CN108863738B

CN108863738B - Method for preparing cyclopentanone

Info

Publication number: CN108863738B
Application number: CN201710317284.0A
Authority: CN
Inventors: 陈长生; 杨恒东; 胡江林; 黎源; 曾伟; 丁可; 王坤; 刘运海
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2017-05-08
Filing date: 2017-05-08
Publication date: 2021-09-07
Anticipated expiration: 2037-05-08
Also published as: CN108863738A

Abstract

The invention provides a method for preparing cyclopentanone. The method comprises the following steps: the method comprises the following steps of isomerizing and hydrogenating furfural into cyclopentanone under the action of hydrogen, carbon dioxide and a catalyst under the conditions of certain reaction temperature and reaction pressure. The reaction is preferably carried out in a mixture of water and the oxygen-containing heterocyclic compound as a solvent. The method of the invention improves the selectivity of cyclopentanone, avoids the adhesion of furfural and/or furfuryl alcohol polymers on the surface of the catalyst, and prolongs the service life of the catalyst.

Description

Method for preparing cyclopentanone

Technical Field

The invention relates to a method for preparing cyclopentanone. In particular to a method for preparing biological cyclopentanone by taking a biological-based platform compound furfural as a raw material.

Background

Cyclopentanone is an important intermediate in the perfume and pharmaceutical industry, and can be used for producing novel perfumes methyl dihydrojasmonate, albronone, and fine chemical products such as anxiolytic buspirone. Can also be used for synthesizing pesticides such as insecticides and herbicides. In addition, cyclopentanone has good solubility and is widely used as a solvent in the electronic industry. The annual demand of cyclopentanone worldwide reaches ten thousand tons.

The synthesis method of cyclopentanone is various, and the conventional synthesis of cyclopentanone is to cyclize adipic acid into cyclopentanone under the action of a catalyst. The method uses acid raw materials, has corrosion effect on equipment, and cyclopentanone is easy to polymerize in the reaction process. In recent years, the research on the production of cyclopentanone from C5 fraction has attracted considerable interest. The current research direction mainly focuses on two processes, namely a direct cyclopentene oxidation process and an indirect cyclopentene hydration process. However, the direct oxidation of cyclopentene is a homogeneous reaction, which makes the separation of catalyst difficult, and has some unsolved problems in process or engineering.

With the depletion of petroleum resources, the development of bio-based chemicals is gradually becoming a trend. Cyclopentanone is a direct human contact field due to its downstream application fields. Such as perfume, the development of bio-based cyclopentanone meets both the development trend and the market demand.

Fang et al (Ruiqi Fang, Hongli Liu, Rafael Luque, Yingwei Li. effective and selective hydrogenation of biological derivative furfuel to cyclic utilization Ru catalysts [ J ]. Green Chemistry,2015,17:4183-4188.) studied the process of Ru catalysts for furfural (FFA) to prepare Cyclopentanone (CPO), including in particular the screening of the Ru content of the catalysts, the comparison of different carriers, the investigation of different temperatures and pressures, the number of times the catalysts can be reused, and the detailed description of the catalytic mechanism and reaction route. Under the condition of a preferable 3 wt% Ru/MIL-101 catalyst and water as a solvent, the furfural conversion rate is up to more than 99% and the cyclopentanone selectivity is up to 96% under the conditions of 160 ℃, 4MPa and 2.5h of reaction.

Zhu et Al (Hongyan Zhu, Minghao Zhuu, Zhuo Zeng, Guomin Xiao, Rui Xiao. Selective hydrogenation of Cu-Ni-Al hydrotalcite-based catalysts [ J ]. Korean J.chem.Eng., 31,593-597.) studied the effect of Cu-Ni-Al hydrotalcite catalysts on FFA CPO production, analyzed the molar ratio of Cu, Ni, Al in detail, optimized composition was optimized, and examined the relevant process conditions including reaction time, reaction temperature, pressure and catalyst amount based on the above, finally the catalyst repeatability was verified, and the corresponding conclusion was reached. The catalyst is also characterized and the reaction process is briefly outlined. Under the catalysis of Cu-Ni-Al hydrotalcite, water is used as a solvent, the reaction is carried out for 8 hours at 140-160 ℃ and 40bar, the conversion rate of furfural is up to 100%, and the selectivity of cyclopentanone is up to 95.8%.

Patent CN104069886A discloses a preparation method of a catalyst for preparing cyclopentanone by aqueous phase furfural hydrogenation, which comprises the steps of firstly, utilizing one-step hydrothermal crystallization to synthesize a hierarchical pore Y-shaped molecular sieve carrier in situ, and then preparing a molecular sieve supported catalyst by an impregnation method. Under the conditions that the temperature is 120-200 ℃, the hydrogen pressure is 2-6 MPa, and the reaction time is 6-12 h, the conversion rate of furfural and the selectivity of cyclopentanone are both as high as 98%.

Patent CN103111299A discloses a method for preparing a supported catalyst for preparing cyclopentanone by furfural hydrogenation, wherein the preparation method of the catalyst is a double-dropper coprecipitation method, and the method is simple to operate, wide in source and strong in flexibility. The catalysis furfural has obvious effect on preparing cyclopentanone. The conversion rate of furfural is as high as 98.5% and the selectivity of cyclopentanone is as high as 96.7% under the conditions of 160 ℃ of temperature, 6MPa of hydrogen pressure and 8 hours of reaction by using water as a solvent.

Patent CN102875334A discloses a synthesis method for synthesizing cyclopentanol and cyclopentanone by taking furfural as a raw material and carrying out catalytic one-step reaction on the furfural and nickel catalysts such as Raney nickel, wherein water and aliphatic alcohol (preferably methanol) are used as solvents, the reaction temperature is 150-230 ℃, the hydrogen pressure is 0-4 MPa, and the reaction time is 4 hours; the furfural: fatty alcohol: the mass ratio of water is 1: 2.5-40: 20-140; the dosage of the catalyst is 1.2-1.5% of the mass of the reaction stock solution consisting of furfural, fatty alcohol and water. The total yield of the cyclopentanone and the cyclopentanol prepared by the method can reach more than 52 percent.

The techniques referred to in the above documents, although reported results can vary from 90 to 99% yield of cyclopentanone. However, in the above technology, it is neglected that furfural and furfuryl alcohol are polymerized in a reactor during the reaction process, furfural and/or furfuryl alcohol are easily polymerized to form a polymer with a multi-furan ring, and the polymer of the type does not peak on gas chromatography. The technology does not solve the problem of polymerization of furfural and/or furfuryl alcohol, so that on one hand, the actual yield of cyclopentanone is far less than 90-99%; on the other hand, as the reaction usually adopts noble metal as a catalyst, after the catalyst is used once, the catalyst cannot be reused due to the fact that furfural and/or furfuryl alcohol polymer is attached to the surface of the catalyst, so that the cost of the catalyst is too high; in addition, the production of polymer also increases the difficulty of catalyst filtration, and the isolation yield of the product is low due to the presence of a large amount of polymer. The above defects hinder the industrialization of the technology for preparing cyclopentanone by a furfural method.

Disclosure of Invention

The invention aims to provide a method for preparing cyclopentanone. The method can effectively avoid the generation of furfural and/or furfuryl alcohol polymers in the reaction process, and simultaneously keep higher cyclopentanone yield. The method has an industrial prospect.

In order to achieve the technical purpose, the following technical scheme is adopted:

a process for the preparation of cyclopentanone, comprising the steps of: the furfural is isomerized and hydrogenated into cyclopentanone under the action of hydrogen, carbon dioxide and a catalyst and under certain temperature and pressure conditions.

According to the method of the invention, the catalyst used is a supported catalyst. The catalyst comprises a main active component, a cocatalyst component and a carrier.

According to the method, the main active component of the catalyst is one or more of Au, Pd, Pt and Ru.

According to the method, the promoter component is one or more of Ni, Co, Fe and Cu.

According to the process of the invention, the support of the catalyst may be TiO₂、Al₂O₃、SiO₂And molecular sieves and the like.

Suitable examples of the molecular sieve according to the process of the present invention include, but are not limited to, 3A, 4A, 5A, 10X, 13X, ZSM-5, and the like types of molecular sieves.

According to the method of the invention, the catalyst can be any combination of the above main active component, cocatalyst component and carrier.

According to the method of the invention, the catalyst is preferably Au-Ni/TiO₂、Au-Cu/SiO₂、Pt-Fe/TiO₂、Pt-Co/Al₂O₃Ru-Cu/molecular sieves; preferably Au-Ni/TiO₂、Pt-Co/Al₂O₃(ii) a More preferably Au-Ni/TiO₂。

According to the method of the invention, the proportion of the main active component of the catalyst in the whole mass of the catalyst is 0.1-0.6%, preferably 0.3-0.5%.

According to the process of the invention, the co-catalyst component of the catalyst is present in a proportion of 0.01 to 0.1%, preferably 0.05 to 0.075%, by mass of the catalyst as a whole.

