CN113860989B - Synthesis method of 1, 6-hexanediol - Google Patents

Synthesis method of 1, 6-hexanediol Download PDF

Info

Publication number
CN113860989B
CN113860989B CN202111315161.6A CN202111315161A CN113860989B CN 113860989 B CN113860989 B CN 113860989B CN 202111315161 A CN202111315161 A CN 202111315161A CN 113860989 B CN113860989 B CN 113860989B
Authority
CN
China
Prior art keywords
catalyst
reaction
hexanediol
synthesis method
cyclohexene
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.)
Active
Application number
CN202111315161.6A
Other languages
Chinese (zh)
Other versions
CN113860989A (en
Inventor
庄大为
杜小宝
杨磊
刘喆
刘新伟
王聪
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.)
China Tianchen Engineering Corp
Original Assignee
China Tianchen Engineering Corp
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 China Tianchen Engineering Corp filed Critical China Tianchen Engineering Corp
Priority to CN202111315161.6A priority Critical patent/CN113860989B/en
Publication of CN113860989A publication Critical patent/CN113860989A/en
Application granted granted Critical
Publication of CN113860989B publication Critical patent/CN113860989B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for synthesizing 1, 6-hexanediol, which takes cyclohexene as a raw material, and comprises the steps of oxidation and hydrogenation, wherein cyclohexene is firstly oxidized into glyoxal, and then the glyoxal is hydrogenated to generate a 1, 6-hexanediol product. Compared with the prior art, the synthesis method has the advantages of low raw material cost, mild reaction conditions, high catalyst activity, high product yield and few byproducts.

Description

Synthesis method of 1, 6-hexanediol
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthesis method of 1, 6-hexanediol.
Background
1, 6-Hexanediol (HDO) with the molecular formula C 6 H 14 O 2 Is white solid at normal temperature, is easy to dissolve in water, methanol, ethanol, butyl acetate, diethyl ether and the like, and is insoluble in toluene. The 1, 6-hexanediol has 2 hydroxyl groups at two ends of a carbon chain, and has higher activity. Is an emerging fine chemical raw material of polyester with high added value.
The 1, 6-hexanediol imparts excellent comprehensive properties to the product in the fields of synthetic raw materials, modifiers and the like, such as enhanced flexibility, impact resistance, color stability, good low-temperature performance and hydrolysis resistance, and the excellent properties lead the application market of the 1, 6-hexanediol to be quite wide.
1, 6-hexanediol can be used in UV coatings. UV coating, i.e. UV curable coating, is widely used because it has excellent anti-pollution and energy-saving effects and rapid curing characteristics. An important determinant of good and fast performance of UV coatings is the reactive monomer. 1, 6-hexanediol and acrylic acid are used as raw materials, and under the action of a catalyst, 1, 6-hexanediol diacrylate (HDDA) which is one of common active monomers is synthesized by adopting an esterification reaction. The addition of the active monomer ensures that the UV coating has a series of excellent performances such as low viscosity, high curing speed, low volatility, flexibility, hydrolysis resistance, heat resistance, chemical reagent resistance and the like. With the pursuit of environmental protection and high quality life, the demand of 1, 6-hexanediol is accelerated. UV coatings are therefore the most promising for excavation by the use of 1, 6-hexanediol.
1, 6-hexanediol can be used for polyurethane adhesives. The polyurethane adhesive has good toughness and adjustability, simple and convenient bonding process, excellent low-temperature tolerance performance even at low temperature and excellent stability, and is deeply favored by wide application. The polyurethane adhesive has the advantages of being excellent in adhesive performance and adhesive adaptability to various base materials, so that the application field of the polyurethane adhesive is continuously expanded, and the polyurethane adhesive is rapidly developed into the adhesive with the largest application in China and abroad. Compared with other alcohol raw material synthetic adhesives, the synthetic polyurethane adhesive with 1, 6-hexanediol as the raw material has better low temperature resistance and stability; and the 1, 6-hexanediol is used as a raw material to produce high-grade polyurethane adhesives with special properties, such as yellowing-resistant adhesives and the like.
1, 6-hexanediol can be used for the epoxy resins. The mechanical properties such as tensile strength, bending strength, compressive strength, impact strength and the like and the adaptation period of the resin cured by taking 1, 6-hexanediol as a curing raw material are superior to those of the resin cured by common curing (such as single dioxy glycidyl ether curing). In addition, the 1, 6-hexanediol is used as a difunctional epoxy resin reactive diluent, can be better mixed with epoxy resin for use, and not only greatly reduces the viscosity of the system, but also reduces the shrinkage and the cost. In addition, epoxy resins are also water-soluble, reactive diluents, and therefore possess excellent wetting ability, not only to enhance the impregnating ability during casting, but also to enhance the flexibility of the article during lamination and adhesion, in daily use.
1, 6-hexanediol can be used in polyurethane elastomers. Polyurethane elastomers are widely used in synthetic rubber, elastic fiber, artificial leather, and the like. The polyester-based polyurethane has excellent mechanical strength and heat resistance, but at the same time, the hydrophilicity of the polyester-based polyurethane is easy to oxidize, is not acid-base corrosion resistant, and is easy to hydrolyze in humid air, so that the stability of the polyester-based polyurethane is insufficient. In order to solve the problems, the 1, 6-hexanediol is added as a raw material in the process of preparing polyurethane, so that the defects of easy hydrolysis, poor stability and the like are overcome, and the unique performance of the 1, 6-hexanediol, which is a polyurethane elastomer, is beneficial to the production of mechanical products, such as automobile components, solid tires and the like.
The synthesis methods of 1, 6-hexanediol currently include the following:
is hydrogenated from adipic acid or its derivatives. Generally, adipic acid is subjected to esterification reaction to obtain an adipic acid ester derivative, and the adipic acid ester derivative can be subjected to hydrogenation reaction to obtain 1, 6-hexanediol. The method has the advantages of easily obtained raw materials, mild technical maturity, less pollution and higher yield, and the hydrogenation catalyst uses more copper-based catalyst. The product of Jieduhua polyurethane Co., ltd. Provides a method for synthesizing 1, 6-hexanediol by gas phase hydrogenation of dimethyl adipate, and provides a corresponding hydrogenation catalyst (50.9% CuO-10.5% Al) 2 O 3 -12.9％MnO-25.7％SiO 2 ). The catalyst is reduced and activated, and then is put into a micro-reactor at 210 ℃ and 6.00MPa, and the ester flow rate is 0.027mL/min and H 2 The activity test is carried out at a flow rate of 730mL/min, and the result shows that the conversion rate of the dimethyl adipate is 93%, the yield of the 1, 6-hexanediol is 82%, and the selectivity of the 1, 6-hexanediol is 88%. They supported Cu and other metal compounds on mesoporous molecular sieves by microwave irradiation. The microwave radiation heating speed is high and stable, so that the active substances can be uniformly loaded on the carrier in a short time, and the physical property and the catalytic property of the catalyst are improved;
adipic acid can be hydrogenated directly to 1, 6-hexanediol without esterification. The direct hydrogenation catalyst mostly uses Sn and transition metal elements (such as Ru, rh, pd, pt, W, re, ir, etc.) as active components. However, the adipic acid has more side reactions in the direct hydrogenation process, and the reaction conditions are more severe, and the efficient catalyst is lacked. Research on the synthetic route has been reported at home and abroad, and Asahi chemical Co., ltd.m.A method for preparing a mixture of 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol from mixed dibasic acids (byproducts of adipic acid production process, including succinic acid, glutaric acid, adipic acid, etc.). Taking mixed dibasic acid as raw material, mixing with water and H 2 And catalyst 5% Ru-3% Sn-5% Rh/active carbonUnder 180 ℃ and 15MPa, the diol mixture is prepared, and the yields of 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol are 75%,98% and 96% respectively. The active component of the catalyst is one or more of Ru, re, in, ir selected by China petrochemical industry Co., ltd, and the carrier is active carbon. Under the conditions of 353K-573K and 3-10 MPa, adipic acid is directly hydrogenated to prepare 1, 6-hexanediol. A great number of experiments prove that the catalyst is an effective catalyst for synthesizing 1, 6-hexanediol by adipic acid one-step method, and the yield of the target product 1, 6-hexanediol reaches 96%;
1, 6-hexanediol can also be prepared from biotechnological starting materials. The biotechnology raw material process is a process which has been raised in recent years, and the scheme has the advantage of environmental friendliness. In general, the method takes 5-hydroxymethylfurfural, levoglucosone or sorbitol and the like as raw materials, and synthesizes the product 1, 6-hexanediol through three-step and four-step reactions. For example, duPont developed a process for preparing 1, 6-hexanediol from L-glucosone. Pt/W/TiO 2 The catalyst and the substrate of the levoglucosone are placed in a reaction kettle to react for 2 hours at 60 ℃ and 5.52MPa, then the temperature is increased to 180 ℃ to react for 4 hours, and the yield of the 1, 6-hexanediol is 62%.
Disclosure of Invention
In view of the above, the invention aims to provide a method for synthesizing 1, 6-hexanediol, which takes cyclohexene as a raw material, and comprises the steps of oxidation and hydrogenation, wherein cyclohexene is firstly oxidized into glyoxal, and then the glyoxal is hydrogenated to generate a 1, 6-hexanediol product.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a synthesis method of 1, 6-hexanediol comprises the following steps:
(1) Placing cyclohexene, a solvent and a catalyst A in a reaction kettle, uniformly mixing and preheating to a certain temperature, continuously adding hydrogen peroxide into the reaction kettle at a certain speed, and keeping the temperature for a period of time to obtain a reaction solution;
(2) Filtering the reaction solution, and rectifying the filtrate to obtain a compound A;
(3) And (3) placing the compound A and the catalyst B in a reaction kettle, uniformly mixing and preheating to a certain temperature, continuously introducing hydrogen into the reaction kettle for hydrogenation reaction, and after the reaction is maintained for a period of time, obtaining a required product.
Further, the catalyst A is one or more of single-layer molybdenum disulfide, multi-layer molybdenum disulfide, molybdenum selenide, molybdenum disilicide, tungsten oxide, tungsten sulfide and tungstic acid, the average particle diameter of the catalyst A is 1-200 μm, for example, 1 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 100 μm, 150 μm and 200 μm, preferably 5 μm-10 μm, and the mass ratio of the cyclohexene to the catalyst A is 1:0.01 to 0.5, for example, 1:0.01, 1:0.05, 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.2, 1:0.3, 1:0.4, 1:0.5, preferably 1:0.1 to 0.15.
Further, the solvent is one or more of methanol, ethanol, glycol, tertiary butanol, acetonitrile, dimethyl sulfoxide, diethyl ether and acetaldehyde, and the mass ratio of the solvent to cyclohexene is 1-10:1, for example, 1:1, 2:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, preferably 3-4:1.
Further, the concentration of the hydrogen peroxide is 30% -70%, for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, preferably 45% -50%, and the mass ratio of the hydrogen peroxide to cyclohexene is 1-3:1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 2:1, 2.5:1, 3:1, preferably 1.2-1.5:1.
Further, the preheating and heat-preserving temperature in the step (1) is 10-70 ℃, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃,30 ℃, 40 ℃,50 ℃,60 ℃,70 ℃, preferably 20-40 ℃, and the hydrogen peroxide is added for 10-60min, for example, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, preferably 15-20min, and the heat-preserving time is 20-120min, for example, 20min, 30min, 35min, 40min, 45min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, preferably 30-50min.
Further, the pore size of the filter membrane used for the filtration in the step (2) is 0.1 to 5. Mu.m, for example, 0.1. Mu.m, 0.2. Mu.m, 0.25. Mu.m, 0.3. Mu.m, 0.4. Mu.m, 0.5. Mu.m, 0.6. Mu.m, 0.7. Mu.m, 0.8. Mu.m, 1.2. Mu.m, 1.4. Mu.m, 1.6. Mu.m, 1.8. Mu.m, 2. Mu.m, 3. Mu.m, 4. Mu.m, 5. Mu.m, preferably 0.25. Mu.m to 2. Mu.m.
Further, the fraction collected in the step (2) by rectification is a fraction at 92-94 ℃, and the obtained compound A is glyoxal.
Further, the catalyst B is one or several of nickel-supported alumina catalyst, raney nickel, platinum-supported alumina catalyst or palladium-supported alumina catalyst, and the mass ratio of the catalyst B to the compound A is 0.001-0.1:1, for example, 0.001:1, 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, and preferably 0.02-0.05:1.
further, the mass ratio of the introduced hydrogen to the compound A is 1:3-30, for example, can be 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:15, 1:20, 1:25, 1:30, preferably 1:5-8.
Further, the hydrogenation reaction temperature in the step (3) is 120 to 260℃and may be, for example, 120℃140℃160℃180℃190℃200℃210℃220℃230℃240℃250℃260℃190℃190 to 220℃190.5 MPa, for example, 1Mpa, 1.5Mpa, 2Mpa, 2.2Mpa, 2.3Mpa, 2.5Mpa, 2.7Mpa, 3Mpa, 3.1Mpa, 3.3Mpa, 3.5Mpa, 4Mpa, 4.5Mpa, 5Mpa, preferably 2.2 to 3.5Mpa, and the hydrogenation reaction time is 2 hours.
Compared with the prior art, the synthesis method of the 1, 6-hexanediol has the following advantages:
compared with the prior art, the synthesis method has the advantages of low raw material cost, mild reaction conditions, high catalyst activity, high product yield and few byproducts.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
16kg of cyclohexene, 50kg of tert-butanol and 2kg of molybdenum sulfide catalyst are placed in a reaction kettle, stirring is started to stir reactants uniformly, and circulating water is started to control the temperature of a reaction solution at 40 ℃. 40kg of hydrogen peroxide with the concentration of 50% is uniformly added into the reaction kettle, and the feeding time is 20min. After the materials are added, the temperature of the reaction kettle is controlled at 40 ℃ through circulating water, and the reaction constant temperature time is 30min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was found to be 89.12% and the selectivity to glyoxal was found to be 95.83%.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.8kg of nickel-supported alumina catalyst are added into a reaction kettle, the reaction kettle is heated to 200 ℃, the pressure is raised to 3MPa, and after the reaction condition is reached, 4kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. According to analysis, the conversion rate of the reactive glyoxal is 68.76%, and the selectivity of the 1, 6-hexanediol reaches 99.81%.
Example 2
16kg cyclohexene, 60kg dimethyl sulfoxide and 2kg molybdenum (IV) selenide catalyst are placed in a reaction kettle, the reactants are stirred uniformly by starting stirring, and the temperature of the reaction liquid is controlled at 40 ℃ by starting circulating water. Then 50kg of 30% hydrogen peroxide is evenly added into the reaction kettle, and the feeding time is 15min. After the materials are added, the temperature of the reaction kettle is controlled at 40 ℃ through circulating water, and the reaction constant temperature time is 30min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was found to be 47.14% and the selectivity to glyoxal was found to be 81.77%.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.5kg of platinum-loaded alumina catalyst are added into a reaction kettle, the reaction kettle is heated to 210 ℃, the pressure is raised to 3MPa, and after the reaction condition is reached, 4kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. The conversion of the glyoxal in the reaction is 34.15% and the selectivity of the 1, 6-hexanediol is 82.49% by analysis.
Example 3
16kg cyclohexene, 50kg ethanol and 2kg molybdenum sulfide catalyst are placed in a reaction kettle, the reactants are stirred uniformly by starting stirring, and the temperature of the reaction solution is controlled at 40 ℃ by starting circulating water. 40kg of hydrogen peroxide with the concentration of 50% is uniformly added into the reaction kettle, and the feeding time is 20min. After the materials are added, the temperature of the reaction kettle is controlled at 40 ℃ through circulating water, and the reaction constant temperature time is 30min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was 97.76% and the selectivity to glyoxal was 47.84% by analysis.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.8kg of Raney nickel catalyst are added into a reaction kettle, the reaction kettle is heated to 210 ℃, the pressure is raised to 3.5MPa, and after the reaction condition is reached, 3kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. According to analysis, the conversion rate of the reactive glyoxal is 97.37%, and the selectivity of the 1, 6-hexanediol reaches 99.34%.
Example 4
16kg cyclohexene, 50kg acetonitrile and 2kg tungsten sulfide catalyst were placed in a reaction kettle, the reactants were stirred to uniformity by starting stirring, and the temperature of the reaction solution was controlled at 35℃by starting circulating water. Then 25kg of 70% hydrogen peroxide is evenly added into the reaction kettle, and the feeding time is 20min. After the materials are added, the temperature of the reaction kettle is controlled at 35 ℃ through circulating water, and the reaction constant temperature time is 30min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was found to be 99.76% and the selectivity to glyoxal was found to be 97.24%.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.9kg of Raney nickel catalyst are added into a reaction kettle, the reaction kettle is heated to 210 ℃, the pressure is raised to 3.5MPa, and after the reaction condition is reached, 4kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. The conversion rate of the glyoxal in the reaction is 98.49%, and the selectivity of the 1, 6-hexanediol reaches 99.22% through analysis.
Example 5
16kg of cyclohexene, 50kg of acetaldehyde and 2kg of monolayer molybdenum disulfide catalyst are placed in a reaction kettle, stirring is started to stir reactants uniformly, and circulating water is started to control the temperature of a reaction liquid at 20 ℃. 40kg of 30% hydrogen peroxide is added into the reaction kettle uniformly for 30min. After the materials are added, the temperature of the reaction kettle is controlled at 20 ℃ through circulating water, and the reaction constant temperature time is 20min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was found to be 97.62% and the selectivity to glyoxal was found to be 94.27%.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.8kg of palladium-loaded alumina catalyst are added into a reaction kettle, the reaction kettle is heated to 200 ℃, the pressure is raised to 3MPa, and after the reaction condition is reached, 4kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. The conversion of the glyoxal in the reaction is 76.96% and the selectivity of the 1, 6-hexanediol is 69.73% by analysis.
Example 6
16kg cyclohexene, 50kg acetonitrile and 2kg tungstic acid catalyst are placed in a reaction kettle, the reactant is stirred to be uniform by starting stirring, and the temperature of the reaction liquid is controlled at 40 ℃ by starting circulating water. 40kg of hydrogen peroxide with the concentration of 50% is uniformly added into the reaction kettle, and the feeding time is 20min. After the materials are added, the temperature of the reaction kettle is controlled at 40 ℃ through circulating water, and the reaction constant temperature time is 30min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was 89.97% and the selectivity to glyoxal was 43.73% by analysis.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.8kg of platinum-loaded alumina catalyst are added into a reaction kettle, the reaction kettle is heated to 190 ℃, the pressure is increased to 2.5MPa, and after the reaction condition is reached, 4kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. According to analysis, the conversion rate of the glyoxal in the reaction is 29.87%, and the selectivity of the 1, 6-hexanediol reaches 83.00%.
Example 7
16kg of cyclohexene, 55kg of diethyl ether and 2kg of molybdenum disilicide catalyst are placed in a reaction kettle, the reactants are stirred uniformly by starting stirring, and the temperature of the reaction liquid is controlled at 40 ℃ by starting circulating water. 40kg of hydrogen peroxide with the concentration of 50% is uniformly added into the reaction kettle, and the feeding time is 20min. After the materials are added, the temperature of the reaction kettle is controlled at 40 ℃ through circulating water, and the reaction constant temperature time is 30min, so that the reaction liquid containing the glyoxal is obtained. The conversion of cyclohexene in this reaction was found to be 12.54% and the selectivity to glyoxal was found to be 46.14%.
The reaction solution is passed through a filter membrane with the aperture of 1.2 mu m, and then the fraction with the temperature of 92-94 ℃ is obtained through rectification, thus obtaining the glyoxal.
20kg of glyoxal and 0.8kg of palladium-loaded alumina catalyst are added into a reaction kettle, the reaction kettle is heated to 190 ℃, the pressure is increased to 2.5MPa, and after the reaction condition is reached, 2kg of H is added 2 And uniformly introducing the mixture into a reaction kettle, wherein the ventilation time is 2 hours, and obtaining a 1, 6-hexanediol product after the reaction is finished. According to analysis, the conversion rate of the glyoxal in the reaction is 66.76%, and the selectivity of the 1, 6-hexanediol reaches 99.90%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (7)

1. The synthesis method of the 1, 6-hexanediol is characterized by comprising the following steps of:
(1) Placing cyclohexene, a solvent and a catalyst A into a reaction kettle, uniformly mixing and preheating, adding hydrogen peroxide, and preserving heat to obtain a reaction solution;
(2) Filtering the reaction solution, and rectifying the filtrate to obtain a compound A;
(3) Placing the compound A and the catalyst B in a reaction kettle, uniformly mixing and preheating, and continuously introducing hydrogen to carry out hydrogenation reaction to obtain a required product;
the catalyst A is one or more of single-layer molybdenum disulfide, multi-layer molybdenum disulfide, molybdenum selenide, molybdenum disilicide, tungsten oxide, tungsten sulfide and tungstic acid, the average particle size of the catalyst A is 1-200 mu m, and the mass ratio of cyclohexene to the catalyst A is 1:0.01-0.5;
the solvent is one or more of methanol, ethanol, glycol, tertiary butanol, acetonitrile, dimethyl sulfoxide, diethyl ether and acetaldehyde, and the mass ratio of the solvent to cyclohexene is 1-10:1;
the catalyst B is one or more of a nickel-supported alumina catalyst, a Raney nickel catalyst, a platinum-supported alumina catalyst or a palladium-supported alumina catalyst, and the mass ratio of the catalyst B to the compound A is 0.001-0.1:1.
2. The synthesis method according to claim 1, wherein: the concentration of the hydrogen peroxide is 30% -70%, and the mass ratio of the hydrogen peroxide to cyclohexene is 1-3:1.
3. The synthesis method according to claim 1, wherein: the preheating and heat preservation temperature in the step (1) is 10-70 ℃, the adding time of hydrogen peroxide is 10-60min, and the heat preservation time is 20-120min.
4. The synthesis method according to claim 1, wherein: the pore size of the filter membrane used in the step (2) is 0.1-5 μm.
5. The synthesis method according to claim 1, wherein: the fraction collected by rectification in the step (2) is a fraction at 92-94 ℃.
6. The synthesis method according to claim 1, wherein: the mass ratio of the introduced hydrogen to the compound A is 1:3-30.
7. The synthesis method according to claim 1, wherein: the hydrogenation reaction temperature in the step (3) is 120-260 ℃, the pressure of the reaction kettle is 1-5Mpa, and the hydrogenation reaction time is 2h.
CN202111315161.6A 2021-11-08 2021-11-08 Synthesis method of 1, 6-hexanediol Active CN113860989B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111315161.6A CN113860989B (en) 2021-11-08 2021-11-08 Synthesis method of 1, 6-hexanediol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111315161.6A CN113860989B (en) 2021-11-08 2021-11-08 Synthesis method of 1, 6-hexanediol

