CN110894696A - Method for bleaching bamboo pulp - Google Patents
Method for bleaching bamboo pulp Download PDFInfo
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- CN110894696A CN110894696A CN201911046801.0A CN201911046801A CN110894696A CN 110894696 A CN110894696 A CN 110894696A CN 201911046801 A CN201911046801 A CN 201911046801A CN 110894696 A CN110894696 A CN 110894696A
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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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
- D21H11/04—Kraft or sulfate pulp
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D5/00—Purification of the pulp suspension by mechanical means; Apparatus therefor
- D21D5/02—Straining or screening the pulp
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Abstract
The invention provides a method for bleaching bamboo pulp, which takes unbleached bamboo pulp prepared by a sulfate method as a raw material and utilizes an acid solubilizing bleaching agent to treat the raw material of the bamboo pulp to obtain the bleached bamboo pulp. The treated bamboo pulp is subjected to a papermaking process, and the fact that the acidic solubilizing bleaching agent can obtain paper with better performance when the acidic solubilizing bleaching agent is in medium and low concentration is found, meanwhile, the method is free of chlorine addition, does not need a high-pressure environment, is good in bleaching selectivity, and less in fiber damage, the acidic solubilizing bleaching agent adopted in experiments can be efficiently recycled and reused through a crystallization technology, the production cost is further reduced, and the method has a wide application prospect in the field of bamboo pulp bleaching.
Description
Technical Field
The invention belongs to the technical field of pulping and papermaking processes, and particularly relates to a method for bleaching bamboo pulp.
Background
Bamboo plant resources in China are quite rich, and the occupied area of the bamboo forest reaches 720 kilohm2The total amount of bamboo forest in the world accounts for 30%, and the varieties, the occupied area, the storage amount of bamboo resources and the total output of bamboo pulp of bamboo plants are all in the leaders of the world, so that the bamboo pulp is a non-wood fiber raw material which is widely applied. The bamboo has the characteristics of fast growth, good toughness and high strength, the bamboo fiber belongs to medium-long fiber in length, the length of the bamboo pulp fiber is usually between that of softwood pulp fiber and that of hardwood pulp fiber, and the bamboo pulp fiber has good pulping and papermaking performances due to the high length-width ratio of the bamboo pulp fiber, so that the bamboo pulp can be well applied to solving the problem of shortage of papermaking wood fiber in China at present, and therefore the bamboo is considered as the best resource for replacing wood production.
The patent (CN106625952B) discloses a wood bleaching method, which comprises the steps of pretreating wood by using sodium bicarbonate, decomposing the sodium bicarbonate at high temperature, releasing carbon dioxide to form micropores in the wood, inducing and culturing puffball by using lignin and X-rays to increase the lignin decomposition capability and reduce the decomposition of cellulose, mixing a bacterial solution with sodium silicate, entering the wood through the micropores to decompose lignin in the wood, filling the micropores generated by decomposing the lignin and pigments by using the sodium silicate to avoid the increase of the porosity of the wood, bleaching the surface of the wood by using oxalic acid, and finally sterilizing the wood. However, the method uses X-rays which are harmful to human bodies to a certain extent, and has high requirements on the content and the type of bacteria in the used bacteria liquid and the growth environment of the bacteria, and the effect of bleaching wood cannot be stabilized.
Patent (CN107151935B) discloses a bleaching process for refined cotton, which comprises the following steps: (1) pre-bleaching; (2) pre-washing with water; (3) bleaching; (4) rinsing after bleaching; (5) alkali treatment; (6) dechlorination; (7) and (5) washing with water. In the pre-bleaching process, discharging 25-30 t of black pulp formed after cooking into a bleaching pool, then injecting 20-25 t of bleached wastewater into the bleaching pool, then adding a hydrochloric acid solution, adjusting the pH value to 4-6, then injecting 5-10 t of an activator sodium hypochlorite solution into the bleaching pool, controlling the available chlorine to be 0.5-1.0 g/L, then starting a stirrer, stirring for 20-30 min, and then discharging 25-35 t of water into a sewage pool. Although the bleaching wastewater is reused by adopting the activating agent in the pre-bleaching process and the bleaching effect is played again, so that the discharge of the bleaching wastewater is reduced and the sewage treatment cost is reduced, the requirements on pH and effective chlorine control are higher, the total process flow is relatively complicated, and the production cost is increased by recycling the hydrochloric acid, the sodium hypochlorite, the activating agent and the like added in the process.
The patent (CN108214779A) discloses a method for bleaching poplar, which comprises the steps of firstly cutting poplar, soaking the cut poplar in water, adding a surfactant, carrying out ultrasonic impregnation, taking out the cut poplar, draining the water to obtain pretreated wood, soaking the pretreated wood in a water-alcohol mixed solvent, adding sodium tripolyphosphate and an alkali liquor, adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride after reaction, continuing the reaction to obtain modified wood, then mixing the modified wood with a metal salt solution, carrying out ultrasonic impregnation and drying, mixing the modified wood with hydrogen peroxide for reaction, mixing the modified wood with isocyanate after drying to a certain water content, carrying out ultrasonic impregnation, drying to a constant weight, and completing the bleaching of the poplar. The method uses ultrasound for many times, the ultrasound can enable chemicals to react with wood more fully, but the ultrasound is harmful to human bodies, and the effect of a laboratory is achieved when the ultrasound method is applied to a factory, so that the method has certain limitation.
The patent (CN 108951255a) discloses a method for bleaching pulp, which comprises the following steps: (1) heating pretreatment is carried out in an acid solution soaked in paper pulp; (2) washing paper pulp, adding a complex enzyme, and performing enzymolysis in an electric field; (3) transferring the paper pulp after enzymolysis to a container, and adding a bleaching agent for heating bleaching; (4) adding sodium perhydride, and performing supplementary bleaching under the action of ultrasonic waves; (5) and washing the paper pulp by using distilled water to obtain bleached paper pulp. The method has two bleaching sections, in the total process flow, not only acid solution, bleaching agent and sodium perhydride are used, but also complex enzyme is added, and finally ultrasonic wave is used, which is equivalent to the scheme that three physical, chemical and biological methods are used for bleaching, although the advantages of different methods are combined, the defects of different methods are remained, such as increased chemical recovery cost, easy secondary pollution, high requirement on reaction environment of enzymolysis, easy damage of ultrasonic wave to human body and the like.
The patent (CN110177909A) discloses a method for bleaching unbleached or prebleached pulp, comprising at least the following successive steps: (1) preparing unbleached or prebleached pulp having a pH of at least 8; (2) contacting the pulp obtained at the end of step (1) with chlorine dioxide; (3) adding at least one bronsted base to the pulp obtained from step (2) when the pH of the pulp is below 10; (4) adding hydrogen peroxide into the pulp obtained at the end of the step (3); (5) holding the pulp obtained at the end of step (4) in a first bleaching tower; (6) optionally, sulfuric acid is added to the resulting pulp at the end of step (5) and the resulting pulp is held in a second bleaching tower, the process not requiring a step of washing the pulp before the end of step (5) and, if applicable, before the end of step (6). The method needs to add acid, alkali and chloride, the recovery and utilization of chemicals increase the cost and easily cause secondary pollution to the environment, and the treatment cost of sewage is increased. The pH value is monitored at the moment of step (2), which has higher requirements for technology and manpower.
The patent (CN109736119A) discloses a novel pulp bleaching method, comprising: (1) an oxygen delignification bleaching section under acidic conditions; (2) an alkali treatment section; (3) an activation treatment section; (4) a hydrogen peroxide bleaching stage; wherein H is used in the oxygen delignification bleaching process2SO4Adjusting the pH value of the paper pulp to 4-5, and adding H2O2And MnO2The peroxy acid formed under acidic conditions oxidizes and delignifies and removes transition metal ions, oxygen promoting MnO2To MnO of4 -Carrying out oxidation-reduction reaction with lignin to fragment lignin macromolecules and dissolve out the lignin macromolecules; oxygen is reduced to HOO, so that the large molecules of lignin are cracked and wood is removedAnd (4) element. The process flow of the method is approximately similar to the bleaching flow used in the current factory, and the used chemicals such as acid, alkali, hydrogen peroxide and the like need to be further recycled, so that the economic cost is further increased, and the used chemicals have large damage to wood and are harmful to human bodies, and the problem of stimulating respiratory mucosa is easily caused after long-term contact.
The existing paper pulp bleaching process uses a plurality of chemical substances to bleach paper pulp, and some processes also use physical methods such as X-rays, ultrasonic waves and the like, so that the process is complex, the requirement on experimental conditions is high, and secondary pollution is easily caused.
Disclosure of Invention
The invention mainly aims to provide a method for bleaching bamboo pulp, which uses an acidic solubilization type bleaching agent, can bleach the bamboo pulp efficiently, has no chlorine addition in the bleaching process, does not need pressure equipment to promote the bleaching process, can be reused, has simple operation process, reduces time cost, energy consumption and cost, and can reduce the pollution of chemicals to the environment and the phenomenon of cost increase caused by long reaction time and high reaction temperature.
A method for bleaching bamboo pulp specifically comprises the following steps:
(1) bleaching reaction: weighing unbleached bamboo pulp raw materials prepared by a sulfate method through cooking, an acidic solubilizing bleaching agent and distilled water, adding the unbleached bamboo pulp raw materials, the acidic solubilizing bleaching agent and the distilled water into a reaction container according to a proportion, heating to a set temperature, stirring for a certain reaction time at the set temperature, and adding the distilled water with the weight equal to the total weight of the reaction raw materials to terminate the reaction after the reaction is finished to prepare a bamboo pulp suspension for later use;
(2) and (3) filtering: filtering the bamboo pulp suspension obtained in the step (1), and separating to obtain a bamboo pulp solid product for later use; diluting the filtrate with distilled water, settling, separating to obtain supernatant and precipitate, recovering acidic solubilizing bleaching agent from the supernatant by crystallization, and reusing the recovered acidic solubilizing bleaching agent.
(3) Washing: washing the bamboo pulp solid product prepared in the step (2) to be neutral by using distilled water, and obtaining bleached bamboo pulp.
Preferably, the acid-solubilizing bleaching agent in step (1) is p-toluenesulfonic acid.
Preferably, the mass percentage concentration of the p-toluenesulfonic acid in the total weight of the experiment is 25% -50%.
Preferably, the set temperature in step (1) is 70 to 80 ℃.
Preferably, the reaction time in step (1) is 30 to 60 min.
Preferably, the washing described in step (3) uses distilled water to wash the bamboo pulp solid product to neutrality.
The invention has the following beneficial effects:
1. the method provided by the invention realizes that the whiteness of the bamboo pulp can be improved to achieve the purpose of bleaching only by utilizing the acid solubilizing bleaching agent which is convenient to recycle, the bleaching agent does not contain chlorine elements, dioxin is not generated in bleaching waste water, the method is an environment-friendly green process, the defect that the cost investment on the recycling of chemical reagents in the traditional process is too large is effectively avoided, and the problem that the pulp bleaching process depends on the combined action of various chemical reagents is solved.
2. The method bleaches the bamboo pulp raw material under the conditions of low temperature and short time, does not need a high-temperature and high-pressure container, can save the production cost, improve the production efficiency and reduce the energy consumption, and can effectively avoid safety accidents such as scalding and the like under the low-temperature operation condition.
3. The bleaching agent is based on lignin dissolution in a low-temperature environment, has good selectivity, avoids the destructive effect on fiber components, has low degradation degree on cellulose and hemicellulose, and thus has high yield of the obtained solid fiber components.
4. The solid fiber product obtained by the method can better preserve the original form of the solid fiber product, can be further used for manufacturing paper, and provides a novel bleaching idea for the pulping and papermaking industry.
The foregoing is only an overview of the technical solutions of the present invention, and in order to more clearly understand the technical solutions of the present invention, the present invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a fiber morphology of bleached bamboo pulp and a bamboo pulp raw material before bleaching manufactured in example 1 of the present invention magnified 40 times under a microscope; wherein, fig. 2-a is a fiber state of the bleached bamboo pulp obtained in example 1, and fig. 2-B is a fiber state of the bamboo pulp raw material before bleaching.
Detailed Description
The invention mainly aims to provide a method for bleaching bamboo pulp, which uses an acidic solubilization type bleaching agent, effectively improves the whiteness of the bamboo pulp without damaging the fiber structure of the bamboo pulp, can effectively improve the whiteness of the bamboo pulp under the conditions of low temperature and short time, can keep better fiber form, can be used for manufacturing paper, and can also be used for hydrolyzing to obtain fermentable monosaccharide and the like. The acidic solubilization type bleaching agent does not contain chlorine, dioxin cannot be generated in bleaching waste water, the medicine can be recycled, the operation process is simple, pressurization is not needed, the bleaching time is short, the reaction temperature is low, the energy consumption is reduced, the cost is saved, and the pollution of chemicals to the environment and the phenomenon of cost increase caused by long reaction time and high reaction temperature can be reduced.
In order to understand the present invention, the following examples are given to further illustrate the present invention.
To examine the influence of different process conditions on solid product yield, weight average length, number average length, width, fines content, kink coefficient, crimp coefficient and whiteness, we set different examination conditions including different acid-solubilizing bleach concentrations, different reaction temperatures, different reaction times, as shown in the following examples:
example 1:
the total weight of the experiment is 200g, wherein the ratio of the raw material weight of the unbleached bamboo pulp to the total weight is 1: 10.
(1) Bleaching reaction: weighing 20g of unbleached bamboo pulp raw material prepared by steaming and boiling by a sulfate method, 50g of p-toluenesulfonic acid and 130g of distilled water, wherein the p-toluenesulfonic acid accounts for 25 percent of the total weight, heating to 70 ℃ in a water bath kettle, stirring for 60min, adding 200g of distilled water into a reaction container to finish reaction, and preparing a bamboo pulp suspension for later use;
the addition of distilled water can cause the temperature to drop rapidly, thus failing to reach the temperature required by the reaction, which can ensure the accuracy of the reaction time.
(2) And (3) filtering: vacuum filtering the bamboo pulp suspension obtained in the step (1), and separating to obtain a bamboo pulp solid product for later use; diluting the filtrate with distilled water, settling, separating to obtain supernatant and precipitate, recovering acidic solubilizing bleaching agent from the supernatant by crystallization, and reusing the recovered acidic solubilizing bleaching agent in bleaching reaction.
The filtration adopts vacuum filtration, and the vacuum filtration can accelerate the filtration speed.
(3) Washing: washing the bamboo pulp solid product prepared in the step (2) to be neutral by using distilled water to prepare bleached bamboo pulp.
The solid product of the bamboo pulp is washed to be neutral, so that the solid product of the bamboo pulp can be ensured not to be attached with an acidic solubilizing bleaching agent, and monosaccharide micromolecule substances on the solid product can be dissolved in water and removed in the washing process.
After the washing, the yield of the bleached bamboo pulp is 87.60%.
Example 2:
the total weight of the experiment is 200g, wherein the ratio of the raw material weight of the unbleached bamboo pulp to the total weight is 1: 10.
(1) Bleaching reaction: weighing 20g of unbleached bamboo pulp raw material prepared by steaming and boiling by a sulfate method, 60g of p-toluenesulfonic acid and 120g of distilled water, wherein the p-toluenesulfonic acid accounts for 30% of the total weight, heating to 75 ℃ in a water bath, stirring for 45min, adding 200g of distilled water into a reaction container to finish reaction, and preparing a bamboo pulp suspension for later use;
(2) and (3) filtering: the procedure is as in example 1;
(3) washing: the procedure is as in example 1.
After the washing, the yield of the bleached bamboo pulp is 87.78%.
Example 3:
the total weight of the experiment is 200g, wherein the ratio of the raw material weight of the unbleached bamboo pulp to the total weight is 1: 10.
(1) Bleaching reaction: weighing 20g of unbleached bamboo pulp raw material prepared by steaming and boiling by a sulfate method, 100g of p-toluenesulfonic acid and 80g of distilled water, wherein the p-toluenesulfonic acid accounts for 50% of the total weight, heating to 70 ℃ in a water bath kettle, stirring for 30min, adding 200g of distilled water into a reaction container to finish reaction, and preparing a bamboo pulp suspension for later use;
(2) and (3) filtering: the procedure is as in example 1;
(3) washing: the procedure is as in example 1.
After the washing, the yield of the bleached bamboo pulp is 87.60%.
Example 4:
the total weight of the experiment is 200g, wherein the ratio of the raw material weight of the unbleached bamboo pulp to the total weight is 1: 10.
(1) Bleaching reaction: weighing 20g of unbleached bamboo pulp raw material prepared by steaming and boiling by a sulfate method, 100g of p-toluenesulfonic acid and 80g of distilled water, wherein the p-toluenesulfonic acid accounts for 50% of the total weight, heating to 80 ℃ in a water bath, stirring for 30min, adding 200g of distilled water, and finishing reaction to obtain bamboo pulp suspension for later use;
(2) and (3) filtering: the procedure is as in example 1;
(3) washing: the procedure is as in example 1.
After the washing, the yield of the bleached bamboo pulp is 87.43%.
Example 5:
the 4 bleached bamboo pulp and unbleached bamboo pulp obtained in examples 1 to 4 were weighed, fluffed by fluffer for 10000 cycles, and the 4 bleached bamboo pulp and unbleached bamboo pulp were papermaking with a basis weight of 70g/m2And naturally drying the paper for 24 hours in a constant temperature and humidity environment to prepare 5 different kinds of paper.
Example 6:
the whiteness of 5 different papers prepared in example 5 was measured at a wavelength of 457nm using a whiteness color measuring instrument and characterized by ISO brightness, 5 papers were randomly drawn, ten points were randomly measured for each paper, and the average value was taken as the whiteness value of the paper.
Example 7:
the 4 bleached bamboo pulp and unbleached bamboo pulp obtained in examples 1 to 4 were weighed and fluffed by fluffer for 10000 cycles, and 5 different pulps after fluffing were analyzed for fiber characteristics by FQA.
The results obtained under different experimental conditions are shown in table 1, and the results of the solid fiber product yield, the weight average length, the number average length, the width, the fine fiber content, the kink coefficient, the crimp coefficient and the whiteness value obtained from different examples and bamboo pulp raw materials.
TABLE 1
Through the analysis of experimental results, the whiteness of the bamboo pulp treated by the p-toluenesulfonic acid is obviously improved, the product yield is higher, and the pulp loss is less. The weight average length, the number average length, the width, the fine fiber content, the kink coefficient and the crimp coefficient are not obviously changed, which indicates that the fiber form of the bamboo pulp before and after bleaching is not obviously changed.
As shown in fig. 2, the morphology of the bleached pulp was observed by microscope, and it was found that the bleached bamboo pulp retained the fiber morphology well, and the fiber morphology was almost identical to that before bleaching, and did not change significantly, and could be used for further making paper or other fiber products.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A method for bleaching bamboo pulp is characterized in that: the method comprises the following steps:
(1) bleaching reaction: weighing bamboo pulp raw materials prepared by a sulfate method, an acidic solubilizing bleaching agent and distilled water, adding the raw materials into a reaction container together according to a proportion, heating to a set temperature, stirring for a certain reaction time at the set temperature, and after the reaction is finished, adding the distilled water with the weight equal to the total weight of the raw materials to terminate the reaction to prepare bamboo pulp suspension for later use;
(2) and (3) filtering: filtering the bamboo pulp suspension obtained in the step (1), and separating to obtain a bamboo pulp solid product for later use; diluting the obtained filtrate with distilled water, settling and separating to obtain supernatant and precipitate, wherein the precipitate containing a large amount of lignin can be further comprehensively utilized, and the supernatant is crystallized to obtain recovered acidic solubilizing bleaching agent for later use and reuse in the bleaching reaction;
(3) washing: washing the bamboo pulp solid product prepared in the step (2) to be neutral by using distilled water to prepare bleached bamboo pulp.
2. A method of bleaching bamboo pulp according to claim 1, characterized in that: the acid-solubilizing bleaching agent in the step (1) is p-toluenesulfonic acid.
3. A method of bleaching bamboo pulp according to claim 2, characterized in that: the mass percentage concentration of the p-toluenesulfonic acid in the total weight of the experiment is 25-50%.
4. A method of bleaching bamboo pulp according to claim 1, characterized in that: the set temperature in step (1) is 70-80 ℃.
5. A method of bleaching bamboo pulp according to claim 1, characterized in that: the reaction time in the step (1) is 30-60 min.
6. A method of bleaching bamboo pulp according to claim 1, characterized in that: the washing in the step (3) uses distilled water to wash the bamboo pulp solid product to be neutral.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112359631A (en) * | 2020-10-29 | 2021-02-12 | 陕西科技大学 | Method for bleaching chlorine-free bamboo pulp |
| CN113293636A (en) * | 2021-04-25 | 2021-08-24 | 齐鲁工业大学 | Preparation method of broadleaf wood dissolving pulp |
| CN113430855A (en) * | 2021-05-20 | 2021-09-24 | 齐鲁工业大学 | Preparation method and application of broadleaf wood dissolving pulp |
| CN114990917A (en) * | 2022-05-19 | 2022-09-02 | 华南理工大学 | Cooking method for preparing moso bamboo lyocell fiber grade dissolving pulp |
| CN117364525A (en) * | 2023-10-08 | 2024-01-09 | 泰盛科技（集团）股份有限公司 | Bamboo fluff pulp board and preparation method thereof |
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| CN112359631A (en) * | 2020-10-29 | 2021-02-12 | 陕西科技大学 | Method for bleaching chlorine-free bamboo pulp |
| CN113293636A (en) * | 2021-04-25 | 2021-08-24 | 齐鲁工业大学 | Preparation method of broadleaf wood dissolving pulp |
| CN113430855A (en) * | 2021-05-20 | 2021-09-24 | 齐鲁工业大学 | Preparation method and application of broadleaf wood dissolving pulp |
| CN114990917A (en) * | 2022-05-19 | 2022-09-02 | 华南理工大学 | Cooking method for preparing moso bamboo lyocell fiber grade dissolving pulp |
| CN117364525A (en) * | 2023-10-08 | 2024-01-09 | 泰盛科技（集团）股份有限公司 | Bamboo fluff pulp board and preparation method thereof |
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