CN108503520B - Process for synthesizing menthone by reactive distillation - Google Patents

Process for synthesizing menthone by reactive distillation Download PDF

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CN108503520B
CN108503520B CN201810494551.6A CN201810494551A CN108503520B CN 108503520 B CN108503520 B CN 108503520B CN 201810494551 A CN201810494551 A CN 201810494551A CN 108503520 B CN108503520 B CN 108503520B
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menthone
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ruthenium
reactive distillation
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CN108503520A (en
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杨彩花
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Hangzhou Zicheng Biotechnology Co ltd
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    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • 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
    • 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
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Abstract

The invention relates to a process for synthesizing menthone by reactive distillation, which adopts a reactive distillation tower as reaction equipment, realizes asymmetric catalytic hydrogenation by hydrogen transfer of molecules under mild reaction conditions and under the action of a catalyst and an auxiliary agent, avoids the use of hydrogen or a hydrogen donor thereof and an oxidant, can continuously extract products, has obvious continuous operability and economy and has better industrial prospect.

Description

Process for synthesizing menthone by reactive distillation
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a process for synthesizing menthone by reactive distillation.
Background
Menthone (Menthone), molecular formula: C10H18O, alias menthone, dissolved in 3 vol 70% ethanol, dissolved in oily fragrance. Molecular weight 154.25. The density was 0.896g/cm 3. Boiling point 205 ℃. The refractive index is 1.450. Is slightly soluble in water. Is soluble in most organic solvents. Dissolving in 70% ethanol at a ratio of 1:3, and dissolving in oily perfume. Has cool and refreshing fragrance like peppermint, and is retained in the bottom of the costus root. The fragrance is emitted, the fragrance is not lasting, the taste is cool, but the unpleasant bitter taste is also available. Has cool and refreshing fragrance like peppermint, and is retained in the bottom of the costus root.
Menthone, also known as menthone, has the cooling characteristic aroma of natural mint. Menthone exists in the form of two stereoisomers: menthone and isomenthone, each of which exists in the form of two enantiomers, are mainly used for preparing mint-type essences, and thus the synthesis of menthone has been receiving attention.
Patent US3124614 reports that menthone can be obtained by hydrogenation of thymol under the action of Pd catalyst, but raw material thymol is not easily available, reaction conditions are severe, and requirements for equipment are high.
Patent CN106061933A reports a method for preparing menthone by contacting isopulegol in gas phase with activated oxidized copper catalyst, in the method, the copper catalyst needs to be pre-activated, the pre-activation method is complicated, the activation effect has a large influence on the reaction yield, and the method is not suitable for large-scale industrial production.
Patent CN104603095A uses a metal complex containing phosphine ligands as catalyst. The process can achieve a menthone yield of more than 85%, but cannot achieve high revolution per revolution (TON), has short catalyst life, and is not suitable for industrial synthesis of menthone in consideration of high cost of the catalyst.
Patent CN106068160A describes a ruthenium-phenol catalyst for transfer hydrogenation reaction and the catalyst has excellent performance in transfer hydrogenation reaction, and the catalyst is used for preparing menthone from isopulegol, and has higher conversion rate and selectivity. However, the process has a limited increase in the number of revolutions per minute (TON), the catalyst life is still short, and a large amount of phenol derivative is used, which has adverse effects on the post-treatment and the environment.
Therefore, a method which is simple in process, mild in reaction conditions, economical, efficient, environment-friendly and easy to realize industrialization is urgently needed to realize the preparation of menthone.
Disclosure of Invention
The invention aims to provide a method for preparing menthone by reactive distillation, so that various problems in the existing menthone preparation process are solved. The term "menthone" refers to any possible stereoisomer, if not otherwise specified.
