CN112194577A - Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement - Google Patents

Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement Download PDF

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CN112194577A
CN112194577A CN202010914947.9A CN202010914947A CN112194577A CN 112194577 A CN112194577 A CN 112194577A CN 202010914947 A CN202010914947 A CN 202010914947A CN 112194577 A CN112194577 A CN 112194577A
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furfural
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cyclopentanone
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王安杰
李岩
遇治权
王瑶
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Dalian University of Technology
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Abstract

The invention provides a method for preparing cyclopentanone compounds from furfural and derivatives thereof through aqueous phase hydrogenation rearrangement, and belongs to the field of biomass resource catalytic conversion. In particular, supported Ni3P catalyst in H2Atmosphere(s)In the method, furfural and derivatives thereof are converted into cyclopentanone compounds; supported Ni of the invention3The P catalyst is prepared by a method of deposition precipitation-chemical plating. The catalyst obtained by the method has high dispersity and small particle size. The catalyst has higher conversion rate of furfural and derivatives thereof and selectivity of cyclopentanone compounds in the reaction of preparing cyclopentanone and derivatives thereof by aqueous phase hydrogenation rearrangement of furfural and derivatives thereof. The invention is at 4MPa H2And at 160 ℃, after the reaction is carried out for 1h, the furfural conversion rate and the cyclopentanone selectivity respectively reach 89.1 percent and 81.3 percent.

Description

Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement
Technical Field
The invention belongs to the technical field of catalytic chemical industry, and particularly discloses a method for preparing cyclopentanone compounds by aqueous phase hydrogenation rearrangement by taking furfural and derivatives thereof as raw materials.
Technical Field
Furfural is produced from renewable agricultural resources such as corncobs, bagasse, cottonseed hulls, wood waste and the like through acidolysis, and is an important chemical raw material synthesized by using renewable biomass resources through reaction. Furfural is active in chemical properties, is considered to be one of the most promising platform compounds extracted directly from biomass, and can be used for preparing various intermediate products such as: cyclopentanone, cyclopentanol, furfuryl alcohol, 2-methylfuran, tetrahydrofurfuryl alcohol, etc., and are widely used in the industries of synthetic plastics, medicines, pesticides, etc.
Cyclopentanone is an important fine chemical intermediate, and can be used for preparing the anxiolytic buspirone and the like in the field of medicine; methyl jasmonate prepared from cyclopentanone in agriculture can play a hormone-like role and plays a role in influencing the secondary metabolism of plants as a signal substance in plants; in the aspect of perfume, cyclopentanone can be used for synthesizing methyl dihydrojasmonate, and the methyl dihydrojasmonate has aromatic and lasting fragrance and is widely applied to the preparation of high-grade perfume and cosmetic essence.
The main synthesis process of cyclopentanone is currently pyrolysis of adipic acid and its derivatives. Mixing adipic acid powder with barium hydroxide catalyst, and heating and distilling to prepare cyclopentanone. Patent CN1594259 adopts a catalytic reaction tower and takes adipic acid as raw material in Ni-Cu/Al2O3Preparing cyclopentanone and cyclopentanol under the condition of catalyst, the method improves the yield of cyclopentanone by reducing the generation of high boiling point substance by further self-polymerization reaction of cyclopentanone in the production process, and 1460Kg of adipic acid is added807Kg of cyclopentanone was obtained with a yield of 96%.
Another technical route for preparing cyclopentanone is the cyclopentene oxidation method, Dubkvo et al (React. Kinet. Catal. Lett., 2002, 77: 197-2And (3) producing cyclopentanone by an O selective liquid-phase oxidation method. Oxidant N2When the O is directly contacted with the liquid cyclopentene at high temperature, the O can directly interact with a C ═ C double bond of a hydrocarbon, and an oxygen atom of the hydrocarbon is transferred to an unsaturated carbon atom, so that the selectivity of 100 percent cyclopentanone can be almost achieved.
The method for preparing cyclopentanone based on the traditional method has the problems of high price of raw materials, great environmental pollution, high requirements on production equipment and the like, in recent years, petroleum resources are gradually exhausted, and a new method for preparing cyclopentanone by using a biomass platform compound furfural as a raw material is provided. The process for preparing cyclopentanone through furfural aqueous phase hydrogenation rearrangement adopts renewable biomass platform compound furfural as a raw material, replaces traditional fossil energy sources such as adipic acid and cyclopentene, solves the consumption problem of the fossil energy sources, meets the market demand of cyclopentanone, and can effectively improve the utilization rate of biomass resources. Therefore, the method is a new route which accords with sustainable development and has follow-up research significance.
The patent CN110041168 synthesizes 10 percent Co-10 percent Ni/TiO by an excess impregnation method2The method for preparing cyclopentanone by catalyzing furfural aqueous phase hydrogenation rearrangement through a bimetallic catalyst at 6MPaH2And the reaction is carried out for 4 hours at 140 ℃, so that 100 percent of furfural conversion rate and 51 percent of cyclopentanone selectivity can be achieved. Patent CN103111299 adopts a double-dropping coprecipitation method to prepare a high-loading activated carbon nanotube-loaded copper, nickel, cobalt and magnesium catalyst, and applies the high-loading activated carbon nanotube-loaded copper, nickel, cobalt and magnesium catalyst to furfural aqueous phase hydrogenation reaction to obtain high-yield cyclopentanone. The prior method has the technical problems of complex catalyst preparation, harsh reaction conditions or low cyclopentanone selectivity.
Disclosure of Invention
The invention aims to provide a novel method for preparing cyclopentanone compounds by efficiently catalyzing furfural and furfural derivatives through aqueous phase hydrogenation rearrangementThe method is independent of fossil resources, takes renewable biomass resources furfural and derivatives thereof as raw materials and carries Ni3Preparing cyclopentanone compounds under the action of the P catalyst. The method is a new route which accords with sustainable development and has follow-up research significance and industrial prospect.
The technical scheme of the invention is as follows:
a method for preparing cyclopentanone compounds by catalyzing furfural and derivatives thereof through aqueous phase hydrogenation rearrangement comprises the steps of taking furfural and derivatives thereof as raw materials, taking water as a solvent and loading Ni3P catalyst in H2In the atmosphere, furfural and derivatives thereof are converted into cyclopentanone compounds through aqueous phase hydrogenation rearrangement; the supported Ni3The active component in the P catalyst is Ni3P, the carrier is one of oxide, molecular sieve, active carbon and rare earth phosphate; the loading of Ni is 5-35 wt.%.
Preferably said Ni3The particle size of P is 3-6 nm.
Preferably, the carrier is gamma-Al2O3、TiO2Al-SBA-15, Al-MCM-41, activated carbon and CePO4One kind of (1).
Preferably, in the reaction system, the concentration of the furfural aqueous solution is 0.5-8 wt.%, and the supported Ni is3The dosage of the P catalyst is 10-50% of the mass of the furfural, the reaction temperature is 100-200 ℃, the pressure of reaction hydrogen is 0.1-4MPa, the reaction time is 0.5-12h, and the stirring speed is 500-1000 rpm. Further, the reaction temperature is 140-180 ℃; the reaction hydrogen is 2-4 MPa; the reaction time is 1-4 h; the concentration of the furfural aqueous solution is 5 percent; the dosage of the catalyst is 20 percent of the mass of the furfural.
Preferably the supported Ni3The P catalyst is prepared by a method combining deposition precipitation and chemical plating, the method is low in cost, and the obtained supported Ni3The P catalyst has high activity for catalyzing furfural aqueous phase hydrogenation rearrangement to prepare cyclopentanone.
Further, the supported Ni3The preparation method of the P catalyst specifically comprises the following steps:
s1, weighing Ni (NO)3)2·6H2Dissolving O in deionized water to form Ni (NO)3)2Aqueous solution, Ni (NO)3)2The concentration range of the aqueous solution is 0.004-0.04 mol/L; taking part of the Ni (NO)3)2Adding a carrier into the aqueous solution, and heating the aqueous solution under stirring to form a suspension; weighing urea to add to the rest of the Ni (NO)3)2Adding concentrated nitric acid into the aqueous solution to form a mixed solution, wherein the amount of urea substances in the mixed solution is 0.1-0.5mol, and the pH value of the solution is 1-2; dropwise adding the obtained mixed solution into the turbid solution, heating to 90-95 ℃ after the dripping is finished, and reacting for 1-24 h; after the reaction is finished, carrying out suction filtration, washing until the filtrate is neutral, and drying to obtain a precursor compound;
s2, preparing an acetic acid-sodium acetate buffer solution with pH of 4-6.5, adding NaH2PO2In which NaH2PO2The concentration of the precursor compound is 0.04-2.5mol/L, the temperature is raised to 80-95 ℃ under stirring, the precursor compound obtained from S1 is added, after the reaction is finished, the filtration is carried out, the washing is carried out until the filtrate is neutral, the drying is carried out, and the reaction is carried out in H2Carrying out heat treatment at 350-500 ℃ for 1-5h in the atmosphere, and then cooling and annealing to obtain the high-dispersion supported Ni3And (3) a P catalyst.
The invention has the advantages of simple reaction process, mild conditions and supported Ni3Active component Ni of P catalyst3P has higher hydrogenation active center and stably exists in water phase, and meanwhile, the carrier provides weak L acid center, Ni3The P is matched with the carrier, so that the conversion rate of the furfural and the derivatives thereof and the selectivity of cyclopentanone compounds are improved; in addition, the invention adopts a method of combining a deposition precipitation method and a chemical plating method to prepare the supported Ni3The P catalyst obviously improves the dispersity and prepares nano-grade supported Ni3The P catalyst has the particle size of 3-6nm and can further catalyze furfural and derivatives thereof to convert to prepare cyclopentanone compounds with high selectivity; in particular, Ni of the invention3P and gamma-Al2O3The mutual synergistic action of carriers, the conversion rate of furfural and derivatives thereof and the selectivity of cyclopentanone compounds are obviousRemarkably improved at 4MPa H2And at 160 ℃, after the reaction is carried out for 1h, the furfural conversion rate and the cyclopentanone selectivity respectively reach 89.1 percent and 81.3 percent.
Drawings
FIG. 1 shows different carriers loaded with Ni3XRD spectrum of P catalyst.
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.
Example 1
Preparing precursor by deposition precipitation method and preparing Ni by chemical plating method3P/γ-Al2O3A catalyst.
2.62g of Ni (NO)3)2·6H2Dissolving O in deionized water to obtain Ni (NO)3)2Solution 4/5 to which was added 2.4g of gamma-Al2O3Heating the carrier to 70 ℃ under continuous stirring to form a suspension; 7.56g of urea are weighed out and added to the remaining Ni (NO)3)2And adding 0.56g of concentrated nitric acid into the solution to form a mixed solution, dropwise adding the mixed solution into the suspension at 70 ℃, heating to 90 ℃ after dropwise adding, and reacting for 16 hours. After the reaction is finished, carrying out suction filtration, washing until the filtrate is neutral, and drying for 12h to obtain a precursor compound; then 100mL of acetic acid-sodium acetate buffer solution with pH of 5.5 is prepared, and 9.55g of NaH is added2PO2Continuously stirring and heating to 90 ℃, and adding a precursor compound; after reacting for two hours, filtering, washing until the filtrate is neutral, drying for 12 hours, and H2Heat treatment is carried out for 2h at 400 ℃ in the atmosphere, then cooling annealing is carried out, and Ni is obtained3P/γ-Al2O3Catalyst, Ni loading 14% wt.%, particle size 3.8nm, XRD spectrum see figure 1.
Example 2
gamma-Al in example 12O3Respectively changing the carrier into TiO2Al-SBA-15, Al-MCM-41, activated carbon and CePO4Obtaining Ni3P/TiO2、Ni3P/Al-SBA-15、Ni3P/Al-MCM-41、Ni3P/AC and Ni3P/CePO4，Ni3P/TiO2And Ni3P/CePO4The XRD pattern of the catalyst is shown in figure 1.
The catalysts obtained in example 2 are respectively subjected to a reaction for preparing cyclopentanone by catalyzing furfural aqueous phase hydrogenation rearrangement.
The reaction steps are as follows: will carry Ni3Adding the P catalyst, furfural and water into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, replacing air in the kettle, filling hydrogen, starting reaction, quickly cooling the reaction kettle after the reaction is finished, and performing chromatographic analysis by adopting an internal standard method after centrifugal treatment. The internal standard substance is 1, 4-dioxane. The analysis was carried out in an Aglient 6890N gas chromatograph on a commercially available HP-Innowax capillary column, hydrogen flame detector.
Reaction conditions are as follows: 0.2g of supported Ni3P catalyst, 20g of 5% aqueous furfural solution, 4MPaH2And reacting at 160 ℃ for 1 h. The reaction results are shown in Table 1.
From the experimental results in table 1, Ni can be preferably selected by comprehensively considering the furfural conversion rate and the target product cyclopentanone selectivity3P/γ-Al2O3The catalyst was subjected to subsequent experimental studies.
TABLE 1 Synthesis of Ni Supported on different Carriers by precipitation-electroless plating3Reaction results of the P catalyst.
Figure BDA0002664696850000041
Figure BDA0002664696850000051
Example 3
Ni of the above example 13P/γ-Al2O3Experimental results of the catalysts at different reaction times.
Reaction conditions are as follows: 0.2g of catalyst, 20g of 5% aqueous furfural solution, 4MPaH2And reacting at 180 ℃ for different times. The reaction results are shown in Table 2. From the experimental results of table 2, the cyclopentanone selectivity increased first and then decreased with increasing reaction time.
TABLE 2 Ni3P/γ-Al2O3Reaction results of different reaction times of the catalyst.
Reaction time (h) Furfural conversion (%) Cyclopentanone selectivity (%)
0.5 78.0 75.0
1 98.9 76.1
2 99.5 53.2
4 99.9 24.9
Example 4
Ni of the above example 13P/γ-Al2O3The catalyst was reacted at different temperatures for 1 h.
Reaction conditions are as follows: 0.2g of catalyst, 20g of 5% aqueous furfural solution, 4MPaH2The reaction was carried out for 1h at different temperatures. The reaction results are shown in Table 3. From the experimental results of Table 3, the furfural conversion rate was continuously increased with the increase of the reaction temperatureHigh, but cyclopentanone selectivity increased first and then decreased, reaching a maximum at 160 ℃.
TABLE 3 Ni3P/Al2O3The reaction results of different reaction temperatures of the catalyst.
Reaction temperature (. degree.C.) Furfural conversion (%) Cyclopentanone selectivity (%)
140 61.5 52.1
160 89.1 81.3
180 98.9 76.1
200 98.2 68.6
Example 5
Ni of the above example 13P/γ-Al2O3The catalyst reacts under different pressures for 1h and at 160 ℃.
Reaction conditions are as follows: 0.2g of catalyst, 20g of 5% furfural water solution, and reacting at 160 ℃ and different pressures for 1 hour. The reaction results are shown in Table 4. From the experimental results in table 4, too low hydrogen pressure fails to cause bond-breaking rearrangement of furfuryl alcohol, which is a reaction intermediate, resulting in reduced cyclopentanone selectivity, similar selectivity between cyclopentanone at 2MPa and cyclopentanone at 4MPa, but furfural at 4MPa has higher conversion rate, and further increasing pressure results in excessive hydrogenation of cyclopentanone to cyclopentanol.
TABLE 4 Ni3P/γ-Al2O3The reaction results of different reaction pressures of the catalyst.
Reaction pressure (MPa) Furfural conversion (%) Cyclopentanone selectivity (%)
1 27.6 66.1
2 60.8 81.7
4 89.1 81.3
Example 6
Ni of the above example 13P/γ-Al2O3The catalyst catalyzes 5-hydroxymethylfurfural or 5-methylfurfural to react.
Reaction conditions are as follows: 0.2g Ni3P/γ-Al2O3Catalysis20g of 5% aqueous solution of 5-hydroxymethylfurfural or 5-methylfurfural at 160 ℃ in 4MPaH2And reacting for 1 h. The reaction results are shown in Table 5. From the experimental results in Table 5, it was found that cyclopentanone compounds were produced in the case of 5-hydroxymethylfurfural or 5-methylfurfural as the starting material, and that synthesized Ni3P/γ-Al2O3The catalyst is generally suitable for hydrogenation rearrangement reaction of furfural and derivatives thereof to prepare cyclopentanone compounds.
TABLE 5 Ni3P/γ-Al2O3The catalyst catalyzes the reaction result of 5-hydroxymethylfurfural or 5-methylfurfural.
Figure BDA0002664696850000061
Comparative examples
Bulk Ni prepared by coprecipitation3P,Co2And catalyzing furfural hydrogenation rearrangement by using P and MoP catalysts to prepare cyclopentanone.
Mixing 8.72g of Ni (NO)3)2·6H2Dissolving O in deionized water to obtain Ni (NO)3)2Solution, 1.32g (NH)4)2·HPO4Dissolving in deionized water, adding (NH)4)2·HPO4Solution addition of Ni (NO)3)2Stirring the solution for 30min, quickly evaporating water to dryness, drying for 12h, roasting at 500 ℃ for 3h to obtain a catalyst precursor, reducing the precursor in a hydrogen atmosphere at 500 ℃ for 2h, and then using 5% O2/Ar2Passivating to obtain Ni3And (3) a P catalyst.
Co can be prepared by the same method2P catalyst (molar ratio Co: P ═ 2) and MoP catalyst (molar ratio Mo: P ═ 1).
Reaction conditions are as follows: 0.2g of catalyst, 20g of 5% furfural aqueous solution, 180 ℃ 4MPaH2And reacting for 1 h. The reaction results are shown in Table 6. From the results of the experiments in table 6,
TABLE 6 Ni3P catalyst, Co2P catalyst, MoP catalyst and example 1Ni3P/γAl2O3Comparison of reaction results
Catalyst and process for preparing same Furfural conversion (%) Cyclopentanone selectivity (%)
Ni3P 99.9 50.8
Co2P 59.5 44.5
MoP 61.1 17.8
Ni3P/γAl2O3 98.9 76.1

Claims (6)

1. A method for preparing cyclopentanone compounds from furfural and derivatives thereof by aqueous phase hydrogenation rearrangement is characterized in that supported Ni3P catalyst in H2Converting furfural and derivatives thereof into cyclopentanone compounds in the atmosphere; the supported Ni3The active component in the P catalyst is Ni3P, the carrier is one of oxide, molecular sieve, active carbon and rare earth phosphate; the loading of Ni is 5-35 wt.%.
2. The method for preparing cyclopentanone compounds from furfural and its derivatives by aqueous phase hydrogenation rearrangement as claimed in claim 1, wherein Ni is3The particle size of P is 3-6 nm.
3. The method for preparing cyclopentanone compounds from furfural and derivatives thereof through aqueous phase hydrogenation rearrangement according to claim 1, wherein the carrier is γ -Al2O3、TiO2Al-SBA-15, Al-MCM-41, activated carbon and CePO4One kind of (1).
4. The method for preparing cyclopentanone compounds by aqueous phase hydrogenation rearrangement of furfural and its derivatives according to claim 1, wherein the concentration of furfural in the aqueous solution is 0.5-8 wt.% and the supported Ni is added3The dosage of the P catalyst is 10-50% of the mass of the furfural, the reaction temperature is 100-200 ℃, the pressure of reaction hydrogen is 0.1-4MPa, the reaction time is 0.5-12h, and the stirring speed is 500-1000 rpm.
5. The method for preparing cyclopentanone compounds by aqueous-phase hydrogenation rearrangement of furfural and its derivatives as claimed in claim 1 or 2, wherein: the supported Ni3The P catalyst is prepared by a method combining deposition precipitation and chemical plating.
6. The method for preparing cyclopentanone compounds from furfural and derivatives thereof by aqueous phase hydrogenation rearrangement according to claim 5, wherein: the supported Ni3The preparation method of the P catalyst specifically comprises the following steps:
s1, weighing Ni (NO)3)2·6H2Dissolving O in deionized water to form Ni (NO)3)2Aqueous solution, Ni (NO)3)2The concentration range of the aqueous solution is 0.004-0.04 mol/L; taking part of the Ni (NO)3)2Adding a carrier into the aqueous solution, and heating the aqueous solution under stirring to form a suspension; weighing urea to add to the rest of the Ni (NO)3)2Dissolving in waterAdding concentrated nitric acid into the solution to form a mixed solution, wherein the amount of urea substances in the mixed solution is 0.1-0.5mol, and the pH value of the solution is 1-2; dropwise adding the obtained mixed solution into the turbid solution, heating to 90-95 ℃ after the dripping is finished, and reacting for 1-24 h; after the reaction is finished, carrying out suction filtration, washing until the filtrate is neutral, and drying to obtain a precursor compound;
s2, preparing an acetic acid-sodium acetate buffer solution with pH of 4-6.5, adding NaH2PO2In which NaH2PO2The concentration of the precursor compound is 0.04-2.5mol/L, the temperature is raised to 80-95 ℃ under stirring, the precursor compound obtained from S1 is added, after the reaction is finished, the filtration is carried out, the washing is carried out until the filtrate is neutral, the drying is carried out, and the reaction is carried out in H2Performing heat treatment at 350-500 ℃ for 1-5h in the atmosphere, and then performing cooling annealing to obtain the highly dispersed load type Ni3And (3) a P catalyst.
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Cited By (6)

* Cited by examiner, † Cited by third party
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CN114292251A (en) * 2022-01-11 2022-04-08 南昌大学 Process method for carrying out water-phase low-pressure hydrogenation catalytic conversion on biomass derivative compound
CN114349617A (en) * 2022-01-11 2022-04-15 南昌大学 Method for synthesizing cyclopentanone from furfural through water-phase low-pressure hydrogenation catalysis
CN115318331A (en) * 2021-05-10 2022-11-11 中国科学院大连化学物理研究所 Catalyst for directly preparing difurfuryl ether by furfural hydrogenation and preparation and application thereof
CN115677629A (en) * 2022-11-04 2023-02-03 合肥工业大学 Method for preparing 5-methylfurfural by using iron-based catalyst
CN116351446A (en) * 2023-03-17 2023-06-30 大连理工大学 Ni preparation by chemical plating 3 P/SiO 2 Method for preparing catalyst and application thereof in hydrodeoxygenation
WO2023144408A1 (en) * 2022-01-31 2023-08-03 Rhodia Operations Bio-based methyl dihydrojasmonate, bio-based cyclopentanone, process for their preparation and use thereof

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CN115318331A (en) * 2021-05-10 2022-11-11 中国科学院大连化学物理研究所 Catalyst for directly preparing difurfuryl ether by furfural hydrogenation and preparation and application thereof
CN115318331B (en) * 2021-05-10 2023-09-26 中国科学院大连化学物理研究所 Catalyst for directly preparing difurfuryl ether by furfural hydrogenation and preparation and application thereof
CN114292251A (en) * 2022-01-11 2022-04-08 南昌大学 Process method for carrying out water-phase low-pressure hydrogenation catalytic conversion on biomass derivative compound
CN114349617A (en) * 2022-01-11 2022-04-15 南昌大学 Method for synthesizing cyclopentanone from furfural through water-phase low-pressure hydrogenation catalysis
CN114292251B (en) * 2022-01-11 2023-06-23 南昌大学 Process method for low-pressure hydrogenation catalytic conversion of biomass derivative compound aqueous phase
CN114349617B (en) * 2022-01-11 2024-03-22 南昌大学 Method for synthesizing cyclopentanone by catalyzing furfural through low-pressure hydrogenation in aqueous phase
WO2023144408A1 (en) * 2022-01-31 2023-08-03 Rhodia Operations Bio-based methyl dihydrojasmonate, bio-based cyclopentanone, process for their preparation and use thereof
CN115677629A (en) * 2022-11-04 2023-02-03 合肥工业大学 Method for preparing 5-methylfurfural by using iron-based catalyst
CN115677629B (en) * 2022-11-04 2024-02-27 合肥工业大学 Method for preparing 5-methylfurfural by using iron-based catalyst
CN116351446A (en) * 2023-03-17 2023-06-30 大连理工大学 Ni preparation by chemical plating 3 P/SiO 2 Method for preparing catalyst and application thereof in hydrodeoxygenation
CN116351446B (en) * 2023-03-17 2024-04-19 大连理工大学 Ni preparation by chemical plating3P/SiO2Method for preparing catalyst and application thereof in hydrodeoxygenation

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