CN106866364B - Method for preparing 1, 3-cyclopentanediol from furfuryl alcohol - Google Patents

Method for preparing 1, 3-cyclopentanediol from furfuryl alcohol Download PDF

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CN106866364B
CN106866364B CN201510923635.3A CN201510923635A CN106866364B CN 106866364 B CN106866364 B CN 106866364B CN 201510923635 A CN201510923635 A CN 201510923635A CN 106866364 B CN106866364 B CN 106866364B
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furfuryl alcohol
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cyclopentanediol
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CN106866364A (en
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李宁
李广亿
张涛
王爱琴
王晓东
丛昱
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C07C29/143—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 ketones
    • C07C29/145—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 ketones 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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings

Abstract

The invention relates to a method for preparing 1, 3-cyclopentanediol from furfuryl alcohol. The method takes furfuryl alcohol as a raw material to prepare 1, 3-cyclopentanediol and comprises two steps of reaction: the first step is that furfuryl alcohol solution is rearranged to prepare hydroxycyclopentenone under the condition of alkali catalyst or no catalyst, and the second step is that the hydroxycyclopentenone reacts with hydrogen to prepare 1, 3-cyclopentanediol under the catalysis of hydrogenation catalyst. The catalyst and raw materials used in the invention are cheap and easy to obtain, the preparation process is simple, and the catalyst has higher activity and selectivity for the rearrangement reaction of furfuryl alcohol and the hydrogenation reaction of hydroxyl cyclopentenone. The invention provides a cheap and efficient synthesis method for synthesizing 1, 3-cyclopentanediol from a lignocellulose-based platform compound and furfuryl alcohol.

Description

Method for preparing 1, 3-cyclopentanediol from furfuryl alcohol
Technical Field
The invention relates to a method for preparing 1, 3-cyclopentanediol from furfuryl alcohol. The method specifically comprises two steps of reactions: the first step is that furfuryl alcohol solution is rearranged to prepare hydroxycyclopentenone under the condition of alkali catalyst or no catalyst, and the second step is that the hydroxycyclopentenone reacts with hydrogen to prepare 1, 3-cyclopentanediol under the catalysis of hydrogenation catalyst. Compared with the method for preparing the 1, 3-cyclopentanediol reported at present, the catalyst of the invention has the advantages of low cost, easy obtainment, simple preparation process and high activity and selectivity of reaction. The invention provides a cheap and efficient synthesis method for synthesizing 1, 3-cyclopentanediol from a lignocellulose-based platform compound and furfuryl alcohol.
Background
The environmental problems such as the decrease of fossil resources and the emission of greenhouse gases caused by the combustion of fossil energy are highlighted, the social demand of energy is continuously increased, the price of petroleum is continuously increased, and the development of new energy capable of replacing fossil resources is imperative. The application of biomass as a renewable organic carbon source in the production of carbon materials, fuels and chemicals is a current hot research.
1, 3-cyclopentanediol is one of important chemical raw materials, and is widely applied to synthesis of polyester, polyurethane, pesticide and other organic synthesis intermediates (CN 103642005A, US 20130244170A 1, WO 2013138161A 1). The 1, 3-cyclopentanediol is synthesized mainly by reducing cyclopentadiene in petrochemical route with borane and oxidizing with hydrogen peroxide (J.Am.chem.Soc., 1963,85 (14): 2066). The route needs to consume virulent borane and hydrogen peroxide with a metering ratio, and is a very non-green and environment-friendly synthesis method. On the other hand, the raw material of the method is derived from products of fossil energy, and has non-regenerability. Furfuryl alcohol is an important platform compound obtained by hydrolysis and dehydration of hemicellulose part in agricultural and forestry waste biomass, and has been industrially produced for decades at present. The synthesis of 1, 3-cyclopentanediol from furfural and its derivatives has been reported internationally. Recently, Huber et al (J.Catal.,2015,330: 19-27) reported the production of 1, 5-pentanediol by the one-step hydrogenation of the biomass platform compound furfuryl alcohol with a small amount of 1, 3-cyclopentanediol by-product (less than 7% yield).
The work of preparing oils and chemicals by catalytic conversion of biomass has long been undertaken in this group of subjects (Chinese patent: application Nos.: 201110346501.1 and ChemSus chem.2012,5, 1958-. A series of routes for efficiently utilizing the biomass and the platform compounds thereof are developed. The preparation method for preparing 1, 3-cyclopentanediol from furfuryl alcohol which is a furfural selective hydrogenation product is described in the patent, and the used catalyst is simple and easy to obtain and low in price; in the preparation process, other reagents with other stoichiometric ratios except hydrogen are not required to be consumed. The whole route is green and environment-friendly, and 1, 3-cyclopentanediol is efficiently prepared by utilizing the renewable biomass platform compound furfuryl alcohol.
Disclosure of Invention
The invention aims to provide a method for preparing 1, 3-cyclopentanediol from furfuryl alcohol.
The invention is realized by the following technical scheme:
the preparation of the 1, 3-cyclopentanediol by taking furfuryl alcohol as a raw material comprises two steps of reaction:
the first step is that furfuryl alcohol solution is rearranged to prepare hydroxycyclopentenone under the condition of alkali catalyst or no catalyst, and the second step is that the hydroxycyclopentenone reacts with hydrogen to prepare 1, 3-cyclopentanediol under the catalysis of hydrogenation catalyst.
Compared with the literature (J.Catal.,2015,330: 19-27), the patent adopts a two-step method to synthesize the 1, 3-cyclopentanediol, firstly synthesizes an intermediate compound of hydroxy cyclopentenone in the first step, and then carries out hydrogenation reaction to obtain the 1, 3-cyclopentanediol with high yield, while the comparative literature adopts one-step hydrogenation, the product is more than dozens, and the yield of the 1, 3-cyclopentanediol is less than 7%. The yield of the 1, 3-cyclopentanediol in the patent can easily reach more than 50 percent, and even can reach more than 90 percent under certain specific reaction conditions, which is the innovation of the patent.
Wherein the alkali catalyst for the reaction of preparing the hydroxy cyclopentenone from the furfuryl alcohol solution in the first step is one or the mixture of more than two of the following catalysts:
NaOH、KOH、Na2CO3、NaHCO3ammonia water, Ca (OH)2、Mg(OH)2CaO, MgO, Mg-Al hydrotalcite, Ni-Al hydrotalcite, CeO2；
Wherein the ratio of the mass of the added catalyst to the mass of the reaction substrate solution is between 0 and 0.05.
The second step of hydroxyl cyclopentenone hydrogenation catalyst is one or the mixture of two or more of the following catalysts:
activated Carbon (AC), Mesoporous Carbon (MC), and silicon oxide (SiO)2) Alumina (Al)2O3) Cerium oxide (CeO)2) Titanium oxide (TiO)2) One or more than two of the above-mentioned materials are used as carrier, and one or more than two of Pt, Pd, Ru, Ir, Ni, Co and Cu are loaded on the carrier, and the carrier is a transition metal carbide or nitride catalyst or Raney nickel catalystAn amorphous alloy catalyst;
the supported metal catalyst is prepared by adopting an isometric impregnation method: preparing a metal precursor solution with the mass concentration of 0.1-10%, adding the metal precursor solution into the carrier according to the metering ratio for equal volume impregnation, wherein the mass content of the metal in the catalyst accounts for 0.01-30%, standing for 2h, drying at 80-120 ℃ for 6-24h, reducing by using hydrogen at 200-600 ℃ for 1-10h, introducing O with the volume concentration of 1% after the temperature is reduced to room temperature2Passivating the nitrogen for more than 4 hours;
wherein the ratio of the mass of the added catalyst to the mass of the reaction substrate solution is between 0.01 and 20 percent.
The solvent for the reaction of preparing the hydroxycyclopentenone from the furfuryl alcohol solution in the first step is water or the mixture of water and one or more than two of the following solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF);
wherein the mass concentration of the furfuryl alcohol is 0.01-99%, and the preferred concentration range is 0.1-10%.
The second step of hydrogenation reaction of the hydroxy cyclopentenone can adopt no solvent, and also can adopt one or more than two of the following solvents: water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF);
wherein the mass concentration of the hydroxy cyclopentenone is 0.01-100%, and the preferred concentration range is 0.1-10%.
The reaction for preparing the hydroxy cyclopentenone from the furfuryl alcohol solution in the first step can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 50 and 300 ℃, preferably between 160 and 250 ℃;
when a kettle type reactor is adopted, the reaction time is between 0.001h and 10h, and the preferable reaction time is between 0.01h and 0.5 h; when a fixed bed reactor is adopted, the mass space velocity is 0.01h-1-100h-1To (c) to (d); the preferred space velocity is 10h-1-100h-1To (c) to (d);
the second step of the hydroxy cyclopentenone hydrogenation reaction can be carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is between 0 and 300 ℃, preferably between 15 and 160 ℃; the hydrogen pressure is between 0.1MPa and 10MPa, and the preferable pressure is between 1MPa and 5 MPa;
when a kettle type reactor is adopted, the reaction time is between 0.001h and 10h, and the preferable reaction time is between 0.1h and 2 h; when a fixed bed reactor is adopted, the mass space velocity is 0.01h-1-100h-1To (c) to (d); the preferred space velocity is 1h-1-10h-1To (c) to (d); the molar ratio of hydrogen to the reaction feed is 20 to 1500.