Publications (2)

Publication Number Publication Date
CN113860989A CN113860989A (en) 2021-12-31
CN113860989B true CN113860989B (en) 2024-04-16

Family

ID=78987472

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111315161.6A Active CN113860989B (en) 2021-11-08 2021-11-08 Synthesis method of 1, 6-hexanediol

Country Status (1)

Country Link
CN (1) CN113860989B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943207A (en) * 2021-11-23 2022-01-18 中国成达工程有限公司 Process for synthesizing butanediol by hydrogenation of succinaldehyde

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB709450A (en) * 1950-10-09 1954-05-26 Du Pont Preparation of adipaldehyde
DE4414274A1 (en) * 1994-04-23 1995-10-26 Chemie Linz Deutschland Alcohol prodn. by catalytic aldehyde hydrogenation
JPH1160524A (en) * 1997-08-13 1999-03-02 Mitsubishi Chem Corp Production of 1,6-hexanediol
CN1222900A (en) * 1996-04-24 1999-07-14 联合碳化化学品及塑料技术公司 Processes for producing 1,6-hexanediols
CN101225022A (en) * 2008-02-13 2008-07-23 上海华谊丙烯酸有限公司 Method for preparing 1,5-pentadiol by hydrogenation of 1,5-glutaraldehyde
CN101270032A (en) * 2008-04-16 2008-09-24 上海华谊丙烯酸有限公司 Method for preparing 1,5-pentanediol
CN108137451A (en) * 2015-10-12 2018-06-08 巴斯夫欧洲公司 For producing the hydroformylation process that 1,6- bis- replaces hexame derivatives
CN110621663A (en) * 2017-06-13 2019-12-27 巴斯夫欧洲公司 Hydroformylation process for the preparation of 1, 6-hexanediol derivatives
CN111138257A (en) * 2019-12-16 2020-05-12 中国科学院大连化学物理研究所 Method for preparing hexanedial
CN112939784A (en) * 2021-02-04 2021-06-11 山西铁峰化工有限公司 Industrial preparation method of hexamethylene diamine

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB709450A (en) * 1950-10-09 1954-05-26 Du Pont Preparation of adipaldehyde
DE4414274A1 (en) * 1994-04-23 1995-10-26 Chemie Linz Deutschland Alcohol prodn. by catalytic aldehyde hydrogenation
CN1222900A (en) * 1996-04-24 1999-07-14 联合碳化化学品及塑料技术公司 Processes for producing 1,6-hexanediols
JPH1160524A (en) * 1997-08-13 1999-03-02 Mitsubishi Chem Corp Production of 1,6-hexanediol
CN101225022A (en) * 2008-02-13 2008-07-23 上海华谊丙烯酸有限公司 Method for preparing 1,5-pentadiol by hydrogenation of 1,5-glutaraldehyde
CN101270032A (en) * 2008-04-16 2008-09-24 上海华谊丙烯酸有限公司 Method for preparing 1,5-pentanediol
CN108137451A (en) * 2015-10-12 2018-06-08 巴斯夫欧洲公司 For producing the hydroformylation process that 1,6- bis- replaces hexame derivatives
CN110621663A (en) * 2017-06-13 2019-12-27 巴斯夫欧洲公司 Hydroformylation process for the preparation of 1, 6-hexanediol derivatives
CN111138257A (en) * 2019-12-16 2020-05-12 中国科学院大连化学物理研究所 Method for preparing hexanedial
CN112939784A (en) * 2021-02-04 2021-06-11 山西铁峰化工有限公司 Industrial preparation method of hexamethylene diamine

Also Published As

Publication number Publication date
CN113860989A (en) 2021-12-31

Similar Documents

Publication Publication Date Title
CN113860989B (en) Synthesis method of 1, 6-hexanediol
CN112321429B (en) Method for continuously preparing bio-based polyol by using micro-channel and multi-stage reaction kettle
CN113416119B (en) Method for synthesizing 4, 4' -dihydroxybiphenyl by adopting loop reactor
CN116621719B (en) Synthesis method of full-biology-based aryl diamine chain extender applied to preparation of polyurethane
CN111215138B (en) Catalyst, preparation method and application of catalyst in preparation of beta-isophorone
CN101381300A (en) Method for synthesizing 2,2-bis(hydroxymenthyl)propinonic acid
CN106866360A (en) A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD
CN114085136B (en) Method for preparing cyclopentanone by catalyzing furfural
CN113667081B (en) Lignin-based polyurethane chain extender and preparation method and application thereof
CN112479823A (en) Method for preparing 4-alkylphenol by auto-reforming hydrogenolysis of lignin or lignin oil
CN113845495B (en) Continuous synthesis method of two-stage glycidyl neodecanoate
CN113956180B (en) Synthesis method of adiponitrile
CN111217660A (en) Method for preparing 2, 6-dimethylanthracene from isoprene and 1, 4-benzoquinone
CN101367904A (en) Synthesis process of bisphenol acid type water soluble phenol resin
CN108299240B (en) Method for preparing isophorone diisocyanate
CN116082170A (en) Preparation method of 4,4' -diaminodiphenyl ether
CN109134259B (en) Bio-based polyol and preparation method and application thereof
CN110963887B (en) Fixed bed reaction process for directly preparing 1, 6-hexanediol from 1, 6-adipic acid
CN114605269B (en) Full-biobased aliphatic bicyclic diamine epoxy resin curing agent, and preparation method and application thereof
CN112142967A (en) Synthesis method of polycaprolactone polyol
CN111592638A (en) Preparation method of high-softening-point light-colored dicyclopentadiene-phenol resin
CN113731393B (en) Preparation method and application of acetone vapor phase condensation aluminum-magnesium composite oxide catalyst
CN111087562A (en) Preparation method of blending modified phenolic resin
CN111704711A (en) Epoxy monomer based on acetal structure and preparation method and application thereof
CN111233655B (en) Method for preparing glutaric acid from aldopentose diacid

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