CN101440287B - Preparation of lignosulphonate graft copolymer chemical sand solidification agent - Google Patents
Preparation of lignosulphonate graft copolymer chemical sand solidification agent Download PDFInfo
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- CN101440287B CN101440287B CN2007101885727A CN200710188572A CN101440287B CN 101440287 B CN101440287 B CN 101440287B CN 2007101885727 A CN2007101885727 A CN 2007101885727A CN 200710188572 A CN200710188572 A CN 200710188572A CN 101440287 B CN101440287 B CN 101440287B
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Abstract
The invention discloses a method for preparing a lignosulfonate graft copolymer chemical sand fixing agent. In the method, neutral papermaking waste liquid is evaporated and condensed; lignosulfonate in the neutral papermaking waste liquid is extracted; an aldehyde compound and an unsaturated acylamide, unsaturated acid or unsaturated ester compound are respectively or simultaneously used as reaction compositions; and the lignosulfonate is subjected to chemical modification to synthesize the serial lignosulfonate graft copolymer chemical sand fixing agent. The method has no environmental pollution, good water solubility, strong capacity for water erosion resistance and high compressive strength performance.
Description
Technical field
The invention belongs to sulfonated lignin organic polymer chemical modification and utilize technical field.
Background technology
Family surplus the existing grass papermaking enterprise 2000 of China, because small scale, backward in technique, starting material and energy consumption are big, the papermaking wastewater of most of enterprise fails well to be administered and utilize, and ecotope has been caused serious pollution.China is subjected to one of the most serious country of desertification hazard in the world, according to statistics, whole nation sandy land area reaches 1,740,000 square kilometres, account for 18% of area, the summation that surpasses national cultivated area, the desertification propagation rate develops into present 3436 square kilometres by expanding 2460 square kilometres the every year before 1994, directly has influence on the national sustainable development implementation.Administer desertification, checking winds and fixing drifting sand becomes current problem demanding prompt solution.Contain a large amount of sulfonated lignin in the papermaking wastewater, if it can be separated the synthetic sand-fixation agent of purifying, not only administered the papermaking wastewater pollution, and the synthetic chemical sand-fixing materials can be used for desertification treatment, the Eco-environment Construction of Western Region based on desert treatment is had great importance.
United States Patent (USP) (USP No.4,303,438) discloses uses acrylic graft-modified sulfonated lignin, and product can be used as soil improvement agent, has the soil aggregation of raising degree, resists the effect of wind erosion.(application number: 01137349.0) disclose directly is raw material with the papermaking wastewater to domestic patent of invention, with vinylformic acid or acrylamide it is carried out the synthetic sandy soil conditioner of chemical modification.Disclosed sandy soil conditioner is directly prepared by papermaking wastewater, and contain a large amount of acid or alkali, inorganic salt and organism in the papermaking wastewater that different pulping methods form, if do not handle, directly be prepared into sand-fixation agent, be used in the desertification control, can pollute environment undoubtedly, in the water that permeates the ground, meeting polluted underground water matter; Disclosed sandy soil conditioner is not promoted the use of as yet, may with its cohesiveness and snappiness, promptly weather-proof property and ultimate compression strength are not that to make us class very satisfied relevant.
Summary of the invention
The objective of the invention is to prepare a kind of environmentally safe, biodegradable, low-cost, have a lignosulphonate graft copolymer chemical sand solidification material of wind erosion-resistance performance and high compression strength preferably.
The present invention is by carrying out evaporation concentration to neutral papermaking wastewater, extract sulfonated lignin wherein, serve as the reaction component with aldehyde compound and unsaturated amides, unsaturated acid or ester compound respectively or simultaneously then, sulfonated lignin are carried out chemical modification, the synthesizing series lignosulphonate graft copolymer chemical sand solidification agent, has environmentally safe, better water solubility, stronger weather-proof ability and high compression strength performance.
A kind of preparation of lignosulphonate graft copolymer chemical sand solidification agent, it is characterized in that this method with neutral papermaking wastewater through evaporation concentration, drying obtains pulverous sulfonated lignin; In the lignosulfonic acid salts solution, add stoichiometric alkaline solution, add aldehyde compound again, be under 50～80 ℃ the condition in temperature, back flow reaction 1～3 hour; Add unsaturated amides then, or unsaturated fatty acids, or the ester compound of unsaturated fatty acids, add initiator again, be warmed up to 80～100 ℃, back flow reaction 1～2 hour; Obtain brown powder shape product through evaporation concentration, drying, process of lapping at last.
Alkali used in the present invention is sodium hydroxide, or potassium hydroxide, or sodium hydrogen carbonate solution, and concentration is 10%～30%, and consumption is 5%～20% (mass percent) of sulfonated lignin.
Aldehyde compound used in the present invention is formaldehyde, acetaldehyde or propionic aldehyde, and consumption is 10%～50% (mass percent) of sulfonated lignin.
Unsaturated amides used herein, or unsaturated fatty acids, or the ester compound of unsaturated fatty acids is selected from acrylamide, maleic acid, vinylformic acid, methacrylic acid, vinyl acetate or methyl methacrylate, consumption are 40%～80% (mass percent) of sulfonated lignin.
Initiator used in the present invention is 30% aqueous hydrogen peroxide solution, and ceric ammonium nitrate, or Sodium Persulfate, consumption are 0.5%～10% (mass percent) of sulfonated lignin.
The using method of the sand-fixation agent of the present invention's preparation: sand-fixation agent is dissolved in the water, its mass percent is 0.15%～1.5%, evenly be sprayed on the sandy soil surface then, the sandy soil surface can form fine and close duricrust, wind tunnel experiment and ultimate compression strength experiment test result show, has wind erosion-resistance performance preferably, high compression strength.
The characteristics of the sand-fixation agent of the present invention's preparation are: the major constituent of sulfonated lignin graft copolymer is sulfonated lignin, through neutral papermaking wastewater evaporation concentration, obtain after the drying, so this sand-fixation agent can not pollute environment; Xylogen in the sand-fixation agent is the bioblast of soil ulmin, can improve content organic in the sandy soil after spraying, and improves the soil, and is biodegradable; The cost of aldehydes is low more a lot of than acrylamide and vinylformic acid, has reduced simple cost with the synthetic sand-fixation agent of unsaturated acid compounds modification significantly; Behind the aldehyde compound modified lignin mahogany sulfonate, the hydroxy number on the sulfonated lignin increases, so the water-soluble enhancing of institute's synthetic sand-fixation agent; Behind the unsaturated acid compounds modified lignin mahogany sulfonate, contain carboxyl in the product, make product have function such as moisture absorption, water conservation preferably; Sand-fixation agent has wind erosion-resistance performance preferably, high compression strength.
Embodiment
Neutral papermaking wastewater carries out concentration and evaporation under decompression or condition of normal pressure, drying is ground, and obtains the powdered sulfonated lignin; Sulfonated lignin are dissolved in the suitable quantity of water, and the back that stirs adds a certain amount of sodium hydroxide solution, and a certain amount of aldehyde compound, is under 50～80 ℃ the condition in temperature, back flow reaction 1～3h; Add a certain amount of unsaturated amides again, or unsaturated fatty acids, or the ester compound of unsaturated fatty acids, and initiator, be warmed up to 80～100 ℃, back flow reaction 1～2h; Obtain brown powder shape sulfonated lignin graft copolymer through distillation, drying, grinding at last; This high-molecular copolymer is dissolved in the water, evenly is sprayed on the sandy soil surface, after the sandy soil surface drying, can form fine and close duricrust.
Embodiment 1:
The 40g sulfonated lignin are dissolved in the 90mL water, add the sodium hydroxide solution 10mL of 0.2mol/L, add propionic aldehyde 8mL again, in temperature are to react 3h under 60～70 ℃ the condition.After reaction finishes, the reaction mixture distillation is concentrated, drying obtains brown powder shape product I after the grinding.
Embodiment 2:
The 40g sulfonated lignin are dissolved in the 90mL water, add the sodium hydroxide solution 4mL of 24g vinyl acetate and 20%, are warmed up to 30 ℃, add 30% aqueous hydrogen peroxide solution 1.6mL again as initiator, back flow reaction 30min.After having reacted, the reaction mixture distillation is concentrated, drying obtains brown powder shape product II after the grinding.
Embodiment 3:
The 40g sulfonated lignin are dissolved in the 90mL water, add the sodium hydroxide solution 10mL of 0.2mol/L, add propionic aldehyde 8mL again, be under 60～70 ℃ the condition in temperature, add the 16mL vinyl acetate behind the reaction 1h, add 30% aqueous hydrogen peroxide solution 1.1mL again, back flow reaction 1h.After having reacted, the reaction mixture distillation is concentrated, drying obtains brown powder shape product III after the grinding.
With product I, II and III are dissolved in the 40mL water, stir, and then respectively with 25,50,75,100g/m
2Metering evenly be sprayed at 6.78 * 10
-3m
2The sandy soil surface on, after the drying, adopt horizontal direction and 30 degree angular direction sand-carrying winds in the wind tunnel experiment, when usage quantity is 25g/m
2The time, it is 10m/s that product I horizontal direction initially corrodes wind speed, it is 8m/s that wind speed is initially corroded in 30 degree angular direction; It is 10m/s that product II horizontal direction initially corrodes wind speed, and it is 8m/s that wind speed is initially corroded in 30 degree angular direction; It is 13m/s that product III horizontal direction initially corrodes wind speed, and it is 10m/s that wind speed is initially corroded in 30 degree angular direction.With product I, II and III are dissolved in the 350mL water, stir, and then respectively with 10,25,50g/m
2Metering evenly be sprayed at 5.27 * 10
-2m
2The sandy soil surface on, after the drying, the ultimate compression strength of specimen is when usage quantity is 25g/m
2The time, product I ultimate compression strength is 144kPa, and product II ultimate compression strength is 113kPa, and product III ultimate compression strength is 189kPa.
Claims (2)
1. preparation of lignosulphonate graft copolymer chemical sand solidification agent, it is characterized in that this method with neutral papermaking wastewater through evaporation concentration, drying obtains pulverous sulfonated lignin; In the lignosulfonic acid salt brine solution, add stoichiometric alkaline solution, add aldehyde compound again, be under 50～80 ℃ the condition in temperature, back flow reaction 1～3 hour; Add acrylamide, maleic acid, vinylformic acid, methacrylic acid, vinyl acetate or methyl methacrylate then, add initiator again, be warmed up to 80～100 ℃, back flow reaction 1～2 hour; Obtain brown powder shape product through evaporation concentration, drying, process of lapping at last; Employed alkaline solution is a sodium hydroxide, or potassium hydroxide, or sodium hydrogen carbonate solution, and concentration is 10%～30%, and consumption is 5%～20% of a sulfonated lignin quality; Employed aldehyde compound is formaldehyde, acetaldehyde or propionic aldehyde, and consumption is 10%～50% of a sulfonated lignin quality; The consumption of acrylamide, maleic acid, vinylformic acid, methacrylic acid, vinyl acetate or methyl methacrylate is 40%～80% of a sulfonated lignin quality.
2. method according to claim 1 is characterized in that employed initiator is 30% aqueous hydrogen peroxide solution, and ceric ammonium nitrate, or Sodium Persulfate, consumption are 0.5%～10% of sulfonated lignin quality.
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| CN2007101885727A CN101440287B (en) | 2007-11-22 | 2007-11-22 | Preparation of lignosulphonate graft copolymer chemical sand solidification agent |
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| CN2007101885727A CN101440287B (en) | 2007-11-22 | 2007-11-22 | Preparation of lignosulphonate graft copolymer chemical sand solidification agent |
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| CN101440287B true CN101440287B (en) | 2010-12-08 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885810B (en) * | 2010-07-12 | 2011-06-15 | 西南科技大学 | Method for preparing amide modified lignosulfonate high-efficiency water reducing agent |
| CN103145926B (en) * | 2013-01-17 | 2016-03-09 | 安徽安生生物化工科技有限责任公司 | The preparation method of a kind of base polyacrylic acid microgel multi-effect adsorption agent |
| CN103243706B (en) * | 2013-05-28 | 2015-03-11 | 中国科学院新疆生态与地理研究所 | Method for spraying chemical sand-fixation agents |
| CN103305228B (en) * | 2013-06-09 | 2016-04-27 | 图们市方正化工助剂厂 | A kind of farm crop keeping crop seedling from drought urgees long agent and preparation method |
| CN104861985B (en) * | 2015-06-11 | 2018-04-20 | 延边大学 | Organic environmental-protection sand-consolidating agent and preparation method |
| CN105693966B (en) * | 2016-03-21 | 2018-01-12 | 北京林业大学 | A kind of preparation method of pyrolysis oil Lauxite sand-consolidating agent |
| WO2019154346A1 (en) * | 2018-02-11 | 2019-08-15 | 北京紫光英力化工技术有限公司 | Use of bio-based sulfonate as nutrient source and conditioning agent |
| CN108503430A (en) * | 2018-04-24 | 2018-09-07 | 吴刚 | A kind of preparation method of humic acid system suspension type liquid fertilizer |
| CN108841369A (en) * | 2018-07-02 | 2018-11-20 | 陕西科技大学 | A kind of preparation method of polyacrylamide Weak Gels |
| CN110129071B (en) * | 2019-06-18 | 2021-05-25 | 福建省地质工程勘察院 | Lignin sand-fixing agent suitable for preventing and treating hillock erosion |
| CN111944534B (en) * | 2020-08-18 | 2022-07-01 | 浙江工业大学 | Composite environment-friendly water-retaining agent and preparation method thereof |
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