CN105504307A - Preparation method of modified lignin for wastewater treatment - Google Patents

Preparation method of modified lignin for wastewater treatment Download PDF

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Publication number
CN105504307A
CN105504307A CN201410497074.0A CN201410497074A CN105504307A CN 105504307 A CN105504307 A CN 105504307A CN 201410497074 A CN201410497074 A CN 201410497074A CN 105504307 A CN105504307 A CN 105504307A
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CN
China
Prior art keywords
colourity
modified lignin
modified
wastewater treatment
lignin resin
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CN201410497074.0A
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Chinese (zh)
Inventor
姚义刚
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南京克瑞特科技信息咨询有限公司
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Priority to CN201410497074.0A priority Critical patent/CN105504307A/en
Publication of CN105504307A publication Critical patent/CN105504307A/en

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Abstract

The invention discloses a preparation method of modified lignin for wastewater treatment. The method includes: a preparation process route, employed modifying materials and proportions, preparation process conditions and a modification evaluation method. The preparation method is simple and is mild in synthetic conditions. The modified product has excellent treatment effects on industrial wastewater.

Description

A kind of preparation method of the modified lignin resin for wastewater treatment

Technical field

The invention belongs to organic chemical industry's synthesis technical field, in particular to a kind of preparation method of the modified lignin resin for wastewater treatment.

Background technology

Xylogen is the byproduct of paper industry, is a kind of macromolecular compound of tridimensional network.The basic structural unit of xylogen is phenylpropyl alcohol alkane, has three kinds of structural units, i.e. guaiacyl propane, Syringa oblata Lindl. base propane and to hydroxyphenyl propane.Containing hydrophilic and oleophilic group in the molecular structure of xylogen, thus there is good surfactivity and dispersiveness, can be used as cement water reducing agent, drilling mud conditioning agent, asphalt emulsifier, binding agent, dispersion agent etc.; The hydroxyl of some amount, carboxyl, carbonyl, alcoholic extract hydroxyl group, phenolic hydroxyl group, methoxyl group, ehter bond, conjugated double bond isoreactivity functional group on its molecular structure; can carry out modification by many chemical reactions such as acidylate, alkylation, sulfonation, amination, condensation and graft copolymerizations to it, modified xylogen has Application Areas and better use properties widely.

When xylogen uses as flocculation agent in the treatment of waste water, its chemical modification method is mainly contained:

(1) with aldehyde and amine, Mannich occurs to react, generate lignin amine, this cationic lignin amine has flocculation and decolorizing effect preferably.

(2) with sulphite and quaternary ammonium salt generation sulfonation and quaternary ammonium reaction, generate the lignin flocculant of both sexes, this flocculation agent has better treatment effect when processing montmorillonite suspension liquid and dyeing waste water.

(3) with vinylformic acid or acrylamide generation graft copolymerization, the multipolymer of gained xylogen-vinylformic acid or xylogen-acrylamide can improve the flocculating effect of single polyacrylic acid or polyacrylamide.

(4) with fatty acid ester or other ester class generation condensation reactions, the small molecules such as water, alcohol or ammonia are released, simultaneously the high molecular polymer of generating functionality.

Although the method for modifying of above xylogen can make modified lignin resin obtain certain modified effect when being used as flocculation agent, also also exist as severe reaction conditions, reaction not exclusively, the various problem such as hazard residue is more in reaction product.

Summary of the invention

Goal of the invention: in order to overcome the deficiency of existing modified lignin resin preparation method, the invention discloses a kind of preparation method of the modified lignin resin for wastewater treatment.Present method is realized by following technological line:

(1) sulfonation reaction of xylogen and oleum obtains lignosulfonic acid;

(2) lignosulfonic acid and alkali reaction obtain sulfonated lignin;

(3) sulfonated lignin and polyoxyethylene glycol carry out polycondensation to benzene sulfonamide acid diesters and obtain sulfomethylated lignin acid polyethylene glycol to benzene sulfonamide acid diesters high molecular polymer.

Beneficial effect

Preparation method's processing step of a kind of modified lignin resin for wastewater treatment of the present invention is few, and synthesis condition is gentle, and operation is simple, final product is without the need to being separated, can be directly used in Industrial Wastewater Treatment, show the test of its Performance Properties Evaluation, flocculation and the desolventing technology of product are respond well.

Embodiment

Embodiment 1.

(1) take 120 grams, the powdery xylogen obtained from the market, be placed in the reactor of band stirring and condensing works, drip oleum 103 grams under vigorous stirring, after adding, under room temperature, continue stirring 2 hours, obtained lignosulfonic acid.

(2) in above-mentioned obtained lignosulfonic acid, drip the N of 35% concentration aoH solution, with the pH value of the in good time detecting reactant of PH test paper, when the PH of reactant reaches 6 ~ 7, obtained lignosulfonic acid sodium solution; Filtrate condensing crystal after filtering, obtained lignosulfonic acid sodium salt.

(3) get above-mentioned sodium lignosulfonate 100 grams, be configured to the aqueous solution of 30% with deionized water, add building block (CH 2cH 2o) polyoxyethylene glycol of n=5 is to benzene sulfonamide acid diesters 240 grams, adds the N of 35% concentration aoH solution 15 grams.Slowly heat, stir, maintain backflow 3 hours, when solution be thickened to be difficult to stir time, then add the N of 150 ml deionized water and 35% concentration aoH solution 7 grams, continues reaction 20 minutes at reflux, after being cooled to room temperature, with the sulfuric acid of proper concn, the PH of reactant being adjusted to 7 and namely obtaining final polycondensation macromolecule product.

(4) get appropriate final product, be configured to the solution for later use of 1000mg/L; Separately getting 100 milliliters of colourities is 200(platinum cobalt colourity), fraction of particle is that the slurry of 2% is in 100 milliliters of tool plug graduated cylinders, the reaction mixture getting 1 milliliter of 1000mg/L adds wherein (production concentration is 10ppm), manual reversing concussion 60 times, the time required when the interfacial layer of clay drops to graduated cylinder half height is observed in timing immediately, does blank simultaneously; The supernatant liquid separately got in appropriate above-mentioned graduated cylinder carries out colour measurement (platinum cobalt chromatmetry), draws concrete chroma data, calculates colourity reduced rate with (1-surveys colourity/200) × 100%.Testing data shows, and product of the present invention is under 10ppm working concentration, and the time that the interfacial layer of suspension clay drops to graduated cylinder half height is 90 seconds, and colourity reduced rate reaches 93%.

Embodiment 2.

(1) polycondensation: the sodium lignosulfonate 100 grams of (2) step gained in Example 1, is configured to the aqueous solution of 30%, adds building block (CH with deionized water 2cH 2o) polyoxyethylene glycol of n=7.5 is to benzene sulfonamide acid diesters 380 grams, adds the N of 35% concentration aoH solution 15 grams.Slowly heat, stir, maintain reflux temperature 4 hours, when solution be thickened to be difficult to stir time, then add the N of 200 ml deionized water and 35% concentration aoH solution 7 grams, continues reaction 20 minutes at reflux, after being cooled to room temperature, with the sulfuric acid of proper concn, the PH of reactant is adjusted to the macromolecule product that namely 7 obtain final polycondensation.

(2) product property evaluation test: get appropriate final product, is configured to the solution for later use of 1000mg/L; Separately getting 100 milliliters of colourities is 200(platinum cobalt colourity), fraction of particle is that the slurry of 2% is in 100 milliliters of tool plug graduated cylinders, the reaction mixture getting 2 milliliters of 1000mg/L adds wherein (production concentration is 20ppm), manual reversing concussion 60 times, the time required when the interfacial layer of clay drops to graduated cylinder half height is observed in timing immediately, does blank simultaneously; The supernatant liquid separately got in appropriate above-mentioned graduated cylinder carries out colour measurement (platinum cobalt chromatmetry), draws concrete chroma data, calculates colourity reduced rate with (1-surveys colourity/200) × 100%.The display of final testing data, this product is under 20ppm working concentration, and the time that the interfacial layer of suspension clay drops to graduated cylinder half height is 70 seconds, and colourity reduced rate reaches 95%.

Embodiment 3.

(1) polycondensation: the sodium lignosulfonate 100 grams of (2) step gained in Example 1, is configured to the aqueous solution of 30%, adds building block (CH with deionized water 2cH 2o) polyoxyethylene glycol of n=10 is to benzene sulfonamide acid diesters 520 grams, adds the N of 35% concentration aoH solution 15 grams.Slowly heat, stir, maintain reflux temperature 6 hours, when solution be thickened to be difficult to stir time, then add the N of 220 ml deionized water and 35% concentration aoH solution 7 grams, continues reaction 20 minutes at reflux, after being cooled to room temperature, with the sulfuric acid of proper concn, the PH of reactant is adjusted to the macromolecule product that namely 7 obtain final polycondensation.

(2) product property evaluation test: get appropriate final product, is configured to the solution for later use of 1000mg/L; Separately getting 100 milliliters of colourities is 200(platinum cobalt colourity), fraction of particle is that the slurry of 2% is in 100 milliliters of tool plug graduated cylinders, the reaction mixture getting 1.5 milliliters of 1000mg/L adds wherein (production concentration is 15ppm), manual reversing concussion 60 times, the time required when the interfacial layer of clay drops to graduated cylinder half height is observed in timing immediately, does blank simultaneously; The supernatant liquid separately got in appropriate above-mentioned graduated cylinder carries out colour measurement (platinum cobalt chromatmetry), draws concrete chroma data, calculates colourity reduced rate with (1-surveys colourity/200) × 100%.The display of final testing data, this product is under 20ppm working concentration, and the time that the interfacial layer of suspension clay drops to graduated cylinder half height is 75 seconds, and colourity reduced rate reaches 93%.

Claims (6)

1. the preparation method of a kind of modified lignin resin for wastewater treatment of the present invention, is characterized in that the method comprises
The preparation were established of modified lignin resin, material modified and proportioning used, prepare the processing parameter of modified lignin resin, evaluate modified lignin resin to the method for wastewater treatment performance index.
2., according to claim 1, the preparation were established of described modified lignin resin is as follows:
The sulfonation reaction of xylogen and oleum obtains lignosulfonic acid;
Lignosulfonic acid and alkali reaction obtain sulfonated lignin;
Sulfonated lignin and polyoxyethylene glycol carry out polycondensation to benzene sulfonamide acid diesters and obtain sulfomethylated lignin acid polyethylene glycol to benzene sulfonamide acid diesters high molecular polymer.
3., according to claim 2, the polyoxyethylene glycol in described operational path (3) is characterized in that the polyalkylene glycol moiety (CH in this compound to benzene sulfonamide acid diesters 2cH 2o) n, n=5 ~ 10 wherein.
4., according to claim 2, sulfonated lignin and polyoxyethylene glycol react 3-6 hour to the polycondensation of benzene sulfonamide acid diesters maintaining under reflux conditions in described operational path (3).
5., according to claim 1, the method for described evaluation modified lignin resin to wastewater treatment performance index is characterized in that:
Be 200(platinum cobalt colourity in colourity) transparent water in add the slurry that massfraction is 2%;
In the tool plug graduated cylinder that 100 milliliters of above-mentioned suspension are housed, add the product of the present invention (5 ~ 20ppm) of different concns, manual reverse back and forth 60 times (1 minutes) leave standstill afterwards, the time required when the interfacial layer that clay is observed in timing immediately drops to graduated cylinder half height.
6. the supernatant liquid got in appropriate above-mentioned graduated cylinder carries out colour measurement (platinum cobalt chromatmetry), draws concrete chroma data, calculates colourity reduced rate with (1-surveys colourity/200) × 100%.
CN201410497074.0A 2014-09-25 2014-09-25 Preparation method of modified lignin for wastewater treatment CN105504307A (en)

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CN105504307A true CN105504307A (en) 2016-04-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105692772A (en) * 2016-04-21 2016-06-22 苏州云舒新材料科技有限公司 Wastewater composite adsorption-flocculation material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105692772A (en) * 2016-04-21 2016-06-22 苏州云舒新材料科技有限公司 Wastewater composite adsorption-flocculation material
CN105692772B (en) * 2016-04-21 2018-11-13 苏州云舒新材料科技有限公司 A kind of waste water composite adsorption-flocculation treatment material

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Application publication date: 20160420

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