catalyst, an auxiliary agent and an organic solvent are uniformly mixed, added into a kettle type reactor, and reacted at the temperature of-70-50 ℃, ozone is introduced for reaction for 0.5-2.0 h, and reduced pressure distillation is carried out after the reaction to obtain the hexanedial.
(2) Reductive amination of hexanedial to hexamethylenediamine: in a high-pressure reaction kettle, carrying out reductive amination reaction in the presence of a catalyst, ammonia, hydrogen and a solvent to generate hexamethylene diamine, wherein the molar ratio of ammonia to hexamethylene dialdehyde is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 1-80: 1. the reaction temperature is 80-200 ℃; the reaction pressure is 1-20 Mpa.
Preferably, the reaction temperature is 80-150 ℃.
Preferably, the reaction pressure is 5-10 MPa.
The method for preparing the hexamethylene diamine by reductive amination of the hexanedial comprises the step of preparing a hexanediamine by using a molecular sieve-encapsulated metal catalyst, wherein the metal is one or two of Ru, Rh and Pd. The content of the metal active component is 0.1-6.0%.
In the method for preparing hexanediamine by reductive amination of hexanediamine, a metal catalyst encapsulated by a molecular sieve is prepared by adopting an in-situ crystal transformation method, and the preparation method comprises the following steps:
(a) soaking HBeta molecular sieve in metal salt precursor solution at room temperature for 24 hr by isovolumetric soaking method, loading metal on HBeta molecular sieve, drying in oven at 100 deg.C for 12 hr, and placing in H2Reducing for 4h at 500 ℃ in atmosphere to obtain the M/HBeta molecular sieve, wherein the metal salt solution can be metal salt precursor and RuCl3·3H2O，RhCl3·3H2O，PdCl2。
(b) Putting the metal-loaded HBeta molecular sieve (M/HBeta) in a TPAOH solution, soaking for 2h at room temperature, and drying in an oven at 100 ℃ for 12h to obtain the M/HBeta molecular sieve with TPAOH adsorbed in pore channels;
(c) SiO of the M/HBeta molecular sieve of TPAOH obtained in the step b2Mixing the obtained product with sodium hydroxide and deionized water according to the mass ratio of 1 (0.05-0.50) to 2-40 to obtain a preparation system, and crystallizing at 80-200 ℃ for 2-10 hours to obtain a molecular sieve containing metal @ ZSM-5;
(d) roasting the metal @ ZSM-5 molecular sieve prepared in the step c at 500 ℃ to remove a template agent, and performing ion exchange in an ammonium nitrate solution to obtain a hydrogen type molecular sieve, wherein the concentration of the solution is 0.2-1 mol/L, the solid-liquid weight ratio is 0.1-0.5: 1, the temperature of the solution is 60-80 ℃, the time is 1-12 hours, and the exchange and roasting times are 2-4 times; and after exchange, performing centrifugal separation on the solid sample, washing with deionized water, drying in an air atmosphere at 80-120 ℃, and roasting in an air atmosphere at 500 ℃ for 3-6 hours to obtain the hydrogen type molecular sieve, namely the catalyst.
In the method for preparing the hexamethylene diamine by reductive amination of the hexanedial, the solvent is one of methanol, ethanol and isopropanol.
The "metal @ ZSM-5 molecular sieve" described in the examples of the present invention does not mean that the metal and the ZSM-5 molecular sieve form a core-shell structure, but means that the ZSM-5 molecular sieve encapsulates the metal, and in the following description of forms similar to A @ B, A means the encapsulated metal and B means the molecular sieve.
The beneficial effects that this application can produce include:
compared with the prior art, the technology adopts cyclohexene as a raw material, the hexamethylenediamine is prepared through oxidation and amination, the use of a highly toxic raw material adiponitrile is avoided, ozone is adopted as an oxidant, a heterogeneous catalyst can be used for preparing the adipaldehyde in a high selectivity manner, a metal catalyst packaged by an HZSM-5 molecular sieve is further adopted, the selectivity of a target product and the stability of the catalyst are effectively improved by utilizing the confinement effect of the molecular sieve, and the route is clean and environment-friendly. Therefore, the invention not only has innovativeness, but also has economic advantages and industrial application prospects.
Drawings
Figure 1 shows the XRD spectrum of the HBeta molecular sieve of example 1.
FIG. 2 shows the XRD pattern of the Ru @ ZSM-5 molecular sieve of example 1.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present invention were all purchased from commercial sources unless otherwise specified.
Wherein the HBeta molecular sieve is purchased from a Nankai catalyst plant; MCM-41 was purchased from a southern catalyst plant; SBA-15 was purchased from Nanjing pioneer nanometer; mesoporous SiO2Purchased from Qingdao ocean chemical Co.
SiO in HBeta molecular sieve2The mass content of (A) was analyzed by ICP-OES.
The analytical methods and conversion, selectivity in the examples were calculated as follows:
automated analysis was performed using an Agilent7890 gas chromatograph with an autosampler. Analysis of cyclohexene oxidation reaction products: adding n-dodecane into the reaction solution after the reaction as an internal standard, and quantifying by adopting an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
cyclohexene conversion (mol) ═ [ (cyclohexene amount in feed) - (cyclohexene amount in discharge) ]/(cyclohexene amount in feed) × 100%
Adipaldehyde selectivity (mol) — (amount of adipaldehyde in the discharge) ÷ (amount of cyclohexene converted) × 100%
Analysis of the amination product of adipaldehyde: analysis was performed using an Agilent7890 gas chromatograph with an autosampler. After the reaction is finished, adding n-octylamine into the reaction solution as an internal standard, and carrying out quantitative analysis by an internal standard method.
In some embodiments of the invention, both conversion and selectivity are calculated based on carbon moles:
conversion of adipaldehyde [ (adipaldehyde carbon mole number in feed) - (adipaldehyde carbon mole number in discharge) ]/(adipaldehyde carbon mole number in feed) × 100%
Hexamethylenediamine selectivity (the mole number of hexamethylenediamine carbon in the discharged material) ÷ (the total mole number of all carbon-containing products in the discharged material) × 100%
The hexamethylenediamine yield (moles of hexamethylenediamine carbon in the output)/moles of hexamethylenedialdehyde carbon converted) 100%.
Examples 1-10 preparation of Supported W, Mo catalysts
First, the support was calcined at 550 ℃ for 4h in a nitrogen atmosphere to remove adsorbed species in the pores. Dissolving ammonium tungstate and ammonium molybdate in water in certain mass, fixing the volume according to the saturated water absorption capacity of the carrier (when MCM-41 is adopted, the volume is 50ml, when SBA-15 is adopted, the volume is 30ml, and when mesoporous silica is adopted, the volume is 20 ml), loading 10g of the carrier on the carrier by adopting an isometric impregnation method to load a metal salt solution, then placing the carrier in an oven at 100 ℃ for drying for 12h, and roasting in a muffle furnace at 500 ℃ for 4h to obtain the catalyst. The types and the masses of the carrier and the metal salt are shown in Table 1.
TABLE 1 preparation parameters of the catalysts
In the catalyst name aW-bMo/X, a represents the mass loading amount of the metal W element, b represents the mass loading amount of the metal Mo element, and X represents the carrier.
Example 11 preparation of hexanedial by Oxidation of cyclohexene
Adding 1.0g of cyclohexene, 0.10g of methyl pyruvate, 25mL of acetonitrile and 0.5W-1.0Mo/MCM-41 catalyst (0.10g) into a 250mL round-bottom flask, raising the temperature to 20 ℃, introducing a mixed gas with the ozone concentration of 100mg/L, wherein the mixed gas consists of ozone and oxygen, the flow of the mixed gas is 80mL/min, rapidly cooling to room temperature after reacting for 1h, and analyzing the composition of a product by using a gas chromatograph.
Examples 12-20 Oxidation of cyclohexene to adipaldehyde
Cyclohexene oxidation was carried out in the same manner as in example 11 except for the specific differences in reaction conditions and the results shown in Table 2.