A process for synthesizing menthone by reactive distillation is characterized by comprising the following steps:
(1) putting isopulegol into a preheater, and heating to 80-90 ℃;
(2) introducing preheated isopulegol and an auxiliary agent into a reactive distillation column, controlling the vacuum degree in the column to be-0.1 to-0.15 Mpa, controlling the temperature of a reboiler to be 120 plus 130 ℃, enabling menthone to be fully contacted with a catalyst on the surface of a packing layer on a column plate to carry out molecular hydrogen transfer to realize asymmetric catalytic hydrogenation, and carrying out distillation by adopting a reflux ratio of 4-5: 1; when the quality of the extracted menthone material part meets the product requirement, the menthone material part is cooled in a cooler, normal-temperature circulating water is filled in the cooler, and finally the menthone material part enters a finished product storage tank to obtain the finished product menthone.
The height of the reactive distillation column is 20-25 m, the diameter of the column DN is DN250-300, and the packing is stainless steel corrugated wire mesh and catalyst.
The catalyst is a ruthenium-loaded catalyst Ru/CNTS, the weight content of Ru is 5-10% of the total mass of the catalyst,
further, the preparation method of the Ru/CNTS catalyst comprises the following steps:
1) weighing a certain amount of carbon nano tubes with the outer diameter of 2-6 nm, and adding HNO with the mass fraction of 30-50%320-50 ml of solution and 15% of H by mass fraction2O2And heating and refluxing the solution at 100-120 ℃ for 2-3 h, taking out, cooling to room temperature, washing, filtering, and drying by a conventional method to obtain the surface-modified carbon nanotube.
2) In the dipping reduction process, the modified carbon nano tube material is crushed, dipped in ruthenium salt water solution for 12 to 24 hours, reduced by a reducing agent, washed to be neutral by deionized water, and dried to obtain a ruthenium catalyst;
3) in the roasting process of the ruthenium catalyst, roasting the ruthenium catalyst to obtain an oxidized ruthenium-based catalyst;
4) adding the oxidized ruthenium-based catalyst obtained in the step 3) into a reaction kettle, introducing hydrogen to replace reaction gas, and carrying out hydrogenation activation at the reaction temperature of 10-40 ℃, preferably 20-30 ℃, maintaining the reaction gauge pressure of 0-1.0 MPaG, preferably 0.1-0.5 MPaG, wherein the reaction time is 6-24 h, preferably 8-12 h.
Preferably, in the step 2), the ruthenium salt is ruthenium trichloride or sodium ruthenium chloride or ruthenium carbonyl chloride, and the concentration of the ruthenium salt is 5-15 g/L.
Preferably, in the step 2), the reducing agent is one of hydrazine hydrate, potassium borohydride and formaldehyde.
Preferably, in the step 3), the roasting temperature is set to be 200-600 ℃, and the roasting time is set to be 3-5 hours.
In the invention, the auxiliary agent is selected from one or more of norbornadiene, cyclopentene, cyclopentadiene, pentamethylcyclopentadiene, ethylcyclopentadiene, cyclooctene, cyclooctadiene, cyclooctatetraene, cycloheptene and cymene, and cyclopentadiene and/or cyclooctadiene are preferred.
The proportion of isomenthone in the product finally obtained by the reaction is 10 to 20 mol%, preferably 10 mol%.
In the invention, the ratio of the solvent to the oil is 0.0001-l percent, preferably 0.001-0.1 percent calculated by the amount of the substance of isopulegol; the molar ratio of the auxiliary agent to the homogeneous catalyst is (0.01-10): 1, preferably (0.1 to 4): 1.
preferably, the chemical selectivity of the final reaction product is 95-99%, and the conversion rate can reach 90-99.9%.
The method has the beneficial effects that:
1) under the action of a catalyst and an auxiliary agent under mild reaction conditions, asymmetric catalytic hydrogenation is realized through hydrogen transfer of molecules, the use of hydrogen or a hydrogen donor thereof and an oxidant is avoided, and meanwhile, a reaction rectifying tower is adopted to continuously extract products, so that the method has remarkable continuous operability and economy; and in addition, other solvents are not involved in the system, so that the introduction of other impurities is reduced, and the method has good environmental friendliness.
