CN111036301B - Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol - Google Patents

Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol Download PDF

Info

Publication number
CN111036301B
CN111036301B CN201911171312.8A CN201911171312A CN111036301B CN 111036301 B CN111036301 B CN 111036301B CN 201911171312 A CN201911171312 A CN 201911171312A CN 111036301 B CN111036301 B CN 111036301B
Authority
CN
China
Prior art keywords
zirconium
organic framework
metal organic
phosphorus
based metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911171312.8A
Other languages
Chinese (zh)
Other versions
CN111036301A (en
Inventor
李锋
李翠勤
张娜
黄金
蒋博龙
王越
李佩
路世玉
张志秋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeast Petroleum University
Original Assignee
Northeast Petroleum University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeast Petroleum University filed Critical Northeast Petroleum University
Priority to CN201911171312.8A priority Critical patent/CN111036301B/en
Publication of CN111036301A publication Critical patent/CN111036301A/en
Application granted granted Critical
Publication of CN111036301B publication Critical patent/CN111036301B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application relates to a phosphorus-modified zirconium-based catalyst, a preparation method thereof and a method for preparing furfuryl alcohol, wherein the preparation method of the phosphorus-modified zirconium-based catalyst comprises the following steps: preparing a zirconium-based metal organic framework; roasting: and roasting the zirconium-based metal organic framework and diammonium hydrogen phosphate in an inert gas atmosphere to obtain the phosphorus-modified zirconium-based catalyst. Compared with the prior art, the brand-new catalyst for modifying the zirconium-based metal organic framework by using the phosphorus is obtained, and the diammonium hydrogen phosphate and the zirconium-based metal organic framework are roasted, so that the phosphorus element is successfully loaded on the zirconium-based metal organic framework.

