CN107604726B - Method for treating papermaking pulp by using compound enzyme liquid - Google Patents
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- CN107604726B CN107604726B CN201710859395.4A CN201710859395A CN107604726B CN 107604726 B CN107604726 B CN 107604726B CN 201710859395 A CN201710859395 A CN 201710859395A CN 107604726 B CN107604726 B CN 107604726B
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A method for treating papermaking pulp by using compound enzyme liquid relates to a method for treating papermaking pulp. The invention aims to solve the problems that the effect of degrading lignin by using multiple enzymes of biological enzyme treated paper pulp in the biological enzyme treated paper pulp is not ideal and the bleaching effect of the enzymes is poor. The lignin degradation rate of the invention can reach about 49%. The whiteness of the treated bleaching pulp can reach 70-85%.
Description
Technical Field
The present invention relates to a method of treating papermaking pulp.
Background
The raw materials adopted in the existing papermaking industry are biomass materials, such as wood, straws, bamboo and the like, the biomass materials contain a large amount of lignin, hemicellulose and cellulose, the lignin is thermoplastic substances, the papermaking adopts cellulose and partial hemicellulose in plant fiber raw materials, and the lignin plays a role of a binder in the fiber raw materials, so that the fiber raw materials cannot be dispersed into single fibers, the combination of paper sheets is realized through hydrogen bond combination among the fibers, and the existence of the lignin enables the paper to be easily yellowed. Thus, most of the lignin is removed during the paper making process, especially in the preparation of pulp.
At present, two main technical routes for papermaking and pulping exist. 1. Chemical pulping method, addition of assistant and adjustment of process pairs
And (5) recycling the polluted dirt. 2. The biological pulping method adopts the biological pulping technology to reduce pollution from the source. For the former, the following: the pollution problem is mainly solved by an international common technology, namely an alkali recovery system, but the alkali recovery system still has the problems of large investment, high treatment cost, secondary pollution of white mud and the like. For the latter: the biological pulping technology is a novel pulping technology which is greatly concerned and developed by experts, scholars and enterprises in recent years, reduces pollution from the source, improves the utilization rate of raw materials, and can convert black liquor after biological treatment into organic fertilizer again for secondary utilization.
The existing biological pulping methods mainly comprise two types: one is to adopt microorganisms to directly treat raw materials; one is to treat the raw material with enzymes.
The invention adopts enzyme to treat raw materials, such as CN1616758A, the invention name is biological pulping process; publication number
Is CN1421570A, is named as a method for enzymatic pulping of grass raw materials and other patents, and has the main defects that: the cost of the enzyme solution is high, and the enzyme solution does not account for the cost advantage in industrial production; meanwhile, the damage of ligninase, xylanase and hemicellulase to corresponding components is difficult to control, and lignin, xylan and hemicellulose can be excessively removed to influence the yield of paper pulp.
The patent with publication number CN 101914510A and title of invention relates to a production method of alkaline pectinase and its application in paper-making and pulping, and discloses an alkaline pectinase and its application in paper-making and pulping, i.e. after the paper-making raw material is acid-soaked, it is soaked in alkaline pectinase liquor, and after the enzyme treatment, it is cooked in a cooking pot. However, the process is complicated, the raw materials need to be subjected to enzyme treatment after being subjected to pickling and alkali leaching, and the following disadvantages exist: firstly, the enzyme species are single, and the enzyme soaking time is long; secondly, new equipment is required to be added
Then, the process is carried out; and thirdly, acid leaching and alkali leaching steps are required to be added, pollution is increased, and the industrial production and use are not facilitated.
In addition, the complex enzyme used at present is only used after combining a plurality of enzymes, the content of related auxiliary agents for adding the enzymes is rarely related, and the existing enzymes are only combined together by a plurality of enzymes with similar functions and have single effect. The lignin removal effect is not ideal, and the lignin removal rate can only be about 30 percent generally.
At present, ligninase is widely used, which is a general name of a class of enzymes with the capacity of catalyzing the oxidative degradation of lignin, catalyzes oxidation-reduction reaction, is called as oxidoreductase in a systematic name and is called as dehydrogenase in a common name, and comprises four components: laccase, namely the systematic name of the oxidoreductase, acts on the oxidation reaction of o-quinol and p-quinol, aminophenol and the phenylenediamine; the lignin peroxidase, namely a system name of lignin hydrogen peroxide oxidation reductase, catalyzes the oxidation reaction of lignin; manganese peroxidase, namely a system name of divalent manganese hydrogen peroxide redox enzyme, catalyzes the reaction of oxidizing divalent manganese into trivalent manganese, and is lignin oxidative degradation; diarylpropane peroxidase is also known as ligninase I, a system known as diarylpropane: oxygen, hydrogen peroxide, oxidizes reductases, catalyzing the cleavage of carbon-carbon bonds and the oxidation of benzyl alcohol to aldehydes or ketones, which are many of the typical compounds of interest.
The ligninase has strong degradation capability on lignin and various organic matters, especially artificially synthesized organic pollutants, and has the characteristics of high spectrum, high efficiency, low consumption, high applicability and the like. This particular degradation mechanism has shown great application prospects in the feed industry, chemical industry, coal chemistry and environmental protection, and has attracted extensive attention in both academia and industry.
How to better exert the function of the enzyme and perform synergistic action with other enzymes is an urgent problem to be solved.
In addition, bleaching is performed after lignin removal, because most raw materials used for papermaking are natural polymer organic matters, the main components of the raw materials are cellulose, hemicellulose, lignin and the like, and the raw materials not only contain carbonyl, unsaturated double-structure and conjugated system chromophoric groups, but also contain chromophoric groups such as hydroxyl groups. The organic combination of the chromophoric groups in the lignin structure and the small amount of brass, lignan and stilbene structures makes the wood present rich and colorful colors. However, the lignin removal process can only achieve a single property, and for example, after cooking removal, a bleaching process is required. This is because the prior lignin removal process cannot combine the bleaching process with the prior lignin removal process to achieve a good bleaching effect. And the strength of the cellulose is very easy to be damaged in the existing removing process.
How to improve the effect of the biological enzyme in the bleaching process does not have a good technology at present.
Disclosure of Invention
The invention aims at the problems that the effect of degrading lignin by using multiple enzymes of the biological enzyme treated paper pulp in the biological enzyme treated paper pulp is not ideal and the bleaching effect by using the enzymes is poor. And provides a method for treating papermaking pulp by using the compound enzyme liquid.
The invention relates to a method for treating papermaking paper pulp by using compound enzyme liquid, which adopts a biological pulping method in the pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: introducing air at the temperature of 20-60 ℃ and the pH of 2-7.0, performing enzymolysis for 36-60 h, treating the composite enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 30-50;
wherein the enzyme activity of laccase in the complex enzyme is 50U/m L-2000U/m L, the enzyme activity of lignin peroxidase is 50U/m L0-1000U/m L1, the enzyme activity of manganese peroxidase is 50U/m L2-2000U/m L3, the enzyme activity of pectinase is 100U/m L4-1000U/m L5, the enzyme activity of cellulase is 100U/m L6-1000U/m L7, the enzyme activity of amylase is 100U/m L8-1000U/m L9, the enzyme activity of pepsin is 100U/m L-1000U/m L, the enzyme activity of papain is 100U/m L-1000U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L and the enzyme activity of peroxidase is 50U/m L-2000U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 1-10 mM MnSO40.1 to 2mM of FeSO40.1 to 6mM of CuSO41 to 8mM Na2SO30.1-2 mM sodium dithionite and 0.08 g/L-0.15 g/L of Tween 80;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 10-30;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L-3000U/m L, the enzyme activity of mannase is 1500U/m L-2000U/m L, the enzyme activity of catalase is 500U/m L-1000U/m L, the enzyme activity of laccase is 50U/m L-2000U/m L, and the enzyme activity of alkaline pectinase is 500U/m L-1500U/m L;
the auxiliary agent of the bleaching enzyme is 0.08 g/L-0.15 g/L N-hydroxyphthalimide or hydroxamic acid.
The invention relates to a method for treating papermaking paper pulp by using compound enzyme liquid, which adopts a biological pulping method in the pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: introducing air at the temperature of 20-48 ℃ and the pH of 2-6.0, performing enzymolysis for 36-60 h, treating the composite enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 30-50;
wherein the enzyme activity of laccase in the complex enzyme is 50U/m L-2000U/m L, the enzyme activity of lignin peroxidase is 50U/m L0-1000U/m L1, the enzyme activity of manganese peroxidase is 50U/m L2-2000U/m L3, the enzyme activity of pectinase is 100U/m L4-1000U/m L5, the enzyme activity of cellulase is 100U/m L6-1000U/m L7, the enzyme activity of amylase is 100U/m L8-1000U/m L9, the enzyme activity of pepsin is 100U/m L-1000U/m L, the enzyme activity of papain is 100U/m L-1000U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L, and the enzyme activity of horseradish peroxidase is 50U/m L-2000U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 1-10 mol/L MnSO41-3 g/L ascorbic acid, 1-2 g/L glucose, 1-2 g/L alginate, 1-2 g/L pectin, 1-2 mol/L KH2PO40.1 to 1.0 g/L g/g of ZnSO40.01-0.1 g/L H2BO31-2 g/L g of NaCl and 1-5 g/L g of glutathione;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 10-30;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L-3000U/m L, the enzyme activity of mannanase is 1500U/m L0-2000U/m L1, the enzyme activity of catalase is 500U/m L2-1000U/m L3, the enzyme activity of laccase is 50U/m L-2000U/m L, the enzyme activity of alkaline pectinase is 500U/m L-1500U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L, and the enzyme activity of horseradish peroxidase is 50U/m L-2000U/m L;
the auxiliary agent of the bleaching enzyme is 0.08 g/L-0.15 g/L N-hydroxyphthalimide or hydroxamic acid.
The papermaking raw material is wood chips or grass plants (such as reed, bamboo, mango straw, wheat straw, Chinese alpine rush, sorghum straw, bagasse and the like) of needle-leaved tree wood (such as larch, red pine, Chinese red pine, Yunnan pine, camphor pine and the like) or broad-leaved tree wood (such as poplar, birch, eucalyptus and the like).
In the using process of the complex enzyme or bleaching enzyme, according to the actual situation, in order to exert the best effect of the complex enzyme or bleaching enzyme, various enzymes in the complex enzyme or bleaching enzyme are added separately, namely, a plurality of enzymes are added firstly and then react for a period of time, and then the rest enzymes are added.
The invention has the following beneficial effects:
the invention degrades lignin by adding amylase to cooperate with laccase, manganese peroxidase and the like, and decomposes the extensin existing in the wood by adding pepsin and papain, so that the enzyme degrading lignin can better contact the lignin, removes the lignin as much as possible, and the added pectinase can decompose pectin, dissolve and soften intercellular layers of tissues, dissociate fiber bundles, and finally turn the paper pulp into dissociated fiber. In order to better improve the degradation effect, the metal inducers such as Mn, Fe, Cu and the like are added to have good induction excitation effect on manganese peroxidase and lignin peroxidase, and have good degradation effect on non-phenolic aromatic hydrocarbon polymers (occupying the main components in the lignin) in the lignin. The addition of the surfactant Tween 80 enables laccase to be better adsorbed to lignin, and the enzymolysis effect is further improved. The lignin degradation rate of the invention can reach about 49%.
In addition, the invention creatively adopts glyoxal dehydrogenase and horseradish peroxidase to produce hydrogen peroxide, and the hydrogen peroxide carries out catalytic reaction in the presence of laccase, manganese peroxidase and lignin peroxidase, so that the degradation effect of the enzyme is improved, no additional hydrogen peroxide is needed to be introduced, and the produced hydrogen peroxide can play a role in bleaching paper pulp;
the added xylanase and mannanase mainly inhibit the action of re-precipitated xylan partially covering residual lignin after cooking, and improve the accessibility of lignin to bleaching chemical (such as chlorine dioxide) used in the post-bleaching process through degradation of the xylanase and mannanase.
After the added N-hydroxyphthalimide or hydroxamic acid is combined with alkaline pectinase, xylanase, mannase and catalase, the unexpected effect is achieved on the bleaching of paper pulp, and the kappa number is reduced from 30 to 10 within 1-4 hours.
Moreover, another innovation of the invention is that: before bleaching enzyme is added, ultraviolet irradiation is carried out, the purpose is to generate negative oxygen ions, because the negative oxygen ions are unstable, electrons are easy to lose and become ozone, ozone is an important reaction substrate in the reaction process of catalase and the like, therefore, the activity of the biological enzyme is greatly increased due to the generation of the ozone, and the negative oxygen ions or the ozone can enter the interior of a wood structure to destroy the reticular macromolecules of the lignin of the wood and link other molecules to loosen, so the method not only improves the removal of the lignin, but also increases the bleaching effect, and can achieve the bleaching effect without subsequent bleaching treatment.
Ozone is an indispensable reaction substrate in the reaction process, so that the activity of the biological enzyme is greatly increased due to the generation of the ozone, and negative oxygen ions or the ozone can enter the interior of the wood structure to destroy the reticular macromolecules of the lignin of the wood and link other molecules to loosen, so that the method not only improves the removal of the lignin, but also increases the bleaching effect, and can achieve the bleaching effect without subsequent bleaching treatment.
The complex enzyme adjuvant can increase the activity of manganese peroxidase by 1.63 times, the activity of lignin peroxidase by 5.7 times, the activity of laccase by 4.1 times and the activity of cellulase by 1.3 times. In addition, the degradation rate of lignin in various raw materials in the aerobic composting process can be improved by 0.7-1.2 times.
Detailed Description
The first embodiment is as follows: in the method for treating papermaking pulp by using the compound enzyme liquid, a biological pulping method is adopted in the pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: introducing air at the temperature of 20-60 ℃ and the pH of 2-7.0, performing enzymolysis for 36-60 h, treating the composite enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 30-50;
wherein the enzyme activity of laccase in the complex enzyme is 50U/m L-2000U/m L, the enzyme activity of lignin peroxidase is 50U/m L0-1000U/m L1, the enzyme activity of manganese peroxidase is 50U/m L2-2000U/m L3, the enzyme activity of pectinase is 100U/m L4-1000U/m L5, the enzyme activity of cellulase is 100U/m L6-1000U/m L7, the enzyme activity of amylase is 100U/m L8-1000U/m L9, the enzyme activity of pepsin is 100U/m L-1000U/m L, the enzyme activity of papain is 100U/m L-1000U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L and the enzyme activity of peroxidase is 50U/m L-2000U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 1-10 mM MnSO40.1 to 2mM of FeSO40.1 to 6mM of CuSO41 to 8mM Na2SO30.1-2 mM sodium dithionite and 0.08 g/L-0.15 g/L of Tween 80;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 10-30;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L-3000U/m L, the enzyme activity of mannase is 1500U/m L-2000U/m L, the enzyme activity of catalase is 500U/m L-1000U/m L, the enzyme activity of laccase is 50U/m L-2000U/m L, and the enzyme activity of alkaline pectinase is 500U/m L-1500U/m L;
the auxiliary agent of the bleaching enzyme is 0.08 g/L-0.15 g/L N-hydroxyphthalimide or hydroxamic acid.
All values within the ranges expressed by the enzyme activity, the auxiliary agent, the ratio of the enzyme to the auxiliary agent, and the reaction conditions described in the present embodiment are applicable to the embodiment of the present embodiment.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: before adding bleaching enzyme mixed liquor, carrying out ultraviolet irradiation on the slurry obtained after enzymolysis of the compound enzyme liquid, and adding bleaching enzyme mixed liquor after irradiation, wherein the ultraviolet irradiation conditions are as follows: irradiating for 10-30 min under the ultraviolet light with the wavelength of 250-380 nm. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: before adding the bleaching enzyme mixed solution, carrying out ultraviolet irradiation on the slurry obtained after the enzymolysis of the compound enzyme solution, stopping the irradiation for 5-10 min, and then adding the bleaching enzyme mixed solution. The rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the laccase is a C. thermophilium laccase (commercially available). The rest is the same as the first embodiment.
The fifth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the glyoxal dehydrogenase and the horseradish peroxidase are fixed by a carrier and then are put into the paper pulp; the method for immobilizing the glyoxal dehydrogenase and the horseradish peroxidase carrier comprises the following steps:
(1) dissolving chitosan powder in an acetic acid aqueous solution, heating to 40-60 ℃ to completely dissolve chitosan, adding macroporous resin into the chitosan solution, reacting for 1-10 h, coating chitosan on the macroporous resin, adding the macroporous resin coated with chitosan into a mixed solution of NaOH aqueous solution and absolute ethyl alcohol, soaking for 30-120 min in the mixed solution of NaOH and absolute ethyl alcohol, carrying out suction filtration to obtain chitosan-coated macroporous resin particles, and finally fully washing with deionized water until the pH value is neutral, wherein the mass volume ratio of chitosan to acetic acid is 1 g: 1-5 m L, the mass ratio of chitosan to macroporous resin is 1: 1-10, the concentration of NaOH in the NaOH aqueous solution is 1-4 mol/L, and the volume ratio of NaOH aqueous solution to absolute ethyl alcohol is 4-8: 1;
(2) adding the chitosan-coated macroporous resin particles obtained in the step (1) into a glutaraldehyde aqueous solution with the mass concentration of 0.0025% -0.05%, placing the mixture in a shaking table at room temperature for crosslinking reaction for 10-60 min, washing the mixture with deionized water to be neutral, adding a double-enzyme solution, placing the mixture in the shaking table for oscillation for 1-6 h, washing away residual double-enzyme solution with deionized water, and refrigerating the mixture for later use, wherein the mass-to-volume ratio of the chitosan-coated macroporous resin particles to the double-enzyme solution is 1 g: 2-10 m L, and the double-enzyme solution is glyoxal dehydrogenase and horseradish peroxidase which are mixed according to the volume ratio of 1: 2-5.
The rest is the same as the first embodiment.
The sixth specific implementation mode: the first difference between the present embodiment and the specific embodiment is: the cellulase is heat-resistant neutral cellulase CelH 61. The heat-resistant neutral cellulase CelH61 is a cellulase disclosed in patent CN 103275956B. The rest is the same as the first embodiment.
The seventh embodiment: the first difference between the present embodiment and the specific embodiment is: preparing paper pulp from papermaking raw materials, and soaking the paper pulp in a compound enzyme solution under the following treatment conditions: the temperature is 30-60 ℃, the pH is 2.5-6.8, air is introduced, and enzymolysis is carried out for 36-60 h; after the compound enzyme liquid is treated, adding bleaching enzyme mixed liquid, and carrying out enzymolysis for 30-80 min at the pH of 7.0-9.0 and the temperature of 40-55 ℃; wherein the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the paper pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the paper pulp. The rest is the same as the first embodiment.
The specific implementation mode is eight: the pulping stage of the embodiment adopts a biological pulping method; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: the temperature is 20-48 ℃, the pH is 2-6.0, air is introduced, and enzymolysis is carried out for 36-60 h; after the compound enzyme liquid is treated, adding bleaching enzyme mixed liquid, and carrying out enzymolysis for 30-80 min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 30-50;
wherein the enzyme activity of laccase in the complex enzyme is 50U/m L-2000U/m L, the enzyme activity of lignin peroxidase is 50U/m L0-1000U/m L1, the enzyme activity of manganese peroxidase is 50U/m L2-2000U/m L3, the enzyme activity of pectinase is 100U/m L4-1000U/m L5, the enzyme activity of cellulase is 100U/m L6-1000U/m L7, the enzyme activity of amylase is 100U/m L8-1000U/m L9, the enzyme activity of pepsin is 100U/m L-1000U/m L, the enzyme activity of papain is 100U/m L-1000U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L, and the enzyme activity of horseradish peroxidase is 50U/m L-2000U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 1-10 mol/L MnSO41-3 g/L ascorbic acid, 1-2 g/L glucose, 1-2 g/L alginate, 1-2 g/L pectin, 1-2 mol/L KH2PO40.1 to 1.0 g/L g/g of ZnSO40.01-0.1 g/L H2BO31-2 g/L g of NaCl and 1-5 g/L g of glutathione;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 10-30;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L-3000U/m L, the enzyme activity of mannanase is 1500U/m L0-2000U/m L1, the enzyme activity of catalase is 500U/m L2-1000U/m L3, the enzyme activity of laccase is 50U/m L-2000U/m L, the enzyme activity of alkaline pectinase is 500U/m L-1500U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L, and the enzyme activity of horseradish peroxidase is 50U/m L-2000U/m L;
the auxiliary agent of the bleaching enzyme is 0.08 g/L-0.15 g/L N-hydroxyphthalimide or hydroxamic acid.
All values within the ranges expressed by the enzyme activity, the auxiliary agent, the ratio of the enzyme to the auxiliary agent, and the reaction conditions described in the present embodiment are applicable to the embodiment of the present embodiment.
The specific implementation method nine: the eighth embodiment is different from the eighth embodiment in that: preparing paper pulp from papermaking raw materials, and soaking the paper pulp in a compound enzyme solution under the following treatment conditions: introducing air at the temperature of 30-60 ℃ and under the condition that the pH value is 2.5-6.8, and carrying out enzymolysis for 36-60 h; after the compound enzyme liquid is treated, adding bleaching enzyme mixed liquid, and carrying out enzymolysis for 30-80 min at the pH of 7.0-9.0 and the temperature of 40-55 ℃; wherein the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the paper pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the paper pulp. The rest is the same as the embodiment eight.
The detailed implementation mode is ten: the eighth embodiment is different from the eighth embodiment in that: before adding bleaching enzyme mixed liquor, carrying out ultraviolet irradiation on the slurry after carrying out enzyme grafting on the compound enzyme liquid, and then adding bleaching enzyme mixed liquor, wherein the ultraviolet irradiation conditions are as follows: irradiating for 10-30 min under the ultraviolet light with the wavelength of 250-380 nm. The rest is the same as the embodiment eight.
The concrete implementation mode eleven: the eighth embodiment is different from the eighth embodiment in that: and before adding the bleaching enzyme mixed solution, carrying out ultraviolet irradiation on the slurry after carrying out enzyme grafting on the composite enzyme solution, stopping irradiation for 5-10 min, and then adding the bleaching enzyme mixed solution. The rest is the same as the embodiment eight.
The specific implementation mode twelve: the eighth embodiment is different from the eighth embodiment in that: the laccase is a C. thermophilium laccase (commercially available). The rest is the same as the embodiment eight.
The specific implementation mode is thirteen: the difference between the embodiment and the eighth embodiment is that the glyoxal dehydrogenase and the horseradish peroxidase are fixed by a carrier and then put into paper pulp; the method for immobilizing the glyoxal dehydrogenase and the horseradish peroxidase carrier comprises the following steps:
(1) dissolving chitosan powder in an acetic acid aqueous solution, heating to 40-60 ℃ to completely dissolve chitosan, adding macroporous resin into the chitosan solution, reacting for 1-10 h, coating chitosan on the macroporous resin, adding the macroporous resin coated with chitosan into a mixed solution of NaOH aqueous solution and absolute ethyl alcohol, soaking for 30-120 min in the mixed solution of NaOH and absolute ethyl alcohol, carrying out suction filtration to obtain chitosan-coated macroporous resin particles, and finally fully washing with deionized water until the pH value is neutral, wherein the mass volume ratio of chitosan to acetic acid is 1 g: 1-5 m L, the mass ratio of chitosan to macroporous resin is 1: 1-10, the concentration of NaOH in the NaOH aqueous solution is 1-4 mol/L, and the volume ratio of NaOH aqueous solution to absolute ethyl alcohol is 4-8: 1;
(2) adding the chitosan-coated macroporous resin particles obtained in the step (1) into a glutaraldehyde aqueous solution with the mass concentration of 0.0025% -0.05%, placing the mixture in a shaking table at room temperature for crosslinking reaction for 10-60 min, washing the mixture with deionized water to be neutral, adding a double-enzyme solution, placing the mixture in the shaking table for oscillation for 1-6 h, washing away residual double-enzyme solution with deionized water, and refrigerating the mixture for later use, wherein the mass-to-volume ratio of the chitosan-coated macroporous resin particles to the double-enzyme solution is 1 g: 2-10 m L, and the double-enzyme solution is glyoxal dehydrogenase and horseradish peroxidase which are mixed according to the volume ratio of 1: 2-5.
The rest is the same as the embodiment eight.
The specific implementation mode is fourteen: the eighth embodiment is different from the eighth embodiment in that: the cellulase is heat-resistant neutral cellulase CelH 61. The heat-resistant neutral cellulase CelH61 is a cellulase disclosed in patent CN 103275956B. The rest is the same as the embodiment eight.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The beneficial effects of the present invention are demonstrated by the following examples:
example 1
In the method for treating papermaking pulp by using the compound enzyme liquid, a biological pulping method is adopted in a pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: the temperature is 30-60 ℃, the pH is 2-7.0, air is introduced, and enzymolysis is carried out for 45 hours; after the compound enzyme liquid is treated, adding a bleaching enzyme mixed liquid, and carrying out enzymolysis for 30min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein the adding amount of the compound enzyme solution is 1 percent of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.5 percent of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 35;
wherein the enzyme activity of laccase in the complex enzyme is 1200U/m L, the enzyme activity of lignin peroxidase is 1000U/m L, the enzyme activity of manganese peroxidase is 1000U/m L, the enzyme activity of pectinase is 800U/m L, the enzyme activity of cellulase is 1000U/m L, the enzyme activity of amylase is 400U/m L, the enzyme activity of pepsin is 400U/m L, the enzyme activity of papain is 500U/m L, the enzyme activity of glyoxal dehydrogenase is 600U/m L, and the enzyme activity of horseradish peroxidase is 700U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 6.3mM MnSO40.7mM of FeSO42.0mM of CuSO42.5mM Na2SO30.8mM sodium dithionite and 0.10 g/L Tween 80;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 23;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L, the enzyme activity of mannase is 1600U/m L, the enzyme activity of catalase is 1000U/m L, the enzyme activity of laccase is 1000U/m L and the enzyme activity of alkaline pectinase is 1000U/m L;
the bleaching enzyme adjuvant is N-hydroxyphthalimide with a concentration of 0.10 g/L g.
In this embodiment, before adding the bleaching enzyme mixed solution, ultraviolet irradiation is performed on the slurry obtained after the enzymolysis of the complex enzyme solution, and the bleaching enzyme mixed solution is added after stopping irradiation for 5min, where the ultraviolet irradiation conditions are as follows: irradiating for 15min under the ultraviolet light with the wavelength of 250 nm-300 nm.
The laccase described in this example is a c. thermophilium laccase.
The cellulase in the embodiment is heat-resistant neutral cellulase CelH61, which is the cellulase disclosed in patent CN 103275956B.
The papermaking raw material described in this embodiment is wood chips of poplar.
The glyoxal dehydrogenase and the horseradish peroxidase are fixed by a carrier and then put into paper pulp; the method for immobilizing the glyoxal dehydrogenase and the horseradish peroxidase carrier comprises the following steps:
(1) dissolving chitosan powder in an acetic acid aqueous solution, heating to 40 ℃ to completely dissolve chitosan, adding macroporous resin into the chitosan solution, reacting for 1h, coating chitosan on the macroporous resin, adding the macroporous resin coated with chitosan into a mixed solution of NaOH aqueous solution and absolute ethyl alcohol, soaking for 30min in the mixed solution of NaOH and absolute ethyl alcohol, carrying out suction filtration to obtain chitosan-coated macroporous resin particles, and finally fully washing with deionized water until the pH value is neutral, wherein the mass-to-volume ratio of chitosan to acetic acid is 1 g: 5m L, the mass ratio of chitosan to macroporous resin is 1:10, the concentration of NaOH in the NaOH aqueous solution is 1 mol/L, and the volume ratio of the NaOH aqueous solution to the absolute ethyl alcohol is 4: 1;
(2) adding the chitosan-coated macroporous resin particles obtained in the step (1) into a glutaraldehyde aqueous solution with the mass concentration of 0.0025%, placing the mixture in a shaking table at room temperature for crosslinking reaction for 10min, washing the mixture to be neutral by deionized water, adding a double-enzyme liquid, placing the mixture in the shaking table for oscillation for 1h, washing away residual double-enzyme liquid by deionized water, and refrigerating the mixture for later use, wherein the mass-to-volume ratio of the chitosan-coated macroporous resin particles to the double-enzyme liquid is 1 g: 5m L, and the double-enzyme liquid is glyoxal dehydrogenase and horseradish peroxidase which are mixed according to the volume ratio of 1: 2.
The highest lignin degradation rate of the pulp treated by the embodiment can reach 49.2 percent. The whiteness of the bleached pulp is 73-81%.
The complex enzyme adjuvant can increase the activity of manganese peroxidase by 1.63 times, the activity of lignin peroxidase by 5.7 times, the activity of laccase by 4.1 times and the activity of cellulase by 1.3 times. In addition, the degradation rate of lignin in various raw materials in the aerobic composting process can be improved by 0.7-1.2 times.
Example 2
In the method for treating papermaking pulp by using the compound enzyme liquid, a biological pulping method is adopted in a pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: the temperature is 30-60 ℃, the pH is 2-7.0, air is introduced, and enzymolysis is carried out for 45 hours; after the compound enzyme liquid is treated, adding bleaching enzyme mixed liquid, and carrying out enzymolysis for 30min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein the adding amount of the compound enzyme solution is 1 percent of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.5 percent of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 35;
wherein the enzyme activity of laccase in the complex enzyme is 1200U/m L, the enzyme activity of lignin peroxidase is 1000U/m L, the enzyme activity of manganese peroxidase is 1000U/m L, the enzyme activity of pectinase is 800U/m L, the enzyme activity of cellulase is 1000U/m L, the enzyme activity of amylase is 400U/m L, the enzyme activity of pepsin is 400U/m L, the enzyme activity of papain is 500U/m L, the enzyme activity of glyoxal dehydrogenase is 600U/m L, and the enzyme activity of horseradish peroxidase is 700U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 5.0mM MnSO42 g/L ascorbic acid, 1 g/L glucose, 1 g/L alginate, 1 g/L pectin, 1 mol/L KH2PO40.3 g/L ZnSO40.05 g/L H2BO31 g/L of NaCl and 1 g/L of glutathione;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 20;
the bleaching enzyme comprises xylanase with the enzyme activity of 2500U/m L, mannanase with the enzyme activity of 1600U/m L, catalase with the enzyme activity of 1000U/m L, laccase with the enzyme activity of 1000U/m L, alkaline pectinase with the enzyme activity of 1000U/m L, glyoxal dehydrogenase with the enzyme activity of 1000U/m L and horseradish peroxidase with the enzyme activity of 1000U/m L;
the bleaching enzyme adjuvant is hydroxamic acid at a concentration of 0.10 g/L.
In this embodiment, before adding the bleaching enzyme mixed solution, ultraviolet irradiation is performed on the slurry after the enzyme grafting of the complex enzyme solution, and the bleaching enzyme mixed solution is added after stopping irradiation for 5min, where the ultraviolet irradiation conditions are as follows: irradiating for 15min under the ultraviolet light with the wavelength of 250 nm-300 nm.
The laccase described in this example is a c. thermophilium laccase.
The cellulase in the embodiment is heat-resistant neutral cellulase CelH61, which is the cellulase disclosed in patent CN 103275956B.
The papermaking raw material described in this example is rice straw.
The glyoxal dehydrogenase and the horseradish peroxidase are fixed by a carrier and then put into paper pulp; the method for immobilizing the glyoxal dehydrogenase and the horseradish peroxidase carrier comprises the following steps:
(1) dissolving chitosan powder in an acetic acid aqueous solution, heating to 40 ℃ to completely dissolve chitosan, adding macroporous resin into the chitosan solution, reacting for 1h, coating chitosan on the macroporous resin, adding the macroporous resin coated with chitosan into a mixed solution of NaOH aqueous solution and absolute ethyl alcohol, soaking for 30min in the mixed solution of NaOH and absolute ethyl alcohol, carrying out suction filtration to obtain chitosan-coated macroporous resin particles, and finally fully washing with deionized water until the pH value is neutral, wherein the mass-to-volume ratio of chitosan to acetic acid is 1 g: 5m L, the mass ratio of chitosan to macroporous resin is 1:10, the concentration of NaOH in the NaOH aqueous solution is 1 mol/L, and the volume ratio of the NaOH aqueous solution to the absolute ethyl alcohol is 4: 1;
(2) adding the chitosan-coated macroporous resin particles obtained in the step (1) into a glutaraldehyde aqueous solution with the mass concentration of 0.0025%, placing the mixture in a shaking table at room temperature for crosslinking reaction for 10min, washing the mixture to be neutral by deionized water, adding a double-enzyme liquid, placing the mixture in the shaking table for oscillation for 1h, washing residual double-enzyme liquid by deionized water, and refrigerating the mixture for later use, wherein the mass-to-volume ratio of the chitosan-coated macroporous resin particles to the double-enzyme liquid is 1 g: 5m L, and the double-enzyme liquid is glyoxal dehydrogenase and horseradish peroxidase which are mixed according to the volume ratio of 1: 2.
The lignin degradation rate of the pulp treated by the embodiment can reach 46 percent at most. The whiteness of the bleached pulp is 70-85%.
The complex enzyme adjuvant can increase the activity of manganese peroxidase by 1.63 times, the activity of lignin peroxidase by 5.7 times, the activity of laccase by 4.1 times and the activity of cellulase by 1.3 times. In addition, the degradation rate of lignin in various raw materials in the aerobic composting process can be improved by 0.7-1.2 times.
Claims (9)
1. A method for utilizing compound enzyme liquid to process the paper pulp of paper making, characterized by that to adopt the biological pulping method in the pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: introducing air at the temperature of 20-60 ℃ and the pH of 2-7.0, performing enzymolysis for 36-60 h, treating the complex enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein, the adding amount of the compound enzyme solution is 0.001 to 5 percent of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 30-50;
wherein the enzyme activity of laccase in the complex enzyme is 50U/m L-2000U/m L, the enzyme activity of lignin peroxidase is 50U/m L0-1000U/m L1, the enzyme activity of manganese peroxidase is 50U/m L2-2000U/m L3, the enzyme activity of pectinase is 100U/m L4-1000U/m L5, the enzyme activity of cellulase is 100U/m L6-1000U/m L7, the enzyme activity of amylase is 100U/m L8-1000U/m L9, the enzyme activity of pepsin is 100U/m L-1000U/m L, the enzyme activity of papain is 100U/m L-1000U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L and the enzyme activity of peroxidase is 50U/m L-2000U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 1-10 mM MnSO40.1 to 2mM of FeSO40.1 to 6mM of CuSO41 to 8mM Na2SO30.1-2 mM sodium dithionite and 0.08 g/L-0Tween 80 at 15 g/L;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 10-30;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L-3000U/m L, the enzyme activity of mannase is 1500U/m L-2000U/m L, the enzyme activity of catalase is 500U/m L-1000U/m L, the enzyme activity of laccase is 50U/m L-2000U/m L, and the enzyme activity of alkaline pectinase is 500U/m L-1500U/m L;
the auxiliary agent of the bleaching enzyme is 0.08 g/L-0.15 g/L N-hydroxyphthalimide or hydroxamic acid, the glyoxal dehydrogenase and the horseradish peroxidase are fixed by a carrier and then put into paper pulp, wherein the method for fixing the glyoxal dehydrogenase and the horseradish peroxidase carrier comprises the following steps:
(1) dissolving chitosan powder in an acetic acid aqueous solution, heating to 40-60 ℃ to completely dissolve chitosan, adding macroporous resin into the chitosan solution, reacting for 1-10 h, coating chitosan on the macroporous resin, adding the macroporous resin coated with chitosan into a mixed solution of NaOH aqueous solution and absolute ethyl alcohol, soaking for 30-120 min in the mixed solution of NaOH and absolute ethyl alcohol, carrying out suction filtration to obtain chitosan-coated macroporous resin particles, and finally fully washing with deionized water until the pH value is neutral, wherein the mass volume ratio of chitosan to acetic acid is 1 g: 1-5 m L, the mass ratio of chitosan to macroporous resin is 1: 1-10, the concentration of NaOH in the NaOH aqueous solution is 1-4 mol/L, and the volume ratio of NaOH aqueous solution to absolute ethyl alcohol is 4-8: 1;
(2) adding the chitosan-coated macroporous resin particles obtained in the step (1) into a glutaraldehyde aqueous solution with the mass concentration of 0.0025% -0.05%, placing the mixture in a shaking table at room temperature for crosslinking reaction for 10-60 min, washing the mixture with deionized water to be neutral, adding a double-enzyme solution, placing the mixture in the shaking table for oscillation for 1-6 h, washing away residual double-enzyme solution with deionized water, and refrigerating the mixture for later use, wherein the mass-to-volume ratio of the chitosan-coated macroporous resin particles to the double-enzyme solution is 1 g: 2-10 m L, and the double-enzyme solution is glyoxal dehydrogenase and horseradish peroxidase which are mixed according to the volume ratio of 1: 2-5.
2. The method for treating papermaking pulp by using compound enzyme liquid according to claim 1, characterized in that before adding bleaching enzyme mixed liquid, the pulp after enzymolysis of compound enzyme liquid is subjected to ultraviolet irradiation, and bleaching enzyme mixed liquid is added after irradiation, wherein the ultraviolet irradiation conditions are as follows: irradiating for 10min to 30min under the ultraviolet light with the wavelength of 250nm to 380 nm.
3. The method for treating papermaking pulp by using the compound enzyme solution according to claim 1, characterized in that before adding the bleaching enzyme mixed solution, ultraviolet irradiation is performed on the slurry after the compound enzyme solution is subjected to enzymolysis, and after stopping irradiation for 5-10 min, the bleaching enzyme mixed solution is added.
4. The method of treating papermaking pulp with the complex enzyme solution according to claim 1, wherein the laccase is a C.
5. The method of claim 1, wherein the cellulase is heat-resistant neutral cellulase CelH 61.
6. The method for treating papermaking pulp by using the compound enzyme liquid as claimed in claim 1, wherein the papermaking raw material is prepared into the pulp, and the compound enzyme liquid is placed into the pulp for soaking treatment under the following treatment conditions: introducing air at the temperature of 30-60 ℃ and the pH of 2.5-6.8, performing enzymolysis for 36-60 h, treating the compound enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.0 and the temperature of 40-55 ℃; wherein, the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the paper pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the paper pulp.
7. A method for utilizing compound enzyme liquid to process the paper pulp of paper making, characterized by that to adopt the biological pulping method in the pulping stage; the specific process is as follows:
preparing papermaking raw materials into coarse pulp, and soaking the coarse pulp in a compound enzyme solution under the following treatment conditions: introducing air at the temperature of 20-48 ℃ and the pH of 2-6.0, performing enzymolysis for 36-60 h, treating the complex enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.5 and the temperature of 40-60 ℃; wherein, the adding amount of the compound enzyme solution is 0.001 to 5 percent of the dry weight of the coarse pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the coarse pulp;
the compound enzyme liquid contains compound enzyme and compound enzyme auxiliary agent; wherein the mass ratio of the complex enzyme to the complex enzyme auxiliary agent is 1: 30-50;
wherein the enzyme activity of laccase in the complex enzyme is 50U/m L-2000U/m L, the enzyme activity of lignin peroxidase is 50U/m L0-1000U/m L1, the enzyme activity of manganese peroxidase is 50U/m L2-2000U/m L3, the enzyme activity of pectinase is 100U/m L4-1000U/m L5, the enzyme activity of cellulase is 100U/m L6-1000U/m L7, the enzyme activity of amylase is 100U/m L8-1000U/m L9, the enzyme activity of pepsin is 100U/m L-1000U/m L, the enzyme activity of papain is 100U/m L-1000U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L, and the enzyme activity of horseradish peroxidase is 50U/m L-2000U/m L;
the complex enzyme adjuvant uses acetic acid as solvent and contains 1-10 mol/L MnSO41-3 g/L ascorbic acid, 1-2 g/L glucose, 1-2 g/L alginate, 1-2 g/L pectin, 1-2 mol/L KH2PO40.1 to 1.0 g/L g/g of ZnSO40.01-0.1 g/L H2BO31-2 g/L g of NaCl and 1-5 g/L g of glutathione;
the bleaching enzyme mixed liquor contains bleaching enzyme and auxiliary agent of bleaching enzyme; wherein the mass ratio of bleaching enzyme to bleaching enzyme adjuvant is 1: 10-30;
the enzyme activity of xylanase in the bleaching enzyme is 2500U/m L-3000U/m L, the enzyme activity of mannanase is 1500U/m L0-2000U/m L1, the enzyme activity of catalase is 500U/m L2-1000U/m L3, the enzyme activity of laccase is 50U/m L-2000U/m L, the enzyme activity of alkaline pectinase is 500U/m L-1500U/m L, the enzyme activity of glyoxal dehydrogenase is 50U/m L-2000U/m L, and the enzyme activity of horseradish peroxidase is 50U/m L-2000U/m L;
the auxiliary agent of bleaching enzyme is 0.08 g/L-0.15 g/L N-hydroxyphthalimide or hydroxamic acid.
8. The method for treating papermaking pulp by using the compound enzyme liquid as claimed in claim 7, wherein the papermaking raw material is prepared into the pulp, and the compound enzyme liquid is placed into the pulp for soaking treatment under the following treatment conditions: introducing air at the temperature of 30-60 ℃ and the pH of 2.5-6.8, performing enzymolysis for 36-60 h, treating the compound enzyme solution, adding a bleaching enzyme mixed solution, and performing enzymolysis for 30-80 min at the pH of 7.0-9.0 and the temperature of 40-55 ℃; wherein, the adding amount of the compound enzyme solution is 0.001-5% of the dry weight of the paper pulp; the addition amount of the bleaching enzyme mixed liquor is 0.1-2% of the dry weight of the paper pulp.
9. The method for treating papermaking pulp by using compound enzyme liquid according to claim 7, characterized in that before adding bleaching enzyme mixed liquid, the pulp after enzymolysis of compound enzyme liquid is subjected to ultraviolet irradiation, and bleaching enzyme mixed liquid is added after irradiation, wherein the ultraviolet irradiation conditions are as follows: irradiating for 10min to 30min under the ultraviolet light with the wavelength of 250nm to 380 nm.
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| CN108505375B (en) * | 2018-03-07 | 2019-02-05 | 山东双圆生物科技有限公司 | Special efficacy composite biological enzyme preparation |
| CN108411672A (en) * | 2018-04-09 | 2018-08-17 | 山东双圆生物科技有限公司 | A kind of new process using special efficacy composite biological enzyme preparation bamboo chemical pulp |
| CN108707321A (en) * | 2018-04-20 | 2018-10-26 | 苏州凌科特新材料有限公司 | A kind of preparation method of compound light blocking film |
| CN111286789B (en) * | 2020-04-08 | 2022-11-15 | 四川玉竹麻业有限公司 | Complex enzyme degumming agent and degumming method |
| CN115404078B (en) * | 2022-09-06 | 2024-02-02 | 太原师范学院 | A method for preparing antioxidants by co-degrading lignin with ionic liquid-complex enzyme |
| CN117887693B (en) * | 2023-12-28 | 2024-10-01 | 河北秸润农业科技有限公司 | Preparation and application methods of novel wheat straw pulping catalyst |
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| US7125471B2 (en) * | 2001-11-29 | 2006-10-24 | Buckman Laboratories International, Inc. | Papermaking process using enzyme-treated sludge, and products |
| CN1190555C (en) * | 2002-12-20 | 2005-02-23 | 山东大学 | Enzymatic straw material pulping process |
| CN1616758A (en) * | 2003-11-13 | 2005-05-18 | 中国印钞造币总公司 | Process for biologically pulping |
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| CN102345244A (en) * | 2010-08-05 | 2012-02-08 | 王凤忠 | Pulping and papermaking process through multiple-composition biological enzyme method |
| CN102174505B (en) * | 2011-01-14 | 2013-07-03 | 华南理工大学 | Preparation method of granular carrier immobilized bienzyme for treating papermaking white water |
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| CN103555702B (en) * | 2013-10-19 | 2015-12-09 | 沅江浣溪沙酶技术有限公司 | The production method of chemical-mechanical pulping complex enzyme liquid and application |
| CN103555701B (en) * | 2013-10-19 | 2016-04-27 | 沅江浣溪沙酶技术有限公司 | The production method of association with pulp bleaching complex enzyme liquid and application |
| CN105441412A (en) * | 2014-09-29 | 2016-03-30 | 湖南新鸿鹰生物工程有限公司 | Paper pulp bleaching compound enzyme and preparation method thereof |
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