CN112023982B - Method for preparing zirconium-loaded PAN (Polyacrylonitrile) composite material through electrostatic spinning and application - Google Patents
Method for preparing zirconium-loaded PAN (Polyacrylonitrile) composite material through electrostatic spinning and application Download PDFInfo
- Publication number
- CN112023982B CN112023982B CN202010690267.3A CN202010690267A CN112023982B CN 112023982 B CN112023982 B CN 112023982B CN 202010690267 A CN202010690267 A CN 202010690267A CN 112023982 B CN112023982 B CN 112023982B
- Authority
- CN
- China
- Prior art keywords
- electrostatic spinning
- polyacrylonitrile
- composite material
- zirconium
- stirring
- 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
Links
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 80
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 93
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000000520 microinjection Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 abstract description 70
- 239000002028 Biomass Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- -1 zirconium ions Chemical class 0.000 abstract description 2
- 238000009901 transfer hydrogenation reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 239000012918 MOF catalyst Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000009891 weiqi Substances 0.000 description 1
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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a zirconium-loaded PAN composite material by an electrostatic spinning method and application, the method mainly comprises the steps of dissolving metal zirconium ions and polyacrylonitrile in N, N-dimethylformamide to prepare electrostatic spinning solution, preparing a heterogeneous phase loaded Zr @ PAN composite material by an electrostatic spinning technology, and applying the prepared composite material to the transfer hydrogenation reduction of furfural, so that a biomass-based energy product furfuryl alcohol is obtained at a high yield.
Description
Technical Field
The invention relates to a method for preparing a zirconium-loaded PAN composite material by electrostatic spinning and application thereof, belonging to the technical field of catalyst preparation and biomass catalytic conversion.
Background
The biomass energy is paid much attention under the global green environmental protection trend, and the biomass derived platform compound not only can realize the secondary utilization of biomass, but also can convert the biomass into a plurality of chemicals to become substitutes of fossil fuels and chemical products. The 3 atoms directly connected with carbonyl carbon atoms in furfural molecules are microscopically on the same plane, the plane configuration of the furfural molecules has small obstruction to reagent attack, and the carbonyl has great polarity and can form a carbonyl positive center, so the furfural molecules have high chemical activity. The route for preparing furfuryl alcohol by catalytic hydrogenolysis by taking furfural as a raw material can utilize the advantages of the natural carbon skeleton of furfural, the process is simple, the raw material is renewable, and the method has wide development prospect. The hydrogenolysis of furfural is an important means for preparing high value-added chemicals by converting furfural, and the prepared furfuryl alcohol can be used as a raw material for organic synthesis and also used for synthesizing resins, varnishes, pesticides, medicines, rubbers, coatings, fuel additives and the like.
The industrial preparation method of furfuryl alcohol is characterized by that it is made up by using furfural hydrogenation process: the hydrogenation is divided into liquid phase hydrogenation and gas phase hydrogenation. The liquid phase hydrogenation method comprises the steps of reacting furfural and hydrogen at a molar ratio of 1:42 (molar ratio) at 190-210 ℃ and under 5-8MPa (or more than 10MPa and 170 ℃ by using a Cu-Cr catalyst) in the presence of a Cu-Cr-Ca catalyst, settling after the reaction is finished, removing the solid catalyst, and obtaining a liquid which is a furfuryl alcohol crude product. The gas phase hydrogenation method is characterized in that furfural and hydrogen react in a shell-and-tube reactor at a molar ratio of 1:42 in the presence of a Ni-Cu or Cr-Cu catalyst at a temperature of 80-170 ℃ and a pressure of 0.1-0.39 MPa to obtain the furfural-hydrogen-containing catalyst. And (3) rectifying the obtained crude furfuryl alcohol under the reduced pressure of 80-87 kPa to remove tar-like substances, washing with sodium bisulfite, drying and dehydrating, and then adding sodium carbonate to perform reduced pressure distillation to obtain the pure product of the furfuryl alcohol. The industrial furfuryl alcohol preparing process has certain limitation, high cost, high toxicity of Cr (VI) metal and great environmental pollution. In addition, furfural can be prepared by a disproportionation method, which takes furfural as a raw material to carry out disproportionation reaction in the presence of caustic soda.
In recent years, in order to realize the catalytic preparation of furfuryl alcohol by furfural more greenly and efficiently, researchers have developed a plurality of new catalytic systems, for example, the weiqi group in mengxiang prepares a highly dispersed metal nano catalyst Au/SBA-15 by a post-modification method, and takes the reaction of furfuryl alcohol preparation by furfural hydrogenation as an example to investigate the influence of reaction temperature, reaction pressure, reaction time and the like on the catalytic performance of the catalyst. The result shows that under the conditions that the mass fraction of gold is 1%, the reaction temperature is 220 ℃, the reaction pressure is 5MPa, the reaction time is 4h and the mass fraction of the catalyst is 2%, the conversion rate of the furfural is 92.1% and the selectivity is 97.8%. But the deficiency is that the experiments are usually in H2The process is carried out under high pressure, has certain dangerousness, and the cost of the noble metal is too high to be suitable for industrial production. The Hu Li topic group utilizes metal zirconium and organic acid to prepare MOF catalyst Zr-FDCA which is applied to the reaction of furfural for preparing furfuryl alcohol, the yield is only 78 percent, and the supported catalyst Zr-FDCA is prepared after continuously adding methyl pyrrolidone and trimethylbenzeneFDCA-T is applied to the reaction of preparing furfuryl alcohol from furfural, and the yield is found to be improved to 96 percent, but the process of a metal and organic acid catalytic system is complicated, the cost is higher, and the loss is large when the catalyst is recovered.
Disclosure of Invention
In order to solve the problems and the defects of the prior art, the polyacrylonitrile is used as the carrier, the metal zirconium is loaded on the PAN nano-fiber through the electrostatic spinning method to prepare the composite material, the raw material is simple, the cost is low, the zirconium-loaded PAN composite material is used as the catalyst to realize the high-efficiency conversion of furfural to furfuryl alcohol, and the loss is small in the catalyst recycling process.
The invention provides a method for preparing a zirconium-loaded PAN composite material (Zr @ PAN) by electrostatic spinning, which specifically comprises the following steps:
(1) adding polyacrylonitrile into N, N-dimethylformamide, and stirring for dissolving to obtain a polyacrylonitrile solution;
(2) zr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain a mixed solution;
(3) stirring the mixed solution obtained in the step (2) in an oil bath, and fully and uniformly mixing the solution to obtain an electrostatic spinning precursor solution;
(4) and (4) carrying out electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (3) to obtain the zirconium-loaded PAN composite material.
The mass-volume ratio of the polyacrylonitrile to the DMF in the step (1) is 56.25:1g/L, and the molecular weight of the polyacrylonitrile is 15 ten thousand.
The stirring in the step (1) is carried out at 20-30 ℃ for 30 minutes at the stirring speed of 300-400 rpm.
The mass ratio of Zr (NO3)4 & 5H2O to polyacrylonitrile in the step (2) is 0.5-2.1: 1.
And (3) the power of ultrasonic dispersion in the step (2) is 20-25 kHz, and the time is 5-10 minutes.
And (3) carrying out oil bath at the temperature of 65-80 ℃ for 1 hour, and stirring at the rotating speed of 15-20 rpm.
The electrostatic spinning conditions in the step (4) are as follows: the flow rate of the micro-injection pump is set to be 0.4-0.8 mL/h, the voltage is 10-14 KV, the distance between the needle head and the receiver is 8-12 cm, and the spinning time is 10 h.
The invention also provides application of the zirconium-loaded PAN composite material (Zr @ PAN) prepared by electrostatic spinning as a furfuryl alcohol reduction reaction catalyst, wherein the catalytic hydrogenation reaction temperature is 150 ℃, and the hydrogenation reaction time is 2 hours.
The invention has the beneficial effects that:
1. the zirconium-loaded PAN composite material (Zr @ PAN) is prepared by an electrostatic spinning method, and the whole system is cheap, easy to obtain, good in catalytic activity and easy to recover.
2. The method has the advantages of simple process, renewable raw materials, mild reaction conditions, green reaction system, safety, environmental protection and wide development prospect.
3. The zirconium-loaded PAN composite material (Zr @ PAN) obtained by the method has extremely high specific surface area and porosity, and shows high catalytic activity in the process of converting furfural into furfuryl alcohol.
Drawings
FIG. 1 is a schematic view of electrospinning according to example 1.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
A method for preparing a zirconium-loaded PAN composite material (Zr @ PAN) through electrostatic spinning specifically comprises the following steps:
(1) adding 2.25g of polyacrylonitrile into 40mL of DMF (dimethyl formamide), wherein the molecular weight of the polyacrylonitrile is 15 ten thousand, stirring at 25 ℃ for 30 minutes for dissolution, and stirring at the rotating speed of 400rpm to obtain a polyacrylonitrile solution;
(2) 2.65gZr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and uniformly dispersing by using ultrasonic, wherein the power of ultrasonic dispersion is 25kHz, and the time is 5 minutes to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into an oil bath pot, heating and stirring, wherein the oil bath temperature is 65 ℃, the time is 1 hour, and the stirring speed is 18rpm, so that the solution is fully and uniformly mixed to obtain an electrostatic spinning precursor solution;
(4) and (3) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (4), wherein the electrostatic spinning conditions are as follows as shown in figure 1: the flow rate of the micro-injection pump is set to be 0.6mL/h, the voltage is 12KV, the distance between the needle head and the receiver is 10cm, the spinning time is 10h, and the Zr @ PAN composite material with the zirconium loading of 20% is obtained.
The method comprises the following steps of mixing 0.3g of furfural, 20mL of isopropanol and 0.1g of Zr @ PAN composite material prepared in the embodiment, adding the mixture into a closed high-pressure reaction kettle, replacing with nitrogen to remove air, introducing nitrogen with the flow rate of 100mL/min for 0.3min, removing gas at intervals of 0.5min, introducing nitrogen again, repeating for 3 times, and carrying out hydrogenation reaction at 150 ℃ for 2h to obtain a target product furfuryl alcohol; the conversion rate of furfural is 94.8%, and the yield of furfuryl alcohol is 99.8%; the Zr @ PAN composite material prepared in the embodiment is recycled, the solution after reaction is filtered, filter residue is washed for 3 times by using absolute ethyl alcohol, the obtained product is placed in a drying oven at 105 ℃ for drying for 12 hours, the furfural conversion rate is 92.5% after the cyclic utilization to catalytic reaction for 4 times, and the furfuryl alcohol yield is 95.2%.
Example 2
A method for preparing a zirconium-loaded PAN composite material (Zr @ PAN) through electrostatic spinning specifically comprises the following steps:
(1) adding 2.25g of polyacrylonitrile into 40mL of DMF, wherein the molecular weight of the polyacrylonitrile is 15 ten thousand, stirring at 26 ℃ for 30 minutes for dissolution, and stirring at the rotating speed of 350rpm to obtain a polyacrylonitrile solution;
(2) 1.18gZr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and uniformly dispersing by using ultrasonic, wherein the power of ultrasonic dispersion is 20kHz, and the time is 10 minutes to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into an oil bath pot, heating and stirring, wherein the oil bath temperature is 70 ℃, the time is 1 hour, and the stirring speed is 20rpm, so that the solution is fully and uniformly mixed to obtain an electrostatic spinning precursor solution;
(4) and (4) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (4), wherein the electrostatic spinning conditions are as follows: the flow rate of the micro-injection pump is set to be 0.8mL/h, the voltage is 14KV, the distance between the needle head and the receiver is 8cm, the spinning time is 10h, and the Zr @ PAN composite material with the zirconium loading of 10% is obtained.
The method comprises the following steps of mixing 0.3g of furfural, 20mL of isopropanol and 0.1g of Zr @ PAN composite material prepared in the embodiment, adding the mixture into a closed high-pressure reaction kettle, replacing with nitrogen to remove air, introducing nitrogen with the flow rate of 100mL/min for 0.3min, removing gas at intervals of 0.5min, introducing nitrogen again, repeating for 3 times, and carrying out hydrogenation reaction at 150 ℃ for 2h to obtain a target product furfuryl alcohol; the conversion rate of furfural is 74.9%, and the yield of furfuryl alcohol is 90.3%; the Zr @ PAN composite material prepared in the embodiment is recycled, the solution after reaction is filtered, filter residue is washed for 3 times by using absolute ethyl alcohol, the obtained product is placed in a drying oven at 105 ℃ for drying for 12 hours, the furfural conversion rate is 66.5% after the cyclic utilization for 4 times of catalytic reaction, and the furfuryl alcohol yield is 95.2%.
Example 3
A method for preparing a zirconium-loaded PAN composite material (Zr @ PAN) through electrostatic spinning specifically comprises the following steps:
(1) adding 2.25g of polyacrylonitrile into 40mL of DMF (dimethyl formamide), wherein the molecular weight of the polyacrylonitrile is 15 ten thousand, stirring at 20 ℃ for 30 minutes for dissolution, and stirring at the rotating speed of 400rpm to obtain a polyacrylonitrile solution;
(2) 4.54gZr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and uniformly dispersing by using ultrasonic, wherein the power of ultrasonic dispersion is 22kHz, and the time is 7 minutes to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into an oil bath pot, heating and stirring, wherein the oil bath temperature is 80 ℃, the time is 1 hour, and the stirring speed is 15rpm, so that the solution is fully and uniformly mixed to obtain an electrostatic spinning precursor solution;
(4) and (4) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (4), wherein the electrostatic spinning conditions are as follows: the flow rate of the micro-injection pump is set to be 0.7mL/h, the voltage is 10KV, the distance between the needle head and the receiver is 12cm, the spinning time is 10h, and the Zr @ PAN composite material with the zirconium loading of 30% is obtained.
The method comprises the following steps of mixing 0.3g of furfural, 20mL of isopropanol and 0.1g of Zr @ PAN composite material prepared in the embodiment, adding the mixture into a closed high-pressure reaction kettle, replacing with nitrogen to remove air, introducing nitrogen with the flow rate of 100mL/min for 0.3min, removing gas at intervals of 0.5min, introducing nitrogen again, repeating for 3 times, and carrying out hydrogenation reaction at 150 ℃ for 2h to obtain a target product furfuryl alcohol; the conversion rate of furfural is 90.2%, and the yield of furfuryl alcohol is 80.4%; the Zr @ PAN composite material prepared in the embodiment is recycled, the solution after reaction is filtered, filter residues are washed for 3 times by using absolute ethyl alcohol, the obtained product is placed in a drying oven at 105 ℃ for drying for 12 hours, the furfural conversion rate is 80.0% after the cyclic utilization for 4 times of catalytic reaction, and the furfuryl alcohol yield is 90.2%.
Example 4
A method for preparing a zirconium-loaded PAN composite material (Zr @ PAN) through electrostatic spinning specifically comprises the following steps:
(1) adding 2.25g of polyacrylonitrile into 40mL of DMF, wherein the molecular weight of the polyacrylonitrile is 15 ten thousand, stirring at 28 ℃ for 30 minutes for dissolution, and stirring at the rotating speed of 350rpm to obtain a polyacrylonitrile solution;
(2) 2.65gZr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and uniformly dispersing by using ultrasonic, wherein the power of ultrasonic dispersion is 24kHz, and the time is 6 minutes to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into an oil bath pot, heating and stirring, wherein the oil bath temperature is 75 ℃, the time is 1 hour, and the stirring speed is 16rpm, so that the solution is fully and uniformly mixed to obtain an electrostatic spinning precursor solution;
(4) and (4) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (4), wherein the electrostatic spinning conditions are as follows: the flow rate of the micro-injection pump is set to be 0.6mL/h, the voltage is 14KV, the distance between the needle head and the receiver is 10cm, the spinning time is 10h, and the Zr @ PAN composite material with the zirconium loading of 20% is obtained.
The method comprises the following steps of mixing 0.3g of furfural, 20mL of isopropanol and 0.1g of Zr @ PAN composite material prepared in the embodiment, adding the mixture into a closed high-pressure reaction kettle, replacing with nitrogen to remove air, introducing nitrogen with the flow rate of 100mL/min for 0.3min, removing gas at intervals of 0.5min, introducing nitrogen again, repeating for 3 times, and carrying out hydrogenation reaction at 150 ℃ for 2h to obtain a target product furfuryl alcohol; the conversion rate of furfural is 92.8%, and the yield of furfuryl alcohol is 94.0%; the Zr @ PAN composite material prepared in the embodiment is recycled, the solution after reaction is filtered, filter residues are washed for 3 times by using absolute ethyl alcohol, the obtained product is placed in a drying oven at 105 ℃ for drying for 12 hours, the furfural conversion rate is 80.5% after the cyclic utilization to catalytic reaction for 4 times, and the furfuryl alcohol yield is 85.2%.
Example 5
A method for preparing a zirconium-loaded PAN composite material (Zr @ PAN) through electrostatic spinning specifically comprises the following steps:
(1) adding 2.25g of polyacrylonitrile into 40mL of DMF (dimethyl formamide), wherein the molecular weight of the polyacrylonitrile is 15 ten thousand, stirring at 30 ℃ for 30 minutes for dissolution, and stirring at the rotating speed of 300rpm to obtain a polyacrylonitrile solution;
(2) 2.65gZr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and performing ultrasonic dispersion uniformly with the ultrasonic dispersion power of 23kHz and the ultrasonic dispersion time of 9 minutes to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into an oil bath pot, heating and stirring, wherein the oil bath temperature is 65 ℃, the time is 1 hour, and the stirring speed is 19rpm, so that the solution is fully and uniformly mixed to obtain an electrostatic spinning precursor solution;
(4) and (4) performing electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (4), wherein the electrostatic spinning conditions are as follows: the flow rate of the micro-injection pump is set to be 0.6mL/h, the voltage is 10KV, the distance between the needle head and the receiver is 8cm, the spinning time is 10h, and the Zr @ PAN composite material with the zirconium loading of 20% is obtained.
The method comprises the following steps of mixing 0.3g of furfural, 20mL of isopropanol and 0.1g of Zr @ PAN composite material prepared in the embodiment, adding the mixture into a closed high-pressure reaction kettle, replacing with nitrogen to remove air, introducing nitrogen with the flow rate of 100mL/min for 0.3min, removing gas at intervals of 0.5min, introducing nitrogen again, repeating for 3 times, and carrying out hydrogenation reaction at 150 ℃ for 2h to obtain a target product furfuryl alcohol; the conversion rate of furfural is 89.3%, and the yield of furfuryl alcohol is 90.6%; the Zr @ PAN composite material prepared in the embodiment is recycled, the solution after reaction is filtered, filter residue is washed for 3 times by using absolute ethyl alcohol, the obtained product is placed in a drying oven at 105 ℃ for drying for 12 hours, the furfural conversion rate is 78.4% after the cyclic utilization for 4 times of catalytic reaction, and the furfuryl alcohol yield is 84.2%.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (7)
1. An application of a zirconium-loaded PAN composite material prepared by electrostatic spinning as a furfuryl alcohol reduction reaction catalyst is provided, wherein the method for preparing the zirconium-loaded PAN composite material by electrostatic spinning specifically comprises the following steps:
(1) adding polyacrylonitrile into N, N-dimethylformamide, and stirring for dissolving to obtain a polyacrylonitrile solution;
(2) zr (NO)3)4·5H2Adding O into the polyacrylonitrile solution obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain a mixed solution;
(3) stirring the mixed solution obtained in the step (2) in an oil bath, and fully and uniformly mixing the solution to obtain an electrostatic spinning precursor solution;
(4) and (4) carrying out electrostatic spinning on the electrostatic spinning precursor solution obtained in the step (3) to obtain the zirconium-loaded PAN composite material.
2. The use according to claim 1, wherein the mass-to-volume ratio of polyacrylonitrile to N, N-dimethylformamide in step (1) is 56.25:1g/L, and the molecular weight of polyacrylonitrile is 15 ten thousand.
3. The use according to claim 1, wherein the stirring in step (1) is performed at 20-30 ℃ for 30 minutes at a stirring speed of 300-400 rpm.
4. Use according to claim 1, characterised in that step (2) Zr (NO)3)4·5H2The mass ratio of the O to the polyacrylonitrile is 0.5-2.1: 1.
5. The use of claim 1, wherein the ultrasonic dispersion in step (2) has a power of 20 to 25kHz and a time of 5 to 10 minutes.
6. The use of claim 1, wherein the oil bath temperature in the step (3) is 65-80 ℃, the time is 1 hour, and the stirring speed is 15-20 rpm.
7. The use of claim 1, wherein the conditions of the electrospinning in the step (4) are as follows: the flow rate of the micro-injection pump is set to be 0.4-0.8 mL/h, the voltage is 10-14 KV, the distance between the needle head and the receiver is 8-12 cm, and the spinning time is 10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010690267.3A CN112023982B (en) | 2020-07-17 | 2020-07-17 | Method for preparing zirconium-loaded PAN (Polyacrylonitrile) composite material through electrostatic spinning and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010690267.3A CN112023982B (en) | 2020-07-17 | 2020-07-17 | Method for preparing zirconium-loaded PAN (Polyacrylonitrile) composite material through electrostatic spinning and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112023982A CN112023982A (en) | 2020-12-04 |
| CN112023982B true CN112023982B (en) | 2021-07-13 |
Family
ID=73579562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010690267.3A Active CN112023982B (en) | 2020-07-17 | 2020-07-17 | Method for preparing zirconium-loaded PAN (Polyacrylonitrile) composite material through electrostatic spinning and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112023982B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112832018B (en) * | 2021-01-29 | 2021-12-10 | 东华大学 | Zirconium hydroxide nanosheet/nanofiber composite membrane and preparation method thereof |
| CN113413923A (en) * | 2021-06-24 | 2021-09-21 | 昆明理工大学 | Method for preparing acid-base difunctional nanofiber material by electrostatic spinning |
| CN113578387B (en) * | 2021-07-08 | 2023-07-25 | 昆明理工大学 | Method for electrostatic spinning self-assembled lignin-loaded zirconium hybrid material and application |
| CN113991130B (en) * | 2021-10-27 | 2024-01-19 | 西安热工研究院有限公司 | Polyacrylonitrile fiber supported cobalt-nickel alloy composite oxygen reduction catalytic material and preparation method thereof |
| CN115888818B (en) * | 2022-07-29 | 2024-04-02 | 南京工业大学 | Microfluidic electrostatic spinning in-situ growth flue gas denitration catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584211A (en) * | 2012-02-24 | 2012-07-18 | 西安理工大学 | Method for preparing micro/nano porous ceramic fibers by low-temperature electrostatic spinning |
| CN107805887A (en) * | 2017-10-27 | 2018-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of electrostatic spinning supported catalyst air filting material and products thereof and application |
| CN108276364A (en) * | 2018-01-29 | 2018-07-13 | 江南大学 | A kind of preparation and application of porous hexa metaphosphoric acid Zr catalyst |
-
2020
- 2020-07-17 CN CN202010690267.3A patent/CN112023982B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584211A (en) * | 2012-02-24 | 2012-07-18 | 西安理工大学 | Method for preparing micro/nano porous ceramic fibers by low-temperature electrostatic spinning |
| CN107805887A (en) * | 2017-10-27 | 2018-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of electrostatic spinning supported catalyst air filting material and products thereof and application |
| CN108276364A (en) * | 2018-01-29 | 2018-07-13 | 江南大学 | A kind of preparation and application of porous hexa metaphosphoric acid Zr catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "Porous zirconium oxide nanotube modified Nafion composite membrane for polymer electrolyte membrane fuel cells operated under dry conditions";Kriangsak Ketpang等;《Journal of Membrane Science》;20150420;第488卷;第155页右栏第2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112023982A (en) | 2020-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112023982B (en) | Method for preparing zirconium-loaded PAN (Polyacrylonitrile) composite material through electrostatic spinning and application | |
| CN101597508B (en) | Method for preparing alkane by high fatty acid ester | |
| CN102153465B (en) | Method for preparing low acid-value fatty acid methyl ester | |
| CN108435230B (en) | Heteroatom-doped ordered mesoporous carbon-supported ruthenium catalyst for efficiently catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde | |
| Yang et al. | Hydrothermal carbon enriched with sulfonic and carboxyl groups as an efficient solid acid catalyst for butanolysis of furfuryl alcohol | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN113368860B (en) | Catalyst for preparing cyclane through catalytic conversion of lignin, and preparation method and application thereof | |
| CN112044450A (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
| CN104177218B (en) | A kind of method reclaiming main ingredient from cyclohexanone by-product X oil | |
| CN107245065B (en) | method for preparing valerolactone by catalytic hydrogenation of ethyl levulinate | |
| CN113502174B (en) | Method for directly preparing aviation gasoline and aviation kerosene from polyolefin waste plastics | |
| CN109678821A (en) | A kind of method that normal pressure gas phase catalysis 5 hydroxymethyl furfural adds hydrogen to prepare 2,5- dimethyl furan | |
| CN102992984A (en) | Methyl ethyl ketone preparation method | |
| CN109999907B (en) | Preparation method and application of sulfonic acid functionalized inorganic-organic hybrid polymer catalyst | |
| CN111545202A (en) | Cheap metal catalyst for lignin oligomer hydrogenation depolymerization synchronous quality improvement and preparation method and application thereof | |
| CN101564696A (en) | Reaction process and catalyst for preparing aromatic hydrocarbon by ethanol with one-step method | |
| CN110270371B (en) | Lignin-based solid acid catalytic benzylation reaction method | |
| CN108658880B (en) | Preparation method of ultraviolet absorbent | |
| CN102492558A (en) | Method of preparing biodiesel in ionic liquid | |
| CN102492559A (en) | Method for preparing biodiesel in novel alkaline ionic liquid | |
| CN103709010A (en) | Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water | |
| CN101195600A (en) | Method for producing 4-hydroxyindole | |
| CN107286004A (en) | The refined method of polyoxymethylene dimethyl ether | |
| CN110981839A (en) | Method for preparing furfuryl alcohol or levulinate by furfural through one-pot method | |
| CN112824368A (en) | Application of tungsten oxide supported monatomic catalyst in preparation of aromatic compounds through hydrogenolysis of lignin |
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 |