Description

Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol
Technical Field
The application relates to the technical field of catalysts, in particular to a phosphorus modified zirconium-based catalyst, a preparation method thereof and a method for preparing furfuryl alcohol.
Background
Furfuryl alcohol is an important fine chemical intermediate, and is used for synthesizing materials such as resin, fiber and the like. The furfuryl alcohol is mainly from deep processing of furfural, and the furfural is obtained by conversion of biomass straws and the like which are renewable resources.
The method is limited by the existing conditions, the furfural liquid phase hydrogenation process is mainly adopted in China to prepare furfuryl alcohol, and catalytic hydrogenation is carried out by taking a copper-chromium catalyst as a catalyst and hydrogen as a hydrogen source. The process technology is relatively mature and is suitable for extensive development mode based on fossil resources. However, this process has the following problems: on one hand, the copper-chromium catalyst contains toxic hexavalent chromium, which causes serious environmental pollution; on the other hand, hydrogen is used as a hydrogen source in the reaction process, and the hydrogen has greater potential safety hazard in the transportation, storage and use processes. In addition, with the exhaustion of fossil resources, the hydrogen generated by the traditional water gas method and the petroleum thermal cracking method is necessarily reduced. Therefore, the development of a process for preparing furfuryl alcohol by catalytic hydrogenation without adding molecular hydrogen is urgently needed.
The catalytic transfer hydrogenation reaction is an organic reduction reaction, and is a reaction in which hydrogen donor is transferred to organic compound reaction substrate under the action of catalyst. The reaction does not use hydrogen as a hydrogen source, and has mild reaction conditions and environmental friendliness. When furfural is subjected to catalytic transfer hydrogenation to prepare furfuryl alcohol, the catalysts used are roughly divided into two types, one is a low-pressure hydrogenation catalyst mainly comprising high-activity raney nickel, platinum, palladium and rhodium, and the other is a high-pressure hydrogenation catalyst mainly comprising common-activity raney nickel, cuprous chromate and the like. Although the prior art has conducted some research on the catalysts used in the catalytic transfer hydrogenation reaction, these catalysts either use noble metals as the active component, or have low furfuryl alcohol selectivity or low catalytic activity, which is not ideal for use, and there is a need to develop catalysts with better catalytic activity and selectivity.
Disclosure of Invention
The application aims to provide a phosphorus-modified zirconium-based catalyst, a preparation method thereof and a method for preparing furfuryl alcohol.
In a first aspect, the present application provides a method for preparing a phosphorus-modified zirconium-based catalyst, the method comprising the steps of:
preparing a zirconium-based metal organic framework;
roasting: and roasting the zirconium-based metal organic framework and diammonium hydrogen phosphate in an inert gas atmosphere to obtain the phosphorus-modified zirconium-based catalyst.
Further, the step of preparing the zirconium-based metal organic framework comprises the following steps: mixing zirconium oxychloride octahydrate, acetic acid, N' -dimethylformamide and terephthalic acid, carrying out solvent heat treatment, and filtering, washing and drying a product to obtain the zirconium-based metal organic framework.
Further, in the step of preparing the zirconium-based metal organic framework, dissolving zirconium oxychloride octahydrate in a mixed solution of acetic acid and N, N' -dimethylformamide, adding terephthalic acid, stirring until the zirconium oxychloride is dissolved to form a reaction solution system, performing solvent heat treatment on the reaction solution system by using an aging kettle, filtering products, washing the products by using an organic solvent for 3 times, and performing vacuum drying at 60 ℃ for 12 hours to obtain the zirconium-based metal organic framework; the amount ratio of the zirconium oxychloride octahydrate to the terephthalic acid is 1: 1-1: 1.5, the volume ratio of acetic acid to N, N '-dimethylformamide is 1: 1-1: 3, the dosage ratio of the zirconium oxychloride octahydrate to the acetic acid is 1mmol:10 mL-1 mmol:20mL, and the organic solvent is N, N' -dimethylformamide and absolute ethyl alcohol.
Wherein the mass ratio of zirconium oxychloride octahydrate to terephthalic acid is 1:1 to 1:1.5 inclusive, e.g., wherein the mass ratio of zirconium oxychloride octahydrate to terephthalic acid is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1: 1.5. The volume ratio of acetic acid to N, N '-dimethylformamide is 1:1 to 1:3 inclusive, e.g., the volume ratio of acetic acid to N, N' -dimethylformamide is 1:1, 1:1.5, 1:2, 1:2.5, or 1: 3. The amount ratio of zirconium oxychloride octahydrate to acetic acid ranges from 1mmol:10mL to 1mmol:20mL inclusive, e.g., the amount ratio of zirconium oxychloride octahydrate to acetic acid ranges from 1mmol:10mL, 1mmol:12mL, 1mmol:15mL, 1mmol:18mL, 1mmol:20 mL.
Preferably, in the step of preparing the zirconium-based metal organic framework, the mass ratio of the zirconium oxychloride octahydrate to the terephthalic acid is 1:1, the volume ratio of the acetic acid to the N, N' -dimethylformamide is 1:2, and the mass ratio of the zirconium oxychloride octahydrate to the acetic acid is 1mmol:15 mL.
Further, the roasting step is as follows: and placing the zirconium-based metal organic framework and diammonium hydrogen phosphate in a constant-temperature area of a heating device, introducing inert gas, and roasting at the constant temperature of 400 ℃, wherein the mass ratio of the diammonium hydrogen phosphate to the substance of the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 0.8: 1-5: 1, and the inert gas is selected from at least one of nitrogen, helium, neon and argon.
Wherein the baking temperature is 300-400 ℃ including any value under the temperature condition, such as 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 380 ℃ and 400 ℃. The amount ratio of diammonium phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 0.8:1 to 5:1 inclusive, for example, the amount ratio of diammonium phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 0.8:1, 1:1, 1.2:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5: 1.
Further, in the roasting step, diammonium hydrogen phosphate is arranged at the front section of the constant temperature area, the zirconium-based metal organic framework is arranged at the rear section of the constant temperature area, the interval between the diammonium hydrogen phosphate and the zirconium-based metal organic framework is more than or equal to 2 cm, the inert gas is introduced at the flow rate of 15-50 mL/min, the temperature of the constant temperature area is raised to 320-380 ℃ at the speed of 2-5 ℃/min, and the constant temperature roasting is carried out for 1-3 hours; wherein the mass ratio of the diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1: 1-2.5: 1.
Wherein the flow rate of the inert gas is 15-50 mL/min inclusive of any point in the flow rate range, such as 15 mL/min, 20 mL/min, 30 mL/min, 40 mL/min, 50 mL/min. The temperature rise speed of the tube furnace is 2-5 ℃/min and includes any point value in the numerical range, for example, the temperature rise speed of the tube furnace is 2 ℃/min, 3 ℃/min, 4 ℃/min and 5 ℃/min. The constant-temperature calcination time of 1 to 3 hours includes any point in the time range, for example, the constant-temperature calcination time of 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours.
Preferably, in the roasting step, the interval between diammonium hydrogen phosphate and the zirconium-based metal organic framework is more than or equal to 5 cm, nitrogen is introduced at the flow rate of 20 mL/min, the temperature of the constant-temperature area is raised to 350 ℃ at the speed of 3 ℃/min, and the constant-temperature roasting is carried out for 2 hours; wherein the mass ratio of the diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1:1.
In a second aspect, the present application provides a phosphorus-modified zirconium-based catalyst prepared by the above-described preparation method.
In a third aspect, the present application provides a process for the preparation of furfuryl alcohol comprising the steps of: adding the phosphorus modified zirconium-based catalyst into an alcoholic solution of furfural to perform catalytic transfer hydrogenation reaction to obtain furfuryl alcohol; the method comprises the following steps of preparing a phosphorus-modified zirconium-based catalyst, and adding an alcohol solution, wherein the reaction temperature is 160-220 ℃, the reaction pressure is 0.1-2 MPa, the reaction time is 1-4 h, the dosage ratio of the phosphorus-modified zirconium-based catalyst to furfural is 1g:1 mol-1 g:2mol, and the alcohol solution is selected from an ethanol solution, an n-propanol solution, an isopropanol solution, an n-butanol solution or an isobutanol solution.
Wherein the reaction temperature is 160-220 ℃ including any point in the temperature range, such as 160 ℃, 180 ℃, 200 ℃ and 220 ℃. The reaction pressure is 0.1 to 2MPa inclusive, and examples thereof include 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, and 2 MPa. The reaction time is 1-4 h and includes any point in the time range, for example, the reaction time is 1h, 2h, 3h and 4 h. The amount ratio of the phosphorus-modified zirconium-based catalyst to the furfural is 1g:1mol to 1g:2mol inclusive, for example, the amount ratio of the phosphorus-modified zirconium-based catalyst to the furfural is 1g:1mol, 1g:1.2mol, 1g:1.5mol, 1g:2 mol.
Further, in the method, the reaction temperature is 180 ℃, the reaction pressure is 2MPa, the reaction time is 2h, the dosage ratio of the phosphorus-modified zirconium-based catalyst to the furfural is 1g:1mol, and the alcohol solution is isopropanol solution.
Compared with the prior art, the beneficial effects of this application are as follows:
firstly, the application obtains a brand new catalyst for modifying a zirconium-based metal organic framework by phosphorus, and the diammonium hydrogen phosphate and the zirconium-based metal organic framework are roasted to successfully load a phosphorus element on the zirconium-based metal organic framework.
Secondly, the process conditions of the preparation method of the phosphorus modified zirconium-based metal organic framework are explored, so that the obtained phosphorus-loaded zirconium-based catalyst has good furfuryl alcohol selectivity and high furfural conversion rate.
Finally, the preparation method of the phosphorus modified zirconium-based catalyst has the characteristics of few process steps, strong operability and the like, and is suitable for industrial popularization and application.
Drawings
FIG. 1 is an SEM image of a phosphorus-modified zirconium-based catalyst of example 2 herein.
FIG. 2 is an EDX spectrum of a phosphorus-modified zirconium-based catalyst of example 2 herein.
Fig. 3 is an SEM image of a zirconium based catalyst of comparative example 1 of the present application.
FIG. 4 is an EDX spectrum of a zirconium based catalyst of comparative example 1 of the present application.
Fig. 5 is an XRD spectrum of examples 1 to 6 of the present application, comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It is noted that the terms "comprises" and "comprising," and any variations thereof, of the embodiments of the present application are intended to cover non-exclusive inclusions.
In addition, the reaction raw materials and solvents used in the examples of the present application include, but are not limited to, zirconium oxychloride octahydrate, acetic acid, N' -dimethylformamide, absolute ethanol, terephthalic acid, diammonium hydrogen phosphate, etc., which are commercially available.
Example 1
This example provides a phosphorus-modified zirconium-based catalyst, and a method for preparing the phosphorus-modified zirconium-based catalyst includes the following steps:
preparing a zirconium-based metal organic framework: dissolving 1mmol of zirconium oxychloride octahydrate in a mixed solution of 15ml of acetic acid and 30ml of N, N '-dimethylformamide, adding 1mmol of terephthalic acid, stirring until the solution is dissolved to form a reaction solution system, carrying out solvent heat treatment on the reaction solution system at 120 ℃ for 24 hours by adopting an aging kettle, filtering a product, washing the product for 3 times by using N, N' -dimethylformamide and absolute ethyl alcohol respectively, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the zirconium-based metal organic framework.
Roasting: placing a zirconium-based metal organic framework and diammonium hydrogen phosphate in a constant-temperature area of a tubular furnace, placing the diammonium hydrogen phosphate in the front section of the constant-temperature area of the tubular furnace, placing the zirconium-based metal organic framework in the rear section of the constant-temperature area, introducing nitrogen at a flow rate of 20 mL/min, heating the constant-temperature area to 350 ℃ at a temperature of 3 ℃/min, and roasting at the constant temperature of 350 ℃ for 2 hours to obtain a phosphorus-modified zirconium-based catalyst, wherein the serial number is R1; wherein the mass ratio of the diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1:1.
Example 2
This example provides a phosphorus modified zirconium based catalyst and a method for preparing the same, and differs from example 1 only in that: in the roasting step, the mass ratio of diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the zirconium-based metal organic framework preparation step is 1.5: 1. The phosphorus-modified zirconium-based catalyst obtained in this example was designated by the reference numeral R2.
Example 3
This example provides a phosphorus modified zirconium based catalyst and a method for preparing the same, and differs from example 1 only in that: in the roasting step, the mass ratio of diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the zirconium-based metal organic framework preparation step is 2: 1. The phosphorus-modified zirconium-based catalyst obtained in this example was designated by the reference numeral R3.
Example 4
This example provides a phosphorus modified zirconium based catalyst and a method for preparing the same, and differs from example 1 only in that: in the roasting step, the mass ratio of diammonium hydrogen phosphate to the mass of zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal-organic framework is 2.5: 1. The phosphorus-modified zirconium-based catalyst obtained in this example was designated by the reference numeral R4.
Example 5
This example provides a phosphorus-modified zirconium-based catalyst and a method for preparing the same, and differs from example 2 only in that: in the roasting step, roasting is carried out for 2 hours at the constant temperature of 300 ℃ to obtain the phosphorus modified zirconium-based catalyst, which is numbered as R5.
Example 6
This example provides a phosphorus-modified zirconium-based catalyst and a method for preparing the same, and differs from example 2 only in that: in the roasting step, roasting is carried out for 2 hours at the constant temperature of 400 ℃ to obtain the phosphorus modified zirconium-based catalyst, which is numbered as R6.
Comparative example 1
The present comparative example provides a zirconium based catalyst, the method of preparing the zirconium based catalyst comprising the steps of:
preparing a zirconium-based metal organic framework: dissolving 1mmol of zirconium oxychloride octahydrate in a mixed solution of 15ml of acetic acid and 30ml of N, N '-dimethylformamide, adding 1mmol of terephthalic acid, stirring until the solution is dissolved to form a reaction solution system, carrying out solvent heat treatment on the reaction solution system at 120 ℃ for 24 hours by adopting an aging kettle, filtering a product, washing the product for 3 times by using N, N' -dimethylformamide and absolute ethyl alcohol respectively, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the zirconium-based metal organic framework.
Roasting: and (3) placing the zirconium-based metal organic framework in a constant-temperature area of a tubular furnace, introducing nitrogen at the flow rate of 20 mL/min, heating the constant-temperature area to 350 ℃ at the speed of 3 ℃/min, and roasting at the constant temperature of 350 ℃ for 2 hours to obtain the zirconium-based catalyst, wherein the serial number of the zirconium-based catalyst is D1.
SEM and EDX tests were performed on the phosphorus-modified zirconium-based catalyst of example 2 and the zirconium-based catalyst of comparative example 1, as shown in fig. 1 to 4, in which fig. 1 and 2 are SEM and EDX spectra, respectively, of the phosphorus-modified zirconium-based catalyst of example 2, and fig. 3 and 4 are SEM and EDX spectra, respectively, of the zirconium-based catalyst of comparative example 1. The following conclusions can be drawn from the above figures: firstly, as can be seen from SEM spectrogram, the phosphorus modified zirconium-based catalyst in the example 2 and the zirconium-based catalyst in the comparative example 1 both present octahedral structures; secondly, as can be seen from the EDX spectrogram, although the carbon element, the zirconium element and the oxygen element in the comparative example 1 are uniformly dispersed, no phosphorus element is present, and the phosphorus element, the carbon element, the zirconium element and the oxygen element are uniformly dispersed in the example 2, which indicates that the phosphorus element is successfully loaded on the zirconium-based metal organic framework, so that the phosphorus-modified zirconium-based catalyst is obtained.
XRD tests were performed on the phosphorus-modified zirconium-based catalysts of examples 1 to 6 and the zirconium-based catalyst of comparative example 1, respectively, and the results are shown in fig. 5. As can be seen from fig. 5, the zirconium-based catalyst as comparative example 1 had a complete crystal structure of the zirconium-based metal organic framework. The crystal structure of the zirconium-based catalyst obtained by phosphorus modification in examples 1 to 6 of the present application was not changed, and no diffraction peak related to phosphorus was observed.
In order to test the catalytic performance of the phosphorus-modified zirconium-based catalyst, a series of application examples and catalyst performance tests are also provided.
Application example 1
The application example provides a method for preparing furfuryl alcohol, which comprises the following steps: weighing 0.01g of the phosphorus-modified zirconium-based catalyst of example 1, placing the phosphorus-modified zirconium-based catalyst in a 50mL high-pressure reaction kettle, adding 10mL of 1mol/L furfural isopropanol solution, sealing, charging and discharging nitrogen for 6 times for replacement, then charging 2MPa of nitrogen, heating to 180 ℃, carrying out catalytic transfer hydrogenation reaction for 2 hours, and stirring at the speed of 800 r/min to obtain furfuryl alcohol, wherein the number is A1.
Application example 2
The present application example provides a method for producing furfuryl alcohol, and differs from application example 1 only in that: the phosphorus-modified zirconium-based catalyst of example 2 was used in this application example to give furfuryl alcohol No. a 2.
Application example 3
The present application example provides a method for producing furfuryl alcohol, and differs from application example 1 only in that: the phosphorus-modified zirconium-based catalyst of example 3 was used in this application example to give furfuryl alcohol No. a 3.
Application example 4
The present application example provides a method for producing furfuryl alcohol, and differs from application example 1 only in that: the phosphorus-modified zirconium-based catalyst of example 4 was used in this application example to give furfuryl alcohol No. a 4.
Application example 5
The present application example provides a method for producing furfuryl alcohol, and differs from application example 1 only in that: the phosphorus-modified zirconium-based catalyst of example 5 was used in this application example to give furfuryl alcohol No. a 5.
Application example 6
The present application example provides a method for producing furfuryl alcohol, and differs from application example 1 only in that: the phosphorus-modified zirconium-based catalyst of example 6 was used in this application example to give furfuryl alcohol No. a 6.
Comparative application example 1
The present comparative application example provides a method for producing furfuryl alcohol, and differs from application example 1 only in that: the zirconium based catalyst of comparative example 1 was used in this application example to give furfuryl alcohol No. B1.
The catalytic performance of the catalyst is judged by testing two indexes of furfural conversion rate and furfuryl alcohol selectivity of the catalyst in the application example.
The furfural conversion rate refers to the conversion rate of furfural transfer hydrogenation reaction, and the conversion rate can reflect how much furfural has undergone hydrogenation reaction, and the calculation formula is as follows:
Figure BDA0002288790070000081
wherein n is1Is the amount (mol) of the material of furfural before reaction, n2Is the amount (mol) of the reacted furfural substance.
The furfuryl alcohol selectivity reflects the selectivity of furfuryl alcohol as the product generated after furfural hydrogenation reaction. Because furfural is subjected to transfer hydrogenation reaction to generate furfuryl alcohol and possibly hydrogenated and converted into other substances (such as 2-methylfuran, 2-methyltetrahydrofuran and the like), analysis and test on furfuryl alcohol selectivity can reflect how much the phosphorus-modified zirconium-based catalyst can play a role in generating product selectivity. The furfuryl alcohol selectivity is calculated as:
Figure BDA0002288790070000082
wherein n is3Is the amount (mol) of furfuryl alcohol formed after the reaction, n4The amount (mol) of the substance as a total product after the reaction.
The results of the furfural conversion and furfuryl alcohol selectivity tests for application examples 1 to 6, comparative application example 1 are shown in table 1 below:
Figure BDA0002288790070000091
table 1: application examples 1 to 6, comparative application example 1 furfural conversion and furfuryl alcohol selectivity
And (4) conclusion: (1) as can be seen from comparison of application examples 1 to 4 and application comparative example 1, when furfural catalytic transfer hydrogenation was performed using an unmodified zirconium-based catalyst to prepare furfuryl alcohol, although the furfuryl alcohol selectivity was as high as 99.0%, the furfural conversion rate was only 59.1%; after the phosphorus modified zirconium-based catalyst provided by the embodiment of the application is used, the higher furfuryl alcohol selectivity is still maintained, and the furfural conversion rate can be obviously improved. This shows that the successful loading of phosphorus can significantly improve the catalytic transfer hydrogenation activity of furfural after phosphorus modification of the zirconium-based catalyst.
(2) By comparing application examples 1 to 4 and application comparative example 1, it can be seen that in the calcination step of the phosphorus-modified zirconium-based catalyst preparation process, the amount ratio of diammonium phosphate to the amount of zirconium oxychloride octahydrate in the zirconium-based metal organic framework preparation step has an important influence on the furfural conversion rate of the catalyst. Specifically, as the amount ratio of this substance increases, the furfural conversion rate significantly increases. When the mass ratio of the diammonium hydrogen phosphate to the substances of the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1.5:1, the method has higher furfural conversion rate and furfuryl alcohol selectivity; when the amount ratio of the substance is continuously increased to 2:1, the conversion rate of the furfural is slightly improved, but the selectivity of the furfuryl alcohol is slightly reduced; the amount ratio of the substance is further increased, and the conversion rate of furfural is slightly reduced. The catalyst is prepared by taking the activity of catalytic transfer hydrogenation of furfural, the selectivity of furfuryl alcohol, the dosage of reaction materials and other factors into comprehensive consideration, and preferably by adopting the condition that the mass ratio of diammonium hydrogen phosphate to the substance of the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1.5: 1.