2) The auxiliary agent can reduce the loss of transition metal in the reaction process and obviously improve the stability of a catalytic system; the system does not add solvent, further simplifies the post purification treatment of reaction products, obviously reduces three wastes and has better industrialization prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
[ example 1 ]
1) Weighing a certain amount of carbon nano tubes with the outer diameter of 2nm, and adding 35% of HNO (HNO)3Solution and 20ml of 15% H2O2Heating and refluxing the solution at 100 ℃ for 2-3 h, taking out, cooling to room temperature, washing, filtering, and drying by a conventional method to obtain a surface-modified carbon nanotube;
2) the dipping reduction process comprises the steps of crushing the modified carbon nano tube material, dipping the crushed carbon nano tube material in a ruthenium trichloride aqueous solution with the concentration of 5g/L for 12 hours, reducing the crushed carbon nano tube material by using a reducing agent hydrazine hydrate, potassium borohydride and formaldehyde, washing the obtained product to be neutral by using deionized water, and drying the obtained product to obtain a ruthenium catalyst;
3) in the roasting process of the ruthenium catalyst, roasting the ruthenium catalyst at the roasting temperature of 500 ℃ for 3-5 hours to obtain a ruthenium-based catalyst with ruthenium surface oxidized;
4) adding the oxidized ruthenium-based catalyst obtained in the step 3) into a reaction kettle, introducing hydrogen to replace reaction gas, and carrying out hydrogenation activation at the reaction temperature of 20 ℃, maintaining the reaction gauge pressure of 0-1.0 MPaG, preferably 0.2MPaG, and the reaction time of 12h to obtain the Ru/CNTS catalyst with the Ru content of 5.1%.
[ example 2 ]
1) Weighing a certain amount of carbon nano tubes with the outer diameter of 2nm, and adding 35% of HNO (HNO)3Solution and 20ml of 15% H2O2Heating and refluxing the solution at 100 ℃ for 2-3 h, taking out, cooling to room temperature, washing, filtering, and drying by a conventional method to obtain a surface-modified carbon nanotube;
2) the dipping reduction process comprises the steps of crushing the modified carbon nano tube material, dipping the crushed carbon nano tube material in a ruthenium trichloride aqueous solution with the concentration of 10g/L for 18 hours, reducing the crushed carbon nano tube material by using a reducing agent potassium borohydride, washing the crushed carbon nano tube material to be neutral by using deionized water, and drying the washed carbon nano tube material to obtain a ruthenium catalyst;
3) in the roasting process of the ruthenium catalyst, roasting the ruthenium catalyst, wherein the roasting temperature is set to be 600 ℃ and 5 hours, and obtaining the ruthenium-based catalyst with oxidized ruthenium surface;
4) adding the oxidized ruthenium-based catalyst obtained in the step 3) into a reaction kettle, introducing hydrogen to replace reaction gas, and carrying out hydrogenation activation at the reaction temperature of 30 ℃, maintaining the reaction gauge pressure of 0.5MPaG and the reaction time of 6h to obtain the Ru/CNTS catalyst with the Ru content of 8.7%.
[ example 3 ]
Catalytic synthesis of menthone:
a method for preparing menthone by reactive distillation comprises the following steps:
(1) putting isopulegol into a preheater, and heating to 80 ℃;
(2) introducing preheated isopulegol and auxiliary agents of norbornadiene and cyclooctadiene into a reaction rectifying tower, controlling the vacuum degree in the tower at-0.15 Mpa, controlling the temperature of a reboiler at 120 ℃, fully contacting menthone on a tower plate with a catalyst on the surface of a packing layer to carry out molecular hydrogen transfer to realize asymmetric catalytic hydrogenation, and rectifying by adopting a reflux ratio of 4: 1; when the quality of the extracted menthone material part meets the product requirement, the menthone material part is cooled in a cooler, normal-temperature circulating water is filled in the cooler, and finally the menthone material part enters a finished product storage tank to obtain the finished product menthone.
Calculated by the amount of substances of isopulegol, the ratio of the solvent to the oil is 0.1 percent; the molar ratio of the auxiliary agent to the homogeneous catalyst is 4: 1.
the height of the reactive distillation column is 20m, the diameter of the column is DN250, and the packing is stainless steel corrugated wire mesh and catalyst; the catalyst is the Ru/CNTS catalyst prepared in example 1 and having 5.1% Ru content.
The conversion and menthol yield were determined by calibration GC analysis and the results are shown in table 1.
[ example 4 ]
Catalytic synthesis of menthone:
a method for preparing menthone by reactive distillation comprises the following steps:
(1) putting isopulegol into a preheater, and heating to 90 ℃;
(2) introducing preheated isopulegol, auxiliary agents namely cyclopentadiene and cyclooctatetraene into a reaction rectifying tower, controlling the vacuum degree in the tower at-0.1 Mpa, controlling the temperature of a reboiler at 130 ℃, fully contacting menthone on a tower plate with a catalyst on the surface of a filler layer to carry out hydrogen transfer of molecules to realize asymmetric catalytic hydrogenation, and rectifying by adopting a reflux ratio of 5: 1; when the quality of the extracted menthone material part meets the product requirement, the menthone material part is cooled in a cooler, normal-temperature circulating water is filled in the cooler, and finally the menthone material part enters a finished product storage tank to obtain the finished product menthone.
Calculated by the amount of substances of isopulegol, the ratio of the solvent to the oil is 0.01 percent; the molar ratio of the auxiliary agent to the homogeneous catalyst is 0.1: 1.
the height of the reactive distillation column is 25 m, the diameter of the column is DN300, and the packing is stainless steel corrugated wire mesh and catalyst; the catalyst was the Ru/CNTS catalyst prepared in example 7 with a Ru content of 8.7%.
The conversion and menthol yield were determined by calibration GC analysis and the results are shown in table 1.
[ example 4 ]
Catalytic synthesis of menthone:
a method for preparing menthone by reactive distillation comprises the following steps:
(1) putting isopulegol into a preheater, and heating to 90 ℃;
(2) introducing preheated isopulegol and auxiliary agent cyclopentadiene into a reactive distillation tower, controlling the vacuum degree in the tower at-0.1 Mpa, controlling the temperature of a reboiler at 130 ℃, fully contacting menthone on a tower plate with a catalyst on the surface of a filler layer to carry out molecular hydrogen transfer to realize asymmetric catalytic hydrogenation, and carrying out distillation by adopting a reflux ratio of 5: 1; when the quality of the extracted menthone material part meets the product requirement, the menthone material part is cooled in a cooler, normal-temperature circulating water is filled in the cooler, and finally the menthone material part enters a finished product storage tank to obtain the finished product menthone.
Calculated by the amount of substances of isopulegol, the ratio of the solvent to the oil is 0.01 percent; the molar ratio of the auxiliary agent to the homogeneous catalyst is 0.1: 1.
the height of the reactive distillation column is 25 m, the diameter of the column is DN300, and the packing is stainless steel corrugated wire mesh and catalyst; the catalyst was the Ru/CNTS catalyst prepared in example 7 with a Ru content of 8.7%.
The conversion and menthol yield were determined by calibration GC analysis and the results are shown in table 1.
Comparative example 1
Catalyzing and synthesizing menthone.
The palladium-ruthenium catalyst prepared in example 1 and isopulegol were all put into a dry 500ml autoclave, high-purity nitrogen gas was introduced to maintain the absolute pressure of the reaction at 4Mpa, and the mixture was heated to 130 ℃ and stirred for 50 hours. The conversion and menthol yield were determined by calibration GC analysis and the results are shown in table 1.
TABLE 1
Figure GDA0001740862720000071
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.