The invention has the following advantages:
the method provided by the invention is used for synthesizing the 1, 3-cyclopentanediol, and the raw material of the 1, 3-cyclopentanediol is derived from renewable lignocellulose platform compound furfuryl alcohol. The rearrangement reaction and the hydrogenation reaction both adopt common alkali catalysts and hydrogenation catalysts, and are simple and easy to obtain, and the catalyst cost is lower. Compared with the method for preparing the 1, 3-cyclopentanediol by hydrogenating furfuryl alcohol reported in the literature, the method has the advantage that the yield is obviously improved. The process of this patent is therefore a very practical method for the synthesis of 1, 3-cyclopentanediol.
Drawings
FIG. 1 shows the reaction product of furfuryl alcohol rearrangement reaction of hydroxycyclopentenone1H-NMR spectrum;
FIG. 2 of furfuryl alcohol rearrangement reaction product hydroxycyclopentenone13A C-NMR spectrum;
FIG. 3 production of 1, 3-cyclopentanediol as a product of hydrogenation of hydroxycyclopentenone1H-NMR spectrum;
FIG. 4 production of 1, 3-cyclopentanediol as a product of hydrogenation of hydroxycyclopentenone13A C-NMR spectrum;
Detailed Description
The invention will now be illustrated by means of specific examples, without restricting its scope to these examples.
1. Experiment on the preparation of hydroxycyclopentenone from furfuryl alcohol (influence of catalyst, kettle reactor)
Adding 50mL of furfuryl alcohol aqueous solution with the mass concentration of 2% into a 100mL reaction kettle, adding a certain amount of alkali catalyst, and reacting for a specific time at a certain temperature.
TABLE 1 rearrangement reactivity of different base catalysts
Figure BDA0000876075790000031
TABLE 1 rearrangement reactivity of different base catalysts (Table II)
Figure BDA0000876075790000032
As can be seen from the results in Table 1, different base catalysts can effectively catalyze the furfuryl alcohol rearrangement reaction to obtain high-yield hydroxycyclopentenone in which the weak-base CeO2The effect is poor. However, even without any catalyst, a yield of 60% of hydroxycyclopentenone can still be obtained under the preferred reaction conditions. The influence of the catalyst amount on the reaction activity is obvious, wherein about 5mg of NaOH can obtain better yield, and the yield of the hydroxycyclopentenone is reduced when the NaOH content is more than or less than the value. The influence of the reaction time is similar to the amount of the catalyst, the optimal yield is obtained in 0.02h, and the target product is further subjected to side reaction due to too long time, so that the product yield is reduced; if the reaction time is too short, a part of the raw materials is not completely converted, resulting in a low yield. The reaction temperature also has an optimal value, the yield of the hydroxycyclopentenone is maximized at 240 ℃, and the yield is reduced slightly due to the excessively high or excessively low temperature.
2. Experiment on the preparation of hydroxycyclopentenone from furfuryl alcohol (influence of solvent, kettle reactor)
50mL of furfuryl alcohol water solution with certain concentration or a mixed solution of water and other solvents is added into a 100mL reaction kettle, NaOH is used as a catalyst, and the reaction is carried out for 0.02h at 240 ℃.
TABLE 2 Effect of different solvents on the rearrangement reactivity
Figure BDA0000876075790000041
TABLE 2 influence of different solvents on the reactivity (Table continuation)
Figure BDA0000876075790000042
As can be seen from the results in Table 2, the yield of hydroxycyclopentenone decreases significantly as the furfuryl alcohol concentration of the reaction substrate increases, but remains at a higher level. This requires a combination of yield and energy efficiency to achieve the optimum concentration in the actual production process. The mixed solvent has little influence on the yield of the target product, and higher yield of the hydroxycyclopentenone can be obtained even if the ratio of the mixed solvent to the water is floated in a larger range.
3. Experiment on the preparation of hydroxycyclopentenone from furfuryl alcohol (fixed bed reactor)
In a fixed bed reactor, furfuryl alcohol aqueous solutions with different concentrations are pumped into the fixed bed reactor at a certain speed by a liquid chromatography pump, and the reaction is carried out at different temperatures by taking magnesium-aluminum hydrotalcite as a catalyst.
TABLE 3 furfuryl alcohol rearrangement reactivity in fixed bed reactor
Figure BDA0000876075790000051
As can be seen from Table 3, higher yields of hydroxycyclopentenone can be obtained at the same furfuryl alcohol concentration in the fixed bed reactor. Too large or too small a space velocity in the fixed bed leads to a reduction in the yield of hydroxycyclopentenones, which is similar to the reason why the reaction time in the tank reactor influences the yield. The temperature has a great influence on the formation of the hydroxycyclopentenone, the temperature is too low to be beneficial to the formation of the target product, and the optimal reaction temperature is 240 ℃.
4. Experiment on Hydroxycyclopentenone hydrogenation (influence of catalyst, kettle reactor)
In a 100mL reaction kettle, 50mL of a 2% by mass solution of hydroxycyclopentenone in Tetrahydrofuran (THF) as a solvent is added, and 0.1g of a hydrogenation catalyst is added to react at a certain temperature for a certain time.
TABLE 4 hydrogenation reactivity of different catalysts
Figure BDA0000876075790000052
Figure BDA0000876075790000061
TABLE 4 hydrogenation reactivity of different catalysts (Table continuation)
Figure BDA0000876075790000062
As can be seen from the data in table 4, almost all the common hydrogenation catalysts have good effect on the hydrogenation of hydroxycyclopentenones, wherein the activities expressed by the metals Ni and Ru are the best. The metal loading and reaction time had a slight, but not significant, effect on the yield of 1, 3-cyclopentanediol. The reaction temperature is relatively much affected, and 160 ℃ is the optimum reaction temperature.
5. Experiment on Hydroxycyclopentenone hydrogenation (influence of solvent, kettle reactor)
50mL of hydroxy cyclopentenone solution with certain concentration is added into a 100mL reaction kettle, Ru/AC or Raney Ni is used as a catalyst, the adding amount of the catalyst is 0.1g, and the reaction is carried out for 1h at 160 ℃.
TABLE 5 Effect of different solvents on hydrogenation reactivity
Figure BDA0000876075790000063
TABLE 5 influence of different solvents on the hydrogenation activity (Table continuation)
Figure BDA0000876075790000064
Figure BDA0000876075790000071
As can be seen from the data in Table 5, the solvent has a great influence on the hydrogenation reaction, and a high yield of 1, 3-cyclopentanediol can be obtained in aprotic solvents such as THF, DMF, DMSO, etc. While the yield of 1, 3-cyclopentanediol in systems such as water and alcohol is relatively low. The mixed solvent effect is between the two. The substrate concentration has a greater influence on the yield of 1, 3-cyclopentanediol, the lower the concentration, the higher the yield.
6. Experiment of Hydroxycyclopentenone hydrogenation (fixed bed reactor)
In a fixed bed reactor, liquid chromatographic pump is used to pump THF solutions of hydroxycyclopentenone in different concentrations into the fixed bed reactor at certain rate, Ru/AC is used as catalyst, and the reaction is carried out at different temperatures.
TABLE 6 hydrogenation activity in fixed bed reactor
Figure BDA0000876075790000072
TABLE 6 hydrogenation activity in fixed bed reactor (continuation of Table)
Figure BDA0000876075790000073
As can be seen from the data in Table 6, the substrate concentration has a great influence on the hydrogenation reaction, and an excessively high substrate concentration leads to a significant decrease in the yield of 1, 3-cyclopentanediol. The space velocity has a relatively small effect on the yield of 1, 3-cyclopentanediol. The reaction temperature has little influence on the yield of the 1, 3-cyclopentanediol at a high temperature of 160-300 ℃, and when the temperature is lower than 100 ℃, the yield of the 1, 3-cyclopentanediol is obviously reduced.
As can be seen from the above examples, the preparation of 1, 3-cyclopentanediol from furfuryl alcohol in high yields is completely achieved by a two-step process. And the catalyst adopted in the process is common and cheap alkali catalyst and hydrogenation catalyst. In the process, except hydrogen, other extra consumables are not required to be added, the whole process is green and environment-friendly, and the method is a very efficient synthesis method of the 1, 3-cyclopentanediol.