Example 21
Essentially the same procedure as for the preparation of example 13, except that methyl trifluoropyruvate was not added, the test results are shown in Table 2.
Example 22
Essentially the same procedure as for the preparation of example 14, except that methyl acetylacetonate was not added, the results of the tests are shown in Table 2.
Example 23
Essentially the same procedure as for the preparation of example 17, except that methyl pyruvate was not added, the results are shown in Table 2.
Example 24
Essentially the same procedure as in example 18 was followed, except that methyl pyruvate was not added and the results are shown in Table 2.
TABLE 2 Performance of the catalyst for the preparation of adipaldehyde by oxidation of cyclohexene
EXAMPLE 1' preparation of Metal @ molecular Sieve catalyst
(1) Adding 0.03 gGluCl3·3H2Dissolving O in water, diluting to 12mL, and taking 10g HBeta molecular Sieve (SiO)2/Al2O3Molar ratio of 800, SiO298.9 percent of mass content), loading the Ru element on HBeta by an isometric impregnation method, drying in a 100 ℃ oven for 12H, and then drying in H2Reducing for 4h at 500 ℃ in the atmosphere to obtain a negative metal Ru/HBeta molecular sieve;
(2) placing the Ru/HBeta molecular sieve loaded with metal in 15mL of TPAOH aqueous solution with the mass fraction of 35.0%, soaking at room temperature for 2h, and drying in a 100 ℃ oven for 12h to obtain the/HBeta molecular sieve with TPAOH adsorbed in pore channels;
(3) mixing the HBeta molecular sieve with TPAOH adsorbed in the pore channel with 0.60g of sodium hydroxide and 20mL of deionized water, and crystallizing at 90 ℃ for 6 hours to obtain a Ru @ ZSM-5 molecular sieve;
(4) roasting the Ru @ ZSM-5 molecular sieve at 500 ℃ for 4 hours to remove a template agent TPAOH, and performing ion exchange in 1.0mol/L ammonium nitrate solution to obtain a hydrogen type molecular sieve, wherein the solid-liquid weight ratio during ion exchange is 1: 10, the solution temperature is 80 ℃, the ion exchange time is 2 hours each time, and the ion exchange is carried out for 3 times;
(5) and after exchange, carrying out centrifugal separation and deionized water washing on a solid sample, drying in an air atmosphere at 100 ℃, and roasting for 4 hours in an air atmosphere at 500 ℃ to obtain a hydrogen type molecular sieve HZSM-5 molecular sieve packaging Ru catalyst which is marked as 0.1Ru @ ZSM-5.
EXAMPLE 2 '-10' preparation of Metal @ molecular Sieve catalyst
M @ ZSM-5 was prepared by the same procedure as in example 1' with the metal species and loading being adjusted by varying the species and concentration of the metal salt solution, and the specific synthesis conditions are listed in Table 3.
TABLE 3 specific Synthesis conditions for the examples
In the table, in the catalyst nA @ ZSM-5, A represents a noble metal, ZSM-5 is HZSM-5, n represents the mass loading of the noble metal in the M/HBeta molecular sieve, and W (%) represents the mass content of the metal in the M @ ZSM-5.
Example 1 '-10' Metal @ molecular Sieve catalyst characterization
FIG. 1 is an XRD spectrum of the HBeta molecular sieve used in example 1'; the catalysts obtained in examples 1-10 are ZSM-5 molecular sieves, typically representing the XRD pattern of the catalyst in example 1 as shown in FIG. 2. The XRD patterns of the catalysts obtained in examples 2 'to 10' are similar to those of example 1, namely, the positions and the shapes of diffraction peaks are basically the same, and relative peak intensities fluctuate within a range of +/-5% according to the change of synthesis conditions, which shows that the catalysts obtained in examples 2 'to 10' have the characteristics of a ZSM-5 structure.
EXAMPLE 11 '-20' evaluation of the reactivity of Metal @ molecular Sieve catalysts
Adding 5.0g of catalyst into a quartz tube, introducing reducing gas into the quartz tube at the flow rate of 30mL/min, and reducing the catalyst at 400 ℃ for 4H, wherein the reducing gas is H2/N21/4 by volume ratio. After the reduction, the temperature was lowered to room temperature, and the catalyst was taken out and charged into a 300mL autoclave.
At room temperature, 20g of adipaldehyde and 100g of methanol are uniformly mixed, added into the 300mL high-pressure reaction kettle, sealed, replaced by nitrogen for three times, injected with 29.75g of liquid ammonia through a high-pressure pump, filled with hydrogen until the pressure in the kettle is 4.0Mpa, raised to 120 ℃, at the moment, the pressure reaches 7.5MPa, quickly cooled after reacting for 2 hours, centrifugally separated out the catalyst, added with a certain amount of n-octylamine, and analyzed by gas chromatography.
Wherein the hexanedial is obtained by reduced pressure distillation at 20 ℃ in example 14, and the hexanedial obtained in other examples is used as a raw material, and the reaction structure is the same as that of example 14.
TABLE 4 reactivity of the catalysts prepared in examples 1' -10
EXAMPLES 21 '-28' evaluation of reactivity of Metal @ molecular Sieve catalysts
Adding 5.0g of catalyst into a quartz tube, introducing reducing gas into the quartz tube at the flow rate of 30mL/min, and reducing the catalyst at 400 ℃ for 4H, wherein the reducing gas is H2/N21/4 by volume ratio. After the reduction is finished, the temperature is reduced to room temperature, and the catalyst is taken out and added into a 300ml high-pressure reaction kettle.
At room temperature, 20g of adipaldehyde and 100g of methanol are uniformly mixed, added into a 300mL high-pressure reaction kettle, sealed, subjected to nitrogen replacement for three times, injected with liquid ammonia through a high-pressure pump, filled with hydrogen to the pressure in the kettle, heated to a certain temperature, reacted for 2 hours, rapidly cooled, centrifugally separated to obtain a catalyst, added with a certain amount of n-octylamine, and analyzed by gas chromatography.
TABLE 5 results of the reactions of examples 21' -28
As can be seen from tables 4 and 5, the catalyst provided by each embodiment of the invention has excellent selectivity on hexamethylene diamine in the reaction of preparing hexamethylene diamine by reductive amination of hexamethylene dialdehyde, wherein the selectivity of the hexamethylene diamine can reach 81.52% at most, and the conversion rate of the hexamethylene dialdehyde can reach 100% at most; when the metal is Ru and the mass loading of the metal is 1-3%, the selectivity of the hexamethylene diamine can reach more than 78.31%, and the conversion rate of the hexamethylene dialdehyde can reach 100%.
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. A method for preparing hexamethylene diamine from cyclohexene is characterized by comprising the following steps:
(a) carrying out oxidation reaction on mixed liquor containing cyclohexene and mixed gas containing ozone under reaction condition I to obtain adipic dialdehyde, wherein the reaction condition I comprises that a supported metal oxide is used as a catalyst I;
(b) introducing the obtained hexanedial, ammonia gas and hydrogen into a reactor containing a catalyst II, and generating hexanediamine under the reaction condition II, wherein the catalyst II is an HZSM-5 molecular sieve-encapsulated metal catalyst.
2. The method of claim 1, wherein: the carrier in the catalyst I is at least one of mesoporous molecular sieve or mesoporous silicon dioxide;
the mesoporous molecular sieve is selected from at least one of MCM-41 or SBA-15;
the metal oxide in the catalyst I consists of W oxide and Mo oxide.
3. The method of claim 2, wherein: the mass loading amount of the metal W is 0.5-5.0%, and the mass loading amount of the metal Mo is 0.02-2.0%.
4. The method of claim 1, wherein: the mixed solution containing cyclohexene in the step (a) also contains an ester auxiliary agent;
the ester auxiliary agent comprises at least one of methyl pyruvate, methyl trifluoropyruvate, methyl acetylacetonate and methyl acetoacetate; the molar ratio of the ester auxiliary agent to the cyclohexene is (0.05-0.5): 1.
