CN111704725B - Preparation method of modified natural bio-based lignin sulfonate high-efficiency water reducing agent - Google Patents
Preparation method of modified natural bio-based lignin sulfonate high-efficiency water reducing agent Download PDFInfo
- Publication number
- CN111704725B CN111704725B CN202010611878.4A CN202010611878A CN111704725B CN 111704725 B CN111704725 B CN 111704725B CN 202010611878 A CN202010611878 A CN 202010611878A CN 111704725 B CN111704725 B CN 111704725B
- Authority
- CN
- China
- Prior art keywords
- alkali lignin
- solution
- water reducing
- reducing agent
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 114
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920005610 lignin Polymers 0.000 claims abstract description 167
- 239000003513 alkali Substances 0.000 claims abstract description 142
- 239000004567 concrete Substances 0.000 claims abstract description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical group CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000001603 reducing effect Effects 0.000 claims abstract description 16
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 13
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 99
- 239000002245 particle Substances 0.000 claims description 37
- 239000008030 superplasticizer Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 18
- 235000011613 Pinus brutia Nutrition 0.000 claims description 18
- 241000018646 Pinus brutia Species 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000008098 formaldehyde solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 10
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- -1 methylol groups Chemical group 0.000 abstract description 3
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 21
- 239000004568 cement Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 1
- YHEWWEXPVKCVFY-UHFFFAOYSA-N 2,6-Dimethoxy-4-propylphenol Chemical compound CCCC1=CC(OC)=C(O)C(OC)=C1 YHEWWEXPVKCVFY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- PXIKRTCSSLJURC-UHFFFAOYSA-N Dihydroeugenol Chemical compound CCCC1=CC=C(O)C(OC)=C1 PXIKRTCSSLJURC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000001785 ferulic acid Nutrition 0.000 description 1
- 229940114124 ferulic acid Drugs 0.000 description 1
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-M naphthalene-2-sulfonate Chemical compound C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-M 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000011376 self-consolidating concrete Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a preparation method of a modified natural bio-based lignin sulfonate high-efficiency water reducing agent, which is used for extracting alkali lignin and carrying out fractional purification to obtain high-molecular-weight and low-molecular-weight alkali lignin. The condensation reaction of acetone and formaldehyde connects the hydroxymethyl acetone group to the molecular chain of high molecular weight alkali lignin; the methylolation reaction of formaldehyde introduces methylol groups on the low molecular weight alkali lignin molecules. Under the conditions of acidity and high temperature, the hydroxymethyl acetone group on the high molecular weight alkali lignin molecule is condensed with the hydroxymethyl group on the low molecular weight alkali lignin molecule to obtain the alkali lignin high polymer. Sodium bisulfite is used for sulfonating the alkali lignin high polymer at high temperature to introduce sulfonic acid groups. The modified lignosulfonate high-efficiency water reducing agent is prepared by using natural lignin, so that the negative influence of artificially synthesized chemicals on the environment in the production of the high-efficiency water reducing agent is avoided. The prepared modified lignosulfonate high-efficiency water reducing agent has higher water reducing rate, better concrete fluidity retentivity and mechanical property than the common lignosulfonate water reducing agent.
Description
Technical Field
The invention relates to the technical field of high-efficiency water reducing agent preparation, in particular to a preparation method of a modified natural bio-based lignin sulfonate high-efficiency water reducing agent.
Background
With the acceleration of village and town and civil engineering construction speed in China, the cement concrete material has been widely used in civil buildings, expressways, bridges, tunnels, docks, drilling platforms and other engineering constructions due to the characteristics of wide material sources and low cost, and is the building material with the largest use amount in the world at present. The cement concrete material mainly comprises a cementing material, coarse aggregate, fine aggregate, water, a high-efficiency water reducing agent and the like. The high-efficiency water reducing agent is an important component in concrete materials. The high-efficiency water reducing agent as an anionic surfactant can be adsorbed on the surface of cement particles to form an interfacial film with certain mechanical strength, and the interfacial film can reduce the resistance among the particles, play a role in lubrication and improve the rheological property of concrete mixture. Under the same slump, the addition of the high-efficiency water reducing agent reduces the mixing water consumption and the water-cement ratio in the concrete, and improves the compactness and the mechanical property of the concrete. The high-efficiency water reducing agent can also increase the frost resistance of concrete and reduce the segregation of the underwater concrete during pouring, so that the preparation of the self-compacting concrete with high fluidity and high strength becomes possible.
At present, water reducing agents commonly used at home and abroad are classified into common water reducing agents and high-efficiency water reducing agents (also called superplasticizers) according to the water reducing effect. The lignosulfonate water reducing agent is used as a common water reducing agent, the water reducing effect is low, the water reducing rate is only 8-12% under the mixing amount of 0.6%, the gas content of concrete doped with the lignosulfonate water reducing agent is large, the concrete is easy to generate a retardation phenomenon, the adaptability of cement is poor, and the lignosulfonate water reducing agent needs to be compounded with other high-efficiency water reducing agents for use, so that the application range of the lignosulfonate water reducing agent is limited. The high-efficiency water reducing agent is mainly represented by naphthalene sulfonate, sulfonated melamine, aliphatic, sulfamate and polycarboxylic acid high-efficiency water reducing agent. The high-efficiency water reducing agent has the advantages of simple production process, small mixing amount and the like, but raw materials for preparing the high-efficiency water reducing agent are artificial synthetic chemicals of industrial naphthalene, melamine, phenol, sulfanilic acid, olefin, unsaturated carboxylic acid copolymer, unsaturated polyether and graft polymer connected with sulfonic acid groups, the high-efficiency water reducing agent has higher price and certain toxicity, and the artificial synthetic chemicals can generate negative effects on the environment and public health in the production of the high-efficiency water reducing agent. The high-efficiency water reducing agent prepared from the modified natural biomass material not only widens the application field of natural biomass, but also has green and environment-friendly production process and good application and development prospect.
The lignin is a natural biomass material with a plant skeleton, which is formed by the polymerization of units such as guaiacyl propane, syringyl propane, p-hydroxy phenyl propane and the like through C-C bonds and C-O-C bonds. The lignin molecule contains active functional groups such as hydroxyl, carbonyl, carboxyl, methoxyl and the like, the hydroxyl exists in two forms of alcoholic hydroxyl and phenolic hydroxyl, and the quantity of the phenolic hydroxyl reflects the lignin etherification and condensation degree. The alpha position and the gamma position of the side chain of the lignin have the molecular configuration of the hydroxy benzoic acid, the vanillic acid, the syringic acid, the p-hydroxy cinnamic acid and the ferulic acid ester, the alpha position has the ester molecular configuration and also presents C-C structures of ethers and biphenyls, and the side chain structure of the lignin molecule is directly related to the chemical activity of the lignin molecule. Lignin is the second largest biomass material in nature in quantities second only to cellulose, with a lignin yield of 600 trillion tons per year in nature. The lignin is mainly from the papermaking industry, the total amount of the lignin in the papermaking and pulping waste liquid reaches 5000 ten thousand tons every year, 95 percent of the lignin in the pulping waste liquid is directly discharged into rivers or is burnt after being concentrated as waste along with the waste water, and only about 1 percent of the lignin in the pulping waste liquid is used for preparing the lignosulfonate water reducing agent. The discharge of a large amount of paper-making waste liquid wastes lignin resources and seriously pollutes underground water, rivers and the environment around a paper mill, and the discharge of the paper-making waste liquid is the most important problem influencing the environment of modern cities. Along with the continuous and deep consciousness of recycling and reusing waste resources, the efficient utilization of natural lignin resources has been widely regarded by various countries in the world. The lignosulfonate water reducing agent prepared by the traditional method has a common water reducing effect, and the using amount is limited. The development of a modified lignosulfonate superplasticizer which has low cost, high water reduction, high retardation and environmental friendliness has become a hotspot in the research field.
Previous researches show that the lignosulfonate can be subjected to polycondensation reaction with formaldehyde and beta-naphthalene sulfonate or sulfonated melamine to prepare the modified lignosulfonate superplasticizer, and the water reducing rate and the durability of concrete can be obviously improved by doping the modified lignosulfonate superplasticizer into the concrete. Under alkaline condition, lignosulfonate can be subjected to condensation reaction with phenol and formaldehyde to generate a sulfonated lignin-phenol-formaldehyde condensate. The modified lignosulfonate water reducing agent prepared from the lignosulfonate-modified grafted carbonyl aliphatic compound can obviously improve the adaptability of the water reducing agent and cement, and overcomes the problem of chromatic aberration of concrete doped with the aliphatic high-efficiency water reducing agent. The air entraining type lignosulfonate superplasticizer can be prepared by modifying lignosulfonate with formaldehyde and sulfanilic acid. The novel polycarboxylate-lignosulfonate copolymer type high-efficiency water reducing agent can be prepared by copolymerizing the esterified macromonomer polyethylene glycol monomethyl ether methacrylate with methacrylic acid, lignosulfonate and sodium methallylsulfonate, the modified lignosulfonate high-efficiency water reducing agent has good plasticizing effect and reinforcing effect, and the dispersing effect of the lignosulfonate water reducing agent on cement particles can be obviously improved by condensation modification of the lignosulfonate water reducing agent. But the existing method for preparing the modified lignosulfonate water reducing agent does not completely solve the problem that artificially synthesized chemicals are used in the production process of the high-efficiency water reducing agent; the artificial chemicals as raw materials have the advantages of limited sources, high price, complex preparation process and serious pollution to the surrounding environment in the production process; the utilization rate of lignin is not obviously improved, and the problem of regeneration and utilization of lignin black liquor waste in the paper industry cannot be completely solved.
Disclosure of Invention
The invention provides a preparation method of a modified natural bio-based lignosulfonate high-efficiency water reducing agent based on the problems in the existing preparation method of the modified lignosulfonate water reducing agent. The method disclosed by the invention is mainly started from the two aspects of improving the molecular weight and the sulfonation degree of the water reducing agent, the performance of the lignosulfonate water reducing agent is improved, the prepared novel modified lignosulfonate high-efficiency water reducing agent has the advantages of good water reducing effect, low air entraining amount and the like, and the high-performance and multi-functionalization of the modified lignosulfonate water reducing agent is realized.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a modified natural bio-based lignin sulfonate high-efficiency water reducing agent is characterized by comprising the following steps:
the method comprises the following steps: crushing pine chips, screening pine particles with proper particle size, mixing the pine particles with water, adding a sodium hydroxide solution, uniformly stirring, putting the mixture into a rotary digester, heating, cooling the cooked product to room temperature, taking out, centrifuging the product, filtering, washing the filtered precipitate with distilled water to neutrality to obtain cellulose, and mixing the filtrate with washing liquid to obtain alkali lignin papermaking black liquor;
step two: placing the alkali lignin papermaking black liquor in a freeze dryer for freeze drying to obtain alkali lignin solid, and then crushing and ball-milling the alkali lignin solid to obtain alkali lignin powder;
step three: placing alkali lignin powder and an acetone solvent in a reaction container, stirring the mixture to form a uniform suspension solution, placing the suspension solution in a centrifuge to separate the suspension solution into layers and solid and liquid, obtaining a high molecular weight alkali lignin solution dissolved in the acetone solvent and a centrifugal precipitate, and placing the centrifugal precipitate in a freeze dryer to freeze and dry to obtain low molecular weight alkali lignin solid powder;
step four: raising the temperature of the high molecular weight alkali lignin solution to 40-50 ℃, adding a sodium hydroxide solution into the high molecular weight alkali lignin solution, adjusting the pH of the solution to 14-15, slowly dropwise adding a formaldehyde solution, finishing the addition in 45-60 minutes, and reacting at the temperature of 50-60 ℃ for 1-2 hours to obtain a high molecular weight alkali lignin clear solution connected with a hydroxymethyl acetone group;
step five: mixing low molecular weight alkali lignin solid powder and water, raising the temperature to 40-50 ℃, stirring the mixture to mix the low molecular weight alkali lignin powder and the water into a uniform solution, then adding a sodium hydroxide solution, adjusting the pH of the solution to 14-15, slowly dropwise adding a formaldehyde solution, finishing the adding within 25-30 minutes, and reacting for 0.5-1 hour at the temperature of 70-75 ℃ to obtain a low molecular weight alkali lignin solution connected with ortho-methylol;
step six: mixing and rapidly stirring a high molecular weight alkali lignin solution connected with a hydroxymethyl acetone group and a low molecular weight alkali lignin solution connected with an ortho-position hydroxymethyl group, adding an acetic acid solution, adjusting the pH value of the solution to 5-6, raising the temperature of the system to 160-180 ℃, continuously stirring for 3-4 hours at the temperature, and condensing high molecular weight alkali lignin molecules connected with the hydroxymethyl acetone group and low molecular weight alkali lignin molecules containing the hydroxymethyl group into an alkali lignin high polymer;
step seven: adding sodium bisulfite into the alkali lignin high polymer solution, adjusting the pH value of the solution to be 14-15 by using sodium hydroxide, raising the temperature of the solution to 180-200 ℃, reacting for 5-6 hours at the temperature, cooling the reaction product to room temperature, and curing for 2-3 hours in a reaction vessel to obtain the modified lignosulfonate superplasticizer.
In order to optimize the technical scheme, the specific measures adopted further comprise:
in the first step, the mixture put into the rotary digester is specifically configured as follows: 30-35kg of pine wood particles are added into 65-70kg of water, and 4kg of sodium hydroxide solution is added to be mixed and stirred uniformly; wherein, the weight percentage concentration of the sodium hydroxide solution is 40%.
In the second step, the crushing and ball milling specifically comprises the following steps: crushing the alkali lignin solid, passing through a 5mm square-hole sieve, taking alkali lignin particles with the particle size of less than 5mm, and putting the alkali lignin particles into a ball mill to perform ball milling for 40-50 minutes at the speed of 80 revolutions per minute to obtain alkali lignin powder; wherein the particle size of the alkali lignin powder is less than 0.6 mm.
In the third step, the mass ratio of the alkali lignin powder to the acetone solvent is 12 (24-26).
In the fourth step, the mass ratio of the high molecular weight alkali lignin solution to the sodium hydroxide solution to the formaldehyde solution is 25 (1.5-1.8) to (58-59); wherein, the weight percentage concentration of the sodium hydroxide solution is 40 percent, and the weight percentage concentration of the formaldehyde solution is 37 percent.
In the fifth step, the mass ratio of the low molecular weight alkali lignin solid powder to the water to the sodium hydroxide solution to the formaldehyde solution is (70-80): 300-310): 7.5-8): 1.7-1.8; wherein, the weight percentage concentration of the sodium hydroxide solution is 40 percent, and the weight percentage concentration of the formaldehyde solution is 37 percent.
In the sixth step, the mass ratio of the high molecular weight alkali lignin solution connected with the hydroxymethyl acetone group, the low molecular weight alkali lignin solution connected with the ortho-position hydroxymethyl group and the acetic acid solution is (20-25): (75-80): (10-12.5).
In the seventh step, 30-35kg of sodium bisulfite and 100-125kg of sodium hydroxide solution are added into 970-975kg of alkali lignin high polymer solution; wherein, the weight percentage concentration of the sodium hydroxide solution is 40%.
The pH value of the modified lignosulfonate superplasticizer prepared in the seventh step is 12-13, the solid content is 15-20%, the weight average molecular weight is 10535-14369, and the sulfonation degree is 1.384-1.427 mmol/g.
And seventhly, detecting the water reducing rate of the modified lignosulfonate high-efficiency water reducing agent and the performance of the concrete doped with the modified lignosulfonate high-efficiency water reducing agent under different doping amounts, and comparing the performance of the concrete doped with the conventional lignosulfonate water reducing agent under the same doping amount.
Furthermore, the invention starts from the molecular design of the high-efficiency water reducing agent and the theory of leading functional groups, and firstly, improves the dispersing performance of the lignosulfonate water reducing agent from the aspects of improving the molecular weight and the sulfonation degree of the water reducing agent. Firstly, alkali lignin in natural biomass materials is extracted by a caustic soda high-temperature cooking method, the molecular weight of the alkali lignin is graded by utilizing an acetone organic solvent, the alkali lignin with high molecular weight is easily dissolved in the acetone solvent, and the alkali lignin with low molecular weight is separated out in a precipitation mode. Then, the condensation reaction of acetone and formaldehyde in the high molecular weight alkali lignin solution is utilized to connect the hydroxymethyl acetone group to the molecular chain of the high molecular weight alkali lignin. C utilizing low molecular weight alkali lignin molecules9The condensation reaction is easy to occur near the phenol methyl on the chain, and the hydroxymethyl is introduced into the low molecular weight alkali lignin molecule through the formaldehyde hydroxymethylation reaction. Under the conditions of acidity and high temperature, the hydroxymethyl acetone group on the high molecular weight alkali lignin molecule and the hydroxymethyl group on the low molecular weight alkali lignin molecule are condensed to obtain the alkali lignin high polymer. Finally, the sodium bisulfite sulfonating agent carries out high-temperature sulfonation on the alkali lignin high polymerSulfonic acid group is introduced by chemical treatment to prepare the product containing-SO3H、-OH、-CH2OH and other groups of modified lignosulfonate superplasticizer.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the invention, low molecular weight alkali lignin and high molecular weight alkali lignin are subjected to condensation reaction under acidic and high temperature conditions, so that the molecular weight of the modified lignin polymer is increased. And (3) carrying out sulfonation modification treatment on the lignin polymer to introduce a sulfonate group with negative charges into a lignin polymer molecular chain. The modified lignosulfonate superplasticizer is added into concrete, so that the electrostatic repulsion on the surface of cement particles is increased, the molecules of the modified lignosulfonate superplasticizer also have a certain comb-shaped structure, and the modified lignosulfonate superplasticizer is adsorbed on the surface of the cement particles to generate a certain steric hindrance effect. The novel modified lignosulfonate superplasticizer prepared has the advantages of good water reducing effect, low air entraining amount and the like, realizes high-performance and multi-functionalization of the modified lignosulfonate superplasticizer,
(2) under the same mixing amount, the modified natural bio-based lignosulfonate superplasticizer has a better water reducing effect than the traditional lignosulfonate superplasticizer. Under the same initial fluidity of concrete, the required mixing amount of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent is smaller, and by using the modified natural bio-based lignin sulfonate high-efficiency water reducing agent, the cost of the water reducing agent can be saved by 0.452 yuan per formula of concrete.
(3) The papermaking black liquor has wide sources and a large amount of waste alkali lignin contained in the papermaking black liquor is not fully utilized. The high molecular weight alkali lignin and the low molecular weight alkali lignin are subjected to fractional purification, condensation and sulfonation instead of artificially synthesized chemicals to prepare the modified lignosulfonate superplasticizer, so that the natural lignin resources rich in resources are fully utilized, and the raw material cost for preparing the modified lignosulfonate superplasticizer is reduced. And 183.2 yuan can be saved in raw material consumption when one ton of the modified lignosulfonate superplasticizer is produced. The modified lignosulfonate superplasticizer prepared by using the alkali lignin in the papermaking industry black liquor also expands the application field of the alkali lignin-containing papermaking black liquor waste.
(4) The natural lignin replaces artificially synthesized chemicals to prepare the modified lignosulfonate superplasticizer, the pollution of the synthesized chemicals to the environment in the preparation process of the superplasticizer is avoided, and the green and environment-friendly production process of the modified lignosulfonate superplasticizer is realized. The preparation method also simplifies the production flow, shortens the production time and improves the production efficiency.
In conclusion, the production cost is saved by 146.56 ten thousand yuan based on 8000 tons of the modified lignosulfonate high-efficiency water reducing agent produced every year. Saving the investment cost of production equipment, simplifying the process and the production time cost, and reaching the environmental protection cost of 13.39 ten thousand yuan. 8000 tons of the high-efficiency water reducing agent can be used for preparing 2.90 multiplied by 106The cost of the modified lignosulfonate water reducing agent can be saved by 131.08 ten thousand yuan based on the square concrete. 8000 tons of modified lignosulfonate superplasticizer is produced every year, and the economic benefit of 291.03 ten thousand yuan can be generated in total.
Drawings
FIG. 1 is a flow chart of the preparation of the modified natural bio-based lignin sulfonate high efficiency water reducing agent of the present invention.
FIG. 2 is a graph comparing water reduction rates of a modified natural bio-based lignosulfonate superplasticizer blended with a commercially available lignosulfonate superplasticizer.
FIG. 3 is a schematic of concrete slump as a function of time with the modified natural bio-based lignosulfonate superplasticizer incorporated therein.
FIG. 4 is a graphical representation of concrete slump as a function of time with a commercial lignosulfonate water reducer.
FIG. 5 is a graph comparing the air content of concrete doped with a modified natural bio-based lignosulfonate superplasticizer and a commercially available lignosulfonate superplasticizer.
FIG. 6 is a schematic diagram of the compressive strength of concrete doped with the modified natural bio-based lignin sulfonate superplasticizer.
FIG. 7 is a graphical representation of the compressive strength of concrete blended with a commercial lignosulfonate water reducer.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
Referring to fig. 1, one ton of modified natural bio-based lignin sulfonate superplasticizer was produced according to the method described in the present invention for concrete application studies.
Preparation of modified natural bio-based lignin sulfonate high-efficiency water reducing agent
1. Extraction of lignin
Jilin 29682and pine wood from spring forest farms are used as raw materials. Pine wood is sliced, sorted, cleaned, dried, crushed and sieved by a 5mm sieve, and impurities in pine wood chips are removed to obtain pine wood particles with certain particle size. 3000kg of pine wood particles are mixed with 6500kg of water, 400kg of sodium hydroxide solution (40% by weight) are added and stirred uniformly. The mixture was heated in a rotary cooker in a water bath, the temperature of the water bath was raised to 90 ℃ and cooked at this temperature for 3 hours. After the reaction is finished, the temperature of the system is reduced to room temperature and the system is taken out, the product is filtered after centrifugal treatment, the filtered precipitate is washed to be neutral by distilled water to obtain cellulose, and the main components of the filtrate and the washing liquid (papermaking black liquor) are alkali lignin. And (3) placing the papermaking black liquor in a freeze dryer for freeze drying for 30-60 minutes to obtain alkali lignin solid. And (3) crushing the alkali lignin solid, sieving the crushed alkali lignin solid through a 5mm square-hole sieve, taking alkali lignin particles with the particle size smaller than 5mm, and putting the alkali lignin particles into a ball mill to perform ball milling for 40-50 minutes at the speed of 80 revolutions per minute to obtain 1254kg of alkali lignin powder. The alkali lignin powder was tested to an average particle size of 0.525mm using a laser particle sizer.
2. Fractional purification of lignin
1200kg of alkali lignin powder and 2450kg of acetone are weighed into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the mixture is stirred at a speed of 400 rpm for 45 minutes to form a uniform suspension solution. Then, the alkali lignin acetone suspension solution was placed in a centrifuge and treated at a centrifugation speed of 1500 rpm for 25 to 30 minutes to allow the suspension solution to be layered and subjected to solid-liquid separation, thereby obtaining 2850kg of a high molecular weight alkali lignin (H-FAL) acetone solution. And freeze-drying the precipitate in a freeze-drying machine for 30-50 min to obtain 765kg low-molecular-weight alkali lignin (L-FAL) solid powder.
3. Preparation of alkali lignin high polymer
2500kg of a high molecular weight alkali lignin acetone solution was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 160kg of sodium hydroxide solution with the weight percentage concentration of 40 percent is added into the high molecular weight alkali lignin acetone solution at the temperature of 45 ℃, the pH value of the solution is adjusted to be 14.46, 5850kg of formaldehyde solution with the concentration of 37 percent is slowly dripped, the addition is finished within 45 minutes, and the reaction is carried out for 1.5 hours at the temperature of 55 ℃ to obtain high molecular weight alkali lignin clear solution (DH-FAL) connected with hydroxymethyl acetone groups.
760kg of a low molecular weight alkali lignin solid powder and 3040kg of water were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. The temperature was raised to 40 ℃ and the mixture was stirred at an accelerated rate to disperse the low molecular weight alkali lignin solid powder evenly into the water. 75kg of 40% strength by weight sodium hydroxide solution were added to adjust the pH of the solution to 14.89. Slowly adding 17kg of 37% formaldehyde solution dropwise, reacting at 70 deg.C for 1 hr, and adding into low molecular weight alkali lignin molecule C9Introducing hydroxymethyl to the chain to obtain low molecular weight alkali lignin solution (TL-FAL) with ortho-hydroxymethyl.
200kg of a high molecular weight alkali lignin solution (DH-FAL) having methylolacetone groups attached thereto and 750kg of a low molecular weight alkali lignin solution (TL-FAL) having ortho-methylol groups attached thereto were put into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube, and rapidly stirred to obtain a uniform solution. Adding 100kg acetic acid solution, adjusting pH to 5.47, heating to 170 deg.C, stirring at the temperature for 4 hr, and condensing the high molecular weight alkali lignin with hydroxymethyl acetone group and low molecular weight alkali lignin containing hydroxymethyl group to obtain alkali lignin polymer.
4. Preparation of modified natural bio-based lignin sulfonate high-efficiency water reducing agent
Heating 970kg of alkali lignin high polymer solution to 200 ℃, adding 30kg of sodium bisulfite, adjusting the pH value of the solution to 14.21 by using 100kg of sodium hydroxide solution with the weight percentage concentration of 40%, reacting for 6 hours at 190 ℃, cooling the reaction product to room temperature, and curing for 2 hours in a reaction container to obtain the light black modified lignosulfonate high-efficiency water reducing agent with the pH value of 12.57, the solid content of 17.49%, the weight average molecular weight of 11562 and the sulfonation degree of 1.403 mmol/g.
Example 2
Preparation of modified natural bio-based lignin sulfonate high-efficiency water reducing agent
1. Extraction of lignin
Jilin 29682and pine wood from spring forest farms are used as raw materials. Pine wood is sliced, sorted, cleaned, dried, crushed and sieved by a 5mm sieve, and impurities in the pine wood chips are removed to obtain pine wood particles with certain particle size. 3500kg of pine wood particles are mixed with 7000kg of water, 400kg of sodium hydroxide (40% strength by weight) solution is added and stirred uniformly. The mixture was heated in a rotary cooker in a water bath, the temperature of the water bath was raised to 90 ℃ and cooked at this temperature for 2 hours. After the reaction is finished, the temperature of the system is reduced to room temperature and the system is taken out, the product is filtered after centrifugal treatment, the filtered precipitate is washed to be neutral by distilled water to obtain cellulose, and the main components of the filtrate and the washing liquid (papermaking black liquor) are alkali lignin. And (3) placing the papermaking black liquor in a freeze dryer for freeze drying for 30-60 minutes to obtain alkali lignin solid. And (3) crushing the alkali lignin solid, sieving the crushed alkali lignin solid through a 5mm square-hole sieve, taking alkali lignin particles with the particle size smaller than 5mm, and putting the alkali lignin particles into a ball mill to perform ball milling for 40-50 minutes at the speed of 80 revolutions per minute to obtain 1268kg of alkali lignin powder. The average particle size of the alkali lignin powder was measured to be 0.577mm using a laser particle sizer.
2. Fractional purification of lignin
1200kg of alkali lignin powder and 2600kg of acetone were weighed into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the mixture was stirred at 400 rpm for 45 minutes to form a uniform suspension solution. Then, the alkali lignin acetone suspension solution was placed in a centrifuge and treated at a centrifugation speed of 1500 rpm for 25-30 minutes to allow the suspension solution to separate layers and solid-liquid separation, and 2778kg of a high molecular weight alkali lignin (H-FAL) acetone solution was obtained. And (3) putting the precipitate after the centrifugal treatment into a freeze dryer for freeze drying for 30-50 minutes to obtain 769kg of low molecular weight alkali lignin (L-FAL) solid powder.
3. Preparation of alkali lignin high polymer
2500kg of a high molecular weight alkali lignin acetone solution was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Adding 165kg of sodium hydroxide solution with the weight percentage concentration of 40% into a high molecular weight alkali lignin acetone solution at the temperature of 45 ℃, adjusting the pH of the solution to be 15.49, slowly dropwise adding 5900kg of formaldehyde solution with the concentration of 37%, finishing the addition within 60 minutes, and reacting for 2 hours at the temperature of 60 ℃ to obtain a high molecular weight alkali lignin clear solution (DH-FAL) connected with hydroxymethyl acetone groups.
760kg of a low molecular weight alkali lignin solid powder and 3040kg of water were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. The temperature was raised to 45 ℃ and the mixture was stirred at an accelerated rate to disperse the low molecular weight alkali lignin solid powder evenly into the water. 80kg of 40% strength by weight sodium hydroxide solution were added to adjust the pH of the solution to 14.25. Slowly adding 18kg of 37% formaldehyde solution dropwise, reacting at 75 deg.C for 1 hr, and adding into low molecular weight alkali lignin molecule C9Introducing hydroxymethyl to the chain to obtain low molecular weight alkali lignin solution (TL-FAL) with ortho-hydroxymethyl.
250kg of high molecular weight alkali lignin solution (DH-FAL) connected with hydroxymethyl acetone groups and 800kg of low molecular weight alkali lignin solution (TL-FAL) connected with ortho-hydroxymethyl groups are put into a reaction vessel provided with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube and are rapidly stirred into uniform solution. Adding 125kg acetic acid solution, adjusting pH to 6.17, heating to 170 deg.C, stirring at the temperature for 4 hr, and condensing the high molecular weight alkali lignin with hydroxymethyl acetone group and low molecular weight alkali lignin containing hydroxymethyl group to obtain alkali lignin polymer.
4. Preparation of modified natural bio-based lignin sulfonate high-efficiency water reducing agent
975kg of alkali lignin high polymer solution is heated to 200 ℃, 35kg of sodium bisulfite is added, 125kg of sodium hydroxide solution with the weight percentage concentration of 40% is used for adjusting the pH value of the solution to 15.21, the reaction is carried out for 6 hours at the temperature of 190 ℃, the reaction product is cooled to room temperature and is aged in a reaction container for 3 hours, and the light black modified lignosulfonate high-efficiency water reducing agent with the pH value of 12.92, the solid content of 18.12 percent, the weight average molecular weight of 13694 and the sulfonation degree of 1.389mmol/g is obtained.
Examples of the experiments
The water reducing rate and the concrete performance of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent.
1. Homogeneity of modified natural bio-based lignosulfonate high-efficiency water reducing agent and commercial lignosulfonate water reducing agent
Homogeneity analyses were carried out on the modified lignosulfonate superplasticizer (GCL-M) prepared in example 1 and a commercially available lignosulfonate superplasticizer (GCL-L, manufactured by Yanbian white foot paper industries, Ltd.). As shown in table 1.
TABLE 1 homogeneity of modified natural bio-based lignosulfonate superplasticizer and commercial lignosulfonate superplasticizer
| Name (R) | Appearance of the product | Solid content (%) | Molecular weight | Alkali content (%) | Na2SO4Content (%) | Cl-Content (%) |
| GCL-M | Light black liquid | 18.94 | 11562 | 18.97 | 3.28 | 0.0352 |
| GCL-L | Black solid powder | 98.47 | 6415 | 10.64 | 6.71 | 0.1064 |
2. Water reducing rate and concrete performance of modified natural bio-based lignosulfonate high-efficiency water reducing agent and commercial lignosulfonate water reducing agent
The water reducing rate and concrete performance of the modified natural bio-based lignosulfonate high-efficiency water reducing agent (GCL-M) and the commercial lignosulfonate water reducing agent (GCL-L) are measured under the mixing amount of 0-0.5% (by solid). The cement is P II grade 52.5 portland cement, the coarse aggregate is crushed stone of 5-20mm and 20-40mm, wherein the crushed stone of 5-20mm accounts for 40%, and the crushed stone of 20-40mm accounts for 60%. The fine aggregate is river sand, and the fineness modulus of the river sand fine aggregate is 2.12. The cement consumption in each concrete sample is 330kg/m3The sand ratio was 39%. The initial slump of the concrete doped with the natural bio-based lignosulfonate high-efficiency water reducing agent (GCL-M) and the commercial lignosulfonate water reducing agent is controlled to be 7.5-8.5cm, and the compounding ratio of the test concrete is shown in Table 2.
TABLE 2 concrete experiment mix proportion
3. Performance testing
FIG. 2 is a comparison graph of water reducing rates of two lignosulfonate water reducing agents GCL-M, GCL-L at different blending amounts, and it can be seen that the GCL-M modified natural bio-based lignosulfonate high-efficiency water reducing agent has a higher water reducing rate than the commercially available GCL-L lignosulfonate water reducing agent at the same blending amount.
FIGS. 3 and 4 are graphs comparing the slump of concrete doped with two lignosulfonate water-reducing agents GCL-M, GCL-L with time, and it can be seen that the concrete doped with GCL-M modified natural bio-based lignosulfonate high-efficiency water-reducing agent has higher slump flow retention than the concrete doped with a commercially available GCL-L lignosulfonate water-reducing agent.
As shown in FIG. 5, which is a graph comparing the gas contents of two types of GCL-M, GCL-L lignosulfonate water-reducing agent concrete, it can be seen that, under the same blending amount, the GCL-M-doped modified natural bio-based lignosulfonate superplasticizer concrete has a lower gas content than the commercially available GCL-L lignosulfonate water-reducing agent concrete.
FIG. 6 and FIG. 7 are comparative graphs showing the compressive strength of concrete doped with two lignosulfonate water-reducing agents GCL-M, GCL-L, respectively, and it can be seen from these graphs that the concrete doped with the GCL-M modified natural bio-based lignosulfonate high-efficiency water-reducing agent has higher compressive strength than the concrete doped with the commercially available GCL-L lignosulfonate water-reducing agent at different curing ages.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. A preparation method of a modified natural bio-based lignin sulfonate high-efficiency water reducing agent is characterized by comprising the following steps:
the method comprises the following steps: crushing pine chips, screening pine particles with proper particle size, mixing the pine particles with water, adding a sodium hydroxide solution, uniformly stirring, putting the mixture into a rotary digester, heating, cooling the cooked product to room temperature, taking out, centrifuging the product, filtering, washing the filtered precipitate with distilled water to neutrality to obtain cellulose, and mixing the filtrate with washing liquid to obtain alkali lignin papermaking black liquor;
step two: placing the alkali lignin papermaking black liquor in a freeze dryer for freeze drying to obtain alkali lignin solid, and then crushing and ball-milling the alkali lignin solid to obtain alkali lignin powder;
step three: placing alkali lignin powder and an acetone solvent in a reaction container, stirring the mixture to form a uniform suspension solution, placing the suspension solution in a centrifuge to separate the suspension solution into layers and solid and liquid, obtaining a high molecular weight alkali lignin solution dissolved in the acetone solvent and a centrifugal precipitate, and placing the centrifugal precipitate in a freeze dryer to freeze and dry to obtain low molecular weight alkali lignin solid powder;
step four: raising the temperature of the high molecular weight alkali lignin solution to 40-50 ℃, adding a sodium hydroxide solution into the high molecular weight alkali lignin solution, adjusting the pH of the solution to 14-15, slowly dropwise adding a formaldehyde solution, finishing the addition in 45-60 minutes, and reacting at the temperature of 50-60 ℃ for 1-2 hours to obtain a high molecular weight alkali lignin clear solution connected with a hydroxymethyl acetone group;
step five: mixing low molecular weight alkali lignin solid powder and water, raising the temperature to 40-50 ℃, stirring the mixture to mix the low molecular weight alkali lignin powder and the water into a uniform solution, then adding a sodium hydroxide solution, adjusting the pH of the solution to 14-15, slowly dropwise adding a formaldehyde solution, finishing the adding within 25-30 minutes, and reacting for 0.5-1 hour at the temperature of 70-75 ℃ to obtain a low molecular weight alkali lignin solution connected with ortho-methylol;
step six: mixing and rapidly stirring a high molecular weight alkali lignin solution connected with a hydroxymethyl acetone group and a low molecular weight alkali lignin solution connected with an ortho-position hydroxymethyl group, adding an acetic acid solution, adjusting the pH value of the solution to 5-6, raising the temperature of the system to 160-180 ℃, continuously stirring for 3-4 hours at the temperature, and condensing high molecular weight alkali lignin molecules connected with the hydroxymethyl acetone group and low molecular weight alkali lignin molecules containing the hydroxymethyl group into an alkali lignin high polymer;
step seven: adding sodium bisulfite into the alkali lignin high polymer solution, adjusting the pH value of the solution to be 14-15 by using sodium hydroxide, raising the temperature of the solution to 180-200 ℃, reacting for 5-6 hours at the temperature, cooling the reaction product to room temperature, and curing for 2-3 hours in a reaction vessel to obtain the modified lignosulfonate superplasticizer.
2. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the first step, the mixture put into the rotary digester is specifically configured as follows: 30-35kg of pine wood particles are added into 65-70kg of water, and 4kg of sodium hydroxide solution is added to be mixed and stirred uniformly; wherein, the weight percentage concentration of the sodium hydroxide solution is 40%.
3. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the second step, the crushing and ball milling specifically comprises the following steps: crushing the alkali lignin solid, passing through a 5mm square-hole sieve, taking alkali lignin particles with the particle size of less than 5mm, and putting the alkali lignin particles into a ball mill to perform ball milling for 40-50 minutes at the speed of 80 revolutions per minute to obtain alkali lignin powder; wherein the particle size of the alkali lignin powder is less than 0.6 mm.
4. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the third step, the mass ratio of the alkali lignin powder to the acetone solvent is 12 (24-26).
5. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the fourth step, the mass ratio of the high molecular weight alkali lignin solution to the sodium hydroxide solution to the formaldehyde solution is 25 (1.5-1.8) to (58-59); wherein, the weight percentage concentration of the sodium hydroxide solution is 40 percent, and the weight percentage concentration of the formaldehyde solution is 37 percent.
6. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the fifth step, the mass ratio of the low molecular weight alkali lignin solid powder to the water to the sodium hydroxide solution to the formaldehyde solution is (70-80): 300-310): 7.5-8): 1.7-1.8; wherein, the weight percentage concentration of the sodium hydroxide solution is 40 percent, and the weight percentage concentration of the formaldehyde solution is 37 percent.
7. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the sixth step, the mass ratio of the high molecular weight alkali lignin solution connected with the hydroxymethyl acetone group, the low molecular weight alkali lignin solution connected with the ortho-position hydroxymethyl group and the acetic acid solution is (20-25): 75-80): 10-12.5.
8. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: in the seventh step, 30-35kg of sodium bisulfite and 100-125kg of sodium hydroxide solution are added into each 970-975kg of alkali lignin high polymer solution; wherein, the weight percentage concentration of the sodium hydroxide solution is 40%.
9. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: the pH value of the modified lignosulfonate superplasticizer prepared in the seventh step is 12-13, the solid content is 15-20%, the weight average molecular weight is 10535-14369, and the sulfonation degree is 1.384-1.427 mmol/g.
10. The preparation method of the modified natural bio-based lignin sulfonate high-efficiency water reducing agent according to claim 1, characterized in that: and seventhly, detecting the water reducing rate of the modified lignosulfonate high-efficiency water reducing agent and the performance of the concrete doped with the modified lignosulfonate high-efficiency water reducing agent under different doping amounts, and comparing the performance with the performance of the concrete doped with the conventional lignosulfonate water reducing agent under the same doping amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010611878.4A CN111704725B (en) | 2020-06-30 | 2020-06-30 | Preparation method of modified natural bio-based lignin sulfonate high-efficiency water reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010611878.4A CN111704725B (en) | 2020-06-30 | 2020-06-30 | Preparation method of modified natural bio-based lignin sulfonate high-efficiency water reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111704725A CN111704725A (en) | 2020-09-25 |
| CN111704725B true CN111704725B (en) | 2022-01-25 |
Family
ID=72543762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010611878.4A Active CN111704725B (en) | 2020-06-30 | 2020-06-30 | Preparation method of modified natural bio-based lignin sulfonate high-efficiency water reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111704725B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180862B (en) * | 2022-08-09 | 2023-08-08 | 佛山建发东方雨虹建材科技有限公司 | Preparation method of high-quality lignosulfonate water reducer |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328037A (en) * | 2008-07-31 | 2008-12-24 | 华南理工大学 | Alkali lignin concrete air-entraining water reducer and its preparation method and application |
| CN101531484A (en) * | 2009-01-21 | 2009-09-16 | 福州大学 | Sulfonated acetone-formaldehyde high-efficiency water reducing agent modified by enzymatic hydrolysis lignin or by derivatives thereof, and preparation method thereof |
| CN101921639A (en) * | 2010-08-28 | 2010-12-22 | 福州大学 | A method for preparing coal-water slurry additives by using enzymatic lignin as raw material |
| CN102395621A (en) * | 2009-03-20 | 2012-03-28 | Sika技术股份公司 | Method for producing chemically modified lignin decomposition products |
| CN102559305A (en) * | 2011-11-10 | 2012-07-11 | 渭南高新区爱心有限责任公司 | Compound efficient coal water slurry additive and preparation method thereof |
| CN103265984A (en) * | 2013-05-16 | 2013-08-28 | 华南理工大学 | Lignin dispersant for phenol-water coal water slurry, and preparation method and application thereof |
| CN103387858A (en) * | 2013-07-23 | 2013-11-13 | 常州中南化工有限公司 | A water-coal-slurry dispersant and a production technology thereof |
| CN103666608A (en) * | 2013-11-20 | 2014-03-26 | 中国东方电气集团有限公司 | Alkali lignin gasification coal-water slurry dispersing agent and preparation method thereof |
| CN104724970A (en) * | 2013-05-02 | 2015-06-24 | 新疆荣能新材料有限公司 | Synthetic process of modified lignin sulfonate water reducer |
| CN108218279A (en) * | 2018-03-26 | 2018-06-29 | 白彤洲 | A kind of building trade cement water reducing agent containing graphene and preparation method thereof |
-
2020
- 2020-06-30 CN CN202010611878.4A patent/CN111704725B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328037A (en) * | 2008-07-31 | 2008-12-24 | 华南理工大学 | Alkali lignin concrete air-entraining water reducer and its preparation method and application |
| CN101531484A (en) * | 2009-01-21 | 2009-09-16 | 福州大学 | Sulfonated acetone-formaldehyde high-efficiency water reducing agent modified by enzymatic hydrolysis lignin or by derivatives thereof, and preparation method thereof |
| CN102395621A (en) * | 2009-03-20 | 2012-03-28 | Sika技术股份公司 | Method for producing chemically modified lignin decomposition products |
| CN101921639A (en) * | 2010-08-28 | 2010-12-22 | 福州大学 | A method for preparing coal-water slurry additives by using enzymatic lignin as raw material |
| CN102559305A (en) * | 2011-11-10 | 2012-07-11 | 渭南高新区爱心有限责任公司 | Compound efficient coal water slurry additive and preparation method thereof |
| CN104724970A (en) * | 2013-05-02 | 2015-06-24 | 新疆荣能新材料有限公司 | Synthetic process of modified lignin sulfonate water reducer |
| CN103265984A (en) * | 2013-05-16 | 2013-08-28 | 华南理工大学 | Lignin dispersant for phenol-water coal water slurry, and preparation method and application thereof |
| CN103387858A (en) * | 2013-07-23 | 2013-11-13 | 常州中南化工有限公司 | A water-coal-slurry dispersant and a production technology thereof |
| CN103666608A (en) * | 2013-11-20 | 2014-03-26 | 中国东方电气集团有限公司 | Alkali lignin gasification coal-water slurry dispersing agent and preparation method thereof |
| CN108218279A (en) * | 2018-03-26 | 2018-06-29 | 白彤洲 | A kind of building trade cement water reducing agent containing graphene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Investigation of grafted sulfonated alkali lignin polymer as dispersant in coal-water slurry";Yanlin Qin;《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》;20150104;第27卷;第192-200页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111704725A (en) | 2020-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101575418B (en) | Lignin-based high-efficiency water reducing agent with high sulfonation degree and high molecular weight and method for preparing same | |
| CN101224958B (en) | Sulfonated alkali lignin modified sulfamic acid series high-efficiency water reducer and preparation method thereof | |
| CN110078877A (en) | A kind of methods and applications preparing dispersing agent using lignin degradation products | |
| JP2011184230A (en) | Lignin-based concrete admixture | |
| CN114127198B (en) | Method for preparing a sulfonated lignin-based composition, the sulfonated lignin-based composition so obtained and its use | |
| CN111704725B (en) | Preparation method of modified natural bio-based lignin sulfonate high-efficiency water reducing agent | |
| WO2014196618A1 (en) | Cement additive | |
| Zheng et al. | Kraft lignin grafted with isopentenol polyoxyethylene ether and the dispersion performance | |
| CA1141620A (en) | Lignin product for lowering the viscosity of cement and other finely-divided mineral material suspensions | |
| CN110282942A (en) | A kind of concrete mix and its production technology | |
| WO1997013733A1 (en) | Lignin-based concrete admixtures | |
| US5233012A (en) | Production of novel condensates comprising bisphenols and aromatic aminosulfonic acids, condensates and dispersant, additive and water-reducing agent based thereon | |
| US5153299A (en) | Production of novel condensates comprising bisphenols and aromatic aminosulfonic acids, condensates and dispersant, additive and water-reducing agent based thereon | |
| CN104785162A (en) | Aminomethylated lignin-based dispersant, and preparation technology and application thereof | |
| CN116731275B (en) | Mud-resistant modified naphthalene water reducer and preparation method thereof | |
| CN109306021B (en) | Starch sulfate retarding superplasticizer and preparation method thereof | |
| CN112375189B (en) | Preparation method of carboxylated lignin high polymer-aminomethylated acrylamide copolymerized amphoteric organic anti-dispersant | |
| WO2020195910A1 (en) | Solid-state cement dispersant, method for producing same and cement composition | |
| CN111560121A (en) | Preparation method of modified lignite humic acid water reducer | |
| CN107033308B (en) | A kind of method using natural chitin to prepare bio-based retarding superplasticizer | |
| CN100398481C (en) | Method for batch polymerization preparation of sulphamate composite high-efficiency water reducing agent and its acid and alkali | |
| Ma et al. | Synthesis and characterization of lignin grafting modification-based aliphatic superplasticizer | |
| CN111592256B (en) | Preparation method of a kind of anti-mud retarding type straw-based polycarboxylate water reducer and its application in concrete | |
| CN107141487A (en) | A kind of preparation method of single aromatic ring type high efficiency water reducing agent | |
| CN107722207B (en) | Preparation method of sulfamate water reducer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |