CN102442795A - Method for preparing water reducing agent by using solid wastes of biomass acidic hydrolysis industry - Google Patents
Method for preparing water reducing agent by using solid wastes of biomass acidic hydrolysis industry Download PDFInfo
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- CN102442795A CN102442795A CN2011103153908A CN201110315390A CN102442795A CN 102442795 A CN102442795 A CN 102442795A CN 2011103153908 A CN2011103153908 A CN 2011103153908A CN 201110315390 A CN201110315390 A CN 201110315390A CN 102442795 A CN102442795 A CN 102442795A
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Abstract
The invention relates to a method for preparing a water reducing agent by using solid wastes of the biomass acidic hydrolysis industry, belonging to the technical field of preparation of the water reducing agent for concretes. The method is characterized by adding alkali, a sulfonating agent, a cross linking agent and a solvent into the solid wastes of the biomass acidic hydrolysis industry; sulfonating for a period of time at a certain temperature, obtaining the water reducing agent. The invention provides technology for resource utilization of the solid wastes of the biomass resource hydrolysis industry, solves the problems in site occupancy and environment pollution due to massive stack of the solid wastes of hydrolysis enterprises, and can change the wastes into things of value as well as provide a new way for high-value utilization of the solid wastes of the biomass resource hydrolysis industry. The water reducing performance of the water reducing agent prepared by the method disclosed by the invention can reach the quality standard of a high-efficient water reducing agent according to the GB8076-1997 (Concrete Additive) standard, and the water reducing agent is functional in delaying coagulation.
Description
Technical field
The present invention relates to the preparing technical field of concrete, particularly a kind of method of utilizing biomass acidic hydrolysis industry solid waste to prepare water reducer with water reducer.
Background technology
Along with the development of human social economy, the demands for energy amount is sharply increased.Compare with traditional fossil fuel, biomass energy is renewable because of it, and the good environmental effects such as carbon dioxide zero discharge of low pollution and energy utilization come into one's own day by day.The annual biomass resource amount of China is near 8.78 hundred million tons, in the agriculture and forestry organic waste material only crop material have 7.05 hundred million tons, and along with urban residents' growth in the living standard, biomass resource has the trend that increases year by year.The biomass resource acidic hydrolysis is changed into liquid fuel and chemical such as fuel alcohol, furfural, levulinic acid, Xylitol and wood sugar again through chemistry or biochemical reaction, for the mankind provide the continuous forever green energy and Chemicals.
But biomass are carried out acid hydrolysis produces the research that solid waste behind fuel and the chemical is used to prepare cement water reducing agent and does not also appear in the newspapers as yet; The power station is mainly transported in the processing of this solid waste to be done fuel used to generate electricity and burns; Added value is low, causes the waste of resource.
Water reducer is present the most widely used a kind of cement additire, because water reducer has the effect of the cement surface of making activatory, and the water consumption in the time of therefore can reducing cement and mix and stir; Reduce wc; Improve concrete workability, improve concrete intensity and density, have early strong effect.Use the concrete of water reducer; Can adapt to the Technology requirement of large formwork construction, slip-form construction technique and pump concrete; So at present in building operation; Water reducer as the 5th kind of composition of cement composition material, has produced significant techno-economic effect, becomes the material that receives much attention in the domestic and international in the last thirty years construction industry.China's cement water reducing agent usage quantity is big, and presents a rapidly rising trend every year, develops that cement water reducing agent is significant cheaply.
Utilized development of raw materials such as biomass resource such as larch extract bark waste residue, cornstalk, wheat straw, straw to go out cement water reducing agent at present both at home and abroad.It like the patent No. 200510019604.1 Chinese invention patent; A kind of method for preparing the composite efficient water reducer with bagasse is disclosed; Make hydrolyzed solution with vitriolization bagasse down at 40-60 ℃ earlier; In hydrolyzed solution, add amido sulfoacid series-aromatic amino sulphonic acid polymkeric substance then; Obtain water reducer solution, the semicellulose that sulphuric acid hydrolysis makes bagasse is dissolved out with the form of oligose, is the water reducer solution with polymolecularity with amido sulfoacid series-aromatic amino sulphonic acid polymer reaction then.Application number is 02104159.8 Chinese invention patent application; A kind of method of utilizing paper-making pulping reaction to prepare cement water reducing agent is disclosed; With fibrous material, reaction solution, sodium hydroxide, S-WAT, formaldehyde, anthraquinone, sodium sulphite boiling, liquid through concentrate, modification or drying obtain water reducer, the complicated component of adding; Resulting water reducer performance just meets the standard of ordinary water-reducing agent, does not reach the index of high efficiency water reducing agent.
Summary of the invention
In order to solve low, the existing bad problem of water reducer performance of utilizing pulping fibre to make of above processing added value, the invention provides a kind of method of utilizing biomass acidic hydrolysis industry solid waste to prepare high efficiency water reducing agent to solid waste behind the biomass acid hydrolysis.
The present invention realizes through following measure:
A kind of method of utilizing biomass acidic hydrolysis industry solid waste to prepare water reducer adds alkali, sulphonating agent, linking agent and solvent in biomass acidic hydrolysis industry solid waste, certain hour is handled in sulfonation at a certain temperature, promptly gets water reducer.
Preferred described biomass acidic hydrolysis industry solid waste is the hydrolytic residue after alcohol fuel is produced in solid waste, the solid waste behind the cotton seed hulls system furfural or the corn cob hydrolysis behind the corn cob acid hydrolysis making xylitol.
Preferred described alkali is sodium hydroxide, Pottasium Hydroxide or yellow soda ash, with the mass ratio of biomass acidic hydrolysis solid waste be 0.05 ~ 0.20:1.
Preferred described sulphonating agent is S-WAT, potassium sulfite, hydrosulphite, sulfurous acid, sodium sulphite or thionamic acid, with the mass ratio of biomass acidic hydrolysis solid waste be 0.03 ~ 0.18:1.
Preferred described linking agent is trimeric cyanamide, formaldehyde, oxalic dialdehyde or LUTARALDEHYDE, with the mass ratio of biomass acidic hydrolysis solid waste be 0.02 ~ 0.06:1.
Preferred described solvent is a water, and solid-to-liquid ratio is 1:3 ~ 7.
Preferred described certain temperature is 110 ~ 170 ℃, and the sulfonation reaction time is 2 ~ 5 hours.
Liquid concentration after the preferred sulfonation obtains the liquid water reducer to 30-50wt%.
Preferred liquid water reducer drying obtains Powdered water reducer.
Though using the pulp preparation cement water reducing agent in the prior art mainly also is the xylogen that utilizes wherein; Also contain a large amount of xylogen in the biomass acidic hydrolysis industry solid waste; Prepare cement water reducing agent with it; It may occur to persons skilled in the art that; Those of ordinary skills were the requirements that the absolute unexpected cement water reducing agent that uses the preparation of biomass acidic hydrolysis industry solid waste can reach high efficiency water reducing agent, so the method for utilizing biomass acidic hydrolysis industry solid waste to prepare high efficiency water reducing agent of the present invention has produced unexpected technique effect before specifically testing and the result comes out.Possibly be because of the acidolysis of biomass acidic hydrolysis industry solid waste process, some variation of lignin structure generation causes.With the patent No. be 200510019604.1 Chinese invention patent disclosure different be that used raw material is different; The raw material of patent utilization of the present invention is that biomass are carried out the solid waste after fuel and chemical are produced in acid hydrolysis; Biomass semicellulose in hydrolytic process has been dissolved in and has been hydrolyzed industry in the hydrolyzed solution and utilizes; And the staple in the remaining solid waste is a hydrolytic lignin, and the present invention is a kind of comprehensive utilization mode to residue behind the biomass by hydrolyzation.
Beneficial effect of the present invention:
(1) the present invention provides technology for the recycling of solid wastes utilization of biomass resource hydrolysis industry; Solved a large amount of stacking occupied grounds and the problem of environmental pollution of the solid waste of hydrolysis enterprise, the higher value application that can turn waste into wealth simultaneously for the solid waste of biomass resource hydrolysis industry provides new way;
(2) water-reducing property that makes of the inventive method reaches the quality standard of high efficiency water reducing agent in GB 8076-1997 " concrete admixture " standard, and has the characteristics of slow setting.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, does not constitute any restriction of the present invention.Remove other and indicate, all umbers among the embodiment all by weight.
Embodiment 1
When the water reducer volume was 0.35% (with respect to cement), the high efficiency water reducing agent sodium naphthalene sulfonate was 205mm to the clean slurry degree of mobilization of cement.
Take by weighing the 1000 parts of reactor drums of packing into of solid waste behind the corn cob dilute acid hydrolysis making xylitol, 200 parts of sodium hydroxide concentrations, 30 parts of S-WATs; 20 parts of trimeric cyanamides, solvent are water, solid-to-liquid ratio 1:7; 170 ℃ of temperature of reaction, soaking time is 2 hours, the liquid portion evaporation concentration behind the sulfonation modifying is to 30-50% concentration; Be liquid water reducer product, or obtain Powdered water reducer product through vacuum-drying or spraying drying again.The yield of gained water reducer product is 58.6%.When the water reducer volume was 0.35% (with respect to cement), it was 185mm to the clean slurry degree of mobilization of cement that the present invention of mensuration reduces agent, has reached the level of high efficiency water reducing agent.Other performance index detected results of the water reducer that present embodiment makes are seen table 1.
The salient features test result of table 1 product water reducer of the present invention
Adopt the corn cob raw material to contrast, corn cob is 85mm at the clean slurry degree of mobilization of measuring through the product for preparing after the reaction identical with above-mentioned condition, explains that the sulfonation of corn cob raw material is difficult to make water reducer, especially prepares high efficiency water reducing agent.
Embodiment 2
When the water reducer volume was 0.25% (with respect to cement), the high efficiency water reducing agent sodium naphthalene sulfonate was 198mm to the clean slurry degree of mobilization of cement.
1000 parts of reactor drums of packing into of solid waste behind the cotton seed hulls system of the taking by weighing furfural, 100 parts of sodium hydroxide concentrations, 100 parts of S-WATs; 40 parts in formaldehyde, solid-to-liquid ratio 1:5,110 ℃ of reaction top temperatures; Soaking time is 5 hours; Liquid portion evaporation concentration behind the sulfonation modifying is liquid water reducer product to 30-50% concentration, or obtains Powdered water reducer product through vacuum-drying or spraying drying again.The yield of gained water reducer product is 53.4%.When the water reducer volume was 0.25% (with respect to cement), it was 166mm to the clean slurry degree of mobilization of cement that the present invention of mensuration reduces agent, has reached the level of high efficiency water reducing agent.
Adopt the cotton seed hulls raw material to contrast; Cotton seed hulls only has 85mm at the clean slurry degree of mobilization of measuring through the product for preparing after the reaction identical with above-mentioned condition; Explain that the sulfonation of cotton seed hulls raw material makes the standard that water reducer only arrives ordinary water-reducing agent, be difficult to the preparation high efficiency water reducing agent.
Embodiment 3
When the water reducer volume was 0.35% (with respect to cement), the high efficiency water reducing agent sodium naphthalene sulfonate was 205mm to the clean slurry degree of mobilization of cement.
Take by weighing the 1000 parts of reactor drums of packing into of hydrolytic residue after alcohol fuel is produced in the corn cob hydrolysis, 50 parts of sodium hydroxide concentrations, 180 parts of S-WATs; 60 parts in acetaldehyde, solid-to-liquid ratio 1:3,155 ℃ of reaction top temperatures; Soaking time is 4 hours; Liquid portion evaporation concentration behind the sulfonation modifying is liquid water reducer product to 30-50% concentration, or obtains Powdered water reducer product through vacuum-drying or spraying drying again.The yield of gained water reducer product is 52.9%.When the water reducer volume was 0.35% (with respect to cement), it was 155mm to the clean slurry degree of mobilization of cement that the present invention of mensuration reduces agent, has reached the level of high efficiency water reducing agent.
Adopt the corn cob raw material to contrast, corn cob is 74mm measuring clean slurry degree of mobilization through the product for preparing after the reaction identical with above-mentioned condition, explains that the sulfonation of corn cob raw material is difficult to make water reducer, especially prepares high efficiency water reducing agent.
Claims (10)
1. method of utilizing biomass acidic hydrolysis industry solid waste to prepare water reducer; It is characterized in that in biomass acidic hydrolysis industry solid waste, adding alkali, sulphonating agent, linking agent and solvent; Certain hour is handled in sulfonation at a certain temperature, promptly gets water reducer.
2. method according to claim 1 is characterized in that described alkali is sodium hydroxide, Pottasium Hydroxide or yellow soda ash, with the mass ratio of biomass acidic hydrolysis solid waste be 0.05 ~ 0.20:1.
3. method according to claim 1 is characterized in that described sulphonating agent is S-WAT, potassium sulfite, hydrosulphite, sulfurous acid, sodium sulphite or thionamic acid, with the mass ratio of biomass acidic hydrolysis solid waste be 0.03 ~ 0.18:1.
4. method according to claim 1 is characterized in that described linking agent is trimeric cyanamide, formaldehyde, oxalic dialdehyde or LUTARALDEHYDE, with the mass ratio of biomass acidic hydrolysis solid waste be 0.02 ~ 0.06:1.
5. method according to claim 1 is characterized in that described solvent is a water, and solid-to-liquid ratio is 1:3 ~ 7.
6. method according to claim 1 is characterized in that described certain temperature is 110 ~ 170 ℃, and the sulfonation reaction time is 2 ~ 5 hours.
7. method according to claim 1 is characterized in that described biomass acidic hydrolysis solid waste is for being that raw material carries out acid hydrolysis and extracts remaining solid waste behind fuel or the chemical with leaf wood, needlebush or stalk.
8. method according to claim 7 is characterized in that described biomass acidic hydrolysis solid waste is the hydrolytic residue after alcohol fuel is produced in solid waste, the solid waste behind the cotton seed hulls system furfural or corn cob hydrolysis behind the corn cob acid hydrolysis making xylitol.
9. method according to claim 1 is characterized in that the liquid concentration after the sulfonation obtains the liquid water reducer to 30-50wt%.
10. method according to claim 9 is characterized in that liquid water reducer drying obtains Powdered water reducer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110315390 CN102442795B (en) | 2011-10-18 | 2011-10-18 | Method for preparing water reducing agent by using solid wastes of biomass acidic hydrolysis industry |
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| CN 201110315390 CN102442795B (en) | 2011-10-18 | 2011-10-18 | Method for preparing water reducing agent by using solid wastes of biomass acidic hydrolysis industry |
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| CN102442795A true CN102442795A (en) | 2012-05-09 |
| CN102442795B CN102442795B (en) | 2013-08-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830806A (en) * | 2017-03-03 | 2017-06-13 | 安徽省宿州市贯华化工有限公司 | A kind of concrete containing waste oil |
| CN108440722A (en) * | 2016-07-15 | 2018-08-24 | 李碧钗 | A kind of composite ceramic water-reducing agent |
| CN108675802A (en) * | 2016-07-15 | 2018-10-19 | 李碧钗 | A kind of preparation method of high-efficiency ceramic water reducing agent |
| CN108892757A (en) * | 2016-07-15 | 2018-11-27 | 李碧钗 | A kind of ceramic water reducing agent with green body reinforcing effect |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337789A (en) * | 2008-08-12 | 2009-01-07 | 姜庆梅 | Method for preparing water reducing agent by condensation and modification of ryegrass alkali lignin |
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- 2011-10-18 CN CN 201110315390 patent/CN102442795B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337789A (en) * | 2008-08-12 | 2009-01-07 | 姜庆梅 | Method for preparing water reducing agent by condensation and modification of ryegrass alkali lignin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440722A (en) * | 2016-07-15 | 2018-08-24 | 李碧钗 | A kind of composite ceramic water-reducing agent |
| CN108675802A (en) * | 2016-07-15 | 2018-10-19 | 李碧钗 | A kind of preparation method of high-efficiency ceramic water reducing agent |
| CN108892757A (en) * | 2016-07-15 | 2018-11-27 | 李碧钗 | A kind of ceramic water reducing agent with green body reinforcing effect |
| CN108892758A (en) * | 2016-07-15 | 2018-11-27 | 李碧钗 | A kind of preparation method of the ceramic water reducing agent with green body reinforcing effect |
| CN108948277A (en) * | 2016-07-15 | 2018-12-07 | 李碧钗 | A kind of ceramic water reducing agent and preparation method thereof |
| CN106830806A (en) * | 2017-03-03 | 2017-06-13 | 安徽省宿州市贯华化工有限公司 | A kind of concrete containing waste oil |
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| CN102442795B (en) | 2013-08-14 |
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