CN116836064A - Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate - Google Patents

Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate Download PDF

Info

Publication number
CN116836064A
CN116836064A CN202310542512.XA CN202310542512A CN116836064A CN 116836064 A CN116836064 A CN 116836064A CN 202310542512 A CN202310542512 A CN 202310542512A CN 116836064 A CN116836064 A CN 116836064A
Authority
CN
China
Prior art keywords
cyclohexylamine
catalyst
cyclohexyl acetate
synthesizing
acetate
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.)
Pending
Application number
CN202310542512.XA
Other languages
Chinese (zh)
Inventor
钟文周
毛丽秋
彭浩宇
唐静
袁莹莹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Normal University
Original Assignee
Hunan Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hunan Normal University filed Critical Hunan Normal University
Priority to CN202310542512.XA priority Critical patent/CN116836064A/en
Publication of CN116836064A publication Critical patent/CN116836064A/en
Pending legal-status Critical Current

Links

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
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/16—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings
    • C07C211/17—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings containing only non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a novel process for directly synthesizing cyclohexylamine from cyclohexyl acetate and preparation and application of a catalyst thereof. The catalyst takes metal Cu or Ni as main catalytic active component, al 2 O 3 、SiO 2 、TiO 2 Or active carbon and the like are used as carriers, and Zn, ca, mg, sr, ba, K, zr and other oxides are added to modify the carrier, wherein the main active component and the auxiliary modification component of the catalyst can be compounded in any ratio. The catalyst is suitable for synthesizing the cyclohexane by directly carrying out hydro-amination on the raw materials of the cyclohexyl acetate and the ammonia gas, can save the amination process for preparing the cyclohexanol by hydrolyzing the cyclohexyl acetate, simplifies the operation flow of the method for preparing the cyclohexane by taking the cyclohexene as the initial raw material, and reduces the production cost.

Description

Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate
Technical Field
The invention belongs to the technical field of production of organic chemical raw materials, and relates to a catalyst which takes metal Cu or Ni as a main catalytic active component and Al as an active component 2 O 3 、SiO 2 、TiO 2 And active carbon and the like are used as carriers, oxide such as Zn, ca, mg, sr, ba, K, zr and the like are added as auxiliary active components to regulate the micro-environment on the surfaces of the carriers, and a series of copper-and nickel-containing supported heterogeneous catalysts are prepared by a deposition-precipitation method and are used for catalyzing the direct amination of cyclohexyl acetateA novel method for synthesizing cyclohexylamine.
Background
Cyclohexylamine is an important chemical raw material in organic synthesis, is widely used for synthesizing chemicals such as dyes, medicines, rubber processing aids and the like, and is also a key intermediate of products such as a synthetic desulfurizing agent, a corrosion inhibitor, a vulcanization accelerator, an emulsifying agent, an antistatic agent, a latex coagulant, an anticorrosive agent, a bactericide, an insecticide and the like. In recent years, the continuous application of these downstream products derived from cyclohexylamine brings new development opportunities to the production of cyclohexylamine, and the demand thereof is also in an increasing trend year by year.
Currently, there are five industrial processes for synthesizing cyclohexylamine: benzene nitration-hydrogenation process, benzene chlorination-hydrogenation-amination process, benzene partial hydrogenation-amination process, cyclohexane nitration-hydrogenation process, cyclohexane oxidation-amination process. Benzene nitration-hydrogenation processes, which are currently the most dominant route for the industrial production of cyclohexylamine, use first of all mixed strong acids (H 2 SO 4 -HNO 3 ) Nitrifying benzene to obtain nitrobenzene, then carrying out high-temperature catalytic hydrogenation to obtain aniline, and finally carrying out reductive hydrogenation on the aniline to obtain cyclohexylamine (Greenfield H, hydrogenation of aniline to cyclohexylamine with platinum metal catalysts, the Journal of Organic Chemistry, 1964, 29 (10): 3082-3084). The synthesis of the raw material aniline requires the use of a large amount of highly toxic and corrosive mixed acid, the equipment load is large, and a large amount of wastewater is generated in the treatment process. Benzene is used as a starting material in the benzene chlorination-hydrogenation-amination process, firstly benzene and chlorine are continuously chlorinated under the action of a catalyst to obtain chlorobenzene, then the chlorobenzene is subjected to hydrogenation reaction to obtain chlorocyclohexane, and finally the chlorocyclohexane is subjected to substitution reaction with ammonia gas to prepare cyclohexylamine (Tao Xiong, qian Zhang, new amination strategies based on nitrogen-centered radical chemistry, chem. Soc. Rev., 2016, 45, 3069-3087). In the amination reaction of chlorocyclohexane, ammonia gas is used as a nucleophilic reagent to carry out nucleophilic substitution with chlorocyclohexane to obtain the product cyclohexylamine, and the alkali or acid catalyst can be used for catalysis. The basic catalyst is usually sodium or potassium, while the acidic catalyst comprises phosphoric acid and sulfuric acid, so the process is costly andthe selectivity of the product is difficult to control and is gradually eliminated in industrial production. The benzene partial hydrogenation-amination process is to hydrogenate benzene selectively to prepare cyclohexene, and then the cyclohexene and molecular ammonia are subjected to amination reaction directly through an acid catalyst to prepare cyclohexylamine. In the process, cyclohexene is directly aminated, and the problems of harsh reaction conditions, low amine yield and the like still exist, so that the amination reaction still has difficulty in realizing industrial production. For example, wen et al use HZSM-5 with a silica to alumina ratio of 38 to catalyze the one-step amination of cyclohexene to cyclohexylamine (Wen J., you K., liu X., et al Highly selective one-step catalytic amination of cyclohexene to cyclohexylamine over HZSM-5. Catalysis Communications, 2019, 127:64-68), which indicated an NH at 260℃of 10.5 MPa 3 Under the reaction condition of (2) the yield of cyclohexene is only 4.3%, and the rochanter adopts an alkali treatment-heavy-crystallization method to prepare a series of ZSM-5 molecular sieves with different silicon-aluminum ratios for catalyzing the gas-phase amination of cyclohexene to synthesize cyclohexane in one step (rochanter, catalytic synthesis research of cyclohexane and nitrocyclohexane, hunan university of standardization, 2021). Experimental results show that the ZSM-5 molecular sieve with the silicon-aluminum ratio of 45-55 is prepared at 300 ℃ and 8 MPa N 2 Under the reaction conditions of pressure, the yield of cyclohexene was 4.1%.
Cyclohexane nitration-hydrogenation processes use cyclohexane as the starting material, nitrocyclohexane is produced by gas phase nitration of cyclohexane, and then nitrocyclohexane is reduced and hydrogenated to give the cyclohexane product (B.Hass, E.B. Hodge, B.M. Vanderbilt, industrial and Enginerring Chemistry, 1936, 28, 339-344; kowalewski E, krawczyk M, S ł owik G, et al, continuous-flow hydrogenation of nitrocyclohexane toward value-added products with CuZnAl hydrotalcite derived materials, applied Catalysis A: general, 2021, 618: 118134). The process has the advantages of mild hydrogenation condition, high product yield, simple operation and low pollution, and has the defects of difficult preparation of nitrocyclohexane raw materials and need of corrosive HNO 3 And NO 2 The gas phase is nitrified by high-temperature gas phase, and the components of the nitrified product are complex, so the process has high separation energy consumption and high production cost. The cyclohexane oxidation-amination process is to prepare cyclohexane alcohol and cyclohexanone (KA oil) by catalyzing air oxidation of cyclohexane and molecular oxygen with soluble cobalt saltThe latter KA oil is hydroaminated with ammonia under the action of a catalyst to give the product cyclohexylamine (Becker J, niederer J P M, keller M, et al Amination of cyclohexanone and cyclohexanol/cyclohexanone in the presence of ammonia and hydrogen using copper or a group VIII metal supported on a carrier as the catalyst, applied Catalysis A: general, 2000, 197 (2): 229-238). In order to achieve higher KA oil selectivity, the single-pass conversion rate of the cyclohexane oxidation to KA oil in the process is less than 8%, so that the process problems of high material consumption and high energy consumption exist. At present, in order to solve the technical bottleneck of preparing KA oil by oxidizing cyclohexane, china petrochemical industry Co., ltd. Petrochemical industry scientific institute develops a method for preparing cyclohexene by partially hydrogenating benzene based on Japanese Asahi chemical industry, and then the cyclohexene is reacted with acetic acid to prepare cyclohexyl acetate, and then the cyclohexyl is industrially prepared by further advanced hydrolysis, but the process still has complex reaction unit process. Under the increasing environmental awareness and the great background of the national advocate of green chemical process, the direct hydro-ammoniation synthesis of cyclohexane by taking cyclohexyl acetate as a raw material is a new technical route of atomic economy (figure 1).
Disclosure of Invention
The invention aims at solving the problems that the current technological process of cyclohexylamine in China is complex, especially the production process can produce environmental pollution, and the quality of the product is not high. The method has the advantages of wide raw material sources, simplified operation, reduced production cost, greatly improved resource utilization, and solves the problems of environmental pollution, harsh reaction conditions and the like.
The technical scheme of the invention is as follows: the main catalytic active components in the heterogeneous catalyst are acetate, chloride, bromide, oxalate, nitrate, sulfate and acetylacetone complex of Cu or Ni; the surface microenvironment is regulated to K 2 O、La 2 O 3 、CeO 2 And auxiliary components such as alkaline earth metal oxide derived from phaseCorresponding acetate, chloride, bromide, oxalate, nitrate, sulfate, and acetylacetonate complexes; the catalyst section is Al 2 O 3 、SiO 2 、TiO 2 And one or more mixtures of activated carbon as a carrier.
Specifically, the load type Al containing copper, zinc and calcium 2 O 3 The preparation method of the catalyst sequentially comprises the following steps: a) Copper acetate, zinc acetate and calcium acetate with different molar ratios are dissolved in 50 parts by weight of deionized water and stirred at room temperature to form a mixed solution; b) 4 parts by weight of Al at 50 DEG C 2 O 3 Adding into a round-bottom flask, and adding 50 parts by weight of deionized water; c) The mixed solution of the metal salt was added dropwise to the round-bottomed flask and stirred for about 10 minutes, followed by dropwise addition of 1 mol/L Na 2 CO 3 The aqueous solution of (2) is such that the pH of the mixed solution is greater than 9; d) Aging at 50deg.C 6 h, filtering, drying at 60deg.C overnight, and calcining at 400deg.C 4 h. e) The catalyst was named Cu according to the molar ratio of copper, zinc, calcium x Zn y Ca z /Al 2 O 3 。
The invention aims at realizing the following steps: in a fixed bed reactor, raw materials of cyclohexyl acetate, ammonia and hydrogen pass through a bed layer filled with the catalyst, the temperature of the catalyst bed layer is controlled to be 200-300 ℃, the reaction time is controlled to be 0-300 h, and cyclohexylamine is prepared by selectively ammonifying the cyclohexyl acetate continuously.
The reaction temperature can be 100-450 ℃, preferably 200-300 ℃, and the reaction time can be 0.1-3000 h, preferably 0.5-2500 h, the reaction pressure is between normal pressure and 8 MPa, preferably between normal pressure and 3 MPa, and the flow of hydrogen and ammonia can be any ratio.
There is no report on the preparation method of the present invention in the literature in the prior art, and the method is used for preparing cyclohexylamine by directly ammonifying cyclohexyl acetate, ammonia and hydrogen at normal pressure. Not only can the process be simplified and the cost be reduced, but also the resource utilization rate can be greatly improved.
Drawings
FIG. 1 novel process for preparing cyclohexylamine from cyclohexyl acetate.
The following examples are intended to illustrate the invention and are not intended to be limiting.
Example 1: ammonia gas flow 40 mL/min, hydrogen gas flow 90mL/min, cyclohexyl acetate continuously injected by plunger type advection pump (3 mL/min), and reaction liquid entering Cu after vaporization in preheating section 1 Zn 1 Ca 1 /Al 2 O 3 The catalyst bed layer is reacted, the reaction temperature is 260 ℃, the reaction time is 9 and h at normal pressure, and the product is condensed by ice bath and enters a collecting bottle. The product was analyzed by gas phase to give 36.0% conversion of cyclohexyl acetate and 58.0% selectivity of cyclohexylamine.
Example 2: the procedure is as in example 1, except for Cu 1.5 Zn 1 Ca 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 24.8% and the selectivity of cyclohexylamine was 61.4%.
Example 3: the procedure is as in example 1, except for Cu 2 Zn 1 Ca 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 30.8% and the selectivity of cyclohexylamine was 65.6%.
Example 4: the procedure is as in example 1, except for Cu 2 Zn 1 Ba 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 23.1% and the selectivity of cyclohexylamine was 40.0%. Example 5: the procedure is as in example 1, except for Cu 2 Zn 1 Mg 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 21.8% and the selectivity of cyclohexylamine was 51.6%.
Example 6: the procedure is as in example 1, except for Cu 2 Zn 1 Sr 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 31.6% and the selectivity of cyclohexylamine was 29.1%.
Example 7: the procedure is as in example 1, except for Cu 2 Zn 1 K 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 35.0% and the selectivity of cyclohexylamine was 19.5%.
Example 8: the procedure is as in example 1, except for Cu 2 Zn 1 Zr 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 27.3% and the selectivity of cyclohexylamine was 2.6%.
Example 9: the procedure is as in example 1, except for Cu 2 Zn 1.5 Ca 1 /Al 2 O 3 The conversion of cyclohexyl acetate was 35.8% and the selectivity of cyclohexylamine was 75.6%.
Example 10: the procedure is as in example 1, except for Cu 2 Zn 1.5 Ca 1 /Al 2 O 3 The reaction temperature was 250 ℃, the conversion of cyclohexyl acetate was 21.8%, and the selectivity of cyclohexylamine was 69.5%.
Example 11: the procedure is as in example 1, except for Cu 2 Zn 1.5 Ca 1 /Al 2 O 3 The reaction temperature was 270 ℃, the conversion of cyclohexyl acetate was 28.5%, and the selectivity of cyclohexylamine was 73.2%.
Example 12: the procedure is as in example 1, except for Cu 2 Zn 1.5 Ca 1 /Al 2 O 3 The ammonia flow is 30 mL/min, the hydrogen flow is 90mL/min, the conversion rate of the cyclohexyl acetate is 25.6%, and the selectivity of the cyclohexylamine is 65.9%.
Example 13: the procedure is as in example 1, except for Cu 2 Zn 1.5 Ca 1 /Al 2 O 3 The ammonia flow rate is 50 mL/min, the hydrogen flow rate is 90mL/min, the conversion rate of the cyclohexyl acetate is 20.6%, and the selectivity of the cyclohexylamine is 53.1%.
Example 14: the procedure is as in example 1, except for Cu 2 Zn 1.5 Ca 1 /Al 2 O 3 The ammonia flow is 40 mL/min, the hydrogen flow is 60mL/min, the conversion rate of the cyclohexyl acetate is 34.0%, and the selectivity of the cyclohexylamine is 63.8%.
Example 15: the procedure is as in example 1, except for Cu 2 Zn1.5Ca1/Al 2 O 3 The ammonia flow is 30 mL/min, the hydrogen flow is 120mL/min, the conversion rate of the cyclohexyl acetate is 34.0%, and the selectivity of the cyclohexylamine is 71.2%.
Example 16: the procedure is as in example 1, except thatAt Ni 2 Zn 1 Ca 1 /Al 2 O 3 The ammonia flow is 30 mL/min, the hydrogen flow is 120mL/min, the conversion rate of the cyclohexyl acetate is 26.2%, and the selectivity of the cyclohexylamine is 42.1%.

