CN103122594B - Production method of dissolving pulp - Google Patents
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- CN103122594B CN103122594B CN201210465141.1A CN201210465141A CN103122594B CN 103122594 B CN103122594 B CN 103122594B CN 201210465141 A CN201210465141 A CN 201210465141A CN 103122594 B CN103122594 B CN 103122594B
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Abstract
The invention relates to a production method of dissolving pulp. The method comprises the steps of pre-hydrolyzing plant fibrous raw materials by water, steam or diluted acid, then digesting the materials by peroxy acid, and processing the materials by hemicellulase, thus obtaining the dissolving pulp. The dissolving pulp produced by the method has the whiteness more than 90% ISO (International Standards Organization), and the content of Alpha-cellulose is more than 92%, and the content of pentosan is less than 2.0%. The method is applicable to wood and non-wood fibrous raw materials.
Description
Technical field
The present invention relates to a kind of dissolving pulp production technology, be specifically related to a kind of timber and non-wood raw material after water or steam or diluted acid prehydrolysis, through peroxy acid slurrying, cellulase treatment and chemical bleaching, prepare again the method for dissolving pulp, belong to dissolving pulp production field.
Background technology
Dissolving pulp is for producing the raw material of the products such as viscose, glassine paper, acetate fiber, nitrocellulose, carboxymethyl cellulose, microcrystalline cellulose, cellulose ether, in the industry such as weaving, medicine, food, is widely used.The raw material that is used for producing dissolving pulp has the non-wood raw materials such as cotton linter, timber and bamboo.At present, the production of dissolving pulp, mainly by adopting kraft cooking to make brown stock after acid sulfite cooking or prehydrolysis, is then produced through bleaching.Wherein, take acid sulfite process as main.The problem that acid sulphite process boiling exists is that the cellulosic degree of polymerization is difficult to control, and viscosity is lower, invests greatlyr, and following bleaching chemical consumption is large.And when after prehydrolysis, kraft cooking is produced dissolving pulp, particularly iron ion is difficult to remove (existence of iron ion can have influence on the reactivity worth of pulp, thereby reduces the quality of pulp), cooking waste liquor is processed the problem difficult, following bleaching chemical consumption is large to exist in slurry heavy metal ion.Therefore, improve production technology and the technique of dissolving pulp, for improving dissolving pulp quality, reducing production costs and reducing environmental pollution has great importance.What is more important, no matter be to prepare in dissolving pulp process at acid sulfite process or prehydrolytic sulfate process at present, the hemicellulose of stripping and lignin all do not obtain higher value application, therefore the utilization based on comprehensive, effective, high-valued to fibrous raw material, improve the production technology of dissolving pulp, for the comprehensive utilization of resource and the ecological environment of the Nature, be of great importance.
China applies for a patent 200810042384.8 and discloses a kind of method that prehydrolysis alkaline cooking is manufactured bamboo dissolved pulp.The condition of prehydrolysis is: sulfuric acid or concentration of hydrochloric acid 0.1-1.0 wt%, and 80-140oC, liquor ratio 1:4-1:15, time 30-400 min, adopts alkaline cooking after prehydrolysis.
Chinese invention patent ZL 99117103.9 relates to a kind of pulping process of eucalyptus dissolving pulp.In prehydrolysis, add aliphatic acid polyethenoxy ether facilitation of hydrolysis.Prehydrolysis condition is: aliphatic acid polyethenoxy ether 0.1-0.4 wt%, and liquor ratio 1:4, temperature 163-168oC, time 90-110 min, carries out alkaline cooking after prehydrolysis.
China applies for a patent 201110141167.6 and discloses a kind of method of utilizing waste of flax to produce dissolving pulp for raw material.Technical process comprises atmospheric pressure or under pressure prehydrolysis, then carries out alkaline cooking.The condition of normal pressure prehydrolysis is: tartaric acid 0-2%, acetic acid 0-5%, liquor ratio 1:0.5-1:100, time 0.5-100 h, temperature 5-100oC; Pressure prehydrolysis: tartaric acid 0-2%, acetic acid 0-5%, liquor ratio 1:1-1:100, time 2-300 min, temperature 100-180oC.
Above-mentioned patent is all to have adopted the technique of carrying out alkaline cooking after traditional prehydrolysis, and particularly iron ion is difficult to remove, cooking waste liquor is difficult to the problem of processing, following bleaching chemical consumption is large, cost is high to exist in slurry metal ion.In addition, the hemicellulose and the lignin that are dissolved in waste liquid are mostly disposed by burning, fail higher value application.
Except adopting sulfate process, soda processes or sulfite cooking technology to prepare dissolving pulp, Organosolv Pulping is also used to produce dissolving pulp.The solvent that organosolv pulping adopts comprises formic acid, acetic acid, ethanol etc., and wherein formic acid slurrying is to adopt formic acid or formic acid and hydrogen peroxide as the pulping process of cooking liquor.The raw material that adopts first acid cooking to produce dissolving pulp is the non-wood raw materials such as leaf wood or crudefiber crop.The people such as Hispanic A Baide etc. have carried out two sections of Milox slurrying to Eucalyptus, and the technological process of two sections of slurrying is: first paragraph, formic acid concn 80%(weight ratio), hydrogen peroxide 4%(is to over dry wood chip), liquor ratio 1:9.1, temperature 70oC, times 70 min.Second segment, temperature is elevated to boiling point, continues reaction 150 min.The paper pulp of boiling gained can be prepared dissolving pulp after TCF bleaching (bleaching process EOZQP).Referring to people such as A Baide, the total chlorine free bleaching of the dissolving pulp of formic acid and peroxyformic acid delignification, timber research, 56 (1): 60-66,2002.（Abad?S.?et?al,?Totally?chlorine?free?bleaching?of?
Eucalyptus?globules?dissolving?pulps?delignified?with?peroxyformic?acid?andformic?acid,?Holzforschung,?56?(1):?60-66,?2002）。
The people such as the Zhuo Han of Bangladesh adopt two sections/tri-sections boilings of formic acid method to make paper pulp to bast-fibre, after hydrogen peroxide bleaching, can prepare dissolving pulp.The technological process that wherein three-stage process adopts is: first paragraph, formic acid concn 90%, hydrogen peroxide 4%, 80oC, digestion time 120 min; Second segment, formic acid concn 90%, 107
oc, digestion time 60 min; The same first paragraph of process conditions of the 3rd section.Referring to people such as Zhuo Han, Taro Aso produces the slurrying flow process of dissolving pulp, living resources, 3(4): 1359-1370,2008. (Jahan M. S. et al, Alternative pulping process for producing dissolving pulp from jute, Bioresources, 3(4): 1359-1370,2008).
The Liang Fang of Beijing University of Chemical Technology etc. adopt first acid cooking to bamboo, and its technological process and condition are: formic acid concn 88%, and liquor ratio 1:8, hydrogen peroxide consumption 3.6%(is to bone dry fiber raw material), pre-preg times 120 min.First paragraph, 80
ounder C, react 120 min; Second segment, directly increases the temperature to 95
oc reacts 180 min; The 3rd section, after cooking liquor suction filtration, add new formic acid and hydrogen peroxide, 80
ounder C, react 120 min, paper pulp that boiling makes adopts 14%(to oven dry stock) hydrogen peroxide bleaching after obtain paper pulp whiteness can reach 91%ISO, alpha-cellulose content reaches more than 94%, inherent viscosity approaches 800 ml/g.Referring to people such as Liang Fang, the research of Milox solvent legal system bleached bamboo pulp, Chinese paper industry, 28(4): 40-43,2007.
More than adopt formic acid/peroxyformic acid boiling technology to produce the technological process complexity of dissolving pulp, the time is long, formic acid consumption is large; What is more important, due to formic acid while dissolved lignin and hemicellulose in digestion process, therefore, the recycling of the residue of cooking waste liquor after distillation reuse is very difficult, can not carry out high-valued application to hemicellulose and lignin resource, ecological environment be had a negative impact simultaneously.
Chinese invention patent ZL 99805811.4 relates to a kind of mixture with formic acid and acetic acid and as cooking chemical, produces the method for paper pulp.The method comprises step: (1) adopts the mixture of formic acid and acetic acid as boiling medicine, formic acid content 80-40% wherein, acetic acid content 10-30%, boiling temperature 110-140
oc, time 20-80 min; (2) evaporating used cooking liquor to solid content is 50-80%, and the mixture that then obtains formic acid, acetic acid by distillation is for boiling.
Chinese invention patent ZL 02813978.X relates to the organic acid that a kind of employing contains furfural and comprises that formic acid and acetic acid etc. carry out the method that paper pulp is prepared in boiling.The method key step is: (1) containing organic acid as the mixture of formic acid, acetic acid and composition thereof and furfural as boiling reagent at 105-160
ounder C, carry out boiling; (2) recovery of boiling reagent, comprises the furfural obtaining from recycling step in boiling reagent.
Chinese invention patent ZL 97199963.5 relates to a kind of with formic acid one step boiling, and with performic acid flushing and oxidative bleaching agent bleaching, prepares the method for high whiteness paper pulp.The method mainly comprises the following steps: (1) uses formic acid, or together with other organic acids, in a step boiling, cellulosic raw material is carried out to fiber separation, and boiling temperature is greater than 85
oc, digestion time is for herbaceous plant 15-80 min, for hardwood 25-90 min; (2) the paper pulp of opening from fiber separation, remove cooking liquor and rinse paper pulp with the formic acid that contains performic acid or other peroxy acids; (3) from paper pulp, remove disacidify; (4) use oxidative bleaching agent bleached pulp, oxidation bleaching comprises the mixed bleach of alkaline hydrogen peroxide bleaching or oxygen and hydrogen peroxide.
Above three patents all relate to the technology of utilizing formic acid boiling to prepare traditional paper pulp, do not relate to the concrete technology of preparing dissolving pulp.The boiling reagent adopting in above three patents is formic acid, acetic acid or its mixture, or the organic acid that contains furfural, does not add hydrogen peroxide in digestion process.Now prove, during formic acid boiling, have facilitation to the degraded of lignin and stripping adding of hydrogen peroxide.Therefore, in formic acid digestion process, whether add hydrogen peroxide to make the degraded of lignin in digestion process and stripping law have essential difference.
What is more important, the formic acid boiling technology that above three patents adopt is all the technology that adopts a step boiling, does not carry out preliminary treatment before boiling, exists obvious difference with the boiling parameter of this patent.The preliminary treatment of this patent before boiling, causes most hemicellulose stripping, and raw material porosity is increased, and therefore follow-up peroxy acid boiling is more rapid.In addition, above three patents are in boiling delignification, also can there is degraded and enter into cooking waste liquor in a large amount of hemicelluloses, thereby cause cooking waste liquor after distillation reuse, the recycling of residue is very difficult, this not only causes adverse effect to ecological environment, can not carry out higher value application to the lignin in cooking waste liquor residue and hemicellulose.
In sum, at present in the production process of dissolving pulp, when dissolving pulp is prepared in acid sulphite process boiling, existing the cellulosic degree of polymerization of dissolving pulp to be difficult to the problem of controlling, viscosity is low, there is the problem that following bleaching chemical consumption is large, metal ion is difficult to removal, liquid waste processing difficulty in the kraft cooking of prehydrolysis.It is long that the technique that dissolving pulp is produced in the boiling of existing employing formic acid/peroxyformic acid exists digestion time, the problem that formic acid consumption is large.Especially in the production of existing dissolving pulp, researcher and the producer are optimized the production procedure of dissolving pulp and technique based on optimized production process, the angle of improving the quality of products, although can improve to a certain extent the quality of dissolving pulp, cause current pulping process can not carry out high value added utilization to half fiber of stripping and lignin.
Summary of the invention
The object of the invention is to propose a kind of based on prehydrolysis, peroxy acid boiling and be aided with the method for the production dissolving pulp that hemicellulase processes.Based on to the fibrous raw material theory of higher value application fully and effectively, take in the production process of the dissolving pulp that cellulose is main component, take into full account the hemicellulose in fibrous raw material and lignin are carried out to higher value application, simultaneously also for the cellulosic degree of polymerization existing in current dissolving pulp production process be difficult to control, bleaching chemical consumption is large, waste liquid is difficult to the problems such as processing, proposes a kind of peroxy acid pulping by cooking method of prehydrolysis.Prehydrolysis can adopt water or steam or diluted acid.After peroxy acid boiling, by follow-up hemicellulase processing, alkali extracting, oxygen delignification, ClO 2 bleaching and hydrogen peroxide bleaching, prepare dissolving pulp.
Prehydrolysis and peroxy acid boiling combined, not only solved that metal ion in the slurry that prehydrolysis alkaline cooking exists is difficult to remove, cooking waste liquor is difficult to the problem of processing, following bleaching chemical consumption is large; But also having solved acid sulphite process boiling while preparing dissolving pulp, the cellulosic degree of polymerization of dissolving pulp is difficult to the problem of controlling, viscosity is low.In addition hemicellulase operation, and the cooperation of each procedure technology condition, reduces the cost of sizing agent of preparation method's production of dissolving pulp of the present invention, and environmental pollution obviously reduces, and product quality obviously improves.Specifically, for solving the problems of the technologies described above, the invention provides following technical scheme.
1, a preparation method for dissolving pulp, comprises the steps:
1) adopt water, steam or diluted acid to carry out prehydrolysis to fibrous raw material;
2) with peroxy acid, carry out boiling, reuse after cooking waste liquor distillation;
3) slurry carries out hemicellulase processing;
4) slurry carries out alkali extracting;
5) slurry carries out oxidation bleaching.
More particularly, the present invention adopts and carries out peroxy acid boiling and enzyme after water, steam or diluted acid prehydrolysis and process and prepare dissolving pulp plant fiber material, and concrete technology step is as follows:
(1) be cut into fibrous raw material employing water or steam or the diluted acid prehydrolysis of suitable dimension, the condition of water prehydrolysis is: during prehydrolysis, temperature is 110-180 ℃, liquor ratio 1:2.5-1:20, time 30-150 min; During steam prehydrolysis, steam pressure is 0.48 MPa-1.00 MPa; Liquor ratio 1:2.5-1:20, time 30-150 min; Diluted acid prehydrolysis condition is: acid concentration 0.005-10 %(weight ratio), and liquor ratio 1:2-1:20, temperature 80-190oC, time 10-150 min.From pre-hydrolyzed solution, extract compound sugar or its catabolite.
(2) raw material after prehydrolysis, after washing, is sent into digesting apparatus and is carried out peroxy acid boiling.Conditions of cooking is: formic acid consumption 30-85%(v/v), the concentration of acetic acid is 0-30%(v/v), hydrogen peroxide consumption 0.01-8%(is to over dry raw material), liquor ratio 1:2.5-1:20, time 10-150 min, temperature 90-140oC.Cooking waste liquor reuse after distillation, owing to can producing other organic acids such as acetic acid in digestion process.Therefore, in the cooking liquor of reuse, contain other organic acids such as small part acetic acid.In waste liquid from boiling, extract lignin and the degradation of organic substances thereof of stripping.
(3) paper pulp after boiling, after formic acid and hot wash, adopts hemicellulase to process.The process conditions of processing are: hemicellulose enzyme dosage 0.5-5 IU/g(oven dry stock), temperature 30-80oC, time 20-120 min, starches dense 2-30%, pH 4-8.
(4) after the pulp washing after hemicellulase processing concentrates, according to raw material and pulp quality requirement, can adopt EOPP or OEPP or OEP or EODP bleaching process to bleach.Wherein E represents alkali treatment, and O represents oxygen delignification, and P represents alkaline hydrogen peroxide bleaching, and D represents ClO 2 bleaching.
(5) condition of alkali extracting is: sodium hydroxide concentration 2-10%(is to oven dry stock), starch dense 8-12%, temperature 70-95oC, time 60-150 min.
(6) condition of oxygen delignification is: oxygen is pressed 0.4-0.8 MPa, NaOH 1-3% (to oven dry stock), MgSO
40-0.2% (to oven dry stock), temperature 80-120oC, time 15-60 min.
(7) condition of hydrogen peroxide single stage bleaching is: sodium hydroxide concentration 1.5-5% (to oven dry stock), hydrogen peroxide consumption 3-8%(is to oven dry stock), temperature 65-85oC, time 60-150 min, starches dense 10-30%.While adopting two sections of hydrogen peroxide bleachings, total hydrogen peroxide consumption is 4-10% (to oven dry stock).
(8) conditions of bleaching of chlorine dioxide is: Chlorine 0.2-0.6% (to oven dry stock), and bleaching starts to add NaOH or sulfuric acid to control bleaching terminal pH 3.5-6.0, temperature 60-90oC, time 60-240 min, starches dense 8-20%.
Compare with the production technology of existing dissolving pulp, the invention has the advantages that:
(1) significantly reduced the carbon emission of traditional dissolving pulp industry.The processing of substantially burning of the dissolved lignin of tradition dissolving pulp industry and glycan, produces a large amount of CO
2.Compare with traditional dissolving pulp technology, adopt every ten thousand tons of dissolving pulps of this technology can save 2.5 ten thousand tons of carbon emissions.
(2) be conducive to fibrous raw material to carry out higher value application fully and effectively.Fibrous raw material, before peroxy acid boiling, adopts steam or diluted acid to carry out preliminary treatment, most of hemicellulose in stripping raw material, and stripping is seldom for cellulose and lignin.In the waste liquid of prehydrolysis, hemicellulose and degradation product purity thereof are higher, effectively separated and utilization hemicellulose and degradation product thereof wherein.Again because most hemicellulose is removed in prehydrolysis section, the lignin in peroxy acid digestion process in main stripping fibrous raw material.Waste liquid after distillation mainly contains lignin, therefore, can effectively to dissolved lignin, carry out separation, purification and higher value application.
(3) after the most of hemicellulose of prehydrolysis stripping, it is loose that fibrocyte wall construction becomes, and is conducive to the infiltration of follow-up digestion process herb liquid.Compare as cooking liquor with independent formic acid or acetic acid, in formic acid or acetic acid digestion process, add hydrogen peroxide, can generate peroxy acid, peroxy acid and lignin reaction are more rapid, selective strong, therefore delignification reaction can be strengthened, and cellulosic degraded can be prevented.Therefore peroxy acid boiling can reduce sour consumption and digestion time, and can, guaranteeing, under the prerequisite of delignification rate, to reduce cellulosic degraded, improve the bleachability of slurry; In peroxy acid digestion process, the sensitiveness to dissolving pulp performance impact due to formic acid and hydrogen peroxide consumption, boiling temperature and time, this technology can be controlled the degree of polymerization of dissolving pulp as the variation of sour and hydrogen peroxide consumption, digestion time, boiling temperature better by conditions of cooking, meets the requirement of different stage dissolving pulp.
(4) in peroxy acid digestion process, delignification efficiency is high, and lignin condensation is few, removed most metal ion, so following bleaching is more prone in acid digestion process simultaneously.By just obtaining dissolving pulp after alkali treatment, oxygen delignification, ClO 2 bleaching and hydrogen peroxide bleaching, and the paper pulp that sulfate process and sulfite cooking obtain generally will adopt the multistage strengthening bleaching of bleaching medicines such as comprising oxygen, chlorine dioxide, ozone just can obtain qualified dissolving pulp, chemical consumption is high, and pulp viscosity loss is large, cost is high.
(5) before the paper pulp alkali treatment after peroxyformic acid boiling, adopt hemicellulase processing, removed targetedly the remaining hemicellulose in paper pulp, reduced the chemical consumption of follow-up alkali treatment, improved the quality of alpha-cellulose content and dissolving pulp.
The process of accompanying drawing 1 explanation the inventive method.
Fibrous raw material joins in prehydrolysis device (1), adds water, steam or diluted acid (7) to carry out prehydrolysis, mainly removes hemicellulose.Compound sugar in prehydrolysis waste liquid (10) etc. can carry out separation and utilization.After fibrous raw material prehydrolysis, carry out washing concentrating, then enter into boiling vessel (2), the cooking liquor (11) that adds reuse in boiling vessel (2), and supplement and to add new formic acid, acetic acid and hydrogen peroxide (8), carry out peroxy acid boiling, mainly carry out delignification, after boiling, adopt the method for multistage counter current washing from paper pulp (3), to extract waste liquid, the acid solution of using in multistage counter current washing is from the cooking liquor (11) of reuse, the cooking waste liquor extracting all enters into distilling apparatus (6), after distillation, be recycled acid solution (11) and raffinate (12), reclaim acid solution for boiling or pulp washing.In addition, in digestion process because meeting produces acetic acid, furfural etc., in still-process, can separating acetic acid, furfural is as byproduct.In raffinate, mainly contain lignin, to the lignin in raffinate (12), can carry out separation and utilization.Paper pulp after washing enters into stock tank or slurry tower (4), adds hemicellulase (9) to carry out enzyme processing, mainly removes the hemicellulose in slurry, enters bleachery (5) after washing, and paper pulp, after bleaching, obtains dissolving pulp by washing.
(4) specific embodiment
Below in conjunction with embodiment, the present invention is described further, but be not limited to this.
accompanying drawing 1: the present invention produces the flow sheet of dissolving pulp.
embodiment 1
Poplar adopts the technology of the present invention to carry out boiling and bleaching, and boiling flow process as shown in Figure 1.After boiling, paper pulp carries out, after hemicellulase processing, successively adopting alkali extracting, oxygen delignification, ClO 2 bleaching and hydrogen peroxide bleaching, adopts EODP bleaching process to bleach, and concrete technology condition and pulp property are as shown in table 1.The addition of bleaching medicine in table 1 is all with respect to oven dry stock.The dissolving pulp whiteness of gained is 91%ISO, and alpha-cellulose content is 97.0%, and inherent viscosity is 810 ml/g, poly-pentose content 1.95%.
table 1 steam prehydrolysis peroxyformic acid cooking schedule
| Processing procedure | Process conditions |
| Prehydrolysis | Steam pressure 0.8 MPa, liquor ratio 1:6, times 45 min |
| Peroxy acid boiling | Formic acid concn 80%(v/v), hydrogen peroxide 2%(is to oven dry stock), liquor ratio 1:6, temperature 120oC, times 40 min |
| Hemicellulase is processed | Zytase 1.0 IU/g(oven dry stocks), starch dense 5%, temperature 50oC, times 60 min, pH 6-8 |
| Alkali extracting | NaOH 5%, starch dense 10%, temperature 80oC, times 90 min |
| Oxygen delignification | Oxygen is pressed 0.6 MPa, and NaOH 2%, MgSO 4 0.1%, starch dense 12%, 110 ℃ of temperature, times 30 min |
| ClO 2 bleaching | Chlorine dioxide 0.3%, starch dense 12%, temperature 80oC, times 120 min, terminal pH 4.5 |
| Hydrogen peroxide bleaching | NaOH 3%, hydrogen peroxide 4%, starch dense 15%, temperature 80oC, times 90 min |
embodiment 2
Eucalyptus adopts the technology of the present invention to carry out boiling and bleaching, and flow process and process conditions are with table 1.The dissolving pulp whiteness of gained is 90%ISO, and alpha-cellulose content is 96.5%, and inherent viscosity is 795 ml/g, poly-pentose content 1.85%.
embodiment 3
Bamboo adopts the technology of the present invention to carry out boiling and bleaching, and flow process and technique are as shown in table 1, and what difference was that prehydrolysis adopts is 0.2% sulfuric acid, and during peroxy acid boiling, formic acid concn is 75%, and hydrogen peroxide consumption is 3%, and the time is 30 min.And without ClO 2 bleaching section, adopt EOP bleaching process to bleach in bleaching process.The whiteness of the dissolving pulp of gained is 91%ISO, and alpha-cellulose content is 96.2%, and inherent viscosity is 745 ml/g, poly-pentose content 1.90%.
embodiment 4
As shown in embodiment 2, difference is after oxygen delignification, to adopt two sections of hydrogen peroxide bleachings.The dissolving pulp whiteness of gained is 91.5%ISO, and alpha-cellulose content is 97.5%, and inherent viscosity is 760 ml/g, poly-pentose content 1.80%.
embodiment 5
As embodiment 3, difference is that the raw material adopting is reed, and the whiteness of the dissolving pulp of gained is 90%ISO, and alpha-cellulose content is 94.0%, and inherent viscosity is 701 ml/g, poly-pentose content 1.85%.
embodiment 6
As shown in embodiment 1, the acid that difference adopts while being peroxy acid boiling is the mixed acid of formic acid and acetic acid, formic acid concn 70%(v/v), acetic acid concentration 10%(v/v).The whiteness of the dissolving pulp of gained is 90%ISO, and alpha-cellulose content is 95.2%, and inherent viscosity is 806 ml/g, poly-pentose content 1.96%.
embodiment 7
As shown in embodiment 3, difference is that the raw material adopting is bagasse, and the whiteness of the dissolving pulp of gained is 93%ISO, and alpha-cellulose content is 95.5%, and inherent viscosity is 647 ml/g, poly-pentose content 1.88%.
embodiment 8
As shown in embodiment 1, difference is that prehydrolysis adopts watery hydrochloric acid, and concentration is 0.6%, and the time is 180oC.
The whiteness of the dissolving pulp of gained is 90.5%ISO, and alpha-cellulose content is 97.0%, and inherent viscosity is 800 ml/g.
embodiment 9
As shown in embodiment 1, difference is that the raw material adopting is dragon spruce, and hemicellulase is processed and adopted mannase to process, after oxygen delignification, adopt two sections of hydrogen peroxide bleachings, the whiteness of the dissolving pulp of gained is 91.0%ISO, and alpha-cellulose content is 98.0%, and inherent viscosity is 890 ml/g.
Claims (3)
1. a preparation method for dissolving pulp, comprises the steps:
1) adopt water, steam or diluted acid to carry out prehydrolysis to fibrous raw material;
2) with peroxy acid, carry out boiling, reuse after cooking waste liquor distillation;
3) slurry carries out hemicellulase processing;
4) slurry carries out bleaching; Wherein said step 1) acid adopting during dilute acid hydrolysis is inorganic acid; The inorganic acid adopting during dilute acid hydrolysis is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid; During water prehydrolysis, temperature is 110-180 ℃, liquor ratio 1:2.5-1:20, time 30-150 min; During steam prehydrolysis, steam pressure is 0.48 MPa-1.00 MPa; Liquor ratio l:2.5-1:20, time 30-150 min; The acid concentration adopting during diluted acid prehydrolysis is 0.005-10% (weight ratio), and prehydrolysis temperature is 80-190 ℃, time 10-150 min, and liquor ratio is 1:2-1:20; Described step 2) peroxy acid described in comprises the mixture of formic acid and hydrogen peroxide or the mixture of formic acid, acetic acid and hydrogen peroxide; Cooking waste liquor is back to use in digestion process after distilling; In peroxy acid digestion process, formic acid concn is 30-85% (v/v), and acetic acid concentration is 0-30% (v/v), and liquor ratio is 1:2.5-1:20, and the addition of hydrogen peroxide is the 0.01-8% of bone dry fiber raw material; In peroxy acid digestion process, temperature is 90-140 ℃, and the time is 10-150 min.
2. the method for claim 1, is characterized in that the 3rd) adopt in step hemicellulase to process; When raw material is used leaf wood or non-wood raw material, adopt xylanase treatment: enzyme dosage is with respect to oven dry stock 0.5-5 IU/g, temperature 30-80 ℃, time 20-120 min, starches dense 2-30%, and pH is 4-8; When raw material is used needlebush, adopt mannase to process: enzyme dosage is with respect to oven dry stock 0.5-5 IU/g, temperature 30-80 ℃, time 20-120 min, starches dense 2-30%, and pH is 4-8.
3. the method for claim 1, is characterized in that the 4th) adopt in step EOPP or OEPP or OEP or EODP bleaching process to bleach; Wherein E represents alkali treatment, and O represents oxygen delignification, and P represents alkaline hydrogen peroxide bleaching, and D represents ClO 2 bleaching.
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