CN111254741A - Dry strength agent and preparation method and application thereof - Google Patents
Dry strength agent and preparation method and application thereof Download PDFInfo
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- CN111254741A CN111254741A CN202010120332.9A CN202010120332A CN111254741A CN 111254741 A CN111254741 A CN 111254741A CN 202010120332 A CN202010120332 A CN 202010120332A CN 111254741 A CN111254741 A CN 111254741A
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- dry strength
- strength agent
- biomass extract
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/02—Material of vegetable origin
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
Abstract
The invention discloses a dry strength agent and a preparation method and application thereof. The preparation method of the dry strength agent specifically comprises the following steps: (1) mixing the biomass extract with cationic starch under the condition that the pH value is 8.5-12 to prepare a mixed material A; (2) mixing the mixed material A and a cross-linking agent, reacting, and adjusting the pH to 2-6; in the step (2), the reaction temperature is 80-110 ℃. The dry strength agent prepared by the invention takes cationic starch, byproduct biomass extract produced in the paper-making pulping process and phosphate compound as raw materials. Not only replaces partial cationic starch, reduces the dosage of the cationic starch, further reduces the cost, but also realizes the waste utilization; the prepared dry strength agent can effectively improve the dry strength performance of paper, and the mechanical property is equivalent to that of the existing dry strength agent.
Description
Technical Field
The invention particularly relates to a dry strength agent and a preparation method and application thereof.
Background
In recent years, as the socioeconomic level is increasing, the quality of paper demanded by consumers is also increasing, wherein the strength of paper is one of the important factors for evaluating the quality of paper. Dry strength agents are an important class of chemicals used in the paper industry to enhance paper strength, and are commonly used to compensate for the decrease in paper strength caused by fillers. At present, natural polymer-based dry strength agents, such as those based on natural starch, cationic starch, anionic starch, and crosslinked starch, are commonly used. But the dosage of the starch is more in the preparation process, which cannot be reduced, and the total preparation cost of the dry strength agent is difficult to reduce.
The pulping and papermaking industry separates about 1.4 million tons of cellulose from plants every year and simultaneously generates a large amount of pulping waste liquid, but most of the pulping waste liquid is directly discharged into rivers or is burnt after being concentrated so far, so that the pulping waste liquid is rarely effectively utilized and the concept of sustainable development is not met.
Therefore, the development of a dry strength agent which has wide raw material sources and low cost and can effectively improve the strength of paper is urgently needed in the field.
Disclosure of Invention
The invention aims to overcome the defects of high cost and the like of a dry strength agent adopting a large amount of cationic starch in the prior art, and provides the dry strength agent, and a preparation method and application thereof. The dry strength agent prepared by the invention takes cationic starch, byproduct biomass extract produced in the paper-making pulping process and phosphate compound as raw materials. Not only replaces partial cationic starch, reduces the dosage of the cationic starch, further reduces the cost, but also realizes the waste utilization; the prepared dry strength agent can effectively improve the dry strength performance of paper, and the mechanical property is equivalent to that of the existing dry strength agent.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a preparation method of a dry strength agent, which comprises the following steps:
(1) mixing the biomass extract with cationic starch under the condition that the pH value is 8.5-12 to prepare a mixed material A;
(2) mixing the mixed material A and a cross-linking agent, reacting, and adjusting the pH to 2-6;
in the step (2), the reaction temperature is 80-110 ℃.
In the step (1), the raw material for preparing the biomass extract may be pulping waste liquid generated after cellulose is stripped in the process of preparing straw pulp and/or wood pulp in the field, and is generally one or more of rotten pulp, pulp residue and waste liquid except finished products, and the liquid material is filtered to remove insoluble substances, for example, pulping waste liquid generated in the process of preparing straw pulp and/or wood pulp by the Jinming new materials Co.
Wherein, the preparation method of the straw pulp and/or the wood pulp can be a conventional method in the field, such as one or more of a mechanical pulping process, a chemical mechanical pulping process and a chemical pulping process.
The mechanical pulp process may be conventional in the art, such as a stone-grinding or thermo-grinding mechanical process, among others.
The chemi-mechanical pulping process may be conventional in the art, such as chemithermomechanical, neutral sulfite semichemical, or alkaline hydrogen peroxide mechanical.
The chemical pulping process may be conventional in the art, such as a soda process, a sulfate process, or a sulfite process.
In a preferred embodiment, the raw material for preparing the biomass extract can be prepared according to patent CN102587179B, specifically: a, selecting eucalyptus pieces and pre-steaming; b, according to the mass ratio of the eucalyptus pieces to the water of 1:3-1:10, pumping the aqueous solution of the eucalyptus pieces to the top of an independent continuous hydrolysis tower by using a pump, wherein the hydrolysis reaction time of the eucalyptus pieces is 1-4h, the reaction temperature is 120-180 ℃, and after the prehydrolysis reaction, extracting hydrolysate from the lower part of the hydrolysis tower; c, cooking the hydrolyzed eucalyptus pieces by adopting a sulfate method, wherein the cooking conditions are as follows: adding hydrolyzed eucalyptus pieces at a constant speed at the top of a cooking pot, taking the absolute dry weight of the eucalyptus pieces as 16-24% of effective alkali calculated by NaOH, wherein the vulcanization degree of the effective alkali is 20-40%, the cooking temperature is 140-.
Preferably, the preparation method of the biomass extract preparation raw material comprises the steps of a, selecting eucalyptus pieces and pre-steaming; b, according to the mass ratio of the eucalyptus pieces to the water of 1:5, pumping the aqueous solution of the eucalyptus pieces to the top of the independent continuous hydrolysis tower by using a pump, wherein the hydrolysis reaction time of the eucalyptus pieces is 2 hours, the reaction temperature is 165 ℃, and after the prehydrolysis reaction, extracting the hydrolysate from the lower part of the hydrolysis tower; and c, cooking the hydrolyzed eucalyptus pieces by adopting a sulfate method under the following cooking conditions, uniformly adding the hydrolyzed eucalyptus pieces to the top of a cooking pot, taking the absolute dry amount of the eucalyptus pieces as 18 percent of available alkali calculated by NaOH, the vulcanization degree of the available alkali as 28 percent, the cooking temperature as 150 ℃, the mass ratio of the eucalyptus pieces to water as 1:5, and the cooking time as 2 hours, and collecting pulping waste liquid.
In the step (1), the preparation method of the biomass extract may be conventional in the art, and preferably, the preparation raw materials of the biomass extract are sequentially subjected to acid treatment and washing until the pH is 6 to 7.
In a preferred embodiment, the preparation method of the biomass extract comprises the following steps of mixing the raw materials for preparing the biomass extract and 50% by mass of hydrochloric acid according to a mass ratio of 1:5, stirring for 20min, filtering to obtain a filter cake, and washing the filter cake with water until the pH of the filtrate is 6-7.
In the present invention, the solid content of the biomass extract may be conventional in the art, and is preferably 45% to 50%.
In step (1), the cationic starch may be a cationic starch conventionally used in the art, preferably a quaternary ammonium salt type cationic starch.
In a preferred embodiment, said cationic starch can be obtained according to the invention patent application CN106243233A, in particular: step one, adding water, native starch and an anti-swelling agent into a detachable reaction kettle, mixing and stirring to prepare starch emulsion, and heating the reaction kettle; step two, after the temperature of the system is raised to 40 ℃, adding liquid caustic soda, an oxidant and an etherifying agent into the starch emulsion to continuously react for 4-8 hours; step three, adding a pH regulator to regulate the pH value 30min before the continuous reaction in the step two is finished, and gradually reducing the temperature of the system; step four, when the temperature of the system is reduced to 35 ℃, adding the bactericide and the mildewproof agent, stopping stirring, and reducing the temperature of the system to 15-25 ℃; step five, carrying out suction filtration and washing on the starch solution obtained in the step four by using a vacuum pump until the product becomes solid; sixthly, putting the product obtained in the fifth step into an oven for drying; and step seven, putting the product dried in the step six into a grinder for grinding and sieving to obtain the cold water soluble cationic starch.
Preferably, the preparation method of the cationic starch comprises the steps of adding 100g of corn starch, 125g of deionized water and 15g of sodium chloride into a detachable reaction kettle, placing the reaction kettle in a constant-temperature water bath kettle, starting stirring for 650r/min, heating the water bath kettle to the reaction temperature of 40 ℃, and then respectively adding 30.6g of NaOH solution, 4g of sodium hypochlorite and 32g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution for reaction for 4 hours; 30g of citric acid is added 30min before the reaction is finished, and 0.5g of tributyltin chloride is added when the temperature is reduced to 35 ℃; after the reaction is finished, carrying out suction filtration, washing and suction filtration on the starch solution by a vacuum pump until the product becomes solid; then the reaction product is dried in an oven at 70-105 ℃ for 1-2h until the water content of the reaction product is less than or equal to 14 percent. And cooling, crushing the dried reaction product by a crusher, and sieving by a 100-mesh sieve to obtain the cationic starch.
In step (1), the mass ratio of the cationic starch to the biomass extract may be a mass ratio conventional in the art, and is preferably (2.5-150): 1, more preferably (7.2-25): 1, e.g. 8: 1.
in step (1), the temperature of the mixing may be a temperature conventional in such operations in the art, and is preferably 25 to 30 ℃.
In the step (1), the pH is preferably 10 to 11.
In step (1), the condition of pH 8.5-12 can be adjusted by a method conventional in the art, and the pH of the system is adjusted to 8.5-12 by adding an alkaline substance.
Among them, the basic substance may be an inorganic base conventionally used in the art, preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.
Wherein the mass ratio of the alkaline substance to the biomass extract can be conventional in the art, and is preferably (0.2-30): 1, more preferably (0.75-2.5): 1, e.g. 1.2: 1 or 1.5: 1.
in step (1), preferably, the biomass extract is mixed with water.
Wherein the water may be water conventionally used in the art, preferably deionized water.
Wherein the mass ratio of the water to the biomass extract can be conventional in the art, and is preferably (3-150): 1, more preferably (5-73): 1, e.g. 7: 1 or 10.5: 1.
in the step (1), after the mixing, the operation of heat preservation is further included.
The temperature of the incubation may be a temperature conventional in such operations in the art, preferably from 50 to 80 ℃, more preferably from 55 to 80 ℃, for example 60 ℃ or 70 ℃.
The time for the incubation may be a time conventional in the art, preferably 0.5 to 2.5 hours, more preferably 0.75 to 2 hours, for example 1 hour.
In the step (2), the crosslinking agent may be a crosslinking agent conventionally used in the art, and is preferably a phosphate compound.
Wherein the phosphate compound may be PO (OR)3Wherein R is C1-C5Alkyl, preferably trimethyl phosphate and/or triethyl phosphate.
In a preferred embodiment, the phosphate ester compound is derived from a waste liquid obtained by extracting a reaction liquid obtained after phosphorylation reaction in the production process of β -nicotinamide mononucleotide, and the waste liquid contains the phosphate ester compound.
The mass percentage of the phosphate ester compound in the waste liquid can be the mass percentage of the phosphate ester compound in the waste liquid in the prior art, and is preferably 20-50%, and more preferably 37%.
Preferably, the preparation method of the waste liquid comprises the steps of mixing a reaction liquid obtained after phosphorylation reaction in the Chinese patent application CN102876759A with ice water, wherein the temperature of the ice water is 0-10 ℃, the mass ratio of the reaction liquid to the ice water is 1: 2, extracting with dichloromethane, the mass ratio of the reaction liquid to the dichloromethane is 1: 2, collecting a dichloromethane phase, removing a solvent, specifically, mixing the reaction liquid obtained by condensation reaction, ammonolysis reaction and phosphorylation reaction with ice water, wherein the temperature of the ice water is 0-10 ℃, the mass ratio of the reaction liquid to the ice water is 1: 2, and extracting with dichloromethane, the mass ratio of the reaction liquid to the dichloromethane is 1: 2, collecting the dichloromethane phase and removing the solvent.
More preferably, the preparation method of the waste liquid is to mix the reaction liquid obtained after the step three in the example 1 of the chinese patent application CN102876759A with ice water, wherein the temperature of the ice water is 0-10 ℃, and the mass ratio of the reaction liquid to the ice water is 1: 2; and extracting with dichloromethane, wherein the mass ratio of the reaction liquid to the dichloromethane is 1: and 2, collecting a dichloromethane phase, and removing the solvent to obtain the product.
In step (2), the temperature of the reaction is preferably 90 to 105 ℃, for example 100 ℃.
In step (2), the reaction time may be the time conventional in such operations in the art, and is preferably 1 to 5 hours, more preferably 1.5 to 4 hours, for example 3.5 hours.
In the step (2), the reaction may further include a cooling treatment.
The cooling treatment conditions and methods may be conventional in the art, and are preferably cooled to room temperature, more preferably to 25-30 ℃.
In step (2), the conditions and method for adjusting pH may be those conventional in the art, and preferably the pH is adjusted to 2-6, more preferably 4-5, by using a pH adjusting agent.
The pH regulator may be a pH regulator conventionally used in the art, and is preferably hydrochloric acid, and more preferably hydrochloric acid with a mass fraction of 36%.
The invention also provides a dry strength agent prepared by the preparation method.
In the present invention, the solid content of the dry strength agent may be 10% to 25%, preferably 12%, 16% or 21%.
The invention also provides the application of the dry strength agent as the dry strength agent in the papermaking process.
The invention also provides application of the biomass extract and the cationic starch as cross-linking raw materials in preparation of the dry strength agent.
Wherein, the cross-linking agent used for the cross-linking can be a cross-linking agent which is conventionally used in the field, and preferably is a phosphate compound PO (OR)3Wherein R is C1-C5An alkyl group.
The phosphate compound can be derived from waste liquid obtained by extracting reaction liquid obtained after phosphorylation reaction in the production process of β -nicotinamide mononucleotide, the waste liquid contains the phosphate compound, the chemical synthesis process of β -nicotinamide mononucleotide comprises a phosphorylation step, and the used reagent phosphate compound accounts for the main part of the waste liquid.
In the invention, the solid content is the mass percentage of the rest part of the adhesive or the coating which is known to those skilled in the art after being dried under specified conditions in the total mass.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: 1. the technical scheme adopted by the invention takes cationic starch, byproduct biomass extract produced in the paper-making pulping process and phosphate compound as raw materials. The biomass extract replaces part of cationic starch, so that the using amount of the cationic starch is reduced, the cost is reduced, and the waste utilization is realized;
2. when the waste liquid rich in the phosphate ester compounds is adopted to prepare the dry strength agent, not only can the resource waste be avoided, the environmental pollution be reduced, but also the treatment cost can be reduced, the investment and energy consumption of the refining and recycling equipment of the waste liquid are avoided, and the production cost of the dry strength agent is also reduced.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The raw materials used in the examples and comparative examples of the present invention were derived as follows:
the biomass extract and cationic starch used in the examples described below were supplied by Jiningmingshi New materials, Inc.;
the preparation process of the biomass extract comprises the following steps: a, selecting eucalyptus pieces and pre-steaming; b, according to the mass ratio of the eucalyptus pieces to the water of 1:5, pumping the aqueous solution of the eucalyptus pieces to the top of the independent continuous hydrolysis tower by using a pump, wherein the hydrolysis reaction time of the eucalyptus pieces is 2 hours, the reaction temperature is 165 ℃, and after the prehydrolysis reaction, extracting the hydrolysate from the lower part of the hydrolysis tower; c, cooking the hydrolyzed eucalyptus pieces by adopting a sulfate method, wherein the cooking conditions are as follows, the hydrolyzed eucalyptus pieces are uniformly added into the top of a cooking pot, the absolute dry amount of the eucalyptus pieces is 18 percent of effective alkali calculated by NaOH, the vulcanization degree of the effective alkali is 28 percent, the cooking temperature is 150 ℃, the mass ratio of the eucalyptus pieces to water is 1:5, the cooking time is 2 hours, and pulping waste liquid after paper pulp separation is obtained; d, mixing the pulping waste liquid obtained in the step c with 50% hydrochloric acid according to the mass ratio of 1:5, stirring for 20min and filtering. And (3) washing the filter cake by using water with the mass of 20 times of that of the filter cake until the pH value of the filtrate is 6-7, and obtaining the biomass extract with the solid content of 45%.
The preparation process of the cationic starch comprises the following steps: 100g of corn starch, 125g of deionized water and 15g of sodium chloride are added into a detachable reaction kettle, the reaction kettle is placed in a constant-temperature water bath kettle, stirring is started for 650r/min, the temperature of the water bath kettle is raised to 40 ℃, and then 30.6g of NaOH solution, 4g of sodium hypochlorite and 32g of 3-chloro-2-hydrocyclopropyl trimethyl ammonium chloride solution are respectively added, and the reaction time is 4 hours. 30g of citric acid is added 30min before the reaction is finished, and 0.5g of tributyltin chloride is added when the temperature is reduced to 35 ℃. And after the reaction is finished, carrying out suction filtration, washing and suction filtration on the starch solution by a vacuum pump until the product becomes solid. Then the reaction product is dried in an oven at 70-105 ℃ for 1-2h until the water content of the reaction product is less than or equal to 14 percent. And cooling, crushing the dried reaction product by a crusher, and sieving by a 100-mesh sieve to obtain the cationic starch.
β -nicotinamide mononucleotide production waste liquid is provided by Zhejiang nation chemical industry Co., Ltd, and the mass percentage of triethyl phosphate in the waste liquid generated after the phosphorylation step in the β -nicotinamide mononucleotide production process is 37%.
β -Process for preparing waste liquid generated after phosphorylation reaction in the process of producing nicotinamide mononucleotide, which comprises adding ice water of 0-10 deg.C into the reaction liquid obtained after the end of step three of step 1 of CN102876759A, controlling the mass ratio of the reaction liquid to ice water to be 1: 2, controlling the adding to be finished within 30min, adding dichloromethane of the same mass as ice water, stirring for 30min, standing, separating organic phase, evaporating organic solvent under the conditions of vacuum degree of-0.09 MPa and temperature of 45-55 deg.C, and the residual liquid is the waste liquid used in the following embodiments of the present invention.
Example 1
(1) Adding 84g of deionized water, 6g of sodium hydroxide, 8g of biomass extract and 65g of cationic starch into a four-neck flask, stirring and dissolving at 25-30 ℃, starting to heat after uniformly mixing, stirring for 45min at 55 ℃ to obtain a mixed material A, wherein the pH value of the system is 10; wherein the solid content of the biomass extract is 50%.
(2) And mixing the mixed material A with 18g of waste liquid, heating to 80 ℃, and stirring for 1.5 hours under the condition of heat preservation. After the reaction is finished, cooling to room temperature, adding 10g of hydrochloric acid with the mass percent of 36%, adjusting the pH to 4, and discharging to obtain the dry strength agent with the solid content of 16%.
Example 2
(1) Adding 74g of deionized water, 12g of potassium hydroxide, 10g of biomass extract and 80g of cationic starch into a four-neck flask, stirring and dissolving at 25-30 ℃, starting to heat after uniform mixing, stirring for 2 hours at 80 ℃ to obtain a mixed material A, wherein the pH value of the system is 12; wherein the solid content of the biomass extract is 50%.
(2) And mixing the mixed material A with 32g of waste liquid, heating to 105 ℃, and stirring for 5 hours under the condition of heat preservation. After the reaction is finished, cooling to room temperature, adding 13g of hydrochloric acid with the mass percent of 36%, adjusting the pH value to 6, and discharging to obtain the dry strength agent with the solid content of 21%.
Example 3
(1) Putting 92g of deionized water, 27g of sodium carbonate, 18g of biomass extract and 130g of cationic starch into a four-neck flask, stirring and dissolving at 25-30 ℃, starting to heat after uniformly mixing, stirring for 1h at 70 ℃ to obtain a mixed material A, wherein the pH value of the system is 8.5; wherein the solid content of the biomass extract is 50%.
(2) And mixing the mixed material B with 56g of waste liquid, heating to 90 ℃, and stirring for 3.5 hours under the condition of heat preservation. After the reaction is finished, cooling to room temperature, adding 30g of hydrochloric acid with the mass percent of 36%, adjusting the pH value to 5, and discharging to obtain the dry strength agent with the solid content of 25%.
Example 4
(1) Adding 145g of deionized water, 5g of potassium carbonate, 2g of biomass extract and 50g of cationic starch into a four-neck flask, stirring and dissolving at 25-30 ℃, starting to heat after uniform mixing, stirring for 2.5 hours at 65 ℃ to obtain a mixed material A, wherein the pH value of the system is 11; wherein the solid content of the biomass extract is 50%.
(2) And mixing the mixed material B with 20g of waste liquid, heating to 100 ℃, and stirring for 4 hours under the condition of heat preservation. After the reaction is finished, cooling to room temperature, adding 22g of hydrochloric acid with the mass percent of 36%, adjusting the pH value to 5, and discharging to obtain the dry strength agent with the solid content of 12%.
Comparative example 1
Adding corn starch, deionized water and sodium chloride into a detachable reaction kettle, placing the reaction kettle in a constant-temperature water bath kettle, starting stirring for 650r/min, heating the water bath kettle to the reaction temperature of 40 ℃, and then respectively adding a NaOH solution, sodium hypochlorite and a 3-chloro-2-hydroxypropyl trimethyl ammonium chloride solution for reaction for 4 h. Adding citric acid 30min before the reaction is finished, and adding tributyltin chloride when the temperature is reduced to 35 ℃. And after the reaction is finished, carrying out suction filtration, washing and suction filtration on the starch solution by a vacuum pump until the product becomes solid. Then the reaction product is dried in an oven at 70-105 ℃ for 1-2h until the water content of the reaction product is less than or equal to 14 percent. And cooling, crushing the dried reaction product by a crusher, and sieving by a 100-mesh sieve to obtain the cationic starch serving as a dry strength agent. The specific values of the materials are as follows: 100g of corn starch, 125g of deionized water, 32g of 3-chloro-2-alkyl propyl trimethyl ammonium chloride, 15g of sodium chloride, 30.6g of NaOH solution, 4g of sodium hypochlorite, 8g of hydrogen peroxide, 30g of citric acid and 0.5g of tributyl tin chloride.
Comparative example 2
The only difference compared to example 1 is that the pH was adjusted to 9 in step 2, and the remaining condition parameters were the same as in example 1.
Comparative example 3
The only difference compared with example 1 is that the reaction temperature of step 2 is 50 deg.C, and the other condition parameters are the same as example 1.
Effects of the embodiment
The recovered waste paper box is used as a raw material for pulping, the dry strength agents prepared in examples 1-4 and comparative examples 1-3 are respectively added after the beating degree reaches 35 DEG SR, and the mixture is stirred for 5 minutes. The pulp is formed by a semi-automatic paper former, squeezed by a standard paper squeezer and naturally dried to prepare the paper. The paper prepared without adding the dry strength agent is used as a blank control group, and the indexes of the folding endurance, the ring crush strength, the ring crush index, the bursting endurance, the bursting strength and the like of the blank control group, the paper added with the dry strength agents of examples 1-4 and the paper added with the dry strength agents of comparative examples 1-3 are respectively detected, and the results are shown in table 1. The ring crush strength and the ring crush index are measured according to the national standard GB/T2679.8-2016; the folding endurance is determined according to the national standard GB/T457-; the burst strength and the burst index are determined according to the national standard GB/T454-.
TABLE 1
From the application data, the preparation method of the dry strength agent has the advantages of mild reaction conditions, low equipment requirements, high waste liquid utilization rate and the like, and the paper can be endowed with remarkable dry strength performance by adding a small amount of the dry strength agent prepared by the preparation method, and the effect is equivalent to that of the conventional cationic starch. The use of the waste liquid containing the phosphate ester compound reduces the treatment cost of the waste liquid, also reduces the production cost of the dry strength agent, and ensures that the product has more advantage in price.
The foregoing detailed description of the embodiments of the invention has been presented by way of example only. Since the concentration of the waste liquid varies and the indexes of the biomass extract of the paper mill are different, the present invention is not limited to the above-described embodiments. It is within the technical scope of the present invention for a person skilled in the art to make any of the dose substitutions, feeding manner changes, simple modifications and modifications to the above examples according to the reaction principle of the present invention.
Claims (10)
1. The preparation method of the dry strength agent is characterized by comprising the following steps:
(1) mixing the biomass extract with cationic starch under the condition that the pH value is 8.5-12 to prepare a mixed material A;
(2) mixing the mixed material A and a cross-linking agent, reacting, and adjusting the pH to 2-6;
in the step (2), the reaction temperature is 80-110 ℃.
2. The method for preparing the dry strength agent according to claim 1, wherein in the step (1), the biomass extract is prepared from pulp waste liquid generated after cellulose is stripped in the process of preparing straw pulp and/or wood pulp; preferably one or more of the liquid materials of the rotten pulp, the pulp residue and the waste liquid except the finished product after insoluble substances are filtered;
and/or, in the step (1), the cationic starch is quaternary ammonium salt type cationic starch;
and/or in the step (1), the mass ratio of the cationic starch to the biomass extract is (2.5-150): 1, preferably (7.2-25): 1.
3. the method for preparing the dry strength agent according to claim 2, wherein the biomass extract is prepared by subjecting a raw material for preparing the biomass extract to acid treatment and washing in sequence until the pH is 6 to 7;
preferably, the preparation method of the biomass extract comprises the following steps of mixing the preparation raw material of the biomass extract and 50% hydrochloric acid according to a mass ratio of 1:5, stirring for 20min, filtering to obtain a filter cake, and washing the filter cake with water until the pH of the filtrate is 6-7.
4. The method for preparing a dry strength agent according to claim 1, wherein the mixing temperature in the step (1) is 25-30 ℃;
and/or, in step (1), the pH is 10-11;
and/or, in the step (1), the pH value of the system is adjusted to be 8.5-12 by adding alkaline substances under the condition that the pH value is 8.5-12; the alkaline substance is preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate; the mass ratio of the alkaline substance to the biomass extract is preferably (0.2-30): 1, more preferably (0.75-2.5): 1;
and/or, in step (1), mixing the biomass extract with water; the water is preferably deionized water; the mass ratio of the water to the biomass extract is preferably (3-150): 1, more preferably (5-73): 1;
and/or, in the step (1), after the mixing, further comprising the operation of heat preservation; the temperature of the heat preservation is preferably 50-80 ℃, and more preferably 55-80 ℃; the time for the heat preservation is preferably 0.5 to 2.5 hours, more preferably 0.75 to 2 hours.
5. The method of any one of claims 1 to 4The preparation method of the dry strength agent is characterized in that in the step (2), the cross-linking agent is a phosphate compound; the phosphate compound is preferably PO (OR)3Wherein R is C1-C5The phosphate compound is preferably derived from a waste liquid obtained by extracting a reaction liquid obtained after phosphorylation reaction in the production process of β -nicotinamide mononucleotide, wherein the waste liquid contains the phosphate compound, and the phosphate compound in the waste liquid accounts for 20-50% by mass of the waste liquid, more preferably 37% by mass of the waste liquid;
and/or, in the step (2), the temperature of the reaction is 90-105 ℃;
and/or, in the step (2), the reaction time is 1-5h, preferably 1.5-4 h;
and/or, in the step (2), further cooling treatment is carried out after the reaction; preferably, the cooling treatment is cooling to room temperature, more preferably, cooling to 25-30 ℃;
and/or, in the step (2), the pH is adjusted to 2-6 by using a pH adjusting agent, preferably to 4-5 by using a pH adjusting agent; the pH regulator is preferably hydrochloric acid, and more preferably hydrochloric acid with a mass fraction of 36%.
6. A dry strength agent, characterized in that the dry strength agent is prepared by the method for preparing the dry strength agent according to any one of claims 1 to 5.
7. Dry strength agent according to claim 6, characterized in that the dry strength agent has a solids content of 10% to 25%, preferably 12%, 16% or 21%.
8. Use of a dry strength agent according to claim 6 or 7 as a dry strength agent in a papermaking process.
9. An application of biomass extract and cationic starch as cross-linking raw materials in preparing dry strength agent.
10. Use according to claim 9, wherein the cross-linking agent used for cross-linking is a phosphate compound PO (OR)3Wherein R is C1-C5An alkyl group;
preferably, the phosphate compound is derived from a waste liquid obtained by extracting a reaction liquid obtained after phosphorylation reaction in the production process of β -nicotinamide mononucleotide, and the waste liquid contains the phosphate compound.
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