5. the method of claim 1, wherein: the mixed solution containing cyclohexene in the step (a) also comprises an organic solvent;
the organic solvent is at least one selected from acetonitrile, dichloromethane and acetone.
6. The method of claim 1, wherein the reaction conditions I further comprise:
the reaction temperature is-70-50 ℃;
the reaction time is 0.5-2 h.
7. The method of claim 1, further comprising:
at least one of oxygen, air, and inert gas;
the concentration of ozone in the mixed gas is 10-140 mg/L.
8. The method according to claim 1, wherein the metal in the catalyst II is a noble metal selected from at least one of Ru, Rh, Pd;
the mass content of the noble metal in the catalyst is 0.1-6.0%.
9. The method of claim 1, wherein in step (b), the step (c) is performed by a computer
The mol ratio of ammonia to adipaldehyde is 5-60: 1, the molar ratio of hydrogen to adipaldehyde is 1-80: 1;
preferably, the reaction conditions II include:
the reaction temperature is 80-200 ℃;
the reaction pressure is 1-20 Mpa.
10. The method of claim 1, wherein the HZSM-5 molecular sieve encapsulated metal catalyst obtained in step (b) is obtained by a method comprising:
carrying out in-situ crystal transformation to obtain a ZSM-5 molecular sieve for encapsulating metal, and then roasting and carrying out ammonium exchange to obtain the HZSM-5 molecular sieve encapsulated metal catalyst;
preferably, the in-situ crystallization obtains a metal-encapsulated ZSM-5 molecular sieve comprising:
(1) placing the metal-loaded HBeta molecular sieve in a template agent solution, and impregnating and drying to obtain the metal-loaded HBeta molecular sieve adsorbed with the template agent;
(2) crystallizing a mixture containing an alkali source, water and the metal-loaded HBeta molecular sieve adsorbed with the template in the step (1) to obtain the metal-encapsulated ZSM-5 molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911296054.6A CN111056955B (en) | 2019-12-16 | 2019-12-16 | Method for preparing hexamethylene diamine from cyclohexene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911296054.6A CN111056955B (en) | 2019-12-16 | 2019-12-16 | Method for preparing hexamethylene diamine from cyclohexene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111056955A true CN111056955A (en) | 2020-04-24 |
| CN111056955B CN111056955B (en) | 2021-05-25 |
Family
ID=70301040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911296054.6A Active CN111056955B (en) | 2019-12-16 | 2019-12-16 | Method for preparing hexamethylene diamine from cyclohexene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111056955B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300008A (en) * | 2020-10-30 | 2021-02-02 | 宿迁联盛科技股份有限公司 | Synthetic method of 1, 6-hexamethylene diamine |
| CN112939784A (en) * | 2021-02-04 | 2021-06-11 | 山西铁峰化工有限公司 | Industrial preparation method of hexamethylene diamine |
| CN114426520A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Synthesis method of cycloheximide, selective ammonification hydrogenation catalyst of adipaldehyde and preparation method thereof |
| CN114602461A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for preparing diamine by catalyzing dialdehyde |
| CN114904563A (en) * | 2022-06-08 | 2022-08-16 | 江苏扬农化工集团有限公司 | ZSM-5 supported noble metal catalyst, preparation method and application |
Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3664810A (en) * | 1968-08-02 | 1972-05-23 | Anatoly Tikhonovich Menyailo | Process for ozonizing unsaturated compounds to form alkali earth metal peroxide,aliphatic aldehydes and aliphatic ketones |
| DE2207700A1 (en) * | 1971-02-19 | 1972-11-23 | Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa, S.P.A., Mailand (Italien) | Process for the production of peroxide derivatives of ozonides |
| DE2343342A1 (en) * | 1973-08-28 | 1975-03-27 | Menjajlo | PROCESS FOR THE CO-PRODUCTION OF EPOXY AND CARBONYL COMPOUNDS |
| US3923903A (en) * | 1972-12-16 | 1975-12-02 | Bayer Ag | Oxidation of cyclic mono-olefins to {60 ,{107 -dialdeydes |
| US3946081A (en) * | 1972-01-13 | 1976-03-23 | Bayer Aktiengesellschaft | Oxidative splitting of unsaturated hydrocarbons |
| US3972944A (en) * | 1972-10-27 | 1976-08-03 | Bayer Aktiengesellschaft | Process for preparing aldehydes from olefins |
| US4298763A (en) * | 1979-03-12 | 1981-11-03 | Basf Aktiengesellschaft | Preparation of α,β-olefinically unsaturated aldehydes of 3 or 4 carbon atoms |
| US4769464A (en) * | 1983-12-23 | 1988-09-06 | Chemie Linz Gesellschaft M.B.H. | Process for the preparation of monocarbonyl or biscarbonyl compounds |
| JPH01190647A (en) * | 1988-01-25 | 1989-07-31 | Tonen Sekiyukagaku Kk | Production of aldehyde and epoxide compound |
| DE10136885C2 (en) * | 2001-07-24 | 2003-09-25 | Inst Angewandte Chemie Berlin | Peroxotungsten catalysts with oxyfunctionalized phosphonic acids and their use |
| CN1629120A (en) * | 2004-09-02 | 2005-06-22 | 湖南大学 | Process for preparing aldehyde ketone and acid by oxidation of olefin |
| JP2005170856A (en) * | 2003-12-11 | 2005-06-30 | National Institute Of Advanced Industrial & Technology | Method for oxidizing olefinic hydrocarbon |
| CN101054355A (en) * | 2007-06-11 | 2007-10-17 | 中国科学院成都生物研究所 | Compound of optically pure disulfenamides and application thereof |
| US20080081803A1 (en) * | 2003-04-17 | 2008-04-03 | Gabor Butora | Heterocyclic cyclopentyl tetrahydroisoquinoline and tetrahydropyridopyridine modulators of chemokine receptor activity |
| CN100384856C (en) * | 2003-04-17 | 2008-04-30 | 麦克公司 | Heterocyclic cyclopentyl tetrahydroisoquinoline and tetrahydropyridopyridine modulators of chemokine receptor activity |
| CN102317247A (en) * | 2009-02-17 | 2012-01-11 | 国立大学法人宇都宫大学 | Method for producing oxygen-containing compound |
| CN102746127A (en) * | 2012-07-23 | 2012-10-24 | 中国平煤神马能源化工集团有限责任公司 | Method for preparing 1,6-adipaldehyde |
| CN102850195A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for oxidizing propylene |
| CN103288611A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing styrene |
| CN104262168A (en) * | 2014-09-22 | 2015-01-07 | 北京旭阳化工技术研究院有限公司 | Preparation method of hexamethylenediamine |
| CN106279035A (en) * | 2015-05-29 | 2017-01-04 | 中国石油化工股份有限公司 | Preparation method and application and the one of the Br φ nsted acidic ion liquid with periodate as anion prepare α, the method for ω-dialdehyde |
| CN109369356A (en) * | 2018-12-29 | 2019-02-22 | 郑州大学 | A kind of cyclohexene selective oxidation preparation 1,6- hexandial method |
| CN109876866A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof for aromatic aldehyde synthesis aromatic amine |
-
2019
- 2019-12-16 CN CN201911296054.6A patent/CN111056955B/en active Active
Patent Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3664810A (en) * | 1968-08-02 | 1972-05-23 | Anatoly Tikhonovich Menyailo | Process for ozonizing unsaturated compounds to form alkali earth metal peroxide,aliphatic aldehydes and aliphatic ketones |
| DE2207700A1 (en) * | 1971-02-19 | 1972-11-23 | Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa, S.P.A., Mailand (Italien) | Process for the production of peroxide derivatives of ozonides |
| US3946081A (en) * | 1972-01-13 | 1976-03-23 | Bayer Aktiengesellschaft | Oxidative splitting of unsaturated hydrocarbons |
| US3972944A (en) * | 1972-10-27 | 1976-08-03 | Bayer Aktiengesellschaft | Process for preparing aldehydes from olefins |
| US3923903A (en) * | 1972-12-16 | 1975-12-02 | Bayer Ag | Oxidation of cyclic mono-olefins to {60 ,{107 -dialdeydes |
| DE2343342A1 (en) * | 1973-08-28 | 1975-03-27 | Menjajlo | PROCESS FOR THE CO-PRODUCTION OF EPOXY AND CARBONYL COMPOUNDS |
| US4298763A (en) * | 1979-03-12 | 1981-11-03 | Basf Aktiengesellschaft | Preparation of α,β-olefinically unsaturated aldehydes of 3 or 4 carbon atoms |
| US4769464A (en) * | 1983-12-23 | 1988-09-06 | Chemie Linz Gesellschaft M.B.H. | Process for the preparation of monocarbonyl or biscarbonyl compounds |
| JPH01190647A (en) * | 1988-01-25 | 1989-07-31 | Tonen Sekiyukagaku Kk | Production of aldehyde and epoxide compound |
| DE10136885C2 (en) * | 2001-07-24 | 2003-09-25 | Inst Angewandte Chemie Berlin | Peroxotungsten catalysts with oxyfunctionalized phosphonic acids and their use |
| US20080081803A1 (en) * | 2003-04-17 | 2008-04-03 | Gabor Butora | Heterocyclic cyclopentyl tetrahydroisoquinoline and tetrahydropyridopyridine modulators of chemokine receptor activity |
| CN100384856C (en) * | 2003-04-17 | 2008-04-30 | 麦克公司 | Heterocyclic cyclopentyl tetrahydroisoquinoline and tetrahydropyridopyridine modulators of chemokine receptor activity |
| JP2005170856A (en) * | 2003-12-11 | 2005-06-30 | National Institute Of Advanced Industrial & Technology | Method for oxidizing olefinic hydrocarbon |
| CN1629120A (en) * | 2004-09-02 | 2005-06-22 | 湖南大学 | Process for preparing aldehyde ketone and acid by oxidation of olefin |
| CN101054355A (en) * | 2007-06-11 | 2007-10-17 | 中国科学院成都生物研究所 | Compound of optically pure disulfenamides and application thereof |
| CN102317247A (en) * | 2009-02-17 | 2012-01-11 | 国立大学法人宇都宫大学 | Method for producing oxygen-containing compound |
| CN102850195A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Method for oxidizing propylene |
| CN103288611A (en) * | 2012-02-29 | 2013-09-11 | 中国石油化工股份有限公司 | Method for oxidizing styrene |
| CN102746127A (en) * | 2012-07-23 | 2012-10-24 | 中国平煤神马能源化工集团有限责任公司 | Method for preparing 1,6-adipaldehyde |
| CN104262168A (en) * | 2014-09-22 | 2015-01-07 | 北京旭阳化工技术研究院有限公司 | Preparation method of hexamethylenediamine |
| CN106279035A (en) * | 2015-05-29 | 2017-01-04 | 中国石油化工股份有限公司 | Preparation method and application and the one of the Br φ nsted acidic ion liquid with periodate as anion prepare α, the method for ω-dialdehyde |
| CN109876866A (en) * | 2017-12-06 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof for aromatic aldehyde synthesis aromatic amine |
| CN109369356A (en) * | 2018-12-29 | 2019-02-22 | 郑州大学 | A kind of cyclohexene selective oxidation preparation 1,6- hexandial method |
Non-Patent Citations (5)
| Title |
|---|
| KIM, BONG M.ETAL: "Synthesis of ω-formyl carboxylic acid by ozone oxidation of cycloolefins", 《KONGOP HWAHAK》 * |
| MIYAMOTO, KAZUNORI ETAL: "Activated Iodosylbenzene Monomer as an Ozone Equivalent: Oxidative Cleavage of Carbon-Carbon Double Bonds in the Presence of Water", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| RAGAN, JOHN A.: "Safe Execution of a Large-Scale Ozonolysis: Preparation of the Bisulfite Adduct of 2-Hydroxyindan-2-carboxaldehyde and Its Utility in a Reductive Amination", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》 * |
| 张明等: "环己烯臭氧化合成1，6-己二醛", 《工业催化》 * |
| 郭昌文等: "环戊烯合成戊二醛催化新材料的研究", 《中国优秀博硕士学位论文全文数据库 (博士) 工程科技Ⅰ辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426520A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Synthesis method of cycloheximide, selective ammonification hydrogenation catalyst of adipaldehyde and preparation method thereof |
| CN114426520B (en) * | 2020-10-29 | 2023-08-08 | 中国石油化工股份有限公司 | Method for synthesizing cyclohexylimine |
| CN112300008A (en) * | 2020-10-30 | 2021-02-02 | 宿迁联盛科技股份有限公司 | Synthetic method of 1, 6-hexamethylene diamine |
| CN112300008B (en) * | 2020-10-30 | 2022-04-01 | 宿迁联盛科技股份有限公司 | Synthetic method of 1, 6-hexamethylene diamine |
| CN114602461A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | Method for preparing diamine by catalyzing dialdehyde |
| CN112939784A (en) * | 2021-02-04 | 2021-06-11 | 山西铁峰化工有限公司 | Industrial preparation method of hexamethylene diamine |
| CN114904563A (en) * | 2022-06-08 | 2022-08-16 | 江苏扬农化工集团有限公司 | ZSM-5 supported noble metal catalyst, preparation method and application |
| CN114904563B (en) * | 2022-06-08 | 2024-02-09 | 江苏扬农化工集团有限公司 | ZSM-5 supported noble metal catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111056955B (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111056955B (en) | Method for preparing hexamethylene diamine from cyclohexene | |
| CN1850330A (en) | Load-type non-crystal-state alloy hydogenation catalyst and preparing method | |
| CN109206339B (en) | Method for preparing cyclohexanone oxime by oxidizing cyclohexylamine | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN109503388B (en) | Method for co-producing cyclohexylamine and dicyclohexylamine and catalyst system used in method | |
| CN111072489B (en) | Method for preparing hexamethylene diamine from hexamethylene dialdehyde in fixed bed reactor | |
| CN114453029B (en) | Oxide surface treatment method and application thereof in reaction for preparing 6-aminocapronitrile from caprolactam | |
| CN111056948B (en) | Process for preparing hexamethylenediamine | |
| CN111533634A (en) | Method for preparing propylene by directly dehydrogenating propane under low-temperature high-efficiency catalysis | |
| CN114950542A (en) | Bimetal supported molecular sieve catalyst and preparation method and application thereof | |
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| CN110756198A (en) | Ruthenium-aluminum oxide catalyst for selective hydrogenation of 4, 4' -diaminodiphenylmethane and preparation method and application thereof | |
| CZ80997A3 (en) | Process for preparing a mixture of aminomethyl cylohaxanes and diaminomethyl cyclohexanes | |
| CN111348661A (en) | ETL molecular sieve, metal modified ETL molecular sieve and application thereof in carbonylation reaction | |
| CN117623327A (en) | Ni modified micropore-mesoporous molecular sieve and preparation method and application thereof | |
| CN111054432B (en) | Catalyst for preparing hexamethylene diamine and preparation method and application thereof | |
| CN111116377B (en) | Method for preparing hexamethylene diamine | |
| CN112159323A (en) | Synthesis method of pentamethyldiethylenetriamine | |
| CN111085247B (en) | Alkaline molecular sieve supported catalyst and preparation method and application thereof | |
| CN111072488B (en) | Preparation process of hexamethylene diamine based on cyclohexene | |
| CN113861065A (en) | Method for preparing asymmetric imine or asymmetric secondary amine compound through photocatalysis | |
| CN1337386A (en) | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn | |
| CN113683582A (en) | Photocatalytic synthesis method of N- (2-morpholinoethyl) substituted benzamide compound | |
| CN112742432B (en) | Method for preparing gamma-butyrolactone by maleic anhydride hydrogenation | |
| US11161797B1 (en) | Process for preparing catalyst for selective hydrogenation of acetylene to ethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |