CN103061181B - Complex enzyme preparation and technique for preparing dissolving pulp by using same - Google Patents
Complex enzyme preparation and technique for preparing dissolving pulp by using same Download PDFInfo
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- CN103061181B CN103061181B CN201210594596.3A CN201210594596A CN103061181B CN 103061181 B CN103061181 B CN 103061181B CN 201210594596 A CN201210594596 A CN 201210594596A CN 103061181 B CN103061181 B CN 103061181B
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Abstract
The invention relates to the technical field of production of regenerated cellulose fiber, in particular discloses a complex enzyme preparation applied in the preparation of dissolving pulp and a technique for preparing the dissolving pulp by using the enzyme preparation. The complex enzyme preparation is divided into a complex enzyme preparation I and a complex enzyme preparation II, wherein the complex enzyme preparation I mainly consists of feruloyl esterase, lipase and the like; and the complex enzyme preparation II mainly consists of xylanase, cellulase and the like. The complex enzyme preparation is applied in the technique for purifying alpha-cellulose and preparing the dissolving pulp; and the technique comprises the following steps of impurity removal for raw materials, enzyme method pretreatment, enzymolysis pulping, chelation treatment, alkali hydroxyl active oxygen cooking, acid treatment, washing, sand removal and pulp mixing. The method has the simple preparation technique, and adopts the complex enzyme preparation to treat the raw material pulp so as to effectively remove lignin, hemicellulose, pectin substance and waxiness and to reduce the degree of polymerization of the alpha-cellulose; the energy consumption is low under the normal pressure condition; the COD (Chemical Oxygen Demand) value of the pulping waste water is low; the yield of the dissolving pulp is high; the alpha-cellulose has high content and uniform degree of polymerization; and the production requirements of viscose can be satisfied.
Description
Technical field:
The invention belongs to regenerated celulose fibre manufacturing technology field, the invention discloses a kind of complex enzyme formulation and utilize this enzyme preparation purifying alpha-cellulose to prepare the technique of dissolving pulp.
Background technology:
Dissolving pulp can be for the production of products such as viscose, cellulose acetate, celluloid, carboxymethyl celluloses by chemical modification.This " special slurry " is the important source material of cellulose derivative product.Current most dissolving pulp is produced by improving sulfate process and sulphite process, and its target is in order to obtain highly purified cellulose, and has lost part cellulose by chemical modification, reduces yield, has improved production cost.Cotton and needlebush are the main raw materials that dissolving pulp is produced, and also have part to use leaf wood raw material, along with the development and utilization of bamboo fibre, utilize bamboo to remove its lignin, hemicellulose, produce the source that high pure cellulose also becomes dissolving pulp.
Due to China Shi Chanmian big country, and timber fractional yield is lower, so in China's dissolving pulp production field, the cotton linter of mainly take is prepared dissolving pulp as main.Its traditional pulping process comprises out bag, dedusting, boiling, washes the steps such as material, making beating, desanding, bleaching, papermaking.Wherein cotton linter boiling will be through feeding intake, once intensifications, once little steam bleeding, secondary temperature elevation, the little steam bleeding of secondary, heat up for three times, insulation, greatly steam bleeding, add warm water, these programs of batch turning.Boiling reaches the object of intensification and cellulose depolymerization by passing into high alkali liquid 17.5-18% and 160-175 ℃ high-temperature water vapor in rotary spherical digester, adopt the method for the little steam bleeding in intensification limit, limit to realize temperature and the gauge pressure requiring while being incubated.During boiling, cotton linter, at holding stage by saponification and emulsification, is removed the impurity such as grease, wax, gray iron, improves the relative amount of alpha-cellulose, fully destroys the primary wall of cotton fiber, reduces the cellulosic degree of polymerization, improves the reactivity worth of dissolving pulp.Pulp fiber length through boiling is still large at 6-10mm and intensity, and beating energy consumption is high.The bleaching of traditional handicraft adopts chlorine to float, and its process comprises pre-acid, chlorination, bleaching, dechlorination, acid treatment, washing, complex procedures, and " plain boiled water " pH that produces of institute is low and contain a large amount of chlorine elements, has increased sewage disposal difficulty.
In traditional handicraft digestion process, produce a large amount of black liquor, its COD is up to 10 * 10
4mg/L, residual alkali 10-15mg/L, mainly comprise lignin, hemicellulose, organic acid and a large amount of black organic matter, and low owing to making in sewage that raw material produces solid content calorific value with cotton linter, be not suitable for to its processing, having brought great inconvenience by the method that concentrated, burning, alkali reclaim, also to environment, brought very big pollution.Boiling simultaneously adopts High Temperature High Pressure, and the consumption of steam energy consumption is large.
In sum, traditional pulp-making of cotton linter industry is a high water consumption, highly energy-consuming, high pollution, high consumption alkali " four height " industry.Along with the raising gradually of environmental requirement, only have traditional THE TECHNICS IN PULPMAKING OF COTTON LINTER of improvement, reduce energy consumption, reduce and pollute, reduce chemicals consumption pulping and paper-making industry and could survival and development go down.
