CN105256629A - Preparation method for pulp - Google Patents
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Abstract
The invention provides a preparation method for pulp. The preparation method comprises the following steps: selection of plant raw materials; material preparation; and cooking. A cooking reagent used in the step of cooking comprises a cooking reagent used for alkali-process cooking, hydrogen peroxide and auxiliary agents; and the auxiliary agents are composed of modified glucose oxidase, at least one modified fatty alcohol polyoxyethylene ether and an acrylamide copolymer, wherein the usage amount of the modified glucose oxidase is 0.5 to 3% of the weight of absolute dry raw materials, the usage amount of the modified fatty alcohol polyoxyethylene ether is 0.5 to 5% of the weight of the absolute dry raw materials, and the usage amount of the acrylamide copolymer is 0.5 to 3% of the weight of the absolute dry raw materials. The method is implemented at a low temperature; damage to cellulose is small; the cooked pulp has high whiteness; and black liquor has low COD content and low chroma.
Description
Technical field
The present invention relates to a kind of method preparing pulp, concrete, relate to one and prepare pulp chemical treatment method, more specifically, the present invention relates to the boiling method of a kind of preparative chemistry slurry.
Background technology
Regenerated celulose fibre, as a kind of textile raw material, with native celluloses such as timber, bamboo, fiber crops, cotton linter, reed, stalks for raw material, obtains through a series of process process such as boiling, acid treatment, bleachings.Its raw material is that occurring in nature can constantly regenerate, the resource of continuous utilization, and resource distribution is extensive, obtains easily, is suitable for developing enduringly.
Prepare one of very crucial step of cellulose fibre for digestion process.Pulping by cooking generally includes soda pulping process, sulfite pulping, soda pulping process is the aqueous solution process plant fiber material utilizing alkali electroless medicament, lignin in raw material and other components are separated with cellulose fibre, obtain cellulose fibre through follow-up process.Soda pulping process can be soda pulping, sulfate pulp-making, in prior art, discloses many pulping and digesting technique.
In existing pulping and digesting method, boiling temperature is high or digestion process is more loaded down with trivial details, and fibrous raw material is dark through the color of boiling disposed slurry, and the COD value of cooking waste liquor is high, for the operations such as follow-up washing and bleaching propose higher technical requirement, cause the cost preparing pulp high.
Such as, China Patent Publication No. CN103243596A discloses a kind of preparation method of Acetate-grade pulp, raw material is one or more in wood, bamboo and straw, can be Eucalyptus, poplar, pine, reed etc., first flood in one or more the composition of raw material in biology enzyme, sodium sulfite and sodium hydrogensulfite, by a lignin stripping part, the short texture of raw material; Then the cellulosic material after dipping carries out steam prehydrolysis, and hydrolysis temperature is 100-200 DEG C, and the pressure of steam prehydrolysis is at 0-1.46MPa, and steam hydrolysis time is 60-230min; The hydrolysate obtained carries out sulphate cook, boiling medicine alkali charge is the 4%-30% of pre-hydrolysate absolute dry mass, the sulphidity 0-40% of described sulphate cook medicine, the liquor ratio of described sulphate cook is 1:(3-10), boiling temperature 80-200 DEG C, the time being warmed up to boiling temperature is 40-200min, and pressure is 0.1-8MPa, and temperature retention time is 20-200min; Slurry after boiling carries out discongesting, screen and washing, and then bleaches, obtains Acetate-grade pulp.This preparation technology is more loaded down with trivial details, and cost is high, and in black liquor, content of organics is high, and the cost disposed waste liquid is very large.
Such as Chinese patent application publication number CN102020788 discloses a kind of preparation method of cellulose pulp, and key step comprises, and selects suitable cotton linter to be raw material; Cotton linter is processed into cellulose paste; Cellulose paste is copied into sheet and does rolling, wherein, adopt two sections of cooking process, comprise temperature rise period and holding stage when preparing fiber pulp, be raised to 90-120 DEG C in temperature rise period temperature in 30-60min, holding stage controls in 80-120min.
In order to the fibrous raw material solving prior art is dark through the color of boiling disposed slurry, COD content is high, technological process very complicated etc. defect, special the present invention is proposed.
Summary of the invention
The object of one aspect of the present invention provides a kind of boiling method preparing pulp, and adopt this preparation method, boiling temperature is low.
The present invention's object on the other hand provides a kind of boiling method preparing pulp, and adopt this preparation method, boiling disposed slurry whiteness is high.
The object of further aspect of the present invention provides a kind of boiling method preparing pulp, adopts this preparation method, and cellulose damage is light, and black liquor COD is low and colourity is low.
The present invention's object on the other hand provides a kind of boiling method preparing pulp, and adopt this preparation method, technological process is simple.
The boiling method preparing pulp provided by the invention, comprises the steps: to choose plant material, get the raw materials ready and boiling; Wherein, in digestion process, steaming preparation comprises the digestant of alkaline cooking, hydrogen peroxide and auxiliary agent, described auxiliary agent comprises the glucose oxidase of modification and aliphatic alcohol polyethenoxy base ether, the acrylamido copolymer of at least one modification, the consumption of the glucose oxidase of modification is the 0.5-3% of over dry raw material weight, the consumption of the aliphatic alcohol polyethenoxy base ether of modification is the 0.5-5% of over dry raw material weight, and the consumption of acrylamido copolymer is the 0.5-3% of over dry raw material weight.
When the present invention carries out boiling to plant material, boiling is the chemical reaction of the complexity that heterogeneous a, multiple compounds participates in, not only there is the degraded stripping of delignification and carbohydrate, also have the condensation of lignin and alkali lye to the reaction of other components of raw material.In this process, especially, the addition of the digestant of alkaline cooking of the present invention is the 3-15% of over dry raw material weight.In this preparation method, the digestant that boiling adds includes but not limited to NaOH, also can be other any strong base substance.
In digestion process, adding of hydrogen peroxide, can react with some construction unit in lignin, for example phenyl ring, other structures making it become colorless, last phenyl ring oxidation cracking forms carboxylic acid and the aromatic acid of a series of binary, destroys various coloured quinoid structure that lignin is formed in digestion process.In the present invention, the consumption of hydrogen peroxide is the 0.5-5% of over dry raw material weight.
According to the requirement to pulp performance after boiling, digestion process temperature of the present invention can be carried out to high temperature at low temperature.Especially, the temperature of digestion process of the present invention controls at 80-160 DEG C.
Compared with prior art, the application carries out at a lower temperature in pulping and digesting method, and cellulose damage is light, and boiling disposed slurry whiteness is high, and whiteness is at 55-80%; Black liquor COD is low and colourity is low, and COD value 0.1-1.5 ten thousand mg/l, colourity 200-2500 are doubly.
Detailed description of the invention
Be described in further detail the boiling method of a kind of slurrying of the present invention below, do not limit protection scope of the present invention, its protection domain defines with claims.Detail disclosed in some provides complete understanding to each disclosed embodiment.But those skilled in the relevant art know, do not adopt these concrete details one or more, and adopt the situation of other material etc. can realize implementing the program yet.
Unless the context otherwise requires, in description and claims, term " comprises ", " comprising " be interpreted as implication that is open, that comprise, is " including, but are not limited to ".
Mentioned in the description " embodiment ", " embodiment ", " another embodiment " or " some embodiment " etc. refer to relevant to described embodiment described by the feature be specifically related to, structure or characteristic comprise at least one embodiment.Therefore, " embodiment ", " embodiment ", " another embodiment " or " some embodiment " there is no need all to refer to identical embodiment.And concrete feature, structure or characteristic can combine in any manner in one or more embodiments.
Prepare a boiling method for pulp, comprise the steps: to choose plant material, get the raw materials ready and boiling; Wherein, in digestion process, steaming preparation comprises the digestant of alkaline cooking, hydrogen peroxide and auxiliary agent, described auxiliary agent comprises the glucose oxidase of modification and aliphatic alcohol polyethenoxy base ether, the acrylamido copolymer of at least one modification, the consumption of the glucose oxidase of modification is the 0.5-3% of over dry raw material weight, the consumption of the aliphatic alcohol polyethenoxy base ether of modification is the 0.5-5% of over dry raw material weight, and the consumption of acrylamido copolymer is the 0.5-3% of over dry raw material weight.
Described plant material is cotton linter, gined cotton.
In certain embodiments, choosing cotton linter is raw material.
In some embodiments, the consumption of hydrogen peroxide is the 0.5-5% of over dry raw material weight.
In embodiments, the digestant that boiling adds includes but not limited to NaOH; Or NaOH and a small amount of sodium carbonate; Or NaOH and vulcanized sodium and a small amount of sodium carbonate and sulfate etc.
In some embodiments, the digestant that boiling adds comprises NaOH.The addition of NaOH is the 3-15% of over dry raw material weight.
In embodiments, the glucose oxidase of modification includes but not limited to that polyhydroxy amine intends glucose oxidase.
Concrete, the glucose oxidase of described modification and polyhydroxy amine intend glucose oxidase.
Polyhydroxy amine is intended glucose oxidase and is prepared from by multiple method, a kind of preparation method is wherein: pass through glutaraldehyde method, amino on polyhydroxy amine and glucose oxidase and aldehyde radical react and generate schiff bases, thus are received by polyhydroxy amine and glucose oxidase forms polyhydroxy amine intend glucose oxidase.Form the enzyme preparation of high stable.
Intend that glucose oxidase institute adopts technological process, process conditions are the technology that this area is commonly used, such as reactions steps, reaction temperature, time, solvent etc. preparing polyhydroxy amine.As long as polyhydroxy amine is received on glucose oxidase.
In some embodiments, the glucose oxidase of described modification comprises EnzaccelAE.
For example, Wu Hanke visits the modified glucose oxidizing ferment " EnzaccelAE " that Science and Technology Ltd. produces.
In embodiments, the aliphatic alcohol polyethenoxy base ether of modification includes but not limited to, the aliphatic alcohol polyethenoxy base ether of alkylethylene diamines modification, or N, the aliphatic alcohol polyethenoxy base ether of N-dimethyl amine modification, or the aliphatic alcohol polyethenoxy base ether of N, N-diethylamide modification.
Concrete, the aliphatic alcohol polyethenoxy base ether of alkylethylene diamines modification is the product that the amido of alkylethylene diamines and the end bonding of aliphatic polyoxyethylene ether are formed.
The aliphatic alcohol polyethenoxy base ether of other modifications is with reference to said method.
Adopt technological process in the aliphatic alcohol polyethenoxy base ether institute of the many modifications of preparation, process conditions are the technology that this area is commonly used, such as reactions steps, reaction temperature, time, solvent etc.As long as by the end bonding of amido and aliphatic polyoxyethylene ether.
In some embodiments, the aliphatic alcohol polyethenoxy base ether of modification comprises IngegscouOK.
For example, Wu Hanke visits the aliphatic alcohol polyethenoxy base ether " IngegscouOK " of the modification that Science and Technology Ltd. produces.
In embodiments, acrylamido copolymer includes but not limited to polynary alkyl carboxylic acid acrylamide copolymer.
Prepare acrylamido copolymer adopt technological process, process conditions are the conventional technology in this area, such as reactions steps, reaction temperature, time, solvent etc.
In some embodiments, described acrylamido copolymer comprises IngegdistaDT.
For example, Wu Hanke visits the acrylamido copolymer " IngegdistaDT " that Science and Technology Ltd. produces.
In the present invention, in plant digestion process, the glucose oxidase of hydrogen peroxide and auxiliary agent such as modification and aliphatic alcohol polyethenoxy base ether, the acrylamido copolymer of at least one modification is added in alkali lye, in some embodiments, auxiliary agent is for example EnzaccelAE and at least one IngegscouOK, IngegdistaDT.
Rely on auxiliary agent cooking liquor constantly to the diffusion inside of raw material, first with pectin, hemicellulose effect being dissolved, then alkali lye is again in lignin effect.The more intermolecular greatly key of lignin will be connected disconnect, and make lignin dissolve and remove out from fiber finer cell wall and intercellular layer.Meanwhile, under the effect of auxiliary agent and hydrogen peroxide, strengthen medicinal liquid osmosis.
In digestion process, described auxiliary agent is the mixing of EnzaccelAE, IngegscouOK and IngegdistaDT three.Hydrogen peroxide discharges oxygen in the basic conditions, the carbonyl in quinoid structure and pigment molecular and double bond structure can be oxidized, open loop and oxidation reaction occur, thus destroy chromophoric group, avoid lignin and transform dark material at digestion process, reduce the colourity of waste liquid.Hydrogen peroxide can produce H simultaneously
+, HO
2 -ion, due in the basic conditions, hydrogen peroxide can discharge more oxygen fast, easily causes cellulose to be degraded by Quick Oxidation, the existence of auxiliary agent EnzaccelAE constantly can consume the oxygen of decomposing hydrogen dioxide solution release in digestion system, and constantly produces hydrogen peroxide; Auxiliary agent IngegdistaDT there is chelated metal ions while, the carboxyl of utilization itself controls the H that decomposing hydrogen dioxide solution produces
+ion, slows down the decomposition rate of hydrogen peroxide, and the existence of auxiliary agent IngegscouOK can make cooking liquor rapid osmotic to the inside of fiber, make liquid equably with the various composition generation chemical actions in raw material.In digestion process of the present invention, the adjuvant system of several material composition, Hydrogen Peroxide that can be stable under boiling temperature, carries out boiling to slurry, evenly completes various chemical action, reaches the high and object that COD content is low of pulp brightness.
In this embodiment, EnzaccelAE, IngegscouOK and IngegdistaDT form multi-catalytic, oxidation ligand, the pH value of active balance system, improve boiling efficiency, and waste liquid is also closed reaction neutralization further by effective chain, form the discharge of ultralow basicity, well degrade and eliminate the pollutant in waste liquid, the COD in waste liquid reduces.
In some embodiments, the consumption of IngegscouOK is the 1.0-3.5% of over dry raw material weight.
In some embodiments, the consumption of EnzaccelAE is the 1.0-2.0% of over dry raw material weight.
In some embodiments, the consumption of IngegdistaDT is the 1.0-2.0% of over dry raw material weight.
In some embodiments, the consumption of hydrogen peroxide is the 1.0-3.5% of over dry raw material weight.
In digestion process, the time of boiling can determine according to the result of actual requirement.In some embodiments of the present invention, digestion time controls at 100-300 minute.It should be noted that when pressure ratio compared with large condition under boiling, digestion time can shorten.Or obtain the slurry of other different purposes, the adjustment that its digestion time also can be suitable.
In some embodiments, the liquor ratio of plant boiling is 1:(3.0-8.0).
Liquor ratio described is in the present invention the term that this area is commonly used.Usually, liquor ratio refers to the ratio of boiling over dry raw material weight and the total liquid measure volume of boiling.
The boiling method of pulping process of the present invention, can be applied to chemical pulping, bleaching aspect that other field extracts fiber from plant widely, for example (,) papermaking, weaving aspect.
Separating in detail further below by specific embodiment illustrates better to understand technical scheme of the present invention and advantage, but, should be appreciated that following examples and nonrestrictive but only for illustration of certain embodiments of the present invention.
Embodiment 1
The preparation method of vinegar-grade Cotton Pulp comprises the steps:
Choose two class cotton linters of 75% maturity, and cotton linter is torn removal of impurities;
Boiling: ready cotton linter joins in digesting apparatus, add 14% NaOH of over dry cotton linter weight, auxiliary agent adopts EnzaccelAE, IngegscouOK and IngegdistaDT, wherein, the consumption of EnzaccelAE is 1.0% of over dry raw material weight, the consumption of IngegscouOK is the consumption of 3%, IngegdistaDT of over dry raw material weight is 2.0% of over dry raw material weight, and the consumption of hydrogen peroxide is 2.5% of over dry raw material weight; Boiling 200 minutes under temperature 130 DEG C of conditions; Boiling shove, removes raffinate, the COD9000mg/l in black liquor, the whiteness 60% of boiling disposed slurry.
Embodiment 2
The preparation method of security paper pulp comprises the steps
Choose a class cotton linter of 75% maturity, and cotton linter is torn removal of impurities;
Boiling: ready cotton linter is joined in digesting apparatus, add 10% NaOH of over dry cotton linter weight, auxiliary agent adopts EnzaccelAE, IngegscouOK and IngegdistaDT, wherein, the consumption of EnzaccelAE is 1.5% of over dry raw material weight, the consumption of IngegscouOK is the consumption of 2.5%, IngegdistaDT of over dry raw material weight is 1.0% of over dry raw material weight, and the consumption of hydrogen peroxide is 5% of over dry raw material weight; Boiling 120 minutes under temperature 120 DEG C of conditions; Boiling shove, remove raffinate, the COD in black liquor is 1000mg/l, the whiteness 78% of boiling disposed slurry.
Embodiment 3
The preparation method of cellulose ether pulp comprises the steps
Choose two class cotton linters of 73% maturity, and cotton linter is torn removal of impurities;
Boiling: ready cotton linter is joined in digesting apparatus, add 8% NaOH of over dry cotton linter weight, auxiliary agent adopts EnzaccelAE and IngegdistaDT, wherein, the consumption of EnzaccelAE is 2.0% of over dry raw material weight, the consumption of IngegdistaDT is 3% of over dry raw material weight, and the consumption of hydrogen peroxide is 3.5% of over dry raw material weight; Boiling 200 minutes under temperature 140 DEG C of conditions; Boiling shove, remove raffinate, the COD in black liquor is 1.4 ten thousand mg/l, the whiteness 62% of boiling disposed slurry.
Embodiment 4
The preparation method of cellulose ether pulp comprises the steps
Choose two class cotton linters of 78% maturity, and cotton linter is torn removal of impurities;
Boiling: ready cotton linter is joined in digesting apparatus, add 4% NaOH of over dry cotton linter weight, auxiliary agent adopts EnzaccelAE, IngegscouOK and IngegdistaDT, wherein, the consumption of EnzaccelAE is 0.5% of over dry raw material weight, the consumption of IngegscouOK is the consumption of 3.0%, IngegdistaDT of over dry raw material weight is 1.5% of over dry raw material weight, and the consumption of hydrogen peroxide is 3.0% of over dry raw material weight; Boiling 100 minutes under temperature 120 DEG C of conditions; Boiling shove, removes raffinate, the COD2000mg/l in black liquor, the whiteness 64% of boiling disposed slurry.
Embodiment 5
The preparation method of cellulose ether pulp comprises the steps
Choose the cotton linter of 71% maturity, and cotton linter is torn;
Boiling: ready cotton linter is joined in digesting apparatus, add 15% NaOH of over dry cotton linter weight, auxiliary agent adopts EnzaccelAE, IngegscouOK and IngegdistaDT, wherein, the consumption of EnzaccelAE is 3% of over dry raw material weight, the consumption of IngegscouOK is the consumption of 3.5%, IngegdistaDT of over dry raw material weight is 2% of over dry raw material weight, and the consumption of hydrogen peroxide is 5% of over dry raw material weight; Boiling 140 minutes under temperature 160 DEG C of conditions; Boiling shove, removes raffinate, the COD14000mg/l in black liquor, the whiteness 55% of boiling disposed slurry.
Embodiment 6
The preparation method of absorbent cotton comprises the steps
Choose the less gined cotton of impurity, and torn;
Boiling: the gined cotton of step (1) is entered in digesting apparatus, add 3% NaOH of over dry gined cotton weight, auxiliary agent adopts EnzaccelAE, IngegscouOK and IngegdistaDT, wherein, the consumption of EnzaccelAE is 0.5% of over dry raw material weight, the consumption of IngegscouOK is the consumption of 2.0%, IngegdistaDT of over dry raw material weight is 1.0% of over dry raw material weight, and the consumption of hydrogen peroxide is 1.5% of over dry raw material weight; Boiling 100 minutes under temperature 100 DEG C of conditions; Boiling shove, removes raffinate, the COD1000mg/l in black liquor, the whiteness 80% of boiling disposed slurry.
Claims (9)
1. prepare a boiling method for pulp, comprise the steps: to choose plant material, get the raw materials ready and boiling; Wherein, in digestion process, steaming preparation comprises the digestant of alkaline cooking, hydrogen peroxide and auxiliary agent, described auxiliary agent comprises the glucose oxidase of modification and aliphatic alcohol polyethenoxy base ether, the acrylamido copolymer of at least one modification, the consumption of the glucose oxidase of modification is the 0.5-3% of over dry raw material weight, the consumption of the aliphatic alcohol polyethenoxy base ether of modification is the 0.5-5% of over dry raw material weight, and the consumption of acrylamido copolymer is the 0.5-3% of over dry raw material weight.
2. the boiling method preparing pulp according to claim 1, is characterized in that, described plant material is cotton linter, gined cotton.
3. the boiling method preparing pulp according to claim 1, is characterized in that, the glucose oxidase of modification comprises polyhydroxy amine and intends glucose oxidase, and preferably, the glucose oxidase of modification is EnzaccelAE; The aliphatic alcohol polyethenoxy base ether of modification comprises the aliphatic alcohol polyethenoxy base ether of alkylethylene diamines modification, and preferably, the aliphatic alcohol polyethenoxy base ether of modification is IngegscouOK; Acrylamido copolymer comprises polynary alkyl carboxylic acid acrylamide copolymer, and preferably, acrylamido copolymer is IngegdistaDT.
4. the boiling method preparing pulp according to any one of claim 1-4, is characterized in that, the consumption of hydrogen peroxide is the 0.5-5% of over dry raw material weight, and it is preferred, and the consumption of hydrogen peroxide is the 1.0-3.5% of over dry raw material weight.
5. the boiling method preparing pulp according to claim 4, is characterized in that, described auxiliary agent is the mixing of EnzaccelAE, IngegscouOK and IngegdistaDT three.
6. the boiling method preparing pulp according to any one of claim 4-6, is characterized in that, the consumption of IngegscouOK is the 1.0-3.5% of over dry raw material weight; The consumption of EnzaccelAE is the 1.0-2.0% of over dry raw material weight; The consumption of IngegdistaDT is the 1.0-2.0% of over dry raw material weight.
7. the boiling method preparing pulp according to any one of claim 1-7, is characterized in that, in digestion process, boiling temperature 80-160 DEG C, digestion time is 100-300 minute.
8. the boiling method preparing pulp according to any one of claim 1-8, it is characterized in that, digestant comprises NaOH; Or NaOH and sodium carbonate mixing; Or the mixing of NaOH, vulcanized sodium, sodium carbonate and sulfate.
9. the boiling method preparing pulp according to any one of claim 1-9, is characterized in that, the digestant that boiling adds comprises NaOH, and the addition of NaOH is the 3-15% of over dry raw material weight.
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| CN112900130A (en) * | 2021-02-02 | 2021-06-04 | 大连工业大学 | Method for reducing whiteness reduction of cooked plant fibers |
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|---|---|
| CN105256629B (en) | 2017-10-17 |
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