CN103254452B - Preparation method of lignin nanoparticle - Google Patents
Preparation method of lignin nanoparticle Download PDFInfo
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- CN103254452B CN103254452B CN201310192787.1A CN201310192787A CN103254452B CN 103254452 B CN103254452 B CN 103254452B CN 201310192787 A CN201310192787 A CN 201310192787A CN 103254452 B CN103254452 B CN 103254452B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The invention discloses a preparation method of a lignin nanoparticle and belongs to the chemical field of nanometer materials. The preparation method comprises the following steps of: dissolving a lignin raw material through an organic solvent; removing impurities; dropwise adding a proper amount of inorganic acid into filtrate to form lignin colloid; adding a cross-linking agent to perform cross-linking reaction with the lignin colloid; and adding water and stirring to dialyze to form lots of lignin nanoparticles of which the particle size is between 20nm to 200nm. The prepared lignin nanoparticle is excellent in dispersing performance and absorbing performance, and is expected to be applied to dispersing agents for wastewater treatment, dye, pesticide, water-coal-slurry systems and the like. The preparation method, disclosed by the invention, is simple and feasible; all the adopted solutions can be recovered, no adverse impacts are brought to the environment, and good application prospect is provided.
Description
Technical field
The present invention relates to nano material chemical field, particularly a kind of preparation method of xylogen nano particle.
Background technology
Xylogen is the main component that forms plant materials skeleton together with Mierocrystalline cellulose, hemicellulose, and its Main Function is that Mierocrystalline cellulose is bonded together, for plant-growth provides support.The storage capacity of xylogen is only second to Mierocrystalline cellulose, is the second abundant biomass resource on the earth.The structure of xylogen is very complicated, is a kind of three-dimensional, amorphous high molecular polymer, and in its molecule, existing phenyl ring has again carbochain, conventionally contains hydroxyl, aldehyde radical, ketone group, carboxyl etc. in carbochain, also contains hydroxyl and a large amount of methoxyl groups on phenyl ring.Industrial xylogen is mainly as the by product entered environment of paper-making pulping industry and wood saccharification industry, if recycling in addition not, will be to environment.Therefore, no matter from the utilization of resources, or from environment protection, the research of xylogen and utilization have all been subject to the attention of domestic and international researcher.
Developed country is in the world as carried out a large amount of research to xylogen in the U.S., Japan, Europe etc., particularly the U.S. in exploitation, utilize aspect xylogen and accumulated rich experience.China recent years also increasing unit and researcher enters into the research and utilization ranks of xylogen, also shoulders heavy responsibilities but develop research for the high added value of xylogen.
Nano material is the transitional region that is in cluster and macro object boundary, has significant surface effects, small-size effect and macro quanta tunnel effect.When material is made into after nano particle, it will demonstrate many unusual characteristics, as the character of its optics, calorifics, electricity, magnetics, mechanics and chemical aspect will occur significantly to change.As the minimizing along with size of particles, surface atom occupies ratio and increases sharply, but surface particle lacks the coordination of neighbour's atom, extremely unstable, be easy to be combined with other atom, show very high activity, so the specific surface area of the nano material of making is large, surfactivity is high, can be widely used as various materials.Therefore; nano material is as a kind of emerge science technology most with market application potential; have a good application prospect at many industrial circles, as nano magnetic material, nano ceramic material, nano-sensor, functional materials, semiconductor material, nano catalytic material, environment protection industry, textile industry, machinery industry etc.Although the research of xylogen has longer history, at present mainly as low value-added product application, as being carried out to suitable modification, industrial lignin can be used for various field of fine chemical, as pesticide dispersing agent, slurries additive agent, water reducer and dye dispersant etc.But it utilizes scale but very limited, up to the present, the recycling that exceedes 95% industrial lignin still rests on directly burning after concentrated, causes the great wasting of resources.Therefore, xylogen is prepared into nano particle, will significantly increases its application added value, be conducive to the utilization of environment protection and biomass resource simultaneously, meet the target of sustainable development, there is positive environment and social effect.
In recent years, report about xylogen nano particle is existing, as Chinese patent CN102002165A provides a kind of overcritical method of producing xylogen nano particle: black liquid obtains paper industry rugose wood element through acid out precipitation, paper industry rugose wood element is again through twice alkali dissolution Acid precipitation, the alkali lye using and acid solution are respectively sodium hydroxide solution and hydrochloric acid soln, obtain highly industry xylogen, refining paper industry xylogen is after cryodrying, dissolve with dioxane, the insoluble lignin recovery of centrifugation is reused, obtain xylogen dioxane solution, use CO 2 supercritical equipment, adopt super-critical anti-solvent legal system for nano wood quality.This method is taked expensive overcritical equipment, and complex treatment process, is therefore difficult to apply.[the Kilpelainen I Ilkka such as Kilpelainen, Xie H Haibo, King A Alistair, et al. Dissolution of Wood in Ionic Liquids. Journal of Agricultural and Food Chemistry, 2007,55 (22): 9142-9148.] application has 1-butyl-3-methyl chloride (BmimCl) ionic liquid dissolving timber of good solubility property, successfully obtains nano level xylogen particle.The effectively auto-polymerization effect of xylogen self phenolic hydroxyl group in shielding processing process taking ionic liquid as solvent, but ionic liquid is expensive, and be difficult for obtaining, therefore make the application of nano wood quality be difficult to promote.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of xylogen nano particle.The preparation technology of the method is simple, and production cost is low, has effectively improved the added value of product of xylogen, is conducive to applying of this technology.
The present invention is achieved through the following technical solutions:
The preparation method of xylogen nano particle first carries out a pre-treatment by xylogen raw material, removes the insolubles in raw material, obtains raw material filtrate; In raw material filtrate, add mineral acid and be prepared into xylogen colloidal sol; Be finally 100: 1 ~ 2 to add linking agent according to xylogen colloidal sol and linking agent weight ratio, carry out crosslinking reaction 1 ~ 2 hour, by cross-linking agent separate out, the dry xylogen nano particle that obtains; Described linking agent is by one or more mixing in following material: acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde, hexanedial.
The concrete grammar of described xylogen raw materials pretreatment is: xylogen raw material is dissolved in organic solvent, the weight ratio of xylogen raw material and organic solvent is: 1: 18 ~ 20, then be heated to 30 ~ 50 DEG C, stirring fully dissolves xylogen in 1 ~ 3 hour, remove by filter the insolubles in raw material, obtain filtrate; Described xylogen raw material comprises alkali lignin and ethanol xylogen.
Described organic solvent comprises one or more mixing in methylene dichloride, ethylene glycol, propylene glycol, glycerol.
The preparation of described xylogen colloidal sol: drip mineral acid to pH=2 ~ 2.5 in raw material filtrate, and keep stirring, obtain xylogen colloid, described mineral acid comprises one or more mixing in sulfuric acid, hydrochloric acid, phosphoric acid.
The temperature of crosslinking reaction of the present invention is 30 ~ 50 DEG C, after finishing, crosslinking reaction is cooled to room temperature, in crosslinking reaction system, drip water, make the continuous dialysis of cross-linking agent out, again with washing, at 60 ~ 80 DEG C, vacuum-drying can obtain xylogen nano-particle material in 12 ~ 18 hours, and xylogen nano particle diameter is 20 ~ 200nm.
Xylogen nano-particle material of the present invention can be applicable to the aspects such as the dispersion agent of the systems such as wastewater treatment and dyestuff, agricultural chemicals, coal water slurry.
The present invention xylogen source used comprises softwood, pourous wood and draft class plant, comprises dragon spruce, Pinus massoniana Lamb, tamarack, birch, Eucalyptus, poplar, wheat straw, straw, maize straw, bagasse, reed etc.Its separation means comprises ethanol cooking process, alkaline cooking, and the xylogen of acquisition is respectively ethanol xylogen and alkali lignin.The xylogen of above-mentioned different material, different separation means gained can be bought from market, also can prepare voluntarily according to disclosed document.
The present invention has the following advantages:
(1) raw material wood element wide material sources of the present invention, comprise softwood, pourous wood and draft class plant, comprise dragon spruce, Pinus massoniana Lamb, tamarack, birch, Eucalyptus, poplar, and wheat straw, straw, maize straw, bagasse, reed etc., be easy to obtain.
(2) organic solvent that the present invention is suitable for environmental protection is prepared xylogen nano particle, and using water as dialysis agent, reagent is all recyclable, pollution-free, and product no solvent residue, for potential market has been opened in the high value utilization of xylogen.
(3) the nano level xylogen particle of preparing, has nanometer size effect, and properties is greatly improved, and as dispersing property, absorption property, reactive behavior etc., has greatly improved the potential range of application of xylogen.
Brief description of the drawings
Fig. 1 is the SEM figure of embodiment 1 gained nano wood quality particle;
Fig. 2 is the SEM figure of embodiment 2 gained nano wood quality particles;
Fig. 3 is the SEM figure of embodiment 3 gained nano wood quality particles;
Fig. 4 is the SEM figure of embodiment 4 gained nano wood quality particles;
Embodiment
Below by embodiment, the invention will be further described by reference to the accompanying drawings.
embodiment 1
The preparation method of xylogen nano particle of the present invention comprises the steps:
(1) pre-treatment of xylogen raw material: the ethanol xylogen of getting 10 parts of quality is dissolved in 180 parts of glycerol organic solvents it, is heated to 30 DEG C, stirs and xylogen is fully dissolved in 2 hours, removes by filter the insolubles in raw material, obtains filtrate.
(2) preparation of xylogen colloidal sol: get 10 parts of quality above-mentioned steps (1) gained filtrate, drip wherein hydrochloric acid to pH=2 with certain speed, keep stirring, obtain xylogen colloid.
(3) crosslinking reaction: get gained xylogen colloid in 50 parts of quality steps (2), heating in water bath to 40 DEG C, drip wherein the glutaraldehyde of 0.5 part of quality as linking agent, stir 2 hours, xylogen colloid and glutaraldehyde generation crosslinking reaction, after finishing, question response is cooled to room temperature, drip wherein water, make the continuous dialysis of cross-linking agent out, wash with water again, at 60 DEG C, vacuum-drying can obtain xylogen nano-particle material in 12 hours, as shown in Figure 1, xylogen nano particle is irregularly shaped, its particle size dispersion is more even, particle diameter is in 50 ~ 200nm.
embodiment 2
(1) pre-treatment of xylogen raw material: the alkali lignin of getting 15 parts of quality is dissolved in 270 parts of ethylene glycol and propylene glycol (60/40) organic solvent it, be heated to 50 DEG C, stir and xylogen was fully dissolved in 1 hour, remove by filter the insolubles in raw material, obtain filtrate.
(2) preparation of xylogen colloidal sol: get 30 parts of quality above-mentioned steps (1) gained filtrate, drip wherein sulfuric acid and hydrochloric acid to pH=2.5 with certain speed, keep stirring, obtain xylogen colloid.
(3) crosslinking reaction: get gained xylogen colloid in 100 parts of quality steps (2), heating in water bath to 30 DEG C, drip wherein acetaldehyde and the butyraldehyde (1:1) of 1 part of quality, stir 1.5 hours, xylogen colloid and linking agent generation crosslinking reaction, after finishing, question response is cooled to room temperature, drip wherein distilled water, make the continuous dialysis of cross-linking agent out, use again distilled water wash, at 80 DEG C, vacuum-drying can obtain xylogen nano-particle material in 18 hours, as shown in Figure 2, xylogen nano particle is irregularly shaped, its particle size dispersion is more even, its grain diameter is in 20 ~ 200nm.
embodiment 3
(1) pre-treatment of xylogen raw material: the alkali lignin of getting 20 parts of quality is dissolved in 400 parts of methylene dichloride and ethylene glycol (20/80) organic solvent it, be heated to 40 DEG C, stir and xylogen was fully dissolved in 1 hour, remove by filter the insolubles in raw material, obtain filtrate.
(2) preparation of xylogen colloidal sol: get 15 parts of quality above-mentioned steps (1) gained filtrate, drip wherein hydrochloric acid and phosphoric acid to pH=2.2 with certain speed, keep stirring, obtain xylogen colloid.
(3) crosslinking reaction: get gained xylogen colloid in 50 parts of quality steps (2), heating in water bath to 40 DEG C, drip wherein butyraldehyde and hexanedial (1:1) linking agent of 0.5 part of quality, stir 1 hour, xylogen colloid and linking agent generation crosslinking reaction, after finishing, question response is cooled to room temperature, drip wherein water, make the continuous dialysis of cross-linking agent out, wash with water again, at 70 DEG C, vacuum-drying can obtain xylogen nano-particle material in 16 hours, as shown in Figure 3, xylogen nano particle is irregularly shaped, its particle size dispersion is more even, its grain diameter is in 20 ~ 200nm.
embodiment 4
(1) pre-treatment of xylogen raw material: the ethanol xylogen of getting 10 parts of quality is dissolved in 180 parts of ethylene glycol, propylene glycol and glycerol (40:40:20) organic solvent it, be heated to 40 DEG C, stir and xylogen was fully dissolved in 1.5 hours, remove by filter the insolubles in raw material, obtain filtrate.
(2) preparation of xylogen colloidal sol: get 10 parts of quality above-mentioned steps (1) gained filtrate, drip wherein sulfuric acid and phosphoric acid to pH=2.0 with certain speed, keep stirring, obtain xylogen colloid.
(3) crosslinking reaction: get gained xylogen colloid in 50 parts of quality steps (2), heating in water bath to 45 DEG C, drip wherein acetaldehyde and the glutaraldehyde cross-linking agent of 0.5 part of quality, stir 2 hours, xylogen colloid and linking agent generation crosslinking reaction, after finishing, question response is cooled to room temperature, drip wherein distilled water, make the continuous dialysis of cross-linking agent out, use again distilled water wash, at 70 DEG C, vacuum-drying can obtain xylogen nano-particle material in 18 hours, as shown in Figure 4, xylogen nano particle is irregularly shaped, its particle size dispersion is more even, its grain diameter is in 80 ~ 200nm.
embodiment 5
(1) pre-treatment of xylogen raw material: the ethanol xylogen of getting 20 parts of quality is dissolved in 350 parts of glycerol organic solvents it, is heated to 30 DEG C, stirs and xylogen is fully dissolved in 2 hours, removes by filter the insolubles in raw material, obtains filtrate.
(2) preparation of xylogen colloidal sol: get 20 parts of quality above-mentioned steps (1) gained filtrate, drip wherein hydrochloric acid to pH=2.1 with certain speed, keep stirring, obtain xylogen colloid.
(3) crosslinking reaction: get gained xylogen colloid in 50 parts of quality steps (2), heating in water bath to 50 DEG C, drip wherein acetaldehyde, propionic aldehyde and hexanedial (1:1:1) linking agent of 0.5 part of quality, stir 2 hours, xylogen colloid and linking agent generation crosslinking reaction, after finishing, question response is cooled to room temperature, drip wherein distilled water, make the continuous dialysis of cross-linking agent out, use again distilled water wash, at 65 DEG C, vacuum-drying can obtain xylogen nano-particle material in 15 hours, and its grain diameter is in 80 ~ 180nm.
embodiment 6
(1) pre-treatment of xylogen raw material: get the alkali lignin of 10 parts of quality and the ethanol xylogen of 10 parts of quality it is dissolved in 360 parts of methylene dichloride, ethylene glycol, propylene glycol (10/50/40) organic solvent, be heated to 45 DEG C, stirring fully dissolves xylogen in 2.5 hours, remove by filter the insolubles in raw material, obtain filtrate.
(2) preparation of xylogen colloidal sol: get 15 parts of quality above-mentioned steps (1) gained filtrate, drip wherein hydrochloric acid and sulfuric acid to pH=2.0 with certain speed, keep stirring, obtain xylogen colloid.
(3) crosslinking reaction: get gained xylogen colloid in 100 parts of quality steps (2), heating in water bath to 35 DEG C, drip wherein acetaldehyde, glutaraldehyde and hexanedial (1:2:1) linking agent of 1 part of quality, stir 2 hours, xylogen colloid and linking agent generation crosslinking reaction, after finishing, question response is cooled to room temperature, drip wherein distilled water, make the continuous dialysis of cross-linking agent out, use again distilled water wash, at 80 DEG C, vacuum-drying can obtain xylogen nano-particle material in 12 hours, and its grain diameter is in 20 ~ 160nm.
Claims (8)
1. a preparation method for xylogen nano particle, is characterized in that: first xylogen raw material is carried out to pre-treatment, remove the insolubles in raw material, obtain raw material filtrate; In raw material filtrate, add mineral acid and be prepared into xylogen colloidal sol; Be finally 100: 1 ~ 2 to add linking agent according to xylogen colloidal sol and linking agent weight ratio, carry out crosslinking reaction 1 ~ 2 hour, by cross-linking agent separate out, the dry xylogen nano particle that obtains; Described linking agent is by one or more mixing in following material: acetaldehyde, propionic aldehyde, butyraldehyde, glutaraldehyde, hexanedial.
2. the preparation method of xylogen nano particle according to claim 1, it is characterized in that: described xylogen preprocessing method of raw materials is: xylogen raw material is dissolved in organic solvent, the weight ratio of xylogen raw material and organic solvent is 1: 18 ~ 20, then be heated to 30 ~ 50 DEG C, stirring fully dissolves xylogen in 1 ~ 3 hour, remove by filter the insolubles in raw material, obtain filtrate; Described xylogen raw material comprises alkali lignin and ethanol xylogen.
3. the preparation method of xylogen nano particle according to claim 2, is characterized in that: described organic solvent comprises one or more mixing in methylene dichloride, ethylene glycol, propylene glycol, glycerol.
4. the preparation method of xylogen nano particle according to claim 1, it is characterized in that: the preparation of described xylogen colloidal sol: in raw material filtrate, drip mineral acid to pH=2 ~ 2.5, and keep stirring, obtain xylogen colloid, described mineral acid comprises one or more mixing in sulfuric acid, hydrochloric acid, phosphoric acid.
5. the preparation method of xylogen nano particle according to claim 1, it is characterized in that: the temperature of described crosslinking reaction is 30 ~ 50 DEG C, after finishing, crosslinking reaction is cooled to room temperature, in crosslinking reaction system, drip water, make the continuous dialysis of cross-linking agent out, wash with water, at 60 ~ 80 DEG C, vacuum-drying can obtain xylogen nano-particle material in 12 ~ 18 hours again.
6. the preparation method of xylogen nano particle according to claim 5, is characterized in that: described xylogen nano particle diameter is 20 ~ 200nm.
7. the preparation method of xylogen nano particle according to claim 1, is characterized in that: the source of described xylogen raw material comprises softwood, pourous wood and draft class plant.
8. the preparation method of xylogen nano particle according to claim 7, is characterized in that: the source of described xylogen raw material comprises dragon spruce, Pinus massoniana Lamb, tamarack, birch, Eucalyptus, poplar, wheat straw, straw, maize straw, bagasse, reed.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3080138B1 (en) | 2013-12-12 | 2019-06-05 | Solenis Technologies, L.P. | Lignin nanoparticle dispersions and methods for producing and using the same |
| WO2017134308A1 (en) * | 2016-02-05 | 2017-08-10 | Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften Ev | Lignin biomaterial as agricultural drug carrier |
| CN106582549A (en) * | 2016-11-10 | 2017-04-26 | 广西大学 | Preparing method for monodisperse lignin microspheres |
| CN106562933A (en) * | 2016-11-10 | 2017-04-19 | 广西大学 | Preparation method for lignin drug sustained release microspheres |
| US11524974B2 (en) | 2017-10-26 | 2022-12-13 | Aalto University Foundation Sr | Aqueous lignin dispersions and methods of preparing the same |
| CN108420751A (en) * | 2018-04-12 | 2018-08-21 | 北京林业大学 | A kind of preparation method of the nano lignin particle with uvioresistant effect |
| AT521393B1 (en) * | 2018-06-27 | 2021-02-15 | Univ Wien Tech | Process for the production of lignin particles as part of a continuous process |
| CN109012609A (en) * | 2018-07-17 | 2018-12-18 | 北京林业大学 | A kind of lignin nanosphere environment-friendly preparation method thereof |
| US20220010077A1 (en) | 2018-11-29 | 2022-01-13 | Aalto University Foundation Sr | Lignin particle based hydrogel and the method for preparation of lignin colloidal particles by solvent evaporation process |
| CN111484587A (en) * | 2019-01-25 | 2020-08-04 | 石河子大学 | Method for preparing lignin-based phenolic resin |
| CN109847714A (en) * | 2019-04-04 | 2019-06-07 | 岭南师范学院 | A kind of preparation method of bagasse microballoon |
| CN110128733B (en) * | 2019-06-10 | 2021-07-27 | 浙江工业大学 | Method for preparing nano lignin composite particles by using microchannel reactor |
| CN115386102B (en) * | 2022-08-19 | 2023-07-21 | 广州大学 | Phosphating lignin sulfonate nanoparticle and preparation method and application thereof |
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| CN102140174A (en) * | 2011-03-08 | 2011-08-03 | 延边石岘白麓纸业股份有限公司 | Preparation method for lignosulfonate |
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