CN100393735C - Lignin-Based cyclodextrin ester multi-purpose sorbent preparation method - Google Patents
Lignin-Based cyclodextrin ester multi-purpose sorbent preparation method Download PDFInfo
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- CN100393735C CN100393735C CNB2006100103959A CN200610010395A CN100393735C CN 100393735 C CN100393735 C CN 100393735C CN B2006100103959 A CNB2006100103959 A CN B2006100103959A CN 200610010395 A CN200610010395 A CN 200610010395A CN 100393735 C CN100393735 C CN 100393735C
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Abstract
The invention discloses a preparing method of multi-effect lignin cyclodextrin ether to adsorb heavy metal, phenol, phenylamine and uric acid, which comprises the following steps: adopting lignin as material; dissolving through alkaline; purifying through acid settling; dissolving disposed lignin in certain density of sodium hydroxide; adding certain quantity of crosslinking agent in the alkaline solution with weight rate at 1:5-1:15; polymerizing under 50-90 deg.c for 1-5h; adding polymer into cyclodextrin with weight rate at 1-5:1; filtering; washing; drying; grinding; obtaining the lignin cyclodextrin ether adsorbent. The lignin is alkali lignin and lignin sulfonate. The crosslinking agent is epichlorohydrin, 1, 2-glycol bisglycidyl ether or 1, 2-butanediol bisglycidyl ether. The cyclodextrin is beta-cyclodextrin, methyl beta-cyclodextrin or hydroxypropyl beta-cyclodextrin.
Description
Technical field
The invention relates to and a kind ofly can adsorb heavy metal and phenol, aniline, the multiple-effect lignin-base preparation of adsorbent method that can also adsorb uric acid simultaneously.
Background technology
The reserves of earth Nonrenewable resources are limited, and mainly relying on oil and natural gas is that synthesized polymer material and other organic chemical industry's product of raw material will face the predicament that raw material sources are petered out.Renewable resources is best alternate resources, and xylogen is one of renewable resources the abundantest on the earth, and the annual whole world can produce 1,500 hundred million tons by plant-growth, and wherein the industrial lignin that produces in the waste liquid of paper industry has 30,000,000 tons.Xylogen is as the by product of wood saccharification industry and paper industry, and utilization still not yet in effect at present becomes one of primary pollution source in the paper industry, not only contaminate environment, and waste resource.Therefore, how to effectively utilize this renewable resources of xylogen, improve its added value, caused association area investigator and entrepreneur's common concern.
The fractionation by adsorption functional materials has very important purposes in a lot of fields, mainly comprises the aspect such as separation and purification, medical use, environment protection, solid phase organic synthesis, analytical technology of water treatment, separating organic matters purifying, hydrometallurgy, chemical industry preparation and purifying products, biologics.China's sorbent material that begins one's study the sixties in 20th century is used more sorbent material at present and is mainly contained molecular sieve, gac and various ion exchange resin, polymeric adsorbent etc.In recent ten years, domestic and international many investigators replace more expensive gac of price or ion exchange resin etc. at the sorbent material of exploring Cheap highly effective.Isolating xylogen from papermaking wastewater, cost specific activity charcoal is low.It is limited that but xylogen is used as the loading capacity of sorbing material separately, thus can further improve the absorption property of lignin product by chemical modification, thereby can obtain to have multi-functional, high performance lignin-base sorbing material by the xylogen derivative reaction.Both at home and abroad about the fractionation by adsorption lignin-base sorbing material of mixed pollutent is developed rare report, demand development urgently so far.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lignin-Based cyclodextrin ester multi-purpose sorbent, simple, the prepared sorbent material of this method preparation technology can be simultaneously to heavy metal, and phenol, aniline and uric acid etc. have bigger adsorptive power, and be cheap.
The present invention is realized by following technical proposals, a kind of method for preparing lignin-Based cyclodextrin ester multi-purpose sorbent, and its feature comprises following process:
1) with the xylogen behind the purifying and 1: 5-1: the linking agent of 15 times of weight is at 50-90 ℃, and stirring reaction 1-5 hour, after having reacted, filter, benzene is washed, washing, drying obtains lignin-base Resins, epoxy;
2) with the cyclodextrin of above-mentioned lignin-base Resins, epoxy and 1-5 times of weight at 30-70 ℃, stirring reaction 1-5 hour, after having reacted, thorough washing filtered, drying obtains the lignin-base cyclodextrin ethers.
Above-mentioned xylogen is alkali lignin, sulfonated lignin.
Above-mentioned linking agent is epoxy chloropropane, 1 diglycidylether or 1, the 2-butanediol diglycidyl ether.
Above-mentioned cyclodextrin is a beta-cyclodextrin, methyl beta-cyclodextrin or hydroxypropyl.
The invention has the advantages that: preparation technology is simple, and obtained adsorbents adsorb speed is fast, binding ability strong, difficult drop-off; And can have bigger adsorptive power to heavy metal, phenol, aniline and uric acid simultaneously, during absorption 4h, to Cu
2+Loading capacity be 0.358mmol/g, Pyrogentisinic Acid's loading capacity is 0.045mmol/g, is 120 μ g/g to the loading capacity of uric acid.
Description of drawings
The present invention is further illustrated below in conjunction with drawings and Examples.
Fig. 1 is the FTIR figure of xylogen, lignin epoxide resin, lignin-base cyclodextrin ethers.
Embodiment
With embodiment the present invention is illustrated below.
The purifying of raw material: raw material with the dissolving of the NaOH solution of 1mol/L, is removed by filter insolubles in the raw material, is 2 with the pH of the HCl regulator solution of 1mol/L, filter, with the distilled water thorough washing to neutrality, 40 ℃ of vacuum-dryings.
Alkali lignin 1g behind the purifying is joined in the 100mL there-necked flask, add 10mL 20%NaOH (massfraction) solution, stir, at room temperature, add the 10g epoxy chloropropane, be warming up to 80 ℃, reacted 3 hours.After having reacted, filter, product washs with benzene, is washed with water to neutrality again, 40 ℃ of vacuum-dryings.Top reaction product 1g is joined in 25mL 20%NaOH (massfraction) solution then, stir, add the 1g beta-cyclodextrin afterwards, 55 ℃ of attemperation reacted 3 hours, filtered, and are extremely neutral with the distilled water thorough washing, 40 ℃ of vacuum-dryings.Obtain the lignin-base cyclodextrin ethers.
Xylogen, lignin-base Resins, epoxy, the infrared spectrum of lignin-base cyclodextrin ethers is seen a in the accompanying drawing 1, b, c.As can be seen from the figure, at 3440.17cm
-1All there is the absorption peak of hydroxyl at the place, and different is that the hydroxyl peak in the lignin-base Resins, epoxy obviously weakens than the hydroxyl peak in the xylogen, illustrates that reaction has taken place phenolic hydroxyl group and the epoxy chloropropane in the xylogen, has generated epoxy group(ing).And the hydroxyl peak in the infrared spectrum of lignin-base cyclodextrin ethers has obviously strengthened than the hydroxyl peak in the Resins, epoxy, its reason be since reactive grafting on cyclodextrin, exist great amount of hydroxy group to cause on the cyclodextrin.And Duoed at 909.12cm in the spectrogram than xylogen in the lignin-base Resins, epoxy spectrogram
-1, 757.22cm
-1Two place's absorption peaks, through examining C-O-C and C-Cl key charateristic avsorption band for epoxy group(ing).This peak, two places has all disappeared again in the FTIR of lignin-base cyclodextrin ethers figure, illustrates that cyclodextrin has been grafted on the xylogen, proves that the lignin-base cyclodextrin ethers generates.
Embodiment 2
Alkali lignin 1g behind the purifying is joined in the 100mL there-necked flask, add in 15mL 20%NaOH (massfraction) solution, stir, at room temperature, add 10g 1 diglycidylether, be warming up to 70 ℃, reacted 3 hours.After having reacted, filter, be washed to neutrality, 40 ℃ of vacuum-dryings.Top reaction product 1.5g is joined in 25ml 20%NaOH (massfraction) solution then, stir, add the 3g beta-cyclodextrin, 55 ℃ of attemperation reacted 3 hours, filtered, and washing is to neutrality, 40 ℃ of vacuum-dryings.Obtain the lignin-base cyclodextrin ethers.
Embodiment 3
Sulfonated lignin 1g behind the purifying is joined in the 100mL there-necked flask, add in 10mL 20%NaOH (massfraction) solution, stir, at room temperature, add the 10g epoxy chloropropane, be warming up to 80 ℃, reacted 3 hours.After having reacted,, be washed to neutrality, filter vacuum-drying with the benzene washing.Top reaction product 1.5g is joined in 30mL 20%NaOH (massfraction) solution then, stir, add 1g methyl beta-cyclodextrin, 50 ℃ of attemperation reacted 4 hours, filtered, and washing is to neutrality, 40 ℃ of vacuum-dryings.Obtain the lignin-base cyclodextrin ethers.
Embodiment 4
Alkali lignin 1g behind the purifying is joined in the 100mL there-necked flask, add in 15mL 20%NaOH (massfraction) solution, stir, at room temperature, add 10g 1 diglycidylether, be warming up to 70 ℃, reacted 3 hours.After having reacted, filter, be washed to neutrality, vacuum-drying.Top reaction product 1g is joined in 25mL 20%NaOH (massfraction) solution then, stir, add the 2g hydroxypropyl, 50 ℃ of attemperation reacted 5 hours, filtered, and washing is to neutrality, 40 ℃ of vacuum-dryings.Obtain the lignin-base cyclodextrin ethers.
Embodiment 5
Sulfonated lignin 1g behind the purifying is joined in the 100mL there-necked flask, add in 15mL 20%NaOH (massfraction) solution, stir, at room temperature, add 10g 1 diglycidylether, be warming up to 80 ℃, reacted 3 hours.After having reacted, filter, be washed to neutrality, 40 ℃ of vacuum-dryings.Top reaction product 1g is joined in 30mL20%NaOH (massfraction) solution then, stir, add 1g methyl beta-cyclodextrin afterwards, 60 ℃ of attemperation reacted 4 hours, filtered, and washing is to neutrality, 40 ℃ of vacuum-dryings.Obtain the lignin-base cyclodextrin ethers.
Claims (4)
1. the preparation method of lignin-base cyclodextrin ethers, it comprises the steps:
1) xylogen behind the purifying is dissolved in the NaOH solution that concentration is 20-30%, by the mass ratio 1 of itself and linking agent: 5-1: 15, in alkaline solution, add linking agent, carry out 1-5 hour polyreaction at 50-90 ℃;
2) in above-mentioned reaction solution, be 1-5 by the mass ratio of polymkeric substance and cyclodextrin: 1 adds cyclodextrin, 30-70 ℃ of reaction 1-5 hour, reaction finishes after washing, dry, grind, obtain the lignin-base cyclodextrin ethers.
2. by the preparation method of the described lignin-base cyclodextrin ethers of claim 1, it is characterized in that: xylogen is alkali lignin, sulfonated lignin.
3. by the preparation method of the described lignin-base cyclodextrin ethers of claim 1, it is characterized in that: linking agent is selected from epoxy chloropropane, 1 diglycidylether or 1,2-butanediol diglycidyl ether.
4. by the preparation method of the described lignin-base cyclodextrin ethers of claim 1, it is characterized in that: cyclodextrin is beta-cyclodextrin, methyl beta-cyclodextrin or hydroxypropyl.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101357323B (en) * | 2008-09-18 | 2010-06-09 | 福州大学 | Globular lignin macroporous adsorption resin and preparation technique thereof |
| CN102527345B (en) * | 2012-01-13 | 2013-08-07 | 大连理工大学 | Preparation method of Mn element-doped cyclodextrin polymer material with adsorptive separation function and application thereof |
| CN103601901B (en) * | 2013-12-04 | 2015-12-02 | 光明乳业股份有限公司 | Reduced cholesterol dairy products and crosslinked beta-cyclodextrin, its preparation method, application |
| CN105087050B (en) * | 2015-09-11 | 2017-01-25 | 中国石油大学(华东) | Fuel oil product denitrifier using supramolecular inclusion effect and application method thereof |
| CN105642254B (en) * | 2016-01-12 | 2019-10-01 | 安徽理工大学 | It is a kind of with adsorbing lignin-base polymer, preparation method and the application of heavy metal ion and organic dyestuff simultaneously |
| CN106977695B (en) * | 2017-04-18 | 2019-06-14 | 江南大学 | A kind of epoxyn and preparation method thereof of original position alkali lignin self-catalysis synthesis |
| CN109897186B (en) * | 2017-12-11 | 2021-07-13 | 神华集团有限责任公司 | Beta-cyclodextrin modified lignosulfonate, preparation method and application thereof, and preparation method of coal water slurry |
| CN110051852A (en) * | 2019-05-24 | 2019-07-26 | 中国林业科学研究院木材工业研究所 | A kind of high encapsulation performance lignin nanosphere as well as preparation method and application thereof |
| CN111072892B (en) * | 2019-11-28 | 2022-01-25 | 万果新材料科技(上海)有限公司 | Polyurethane foam filling material for sound-insulation heat-insulation aluminum door |
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| CN1660129A (en) * | 2004-12-13 | 2005-08-31 | 天津大学 | Method for preparing agent of cyclodextrin-cellulose for adsorbing uric acid |
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| CN1660129A (en) * | 2004-12-13 | 2005-08-31 | 天津大学 | Method for preparing agent of cyclodextrin-cellulose for adsorbing uric acid |
Non-Patent Citations (6)
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| Lignin-a useful bioresource for the production ofsorption-active materials. Dizhbite T. Zakis G. Kizima A.Bioresource Tchnol,Vol.67 No.3. 1999 |
| Lignin-a useful bioresource for the production ofsorption-active materials. Dizhbite T. Zakis G. Kizima A.Bioresource Tchnol,Vol.67 No.3. 1999 * |
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