CN109485804B - Paper coating adhesive prepared by extracting protein from excess sludge and preparation method thereof - Google Patents
Paper coating adhesive prepared by extracting protein from excess sludge and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/22—Polyalkenes, e.g. polystyrene
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Abstract
The invention relates to a method for preparing a paper coating adhesive by extracting protein from excess sludge, which comprises the steps of extracting the excess activated sludge by an alkaline method to obtain a sludge protein extracting solution, and performing alcohol precipitation to obtain sludge extracted protein; modifying the sludge extracted protein serving as a raw material to prepare a paper coating adhesive; the solubility and the hydrophilic performance of the sludge extracted protein are improved by carboxymethylation modification of the sludge extracted protein obtained by alcohol precipitation; and thirdly, performing graft modification on carboxymethylation modified sludge extracted protein by an RATF technology to prepare the modified sludge protein-based paper coating adhesive, improving the film forming property and the water resistance of the modified protein, and being used for partially replacing styrene-butadiene latex/styrene-acrylic latex for paper coating processing.
Description
Technical Field
The invention belongs to the field of coating auxiliaries for coated and processed paper, and particularly relates to a method for preparing a paper coating adhesive by extracting protein from excess sludge.
Background
The pulping and papermaking industry is the traditional processing industry in China, the paper yield in China currently exceeds 1 hundred million tons, accounts for more than 1/4 of the total amount of the world, and is the first world producing and consuming nation. In addition, with the continuous improvement of living standard of people, the demand of people on coated paper is continuously increased, so the demand of the coating adhesive is also increased year by year. The coating adhesives used in the market at present are mainly synthetic latex adhesives, such as styrene-butadiene latex, styrene-acrylic latex and the like, and a small amount of biological latex, such as starch, protein and the like, is applied in a small amount. The synthetic latex is not only relatively expensive, but also not beneficial to the regeneration and reuse of waste paper. The synthetic latex can cause obstacles in the process of regeneration pulping and is difficult to regenerate and recycle. According to the development and planning of pulping and papermaking industry, the development trend of papermaking chemicals in the future is mainly reflected in green and functionality, and particularly, green chemicals taking biomass as a main raw material are the key points of future development. The green coating adhesive product is mainly characterized by being beneficial to the regeneration and reuse of waste paper and being the key of the development road of the recycling economy of the paper industry. The development direction of the adhesive is biomass-based coating adhesive mainly comprising protein and starch.
As a traditional coating adhesive material, the protein coating adhesive has good cohesiveness, belongs to renewable biological resources, and is beneficial to the regeneration and reuse of waste paper, once the coating adhesive is the mainstream coating adhesive, mainly soybean protein and casein adhesive, but the source of the coating adhesive is limited, the cost is higher, the water resistance is poor, the biological stability is poor, the foam control is difficult, and meanwhile, the problem of competing for protein resources with human and livestock exists, and the coating adhesive is gradually replaced by fossil synthetic auxiliary agents with more stable performance.
Urbanization is a main development trend of China in a period of time as a way of improving the living conditions of people. The biological treatment of domestic wastewater can generate a large amount of biological excess sludge, wherein the mycoprotein content can reach 40-50 percent, and the biological excess sludge is a huge renewable protein resource. The development of the green biomass-based papermaking chemical by using the sludge protein meets the development requirements of the industry at present, the problem of extraction of protein from excess sludge can be solved, waste is turned into wealth, the problem of competition for protein resources with human and livestock does not exist, and multiple purposes are achieved.
Modification of proteins is a major means for improving the performance of protein-based paper coating adhesives, and has been a focus of research and development in recent years. Various researches are carried out on plant extracted proteins such as soybean extracted protein, glutelin and the like, and common modification methods comprise carboxymethylation, cationization, graft modification and the like, and aim to improve the indexes of water resistance, biological stability, paper surface strength, smoothness and the like of the protein adhesive.
The protein extracted from the residual biological sludge has complex components, the protein molecules are 5000-60000 daltons, the protein comes from various mixed microbial floras, the composition difference is large, the protein molecules are seriously denatured in the extraction process, hydrophobic groups leak out, the hydrophilicity is poor, and the reaction efficiency and the effect are difficult to ensure. Aiming at the characteristics of extracting protein from biological sludge, the invention provides a method for preparing a paper coating adhesive by step modification and by using the biological sludge to extract protein.
Disclosure of Invention
The invention relates to a method for preparing a paper coating adhesive by extracting protein from excess sludge, which comprises the steps of carrying out alcohol precipitation on a sludge alkaline method extracted protein liquid to obtain sludge extracted protein, carrying out carboxymethylation modification to improve the hydrophilic property of the sludge protein, carrying out grafting reaction by an RATF (reversible addition transfer radical polymerization) technology to improve the film forming property and water resistance of the modified protein, and obtaining the modified excess sludge protein based paper coating adhesive which is used for partially replacing styrene-butadiene latex/styrene-acrylic latex to be used for paper coating processing.
The technical scheme for realizing the purpose of the invention is as follows:
a paper coated adhesive modified protein raw material is prepared by performing carboxymethylation modification on sludge derived protein, and then performing graft modification by an RATF method to obtain an adhesive modified protein raw material.
A method for preparing paper coating adhesive by extracting protein from excess sludge comprises the following steps
The method comprises the steps of extracting sludge protein extracting solution obtained by extracting residual activated sludge through an alkaline method, and extracting protein from the sludge obtained through alcohol precipitation; modifying the sludge extracted protein serving as a raw material to prepare a paper coating adhesive;
the solubility and the hydrophilic performance of the sludge extracted protein are improved by carboxymethylation modification of the sludge extracted protein obtained by alcohol precipitation;
and thirdly, carrying out graft modification on carboxymethylation modified sludge extracted protein by an RATF technology to prepare the modified sludge protein-based paper coating adhesive, so that the film forming property and the water resistance of the modified protein are improved.
Moreover, the biological sludge protein extract is residual protein extract obtained by extracting residual sludge of an urban sewage treatment plant by an alkaline process, the protein content is 30-35%, and the solid content is 40-45%.
And the sludge protein extracting solution is firstly heated to 60-75 ℃, and then the sludge protein extracting solution is prepared by the following steps: the volume ratio of ethanol is 1: adding 95% ethanol solution at a ratio of 1-1.5, stirring for 15min, centrifuging, vacuum drying solid at 60 deg.C, and pulverizing to obtain sludge protein.
And, taking a proper amount of sludge extracted protein prepared according to claim 3, adding water to prepare 10% -25% suspension, stirring, adjusting the pH value to 7.5-8.0 by using alkali, then heating to 50-75 ℃, adding chloroacetic acid which is 1.2 times of the mass of the sludge extracted protein in a dropwise adding mode, stirring for reacting for 1.0 hour within 30min, heating to 80 ℃ after the reaction is finished, then adding 95% ethanol which is 2 times of the volume ratio of the reaction solution, centrifugally separating and precipitating, drying in vacuum at 60 ℃, and crushing to obtain the chloroacetic acid modified sludge extracted protein. The substitution degree of the modified protein can reach more than 0.25.
The alkali used for adjusting the pH can adopt one or two of sodium hydroxide, sodium carbonate and magnesium hydroxide, preferably the combination of the sodium carbonate and the magnesium hydroxide, and the mass ratio of the sodium carbonate to the magnesium hydroxide is 5: 0.5-1.0.
Taking a proper amount of monomers, adding dithiobenzoic acid-2-cyano isopropyl ester (RATF) accounting for 0.25-1.0% of the mass ratio of the monomers and azobisisobutyronitrile accounting for 0.01-0.025% of the mass ratio of the monomers, and introducing nitrogen at 60 ℃ for protection reaction for 20-60 min; then adding an emulsifier and a proper amount of water in an amount of 0.5-2.0% by mass of the monomers, rapidly stirring for 10 minutes, and adding the chloroacetic acid-modified sludge extracted protein prepared by the method of claim 4 in the following amounts: the mass ratio of the modified protein to the monomer is 1:1-1.2, the solution concentration is 10% -25%, and the reaction is carried out for 60-120min at 65 ℃ to prepare the modified excess sludge extracted protein paper coating adhesive.
The monomer is one or two of methyl methacrylate, 2-hydroxyethyl methacrylate, maleic anhydride, styrene and acrylic acid;
the emulsifier is one or two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and Tween 60, preferably sodium dodecyl benzene sulfonate.
In addition, the prepared modified excess sludge extracted protein paper coating adhesive is mixed with synthetic adhesives such as styrene-acrylic latex, styrene-butadiene latex and the like according to the proportion of 1-2:11-10, so that the fluid performance and paper smoothness of the coating can be improved.
The invention has the advantages and beneficial effects that:
1. the invention utilizes sludge protein as a raw material to develop green biomass-based papermaking chemicals, and meets the development requirements of the current industry. Meanwhile, the problem of protein extraction from excess sludge can be solved, waste is turned into wealth, the sludge protein resource is renewable, the source is relatively centralized and stable, the collection is easy, and multiple purposes are achieved.
2. The modified residual sludge extracted protein is used as a coating adhesive for partially replacing fossil synthetic adhesives such as styrene-butadiene latex and styrene-acrylic latex, and the film forming property and the water resistance of the coating adhesive are effectively improved; the colloidal rheological properties are improved.
3. The invention uses sludge protein as raw material, improves the problems of high content of microbial protein and poor water solubility in the existing sludge after the first carboxylation modification, improves the water resistance of the protein by adopting a chain transfer mode through the second grafting modification, and improves the solubility of the protein, so that the protein becomes the protein which can be really applied.
4. Under the conditions that the amount of the modified sludge extracted protein is 2 parts and the amount of the styrene-acrylic latex is 10 parts, the dry napping speed of the coated paper is improved by 5-15% compared with that of 12 parts of the styrene-acrylic latex adhesive; the longitudinal and transverse tensile strength is improved by 3 to 12 percent; the coated paper has good smoothness, the PPS roughness is minimum, and the coating has good thermal stability.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
The raw material used by the invention is the residual activated sludge of the urban sewage treatment plant, and the sludge protein extract is obtained by alkaline extraction, wherein the protein content of the extract is 30-35%, and the solid content is 40-45%. The protein extract contains protein, a small amount of polysaccharide and inorganic salt brought in the extraction process. Because the protein extracting solution has deep chroma and high impurity content, further purification is needed. Purifying by an alcohol precipitation method to obtain solid sludge extracted protein through alcohol precipitation; modifying the extracted protein to prepare a coating adhesive;
the alcohol precipitation process is as follows: heating the sludge protein extracting solution to 60-75 ℃, and then mixing the sludge protein extracting solution: the volume ratio of ethanol is 1: 1-1.5, stirring for 15min, centrifuging, vacuum drying solid at 60 deg.C, and pulverizing to obtain sludge protein.
The sludge protein obtained by alcohol precipitation is affected by severe treatment conditions in the alkali extraction process, protein molecules are seriously denatured, and the hydrophobicity is strong, so that the carboxymethyl modification is firstly carried out on the sludge protein, and the solubility and the hydrophilic performance of the sludge protein are improved;
the carboxymethylation modification method comprises the following steps: taking a proper amount of sludge protein extract, adding water to prepare 10-25% suspension, stirring, adjusting the pH value to 7.5-8.0 by using alkali, then heating to 50-75 ℃, adding chloroacetic acid which is 1.2 times of the mass of the sludge protein extract in a dropwise adding mode, after dropwise adding within 30min, stirring and reacting for 1.0 h, heating to 80 ℃ after the reaction is finished, then adding 95% ethanol which is 2 times of the volume ratio of reaction liquid, centrifugally separating and precipitating, drying in vacuum at 60 ℃, and crushing to obtain the chloroacetic acid modified sludge protein extract. The substitution degree of the modified protein can reach more than 0.25.
The sludge extracted protein after chloroacetic acid modification has good hydrophilicity, but the film-forming property and the water resistance of the coating are poor, and further modification treatment is needed. According to the invention, the RATF technology is adopted for grafting modification, so that the modified sludge protein-based paper coating adhesive is prepared, and the film forming property and the water resistance of the modified protein are improved. The method comprises the following specific steps:
taking a proper amount of monomer, adding dithiobenzoic acid-2-cyano isopropyl ester (RATF) accounting for 0.25-1.0% of the mass ratio of the monomer and azobisisobutyronitrile accounting for 0.01-0.025% of the mass ratio of the monomer, and introducing nitrogen at 60 ℃ for protection reaction for 20-60 min; then adding an emulsifier and a proper amount of water in an amount of 0.5-2.0% by mass of the monomers, rapidly stirring for 10 minutes, adding chloroacetic acid modified sludge extracted protein prepared by the method in claim 4 in an amount of 1:1-1.2 by mass of the modified protein and the monomers, reacting at 65 ℃ for 60-120min to obtain the modified residual sludge extracted protein paper coating adhesive.
The prepared modified excess sludge extracted protein paper coating adhesive is prepared according to the following steps of 1-2:11-10 parts of the modified styrene-acrylic latex, styrene-butadiene latex and other synthetic adhesives can improve the fluid performance of the coating and the smoothness of paper.
Example 1:
the residual sludge protein extracting solution is produced by Tianjin Yuchuan microbial product limited, is obtained by extracting residual sludge of an urban sewage treatment plant by an alkaline method, and has the protein content of 33 percent and the solid content of 42 percent.
The alcohol precipitation process comprises the steps of heating the sludge protein extracting solution to 70 ℃, adding 95% ethanol solution with the same volume as the sludge protein extracting solution, stirring and reacting for 15min, centrifugally separating precipitate at 3000rpm, taking solid substances, drying in vacuum at 60 ℃, and crushing to obtain the residual sludge extracted protein. The protein content of the residual sludge extracted is 67%.
Taking a proper amount of residual sludge protein extract, adding water to prepare 15% suspension, stirring, adjusting the pH value to 8.0 by using alkali, then heating to 70 ℃, adding chloroacetic acid which is 1.2 times of the mass of the sludge protein extract in a dropwise adding mode, stirring and reacting for 1.0 hour within 30min, heating to 80 ℃ after the reaction is finished, adding 95% ethanol which is 2 times of the volume of the reaction solution, centrifugally separating and precipitating at 3000rpm, drying in vacuum at 60 ℃, and crushing to obtain the chloroacetic acid modified sludge protein extract. The degree of substitution of the modified protein at this time was 0.25.
The alkali used for adjusting the pH is two combinations of sodium carbonate and magnesium hydroxide, and the mass ratio of the sodium carbonate to the magnesium hydroxide is 8.0: 1.0. The chloroacetic acid modified sludge extracted protein needs to further improve the film forming property and the water resistance of the coating: the graft modification is carried out by adopting a chain transfer technology, which comprises the following steps:
taking a proper amount of monomer, adding dithiobenzoic acid-2-cyano isopropyl ester (chain transfer agent, RATF) accounting for 0.5 percent of the mass ratio of the monomer and azodiisobutyronitrile accounting for 0.01 percent of the mass ratio of the monomer, and introducing nitrogen at 60 ℃ for protection reaction for 30 min; then adding an emulsifier with the monomer mass ratio of 1.0% and a proper amount of water, quickly stirring for 10 minutes, adding chloroacetic acid modified sludge extracted protein with the same monomer mass, reacting for 2 hours at 65 ℃ with the solution concentration of 20%, and preparing the modified residual sludge extracted protein paper coating adhesive.
The monomer is the combination of methyl methacrylate and styrene, and the mass ratio of the methyl methacrylate to the styrene is 3.0: 1.0;
the emulsifier is sodium dodecyl benzene sulfonate.
The prepared modified excess sludge extracted protein paper coating adhesive is mixed with a styrene-acrylic latex agent according to the proportion of 2:10, and the dry napping speed of the coated paper is improved by 12%; the longitudinal and transverse tensile strength is improved by 7-11%; the smoothness of the coated paper is improved by 6 percent, and the PPS roughness is reduced by 12 percent.
Example 2:
the residual sludge protein extracting solution is produced by Tianjin Yuchuan microbial product limited company, is obtained by extracting residual sludge of an urban sewage treatment plant by an alkaline method, and has the protein content of 35 percent and the solid content of 45 percent.
The alcohol precipitation process comprises the steps of heating the sludge protein extracting solution to 65 ℃, adding a 95% ethanol solution which is 1.2 times of the volume of the sludge protein extracting solution, stirring and reacting for 15min, centrifugally separating precipitate at 3000rpm, taking solid substances, drying in vacuum at 60 ℃, and crushing to obtain the residual sludge extracted protein. The protein content of the residual sludge extracted is 65%.
Taking a proper amount of residual sludge extracted protein, adding water to prepare 12% suspension, stirring, adjusting the pH value to 7.5 by using alkali, then heating to 65 ℃, adding chloroacetic acid with the same mass as the sludge extracted protein in a dropwise adding mode, stirring and reacting for 45 minutes after dropwise adding is finished within 30min, heating to 80 ℃ after the reaction is finished, adding 95% ethanol with 2 times of the volume of the reaction liquid, centrifugally separating and precipitating at 3000rpm, drying in vacuum at 60 ℃, and crushing to obtain the chloroacetic acid modified sludge extracted protein. The degree of substitution of the modified protein at this time was 0.28.
The base used to adjust the pH was sodium carbonate.
The chloroacetic acid modified sludge extracted protein needs to further improve the film forming property and the water resistance of the coating: the graft modification is carried out by adopting a chain transfer technology, which comprises the following steps:
taking a proper amount of monomer, adding dithiobenzoic acid-2-cyano isopropyl ester (chain transfer agent, RATF) accounting for 0.3 percent of the mass ratio of the monomer and azodiisobutyronitrile accounting for 0.01 percent of the mass ratio of the monomer, and introducing nitrogen at 60 ℃ for protection reaction for 30 min; then adding an emulsifier with the monomer mass ratio of 0.5% and a proper amount of water, quickly stirring for 10 minutes, adding chloroacetic acid modified sludge extracted protein with the same monomer mass, wherein the solution concentration is 25%, and reacting at 65 ℃ for 1.5 hours to obtain the modified excess sludge extracted protein paper coating adhesive.
The monomer used was methyl methacrylate.
The emulsifier is a combination of sodium dodecyl benzene sulfonate and tween, and the mass ratio of the sodium dodecyl benzene sulfonate to the tween is 4: 1.
The prepared modified excess sludge extracted protein paper coating adhesive is mixed with a styrene-acrylic latex agent according to the proportion of 1:10, and the dry napping speed of the coated paper is improved by 6%; the longitudinal and transverse tensile strength is improved by 5-10%; the smoothness of the coated paper is improved by 5 percent, and the PPS roughness is reduced by 6 percent.
Claims (10)
1. A modified protein used as a raw material of a paper coating adhesive is characterized in that: performing carboxymethylation modification on sludge source protein, and then performing graft modification by using an RAFT (reversible addition-fragmentation chain transfer) method to obtain modified protein which can be used as a paper coating adhesive raw material; the RAFT method adopts monomer which is one or the combination of two of methyl methacrylate, 2-hydroxyethyl methacrylate, maleic anhydride, styrene and acrylic acid.
2. A method for preparing a paper coating adhesive by extracting protein from excess activated sludge is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the steps of extracting residual activated sludge by an alkaline method to obtain a sludge protein extracting solution, and performing alcohol precipitation to obtain sludge extracted protein;
performing carboxymethylation modification on the sludge extracted protein obtained by alcohol precipitation to obtain carboxymethylation modified sludge extracted protein, wherein the carboxymethylation modification improves the solubility and the hydrophilic performance of the sludge extracted protein;
performing graft modification on carboxymethylation modified sludge extracted protein by using an RAFT (reversible addition-fragmentation chain transfer) method to prepare a modified sludge protein-based paper coating adhesive, so that the film forming property and the water resistance of the modified protein are improved;
the RAFT method adopts monomer which is one or the combination of two of methyl methacrylate, 2-hydroxyethyl methacrylate, maleic anhydride, styrene and acrylic acid.
3. The method for preparing paper coating adhesive by using residual activated sludge extracted protein according to claim 2, which is characterized in that: the method comprises the steps of enabling the protein content of the sludge protein extracting solution to be 30% -35% and enabling the solid content to be 40% -45%.
4. The method for preparing paper coating adhesive by using residual activated sludge extracted protein according to claim 2, which is characterized in that: the method comprises the steps of firstly heating the sludge protein extracting solution to 60-75 ℃, and then mixing the sludge protein extracting solution: the volume ratio of ethanol is 1: adding 95% ethanol solution at a ratio of 1-1.5, stirring for 15min, centrifuging, vacuum drying solid at 60 deg.C, and pulverizing to obtain sludge protein.
5. The method for preparing paper coating adhesive by using residual activated sludge extracted protein according to claim 2, which is characterized in that: the method for carboxymethylation modification comprises the following steps: taking sludge protein extract, adding water to prepare 10-25% suspension, stirring, adjusting the pH value to 7.5-8.0 by using alkali, then heating to 50-75 ℃, adding chloroacetic acid which is 1-2 times of the mass of the sludge protein extract in a dropwise adding mode, completing dropwise adding within 30min, stirring and reacting for 1.0 hour, heating to 80 ℃ after the reaction is finished, then adding 95% ethanol which is 1-5 times of the volume ratio of reaction liquid, centrifugally separating and precipitating, drying in vacuum, and crushing to obtain carboxymethylated modified sludge protein extract.
6. The method for preparing paper coating adhesive by using residual activated sludge extracted protein according to claim 5, which is characterized in that: the alkali used for adjusting the pH adopts one or the combination of two of sodium hydroxide, sodium carbonate and magnesium hydroxide.
7. The method for preparing paper coating adhesive by using residual activated sludge extracted protein according to claim 2, which is characterized in that: the grafting modification method by the RAFT method in the step three is as follows: taking a proper amount of monomers, adding dithiobenzoic acid-2-cyano isopropyl ester accounting for 0.25-1.0 percent of the mass ratio of the monomers and azobisisobutyronitrile accounting for 0.01-0.025 percent of the mass ratio of the monomers, and introducing nitrogen at 60 ℃ for protection reaction for 20-60 min; then adding an emulsifier and a proper amount of water in an amount which is 0.5-2.0% of the mass ratio of the monomers, rapidly stirring for 10 minutes, and adding the carboxymethylation modified sludge extracted protein prepared in the step II, wherein the adding amount is as follows: the mass ratio of the carboxymethylated modified sludge extracted protein to the monomer is 1:1-1.2, the concentration of the solution is 10% -25%, and the reaction is carried out for 60-120min at 65 ℃ to prepare the modified sludge protein-based paper coating adhesive.
8. The method for preparing paper coating adhesive by extracting protein from excess sludge according to claim 7, wherein the method comprises the following steps: the emulsifier is one or two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and Tween 60.
9. An adhesive composition comprising a paper coating adhesive and a synthetic adhesive prepared by extracting protein from excess activated sludge, characterized in that: the paper coating adhesive prepared by extracting protein from excess activated sludge according to any one of claims 2 to 8, further comprising synthetic adhesive, protein adhesive: the weight ratio of the synthetic adhesive is 1-2: 11-10.
10. The excess activated sludge extracted protein containing paper coating adhesive prepared according to claim 9, wherein: the synthetic adhesive is styrene-acrylic latex or styrene-butadiene latex.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141260A (en) * | 2014-07-04 | 2014-11-12 | 陕西科技大学 | Degradable neutral sizing agent for papermaking and preparation method thereof |
| CN107602778A (en) * | 2017-09-18 | 2018-01-19 | 四川大学 | It is a kind of using tanned wastes as albumen based amphiprotic absorbent resin prepared by raw material and preparation method thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141260A (en) * | 2014-07-04 | 2014-11-12 | 陕西科技大学 | Degradable neutral sizing agent for papermaking and preparation method thereof |
| CN107602778A (en) * | 2017-09-18 | 2018-01-19 | 四川大学 | It is a kind of using tanned wastes as albumen based amphiprotic absorbent resin prepared by raw material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Sludge dewaterability of a starch-based flocculant and its combined usage with ferric chloride";Hua Wei et al.,;《Chemical Engineering Journal》;20181001;第349卷;第737-747页 * |
| 生物污泥蛋白作为增强剂在瓦楞原纸中的应用;李祥祥等;《天津造纸》;20161215(第04期);第26页"1.1污泥蛋白增强剂的制备"，第30页"3结论" * |
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