CN114292251B - Process method for low-pressure hydrogenation catalytic conversion of biomass derivative compound aqueous phase - Google Patents
Process method for low-pressure hydrogenation catalytic conversion of biomass derivative compound aqueous phase Download PDFInfo
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Abstract
The invention discloses a process method for carrying out low-pressure hydrogenation catalytic conversion on a biomass derivative compound aqueous phase, and belongs to the technical field of biomass chemical conversion processes. The Y-Co-Ni-P compound is used as a catalyst, water is used as a solvent, and under the conditions of the pressure of 0.1-1.0MPa and the temperature of 100-170 ℃ in the hydrogen atmosphere, the furfural is directly subjected to hydrogenation catalysis to convert into cyclopentanone or the levulinic acid is directly subjected to hydrogenation catalysis to convert into gamma-valerolactone. The yield of converting the furfural into the cyclopentanone can reach more than 90 percent, and the yield of converting the levulinic acid into the gamma-valerolactone can reach more than 95 percent. The process method provided by the invention has the advantages of low price, durability, no toxicity, green and controllable reaction condition, high reaction efficiency, convenient large-scale application and remarkable economic and environmental protection benefits.
Description
Technical Field
The invention belongs to the technical field of biomass chemical conversion processes, and particularly relates to a process method for performing low-pressure hydrogenation catalytic conversion on a biomass derivative compound water phase.
Background
With the development of human society, the dependent fossil resources are increasingly exhausted, and the environmental pollution caused by the production and living by using the resources is also increasingly serious. Biomass, as a renewable resource with abundant reserves in nature, is considered as a green sustainable development application resource that can replace fossil raw materials to produce fuels and other high value-added chemicals. At present, in the mainstream biomass chemical conversion process, biomass coarse materials such as cellulose, hemicellulose and lignin are acidolyzed into primary derivatives such as Furfural (FAL), levulinic Acid (LA) and the like, and then the derivative compounds are used as raw materials for conversion production of related high-added-value chemicals such as Cyclopentanone (CPO) or gamma-valerolactone (GVL). Based on the huge application prospect of the conversion paths in the fields of biofuel, chemical solvents, medicine, spice production and the like, the development of related process methods is attracting attention.
The conversion synthesis process is usually realized in a liquid phase system by taking hydrogen as a hydrogen source and through hydrogenation catalytic reaction by a certain catalyst, and although a great deal of researches are carried out, the reported process system is still immature and is difficult to carry out large-scale industrial application, and the bottleneck problem is mainly in the following two aspects: 1) In a liquid phase reaction system, when water is used as a solvent, most of the liquid phase reaction system relies on a noble metal catalyst, has high cost and is difficult to practically apply, and a low-cost transition metal catalyst is used instead, so that the reaction effect in a water phase is poor, and the stability is poor and the liquid phase reaction system is not durable; 2) Regardless of the solvent used and the catalyst used, the hydrogen pressure is typically maintained above 20 atmospheres (2.0 MPa) to achieve acceptable yields of the desired product, high pressure hydrogen results in difficult and dangerous handling.
Disclosure of Invention
Aiming at the blank that a practical catalytic system and a corresponding process method are not available in the green chemical process of 'biomass derivative compound aqueous phase low-pressure hydrogenation catalytic conversion', the invention provides a process method for preparing cyclopentanone by catalyzing furfural aqueous phase low-pressure hydrogenation with a Y-Co-Ni-P compound or preparing gamma-valerolactone by catalyzing levulinic acid aqueous phase low-pressure hydrogenation.
In order to achieve the above purpose, the present invention proposes the following technical scheme:
a process for the aqueous phase low-pressure hydrogenation catalytic conversion of biomass derivative compounds uses Y-Co-Ni-P compound as catalyst and water as solvent, and under the condition of 0.1-1.0MPa and 100-170 ℃, furfural is directly converted into cyclopentanone or levulinic acid is directly converted into gamma-valerolactone through hydrogenation catalytic conversion in hydrogen atmosphere.
Further, the process method comprises the following steps:
mixing the Y-Co-Ni-P compound with an aqueous solution of a biomass derivative compound, placing the mixture in a closed reaction kettle, introducing hydrogen for 5 times for replacement, maintaining the pressure at 0.1-1.0MPa, and heating to 100-170 ℃ for reaction. Preferably 0.5MPa.
Further, the Co-Ni-P component in the composite catalyst is Co y -Ni 2-y -P cobalt nickel alloy phase phosphide with a molar ratio y of 0.5-1.5, preferably y=1.0; on the basis, the Y-Co-Ni-P compound is (YPO) formed by cobalt-nickel alloy phase phosphide and yttrium phosphate 4 ) x /Co 1.0 Ni 1.0 P composite structure, wherein the molar ratio x is 0.1-0.3, preferably x=0.2.
Further, the concentration of the aqueous solution of the biomass-derived compound is 0.05 to 1.0mol/L. Preferably 0.1mol/L.
Further, the mass to volume ratio of the Y-Co-Ni-P complex to the aqueous solution of the biomass-derived compound is (20-80) mg:10mL. Preferably 50mg:10mL.
Further, the biomass-derived compound is furfural or levulinic acid. When the biomass-derived compound is furfural, the cyclopentanone is prepared by low-pressure hydrogenation of an aqueous phase, the reaction temperature is 130-170 ℃, preferably 150 ℃, and the reaction time is 4-8 hours, preferably 6 hours; when the biomass-derived compound is levulinic acid, the gamma-valerolactone is prepared by low-pressure hydrogenation of the aqueous phase at a reaction temperature of 100-140 ℃, preferably 120 ℃ for a reaction time of 1-4 hours, preferably 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
aiming at practical and large-scale popularization bottleneck problems such as low conversion efficiency, high-pressure hydrogen (more than 2.0 MPa) operation and the like of a non-noble metal catalytic synthesis process of a water-phase hydroconversion reaction of a biomass derivative compound, the invention provides a solution idea from two aspects, namely, constructing alloy-phase phosphide of Co and Ni binary metals so as to further strengthen the activation effect of a metal phosphide catalytic component on furfural or levulinic acid of the biomass derivative compound on the premise of considering structural stability; secondly, YPO is further introduced to make up the defect that the metal phosphide has no obvious effect on hydrogen activation 4 As catalytic component of activated hydrogen, thereby constructing valenceThe cheap and stable Y-Co-Ni-P composite catalyst has not been reported in any way. Through our technological investigation, it is finally determined that the synthesized Y-Co-Ni-P catalyst with proper metal element proportion can be used for efficiently converting furfural into cyclopentanone in water solution (water phase) under low pressure hydrogen (0.1-1 MPa) and below 170 ℃, for example, the yield of cyclopentanone can reach 96% under 0.5MPa hydrogen and 150 ℃; the levulinic acid can be efficiently converted into gamma-valerolactone, and the yield of the gamma-valerolactone can reach 98 percent under the condition of 0.5MPa of hydrogen and 120 ℃; the catalyst of the process method has the advantages of low price, durability, green and controllable reaction condition, high reaction efficiency, convenient large-scale application and obvious economic and environmental protection benefits.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows an example of the (YPO) 4 ) x /Co 1.0 Ni 1.0 P and YPO 4 Catalyst and Co used in comparative example y Ni 2-y XRD pattern of P catalyst;
FIG. 2 is (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P and Co 1.0 Ni 1.0 Scanning Electron Microscope (SEM) image of P-catalyst.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The preparation method of the Y-Co-Ni-P compound in the invention specifically comprises the following steps:
the invention firstly explores a preparation method of Co-Ni-P bimetallic alloy phase phosphide, which comprises the following steps of respectively mixing metal components in a molar ratio of 0.5:1.5;1.0:1.0;1.5: dissolving cobalt nitrate and nickel nitrate of 0.5 in absolute ethanol with a certain volume, adding excessive diammonium hydrogen phosphate aqueous solution, stirring at room temperature for 4 hr to form metal component precipitate, centrifuging, collecting precipitate, washing with water and ethanol, drying, and reducing precipitate with hydrogen at 600deg.C for 2 hr to obtain Co y Ni 2-y The values of y in the obtained typical catalyst are respectively 0.5,1.0 and 1.5 according to the content analysis of the P catalyst sample; in this prescriptionBased on the method, when two metal nitrates are dissolved by water, a proper amount of yttrium nitrate is added at the same time, and other steps and conditions are unchanged, so that (YPO) formed by cobalt-nickel alloy phase phosphide and yttrium phosphate can be obtained 4 ) x /Co y Ni 2-y The P composite structure, as analyzed by the test, gives a sample in which the sum of the molar amounts of Co and Ni is 2.0 moles, wherein the relative molar composition Y of Co is 0.5,1.0,1.5, preferably y=1.0, respectively, and the relative molar composition x of yttrium metal (Y) is 0.1,0.2,0.3, respectively, at the preferred ratio of y=1.0.
FIG. 1 is an X-ray diffraction (XRD) pattern of various catalysts; the left figure shows that Co can be observed 2 P、Ni 2 Diffraction peak of P, and Ni 2 The characteristic diffraction peak of P is shifted, which indicates that Co is successfully doped 2 P, showing that Co was successfully produced y Ni 2-y A P catalyst; the right figure shows that NiCoP and YPO can be observed 4 And with YPO 4 Is attributed to YPO with increased content 4 The diffraction peak of (C) is continuously enhanced and the diffraction peak belonging to NiCoP is continuously weakened, which indicates that the Y-Co-Ni-P compound is mainly composed of NiCoP and YPO 4 Composite crystalline phase composition.
FIG. 2 is (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P and Co 1.0 Ni 1.0 Scanning Electron Microscope (SEM) image of P-catalyst. It can be seen that the sample appears as an aggregate of two scale particles, large particles with a scale close to micrometers are attached by small particles with a few nanometer scales, and the particle size of the compounded sample is obviously reduced, exposing more specific surface area.
Example 1
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
by Co y Ni 2-y P is the catalyst of this example.
Preparation of cyclopentanone: 10mL of 0.1mol/L furfural aqueous solution was taken, 50mgCo y Ni 2-y P (y= 0.5,1.0,1.5)) catalyst, loading into a 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; adding hydrogen with the pressure of 0.5MPaAnd (3) heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, starting to record the change of the concentration of the substances in the reaction system, and carrying out GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
The reaction efficiency of the metal phosphide alloy catalyst is not high, the catalytic efficiency of the sample is improved along with the improvement of the molar ratio of Co, but at the same time, the Co is easier to be separated out into an aqueous solution compared with Ni, and the high content of Co can lead the reaction system to be polluted by metal residues, so that the two phases are balanced, and the molar ratio y is preferably 1.0.
Example 2
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: 10mL of 0.1mol/L aqueous furfural solution (50 mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) after filling 0.5MPa of hydrogen, heating the furfural water solution to 130 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
Example 3
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: 10mL of 0.1mol/L aqueous furfural solution (50 mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) filling hydrogen of 0.5MPa, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. Tool withThe results are shown in Table 1.
Example 4
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: 10mL of 0.1mol/L aqueous furfural solution (50 mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) after filling 0.5MPa of hydrogen, heating the furfural water solution to 170 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
As can be seen from the comparison of examples 2-4 above, (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 The performance of the P sample is optimal, namely the molar ratio x is preferably 0.2; and the reaction efficiency is highest when the yield of cyclopentanone on the catalyst is 150 ℃, so that the reaction temperature is preferably 150 ℃ when the cyclopentanone is converted by hydrogenation of furfural.
Example 5
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: 10mL of each of 0.1mol/L aqueous furfural solution was added with 50mg (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P catalyst is filled into a 50mL polytetrafluoroethylene lining kettle, the kettle is put into a pressure reaction kettle, the kettle is sealed and replaced by hydrogen for 5 times, and air in the kettle is purged and removed; and then filling normal pressure and 1MPa hydrogen respectively, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
As can be seen from the comparison between the results of example 5 and example 3, the reaction efficiency is highest when the hydrogen pressure is 0.5MPa, so that the reaction pressure is preferably 0.5MPa for the hydroconversion of cyclopentanone from furfural.
Example 6
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: 10mL of 0.1mol/L aqueous furfural solution was taken and 50mg (YPO) was added 4 ) 0.2 /Co 1.0 Ni 1.0 P catalyst is filled into a 50mL polytetrafluoroethylene lining kettle, the kettle is put into a pressure reaction kettle, the kettle is sealed and replaced by hydrogen for 5 times, and air in the kettle is purged and removed; and (3) after filling 0.5MPa of hydrogen, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, respectively reacting for 4h and 8h, starting to record the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
As can be seen from the comparison of example 6 and example 3, the reaction efficiency is highest when the reaction time is 6 hours, so that the reaction time is preferably 6 hours when the reaction is carried out on the hydroconversion of cyclopentanone from furfural.
Example 7
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: taking 10mL of 0.1mol/L furfural aqueous solution, respectively adding 20mg and 80mg (YPO 4 ) 0.2 /Co 1.0 Ni 1.0 P catalyst is filled into a 50mL polytetrafluoroethylene lining kettle, the kettle is put into a pressure reaction kettle, the kettle is sealed and replaced by hydrogen for 5 times, and air in the kettle is purged and removed; and (3) filling hydrogen of 0.5MPa, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
As can be seen from the comparison of example 7 and example 3, the catalyst was used in an amount of 50mg per 10mL of water, and the reaction efficiency was the highest, so that the catalyst was optimized for the hydroconversion of cyclopentanone from furfural.
Example 8
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
to (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of cyclopentanone: taking 10mL of 0.05mol/L and 1.0mol/L furfural aqueous solution, respectively adding 50mg (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P catalyst is filled into a 50mL polytetrafluoroethylene lining kettle, the kettle is put into a pressure reaction kettle, the kettle is sealed and replaced by hydrogen for 5 times, and air in the kettle is purged and removed; and (3) filling hydrogen of 0.5MPa, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
As can be seen from the comparison of the results of the examples 8 and 3, the reaction efficiency is highest when the concentration of the aqueous solution of the furfural is 0.1mol/L, so that the hydro-conversion of the furfural into cyclopentanone is carried out, and the concentration of the furfural is optimized under the condition.
Comparative example 1
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
by YPO 4 Is the catalyst of this example.
Preparation of cyclopentanone: 10mL of 0.1mol/L aqueous furfural solution was taken and 50mg YPO was added thereto 4 Filling the catalyst into a 50mL polytetrafluoroethylene lining kettle, putting the catalyst into a pressure reaction kettle, sealing, replacing the catalyst with hydrogen for 5 times, and purging to remove air in the kettle; and (3) filling hydrogen of 0.5MPa, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
Comparative example 2
The hydrogenation catalysis of furfural to prepare cyclopentanone comprises the following steps:
in Pt/SiO 2 The catalyst of this example was purchased from Alfa commercial catalyst.
Preparation of cyclopentanone: taking 10mL of 0.1mol/L furfural water solution,adding 50mgPt/SiO 2 Filling the catalyst into a 50mL polytetrafluoroethylene lining kettle, putting the catalyst into a pressure reaction kettle, sealing, replacing the catalyst with hydrogen for 5 times, and purging to remove air in the kettle; and (3) filling hydrogen of 0.5MPa, heating the furfural water solution to 150 ℃, keeping the rotating speed at 400r/min, reacting for 6 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 1.
The commercial noble metal catalyst has low reaction efficiency under the same condition, namely the reaction efficiency of the preparation process related by the invention is obviously higher than that of the traditional noble metal catalyst, and the invention further shows the creativity and innovation.
TABLE 1 reaction conditions for Furfural conversion to cyclopentanone and sample Performance results
The following is an application example for preparing gamma-valerolactone by hydrogenating levulinic acid, and the comparison and screening optimization experiments of reaction conditions and reaction effects are similar to those of the previous examples 1-8 and comparative examples 1-2, so that the description thereof will not be repeated.
Example 9
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
by Co y Ni 2-y P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution was taken, and 50mgCo was added y Ni 2-y P (y= 0.5,1.0,1.5) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 120 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. Concrete knotThe results are shown in Table 2.
Example 10
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution, 50mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 100 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Example 11
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution, 50mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 120 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Example 12
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution, 50mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 140 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Example 13
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution, 50mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and then charging normal pressure and 1MPa hydrogen respectively, heating the levulinic acid aqueous solution to 120 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Example 14
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution, 50mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 120 ℃, keeping the rotating speed at 400r/min, respectively reacting for 1h and 4h, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Example 15
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution was added with 20 mg/80 mg (YPO) 4 ) 0.2 /Co 1.0 Ni 1.0 P catalyst is filled into a 50mL polytetrafluoroethylene lining kettle, the kettle is put into a pressure reaction kettle, the kettle is sealed and replaced by hydrogen for 5 times, and air in the kettle is purged and removed; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 140 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Example 16
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
to (YPO) 4 ) x /Co 1.0 Ni 1.0 P is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.05mol/L and 1.0mol/L of an aqueous levulinic acid solution was taken, 50mg (YPO) 4 ) x /Co 1.0 Ni 1.0 P (x= 0.1,0.2,0.3) catalyst, loading into 50mL polytetrafluoroethylene lining kettle, placing into a pressure reaction kettle, sealing, replacing with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 140 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Comparative example 3
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
by YPO 4 Is the catalyst of this example.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution was taken, and 50mg of YPO was taken 4 The catalyst is filled into a 50mL polytetrafluoroethylene lining kettle, and is put into a pressure reaction kettle,after sealing, replacing for 5 times by hydrogen, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 120 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
Comparative example 4
The hydrogenation catalysis of levulinic acid to prepare gamma-valerolactone comprises the following steps:
in Pt/SiO 2 The catalyst of this example was purchased from Alfa commercial catalyst.
Preparation of gamma valerolactone: 10mL of 0.1mol/L levulinic acid aqueous solution was taken, and 50mg of Pt/SiO was taken 2 Filling the catalyst into a 50mL polytetrafluoroethylene lining kettle, putting the catalyst into a pressure reaction kettle, sealing, replacing the catalyst with hydrogen for 5 times, and purging to remove air in the kettle; and (3) charging 0.5MPa hydrogen, heating the levulinic acid aqueous solution to 120 ℃, keeping the rotating speed at 400r/min, reacting for 2 hours, recording the change of the concentration of the substances in the reaction system, and performing GC quantitative analysis on the reaction product. The specific results are shown in Table 2.
TABLE 2 reaction conditions and sample Performance results for the conversion of levulinic acid to gamma valerolactone
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (4)
1. A process method for performing low-pressure hydrogenation catalytic conversion on biomass derivative compound water phase is characterized in that Y-Co-Ni-P compound is used as a catalyst, water is used as a solvent, and under the conditions of 0.1-1.0MPa of pressure and 100-170 ℃, furfural is directly subjected to hydrogenation catalytic conversion into cyclopentanone or levulinic acid is directly subjected to hydrogenation catalytic conversion into gamma-valerolactone;
the process method comprises the following steps:
mixing the Y-Co-Ni-P compound with an aqueous solution of a biomass derivative compound, placing the mixture in a closed reaction kettle, introducing hydrogen for 5 times for replacement, maintaining the pressure at 0.1-1.0MPa, and heating to 100-170 ℃ for reaction;
the Y-Co-Ni-P compound is formed by cobalt-nickel alloy phase phosphide and Yttrium Phosphate (YPO) 4 ) x /Co y Ni 2-y A P composite structure; wherein x is 0.1-0.3, and y is 0.5-1.5;
the concentration of the biomass-derived compound aqueous solution is 0.05-1.0mol/L.
2. The process according to claim 1, characterized in that the mass-to-volume ratio of the Y-Co-Ni-P complex to the aqueous solution of biomass-derived compound is (20-80) mg:10mL.
3. The process of claim 1, wherein the biomass-derived compound is furfural or levulinic acid.
4. The process according to claim 1, wherein the reaction time is 1-8h.
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| CN109701569A (en) * | 2019-02-18 | 2019-05-03 | 南昌大学 | A kind of acidproof Ce-P-Co catalyst and preparation method and the application in gamma-valerolactone synthesis |
| CN112194577A (en) * | 2020-09-03 | 2021-01-08 | 大连理工大学 | Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement |
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| CN109701569A (en) * | 2019-02-18 | 2019-05-03 | 南昌大学 | A kind of acidproof Ce-P-Co catalyst and preparation method and the application in gamma-valerolactone synthesis |
| CN112194577A (en) * | 2020-09-03 | 2021-01-08 | 大连理工大学 | Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement |
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| Promotion effects of PrPO4 for the hydrogenation transformation of biomass-derived compounds over Pr–Ni–P composites;Ya-Fang Zhang et al.;Mater. Adv.;第 2卷;3927-3939 * |
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