CN115260540B - Method for rapidly preparing lignin/zinc oxide composite material based on DES - Google Patents
Method for rapidly preparing lignin/zinc oxide composite material based on DES Download PDFInfo
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- CN115260540B CN115260540B CN202211007192.XA CN202211007192A CN115260540B CN 115260540 B CN115260540 B CN 115260540B CN 202211007192 A CN202211007192 A CN 202211007192A CN 115260540 B CN115260540 B CN 115260540B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229920005610 lignin Polymers 0.000 title claims abstract description 136
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 33
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 239000011592 zinc chloride Substances 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004202 carbamide Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 27
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000005303 weighing Methods 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 230000005496 eutectics Effects 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 241000218631 Coniferophyta Species 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 3
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000011259 mixed solution Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 125000003118 aryl group Chemical class 0.000 description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000147041 Guaiacum officinale Species 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229940091561 guaiac Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003711 photoprotective effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for rapidly preparing lignin/zinc oxide composite material based on DES, which comprises the following steps: step 1: preparation of DES: respectively weighing zinc chloride and urea with corresponding mass, adding the zinc chloride and the urea into a reactor, and heating and stirring to obtain DES; step 2: dissolving lignin: weighing a certain mass of DES, placing the DES in a reaction vessel, adding lignin raw materials, heating and stirring to obtain a homogeneous phase solution of DES-lignin; step 3: preparing lignin/zinc oxide composite material: adding ammonia water solution into the homogeneous phase liquid obtained in the step 2, fully stirring, mixing and reacting uniformly to obtain mixed liquid, soaking, standing, separating and washing to obtain precipitate, drying the precipitate, and grinding to obtain the lignin/zinc oxide composite material. The invention is characterized in that Zn 2+ 、NH 3 ·H 2 O and Cl ‑ The lignin/zinc oxide composite material is obtained in the system, so that not only is the dispersibility of zinc oxide improved, but also the chromaticity of lignin is reduced, and the synergistic ultraviolet radiation resistance effect of lignin and zinc oxide is realized.
Description
Technical Field
The invention belongs to the technical field of biomass-based composite materials, and particularly relates to a method for rapidly preparing a lignin/zinc oxide composite material based on DES.
Background
Zinc oxide (ZnO) is a low-cost, environmentally friendly and non-toxic metal oxide, and has a high exciton binding energy and a large forbidden bandwidth, thus exhibiting good potential for absorbing, reflecting and refracting uv radiation, and thus acting as a photo-protective agent, in particular for uv radiation. However, znO has the problems of easy aggregation, low dispersibility, poor acid and alkali resistance and the like due to higher hydrophilicity and polarity, and the traditional ways for synthesizing ZnO are mainly physical methods (such as ultrasonic waves), chemical methods (such as oxidation-reduction reaction), physical-chemical combination methods (such as chemical vaporization and spray pyrolysis) and the like, so that higher energy is consumed, and harmful byproducts are generated.
The lignin molecular structure contains rich chromophoric groups such as benzene rings, carbonyl groups, unsaturated double bonds, conjugated structures and the like and auxiliary chromophoric groups such as hydroxyl groups, methoxy groups and the like, so that the lignin molecular structure shows natural broad-spectrum ultraviolet protection performance, oxidation resistance and the like. However, lignin has the problems of poor dispersibility, difficult compounding, deep chromaticity and the like when being directly used as a composite material with an ultraviolet resistance function because of poor water solubility and heavy color. Xueqing the subject group finds that the alkali lignin is subjected to quaternization grafting modification to obtain the amphoteric quaternized alkali lignin containing quaternary ammonium groups and carboxyl/hydroxyl groups, and the active functional groups of the amphoteric quaternized alkali lignin can be efficiently, uniformly and regularly compounded with zinc oxide nano-particles in an aqueous solution through electrostatic adsorption, so that the problems of serious aggregation and poor dispersibility of the lignin-based nano-composite material are effectively solved. However, the preparation process adopts a two-step method, namely, the quaternized lignin powder is obtained by performing quaternization modification on lignin for 4 hours, and then performing dialysis, purification, freeze drying and other complex processes on the reaction solution; and then mixing the quaternized lignin with zinc acetate, sodium hydroxide solution and the like, and carrying out heat preservation reaction for 4 hours to obtain lignin/zinc oxide composite particles, so that the defects of complex preparation operation and complex process exist.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing NH 3 ·H 2 A method for rapidly preparing lignin/zinc oxide composite material in urea/zinc chloride DES under O environment fully plays the synergistic effect of lignin and zinc oxide in ultraviolet resistance.
The technical solution for achieving the above purpose is as follows:
a method for rapidly preparing lignin/zinc oxide composite material based on DES, comprising the following steps:
step 1: preparation of eutectic solvent (DES): respectively weighing zinc chloride and urea with corresponding mass, adding the zinc chloride and the urea into a reactor, and heating and stirring to obtain DES;
step 2: dissolving lignin: weighing a certain mass of DES, placing the DES in a reaction vessel, adding lignin raw materials, heating and stirring to obtain a homogeneous phase solution of DES-lignin;
step 3: preparing lignin/zinc oxide composite material: adding ammonia water solution into the homogeneous phase liquid obtained in the step 2, fully stirring, mixing and reacting uniformly to obtain mixed liquid, soaking, standing, separating and washing to obtain precipitate, drying the precipitate, and grinding to obtain the lignin/zinc oxide composite material.
Further, after the mixed solution is obtained in the step 3, a certain amount of deionized water is added into the mixed solution to terminate the reaction, and after the mixed solution is fully stirred and dispersed, the mixed solution is soaked at room temperature and stands for a preset time.
Further, in the step 3, soaking and standing for 6-24 hours at room temperature, and placing the precipitate in a drying oven at 80 ℃ for drying and grinding to obtain the lignin/zinc oxide composite material.
Further, the preparation method of the lignin raw material in the step 2 comprises the following steps: mechanically grinding lignin particles, screening, taking a part with the particle size of 40-60 meshes, and naturally air-drying to obtain lignin raw materials, wherein the lignin source comprises broadleaf wood, conifer wood or gramineous plants, and the lignin source comprises at least one of alkali lignin, enzymolysis lignin or organic solvent lignin.
Further, the step 1 specifically includes: the dried zinc chloride and urea are respectively weighed according to the mol ratio of 3:10-9:10, added into a reactor, heated and stirred at 100 ℃ in an oil bath until the mixture is completely transparent, thus obtaining the DES, the heating time is 30-120 min, the stirring speed is 20-40 rpm, and the drying method of the urea and the zinc chloride comprises the following steps: weighing a certain amount of urea and zinc chloride solid particles, respectively placing the urea and the zinc chloride solid particles in an electrothermal constant-temperature blast drying oven at 95 ℃ for 2 hours, then placing the dried urea and zinc chloride in a dryer, cooling to room temperature, weighing the mass of the dried urea and zinc chloride, and repeating the drying method until the mass of the dried urea and zinc chloride is basically constant (within an error allowable range).
Further, the step 2 specifically includes: weighing a certain mass of DES, placing the DES in a reaction vessel, adding lignin raw material with the mass of 0.5-10.0% of the DES, placing the mixture in an oil bath at 90-110 ℃, heating and stirring to ensure that lignin is fully dissolved, and obtaining homogeneous phase liquid of the DES-lignin.
Further, the specific process of obtaining the mixed solution in the step 3 is as follows: and 2, adding an ammonia water solution with the mass of 2.5-30% relative to the mass of DES into the homogeneous phase liquid obtained in the step 2, fully stirring and uniformly mixing, and continuously preserving heat at 90-120 ℃ for 2-6 hours to obtain a mixed liquid, wherein the mass concentration of the ammonia water solution is 25-28%.
Further, the adding amount of deionized water in the step 3 is at least 9 times of the mass of DES, and when the deionized water is added for full dispersion, the mode of adding the deionized water while stirring is adopted, and the stirring speed is more than 200rpm.
Further, the separation in the step 3 is carried out by adopting a centrifugal machine to carry out multiple centrifugation on the soaking liquid, the centrifugation time is 8 min/time to 15 min/time, the centrifugation rotating speed is 4000rpm, the obtained centrifugal precipitate is collected, and deionized water is used for washing the supernatant liquid for multiple times to be nearly neutral; or a vacuum filtration device is adopted, the soaking solution is filtered through water-based filter paper with the thickness of 0.45 mu m to obtain a solid phase part, and then deionized water is used for washing the solid phase to be neutral, wherein the pH value at the time of near neutral is 6-8.
The lignin/zinc oxide composite material is prepared by the method.
Compared with the prior art, the invention has the advantages that:
(1) The invention uses NH 3 ·H 2 The multiple functions of dilution, dissolution, degradation, catalysis, reaction and the like of O and urea-zinc chloride DES are realized, and the lignin/oxygen preparation by a one-pot method is realizedThe zinc-zinc composite material has the advantages of simple operation, low cost, high yield, green environmental protection and the like;
(2) The invention is characterized in that Zn 2+ 、NH 3 ·H 2 O and Cl - The lignin/zinc oxide composite material obtained in the system not only improves the dispersibility of zinc oxide, but also reduces the chromaticity of lignin, overcomes the defects of independent use, and realizes the synergistic ultraviolet radiation resistance effect of lignin and zinc oxide;
(3) The solubility of lignin in the invention can reach 10%, the yield of the obtained lignin/zinc oxide composite material can reach 1400%, and NH is not added respectively 3 ·H 2 3.3 times and 3 times O.
Description of the drawings:
FIG. 1 is an ultraviolet absorbance spectrum of lignin/zinc oxide composite materials prepared in comparative example 1 and examples 1 to 4 of the present invention.
FIG. 2 is a Fourier infrared (FT-IR) spectrum of lignin/zinc oxide composites prepared in examples 1 to 4 of the present invention.
FIG. 3 is an X-ray diffraction (XRD) spectrum of lignin/zinc oxide composites and raw zinc oxide prepared in examples 1 and 3 of the present invention.
The specific embodiment is as follows:
the invention will be further illustrated with reference to examples; the following examples are illustrative, not limiting, and are not intended to limit the scope of the invention.
The raw materials used in the invention are conventional commercial products unless specified; the methods used in the present invention are conventional in the art unless otherwise specified.
Example 1
A method for rapidly preparing lignin/zinc oxide composite material based on DES comprises the following steps:
(1) Preparation of lignin raw material: mechanically grinding corncob enzymolysis lignin particles (EHL), screening, taking a part with the particle size of 40-60 meshes, and naturally air-drying to obtain lignin raw materials;
(2) Preparation of DES: respectively weighing corresponding masses of zinc chloride and urea after being dried by a 95 ℃ electrothermal constant-temperature forced air drying oven according to a molar ratio of 3:10, adding the zinc chloride and the urea into a reactor, heating the mixture at a constant temperature for 1h under an oil bath at a temperature of 100 ℃, and fully stirring the mixture (the rotating speed is 20 rpm) until the mixture is completely transparent to obtain DES; cooling to room temperature, and storing in a dryer for later use;
(3) Dissolution of lignin: accurately weighing 50g of DES, placing in a round bottom flask, adding 1g of EHL, placing in an oil bath at 90 ℃, and continuously stirring at a stirring speed of 200rpm for 20min to fully dissolve lignin and obtain a homogeneous phase solution of DES-lignin;
(4) Preparation of lignin/zinc oxide composite material: adding an ammonia water solution with the mass fraction of 25% into the homogeneous phase liquid obtained in the step (3), wherein the addition amount is 12.5wt% of the mass of DES, fully stirring at 100 ℃, uniformly mixing, and continuously reacting for 4 hours to obtain a mixed liquid;
(5) Adding 450g of deionized water into the mixed solution to terminate the reaction, stirring while adding at a stirring speed of 1500rpm, fully dispersing the mixed solution, and standing at room temperature for soaking for 14h;
(6) After standing, centrifugally separating the soaking solution by using a centrifugal machine, wherein the centrifugal speed is 4000rpm, the time is 15min, collecting the obtained centrifugal precipitate, washing the obtained centrifugal precipitate with deionized water for a plurality of times until the supernatant is nearly neutral, and measuring the pH value of the supernatant to be 6-7; and (3) placing the precipitate washed to be neutral in an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 24 hours, and grinding to obtain the lignin/zinc oxide composite material.
The detection result shows that the yield of the lignin-zinc oxide composite material obtained by the method is 1384%.
Example 2
A method for rapidly preparing lignin/zinc oxide composite material based on DES comprises the following steps:
(1) Preparation of lignin raw material: mechanically grinding corncob enzymolysis lignin particles (EHL), screening, taking a part with the particle size of 40-60 meshes, and naturally air-drying to obtain lignin raw materials;
(2) Preparation of DES: respectively weighing corresponding mass of zinc chloride and urea after constant weight by a 95 ℃ electrothermal constant temperature blast drying oven according to a molar ratio of 3:10, adding the zinc chloride and the urea into a reactor, heating the mixture at constant temperature for 1h under an oil bath at 100 ℃, and fully stirring the mixture (the rotating speed is 20 rpm) until the mixture is completely transparent to obtain DES; cooling to room temperature, and storing in a dryer for later use;
(3) Dissolution of lignin: accurately weighing 50g of DES, placing in a round bottom flask, adding 1g of EHL, placing in an oil bath at 90 ℃, and continuously stirring at a stirring speed of 200rpm for 20min to fully dissolve lignin and obtain a homogeneous phase solution of DES-lignin;
(4) Preparation of lignin/zinc oxide composite material: adding an ammonia water solution with the mass fraction of 25% into the homogeneous phase liquid obtained in the step (3), wherein the addition amount is 20.0wt% of the mass of DES, fully stirring at 100 ℃, uniformly mixing, and continuously reacting for 4 hours to obtain a mixed liquid;
(5) Adding 500g of deionized water into the mixed solution to terminate the reaction, stirring while adding at a stirring speed of 1500rpm, fully dispersing the mixed solution, and standing at room temperature for soaking for 12 hours;
(6) After standing, carrying out centrifugal separation on the soaking solution for multiple times by using a centrifugal machine, wherein the centrifugal speed is 4000rpm, the centrifugal time is 15min each time, collecting the obtained centrifugal precipitate, washing the obtained centrifugal precipitate with deionized water for multiple times until the supernatant is nearly neutral, and measuring the pH value of the supernatant to be 6-7; and (3) placing the precipitate washed to be neutral in an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 24 hours, and grinding to obtain the lignin/zinc oxide composite material.
The detection result shows that the yield of the lignin-zinc oxide composite material obtained by the method is 1339%.
Example 3
A method for rapidly preparing lignin/zinc oxide composite material based on DES comprises the following steps:
(1) Preparation of lignin raw material: mechanically grinding sodium lignin sulfonate particles (SL), screening, taking a part with the particle size of 40-60 meshes, and naturally air-drying to obtain lignin raw materials;
(2) Preparation of DES: respectively weighing corresponding mass of zinc chloride and urea after constant weight by a 95 ℃ electrothermal constant temperature blast drying oven according to a molar ratio of 3:10, adding the zinc chloride and the urea into a reactor, heating the mixture at constant temperature for 2 hours under an oil bath at 100 ℃, and fully stirring the mixture (the rotating speed is 20 rpm) until the mixture is completely transparent to obtain DES; cooling to room temperature, and storing in a dryer for later use;
(3) Dissolution of lignin: accurately weighing 50g of DES, placing in a round bottom flask, adding 1gSL, placing in an oil bath at 90 ℃, and continuously stirring at a stirring speed of 200rpm for 20min to fully dissolve lignin and obtain a homogeneous phase solution of DES-lignin;
(4) Preparation of lignin/zinc oxide composite material: adding 28% ammonia water solution into the homogeneous phase liquid obtained in the step (3), wherein the addition amount of the ammonia water solution is 10.0% of the mass of DES, fully stirring the mixture at 100 ℃, uniformly mixing the mixture, and continuously reacting the mixture for 4 hours to obtain a mixed liquid;
(5) Adding 450g of deionized water into the mixed solution to terminate the reaction, stirring while adding at a stirring speed of 1500rpm, fully dispersing the mixed solution, and standing at room temperature for soaking for 12 hours;
(6) After standing, carrying out centrifugal separation on the soaking solution for multiple times by using a centrifugal machine, wherein the centrifugal speed is 4000rpm, the centrifugal time is 15min each time, collecting the obtained centrifugal precipitate, washing the obtained centrifugal precipitate with deionized water for multiple times until the supernatant is nearly neutral, and measuring the pH value of the supernatant to be 6-7; and (3) placing the precipitate washed to be neutral in an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 24 hours, and grinding to obtain the lignin/zinc oxide composite material.
The detection result shows that the yield of the lignin-zinc oxide composite material obtained by the method is 1194%.
Example 4
A method for rapidly preparing lignin/zinc oxide composite material based on DES comprises the following steps:
(1) Preparation of lignin raw material: mechanically grinding sodium lignin sulfonate particles (SL), screening, taking a part with the particle size of 40-60 meshes, and naturally air-drying to obtain lignin raw materials;
(2) Preparation of DES: respectively weighing corresponding mass of zinc chloride and urea after constant weight by a 95 ℃ electrothermal constant temperature blast drying oven according to a molar ratio of 3:10, adding the zinc chloride and the urea into a reactor, heating the mixture at constant temperature for 2 hours under an oil bath at 100 ℃, and fully stirring the mixture (the rotating speed is 20 rpm) until the mixture is completely transparent to obtain DES; cooling to room temperature, and storing in a dryer for later use;
(3) Dissolution of lignin: accurately weighing 50g of DES, placing in a round bottom flask, adding 1gSL, placing in an oil bath at 90 ℃, and continuously stirring at a stirring speed of 200rpm for 20min to fully dissolve lignin and obtain a homogeneous phase solution of DES-lignin;
(4) Preparation of lignin/zinc oxide composite material: adding an ammonia water solution with the mass fraction of 25% into the homogeneous phase liquid obtained in the step (3), wherein the addition amount is 20.0wt% of the mass of DES, fully stirring at 100 ℃, uniformly mixing, and continuously reacting for 4 hours to obtain a mixed liquid;
(5) Adding 600g of deionized water into the mixed solution to terminate the reaction, stirring while adding at a stirring speed of 1500rpm, fully dispersing the mixed solution, and standing at room temperature for soaking for 13h;
(6) After standing, carrying out centrifugal separation on the soaking solution for multiple times by using a centrifugal machine, wherein the centrifugal speed is 4000rpm, the centrifugal time is 15min each time, collecting the obtained centrifugal precipitate, washing the obtained centrifugal precipitate with deionized water for multiple times until the supernatant is nearly neutral, and measuring the pH value of the supernatant to be 6-7; and (3) placing the precipitate washed to be neutral in an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 24 hours, and grinding to obtain the lignin/zinc oxide composite material.
The detection result shows that the yield of the lignin-zinc oxide composite material obtained by the method is 1341%.
Comparative example 1
A method for rapidly preparing lignin/zinc oxide composite material based on DES comprises the following steps:
(1) Preparation of lignin raw material: screening sodium lignin sulfonate particles (SL), passing through a mesh screen with 40-60 meshes, and then naturally airing in the environment to obtain lignin raw materials;
(2) Preparation of DES: respectively weighing corresponding mass of zinc chloride and urea after constant weight by a 95 ℃ electrothermal constant temperature blast drying oven according to a molar ratio of 3:10, adding the zinc chloride and the urea into a reactor, heating the mixture at constant temperature for 2 hours under an oil bath at 100 ℃, and fully stirring the mixture (the rotating speed is 20 rpm) until the mixture is completely transparent to obtain DES; cooling to room temperature, and storing in a dryer for later use;
(3) Dissolution of lignin: accurately weighing 50gDES, placing in a reaction vessel, adding lignin raw material with the addition amount of 2.0wt% (relative to the mass of DES), then placing the reaction vessel containing lignin and DES mixed solution in an oil bath at 100 ℃, heating at constant temperature for 4h and at the rotation speed of 200rpm, and ensuring that lignin and DES are fully and uniformly mixed to obtain the DES-lignin mixed solution;
(4) Preparation of lignin/zinc oxide composite material: adding 600g of deionized water into the homogeneous phase liquid obtained in the step (3) to terminate the reaction, stirring while adding at a stirring speed of 1500rpm, fully dispersing the mixed liquid, and standing at room temperature for soaking for 13 hours;
(5) After standing, carrying out centrifugal separation on the soaking solution for multiple times by using a centrifugal machine, wherein the centrifugal speed is 4000rpm, the centrifugal time is 15min each time, collecting the obtained centrifugal precipitate, washing the obtained centrifugal precipitate with deionized water for multiple times until the supernatant is nearly neutral, and measuring the pH value of the supernatant to be 6-7; and (3) placing the precipitate washed to be neutral in an electrothermal constant-temperature blast drying oven at 80 ℃ for drying for 24 hours, and grinding to obtain the lignin/zinc oxide composite material.
As no ammonia water solution is added in the step 4, the detection result shows that the yield of the lignin-zinc oxide composite material obtained by the method is 451%.
FIG. 1 is an ultraviolet absorbance spectrum of lignin/zinc oxide composite materials prepared in comparative example 1 and examples 1 to 4 of the present invention. The abscissa shown in the figure is the wavelength of the lignin/zinc oxide composite material, wherein 200-400 nm is an ultraviolet region, 400-800 is a visible light region, and the ordinate is the absorbance value corresponding to different wavelengths, and the higher the absorbance value, the better the material can absorb light with corresponding wavelength. The absorbance values of examples 1-4 and comparative example 1 in the ultraviolet region are higher than that in the visible region, indicating that the prepared lignin/zinc oxide composite material has the ability of absorbing ultraviolet rays; in addition, the absorption value of the ammonia water added in the ultraviolet light range of the examples 1-4 is obviously higher than that of the comparative example 1 without ammonia water, so that the addition of ammonia water can promote the generation of zinc oxide and improve the ultraviolet light absorption performance of the lignin/zinc oxide composite material.
FIG. 2 is a Fourier infrared (FT-IR) spectrum of lignin/zinc oxide composites prepared in examples 1 to 4 of the present invention. The four curves shown in the figure are very similar in profile, at 1600, 1509 and 1457cm -1 The characteristic absorption peak of the functional group at the position is the skeleton of aromatic benzene ring and the stretching vibration of the aromatic benzene ring, and 1420cm -1 The absorption peak is from C-H vibration of methyl or methylene, is the basic skeleton of lignin component, and shows that the basic skeleton of lignin remains intact after DES treatment, and the-C-O absorption peak of syringyl (S) ring is at 1328cm -1 The stretching vibration of the guaiac ring (G) and C=O is reflected in 1265cm -1 The signal attribution of the position shows that the composite material contains an aromatic ring structure of G and S, and ZnO is 491cm -1 The characteristic peak of Zn-O appears at the position, and when lignin is compounded with ZnO, the characteristic peak appears to be obviously red-shifted (to 476 cm) -1 At) this point, because ZnO will have a strong interaction with hydroxyl groups in lignin, further indicating successful complexing of lignin and zinc oxide.
FIG. 3 is an X-ray diffraction (XRD) spectrum of lignin/zinc oxide composites and raw zinc oxide prepared in examples 1 and 3 of the present invention. The abscissa in the figure is twice the incident angle of the X-ray, and the ordinate is the diffraction intensity of the sample after the corresponding incidence. Compared with the spectrograms of raw zinc oxide, the lignin/zinc oxide composite materials obtained in the example 1 and the example 3 show obvious diffraction peaks within the range of 30-40 degrees, which shows that the prepared composite materials contain zinc oxide crystals; however, the peak height is relatively weak, and the composite material consists of zinc oxide and lignin, wherein the lignin is of an amorphous structure, so that the peak height of the zinc oxide in the graph is influenced.
The foregoing has outlined and described the basic principles, features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A method for rapidly preparing a lignin/zinc oxide composite material based on a eutectic solvent, which is characterized by comprising the following steps:
step 1: preparing a eutectic solvent: respectively weighing zinc chloride and urea with corresponding mass, adding the zinc chloride and the urea into a reactor, heating and stirring until the zinc chloride and the urea are colorless and transparent to obtain a eutectic solvent;
step 2: dissolving lignin: weighing a certain mass of eutectic solvent, placing the eutectic solvent into a reaction container, adding lignin raw material, heating and stirring to obtain eutectic solvent-lignin homogeneous phase liquid;
step 3: preparing lignin/zinc oxide composite material: adding an ammonia solution into the homogeneous phase liquid obtained in the step 2, adding 2.5% -30% of the ammonia solution relative to the mass of the eutectic solvent, fully stirring and uniformly mixing, continuously preserving heat and reacting for 2-6 hours at 90-120 ℃ to obtain a mixed liquid, wherein the mass concentration of the ammonia solution is 25% -28%, adding a certain amount of deionized water into the mixed liquid to terminate the reaction after the mixed liquid is obtained, fully stirring and dispersing the mixed liquid, soaking and standing for 6-24 hours at room temperature, separating and washing after soaking and standing to obtain a precipitate, and drying and grinding the precipitate in a drying box at 80 ℃ to obtain the lignin/zinc oxide composite material.
2. The method for rapidly preparing lignin/zinc oxide composite material based on eutectic solvent according to claim 1,
the preparation method of the lignin raw material in the step 2 comprises the following steps: mechanically grinding lignin particles, screening, taking a part with the particle size of 40-60 meshes, and naturally air-drying to obtain lignin raw materials, wherein the lignin source comprises broadleaf wood, conifer wood or gramineous plants, and the lignin source comprises at least one of alkali lignin, enzymatic lignin or organic solvent lignin.
3. The method for rapidly preparing lignin/zinc oxide composite material based on eutectic solvent according to claim 2, wherein the step 1 specifically comprises:
and respectively weighing corresponding masses of the dried zinc chloride and urea according to a molar ratio of 3:10-9:10, adding the zinc chloride and the urea into a reactor, heating and stirring the mixture at 100 ℃ in an oil bath until the mixture is completely transparent, and obtaining the eutectic solvent, wherein the heating time is 30-120 min, and the stirring speed is 20-40 rpm.
4. A method for rapidly preparing lignin/zinc oxide composite materials based on eutectic solvents according to claim 3 wherein step 2 comprises:
weighing a certain mass of eutectic solvent, placing the eutectic solvent into a reaction vessel, adding lignin raw materials with the mass of 0.5% -10.0% of that of the eutectic solvent, placing the mixture into an oil bath with the temperature of 90 ℃ -110 ℃, heating and stirring to ensure that lignin is fully dissolved, and obtaining a homogeneous phase liquid of the eutectic solvent-lignin.
5. The method for rapidly preparing lignin/zinc oxide composite material based on eutectic solvent according to claim 1, wherein the adding amount of deionized water in the step 3 is at least 9 times of the mass of the eutectic solvent, and when the deionized water is added for full dispersion, the stirring speed is higher than 200rpm by adopting a stirring-while-adding mode.
6. The method for rapidly preparing lignin/zinc oxide composite material based on eutectic solvent according to claim 1, wherein the separation in step 3 is characterized in that the soaking solution is centrifuged for a plurality of times by adopting a centrifuge, the centrifugation time is 8 min/time to 15 min/time, the centrifugation rotation speed is 4000rpm, the obtained centrifugal precipitate is collected, and the supernatant is washed for a plurality of times by deionized water to be nearly neutral; or a vacuum filtration device is adopted, the soaking liquid is filtered through water-based filter paper with the thickness of 0.45 mu m, a solid phase part is obtained, then deionized water is used for washing the solid phase to be neutral, and the pH value at the time of near neutral is 6-8.
7. A lignin/zinc oxide composite material, characterized in that the lignin/zinc oxide composite material is prepared by the method for rapidly preparing lignin/zinc oxide composite material based on eutectic solvents according to any one of claims 1-6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN107282030A (en) * | 2017-05-11 | 2017-10-24 | 华南理工大学 | A kind of three-dimensional lignin porous carbon/zinc oxide composite and its preparation and the application in photocatalysis field |
| CN112072085A (en) * | 2020-08-20 | 2020-12-11 | 华南理工大学 | Nano lignin zinc oxycarbide composite material and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN107282030A (en) * | 2017-05-11 | 2017-10-24 | 华南理工大学 | A kind of three-dimensional lignin porous carbon/zinc oxide composite and its preparation and the application in photocatalysis field |
| CN112072085A (en) * | 2020-08-20 | 2020-12-11 | 华南理工大学 | Nano lignin zinc oxycarbide composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Processing of lignin in urea–zinc chloride deep-eutectic solvent and its use as a filler in a phenol-formaldehyde resin;Lian H et al;RSC Advances;第5卷(第36期);第28778-28785页 * |
| 丁琦等.《纳米氧化锌与金刚石复合结构的研究与应用》.北京邮电大学出版社,2016,第25页. * |
| 路瑶等.《稻壳和麦秆及其萃余物的逻级氧化》.中国矿业大学出版社,2017,第11页. * |
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