Claims (6)

1. A one-step synthesis method of cyclohexylamine is characterized in that a series of negative cut-off type heterogeneous catalysts containing copper or nickel are prepared by adopting a deposition-precipitation method from cyclohexyl acetate as a raw material, and the cyclohexyl acetate is directly hydroaminated by ammonia gas to form a new one-step synthesis process of cyclohexylamine.
2. A process for synthesizing cyclohexylamine as claimed in claim 1, wherein the main catalytic active components in the catalyst are Cu and Ni acetates, chlorides, bromides, oxalates, nitrates, sulfates and acetylacetonates.
3. The method for preparing the composite solid catalyst according to claim 1, wherein the K is controlled by the surface microenvironment in the catalyst 2 O、La 2 O 3 、CeO 2 And alkaline earth metal oxide, etc., and is derived from corresponding acetate, chloride, bromide, oxalate, nitrate, sulfate, and acetylacetone complex, the catalyst section is Al 2 O 3 、SiO 2 、TiO 2 And one or more mixtures of activated carbon.
4. The preparation method of the composite solid catalyst according to claim 1, wherein the main active component and the modification component can be compounded in any ratio, and the preparation method is characterized in that the mass ratio of acetate to carrier is (0.1-0.9): 1, aging for 2-15 hours, drying overnight at 40-180 ℃, and calcining for 1-20 hours at 300-800 ℃.
5. The method for synthesizing cyclohexylamine according to claim 1, wherein the reaction temperature is 100 to 450 ℃, preferably 200 to 300 ℃, the reaction pressure is between normal pressure and 8 MPa, preferably between normal pressure and 3 MPa, the reaction time is between 0.1 to 3000 hours, preferably between 0.5 to 2500 hours, and the reaction pressure is between normal pressure and 8 MPa, preferably between normal pressure and 3 MPa.
6. The method for synthesizing cyclohexylamine according to claim 1, wherein the flow rate of hydrogen and the flow rate of ammonia can be arbitrarily proportioned.
CN202310542512.XA 2023-05-15 2023-05-15 Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate Pending CN116836064A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310542512.XA CN116836064A (en) 2023-05-15 2023-05-15 Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310542512.XA CN116836064A (en) 2023-05-15 2023-05-15 Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate

Publications (1)

Publication Number Publication Date
CN116836064A true CN116836064A (en) 2023-10-03

Family

ID=88165947

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310542512.XA Pending CN116836064A (en) 2023-05-15 2023-05-15 Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate

Country Status (1)

Country Link
CN (1) CN116836064A (en)

Similar Documents

Publication Publication Date Title
US5773657A (en) Hydrogenation of aromatic compounds in which at least one amino group is bonded to an aromatic nucleus
CN109503388B (en) Method for co-producing cyclohexylamine and dicyclohexylamine and catalyst system used in method
US20240150274A1 (en) Method for producing adipic acid and cyclohexanone oxime from cyclohexane
CN106957231A (en) The preparation method of N, N '-bis- (alkyl)-p-phenylenediamine
JPS596699B2 (en) supported ruthenium catalyst
CN100519516C (en) Process for preparation of cyclohexanone oxime
CN113121368A (en) Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof
CN111253281B (en) Preparation method of cyclohexanone oxime
CN110372516B (en) Method for preparing cyclohexylamine
CN116836064A (en) Novel method for synthesizing cyclohexylamine by directly hydroamination of cyclohexyl acetate
CN102319562A (en) The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method
CN103012262B (en) Caprolactam production method
CN107628957A (en) A kind of new method research of the direct ammonification synthesizing cyclohexane 1 amine of cyclohexene
CN1337386A (en) Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn
EP3770141B1 (en) Method for preparing 2-cyclohexyl cyclohexanol
CN111841573A (en) Benzene partial hydrogenation non-supported crystalline catalyst and preparation method thereof
JPS59186932A (en) Process for producing cycloolefin
US20230029768A1 (en) Process for producing cyclohexanol and cyclohexanone
CN114247449B (en) Catalyst for synthesizing piperazine by hydroxyethyl ethylenediamine, and preparation method and application thereof
CN112661620A (en) Preparation method of cyclopentanone
CN115819304B (en) Preparation method of molybdenum disulfide catalyzed tetraethyl thiuram disulfide
CN115414942B (en) Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof
CN108047059B (en) Method for preparing aromatic amine by aromatic ketone one-pot method
WO2012018310A1 (en) Process for the production of highly pure dicyclohexylamine from by-products resulting from the producton of cyclohexylamine
JPH061758A (en) Production of amino compound

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