Summary of the invention
For the problems referred to above, the present invention proposes a kind of complex enzyme formulation prepared by dissolving pulp and technique of applying this enzyme preparation dissolving pulp of being applied to, this complex enzyme formulation is divided into complex enzyme formulation I and complex enzyme formulation II; Complex enzyme formulation I is mainly comprised of feruloyl esterase and lipase etc.; Complex enzyme formulation II is mainly comprised of zytase, cellulase etc.The technique that this complex enzyme formulation is applied to purifying alpha-cellulose and prepares dissolving pulp comprises the steps: that impurity removing, enzyme process preliminary treatment, enzymolysis making beating, chelation treatment, the boiling of alkaline hydroxyl activity oxygen, acid treatment, washing, desanding, papermaking can complete.Method preparation technology of the present invention is simple, by complex enzyme formulation, processing former slip can effectively remove lignin, hemicellulose, pectic substance and wax, reduce the degree of polymerization of alpha-cellulose simultaneously, and the method is the biochemical pulping process that biological enzyme is combined with chemical method, make the required temperature conditions of alpha-cellulose purifying and depolymerization from 170 ℃ of traditional alkaline boiling, be reduced to 80-130 ℃, greatly reduced reaction condition and energy consumption; And chemicals NaOH consumption is down to 5-15% from 17.5-18% and is made pulp-making waste-water COD value little, and dissolving pulp yield is high, the high and degree of polymerization homogeneous of alpha-cellulose content, can meet the production requirement of dissolving pulp and viscose for weaving.
One of object of the present invention is to provide a kind of complex enzyme formulation for cellulose purification and dissolving pulp conversion, this complex enzyme formulation is divided into complex enzyme formulation I and complex enzyme formulation II, and wherein each constituent of complex enzyme formulation I and weight percent content are: feruloyl esterase 0.1-5%, lipase 1-10%, pectase 1-10%, laccase 1-5%, antioxidant 0.5-2%, mould inhibitor 0.5-2%, pest repellant 0.1-0.5%, all the other are carrier;
Described each constituent of complex enzyme formulation II and weight percent content are: zytase 1-10%, cellulase 1-10%, dextranase 1-10%, arabinase 1-10%, antioxidant 0.5-2%, mould inhibitor 0.5-2%, pest repellant 0.1-0.5%, all the other are carrier;
Described carrier is soluble starch or dextrin or its mixture.
The optimum ratio that further inventor obtains is: the constituent of described complex enzyme formulation I and percentage by weight are: feruloyl esterase 0.2-2%, lipase 1-5%, pectase 1-5%, laccase 1-3%, antioxidant 0.5-1.5%, mould inhibitor 0.5-1.5%, pest repellant 0.1-0.3%, surplus are soluble starch;
Described complex enzyme formulation II constituent and percentage by weight are: zytase 1-5%, cellulase 1-5%, dextranase 1-5%, arabinase 1-5%, antioxidant 0.5-2%, mould inhibitor 0.5-2%, pest repellant 0.1-0.5%, surplus are soluble starch.
Wherein said antioxidant is: the mixture of one or more in Tea Polyphenols, ascorbic acid, phytic acid;
Wherein said mould inhibitor is polysaccharide adsorbent, can be one or both the mixture in trehalose, pulullan polysaccharide etc.; Wherein said pest repellant is wherein a kind of of arprinocid, Amprolium Hydrochloride;
In complex enzyme formulation I of the present invention, contain feruloyl esterase, can break the compact texture that forulic acid is connected with cellulose, hemicellulose, lignin, interrupt the ester bond in plant cell, make cotton linter short texture, expose the site of other enzyme effects, strengthen the action effect of other enzyme, be beneficial to soaking into of liquid simultaneously; Lipase in complex enzyme formulation I, pectase can reduce fat, pectic substance content in Cotton Pulp, reduce the hydrophobicity of cotton linter, make chemicals be more prone to infiltrate, and have reduced the consumption of NaOH consumption at fat, pectin.
Complex enzyme formulation II of the present invention contains hemicellulase (zytase, arabinase), cellulase, and hemicellulose in hemicellulose enzyme hydrolysis cotton linter, reduces its hemicellulose level; Endoglucanase in cellulase, exoglucanase, beta-glucosidase degraded cellulose reduce its fibre crystallinity under three coordinates mutually.Two kinds of enzymes are used in conjunction with has obtained splendid effect.
Another object of the present invention is to provide a kind ofly applies above-mentioned complex enzyme formulation in the technical scheme of dissolving pulp preparation process, utilize complex enzyme formulation to prepare the method for dissolving pulp, the method is the biochemical pulping process that utilizes biological enzyme to be combined with chemical method, mainly comprises the steps:
(1) impurity removing: cotton linter is sent into cyclone separator and remove the impurity in cotton linter;
(2) enzyme process preliminary treatment: adopting screw press is 5-15%(w/v by cotton linter according to slurry concentration) add water and mix, the pH of material is adjusted between 5.5-6.5; Described complex enzyme formulation I is added in slurry, and addition is the 0.1-5% of over dry material gross weight, under 35-60 ℃ of condition, processes 4-48h;
(3) enzymolysis making beating removal of impurities: adjust between the material pH to 4-6 after above-mentioned processing, described complex enzyme formulation II is added in above-mentioned slurry, addition is the 0.1-5% of over dry material gross weight, processes 4-48h under 35-60 ℃ of condition; Running water is adjusted slurry concentration to 3-3.5%(w/v), under 20-50 ℃ of condition, discongest 20-60min, adopt beater making beating; Making beating disposed slurry carries out recleaning desanding, in dense desander to enter to starch concentration be 1.5-2%(w/v), entering to starch pressure is 0.2-0.3MPa, enters afterwards low dense desander, concentration is 0.6-0.8%(w/v), pressure is 0.25-0.35MPa;
(4) chelation treatment: the slurry after making beating removal of impurities is according to total liquor ratio 1:8-12(w/v) add water, add chelating agent EDTA simultaneously, consumption is the 0.2-0.8%(w/w of relative over dry material gross weight), mix and regulate slurry pH between 3-9, process 30-90min at 50-80 ℃;
(5) alkaline hydroxyl activity oxygen digestion process: after chelation treatment, running water filtering stock is neutral to pH, adjusts slurry concentration at 40-60%(w/v) rear input in rotary spherical digester; NaOH is according to the 9-15%(w/w of relative over dry material gross weight) be made into the high alkali liquid of 50-100g/L, MgSO
4according to the 0.1-0.5%(w/w of relative over dry material gross weight) be made into solution, the H of 10-50g/L
2o
2according to the 1-9%(w/w of relative over dry material gross weight) add in rotary spherical digester successively, and according to total liquor ratio 1:3-12(w/v) add running water; Seal rotary 5-10min, makes slurry mix with chemical liquid; Then lentamente temperature is risen to 80-130 ℃, be incubated 60-150min after reaching temperature; After boiling completes, steam bleeding is cooling, emits afterwards slurry, and running water washs to pH neutral;
(6) acid treatment: the slurry that upper step is obtained mixes according to total liquor ratio 1:7-15 with water, adds 70-100g/L hydrochloric acid 2-6%(w/v), mix, at 50-90 ℃, process 30-90min, running water washs to pH neutral;
(7) wash, make the dregs of rice: the slurry after washing regulates the dense 0.2-1%(w/v of slurry), enter hydrocyclone, pressure is 274-350kPa, outlet pressure is 0-20kPa; After washing, enter pulp machine and make the dregs of rice.
The more concrete technology treatment step of biochemical legal system dissolving pulp of the present invention is as follows:
(1) impurity removing: cotton linter is opened to bag, sent into cyclone separator, because cotton fiber and impurity weight differ larger, large dust impurity falls into bottom cotton fiber and parts of fine small impurities is sent into spiral pressure bundle machine together with the wind, by cyclonic separation, by the large Impurity removals such as boll hull of the overwhelming majority, can effectively improve the pretreated efficiency of next step biology enzyme;
(2) enzyme process preliminary treatment: the concentration of adjusting former slip is 5-15%(w/v), the pH of material is adjusted between 5.5-6.5; Described complex enzyme formulation I is added in slurry, and addition is the 0.1-5% of over dry material gross weight, under 35-60 ℃ of condition, processes 4-48h;
Enzyme is processed rear lipase and is removed fatty 40-80wt% in cotton fiber, and pectase is removed pectic substance 40-80wt% in cotton linter; By electron microscopic observation, show that cotton fiber primary cell wall is evenly destroyed by feruloyl esterase, the microfibre of part S1 layer is destructurized;
(3) enzymolysis making beating removal of impurities: adjust between material pH to 4-6, described complex enzyme formulation II is added in above-mentioned slurry, addition is over dry material gross weight 0.1-5%, processes 4-48h under 35-60 ℃ of condition; Running water is adjusted slurry concentration 3-3.5%(w/v), under 20-50 ℃ of condition, discongest 20-60min, adopt beater making beating; Making beating disposed slurry carries out recleaning desanding, in dense desander to enter to starch concentration be 1.5-2%(w/v), entering to starch pressure is 0.2-0.3MPa, enters afterwards low dense desander, concentration is 0.6-0.8%(w/v), pressure is 0.25-0.35MPa;
Fibre length is shortened as 1-3mm by original 10-13mm; After enzymolysis fiber shorten, strength decreased, make beating energy consumption reduce 40-80%; Adopt selected desanding device, remove percentage of admixture and reach 30-70%, thereby reduced NaOH, the H of alkaline hydroxyl activity oxygen digestion process
2o
2consumption, reduced cost and the pollution to environment;
(4) chelation treatment: the slurry after making beating removal of impurities is according to total liquor ratio 1:8-12(w/v) add water, add chelating agent EDTA simultaneously, consumption is the 0.2-0.8%(w/w of relative over dry material gross weight), mix and regulate slurry pH between 3-9, process 30-90min at 50-80 ℃;
Because the hydrogen peroxide that needs to use in lower step is extremely unstable, in all steps, adopt chelating agent preliminary treatment slurry, remove the most transition metal ionss in slurry, the decomposition of hydrogen peroxide when reducing alkaline hydroxyl activity oxygen boiling; After chelation treatment, alkaline hydroxyl activity oxygen boiling disposed slurry whiteness improves 30-60% with comparing without the slurry of chelation treatment;
(5) alkaline hydroxyl activity oxygen atmospheric cooking process: after chelation treatment, running water filtering stock is neutral to pH, adjusts slurry concentration at 40-60%(w/v) rear input in rotary spherical digester; NaOH is according to the 9-15%(w/w of relative over dry material gross weight) be made into the high alkali liquid of 50-100g/L, MgSO
4according to the 0.1-0.5%(w/w of relative over dry material gross weight) be made into solution, the H of 10-50g/L
2o
2according to the 1-9%(w/w of relative over dry material gross weight) add in rotary spherical digester successively, and according to total liquor ratio 1:3-12(w/v) add running water; Seal rotary 5-10min, makes slurry mix with chemical liquid; Then lentamente temperature is risen to 80-130 ℃, be incubated 60-150min after reaching temperature; After boiling completes, steam bleeding is cooling, emits afterwards slurry, and running water washs to pH neutral;
Hydrogen peroxide easily decomposes under high-temperature alkaline condition, generates hydroxyl radical free radical and active oxygen radical, and reaction equation is as follows:
Wherein Hydroxyl radical HO oxidizing potential is 2.8V, is the oxidant that occurring in nature is only second to fluorine.Its character is active, can rapid permeability oxidized fibre, reduce the fiber degree of polymerization; And hydrogen is crossed oxygen anion HOO
-tool nucleation, can make it to become colourless group effectively in conjunction with the chromophoric group structure in lignin, and dissolved lignin to a certain extent;
Alkalescence hydroxyl activity oxygen atmospheric cooking disposed slurry alpha-cellulose content 95-96%, the degree of polymerization 500 ± 20, ash content (725 ℃) 0.18-0.25%, iron content 25-35mg/Kg; Adopt alkaline hydroxyl activity oxygen atmospheric cooking, the hydrogen that its digestion process produces is crossed oxygen anion can be effectively in conjunction with the chromophoric group structure in lignin, make it to become colourless group, and dissolved lignin to a certain extent, make pulp brightness reach 85-90%, a step pulping, reduce traditional handicraft bleachery, stop chlorine and float, shortened technological process, avoided the pollution of chlorine to environment; Simultaneously the low 100-1000 of the more traditional black liquor of Colority of Sewage Water of boiling gained doubly and be yellow, COD
crvalue is at 6000-17000mg/L, far below traditional black liquor; Simultaneously this technique boiling temperature is at 80-130 ℃, atmospheric cooking, and more traditional 170 ℃, boiling under 0.7Mpa condition, reduces energy consumption 30-50%.
(6) acid treatment: the slurry that upper step is obtained mixes according to total liquor ratio 1:7-15 with water, adds 70-100g/L hydrochloric acid 2-6%(w/v), mix, at 50-90 ℃, process 30-90min, running water washs to pH neutral;
(7) wash, make the dregs of rice: the slurry after washing regulates the dense 0.2-1%(w/v of slurry), enter hydrocyclone, pressure is 274-350kPa, outlet pressure is 0-20kPa; After washing, enter pulp machine and make the dregs of rice.
The operation of the adjusting pH mentioning in above-mentioned technique, all adopts conventional dose of the prior art, does not repeat them here.
Through dissolving pulp alpha-cellulose content >=95.0% of this explained hereafter, ash content (725 ℃)≤0.10%, iron content≤20mg/Kg, whiteness >=88%, inhales base number >=500%, reactivity worth≤100s.According to standard FZ51001-2009, through the dissolving pulp of this explained hereafter, meet and be better than short rayon fiber Wesy pulp Grade A standard.
The above-mentioned method of utilizing complex enzyme formulation to produce dissolving pulp, the optimum condition of each process is:
(1) impurity removing: cotton linter is opened to bag, enter cyclone separator and remove impurity larger in cotton linter;
(2) enzyme preliminary treatment: adopting screw press is 5-15%(w/v by cotton linter according to slurry concentration) add water and mix; The pH of material adjusts between 5.5-6.5; Described complex enzyme formulation I is added in slurry, and addition is the 0.2-0.5% of over dry material gross weight, under 45-55 ℃ of condition, processes 12-48h, removes hemicellulose, lignin, wax and pectic substance in slurry;
(3) enzymolysis making beating removal of impurities: adjust between material pH to 4-6, described complex enzyme formulation II is added in above-mentioned slurry, addition is over dry material gross weight 0.1-0.5%, processes 12-48h under 45-55 ℃ of condition; Running water is adjusted slurry concentration 3-3.5%(w/v), under 20-40 ℃ of condition, discongest 20-60min, adopt a watt power beater making beating; Making beating disposed slurry carries out recleaning desanding, in dense desander to enter to starch concentration be 1.5-2%(w/v), entering to starch pressure is 0.2-0.3MPa, enters afterwards low dense desander, concentration is 0.6-0.8%(w/v), pressure is 0.25-0.35Mpa, edulcoration rate reaches 20-50%;
(4) chelation treatment: the slurry after making beating removal of impurities is according to total liquor ratio 1:9-12(w/v) add water, add chelating agent EDTA simultaneously, consumption is the 0.2-0.6%(w/w of relative over dry material gross weight), mix and regulate slurry pH between 3-7, at 60-80 ℃, process 60-90min, running water washing is to neutral;
(5) alkaline hydroxyl activity oxygen digestion process: above-mentioned slurry is adjusted slurry concentration and dropped in rotary spherical digester after 40-60%; NaOH is according to the 9-15%(w/w of relative over dry material gross weight) be made into the high alkali liquid of 50-100g/L, MgSO
4according to the 0.1-0.5%(w/w of relative over dry material gross weight) be made into solution, the H of 10-50g/L
2o
2according to the 1-9%(w/w of relative over dry material gross weight) add in rotary spherical digester successively, and according to total liquor ratio 1:3-8(w/v) add running water.Seal rotary 5-10min, makes slurry mix with chemicals.Then slowly temperature is risen to 100-130 ℃, be incubated 90-150min after reaching temperature.After boiling completes, steam bleeding is cooling, emits afterwards slurry, and running water washs to pH neutral;
(6) acid treatment: the slurry that upper step is obtained mixes according to total liquor ratio 1:9-12 with water, adds 70-90g/L hydrochloric acid 3-6%(w/v), mix, at 60-90 ℃, process 40-70min, running water washs to pH neutral;
(7) wash, make the dregs of rice: the slurry after washing regulates the dense 0.2-1% of slurry, enters hydrocyclone, and pressure is 274-350kPa, and outlet pressure is 0-20kPa.Washing disposed slurry is sent into pulp machine.
Under above-mentioned optimum condition, dissolving pulp yield >=85%, wherein alpha-cellulose content >=95.0%, ash content (725 ℃)≤0.08%, iron content≤15mg/Kg, whiteness >=88%, inhale base number >=500%, reactivity worth≤50s, the degree of polymerization 500 ± 20 is higher than the requirement of dissolving pulp Grade A weight.
The production technology raw material of above-mentioned dissolving pulp pulp is cotton linter.
Adopt above-mentioned process conditions to prepare dissolving pulp, have advantages of following outstanding:
1, in complex enzyme formulation I, contain feruloyl esterase, can break the compact texture that forulic acid is connected with cellulose, hemicellulose, lignin, interrupt the ester bond in plant cell, make cotton linter short texture, expose the site of other enzyme effects, strengthen the action effect of other enzyme, be beneficial to soaking into of liquid simultaneously;
2, the lipase in complex enzyme formulation I, pectase can reduce fat, pectic substance content in Cotton Pulp, have effectively strengthened the chemical oxidation effect of liquid, improve chemicals effective rate of utilization.
3, each enzyme interacting in complex enzyme formulation II, can reduce the degree of polymerization of pulp, makes the fibre length of pulp shorten simultaneously, improves beatability, and beating energy consumption reduces 40-80%;
4, adopt the boiling of alkaline hydroxyl activity oxygen, reaction temperature 100-130 ℃, mild condition, saves high pressure-temperature condition, further reduces energy consumption;
Traditional handicraft sodium hydroxide concentration is in 17.5-18% left and right, and this technique has reduced 25-50% compared with traditional handicraft, greatly reduces the consumption of chemicals; Traditional handicraft is at 160-175 ℃ of autoclaving 2.5h, and this technique boiling 60-150min under 90-130 ℃ of normal pressure reduces energy consumption 30-50%; Traditional handicraft boiling, bleaching are carried out in two steps, and adopt chlorine to float, and environmental pollution is larger; And this process using hydrogen peroxide reinforced alkaline boiling and bleaching one, shortened the step of producing, and its Colority of Sewage Water, residual alkali be all far below traditional handicraft, its COD is 10000-20000mg/L, compared with conventional method, reduce more than 60%, greatly reduce the difficulty of sewage disposal.
5, the pulp yield that this technique obtains is high, reaches more than 85%; Especially reactivity worth is less than 50s, alpha-cellulose content higher than 95%, and whiteness is higher than 88%, higher than national dissolving pulp primes standard.
In sum, production technology of the present invention is simple, production process can carry out continuously and yield high, the most important thing is that it has reduced the use amount of energy consumption and chemicals, make produced black liquor be easy to process, thereby reduced the institute's pollution of the black liquor that produces to environment, more there is no white clay generation.
Figure of description
Fig. 1 tradition dissolving pulp preparation technology flow chart;
Fig. 2 process chart of the present invention.
The specific embodiment
Embodiment 1
A kind of complex enzyme formulation, complex enzyme formulation I and complex enzyme formulation II, consist of, wherein each constituent of complex enzyme formulation I and mass percentage content are: feruloyl esterase 0.3%, lipase 1%, pectase 1%, laccase 1%, antioxidant 0.5%, mould inhibitor 0.5%, pest repellant 0.1%, all the other are soluble starch;
Each constituent of complex enzyme formulation II and mass percentage content are: zytase 5%, cellulase 2%, dextranase 3%, arabinase 4%, antioxidant 0.5%, mould inhibitor 0.5%, pest repellant 0.1%, all the other are soluble starch;
The dissolving pulp production technology of applying above-mentioned complex enzyme formulation, specifically comprises the steps:
Cotton linter 6t after preliminary artificial dedusting, adjusts slurry concentration to 10%, adjusts the pH=6.5 of solution, adds complex enzyme I agent processed 12kg, processes 24h for 55 ℃.Adjusting material pH is 4, adds complex enzyme formulation II 12kg and process 12h under 40 ℃ of conditions.Running water is adjusted slurry concentration 3%(w/v afterwards), discongest 50min at 30 ℃, discongested rear making beating; Adopt recleaning desanding, in dense desander to enter to starch concentration be 2%, entering to starch pressure is 0.2MPa, entering afterwards low dense desander concentration is 0.8%, pressure is 0.25Mpa.By total liquor ratio 1:10, add water afterwards, add chelating agent EDTA18kg simultaneously, adjusting material pH is 3, at 60 ℃, processes 70min.Through the slurry washing of chelation treatment, to adjusting slurry dense after neutrality, be 50%, drop into rotary spherical digester; 780kgNaOH is made into the high alkali liquid of 60g/L, 24KgMgSO
4be made into 50g/L solution, 30%(w/w) H
2o
21.8t, adds water according to total liquor ratio 1:7.3 afterwards, 100 ℃ of boiling 2h.
Above-mentioned slurry is washed with water to after neutrality, adds 90g/L hydrochloric acid 180m
3, and add water according to total liquor ratio 1:10, at 60 ℃, process 70min.Then washing is to neutral, and papermaking is made the dregs of rice.
Alpha cellulose after testing: 95.2%, ash content (725 ℃): 0.03%, iron content: 11.3mg/Kg, whiteness: 88%, reactivity worth 50s, the degree of polymerization 520.
Boiling density wastewater 40t, 500 times of colourities, slightly yellow, COD
crfor 7500mg/L, BOD
5for 3200mg/L; The waste water that the steps such as enzyme processing, washing produce is 70t altogether, COD
crfor 500mg/L, BOD5 is 198mg/L.
Embodiment 2
A kind of complex enzyme formulation, complex enzyme formulation I and complex enzyme formulation II, consist of, wherein each constituent of complex enzyme formulation I and mass percentage content are: feruloyl esterase 0.5%, lipase 2%, pectase 1%, laccase 3%, antioxidant 2%, mould inhibitor 1.5%, pest repellant 0.3%, all the other are dextrin;
Each constituent of complex enzyme formulation II and mass percentage content are: zytase 4%, cellulase 1%, dextranase 2%, arabinase 1%, antioxidant 2%, mould inhibitor 2%, pest repellant 0.5%, all the other are soluble starch;
The dissolving pulp production technology of applying above-mentioned complex enzyme formulation, specifically comprises the steps:
The three class secondary cotton linter 6t after preliminary artificial dedusting that learn from else's experience, adjust slurry concentration to 8%, adjust the pH=5.5 of solution, add complex enzyme formulation I 24kg, process 24h for 50 ℃.Adjusting material pH is 6, adds complex enzyme formulation II 12kg and process 12h under 40 ℃ of conditions.Running water is adjusted slurry concentration 3%(w/v afterwards), discongest 50min at 30 ℃, discongested rear making beating; Recleaning desanding after making beating, in dense desander to enter to starch concentration be 2%, entering to starch pressure is 0.2MPa, entering afterwards low dense desander concentration is 0.8%, pressure is 0.25Mpa.Chelating agent EDTA24kg is made into the solution of 100g/L and adds water by total liquor ratio 1:12, and adjusting material pH is 6, at 70 ℃, processes 90min.
Through the slurry washing of chelation treatment, to adjusting slurry dense after neutrality, be 50%, drop into rotary spherical digester; 720kgNaOH is made into the high alkali liquid of 70g/L, 24KgMgSO
4be made into 50g/L solution,, 30%H
2o
21.8t, according to liquor ratio, 1:6 adds water, 100 ℃ of boiling 1.5h.
Be washed with water to after neutrality, add 80g/L hydrochloric acid 240m
3and add water according to total liquor ratio 1:10, at 70 ℃, process 60min.Then washing is to neutral, and papermaking is made the dregs of rice.
Above-mentioned slurry is alpha cellulose after testing: 95.0%, and ash content (725 ℃): 0.09%, iron content: 15mg/Kg, whiteness: 85%, reactivity worth 10s, the degree of polymerization 550.
Boiling density wastewater 37t, 800 times of colourities, slightly yellow, COD
crfor 11000mg/L, BOD
5for 45280mg/L; The waste water that the steps such as enzyme processing, washing produce is 72t altogether, COD
cr980mg/L, BOD5 is 422mg/L.
Embodiment 3
A kind of complex enzyme formulation, complex enzyme formulation I and complex enzyme formulation II, consist of, wherein each constituent of complex enzyme formulation I and mass percentage content are: feruloyl esterase 2%, lipase 1%, pectase 5%, laccase 3%, antioxidant 1%, mould inhibitor 1%, pest repellant 0.2%, soluble starch 80%, dextrin 6.8%;
Each constituent of complex enzyme formulation II and mass percentage content are: zytase 3%, cellulase 5%, dextranase 5%, arabinase 1%, antioxidant 1%, mould inhibitor 1.5%, pest repellant 0.2%, all the other are soluble starch;
The dissolving pulp production technology of applying above-mentioned complex enzyme formulation, specifically comprises the steps:
The preliminary artificial three grades of cotton linter 6t of dedusting two class that learn from else's experience, adjust slurry concentration to 12%, adjust the pH=6.5 of solution, add complex enzyme formulation I 30kg, process 16h for 45 ℃.Adjusting material pH is 5, adds complex enzyme formulation II 24kg and process 12h under 50 ℃ of conditions.Running water is adjusted slurry concentration 3%(w/v afterwards), discongest 50min at 40 ℃, discongested rear making beating; Recleaning desanding after making beating, in dense desander to enter to starch concentration be 2%, entering to starch pressure is 0.2MPa, entering afterwards low dense desander concentration is 0.8%, pressure is 0.25Mpa.
Chelating agent EDTA36kg is made into 100g/L solution and adds, and adds water process 60min according to liquor ratio 1:10 at 80 ℃.
Through the slurry washing of chelation treatment, to adjusting slurry dense after neutrality, be 60%, drop into rotary spherical digester; 660kgNaOH is made into the high alkali liquid of 70g/L, 27kgMgSO
4be made into 50g/L solution, 30%H
2o
21.4t adds successively, according to total liquor ratio 1:5, adds water, 130 ℃ of boiling 2.5h.
Above-mentioned slurry is washed with water to after neutrality, adds 60g/L hydrochloric acid 360m
3according to total liquor ratio, be that 1:10 adds water, at 80 ℃, process 40min.Then washing is to neutral, and papermaking is made the dregs of rice.Alpha cellulose after testing: 96.4%, ash content (725 ℃): 0.05%, iron content: 12mg/Kg, whiteness: 89%, reactivity worth 10s, the degree of polymerization 515.
Boiling density wastewater 31t, 900 times of colourities, slightly yellow, COD
crfor 12400mg/L, BOD
5for 5118mg/L; The waste water that the steps such as enzyme processing, washing produce is 76t altogether, COD
crfor 465mg/L, BOD5 is 199mg/L.
Embodiment 4
A kind of complex enzyme formulation, complex enzyme formulation I and complex enzyme formulation II, consist of, wherein each constituent of complex enzyme formulation I and mass percentage content are: feruloyl esterase 0.9%, lipase 2%, pectase 4%, laccase 1%, antioxidant 1.5%, mould inhibitor 1.5%, pest repellant 0.3%, all the other are dextrin;
Each constituent of complex enzyme formulation II and mass percentage content are: zytase 4%, cellulase 5%, dextranase 5%, arabinase 3%, antioxidant 0.5%, mould inhibitor 1%, pest repellant 0.2%, all the other are dextrin;
The dissolving pulp production technology of applying above-mentioned complex enzyme formulation, specifically comprises the steps:
The preliminary artificial three grades of cotton linter 6t of dedusting two class that learn from else's experience, adjust slurry concentration to 6%, adjust the pH=6 of solution, add complex enzyme formulation I 12kg, process 12h for 45 ℃.Adjusting material pH is 5.5, adds complex enzyme formulation II 15kg and process 24h under 55 ℃ of conditions.Running water is adjusted slurry concentration 3%(w/v afterwards), discongest 50min at 40 ℃, discongested rear making beating; Recleaning desanding after making beating, in dense desander to enter to starch concentration be 2%, entering to starch pressure is 0.2MPa, entering afterwards low dense desander concentration is 0.8%, pressure is 0.25Mpa.Then regulating material pH is 7, and chelating agent EDTA48kg is made into 100g/L solution and adds, and adds water according to liquor ratio 1:10, at 80 ℃, processes 60min.
Through the slurry washing of chelation treatment, to adjusting slurry dense after neutrality, be 60%, drop into rotary spherical digester; 900kgNaOH is made into the high alkali liquid of 80g/L, 26kgMgSO
4be made into 50g/L solution, 30%H
2o
20.4t adds successively, according to total liquor ratio 1:3.4, adds water, boiling 2h at 110 ℃.
Above-mentioned slurry is washed with water to after neutrality, adds 70g/L hydrochloric acid 180m
3according to total liquor ratio, be that 1:12 adds water, at 90 ℃, process 40min.Then washing is to neutral, and papermaking is made the dregs of rice.
Alpha cellulose after testing: 94.8%, ash content (725 ℃): 0.07%, iron content: 18mg/Kg, whiteness: 87%, reactivity worth 7s, the degree of polymerization 489.
Boiling density wastewater 20t, 1000 times of colourities, slightly yellow, COD
crfor 13200mg/L, BOD
5for 5500mg/L; The waste water that the steps such as enzyme processing, washing produce is 75t altogether, COD
crfor 650mg/L, BOD5 is 265mg/L.
Claims (5)
1. a complex enzyme formulation, by complex enzyme formulation I and complex enzyme formulation II, formed, it is characterized in that: described each constituent of complex enzyme formulation I and weight percent content are: feruloyl esterase 0.1-5%, lipase 1-10%, pectase 1-10%, laccase 1-5%, antioxidant 0.5-2%, mould inhibitor 0.5-2%, pest repellant 0.1-0.5%, all the other are carrier;
Described each constituent of complex enzyme formulation II and weight percent content are: zytase 1-10%, cellulase 1-10%, dextranase 1-10%, arabinase 1-10%, antioxidant 0.5-2%, mould inhibitor 0.5-2%, pest repellant 0.1-0.5%, all the other are carrier;
Described carrier is soluble starch or dextrin or its mixture.
2. complex enzyme formulation as claimed in claim 1, is characterized in that: the constituent of described complex enzyme formulation I and percentage by weight are: feruloyl esterase 0.2-2%, lipase 1-5%, pectase 1-5%, laccase 1-3%, antioxidant 0.5-1.5%, mould inhibitor 0.5-1.5%, pest repellant 0.1-0.3%, surplus are soluble starch;
Described complex enzyme formulation II constituent and percentage by weight are: zytase 1-5%, cellulase 1-5%, dextranase 1-5%, arabinase 1-5%, antioxidant 0.5-2%, mould inhibitor 0.5-2%, pest repellant 0.1-0.5%, surplus are soluble starch.
3. according to claim 1 or complex enzyme formulation claimed in claim 2, it is characterized in that: described mould inhibitor is polysaccharide adsorbent; Described antioxidant is one or more the mixture in Tea Polyphenols, ascorbic acid, phytic acid; Described pest repellant is arprinocid or Amprolium Hydrochloride.
4. application rights requires the dissolving pulp production technology of the complex enzyme formulation described in 1, it is characterized in that: specifically comprise the steps:
(1) impurity removing: cotton linter is sent into cyclone separator and remove the impurity in cotton linter;
(2) enzyme process preliminary treatment: adopting screw press is that 5-15% (w/v) adds water and mixes by cotton linter according to slurry concentration, and the pH of material is adjusted between 5.5-6.5; Described complex enzyme formulation I is added in slurry, and addition is the 0.1-5% of over dry material gross weight, under 35-60 ℃ of condition, processes 4-48h;
(3) enzymolysis making beating removal of impurities: adjust between the material pH to 4-6 after above-mentioned processing, described complex enzyme formulation II is added in above-mentioned slurry, addition is the 0.1-5% of over dry material gross weight, processes 4-48h under 35-60 ℃ of condition; Running water is adjusted slurry concentration to 3-3.5% (w/v), under 20-50 ℃ of condition, discongests 20-60min, adopts beater making beating; Making beating disposed slurry carries out recleaning desanding, in dense desander to enter to starch concentration be 1.5-2% (w/v), entering to starch pressure is 0.2-0.3MPa, enters afterwards low dense desander, concentration is 0.6-0.8% (w/v), pressure is 0.25-0.35MPa;
(4) chelation treatment: the slurry after making beating removal of impurities adds water according to total liquor ratio 1:8-12 (w/v), add chelating agent EDTA simultaneously, consumption is the 0.2-0.8% (w/w) of relative over dry material gross weight, mix and regulate slurry pH between 3-9, process 30-90min at 50-80 ℃;
(5) alkaline hydroxyl activity oxygen digestion process: after chelation treatment, running water filtering stock is neutral to pH, adjusts slurry concentration and after 40-60% (w/v), drops in rotary spherical digester; NaOH is made into the high alkali liquid of 50-100g/L according to the 9-15% (w/w) of relative over dry material gross weight, solution, H2O2 that MgSO4 is made into 10-50g/L according to the 0.1-0.5% (w/w) of relative over dry material gross weight add in rotary spherical digester successively according to the 1-9% (w/w) of relative over dry material gross weight, and add running water according to total liquor ratio 1:3-12 (w/v); Seal rotary 5-10min, makes slurry mix with chemical liquid; Then lentamente temperature is risen to 80-130 ℃, be incubated 60-150min after reaching temperature; After boiling completes, steam bleeding is cooling, emits afterwards slurry, and running water washs to pH neutral;
(6) acid treatment: the slurry that upper step is obtained mixes according to total liquor ratio 1:7-15 with water, adds 70-100g/L hydrochloric acid 2-6% (w/v), mixes, and processes 30-90min at 50-90 ℃, running water washs to pH neutral;
(7) wash, make the dregs of rice: the slurry after washing regulates slurry dense 0.2-1% (w/v), enters hydrocyclone, and pressure is 274-350kPa, and outlet pressure is 0-20kPa; After washing, enter pulp machine and make the dregs of rice.
5. complex enzyme formulation according to claim 4 is applied to the production technology of dissolving pulp, it is characterized in that: final dissolving pulp yield >=85% obtaining, alpha-cellulose >=95.0%, whiteness >=88%, reactivity worth≤50s.
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| CN115637603B (en) * | 2022-11-14 | 2023-06-02 | 山东银鹰股份有限公司 | Method for preparing pulp from waste pure cotton fabric, product obtained by method and application of pulp |
| CN117005231A (en) * | 2023-09-07 | 2023-11-07 | 齐鲁工业大学(山东省科学院) | Method for improving wheat straw oxygen alkali pulp performance through biological enzyme composite pretreatment |
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| EP1752533A1 (en) * | 2005-08-12 | 2007-02-14 | Institut National de la Recherche Agronomique | Fusion proteins between plant cell-wall degrading enzymes, and their uses |
| CN101235547A (en) * | 2008-03-06 | 2008-08-06 | 北京林业大学 | Method for producing bamboo dissolving pulp |
| CN101492700B (en) * | 2009-03-05 | 2012-07-04 | 王建设 | Intensive processing method for stalk articles or agricultural castoff |
| CN101736632B (en) * | 2009-12-17 | 2011-09-14 | 宜宾长毅浆粕有限责任公司 | Digestion process for preparing wood dissolving pulp by natural-color unbleached wood pulp in a modifying way |
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