Claims (5)

1. A process for the preparation of 1, 3-cyclopentanediol from furfuryl alcohol, which comprises:
the preparation of the 1, 3-cyclopentanediol by taking furfuryl alcohol as a raw material comprises two steps of reaction:
the first step is that furfuryl alcohol solution is rearranged to prepare hydroxy cyclopentenone under the condition of alkali catalyst, and the second step is that hydroxy cyclopentenone reacts with hydrogen to prepare 1, 3-cyclopentanediol under the catalysis of hydrogenation catalyst;
the first step of preparing hydroxy cyclopentenone with furfuryl alcohol solution is carried out in a kettle type reactor or a fixed bed reactor;
the alkali catalyst for the reaction of preparing the hydroxy cyclopentenone from the furfuryl alcohol solution in the first step is one or the mixture of more than two of the following catalysts:
NaOH、KOH、Na2CO3、NaHCO3ammonia water, Ca (OH)2、Mg(OH)2CaO, MgO, Mg-Al hydrotalcite, Ni-Al hydrotalcite, CeO2。
2. The method of claim 1, wherein:
the alkali catalyst for the reaction of preparing the hydroxy cyclopentenone from the furfuryl alcohol solution in the first step is one or the mixture of more than two of the following catalysts:
NaOH、KOH、Na2CO3、NaHCO3ammonia water, Ca (OH)2、Mg(OH)2CaO, MgO, Mg-Al hydrotalcite, Ni-Al hydrotalcite, CeO2；
The second step of hydroxyl cyclopentenone hydrogenation catalyst is one or the mixture of two or more of the following catalysts:
one or more than two of active carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide and titanium oxide are taken as carriers, and one or more than two of metals of Pt, Pd, Ru, Ir, Ni, Co and Cu are loaded on the carriers, such as supported metal catalysts, transition metal carbide or nitride catalysts, Raney nickel catalysts and amorphous alloy catalysts;
the supported metal catalyst is prepared by adopting an isometric impregnation method: preparing a metal precursor solution with the mass concentration of 0.1-10%,adding the carrier according to the metering ratio, soaking in a medium volume, wherein the mass content of the metal in the catalyst accounts for 0.01-30%, standing for 2h, and soaking in a medium volume of 80-120%oDrying for 6-24h at C, and then drying for 600 h at 200-oReducing with hydrogen for 1-10h at C, introducing O with volume concentration of 1% after the temperature is reduced to room temperature2Passivating the nitrogen for more than 4 hours;
wherein the ratio of the mass of the added catalyst to the mass of the reaction substrate solution is between 0.01 and 20 percent.
3. The method of claim 1, wherein:
the solvent for the reaction of preparing the hydroxycyclopentenone from the furfuryl alcohol solution in the first step is water or the mixture of water and one or more than two of the following solvents: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide;
wherein the mass concentration of the furfuryl alcohol is 0.01-99%;
in the second step, the hydrogenation reaction of the hydroxy cyclopentenone is carried out without solvent, or by adopting one or more than two of the following solvents: water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide;
wherein the mass concentration of the hydroxy cyclopentenone is 0.01-100%.
4. The method of claim 1, wherein:
the first step of the reaction for preparing the hydroxy cyclopentenone from the furfuryl alcohol solution is carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is 50 DEGoC-300oC is between;
when a kettle type reactor is adopted, the reaction time is between 0.001h and 10 h; when a fixed bed reactor is adopted, the mass space velocity is 0.01h-1-100 h-1To (c) to (d);
the second step of the hydroxy cyclopentenone hydrogenation reaction is carried out in a kettle type reactor or a fixed bed reactor, and the reaction temperature is 0oC-300oC is between; hydrogen pressure thereofBetween 0.1MPa and 10 MPa;
when a kettle type reactor is adopted, the reaction time is between 0.001h and 10 h; when a fixed bed reactor is adopted, the mass space velocity is 0.01h-1-100 h-1To (c) to (d); the molar ratio of hydrogen to the reaction feed is 20 to 1500.
5. The production method according to any one of claims 1,3 or 4, characterized in that:
the first step, wherein the mass concentration range of furfuryl alcohol is 0.1-10%; the reaction temperature is 160 DEGoC- 250oC, during the process; when a kettle type reactor is adopted, the reaction time is between 0.01h and 0.5 h; when a fixed bed reactor is adopted, the mass space velocity is 10h-1-100 h-1To (c) to (d);
step two, the mass concentration of the hydroxy cyclopentenone is 0.1-10%; the reaction temperature is 15 deg.CoC- 160oC, during the process; the hydrogen pressure is between 1MPa and 5 MPa; when a kettle type reactor is adopted, the reaction time is between 0.1h and 2 h; when a fixed bed reactor is adopted, the mass space velocity is 1h-1-10 h-1In the meantime.
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