Background technology
Dissolving pulp is the raw material of producing the products such as viscose, glassine paper, acetate fiber, nitrocellulose, carboxymethyl cellulose, microcrystalline cellulose, cellulose ether, is widely used in the industry such as weaving, medicine, food.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 the acid sulphite process boiling exists is that the cellulosic degree of polymerization is difficult to control, and viscosity is lower, invests greatlyr, and the 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, that the 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 the dissolving pulp quality, reducing production costs and environmental contamination reduction has great importance.What is more important, no matter at present in acid sulfite process or prehydrolytic sulfate process prepare the dissolving pulp process, the hemicellulose of stripping and lignin all do not obtain higher value application, therefore based on the utilization comprehensive, effective, high-valued to fibrous raw material, improve the production technology of dissolving pulp, be of great importance for the comprehensive utilization of resource and the ecological environment of the Nature.
China applies for a patent 200810042384.8 and discloses a kind of method that prehydrolysis alkaline cooking is made 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.Add the aliphatic acid polyethenoxy ether facilitation of hydrolysis in prehydrolysis.The 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 waste of flax that utilizes and be that raw material produces the method for dissolving pulp.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, exists the problem that particularly iron ion is difficult to remove, cooking waste liquor is difficult to process, the following bleaching chemical consumption is large, cost is high of metal ion in slurry.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 also is 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 the boiling of formic acid method 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 Milox slurrying to Eucalyptus, and the technological process of two sections slurrying is: first paragraph, formic acid concn 80%(weight ratio), hydrogen peroxide 4%(is to the 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 prepare 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/three sections boilings of formic acid method to make paper pulp to bast-fibre, can prepare dissolving pulp after the hydrogen peroxide bleaching.Wherein the technological process of three-stage process employing 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 the boiling of formic acid method 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 the bone dry fiber raw material), pre-preg times 120 min.First paragraph, 80
oReaction 120 min under C; Second segment directly increases the temperature to 95
oC reacts 180 min; The 3rd section, after the cooking liquor suction filtration, add new formic acid and hydrogen peroxide, 80
oReaction 120 min under C, 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 is near 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.
It is complicated that above employing formic acid/peroxyformic acid boiling technology is produced the technological process of dissolving pulp, and the time is long, the 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 the distillation reuse is very difficult, can not carry out high-valued application to hemicellulose and lignin resource, simultaneously ecological environment be had a negative impact.
Chinese invention patent ZL 99805811.4 relates to a kind of mixture with formic acid and acetic acid and produces the method for paper pulp as cooking chemical.The method comprises step: (1) adopts the mixture of formic acid and acetic acid as the boiling medicine, formic acid content 80-40% wherein, acetic acid content 10-30%, boiling temperature 110-140
oC, time 20-80 min; (2) evaporation used cooking liquor to solid content is 50-80%, then obtains the mixture of formic acid, acetic acid for boiling by distillation.
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 boiling prepares paper pulp.The method key step is: the mixture that (1) contains organic acid such as formic acid, acetic acid and composition thereof and furfural as boiling reagent at 105-160
oCarry out boiling under C; (2) recovery of boiling reagent comprises the furfural that obtains from recycling step in boiling reagent.
Chinese invention patent ZL 97199963.5 relates to a kind of with formic acid one step boiling, and prepares the method for high whiteness paper pulp with performic acid flushing and oxidative bleaching agent bleaching.The method mainly comprises the following steps: (1) uses formic acid, or and other organic acids together, cellulosic raw material is carried out fiber separation in a step in boiling, boiling temperature is greater than 85
oC, digestion time are for herbaceous plant 15-80 min, for hardwood 25-90 min; (2) remove cooking liquor from the paper pulp that fiber separation is opened and also rinse paper pulp with the formic acid that contains performic acid or other peroxy acids; (3) remove disacidify from paper pulp; (4) use the 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 the formic acid boiling to prepare traditional paper pulp, do not relate to the concrete technology for preparing dissolving pulp.The boiling reagent that adopts in above three patents is formic acid, acetic acid or its mixture, perhaps contains the organic acid of furfural, does not add hydrogen peroxide in digestion process.Now prove, during the formic acid boiling, add degraded and the stripping to lignin of hydrogen peroxide has facilitation.Therefore, whether add hydrogen peroxide to make the degraded of lignin in digestion process and the difference that there is essence in stripping law in the formic acid digestion process.
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, makes the raw material porosity increase, and therefore follow-up peroxy acid boiling is more rapid.In addition, above three patents are in the boiling delignification, degraded also can occur and enter into cooking waste liquor in a large amount of hemicelluloses, thereby cause cooking waste liquor after the 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 the cooking waste liquor residue and hemicellulose.
In sum, at present in the production process of dissolving pulp, when the acid sulphite process boiling prepares dissolving pulp, the problem that exist the cellulosic degree of polymerization of dissolving pulp to be difficult to control, viscosity is low, the kraft cooking of prehydrolysis exist that the following bleaching chemical consumption is large, metal ion is difficult to remove, the liquid waste processing hard problem.It is long that the technique that dissolving pulp is produced in existing employing formic acid/peroxyformic acid boiling exists digestion time, the problem that the formic acid consumption is large.Especially in the production of existing dissolving pulp, the angle that researcher and the producer be based on optimized production process, improve the quality of products is optimized production procedure and the technique of dissolving pulp, although can improve to a certain extent the quality of dissolving pulp, cause present pulping process can not carry out high value added utilization to half fiber and the lignin of stripping.
Summary of the invention
The objective 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, in the production process of the dissolving pulp take cellulose as main component, take into full account the hemicellulose in fibrous raw material and lignin are carried out higher value application, simultaneously also for the cellulosic degree of polymerization that exists in present dissolving pulp production process be difficult to control, the bleaching chemical consumption is large, waste liquid is difficult to the problems such as processings, the peroxy acid pulping by cooking method of a kind of prehydrolysis of proposition.Prehydrolysis can be adopted water or steam or diluted acid.Prepare dissolving pulp by follow-up hemicellulase processing, alkali extracting, oxygen delignification, ClO 2 bleaching and hydrogen peroxide bleaching after the peroxy acid boiling.
Prehydrolysis and peroxy acid boiling combined, the problem that solved not only that metal ion in the slurry that the prehydrolysis alkaline cooking exists is difficult to remove, cooking waste liquor is difficult to process, the following bleaching chemical consumption is large; But also solved the acid sulphite process boiling when preparing dissolving pulp, the problem that the cellulosic degree of polymerization of dissolving pulp is difficult to control, viscosity is low.Hemicellulase operation, and the cooperation of each procedure technology condition in addition makes the cost of sizing agent of preparation method's production of dissolving pulp of the present invention reduce, 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 kind of preparation method of dissolving pulp, comprise the steps:
1) adopt water, steam or diluted acid to carry out prehydrolysis to fibrous raw material;
2) carry out boiling with peroxy acid, reuse after the cooking waste liquor distillation;
3) slurry carries out the hemicellulase processing;
4) slurry carries out the alkali extracting;
5) slurry carries out oxidation bleaching.
More particularly, the present invention carries out peroxy acid boiling and enzyme processing preparation dissolving pulp after plant fiber material is adopted water, steam or diluted acid prehydrolysis, and the concrete technology step is as follows:
(1) fibrous raw material that is cut into suitable dimension adopts water or steam or diluted acid prehydrolysis, and 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.Extract compound sugar or its catabolite from pre-hydrolyzed solution.
(2) raw material after prehydrolysis through after washing, is sent into digesting apparatus and is carried out the 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 the over dry raw material), liquor ratio 1:2.5-1:20, time 10-150 min, temperature 90-140oC.Cooking waste liquor is through reuse after distilling, because meeting in digestion process produces other organic acids such as acetic acid.Therefore, contain other organic acids such as small part acetic acid in the cooking liquor of reuse.Extract lignin and the degradation of organic substances thereof of stripping waste liquid after boiling.
(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 is processed is concentrated, 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%.When adopting two sections 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 begins to add NaOH or sulfuric acid to control bleaching terminal point 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) decrease the carbon emission of traditional dissolving pulp industry.The processing of basically burning of the dissolved lignin of tradition dissolving pulp industry and glycan produces a large amount of CO
2Compare 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 is carried out higher value application fully and effectively.Fibrous raw material adopts steam or diluted acid to carry out preliminary treatment before the peroxy acid boiling, and stripping is seldom for most of hemicellulose in the stripping raw material, cellulose and lignin.In the waste liquid of prehydrolysis, hemicellulose and degradation product purity thereof are higher, can effectively separate and utilize wherein hemicellulose and degradation product thereof.Again because most hemicellulose is removed in the prehydrolysis section, the lignin in the peroxy acid digestion process in main stripping fibrous raw material.Waste liquid after distillation mainly contains lignin, therefore, can be effectively to dissolved lignin separate, purification and higher value application.
(3) after the most of hemicellulose of prehydrolysis stripping, it is loose that the 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, add hydrogen peroxide in formic acid or acetic acid digestion process, 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 the peroxy acid boiling can reduce sour consumption and digestion time, and can reduce cellulosic degraded under the prerequisite that guarantees delignification rate, improves the bleachability of slurry; In the peroxy acid digestion process, due to formic acid and hydrogen peroxide consumption, boiling temperature and the time sensitiveness to the dissolving pulp performance impact, 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, satisfies the requirement of different stage dissolving pulp.
(4) in the peroxy acid digestion process, delignification efficient is high, and the lignin condensation is few, removed most metal ion simultaneously in acid digestion process, so following bleaching is more prone to.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 reinforcement bleaching of bleaching medicines such as comprising oxygen, chlorine dioxide, ozone just can obtain qualified dissolving pulp, chemical consumption is high, and the pulp viscosity loss is large, cost is high.
(5) adopt the hemicellulase processing before the paper pulp alkali treatment after the peroxyformic acid boiling, 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 entry, steam or diluted acid (7) and carries out prehydrolysis, mainly removes hemicellulose.Compound sugar in prehydrolysis waste liquid (10) etc. can separate and utilize.carry out washing concentrating after fibrous raw material prehydrolysis, then enter into boiling vessel (2), the cooking liquor (11) that adds reuse in boiling vessel (2), and replenish and to add new formic acid, acetic acid and hydrogen peroxide (8), carry out the peroxy acid boiling, mainly carry out delignification, adopt the method for multistage counter current washing to extract waste liquid after boiling from paper pulp (3), the acid solution of using in the multistage counter current washing is from the cooking liquor (11) of reuse, the cooking waste liquor that extracts all enters into distilling apparatus (6), through being recycled acid solution (11) and raffinate (12) after distillation, reclaim acid solution and be used 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.Mainly contain lignin in raffinate, the lignin in raffinate (12) can be separated and utilize.Paper pulp after washing enters into stock tank or slurry tower (4), adds hemicellulase (9) to carry out enzyme and processes, and mainly removes the hemicellulose in slurry, enters bleachery (5) after washing, and paper pulp obtains dissolving pulp through after bleaching by washing.
(4) specific embodiment
The present invention is described further below in conjunction with embodiment, 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 the boiling flow process as shown in Figure 1.After after boiling, paper pulp carries out the hemicellulase processing, successively adopt alkali extracting, oxygen delignification, ClO 2 bleaching and hydrogen peroxide bleaching, namely adopt the EODP bleaching process to bleach, concrete technology condition and pulp property are as shown in table 1.In table 1, the addition of bleaching medicine 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 |
The 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 |
The 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 point 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 the peroxy acid boiling, formic acid concn is 75%, and the hydrogen peroxide consumption is 3%, and the time is 30 min.And without the ClO 2 bleaching section, namely adopt the 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 implement as shown in example 2, difference is to adopt two sections hydrogen peroxide bleachings after oxygen delignification.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 implement example 3, and difference is that the raw material that adopts 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 implement as shown in example 1, the acid that difference adopts when being the 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 implement as shown in example 3, difference is that the raw material that adopts 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 implement as shown in example 1, difference is that watery hydrochloric acid is adopted in prehydrolysis, 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 implement as shown in example 1, difference is that the raw material that adopts is dragon spruce, hemicellulase is processed and is adopted mannase to process, adopt two sections hydrogen peroxide bleachings after oxygen delignification, 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.