According to the method, the catalyst is prepared by a conventional impregnation method.

According to the method of the invention, the impregnation process generally comprises the following steps: according to the proportion, firstly, the solution containing the salt of the main active component and the salt of the auxiliary catalyst component is heated to 60-90 ℃, and the pH value of the solution is adjusted to 6.5-7.5; then adding a carrier into the solution, and adjusting the pH value of the solution to 6.5-7.5; fully mixing the mixture at 60-90 ℃ for 2-4 hours, then cooling, filtering and washing to obtain filter residue, drying for 12-24 hours and calcining at 350-550 ℃ for 2-4 hours to obtain the catalyst.

According to the method, the furfural is subjected to isomerization hydrogenation to cyclopentanone under the action of the catalyst and at a certain temperature and pressure.

According to the method of the present invention, the reaction temperature is 120-160 ℃. Preferably 130 ℃ and 150 ℃.

According to the process of the invention, the reaction pressure is from 1 to 5MPa (G), preferably from 2 to 4MPa (G).

According to the method of the invention, the reactor can be a tank reactor or a fixed bed reactor, preferably a tank reactor, preferably a continuous or semi-continuous tank reactor.

According to the method, the concentration of the furfural in a reaction system in the reactor is ensured to be not more than 0.01wt% by controlling the furfural feeding rate/the quality of the catalyst.

According to the process of the invention, the furfural feed rate per catalyst mass does not exceed 4g furfural/(g catalyst x h).

According to the process of the present invention, the isomerization hydrogenation is preferably carried out in the presence of a solvent.

According to the method, the raw material furfural can be directly fed without being diluted by a solvent, or can be fed in the form of a furfural solution after being diluted by the solvent.

According to the method of the present invention, the solvent comprises at least water.

Preferably, according to the method of the present invention, the solvent comprises at least one oxygen-containing heterocyclic compound in addition to water, and the oxygen-containing heterocyclic compound includes but is not limited to: one or more of dioxane, tetrahydrofuran and tetrahydropyran.

According to the method of the present invention, the solvent is preferably a mixture of water and dioxane, a mixture of water and tetrahydrofuran, a mixture of water and tetrahydropyran, or the like, preferably a mixture of water and dioxane, a mixture of water and tetrahydrofuran.

According to the method of the invention, the mass ratio of water to the oxygen-containing heterocyclic compound in the solvent is 10:1 to 1:10, preferably 2:1 to 1: 2.

According to the method, the mass sum of the furfural and the reaction product thereof accounts for no more than 50% of the mass fraction of the reaction system.

According to the process of the present invention, it is preferred that the carbon dioxide and hydrogen are thoroughly mixed before entering the reactor. The volume content of carbon dioxide in the mixed gas of carbon dioxide and hydrogen in the reactor is 1-100ppm, preferably 20-60 ppm.

According to the method, water and the oxygen-containing heterocyclic compound form a microscopic two-phase, wherein the water coats the catalyst, furfural or furfuryl alcohol is subjected to isomerization and hydrogenation reactions in a microscopic water-phase layer containing water on the surface of the catalyst, and carbon dioxide is dissolved in a water phase, so that the microscopic water phase is weakly acidic, and the selectivity of cyclopentanone is improved; in addition, as the furfural and/or furfuryl alcohol are extremely unstable, polymerization reaction can occur under the reaction condition, compared with a water phase, a polymerization product has higher solubility in an oxygen-containing heterocyclic compound phase, and a generated polymer can be timely transferred to the oxygen-containing heterocyclic compound phase, so that the condition that the polymer is attached to the surface of the catalyst to cause the rapid inactivation of the catalyst is avoided.

According to the method disclosed by the invention, a system consisting of carbon dioxide, water, oxygen-containing heterocyclic compounds and reaction raw materials (products) is particularly favorable for the isomerization hydrogenation of furfural and/or furfuryl alcohol to generate cyclopentanone, the yield of cyclopentanone in the reaction process is high, and the service life of the catalyst is long.

Detailed Description

The present invention is further illustrated by the following specific examples, which should be understood by those skilled in the art, but not limited thereto.

The quantitative analysis of cyclopentanone in the following examples was carried out on an Agilent-7980 gas chromatograph under the following conditions:

a chromatographic column: agilent HP-5 (specification of 30m × 0.32mm × 0.25mm)

Sample inlet temperature: 280 deg.C

The split ratio is as follows: 30:1

Column flow rate: 1.5ml/min

Column temperature: starting: 100 deg.C

The heating rate is as follows: raising the temperature to 260 ℃ at a rate of 15 ℃/min, and keeping the temperature for 8min after the temperature is 260 DEG C

Detector temperature: 280 deg.C

H₂Flow rate: 35ml/min

Air flow rate: 350ml/min

And determining the concentration of cyclopentanone in the reaction solution by adopting an external standard method, wherein the concentration of cyclopentanone is determined to be X by adopting the external standard method, and the proportion of the cyclopentanone in the gas chromatography normalized area is Y. The mass W of the corresponding furfural is:

w is M X/Y; wherein W represents the mass of furfural required for the production of cyclopentanone, M represents the mass of the reaction solution, X represents the concentration of cyclopentanone in the reaction solution determined by an external standard method, and Y represents the proportion of the normalized area of cyclopentanone in a gas chromatograph.

Yield of polymer N ═ W₀-W)/W₀Wherein W is₀The mass of the raw material furfural.

The preparation method of the catalyst comprises the following steps:

the catalysts in the examples were prepared by using HAuCl in an amount of 10 wt% in accordance with the amounts of the raw materials in Table 1₄Aqueous solution and 10 wt% NiNO₃The aqueous solution was heated with stirring, and when the temperature reached 80 ℃, 0.2M NaOH solution was added to the solution until the pH of the solution reached 7. Then adding TiO in anatase form₂And stirred well. To the mixture was added dropwise NaOH at a concentration of 0.2M until the pH reached 7. The mixture was stirred at 80 ℃ for 2 hours. Then cooling to 25 ℃, filtering, and washing the filter residue with deionized water until no Cl ions are detected in the washing water. The filter residue was collected and placed in a vacuum oven at 25 ℃ for 12 hours and then calcined in a muffle at 350 ℃ for 2 hours.

By the above method, Au-Ni/TiO with the composition shown in Table 1 was prepared₂A catalyst.

TABLE 1 feed and catalyst compositions

Example 1

2kg of a solvent (water: tetrahydrofuran 2:1, mass ratio) was charged into a 10L 316L stainless steel autoclave equipped with a stirrer, and about 50g of 1# Au-Ni/TiO was added₂A catalyst. The reactor was sealed and replaced three times with 1MPa nitrogen and three times with 1MPa hydrogen containing 50ppm carbon dioxide. Then the reaction kettle is started to stir for 600 revolutions per minute, the temperature in the reaction kettle is increased to 130 ℃, the pressure in the reaction kettle is increased to 3MPa by utilizing the hydrogen containing 50ppm of carbon dioxide, and then a hydrogen gas source is switched from the hydrogen containing 50ppm of carbon dioxide to the hydrogen containing 99.999 percent of purity and no CO₂Hydrogen (c) is used. Then furfural is added into the reaction kettle at the speed of 200g/h by using a high-pressure advection pump, and the temperature of the reaction kettle is kept at 130 ℃ and the pressure is kept at 3Mpa (G) in the process. The reaction was stopped after 10 hours. Sampling analysis shows that the yield of cyclopentanone is about 98% and the polymer is less than 0.01%.

Examples 2 to 6

The other conditions were the same as in example 1, the other conditions were changed to the parameters shown in the following table, and the reaction product was sampled and analyzed and the product was separated by rectification to obtain cyclopentanone product. The experimental conditions and the analysis results are shown in table 2 below.

Table 2 examples 2-6 reaction conditions and results

Note: THF: tetrahydrofuran DOX: dioxane (dioxane)

Example 8

2kg of solvent (THF/water ratio 1: 1) was added to a 10L 316L stainless steel autoclave equipped with a stirrer, and about 50g of 1# Au-Ni/TiO₂A catalyst. The reactor was sealed and replaced three times with 1MPa nitrogen and three times with 1MPa hydrogen containing 50ppm carbon dioxide. The reactor was then started to stir at 600 rpm and the temperature in the reactor was raised to 130 ℃ and the pressure was raised to 3 MPa. Adding a furfural solution (the mass ratio of furfural to solvent is 1:1, and the solvent is a mixture of THF and water with the mass ratio of 1: 1) at the speed of 200g/h, and continuously extracting cyclopentanone reaction mother liquor by controlling the liquid level of the reaction kettle to be unchanged. The content of carbon dioxide in the gas phase in the reaction kettle is detected through an online gas detection device on the reaction kettle, and the content of carbon dioxide in the gas phase in the reaction kettle is kept at 50ppm through the switch of a carbon dioxide flow control valve. The temperature of the reactor was maintained at 130 ℃ and the pressure at 3MPa during this time. The reaction was stopped after 500 hours. The reaction solution was sampled every 50 hours. The results are shown in Table 3.

Table 3 example 8 reaction results

Comparative example 1

The conditions were the same as in example 1, except that the catalyst was made of 50g of 1# Au-Ni/TiO₂The catalyst is changed into 50g of No. 4 Au/TiO₂A catalyst. The reaction was stopped after 10 hours. Sampling analysis showed cyclopentanone yield of about 88% in the product, with about 10% polymer.

Comparative example 2

The conditions were the same as in example 8 except that the solvent used was only water and no tetrahydrofuran was included.

The reaction was stopped after 200 hours. The reaction solution was sampled every 20 hours. The results are shown in Table 4.

Table 4 reaction results of comparative example 2

Comparative example 3

2kg of a solvent (water: tetrahydrofuran 2:1, mass ratio) was charged into a 10L 316L stainless steel autoclave equipped with a stirrer, and about 50g of 1# Au-Ni/TiO was added₂A catalyst. The reactor was sealed and replaced three times with 1Mpa nitrogen and three times with 1Mpa 99.999% hydrogen. Then starting the reaction kettle, stirring to 600 revolutions per minute, raising the temperature in the reaction kettle to 130 ℃, raising the pressure in the reaction kettle to 3MPa by using hydrogen, then adding furfural into the reaction kettle at a speed of 200g/h by using a high-pressure advection pump, and keeping the temperature of the reaction kettle at 130 ℃ and the pressure at 3MPa (G) in the process. The reaction was stopped after 10 hours. Sampling analysis shows that the yield of cyclopentanone in the product is about 88% and the polymer is about 10%.

Claims

1. A process for the preparation of cyclopentanone, comprising the steps of: isomerizing and hydrogenating furfural into cyclopentanone under the action of hydrogen, carbon dioxide and a catalyst and under certain reaction temperature and reaction pressure conditions; the volume content of the carbon dioxide in the mixed gas of the hydrogen and the carbon dioxide is 20-100ppm, the reaction is carried out in the presence of a solvent, and the solvent is selected from a mixture of water and an oxygen-containing heterocyclic compound; the oxygen-containing heterocyclic compound is selected from one or more of dioxane, tetrahydrofuran and tetrahydropyran;

the catalyst comprises a main active component, a cocatalyst component and a carrier; the main active component is selected from one or more of Au, Pd, Pt and Ru; the promoter component is selected from one or more of Ni, Co, Fe and Cu; the carrier is selected from TiO₂、Al₂O₃、SiO₂And a molecular sieve.

2. The method of claim 1, wherein the catalyst is selected from the group consisting of Au-Ni/TiO₂、Au-Cu/SiO₂、Pt-Fe/TiO₂、Pt-Co/Al₂O₃And Ru-Cu/molecular sieves.

3. The method of claim 2, wherein the catalyst is selected from the group consisting of Au-Ni/TiO₂And/or Pt-Co/Al₂O₃。

4. The method of claim 3, wherein the catalyst is selected from the group consisting of Au-Ni/TiO₂。

5. The method according to claim 1, wherein the mass of the main active component accounts for 0.1-0.6% of the mass of the catalyst; the mass of the cocatalyst component accounts for 0.01-0.1% of the mass of the catalyst.

6. The method according to claim 5, wherein the mass of the main active component accounts for 0.3-0.5% of the mass of the catalyst; the mass of the cocatalyst component accounts for 0.05-0.075% of the mass of the catalyst.

7. The method as claimed in claim 1, wherein the reaction temperature is 120-160 ℃; the reaction pressure is 1-5Mpa gauge pressure.

8. The method as claimed in claim 7, wherein the reaction temperature is 130-150 ℃; the reaction pressure is 2-4MPa gauge pressure.

9. The method according to claim 1, wherein the concentration of furfural in the reaction system is not more than 0.01 wt%; the furfural feed rate did not exceed 4g furfural/(g catalyst x h).

10. The method according to claim 1, wherein the mass ratio of water to the oxygen-containing heterocyclic compound in the solvent is 10:1 to 1: 10.

11. The method according to claim 10, wherein the mass ratio of water to the oxygen-containing heterocyclic compound in the solvent is 2:1 to 1: 2.

12. The method according to claim 1, wherein the carbon dioxide is contained in an amount of 20 to 60ppm by volume in the mixed gas of hydrogen and carbon dioxide.