CN112593435B - Method for improving papermaking quality by alkaline pectinase combined with chemical reagent degumming - Google Patents
Method for improving papermaking quality by alkaline pectinase combined with chemical reagent degumming Download PDFInfo
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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
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
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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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
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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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/006—Pulping cellulose-containing materials with compounds not otherwise provided for
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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
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
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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
- D21H17/005—Microorganisms or enzymes
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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
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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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
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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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The invention belongs to the technical field of papermaking, and relates to a biochemical combined degumming papermaking and pulping process, in particular to application of synergistic effect of alkaline pectinase and part of cationic additives in papermaking and pulping. The method comprises the steps of pretreating raw materials, soaking the raw materials in pulping waste liquor for a period of time after acid leaching, selecting pulp treated by the joint action of 3 cationic additives and alkaline pectinase, wherein the demand of cationic additives (CD) in a system can be reduced by 49.51%, the pulp whiteness can reach 81-87% after bleaching with chlorine dioxide, the breaking length can reach 6500-7400m, the paper quality is improved, the alkali consumption is reduced by 40-45%, and the production cost is saved by 15-30%.
Description
The technical field is as follows:
the invention belongs to the technical field of papermaking, and relates to a biochemical combined degumming papermaking and pulping process, in particular to application of synergistic effect of alkaline pectinase and part of cationic additives in papermaking and pulping.
Background art:
the rapid development of the current society brings great changes to the material consumption of various industries, and the requirements of the society on paper and paper products are increasing day by day in life and work. High quality and low cost of paper and paper products are new goals for the paper industry. The traditional chemical pulping process has the defects of high energy consumption, high risk, high cost, low yield, low paper fiber strength, easy generation of pollutants difficult to treat in the process and the like. The biological pulping technology is a novel pulping technology which is valued by extensive professional scholars and enterprises in recent years, and has the advantages of high safety, simple process, low energy consumption, high utilization rate of raw materials, capability of treating generated pollutants into organic fertilizers for secondary utilization and the like.
There are two major types of bio-pulping internationally recognized at present: one is to directly treat the raw materials by microorganisms; one is to treat the raw material with enzyme preparation. The invention relates to a process for papermaking biological pulping, which adopts microorganisms to directly treat raw materials, for example, the publication number is CN 1683711A; the publication number is CN1420229A, the invention name is a pulping process of papermaking straw pulp; the publication number is CN101225614A, the invention name is a papermaking process method which replaces a chemical pulping process with a biological fermentation pulping method, and the main problems of the method are as follows: (1) The microbial treatment needs special environments, such as an aseptic environment, controllable temperature, humidity and ventilation quantity, and the like, so that the production cost is increased, and raw materials are possibly damaged to a certain extent; (2) The controllability of the raw materials in the microbial treatment process has certain limitation, and the conditions of poor uniformity of the treated raw materials and reduced pulping quality are easily caused; (3) The physical property and bleaching property of the paper pulp produced by the microbial treatment are lower than those of the paper pulp produced by the common chemical pulp, so that the produced paper quality is lower. The invention adopts enzyme preparation to treat raw materials, such as CN1616758A, the invention name is biological pulping process; the invention discloses a method for enzymatic pulping of grass raw materials with publication No. CN1421570A, and the main problems of the process are as follows: (1) The pure enzyme liquid is used for production, the use cost is high, and the cost advantage is not occupied in industrial production; (2) The damage degree of the pure enzyme liquid to the corresponding components of the raw materials is not effectively controlled at present, and the situation of removing too many corresponding components possibly exists, so that the yield of the paper pulp is reduced.
In the papermaking production process, a large amount of non-cellulose and other Dissolved Substances (DS) and Colloidal Substances (CS) in the slurry are accumulated more and more, and DCS substances (the general name of DS and CS) are deposited on the surface of equipment, so that the physical performance and the optical performance of paper are reduced, and the strength of the paper is influenced. DCS material has higher negative charge and can be preferentially combined with a cation retention aid, so that the efficiency of the retention aid is reduced, the production burden and cost of papermaking are increased, and the papermaking quality is reduced. The prior commonly used method for controlling DCS substances is a resin control method and a biological control method, wherein the resin control method utilizes some resin control agents to enable the resin control agents to exist in a system in an attached or stably dispersed mode, so that the resin control agents are prevented from being deposited on equipment to cause influence; the biological control method utilizes fungi and other strains or enzyme preparations to treat raw materials to react and prevent deposition from influencing the production process, but the biological control method is still in the development stage at present, the production cost and some uncontrollable factors are still problems to be solved urgently at present, so the resin control method is still the most common and effective method in the current industrial production, and the resin control agent with cheap cationic property is generally added before the cationic retention aid is added in the industrial production process to reduce the cost.
The invention content is as follows:
the invention aims to provide the application of the cationic additive in cooperation with alkaline pectinase to treat the raw material for degumming and pulping in the paper making process, the process effectively reduces the cationic demand of paper machine pulp and papermaking white water thereof, improves the retention and drainage performance of the pulp, reduces the using amount of a chemical control agent and biological enzyme, reduces the papermaking production cost and environmental pollution, has simple and easily-controlled process and high industrialization degree, and is beneficial to improving the product quality.
The invention adopts the following technical scheme to realize the purpose, after the pretreatment and the acid treatment of the papermaking raw material, a certain amount of cationic additive is added for cooking, then alkaline pectinase is added for enzyme treatment, and the cooking is continued after the enzyme treatment;
the addition amount of the cationic additive is as follows: 4.95-7.25% of cationic talcum powder, 0.15-0.85% of cationic starch and 0.02-0.07% of Cationic Polyacrylamide (CPAM) (wherein "%" refers to the weight ratio of the cationic additive in the raw materials);
furthermore, the cooking temperature is 50-65 ℃, the cooking time is 5-10min, and the mass ratio of the oven-dried raw materials to water is 1;
the enzyme treatment conditions were: the enzyme activity of the alkaline pectinase is 90-300U/mg, the temperature is 45-65 ℃, the pH value is 7.5-9.5, the enzyme soaking time is 50-160min, and the mass ratio of alkaline pectinase liquid (prepared according to the material-liquid ratio of 1.
Preferably, the enzyme treatment conditions are: alkaline pectinase (enzyme activity is 150-285U/mg), the temperature is 50-65 ℃, the pH value is 8.5-9.5, the enzyme soaking time is 120-150min, and the mass ratio of alkaline pectinase liquid (prepared according to a ratio of 1;
the cooking conditions after the enzyme treatment were: adding NaOH to a final concentration of 8-14%, at 120-150 deg.C for 40-120min;
preferably, after the paper making raw material is pretreated and subjected to acid treatment and before the cationic additive is treated, the paper making raw material is presoaked for 15 to 45 minutes by using pulping waste liquid, and the concentration of residual alkali in the waste liquid is adjusted to be 1.5 to 7.5g/L; the production cost can be reduced, the slurry can be recycled, and the waste discharge and the environmental pollution are reduced;
furthermore, the papermaking raw materials mainly comprise flax, wheat straw, corn straw or poplar and the like.
The pretreatment and the acid treatment are that the raw materials are crushed and then soaked in water, the pH value is adjusted to 5.5-5.8 by concentrated sulfuric acid, the temperature is raised to 55-65 ℃, the raw materials are soaked for 60-70min, and the raw materials are filtered and washed clean.
Has the advantages that:
by adopting the technical scheme of the invention, the cation demand of paper machine pulp and paper making white water thereof is effectively reduced, the Cation Demand (CD) in the system can be reduced by 49.51%, the retention and drainage performance of the pulp is improved, the consumption of chemical control agents and biological enzymes is reduced, the paper making production cost and the environmental pollution are reduced, the industrialization degree is high, and the product index meets the related national or industrial standard. The whiteness of the pulp treated by the scheme can reach 81-87%, the breaking length can reach 7000-7500m, the alkali consumption in the scheme process is reduced by 40-45%, and the production cost is saved by 15-30%.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the patent and do not delimit the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1:
in the embodiment, corn straws are used as raw materials. Firstly, crushing corn stalks into filaments with the length of 3-5cm by using a crusher, adding water according to the ratio of the absolute dry mass (g) of the corn stalks to the volume (mL) of the water of 7-9 (10 kg of the corn stalks: 71L of water in the embodiment), adjusting the pH value to 5.5 by using concentrated sulfuric acid, heating to 55 ℃, soaking for 60min, filtering and washing cleanly.
In order to reduce the production cost, recycle the slurry and reduce the waste discharge and environmental pollution, the invention uses the pulping waste liquid for presoaking for 35min before the cationic additive is treated after the pretreatment and the acid treatment of the paper making raw materials, and the concentration of the residual alkali in the waste liquid is 2.5g/L.
Transferring the cleaned raw materials into a cooking pot, and then treating the slurry by using 3 cationic additives, namely cationic talcum powder, cationic starch and Cationic Polyacrylamide (CPAM), wherein the treatment conditions are as follows: the adding amount of the cationic talcum powder is 4.95 percent, the adding amount of the cationic starch is 0.6 percent, the adding amount of the cationic polyacrylamide is 0.03 percent, the mixture is steamed and boiled at 65 ℃ for 10min, and the mass ratio of the oven-dried raw material to water is 1.
Then adding alkaline pectinase, wherein the enzyme treatment conditions are as follows: soaking alkaline pectinase (with enzyme activity of 235U/mg) for 120min at 55 ℃ and under the condition of pH 8.5, wherein the oven-dry mass ratio of alkaline pectinase liquid (prepared according to the proportion of enzyme: water = 1).
The raw materials after the enzyme treatment are cooked in a cooking pot, and the cooking strips are as follows: the final concentration of NaOH is 8%, the temperature is 150 ℃, and the time is 50min.
And (3) after cooking, putting the pulp in a pot, filtering and extruding black liquor and waste liquid in the pulp, washing the pulp, spin-drying the pulp, detecting indexes, and sending the waste liquid into a waste liquid storage tank for pretreatment of the next raw material to realize recycling of the waste liquid.
The paper pulp prepared by the process has the yield of 56.74 percent, and the residual alkali: 10.3g/L, K value (KMnO) 4 Value) 9.6, average fiber length 0.91mm, reduction of the Cation Demand (CD) in the system (blank 1 without cationic additive compared to blank 1) 42.41% (473 μ eq/L in this example), reduction (blank 2 without alkaline pectinase, only cationic additive compared to blank 2) more than 10.86% of the cationic additive alone, pulp processing two timesThe bleaching equipment with chlorine oxide reacts for 15min at 70 ℃, the pulp whiteness (ISO) reaches 83.69 percent, and the fracture length is 6500m.
Example 2:
in the embodiment, flax is used as a raw material. Firstly, selecting flax with roots and tops removed, crushing the flax into small segments with the length of 6-8cm, adding water according to the ratio of absolute dry mass (g) of the flax to water volume (mL) of 1.
Transferring the cleaned raw materials into a cooking pot, and then treating the slurry by using 3 cationic additives, namely cationic talcum powder, cationic starch and Cationic Polyacrylamide (CPAM), wherein the treatment conditions are as follows: the additive amount of the cationic talcum powder is 6.80 percent, the additive amount of the cationic starch is 0.15 percent, the additive amount of the cationic polyacrylamide is 0.07 percent, the cooking temperature is 50 ℃, the cooking time is 8min, and the mass ratio of the oven-dried raw material to water is 1.
Then adding alkaline pectinase, wherein the enzyme treatment conditions are as follows: alkaline pectinase (enzyme activity 185U/mg), temperature 55 ℃, pH value 8.5, enzyme soaking time 120min, and the mass ratio of alkaline pectinase liquid (prepared according to the proportion of 1.
The raw materials after the enzyme treatment are cooked in a cooking pot, and the cooking strips are as follows: the final concentration of NaOH is 10%, the temperature is 150 ℃, and the time is 100min.
The paper pulp prepared by the process has the yield of 51.22 percent, and the residual alkali: 10.1g/L, K value (KMnO) 4 Value) 9.8, average fiber length 0.66mm, the Cation Demand (CD) in the system is reduced (blank 1 is not added with cation additive compared with blank 1) by 36.89% (523 mu eq/L in the embodiment), the reduction range (blank 2 is not added with alkaline pectinase and only added with cation additive compared with blank 2) is higher than 7.33% of that only added with cation additive), the pulp whiteness (ISO) reaches 81.63% after the pulp is reacted for 15min by chlorine dioxide bleaching equipment at 70 ℃, and the fracture length is 7100m.
The same as in example 1.
Example 3:
in this embodiment, poplar is used as a raw material. Firstly, peeling and cutting poplar into 10-12cm long small pieces, adding water according to the ratio of the absolute dry mass (g) of the poplar to the volume (mL) of the water of 1.
Transferring the cleaned raw materials into a cooking pot, and then treating the slurry by using 3 cationic additives, namely cationic talcum powder, cationic starch and Cationic Polyacrylamide (CPAM), wherein the treatment conditions are as follows: the adding amount of the cationic talcum powder is 7.25%, the adding amount of the cationic starch is 0.85%, the adding amount of the cationic polyacrylamide is 0.02%, the cooking temperature is 65 ℃, the cooking time is 10min, and the mass ratio of the oven-dried raw material to water is 1.
Then adding alkaline pectinase, wherein the enzyme treatment conditions are as follows: alkaline pectinase (enzyme activity 285U/mg), temperature 65 ℃, pH value 9.5, enzyme soaking time 150min, and the mass ratio of alkaline pectinase liquid (prepared according to the proportion of 1.
The raw materials after the enzyme treatment are cooked in a cooking pot, and the cooking strips are as follows: the final concentration of NaOH is 10%, the temperature is 150 ℃, and the time is 110min.
The paper pulp prepared by the process has the yield of 58.66 percent, and the residual alkali: 10.6g/L, K value (KMnO) 4 Value) 9.5, average fiber length 0.43mm, reduction of the Cationic Demand (CD) in the system (blank 1 without cationic additive compared to blank 1) 49.51% (421 μ eq/L in this example), reduction (blank 2 without alkaline pectinase and with cationic additive only compared to blank 2) higher than 22.81% with cationic additive only), pulp whiteness (ISO) 86.93% after 15min reaction in chlorine dioxide bleaching equipment, and a break length 7400m.
The same as in example 1.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. A method for degumming and pulping by using a cation additive and alkaline pectinase to treat raw materials in a papermaking process is characterized in that a certain amount of cation additive is added for cooking after pretreatment and acid treatment of papermaking raw materials, then alkaline pectinase is added for enzyme treatment, cooking is continued after enzyme treatment, waste liquid is discharged, and pulp is obtained after washing pulp;
the cationic additive accounts for the weight ratio of the raw materials and comprises the following additive amounts: 4.95-7.25% of cationic talcum powder, 0.15-0.85% of cationic starch and 0.02-0.07% of cationic polyacrylamide;
the cooking process after the cationic additive is added comprises the following steps: the cooking temperature is 50-65 ℃, the cooking time is 5-10min, and the mass ratio of the oven-dried raw materials to water is 1;
the enzyme treatment conditions were: the alkaline pectinase with enzyme activity of 90-300U/mg, the temperature is 45-65 ℃, the pH value is 7.5-9.5, the enzyme soaking time is 50-160min, and the mass ratio of alkaline pectinase liquid prepared according to the material-water ratio of 1;
the cooking conditions after the enzyme treatment were: adding NaOH to a final concentration of 8-14%, at 120-150 deg.C, and maintaining for 40-120min.
2. The method for degumming and pulping by treating a raw material with a cationic additive in cooperation with an alkaline pectinase in a papermaking process according to claim 1, wherein the pretreatment and the acid treatment are carried out by crushing the raw material, soaking in water, adjusting the pH value to 5.5-5.8 with concentrated sulfuric acid, heating to 55-65 ℃, soaking for 60-70min, filtering, and washing.
3. The method of degumming and pulping a paper making process by treating the raw material with a cationic additive in conjunction with an alkaline pectinase according to claim 1, wherein the paper making raw material is pre-treated and acid-treated, and the pulp is pre-soaked with the pulp waste liquor for 15-45min, after the cationic additive is treated, and the residual alkali concentration in the liquor is adjusted to 1.5-7.5g/L.
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| US5256252A (en) * | 1992-07-15 | 1993-10-26 | Nalco Chemical Company | Method for controlling pitch deposits using lipase and cationic polymer |
| US9051692B2 (en) * | 2009-01-06 | 2015-06-09 | Enzymatic Deinking Technologies, L.L.C. | Method of increasing enzyme stability and activity for pulp and paper production |
| CN101914510B (en) * | 2010-07-28 | 2011-08-31 | 沅江浣溪沙酶技术有限公司 | Alkaline pectinase production method and application in papermaking pulping |
| CN104047206A (en) * | 2013-03-12 | 2014-09-17 | 金东纸业（江苏）股份有限公司 | Method for improving slurry-made paper strength, and slurry and paper prepared by the method |
| CN104562830B (en) * | 2014-07-09 | 2016-08-17 | 东莞玖龙纸业有限公司 | A kind of method for improving regenerated fiber cultural paper wet end retention rate |
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