CN116078374A - Preparation method and application of wood-based carbon supported heteropolyacid catalyst - Google Patents
Preparation method and application of wood-based carbon supported heteropolyacid catalyst Download PDFInfo
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- CN116078374A CN116078374A CN202211719805.2A CN202211719805A CN116078374A CN 116078374 A CN116078374 A CN 116078374A CN 202211719805 A CN202211719805 A CN 202211719805A CN 116078374 A CN116078374 A CN 116078374A
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- 239000002023 wood Substances 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 26
- 239000008158 vegetable oil Substances 0.000 claims abstract description 26
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 150000002989 phenols Chemical class 0.000 claims abstract description 9
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 39
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002383 tung oil Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 241000196324 Embryophyta Species 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 244000153888 Tung Species 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000004359 castor oil Substances 0.000 claims description 5
- 235000019438 castor oil Nutrition 0.000 claims description 5
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 240000007817 Olea europaea Species 0.000 claims description 4
- 235000019483 Peanut oil Nutrition 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000312 peanut oil Substances 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 235000002725 Olea europaea Nutrition 0.000 claims description 3
- 235000004443 Ricinus communis Nutrition 0.000 claims description 3
- 239000004006 olive oil Substances 0.000 claims description 3
- 235000008390 olive oil Nutrition 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- 240000000528 Ricinus communis Species 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 9
- 239000011973 solid acid Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000007306 functionalization reaction Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 13
- 235000013824 polyphenols Nutrition 0.000 description 11
- 150000008442 polyphenolic compounds Chemical class 0.000 description 10
- 238000010000 carbonizing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 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
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention belongs to the technical field of supported solid acid catalysts, and particularly relates to a preparation method and application of a wood-based carbon supported heteropolyacid catalyst. According to the invention, plant fruit cakes obtained after vegetable oil is squeezed are used as raw materials, the wood-based carbon is prepared by a solid microwave technology, and then the wood-based carbon supported heteropolyacid catalyst is obtained by an impregnation method. The wood-based carbon has higher specific surface area and aperture, and can be used as an excellent adsorbent and catalyst carrier; the wood-based carbon supported heteropolyacid catalyst with microspheres on the surface is obtained by an impregnation method, and the total acid content of the catalyst reaches 2408.4 mu mol/g, which is comparable to industrial liquid acid catalysts; the catalyst rich in acid sites is applied to the reaction of vegetable oil and phenolic compounds for preparing vegetable oil-based polyol, so that the method widens the way for refining and functionalization utilization of vegetable oil. The preparation method is simple in preparation process, relatively low in cost, green and sustainable.
Description
Technical Field
The invention belongs to the technical field of supported solid acid catalysts, and particularly relates to a preparation method and application of a wood-based carbon supported heteropolyacid catalyst.
Background
The vegetable oil-based polyol is an important chemical intermediate and has wide application in the aspects of daily life, such as food, cosmetics, sanitary products, chemical industry, medicines and the like. With the development of global industry, non-renewable resources such as petroleum and the like are exhausted within a certain period of time, and the preparation of polymer materials based on vegetable oil is increasingly attracting general attention. The main preparation methods of the vegetable oil-based polyol include a transesterification method, an epoxidation method, a Diels-Alder method and a Friedel-crafts alkylation method. Compared with the former production methods, the Friedel-crafts alkylation reaction process is simple, and the vegetable oil-based polyol can be prepared under the conditions of rapidness, mildness and environmental protection. However, the friedel-crafts alkylation reaction generally adopts inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and the like as catalysts, and has the disadvantages of large acid consumption, complex subsequent treatment process and strong corrosiveness of a reaction system, so that the requirement on equipment materials is high, and the equipment investment is increased.
Compared with the traditional inorganic acid catalyst, the solid acid catalyst has the advantages of no toxicity, no harm, small corrosion to equipment and easy separation and recovery, thus being an important way for realizing the environment-friendly new catalytic process. As an important member in the solid acid catalyst, the supported heteropolyacid catalyst not only inherits the advantages of high catalytic activity, small corrosiveness, high stability and adjustable phase transfer of the heteropolyacid, but also solves the problem of difficult separation and recovery from a reaction system, and simultaneously increases the utilization rate and stability of active components, thereby having wide application prospect; the plant fruit cake refers to plant fruit waste after the plant oil is squeezed, has the advantages of wide sources, natural and renewable properties, low price, environmental protection and the like, combines the utilization of the plant fruit cake with a polyacid catalyst, can provide a new development space for a large amount of waste materials, and has important value for the increment of the plant fruit cake and the reduction of the catalyst cost.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method and application of a wood-based carbon supported heteropolyacid catalyst.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the wood-based carbon supported heteropolyacid catalyst comprises the following steps:
s1: mixing plant fruit cake powder with phosphoric acid, acidifying, and drying at 80-100deg.C to obtain activated fruit cake;
s2: placing the activated fruit cake into a microwave reactor for carbonization to obtain wood-based carbon;
s3: dispersing wood-based carbon in a heteropolyacid aqueous solution, heating to 70-90 ℃ for reaction, and washing and drying after the reaction is finished to obtain the wood-based carbon supported heteropolyacid catalyst.
Optionally, the specific conditions for carbonizing the microwave reactor are as follows: the temperature is set to 300-600 ℃, the power is set to 500-800W, and the reaction time is 2-10 min under the nitrogen atmosphere.
Optionally, the heating reaction temperature in S3 is: 60-80 ℃.
Optionally, the mass usage ratio of the mass of the heteropolyacid to the wood-based carbon is expressed in mmol/g: (1-8): 1.
optionally, the heteropolyacid is any one of silicotungstic acid, phosphotungstic acid and phosphomolybdic acid.
Optionally, the fruit cake is any one of tung tree, castor bean, soybean, olive tree and peanut.
The wood-based carbon supported heteropolyacid catalyst prepared by the method is applied to the preparation of vegetable oil-based polyol.
Optionally, under the catalysis of a wood-based carbon supported heteropolyacid catalyst, performing Friedel-crafts alkylation reaction on vegetable oil and a phenolic compound, and purifying to obtain the vegetable oil-based polyol.
Optionally, the vegetable oil is one or more of tung oil, castor oil, soybean oil, olive oil and peanut oil; the phenolic compound is one or more of phenol, catechol and guaiacol; the reaction temperature is 80-100 ℃.
Optionally, the dosage of the wood-based carbon supported heteropolyacid catalyst accounts for 0.5-3% of the total mass of the vegetable oil and the phenolic compound.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes natural and renewable plant fruits as raw materials, and the fruit cake has stronger microwave absorbing capability after phosphoric acid activation, and can be quickly carbonized in solid microwaves to obtain the wood-based carbon carrier. The solid microwave technology can rapidly increase local temperature by directly heating on the molecular level of the material, greatly shorten the time required by pyrolysis carbonization, achieve the purpose of energy saving, and the specific surface area and the aperture of the wood-based carbon reach 1132.8m 2 And 3.0nm, and can be used as an excellent adsorbent and catalyst carrier.
(2) The wood-based carbon catalyst is prepared by taking wood-based carbon as a carrier through an impregnation method, and the total acid content of the prepared wood-based carbon supported heteropolyacid catalyst is up to 2408.4 mu mol/g, which can be compared with industrial liquid acid catalyst, and the activity of the catalyst is greatly improved.
(3) The woody carbon supported heteropolyacid catalyst is applied to the preparation of vegetable oil-based polyol from vegetable oil and phenolic compounds, so that the cost for preparing the vegetable oil-based polyol is reduced, and the way for the fine and functional utilization of vegetable oil is widened.
Drawings
FIG. 1 is an XRD test curve of wood-based carbon and wood-based carbon-supported phosphotungstic acid obtained in example 1 of the present invention;
FIG. 2 is an infrared test curve of wood-based carbon and wood-based carbon-supported phosphotungstic acid obtained in example 1 of the present invention;
FIG. 3 is XPS test curves of wood-based carbon and wood-based carbon-supported phosphotungstic acid obtained in example 1 of the present invention;
FIG. 4 is a BET test curve of wood-based carbon and wood-based carbon-supported phosphotungstic acid obtained in example 1 of the present invention;
FIG. 5 is a schematic representation of NH/phosphotungstic acid supported on wood-based carbon and wood-based carbon obtained in example 1 of the present invention 3 -TPD test curve;
FIG. 6 is an SEM test chart of wood-based carbon and wood-based carbon-supported phosphotungstic acid obtained in example 1 of the present invention;
FIG. 7 is an SEM and microsphere particle size test chart of a wood-based carbon-supported phosphotungstic acid having microspheres on the surface thereof obtained in example 1 of the present invention.
FIG. 8 is an infrared spectrum of the tung oil-based polyphenol obtained in example 1 of the present invention;
FIG. 9 is a chart showing nuclear magnetic resonance hydrogen spectrum test of the tung oil-based polyphenol obtained in example 1 of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments.
Raw material source
Fruit withering: are purchased in Sichuan China, and the grain diameter ranges from 80 meshes to 120 meshes;
vegetable oil source such as tung oil, castor oil, etc.: all purchased from plant oil processing plants of nature in Nanxi district of Yibin, and industrially pure;
the rest raw materials are all commercially available conventional chemicals.
A microwave reactor: XH-200C, a company of Beijing and Xiangna technology development Co., ltd.
Example 1
The tung tree fruit cake powder and phosphoric acid with the concentration of 95% are immersed for 10 hours according to the mass ratio of 1:4, and then dried for 12 hours in an oven at 100 ℃. And (3) transferring the activated solid powder into a microwave reactor, and carbonizing at 500 ℃ and power of 700W for 6 minutes to obtain the wood-based carbon (TC). Dispersing the obtained wood-based carbon in a heteropoly acid (phosphotungstic acid) aqueous solution with the mass fraction of 12% for reaction for 10 hours at 80 ℃, wherein the mass usage ratio of the mass of the heteropoly acid to the wood-based carbon is 4 in mmol/g: 1. and after the reaction is finished, sequentially carrying out water removal, washing and drying treatment to obtain the wood-based carbon supported phosphotungstic acid catalyst.
Tung oil (100 g), guaiacol (200 g) and 3wt% of wood-based carbon-supported phosphotungstic acid catalyst (based on the total mass of the raw materials) were added to a three-necked flask of 100 mL, heated to 80 ℃ and reacted for 4 hours under stirring. After the reaction, adding 3wt.% NaOH solution to remove unreacted phenolic compounds, collecting an organic phase, washing the organic phase with deionized water for 2 times, collecting the organic phase, and removing water by rotary evaporation to obtain the tung oil-based polyphenol.
Example 2
The castor fruit cake powder and phosphoric acid with the concentration of 95% are immersed for 10 hours according to the mass ratio of 1:4, and then dried for 12 hours in an oven at 100 ℃. And (3) transferring the activated solid powder into a microwave reactor, and carbonizing at 500 ℃ and 700W for 6 minutes to obtain the wood-based carbon. Dispersing the obtained wood-based carbon in a heteropoly acid (phosphotungstic acid) aqueous solution with the mass fraction of 12% for reaction for 10 hours at 80 ℃, wherein the mass usage ratio of the mass of the heteropoly acid to the wood-based carbon is1 in mmol/g: 1. and after the reaction is finished, sequentially carrying out water removal, washing and drying treatment to obtain the wood-based carbon supported phosphotungstic acid catalyst.
Castor oil (100 g), guaiacol (200 g) and 3wt% of a wood-based carbon-supported phosphotungstic acid catalyst (based on the total mass of the raw materials) were added to a three-necked flask of 100 mL, heated to 80 ℃, and reacted for 4 hours with stirring. After the reaction, adding 3wt.% NaOH solution to remove unreacted guaiacol, collecting an organic phase, washing the organic phase with deionized water for 2 times, collecting the organic phase, and removing water by rotary evaporation to obtain castor oil-based polyphenol.
Example 3
The soybean fruit cake powder and phosphoric acid with the concentration of 95% are immersed for 10 hours according to the mass ratio of 1:4, and then dried for 12 hours in an oven at 100 ℃. And (3) transferring the activated solid powder into a microwave reactor, and carbonizing at 500 ℃ and 700W for 6 minutes to obtain the wood-based carbon. Dispersing the obtained wood-based carbon in a heteropoly acid (phosphotungstic acid) aqueous solution with the mass fraction of 12% for reaction for 10 hours at 80 ℃, wherein the mass usage ratio of the mass of the heteropoly acid to the wood-based carbon is expressed in mmol/g: 5:1. and after the reaction is finished, sequentially carrying out water removal, washing and drying treatment to obtain the wood-based carbon supported phosphotungstic acid catalyst.
Soybean oil (100 g), guaiacol (200 g) and 3wt% of a wood-based carbon-supported phosphotungstic acid catalyst (based on the total mass of the raw materials) were added to a three-necked flask of 100 mL, and the temperature was raised to 80 ℃ and reacted for 4 hours under stirring. After the reaction, adding 3wt.% NaOH solution to remove unreacted guaiacol, collecting an organic phase, washing the organic phase with deionized water for 2 times, collecting the organic phase, and removing water by rotary evaporation to obtain soybean oil-based polyphenol.
Example 4
The olive tree fruit cake powder and phosphoric acid with the concentration of 95% are immersed for 10 hours according to the mass ratio of 1:4, and then dried for 12 hours in an oven at 100 ℃. And (3) transferring the activated solid powder into a microwave reactor, and carbonizing at 500 ℃ and 700W for 6 minutes to obtain the wood-based carbon. Dispersing the obtained wood-based carbon in a heteropoly acid (phosphotungstic acid) aqueous solution with the mass fraction of 12% for reaction for 10 hours at 70 ℃, wherein the mass usage ratio of the mass of the heteropoly acid to the wood-based carbon is expressed in mmol/g: 4:1. and after the reaction is finished, sequentially carrying out water removal, washing and drying treatment to obtain the wood-based carbon supported phosphotungstic acid catalyst.
Olive oil (100 g), guaiacol (200 g) and 3wt% of a wood-based carbon-supported phosphotungstic acid catalyst (based on the total mass of the raw materials) were added to a three-necked flask of 100 mL, heated to 80 ℃, and reacted for 4 hours with stirring. After the reaction, 3wt.% NaOH solution was added to remove unreacted guaiacol, the organic phase was collected, washed 2 times with deionized water, the organic phase was collected, and water was removed by rotary evaporation to obtain olive-based polyphenol.
Example 5
Peanut kernel cake powder and phosphoric acid with a concentration of 95% are immersed for 10 hours according to a mass ratio of 1:4, and then dried for 12 hours in an oven at 100 ℃. And (3) transferring the activated solid powder into a microwave reactor, and carbonizing at 500 ℃ and 700W for 6 minutes to obtain the wood-based carbon. Dispersing the obtained wood-based carbon in a heteropoly acid (phosphotungstic acid) aqueous solution with the mass fraction of 12% for reaction for 10 hours at 90 ℃, wherein the mass usage ratio of the mass of the heteropoly acid to the wood-based carbon is expressed in mmol/g: 8:1. and after the reaction is finished, sequentially carrying out water removal, washing and drying treatment to obtain the wood-based carbon supported phosphotungstic acid catalyst.
Peanut oil (100 g), guaiacol (200 g) and 3wt% of a wood-based carbon-supported phosphotungstic acid catalyst (based on the total mass of the raw materials) were added to a three-necked flask of 100 mL, heated to 80℃and reacted for 4 hours under stirring. After the reaction, adding 3wt.% NaOH solution to remove unreacted guaiacol, collecting the organic phase, washing with deionized water for 2 times, collecting the organic phase, and removing water by rotary evaporation to obtain the peanut oil-based polyphenol.
XRD, infrared spectrum and XPS, BET, SEM, NH were carried out on the wood-based carbon and the wood-based carbon-supported phosphotungstic acid catalyst obtained in example 1 3 TPD, etc.
XRD test: the results obtained by the test using RINT2000 type X-ray diffractometer from Tokyo corporation of Japan are shown in FIG. 1.
As can be seen from FIG. 1, the characteristic peaks at 24.94℃and 43.35 ℃are attributed to the 002 and 100 crystal planes of amorphous and graphitic carbon, respectively, and the presence of the diffraction peaks indicates successful carbonization of the tung tree fruit cake powder, and the absence of sharp peaks means lower crystallinity. The diffraction peak of the wood-based carbon-supported phosphotungstic acid catalyst is consistent with the position of the diffraction peak of the phosphotungstic acid, which shows that the phosphotungstic acid is successfully supported in the carbon skeleton.
Infrared spectrum testing: the results obtained by the test using Nicolet IS10 type FT-IR apparatus in the U.S. are shown in FIG. 2.
As can be seen from FIG. 2, 3400 and 1650 and cm for wood-based carbons -1 The diffraction peaks at are attributed to the C-OH and c=o groups, respectively. This indicates that the surface of TC is rich in oxygen-containing functional groups such as hydroxyl, ester, and carboxyl groups. 1180-1210 and 1210 cm -1 The two diffraction peaks at these are the stretching modes of the P-O, P-O-C and p=ooh groups, the presence of which demonstrates that phosphoric acid successfully works with tung fruitsActivating the solid cake powder. The four newly appeared characteristic peaks for the wood-based carbon-supported phosphotungstic acid catalyst correspond to P-O respectively (at 1080 cm) -1 Left-right), w=o (β -peak, at 982 cm -1 Left and right) and W-O-W (gamma-peak and delta-peak, at 893-798 cm) -2 Where) this indicates that phosphotungstic acid was successfully loaded and retained the typical Keggin structure.
XPS test: the results obtained by the test using an X-ray photoelectron spectrometer (5000 VP II) produced by ULVAC-PHI, japan, are shown in FIG. 3.
As can be seen from fig. 3, the satellite spectrogram shows that the wood-based carbon material is composed of C, N, O, P elements, after the phosphotungstic acid is loaded, the wood-based carbon loaded phosphotungstic acid catalyst has a diffraction peak of W element at about 35eV, which shows that the phosphotungstic acid is successfully loaded, and the analysis results are consistent with the analysis results of XRD and FT-IR spectrograms.
BET test: the results obtained by the test using ASAP 2020 type specific surface area and porosity analyzer manufactured by Micromeritics Inc. of U.S. are shown in FIG. 4.
As can be seen from FIG. 4, the wood-based carbon and the wood-based carbon supported phosphotungstic acid catalyst are both of the mixed type of I type and IV type isotherms, and the curve has an ascending trend when P/P0 is less than 0.05, which indicates that micropores exist in the sample, but the ascending amplitude is smaller, which indicates that nitrogen is not adsorbed in a large amount; the curves all show a narrow hysteresis regression line at P/P0 > 0.4, due to the presence of mesopores in the catalyst. In addition, due to successful loading of phosphotungstic acid, the specific surface area and pore volume of the wood-based carbon are compared with those of the Yu Muzhi-based carbon loaded phosphotungstic acid catalyst respectively formed by 1132.8m 2 g -1 And 1.13cm 3 g -1 Reduced to 413.8m 2 g -1 And 0.26 cm 3 g -1 。
NH 3 TPD test: the test was performed using an Auto-chem 2920 multifunctional automated temperature programmed chemisorption instrument manufactured by Micromeritics, inc. of America, and the results are shown in FIG. 5.
As can be seen from fig. 5, the diffraction peak below 220 ℃ is attributed to the weak acid center, the diffraction peak in the range of 220 ℃ to 520 ℃ is derived from the medium strong acid center, and the diffraction peak above 520 ℃ is attributed to the strong acid center. It can be seen that the wood-based carbon carrier has a small amount of weak acid and medium strong acid active sites, and the acid content of the strong acid and the strong acid in the catalyst after supporting the phosphotungstic acid is obviously improved, and the strong acid content is as high as 2408.4 mu mol/g.
SEM test: the test was conducted using a scanning electron microscope model S-4800 manufactured by Hitachi, japan, and the results obtained are shown in FIGS. 6 and 7.
As can be seen from fig. 6 and 7, the wood-based carbon surface was slightly roughened after phosphoric acid activation, and there were small balls adhering to the roughened surface, which formed agglomerates of about 50-100 a nm a size. The roughness of the surface increases after the wood-based carbon is loaded with phosphotungstic acid, and spherical particles uniformly distributed around 300 nm can be observed. As can be seen from Mapping scans, C, O, P, W is present in the spherical particles, possibly stacked on top of each other during phosphotungstic acid loading.
The tung oil-based polyphenol obtained in example 1 was subjected to infrared spectrum and nuclear magnetic hydrogen spectrum tests, respectively.
As can be seen from fig. 8, the tung oil-based polyphenols did not exhibit the absorption characteristics of tung oil at 3104cm "1 (=c-H stretching), 992 cm" 1 (=c-H bending) and 1643cm "1 (c=c stretching), indicating that the c=c double bonds in the tung oil had reacted. The new absorption peaks appear at approximately 3388 cm-1 and 1227cm-1, which are attributed to the stretching and bending vibrations of the phenolic hydroxyl groups, respectively. Absorption peaks at 1595cm-1 and 1500cm-1 represent vibrations of the benzene ring c=c bond. FI-IR data indicated successful grafting of guaiacol onto alkyl chains of tung oil.
Hydrogen nuclear magnetic resonance spectroscopy test: the results obtained are shown in FIG. 9, tested using a Bruker ARX300 spectrometer (BrukerInstrument Crop, germany).
As can be seen from fig. 9, the chemical shift of proton (-ch=ch-) of the conjugated triene bond of the tung oil appears in the vicinity of 5.36 to 6.38 ppm, and the chemical shift of-ch=ch-proton is found to be transferred to the low frequency in the tung oil-based polyphenol, which proves that the c=c double bond in the tung oil molecule disappears. In addition, the new multiple peaks at 6.75-7.25 ppm correspond to the chemical shift of H on the benzene ring. The nuclear magnetic resonance hydrogen spectrum result shows that the alkyl chain of the tung oil is successfully grafted with guaiacol.
Claims (10)
1. The preparation method of the wood-based carbon supported heteropolyacid catalyst is characterized by comprising the following steps of:
s1: mixing plant fruit cake powder with phosphoric acid, acidifying, and drying at 80-100deg.C to obtain activated fruit cake;
s2: placing the activated fruit cake into a microwave reactor for carbonization to obtain wood-based carbon;
s3: dispersing wood-based carbon in a heteropolyacid aqueous solution, heating to 70-90 ℃ for reaction, and washing and drying after the reaction is finished to obtain the wood-based carbon supported heteropolyacid catalyst.
2. The preparation method of the wood-based carbon supported heteropolyacid catalyst according to claim 1, wherein the specific conditions for carbonization in the microwave reactor are as follows: the temperature is set to 300-600 ℃, the power is set to 500-800W, and the reaction time is 2-10 min under the nitrogen atmosphere.
3. The method for preparing the wood-based carbon supported heteropolyacid catalyst according to claim 1, wherein the heating reaction temperature in S3 is: 60-80 ℃.
4. The method for preparing the wood-based carbon supported heteropolyacid catalyst according to claim 1, wherein the mass usage ratio of the mass of the heteropolyacid to the wood-based carbon is as follows in mmol/g: (1-8): 1.
5. the method for preparing a wood-based carbon supported heteropolyacid catalyst according to claim 1, wherein the heteropolyacid is any one of silicotungstic acid, phosphotungstic acid and phosphomolybdic acid.
6. The method for preparing the wood-based carbon supported heteropolyacid catalyst according to claim 1, wherein the fruit cake is any one of tung tree, castor bean, soybean, olive tree and peanut.
7. Use of a wood-based carbon supported heteropolyacid catalyst prepared according to any one of claims 1-6 in the preparation of a vegetable oil-based polyol.
8. The use of a wood based carbon supported heteropolyacid catalyst according to claim 7 in the preparation of a vegetable oil based polyol, characterized in that: under the catalysis of a wood-based carbon supported heteropolyacid catalyst, performing Friedel-crafts alkylation reaction on vegetable oil and a phenolic compound, and purifying to obtain the vegetable oil-based polyol.
9. The use of a wood based carbon supported heteropolyacid catalyst according to claim 8 in the preparation of a vegetable oil based polyol, characterized in that: the vegetable oil is one or more of tung oil, castor oil, soybean oil, olive oil and peanut oil; the phenolic compound is one or more of phenol, catechol and guaiacol; the reaction temperature is 80-100 ℃.
10. The use of a wood based carbon supported heteropolyacid catalyst according to claim 8 in the preparation of a vegetable oil based polyol, characterized in that: the dosage of the wood-based carbon supported heteropolyacid catalyst accounts for 0.5-3% of the total mass of the vegetable oil and the phenolic compound.
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