Claims (10)

1. A process for synthesizing menthone by reactive distillation is characterized by comprising the following steps:
(1) putting isopulegol into a preheater, and heating to 80-90 ℃;
(2) introducing preheated isopulegol and an auxiliary agent into a reaction rectifying tower, controlling the vacuum degree in the tower to be-0.1-0.15 Mpa, controlling the temperature of a reboiler to be 120-130 ℃, enabling the isopulegol to be fully contacted with a catalyst on the surface of a packing layer on a tower plate to carry out molecular hydrogen transfer to realize asymmetric catalytic hydrogenation, and rectifying by adopting a reflux ratio of 4-5: 1; when the quality of the extracted menthone material part meets the product requirement, the menthone material part is cooled in a cooler, normal-temperature circulating water is filled in the cooler, and finally the menthone material part enters a finished product storage tank to obtain a finished product menthone; the catalyst is a supported ruthenium catalyst Ru/CNTS;
the auxiliary agent is selected from one or more of norbornadiene, cyclopentene, cyclopentadiene, pentamethylcyclopentadiene, ethylcyclopentadiene, cyclooctene, cyclooctadiene, cyclooctatetraene and cycloheptene;
the preparation method of the Ru/CNTS catalyst comprises the following steps:
1) weighing a certain amount of carbon nano tubes with the outer diameter of 2-6 nm, and adding HNO with the mass fraction of 30-50%320-50 ml of solution and 15% of H by mass fraction2O2Heating and refluxing the solution at 100-120 ℃ for 2-3 h, taking out, cooling to room temperature, washing, filtering, and drying by a conventional method to obtain a surface-modified carbon nanotube;
2) in the dipping reduction process, the modified carbon nano tube material is crushed, dipped in ruthenium salt water solution for 12 to 24 hours, reduced by a reducing agent, washed to be neutral by deionized water, and dried to obtain a ruthenium catalyst;
3) in the roasting process of the ruthenium catalyst, roasting the ruthenium catalyst to obtain an oxidized ruthenium-based catalyst;
4) adding the oxidized ruthenium-based catalyst obtained in the step 3) into a reaction kettle, introducing hydrogen to replace reaction gas, and carrying out hydrogenation activation at the reaction temperature of 10-40 ℃, maintaining the reaction gauge pressure of 0-1.0 MPaG, wherein the reaction time is 6-24 h.
2. The reactive distillation process for synthesizing menthone according to claim 1, characterized in that: the height of the reactive distillation column is 20-25 m, the diameter of the column DN is DN250-300, and the packing is stainless steel corrugated wire mesh and catalyst.
3. The reactive distillation process for synthesizing menthone according to claim 1, characterized in that: the Ru/CNTS catalyst comprises 5-10% of Ru by weight based on the total mass of the catalyst;
the auxiliary agent is selected from cyclopentadiene and/or cyclooctadiene.
4. The reactive distillation process for synthesizing menthone according to claim 1, characterized in that: calculated by the amount of the substance of the isopulegol, the agent-oil ratio is 0.0001 percent to l percent; the molar ratio of the auxiliary agent to the heterogeneous catalyst is (0.01-10): 1.
5. the reactive distillation process for synthesizing menthone according to claim 1, characterized in that: the chemical selectivity of the final reaction product is 95-99%, and the conversion rate reaches 90-99.9%.
6. The reactive distillation process for synthesizing menthone according to claim 1, characterized in that: in the step 2) of the preparation method of the Ru/CNTS catalyst, the ruthenium salt is ruthenium trichloride or sodium ruthenium chloride or ruthenium carbonyl chloride, and the concentration of the ruthenium salt is 5-15 g/L.
7. The reactive distillation process for synthesizing menthone according to claim 1, characterized in that: in step 2) of the preparation method of the Ru/CNTS catalyst, the reducing agent is one of hydrazine hydrate, potassium borohydride and formaldehyde.
8. The reactive distillation process for synthesizing menthone according to claim 1, characterized in that: in the step 3) of the preparation method of the Ru/CNTS catalyst, the roasting temperature is set to be 200-600 ℃, and the roasting time is set to be 3-5 hours.
9. The reactive distillation process for synthesizing menthone according to claim 4, characterized in that: calculated by the amount of substances of isopulegol, the agent-oil ratio is 0.001 to 0.1 percent; the molar ratio of the auxiliary agent to the catalyst is (0.1-4): 1.
10. the reactive distillation process for synthesizing menthone according to claim 1, characterized in that: in the step 4) of the preparation method of the Ru/CNTS catalyst, hydrogenation activation is carried out, the reaction temperature is 20-30 ℃, the reaction gauge pressure is maintained at 0.1-0.5 MPaG, and the reaction time is 8-12 h.
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