(3) As can be seen from comparison of application examples 2, 5 and 6, the calcination temperature greatly affects the production of the phosphorus-modified zirconium-based catalyst. Specifically, when the roasting temperature is too low, the phosphorus-containing substances decomposed from diammonium phosphate by roasting are less, so that only a few phosphorus elements can be loaded on the zirconium-based metal organic framework, and the catalytic performance of the catalyst is further influenced. When the roasting temperature is too high, experiments show that the too high roasting temperature can cause the collapse of the structure of the zirconium-based metal organic framework, and further can influence the catalytic performance. Experiments prove that the optimum roasting temperature for preparing the phosphorus-modified zirconium-based catalyst is 350 ℃, and the catalytic transfer hydrogenation activity of furfural is reduced by increasing or decreasing the roasting temperature. Therefore, the optimum roasting temperature of the phosphorus modified zirconium-based catalyst is 350 ℃.
Research on alcohol types in reaction for preparing furfuryl alcohol by catalytic transfer hydrogenation of furfural
Through the experiment, the phosphorus-modified zirconium-based catalyst in the embodiment 2 has higher furfural conversion rate and furfuryl alcohol selectivity. However, in the method for preparing furfuryl alcohol by catalytic transfer hydrogenation of furfural, the used alcohol solution serves as a solvent on one hand and a hydrogen donor on the other hand. Therefore, the application also carries out detailed research on the alcohol types in the method for preparing the furfuryl alcohol by catalytic transfer hydrogenation of the furfural. Specifically, with the method of application example 2, only the kind of the alcohol solution used in the catalytic transfer hydrogenation reaction is changed (for example, a furfural methanol solution is used instead of a furfural isopropanol solution), and the furfural conversion rate and the furfuryl alcohol selectivity after the catalytic transfer hydrogenation reaction are tested, and the test results are shown in table 2.
Figure BDA0002288790070000101
Table 2: influence of different alcohol species on reaction for preparing furfuryl alcohol by catalytic transfer hydrogenation of furfural
And (4) conclusion: as can be seen from table 2, the methods No. 4 and No. 6 have higher furfural conversion and furfuryl alcohol selectivity, and particularly No. 4 (application example 2) uses an isopropanol solution as a solvent/hydrogen donor, and the catalytic performance is the best, indicating that the furfural conversion and furfuryl alcohol selectivity are the highest when the isopropanol solution is used, and the second time when isobutanol is used. As for other alcohol solutions, it is difficult to achieve high furfural conversion and furfuryl alcohol selectivity at the same time, so that an isopropanol solution or an isobutanol solution is preferably used, and an isopropanol solution is most preferably used.
In summary, firstly, the present application successfully explores a preparation method to obtain a brand-new catalyst, namely a phosphorus-modified zirconium-based catalyst, and specifically, co-calcines diammonium phosphate and a zirconium-based metal organic framework to enable diammonium phosphate to decompose phosphorus-containing substances and successfully load the phosphorus-containing substances on the zirconium-based metal organic framework. This is one of the important points of the present application, and there has been no literature describing successful loading of a phosphorus element on a zirconium-based metal organic framework by a firing method.
Secondly, on the basis of obtaining the phosphorus modified zirconium based catalyst, the method for preparing the catalyst optimizes and explores reaction conditions, so that the phosphorus modified zirconium based catalyst has high furfural conversion rate and furfuryl alcohol selectivity, which is another important invention point of the method. In fact, the inventors of the present application have also conducted a catalytic performance study on the zirconium-based metal organic framework itself, but the results show that although the furfuryl alcohol selectivity is good, the furfural conversion rate is not high, indicating that there is still a great room for improvement of this catalyst. For this reason, the inventors have made various attempts, for example, the inventors have attempted to use an impregnation method to support a phosphorus element on a zirconium-based metal organic framework, but the results show that this method does not improve furfural conversion. And the phosphorus element in the diammonium phosphate can be successfully loaded on the zirconium-based metal organic framework by using the roasting method, and particularly, the zirconium-based metal organic framework can still keep the crystal structure of the zirconium-based metal organic framework while the phosphorus element can be successfully loaded on the zirconium-based metal organic framework by controlling the roasting temperature condition. This property is very important for the phosphorus-modified zirconium-based catalyst of the present application, because the structure of the zirconium-based metal-organic framework itself plays an important role in improving the catalytic performance of the catalyst, which is also affected if the phosphorus element is supported but the metal-organic framework structure itself collapses.
The phosphorus-modified zirconium-based catalyst, the preparation method thereof and the method for preparing furfuryl alcohol disclosed in the examples of the present application are described in detail above, and the principle and the embodiments of the present application are explained in detail herein by using specific examples, and the description of the examples is only used to help understanding the method and the core concept thereof; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (10)

1. A preparation method of a phosphorus-modified zirconium-based catalyst is characterized by comprising the following steps of:
preparing a zirconium-based metal organic framework;
roasting: and roasting the zirconium-based metal organic framework and diammonium hydrogen phosphate at the constant temperature of 400 ℃ in an inert gas atmosphere to obtain the phosphorus-modified zirconium-based catalyst.
2. The method according to claim 1, wherein the step of preparing the zirconium-based metal organic framework comprises: mixing zirconium oxychloride octahydrate, acetic acid, N' -dimethylformamide and terephthalic acid, carrying out solvent heat treatment, and filtering, washing and drying a product to obtain the zirconium-based metal organic framework.
3. The preparation method according to claim 2, wherein in the step of preparing the zirconium-based metal organic framework, zirconium oxychloride octahydrate is dissolved in a mixed solution of acetic acid and N, N' -dimethylformamide, terephthalic acid is added and stirred until the zirconium oxychloride is dissolved to form a reaction solution system, the reaction solution system is subjected to solvent heat treatment by using an aging kettle, products are filtered, washed with organic solvents for 3 times respectively, and vacuum-dried at 60 ℃ for 12 hours to obtain the zirconium-based metal organic framework; the amount ratio of the zirconium oxychloride octahydrate to the terephthalic acid is 1: 1-1: 1.5, the volume ratio of acetic acid to N, N '-dimethylformamide is 1: 1-1: 3, the dosage ratio of the zirconium oxychloride octahydrate to the acetic acid is 1mmol:10 mL-1 mmol:20mL, and the organic solvent is N, N' -dimethylformamide and absolute ethyl alcohol.
4. The method according to claim 3, wherein in the step of preparing the zirconium-based metal organic framework, the mass ratio of zirconium oxychloride octahydrate to terephthalic acid is 1:1, the volume ratio of acetic acid to N, N' -dimethylformamide is 1:2, and the mass ratio of zirconium oxychloride octahydrate to acetic acid is 1mmol:15 mL.
5. The method according to any one of claims 2 to 4, wherein the firing step is: and placing the zirconium-based metal organic framework and diammonium hydrogen phosphate in a constant-temperature area of a heating device, introducing inert gas, and roasting at the constant temperature of 400 ℃, wherein the mass ratio of the diammonium hydrogen phosphate to the substance of the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 0.8: 1-5: 1, and the inert gas is selected from at least one of nitrogen, helium, neon and argon.
6. The preparation method as claimed in claim 5, wherein in the roasting step, diammonium hydrogen phosphate is placed at the front section of the constant temperature zone, the zirconium-based metal organic framework is placed at the rear section of the constant temperature zone, the interval between diammonium hydrogen phosphate and the zirconium-based metal organic framework is greater than or equal to 2 cm, the inert gas is introduced at the flow rate of 15-50 mL/min, the temperature of the constant temperature zone is raised to 320-380 ℃ at the rate of 2-5 ℃/min, and the roasting is carried out for 1-3 hours at the constant temperature; wherein the mass ratio of the diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1: 1-2.5: 1.
7. The preparation method according to claim 6, wherein in the roasting step, the spacing between the diammonium hydrogen phosphate and the zirconium-based metal organic framework is greater than or equal to 5 cm, nitrogen is introduced at a flow rate of 20 mL/min, the temperature of the constant-temperature area is raised to 350 ℃ at a rate of 3 ℃/min, and the constant-temperature area is roasted for 2 hours at a constant temperature; wherein the mass ratio of the diammonium hydrogen phosphate to the zirconium oxychloride octahydrate in the step of preparing the zirconium-based metal organic framework is 1:1.
8. A phosphorus-modified zirconium-based catalyst, characterized in that it is obtained by the production method according to any one of claims 1 to 7.
9. A process for the preparation of furfuryl alcohol, characterized in that it comprises the steps of: adding a phosphorus modified zirconium-based catalyst into an alcoholic solution of furfural to perform catalytic transfer hydrogenation reaction to obtain furfuryl alcohol; the preparation method of any one of claims 1 to 7, wherein the phosphorus-modified zirconium-based catalyst is prepared by the preparation method of any one of claims 1 to 7, the reaction temperature is 160 to 220 ℃, the reaction pressure is 0.1 to 2MPa, the reaction time is 1 to 4 hours, the dosage ratio of the phosphorus-modified zirconium-based catalyst to the furfural is 1g:1mol to 1g:2mol, and the alcohol solution is selected from an ethanol solution, an n-propanol solution, an isopropanol solution, an n-butanol solution or an isobutanol solution.
10. The method according to claim 9, wherein in the method, the reaction temperature is 180 ℃, the reaction pressure is 2MPa, the reaction time is 2 hours, the use ratio of the phosphorus-modified zirconium-based catalyst to the furfural is 1g:1mol, and the alcohol solution is an isopropanol solution.
CN201911171312.8A 2019-11-26 2019-11-26 Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol Active CN111036301B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911171312.8A CN111036301B (en) 2019-11-26 2019-11-26 Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911171312.8A CN111036301B (en) 2019-11-26 2019-11-26 Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol

Publications (2)

Publication Number Publication Date
CN111036301A CN111036301A (en) 2020-04-21
CN111036301B true CN111036301B (en) 2020-08-11

Family

ID=70234082

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911171312.8A Active CN111036301B (en) 2019-11-26 2019-11-26 Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol

Country Status (1)

Country Link
CN (1) CN111036301B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928167A (en) * 2017-03-14 2017-07-07 中国科学院广州能源研究所 A kind of method that utilization hydrogen transfer reaction catalysis furfural prepares furfuryl alcohol
CN109731616A (en) * 2019-02-01 2019-05-10 上海应用技术大学 A kind of catalyst of zirconium metal-organic framework materials load and its preparation and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101856709B1 (en) * 2016-05-03 2018-05-10 한국화학연구원 MOF-808 based Metal-Organic Frameworks as Catalyst for Transfer Hydrogenation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928167A (en) * 2017-03-14 2017-07-07 中国科学院广州能源研究所 A kind of method that utilization hydrogen transfer reaction catalysis furfural prepares furfuryl alcohol
CN109731616A (en) * 2019-02-01 2019-05-10 上海应用技术大学 A kind of catalyst of zirconium metal-organic framework materials load and its preparation and application

Also Published As

Publication number Publication date
CN111036301A (en) 2020-04-21

Similar Documents

Publication Publication Date Title
CN106279075B (en) A method of catalysis 5 hydroxymethyl furfural prepares 2,5- dimethyl furans
CN108435230B (en) Heteroatom-doped ordered mesoporous carbon-supported ruthenium catalyst for efficiently catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde
Mondal et al. One‐Pot Synthesis of Polyhydroquinoline Derivatives through Organic‐Solid‐Acid‐Catalyzed Hantzsch Condensation Reaction
CN108164555B (en) Synthesis method of boric acid ester
CN108620127B (en) Catalyst for preparing 1, 5-pentanediol through hydrogenolysis of tetrahydrofurfuryl alcohol, preparation method and application thereof
CN105399705B (en) A kind of method that furfuryl alcohol is prepared using hydrogen transfer reaction
CN110961110A (en) Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine
Wang et al. Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium (IV) Schiff base complexes on mesoporous silica with isopropanol as hydrogen source
CN106631762A (en) Method for preparing pyrovinic acid through catalysis of itaconic acid for hydrogenation by ruthenium carbon catalyst after carbon thermal reduction
CN111087370B (en) Method for preparing furfuryl alcohol by furfural transfer hydrogenation under catalysis of nitrogen-doped carbon supported by non-noble metal
CN111036301B (en) Phosphorus modified zirconium-based catalyst, preparation method thereof and method for preparing furfuryl alcohol
CN107245065A (en) A kind of method that catalytic hydrogenation ethyl levulinate prepares valerolactone
CN113877583A (en) Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application
CN102872862B (en) Carrier type platinum-ruthenium catalyst and application of carrier type platinum-ruthenium catalyst in hydrogenation of aromatic nitro compound
CN102218304A (en) Catalyst for producing difluoro acetylfluoride and preparation method thereof
CN105709855B (en) A kind of preparation method of palladium hydrogenation catalyst, the catalyst prepared by this method and the method for using the catalyst preparation piperidines
CN109535108A (en) A kind of preparation method of 2,5- dimethyl furan
CN108047173B (en) Method for preparing gamma-valerolactone
CN109622031A (en) The preparation method of 2- hydroxyphosphonoacetic acid zirconium and its application in furfuryl alcohol synthesis
CN113117682A (en) Method for catalytic hydrogenation upgrading of Pickering emulsion system biomass platform compound
CN109400452A (en) A kind of method that furan derivatives acid catalysis adds hydrogen 3- acetylpropyl alcohol and 1,4- pentanediol
CN109772337B (en) Supported nickel-based nano catalyst and preparation method and application thereof
CN110078687A (en) A kind of preparation method of 2- methyltetrahydrofuran
CN116459857B (en) High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system
CN112538096A (en) Semi-sandwich rhodium complex with ortho-carborane benzoxazole structure and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant