CN102388177A - Pulping process for quality protection including methods for hemicellulose extraction and treatment of hemicellulose -extracted lignocellulosic materials - Google Patents

Pulping process for quality protection including methods for hemicellulose extraction and treatment of hemicellulose -extracted lignocellulosic materials Download PDF

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Publication number
CN102388177A
CN102388177A CN2010800154207A CN201080015420A CN102388177A CN 102388177 A CN102388177 A CN 102388177A CN 2010800154207 A CN2010800154207 A CN 2010800154207A CN 201080015420 A CN201080015420 A CN 201080015420A CN 102388177 A CN102388177 A CN 102388177A
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ligno
cellulosic materials
extraction
polysulfide
technology
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尹相勋
H·T·库里南
G·A·克里希纳戈帕拉
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Auburn University
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Auburn University
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/02—Pretreatment of the finely-divided materials before digesting with water or steam
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D21C3/022—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of S-containing compounds

Abstract

A method for producing pulp by extracting hemicellulosic materials from lignocellulosic materials using water in an extraction stage, wherein the extraction stage is either a single extraction or a double extraction process; treating the lignocellulosic materials with an oxidizing agent in a treatment stage, wherein the treatment stage is selected from the group consisting of a second extraction process, an agent impregnation process, and a first pretreatment process; treating the lignocellulosic materials with a reducing agent in the treatment stage, wherein the treatment stage is selected from the group consisting of the second extraction process, the agent impregnation process, and a second pretreatment process; and then subjecting the lignocellulosic materials to a modified Kraft pulping process to produce pulp.

Description

The pulping process that is used for the quality protection that comprises the processing method of the method for distilling of hemicellulose and the ligno-cellulosic materials that extracts hemicellulose
The statement of related application
The priority and the rights and interests of the U.S. Provisional Patent Application that present patent application requires to submit on April 2nd, 2009 numbers 61165995, this provisional application is incorporated into this as a reference and all.
Technical field
The pulping process field of extracting through hemicellulose before the present invention relates generally to; More specifically, the present invention relates to the modification pulping process, particularly modified sulphur hydrochlorate method pulping process; Before through the hemicellulose extraction process, to keep the productive rate and the quality of paper pulp.Compare with the sulfate pulping technology of not extracting before, the invention still further relates to through attainable productive rate of modification pulping process and strength advantage field through hemicellulose.
Background technology
Slurrying is for being converted into timber or other ligno-cellulosic materials the technology of the paper pulp fiber of separation, and this paper pulp fiber is used for, for example, and papermaking.Common simple pulping process, for example as shown in Figure 1, comprise that (a) becomes the lignin that fiber and (b) chemical degradation and dissolving combine fiber with ligno-cellulosic materials mechanical lapping.Chemical pulping comprises that wood chip in the aqueous mixture of boiling chemicals with dissolved lignin, makes to produce the fiber that separates, washing the fibre, and subsequently alternatively bleaching produce the fiber of paper pulp.Can washes be delivered to recirculation and chemical recovery technology.
Sulfate process technology; For example as shown in Figure 2; Be common chemical pulping process; Wherein with ligno-cellulosic materials (for example cellulose, hemicellulose and lignin) and white liquid (NaOH, vulcanized sodium and sodium carbonate) boiling in digester(-tor), produce paper pulp and black liquor (lignin of dissolving, the catabolite of chemicals, other chemicals and the cellulose and the hemicellulose of usefulness not in the liquid) in vain.Sulfate process technology and other current chemical technologies maybe be invalid, produce significant waste stream, and produce the chemical waste that contains other available components, can these other available component be converted into the product of added value.
Summary of the invention
Say briefly, through the modification pulping process of hemicellulose extraction process, wherein, before slurrying, from ligno-cellulosic materials, extract hemicellulosic materials before the present invention includes, for example polysaccharide and other organic compound.Extract hemicellulosic materials before the slurrying, and before slurrying or during chemicals and/or other compounds are joined in the ligno-cellulosic materials, with the loss of compensation hemicellulosic materials.Use the present invention; Can hemicellulosic materials be removed; As the byproduct that added value is arranged of pulping process, produce and the similar paper pulp of productive rate and quality of conventional pulping process (for example sulfate pulping technology) yet in ligno-cellulosic materials, add chemicals and/or other compounds.Therefore, the present invention produces more economical pulping process, wherein, can byproduct extracted and sell, yet not have removing and capturing of this byproduct, will produce the paper pulp with similar quantity of conventional pulping process and quality.
The paper pulp industry has recognized that, must produce chemical pulp continuously and must from existing technology, seek other revenue stream.For example; In the present invention, not to bring wood chip simply and take out lignin, can hemicellulosic materials be removed; It is medium pending hemicellulosic materials to be stayed black liquor, but can some hemicellulosic materials removed and are used to produce the more byproduct of high value.Most of byproducts are the polysaccharide (sugar) with potential high value, and for example, it can be used for preparing ethanol or other chemicals.Yet, in typical extraction process, some hemicellulosic materials are shifted out have reduced the amount that can carry out the timber of slurrying.If remove the hemicellulosic materials of significant quantity, then this paper pulp can have the paper pulp different characteristic with prior art.Keep pulp yield and pulp property simultaneously through preparing, the invention solves this problem for the extraction hemicellulosic materials.
The present invention includes a kind of in alkaline pulp-making technology the ligno-cellulosic materials of protection preextraction hemicellulose, wood chip for example, the continuous processing of protected from degradation.One side of the present invention is the timber biological refinery plant (IFBR) of the product that is used to produce added value for existing chemical pulp grinding machine is evolved.For example, use the present invention, people can be before slurrying preextraction hemicellulose optionally and effectively, keep the productive rate and the quality of paper pulp simultaneously.Another aspect of the present invention is to use the modification pulping process to replace sulfate process technology, realize that with under removing at the lignin of par productive rate increases, and pulp property has no reduction.
Herein disclosed is several kinds of representative processes.Each technology comprises preextraction hemicellulosic materials from ligno-cellulosic materials (for example wood chip).Preextraction can be water extraction or with the extraction of the other types of the chemicals that adds.After preextraction, make ligno-cellulosic materials stand modification pulping process (the for example modification sulfate process technology in digester(-tor)) before, with certain chemicals preliminary treatment and/or processing ligno-cellulosic materials.
First kind of technology is two extraction processes, at the phase I water, then adds the modification sulfate pulping (SK or single sulfate process) with anthraquinone with alkaline vulcanized sodium and additive (DE or two extraction).Second kind of technology is the single stage of water to extract (SE or single extraction), then is two stages modification sulfate pulping (DK or two sulfate process).The third technology is single stage polysulfide pretreating process.The 4th kind of technology is single stage polysulfide and sodium borohydride pretreating process.The 5th kind of technology is two stage pretreating process, comprises polysulfide first pretreatment stage, then is polysulfide/sodium borohydride/anthraquinone second pretreatment stage, in first pretreatment stage, uses polysulfide recirculation simultaneously.The 6th kind of technology is the single stage polysulfide/reductant/anthraquinone pretreating process of the ligno-cellulosic materials alkaline pulp-making that is used to use polysulfide recirculation to make the preextraction hemicellulose.The 7th kind of technology is single stage polysulfide/reductant/anthraquinone preliminary treatment, does not have polysulfide recirculation.The 8th kind of technology is two stage pretreating process, comprises polysulfide/anthraquinone first pretreatment stage, then is polysulfide/reductant/anthraquinone second pretreatment stage, in first pretreatment stage, uses polysulfide recirculation simultaneously.Also consider other technologies and variant.
According to the present invention, after hemicellulosic materials is extracted, keep the productive rate of paper pulp and a kind of mode of quality to comprise use reductant and/or oxidant for example polysulfide and/or sodium borohydride and the ligno-cellulosic materials of use anthraquinone processing through extracting.In fact, because the relative cost of each material preferably uses polysulfide to replace sodium borohydride, or use the polysulfide of bigger relative quantity with respect to sodium borohydride.Under normal pressure, increase the processing stage preferably between about 120 ℃-180 ℃, carry out.Be lower than under about 120 ℃ temperature, process progress has economy too slowly and not.
In conjunction with accompanying drawing, by the following description of preferred implementation, of the present invention these with other aspects will be conspicuous.It will be apparent to those of ordinary skill in the art that under the situation of spirit that does not depart from novel concepts of the present disclosure and scope, can realize many variants of the present invention and modification.
Description of drawings
Fig. 1 represents the prior art pulping process.
Fig. 2 represents prior art sulfate pulping technology.
Fig. 3 is the block diagram of two extraction processes, at the phase I water, then adds the modification sulfate pulping (SK or single sulfate process) with anthraquinone with alkaline vulcanized sodium and additive (DE or two extraction).
Fig. 4 extracts (SE or single extraction) in the single stage of water, then is the block diagram of two stages modification sulfate pulping (DK or two sulfate process).
Fig. 5 is the block diagram of single stage polysulfide pretreating process that is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose.
Fig. 6 is single stage polysulfide and the block diagram of sodium borohydride pretreating process that is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose.
Fig. 7 is the block diagram of two stage pretreating process; In the phase I, use polysulfide; The use polysulfide as reductant and use anthraquinone, is used for using the ligno-cellulosic materials alkaline pulp-making that makes the preextraction hemicellulose in the first pretreatment stage polysulfide recirculation with sodium borohydride in second stage.
Fig. 8 is the block diagram of the single stage polysulfide pretreating process of the ligno-cellulosic materials alkaline pulp-making that is used to use polysulfide recirculation to make the preextraction hemicellulose.
Fig. 9 is the polysulfide of the ligno-cellulosic materials alkaline pulp-making that is used for not using polysulfide recirculation to make the preextraction hemicellulose and two pretreated block diagrams of single stage of reductant.
Figure 10 be the ligno-cellulosic materials alkaline pulp-making that is used to use polysulfide recirculation to make the preextraction hemicellulose with polysulfide then with the block diagram of two stage pretreating process of reductant.
Enclose form and various chart at this specification, and more be specified in detailed description of the preferred embodiment.
The specific embodiment
With reference to accompanying drawing, various embodiment of the present invention is described.For easy understanding, accompanying drawing and following explanation are used for the embodiment of limited quantity.Yet the present invention is not limited to these illustrative embodiments.Also consider other technologies and variant.For example, Fig. 3-10 explains the block diagram of representative processes 1-8 respectively.Table 1 is described the condition of various illustrative processes.Chart 1-28 explains the result of various illustrative processes, and compares with contrast (the for example paper pulp of prior art and the paper processed by the paper pulp of prior art).
The present invention includes the ligno-cellulosic materials that is used at alkaline pulp-making technology protection preextraction hemicellulose, wood chip for example, the continuous processing of protected from degradation.After preextraction, before the alkaline pulp-making technology or during with reductant and/or oxidizer treatment ligno-cellulosic materials, with the productive rate and the quality of the paper pulp that keeps production.
Herein disclosed is several kinds of representative processes.Technology 1 is two extraction processes, at the phase I water, then adds the modification sulfate pulping (SK or single sulfate process) with anthraquinone with alkaline vulcanized sodium and additive (DE or two extraction).Technology 2 is the single stage of water to extract (SE or single extraction), then is two stages modification sulfate pulping (DK or two sulfate process).Technology 3 is single stage polysulfide pretreating process.Technology 4 is single stage polysulfide and sodium borohydride pretreating process.Technology 5 is two stage pretreating process, comprises polysulfide first pretreatment stage, then is polysulfide/sodium borohydride/anthraquinone second pretreatment stage, in first pretreatment stage, uses polysulfide recirculation simultaneously.Technology 6 is the single stage polysulfide/reductant/anthraquinone pretreating process of the ligno-cellulosic materials alkaline pulp-making that is used to use polysulfide recirculation to make the preextraction hemicellulose.Technology 7 is single stage polysulfide/reductant/anthraquinone preliminary treatment, does not have polysulfide recirculation.Technology 8 is two stage pretreating process, comprises polysulfide/anthraquinone first pretreatment stage, then is polysulfide/reductant/anthraquinone second pretreatment stage, in first pretreatment stage, uses polysulfide recirculation simultaneously.
After hemicellulosic materials is extracted, keep the productive rate of paper pulp and a kind of mode of quality to comprise the ligno-cellulosic materials that uses polysulfide to extract with reductant (for example sodium borohydride) and use anthraquinone processing warp alternatively.In fact, because the relative cost of each material preferably uses polysulfide to replace sodium borohydride, or use the polysulfide of bigger relative quantity with respect to sodium borohydride.Under normal pressure, increase the processing stage preferably between about 120 ℃-180 ℃, carry out.Be lower than under about 120 ℃ temperature, process progress has economy too slowly and not.
Combine accompanying drawing to disclose various representative processes of the present invention now.
Fig. 3 is the block diagram of technology 1, and two extraction processes at the phase I water, then add the modification sulfate pulping (SK or single sulfate process) with anthraquinone with alkaline vulcanized sodium and additive (DE or two extraction).In the first extraction stage, water is joined in the ligno-cellulosic materials.Under the temperature of the rising between 120 ℃-180 ℃, handle lignocellulose and water substance subsequently.Be mainly plant polyose, acetate and a spot of lignin in this operating period by the organic matter that fragment discharges, and be removed as sugar stream 1.With alkaline vulcanized sodium (ASS) and sodium borohydride (SBH), will join together in the second extraction stage through ligno-cellulosic materials and the water that extracts, and under the temperature of the rising between 120 ℃-180 ℃, handle.With NaOH and vulcanized sodium, will join together in the digester(-tor) through the ligno-cellulosic materials and the water of two extractions, to produce paper pulp.The black liquor that is discharged by digester(-tor) comprises, for example, and the lignin of dissolving, vulcanized sodium, sodium borohydride, NaOH, vulcanized sodium, other chemicals and cellulose and hemicellulose catabolite.
Chart 1 illustrates the two losses in weight of extracting that in technology 1, produce.This caption is with respect to contrast (that is, only use single water extraction and do not use second of sodium borohydride or another kind of reductant to extract), the insensitivity of extraction.In this chart, the loss in weight for hemicellulosic materials during extraction process dissolved with the amount that is extracted.As being seen, use additive, compared with simple water extraction, can extract more organic matter.The degree in x-axle explanation extraction stage, the H-factor, it is the time of extraction and the combination of temperature.
Chart 2 illustrates the total sugar extract in technology 1.The amount of the sugar that this caption extracts during extraction process is as the function of the loss in weight.As stated, use additive,, can extract more sugar compared with simple water extraction.Because sugar is valuable as the accessory substance that is removed, therefore sugared the extraction is gainful.
Chart 3 illustrates to use in the typical sulfate process technology of water extraction in contrast and extracts with technology 1 two that the productive rate for water extraction increases or loss in the single sulfate process technology.This graph shows is compared with the contrast technology that only comprises water extraction and sulfate process technology, and this technology provides better productive rate, even hemicellulosic materials is removed in extraction process.Particularly, curve and the intersection point of level 0 line have been explained contrast and the technology 1 different loss in weight under same productive rate.This for example understands in common processes of the present invention, can hemicellulosic materials be removed, and productive rate is not had adverse influence.
In conjunction with chart 4-10 such as following disclosed, use like 1 illustrational two single sulfate process technology of extracting of the present invention of technology, the wood substance of 19-24% (about 9-13% sugar) is extracted, and the not significant loss of pulp yield.Use this technology, recyclable other chemicals, and still have similar pulp yield.
Fig. 4 is the block diagram of technology 2, and the single stage of water is extracted (SE or single extraction), then is two stages modification sulfate pulping (DK or two sulfate process).In the extraction stage, water is joined in the ligno-cellulosic materials.Under the temperature of the rising between 120 ℃-180 ℃, handle lignocellulose and water substance subsequently.Be mainly plant polyose, acetate and a spot of lignin in this operating period by the organic matter that fragment discharges, and be removed as sugar stream.To join in the preliminary treatment/digester(-tor) of combination with water through the ligno-cellulosic materials that extracts.At preprocessing part; Alkaline vulcanized sodium and sodium borohydride are joined in the ligno-cellulosic materials; And at digester(-tor) part this material of processing under the temperature of the rising between 120 ℃-180 ℃, will be through pretreated ligno-cellulosic materials with NaOH and vulcanized sodium digestion, to produce paper pulp.The black liquor that is discharged by digester(-tor) comprises, for example, and the lignin of dissolving, vulcanized sodium, sodium borohydride, NaOH, vulcanized sodium, other chemicals and cellulose and hemicellulose catabolite.
Use single extraction two stages modification sulfate process technology of the present invention, 14% wood substance (about 10% sugar) is extracted, and the not significant loss of pulp yield.Expection uses technology 2 can realize that 10-14% extracts (about 7-10% sugar yield), keeps pulp yield simultaneously.Also expection uses technology 2 can keep the productive rate and the strength character of paper pulp, and has 7-8% extraction sugar yield.
The two stages modification sulfate pulping of technology 2 is included in pretreatment stage and depresses the use strong reductant adding; For example sodium borohydride, sodium dithionite (sodium dithionate), in-situ hydrogen etc. then use anthraquinone to carry out sulfate pulping as additive in second stage.Reductant helps to keep remaining hemicellulose in final paper pulp, to keep pulp property.
Chart 3 also illustrate contrast use in the typical sulfate process technology of water extraction with the two sulfate process technologies of the single extraction of technology 2 in increase or loss for the productive rate of water extraction.This graph shows is compared with the contrast technology that only comprises water extraction and sulfate process technology, and this technology provides better productive rate, even hemicellulosic materials is removed in extraction process.Particularly, curve and the intersection point of level 0 line have been explained contrast and the technology 2 different loss in weight under same productive rate.This for example understands in common processes of the present invention, can hemicellulosic materials be removed, and productive rate is not had adverse influence.
Chart 4 illustrates the influence of sodium borohydride preliminary treatment to the two sulfate process pulp yields of single extraction of technology 2.Add sodium borohydride as reductant, and when adding sodium borohydride, find to keep pulp yield, even extract hemicellulosic materials according to the present invention.Particularly, this caption recovers the level of the required sodium borohydride of loss of yield, and this is the influence of sodium borohydride to pulp yield.Through adding more sodium borohydride, productive rate improves.The sulfate process contrast is all-fulfate method technology.Article three, curve illustrates the technology 2 of under different water extraction parameter (9%, 12% and 14% water extraction), carrying out.
To compare with the paper product of contrast by the paper product of technology 1 and 2 preparations.PFI making beating response (PFI beating response), handmade paper density, TENSILE STRENGTH, burst strength, tear resistance and the folding resistance of paper pulp that will be through technology 1 and 2 preparations with by the paper pulp of all-fulfate method prepared and before the paper pulp of the sulfate process prepared through water extraction compare.Chart 5-10 illustrates these relatively, and shows, paper product through technology 1 and 2 preparations and the paper product through all-fulfate method prepared have comparativity.Three kinds of diverse ways of technology have been carried out.The parameter of contrast technology and technology of the present invention can be referring to table 1.
Chart 5 illustrates with contrasting paper pulp and compares, by the PFI making beating response of the paper pulp of technology 1 and 2 preparations.Chart 6 illustrates with contrasting paper product and compares, by the handmade paper density of paper product of technology 1 and 2 preparations.Chart 7 illustrates with contrasting paper product and compares, by the TENSILE STRENGTH of paper product of technology 1 and 2 preparations.Chart 8 illustrates with contrasting paper product and compares, by the burst strength of paper product of technology 1 and 2 preparations.Chart 9 illustrates with contrasting paper product and compares, by the tearing strength of paper product of technology 1 and 2 preparations.Chart 10 illustrates with contrasting paper product and compares, by the folding resistance of paper product of technology 1 and 2 preparations.
As being seen; With respect to contrast paper, explain that by the technology 1 and the Papermaking Performance of paper pulp of 2 preparations refining faster responds (refining response), high slightly density, comparable or higher TENSILE STRENGTH, comparable or higher burst strength, comparable or higher folding resistance and comparable tear resistance.The characteristic of the paper that the paper pulp of in other words, being produced by technology 1 and 2 is produced and the paper of prior art have comparativity.The combined effect of alkalescence vulcanized sodium and sodium borohydride can also make technology 1 and 2 when having significant wood sugar extraction and keep pulp yield and paper intensity.Particularly, technology 1 is extracted the wood substance of 19-24%, paper pulp and the less variation of paper performance; And the wood substance that technology 2 is extracted up to 12%, pulp yield and paper intensity is loss not.
For productive rate keeps, also can use other pre-treatment step to carry out technology of the present invention, herein disclosed is wherein several kinds.A kind of preliminary treatment is for using the preliminary treatment of polysulfide oxidisability.Another kind of preliminary treatment is for using the two preliminary treatment of polysulfide and sodium borohydride oxidisability-reducibility.The another kind preliminary treatment is use polysulfide oxidisability and the two stages preliminary treatment of oxidisability-reducibility, and uses polysulfide and the two processing of sodium borohydride, has polysulfide recirculation.Fig. 5-7 illustrates the embodiment more generally of polysulfide pretreating process, and Fig. 8-10 illustrates the embodiment more specifically according to polysulfide pretreating process of the present invention.
Fig. 5 is the block diagram of technology 3, comprises the polysulfide pretreating process in water extraction stage, polysulfide pretreatment stage and digester(-tor) stage.The water extraction stage is that exemplary extraction stage and available other method for distilling replace.In the water extraction stage, the ligno-cellulosic materials of wood chip form is contacted with steam with pure water.The hemicellulosic materials of the extraction that sugar is streamed is removed.Steam recirculation is back to extractor.To be incorporated into pretreatment stage with polysulfide solution through the ligno-cellulosic materials that extracts, and under the temperature between 120 ℃-140 ℃, use the polysulfide solution preliminary treatment to reach about 2 hours time through the ligno-cellulosic materials that extracts.After this pretreatment stage, ligno-cellulosic materials is incorporated into digester(-tor), here handle, to produce paper pulp and black liquor with white liquid.Pretreatment stage and digester(-tor) stage can carry out in same container.Under 14% water extraction and the polysulfide aqueous solution (6%, 10%, 15% and 20%), carry out technology 3 at four kinds of variable concentrations.
Chart 11 illustrates polysulfide and handles the influence to the productive rate recovery of technology 3.Contrast 1 is simple sulfate process technology.Contrast 2 is for using the simple water extraction of sulfate process technology.Other four curves are under the above polysulfide concentration that provides, according to the polysulfide preliminary treatment of technology 3.Kappa number is used in the paper pulp industry has stay in the paper pulp with explanation for how many lignin.The pulp yield that this caption is compared with various Kappa numbers, and total pulp yield of explanation technology 3 is comparable with two kinds of contrast technologies, and contrast between the technology at these two kinds usually.
Chart 12 illustrates the influence that productive rate is recovered for technology 3 polysulfide preliminary treatment, is that 30 o'clock gross production rate is 44.64% to impinging upon Kappa number wherein.This chart uses the data from chart 11, and how explanation uses the polysulfide solution of various concentration to obtain productive rate under constant Kappa number.For with the bleaching paper pulp, Kappa number be 30 in the paper pulp industry employed typical Kappa number.
Fig. 6 is the block diagram of technology 4, comprises the two pretreating process of water extraction stage, polysulfide and sodium borohydride pretreatment stage and the polysulfide in digester(-tor) stage and sodium borohydride.The water extraction stage is that exemplary extraction stage and available other method for distilling replace.In the water extraction stage, the ligno-cellulosic materials of wood chip form is contacted with steam with pure water.The hemicellulosic materials of the extraction that sugar is streamed is removed.Steam recirculation is back to extractor.To be incorporated into pretreatment stage with polysulfide solution and sodium borohydride solution through the ligno-cellulosic materials that extracts; And under the temperature between 120 ℃-140 ℃, use polysulfide solution and sodium borohydride solution preliminary treatment to reach about 2 hours time through the ligno-cellulosic materials that extracts.After this pretreatment stage, ligno-cellulosic materials is incorporated into digester(-tor), here handle, to produce paper pulp and black liquor with white liquid.Pretreatment stage and digester(-tor) stage can carry out in same container.Under the polysulfide solution of 14% water extraction and five kinds of variable concentrations and sodium borohydride, carry out technology 4:6%PS+0.5%SBH; 10%PS+0.5%SBH; 15%PS+0.5%SBH; 20%PS+0.5%SBH; And 15%PS+0.4%SBH.
Chart 13 illustrates the two influences of handling the productive rate recovery of technology 4 of polysulfide sodium borohydride.The same with chart 11, contrast 1 is simple sulfate process technology.Contrast 2 is for using the simple water extraction of sulfate process technology.Other five curves under the polysulfide aqueous solution of the above variable concentrations that provides and sodium borohydride according to the polysulfide preliminary treatment of technology 4.The pulp yield of this caption under various Kappa numbers, and total pulp yield of explanation technology 4 is comparable with two kinds of contrast technologies, and contrast between the technology at these two kinds usually.
Chart 14 illustrates the influence that productive rate is recovered for technology 4 polysulfide solution and sodium borohydride preliminary treatment, is that 30 o'clock gross production rate is 44.64% to impinging upon Kappa number wherein.This chart uses the data from chart 13, and explains that how under constant Kappa number, using various polysulfide solution to add 0.5% sodium borohydride obtains productive rate.
Fig. 7 is the block diagram of technology 5, comprises the water extraction stage, uses the two stage pretreating process in polysulfide first pretreatment stage, polysulfide and sodium borohydride second pretreatment stage and the digester(-tor) stage of polysulfide recirculation.The water extraction stage is that exemplary extraction stage and available other method for distilling replace.In the water extraction stage, the ligno-cellulosic materials of wood chip form is contacted with steam with pure water.The hemicellulosic materials of the extraction that sugar is streamed is removed.Steam recirculation is back to extractor.To be incorporated into first pretreatment stage with polysulfide solution through the ligno-cellulosic materials that extracts, and under the temperature between 120 ℃-140 ℃, use the polysulfide solution preliminary treatment to reach about 2 hours time through the ligno-cellulosic materials that extracts.The polysulfide solution recirculation that to remove from first pretreatment stage.In this example, the material that gets into first pretreatment stage comprises the polysulfide solution that 30% volume is fresh and the polysulfide solution of 70% volume recirculation.Through extract more liquid from fragment, can improve recirculation percentage.Owing to have polysulfide recirculation, first pretreatment stage must carry out in independent container.
After first pretreatment stage; Under about 140 ℃ temperature; With ligno-cellulosic materials and other polysulfide solution and white liquid (in sulfate process technology; For containing the cooking liquor of NaOH and vulcanized sodium, in industrial system, also contain sodium carbonate) be incorporated into about 1 hour time of second pretreatment stage together.Add anthraquinone, to obtain slight yield advantage.After second pretreatment stage, ligno-cellulosic materials is incorporated into digester(-tor), to produce paper pulp and black liquor.Second pretreatment stage and digester(-tor) stage can carry out in same container.Under the polysulfide solution of 14% water extraction and six kinds of variable concentrations and sodium borohydride, carry out technology 5:15%PS and 0%PS+0.5%SBH subsequently; 15%PS and 2%PS+0.5%SBH subsequently; 15%PS and 4%PS+0.5%SBH subsequently; 15%PS and 5%PS+0.5%SBH subsequently; 15%PS and 6%PS+0.5%SBH subsequently; And 15%PS and 6%PS+0.4%SBH subsequently.
Chart 15 illustrates the influence of polysulfide sodium borohydride two stages preliminary treatment to the productive rate recovery of technology 5.The same with chart 11 and 13, contrast 1 is simple sulfate process technology.Contrast 2 is for using the simple water extraction of sulfate process technology.Other six curves are under the polysulfide aqueous solution and sodium borohydride of the above variable concentrations that provides, according to polysulfide first preliminary treatment and the polysulfide and sodium borohydride second preliminary treatment of technology 5.The pulp yield that this caption is compared with various Kappa numbers, and total pulp yield of explanation technology 5 is comparable with two kinds of contrast technologies, and contrast between the technology at these two kinds usually.
Chart 16 illustrates the influence that the preliminary treatment of two stages recovers the second preliminary treatment productive rate of technology 5, is that the gross production rate of contrast 1 in 30 o'clock is 44.64% at Kappa number wherein, and the gross production rate of contrast 2 is 37.82%.At Kappa number is the productive rate that the center line representative of 30 o'clock productive rates 40.73% obtains through the 15% polysulfide solution preliminary treatment of using polysulfide solution recirculation, that is, and and the productive rate that obtains through fortress (forts) preliminary treatment.This chart uses the data from chart 15, and how explanation obtains productive rate after the polysulfide solution of using various concentration under the constant Kappa number and sodium borohydride second preliminary treatment.
Chart 17 illustrates the influence of 15% polysulfide solution recirculation to pulp yield, and wherein 70% is the polysulfide of recirculation, and 30% is fresh polysulfide.This graph shows polysulfide solution recirculation does not have negative influence, is positive result.
The aspect of a novelty of the present invention is before slurrying, to use the for example ligno-cellulosic materials (technology 3 among Fig. 5) of alkali metals polysulfide (PS) preliminary treatment preextraction hemicellulose of oxidant (OA); Perhaps use Oxidizing and Reducing Agents (technology 4 among Fig. 6) simultaneously; Perhaps use two-stage process; Comprising the polysulfide dipping, then is in the white liquid of aqueous alkaline, to use or do not use the reductant of polysulfide and anthraquinone or derivatives thereof to handle (technology 5 among Fig. 7).In the present invention, before alkaline pulp-making, for stablizing of residual carbon hydrate, in the processing of the ligno-cellulosic materials that extracts hemicellulose, the combination of Oxidizing and Reducing Agents causes having kept pulp yield, and this also is novel operation.
To compare with the contrast paper product by the paper product of technology 3-5 preparation.The PFI of paper pulp that will be through technology 3-5 preparation grinds refining response (PFI mill refining response), apparent density, breaking length, explosive index, tear index and folding resistance and compares by the paper pulp of all-fulfate method prepared with by the paper pulp of the sulfate process prepared through water extraction before.Chart 18-28 illustrates these relatively, and shows, the paper product through technology 3-5 preparation and paper product through all-fulfate method prepared and through before the paper product of sulfate process prepared through water extraction have comparativity.The paper product that will be obtained by each representative version of technology 3-5 is compared with two kinds of contrasts: technology 3:20%PS; Technology 4:15%PS+0.5%SBH; And technology 5:15%PS and 6%PS+0.5%SBH subsequently.
Chart 18 illustrates with respect to contrast sulfate process technology, and the PFI of technology 3-5 grinds the refining response.Chart 19 illustrates with respect to contrast sulfate process technology, the apparent density of technology 3-5.Chart 20 illustrates with respect to contrast sulfate process technology, the apparent density of technology 3-5 under 400ml and 500ml Canadian Standard Freeness (CSF) in more detail.Chart 21 illustrates with respect to contrast sulfate process technology, the breaking length relative with CSF of technology 3-5.Chart 22 illustrates with respect to contrast sulfate process technology, the breaking length relative with CSF of technology 3-5 under the CSF of 400ml and 500ml in more detail.Chart 23 illustrates with respect to contrast sulfate process technology, the explosive index of technology 3-5.Chart 24 illustrates with respect to contrast sulfate process technology, the explosive index of technology 3-5 under the CSF of 400ml and 500ml in more detail.Chart 25 illustrates with respect to contrast sulfate process technology, the tear index relative with breaking length of technology 3-5.Chart 26 illustrates with respect to contrast sulfate process technology, the tear index relative with breaking length of technology 3-5 under the CSF of 400ml and 500ml in more detail.Chart 27 explanations are with respect to contrast sulfate process technology, the folding resistance of technology 3-5.Chart 28 illustrates with respect to contrast sulfate process technology, the number of folds of technology 3-5 under the CSF of 400ml and 500ml in more detail.
Chart 18-28 shows; Similar paper can produced and contrast to this technology; Because have comparativity by the Papermaking Performance of the paper pulp of technology 3-5 preparation and the paper of prior art; And show that this technology can be produced the identical paper of producing with prior art before of paper, but have the added benefit that this technology can be produced other value products.
Fig. 8-10 illustrates the variant of technology 3-5, comprises in the preliminary treatment thing, adding reductant and/or anthraquinone.
Fig. 8 is the block diagram of technology 6, and hemicellulose extracts stage and polysulfide impregnation stage, then uses polysulfide recirculation to make the ligno-cellulosic materials alkaline pulp-making.In the extraction stage, pure water is joined in the fresh ligno-cellulosic materials.Under the temperature of the rising between 120 ℃-180 ℃, handle lignocellulose and water substance subsequently.Be mainly plant polyose, acetate and a spot of lignin in this operating period by the organic matter that fragment discharges.With extract flash distillation (flash), with production preheating steam.A part of aqueous extract recirculation is back to extraction vessel, is used to increase the sugared content of extract.At pretreatment stage; Under the temperature between 80 ℃-180 ℃; Use or do not use anthraquinone (AQ) or derivatives thereof, and use or do not use reductant (RA), handle ligno-cellulosic materials through preextraction with the aqueous based solution of the alkali metals polysulfide that contains q.s.Subsequently polysulfide liquid is taken out and deliver to the polysulfide storage tank, be used for recirculation.In this polysulfide dip operation; The carbohydrate of the remnants of the signal portion of the ligno-cellulosic materials of extraction hemicellulose is converted into carboxyl; This carboxyl is stable, with the alkaline stripping reaction of opposing in the alkaline boiling stage subsequently, thereby improves pulp yield.Use polysulfide recirculation, people must have the independent pretreating containers that separates with the digester(-tor) container.
Fig. 9 is the block diagram of technology 7, uses two preliminary treatment of single stage of polysulfide and RA, and use or do not use the anthraquinone or derivatives thereof is used for the ligno-cellulosic materials of alkaline boiling preextraction hemicellulose.Polysulfide in this technology is arranged in the white liquid of alkalescence, and does not relate to polysulfide recirculation.In the extraction stage, pure water is joined in the fresh ligno-cellulosic materials.Under the temperature of the rising between 120-180 ℃, handle lignocellulose and water substance subsequently.In this operating period, the organic matter that is discharged by fragment is mainly plant polyose, acetate and a spot of lignin.With the extract flash distillation, with production preheating steam.A part of aqueous extract recirculation is back to extraction vessel, is used to improve the sugared content of extract.At pretreatment stage; Under the temperature between 80 ℃-180 ℃; Use or do not use anthraquinone (AQ) or derivatives thereof, use or do not use reductant (RA), handle ligno-cellulosic materials through preextraction with the aqueous based solution of sodium borohydride that contains q.s and alkali metals polysulfide.In this pretreatment operation; The carbohydrate of the remnants of the signal portion of the ligno-cellulosic materials of extraction hemicellulose is converted into carboxyl; This carboxyl is stable, with the alkaline stripping reaction of opposing in the alkaline boiling stage subsequently, thereby improves pulp yield.Do not have polysulfide recirculation, preliminary treatment and digester(-tor) can carry out in same container.
Figure 10 is the block diagram of technology 8, is used to make the two stages preliminary treatment of the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose.In first pretreatment stage, under the temperature of the rising between 120-180 ℃, use or do not use the anthraquinone or derivatives thereof, use polysulfide liquid to handle the ligno-cellulosic materials of preextraction hemicellulose.Subsequently polysulfide liquid is taken out, be used for recirculation.In second pretreatment stage; Use or do not use anthraquinone and derivative thereof; Handle ligno-cellulosic materials with the white liquid of the sulfate process that contains polysulfide and reductant; Kept at least 30 minutes being lower than under 150 ℃ the temperature, continuous subsequently alkaline boiling is being separable fiber with ligno-cellulosic materials delignification.Second handle in the operation at this, the end group of the remnants of the signal portion of ligno-cellulosic materials further is converted into sugar alcohol and carboxyl respectively through reductant and polysulfide or anthraquinone.Polysulfide recirculation is wherein used in preliminary treatment 1, must be in the independent container that separates with preliminary treatment 2 and digester(-tor), and preliminary treatment 2 can be in same container with digester(-tor).
Exemplary process of the present invention may further comprise the steps:
A) at first impregnation stage, being lower than 180 ℃, preferably under the temperature of the rising between 120 ℃-180 ℃, be under the 7.0-13.0 at pH, extract the ligno-cellulosic materials of hemicellulose with the aqueous solution dipping that contains the polysulfide ion; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is oxidized to carboxyl, then takes out to contain the polysulfide ion solution, is used for recirculation;
B) ligno-cellulosic materials that floods with reductant processing first; Said reductant is lithium aluminium hydride reduction, alkali metal borohydride, alkali metal dithionite (alkali metal dithionite (hydrosulfite)), the amalgam of alkali-metal, diisobutylaluminium hydride, oxalic acid, formic acid and/or the hydrogen that in the white liquid of hydroxyl ion solution preferably sulfuric acid salt method, exists for example; The aldehyde end group of remnants that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; Continuous subsequently digestion; Make under the situation that does not have a lot of mechanical actions, ligno-cellulosic materials is separated into fiber.
In step a) and step b) one or both of, also can add other additive (for example anthraquinone or derivatives thereof) and reductant, to improve the productive rate of resulting paper pulp.Pulp yield that this method produces and pulp quality and only alkaline boiling ligno-cellulosic materials are resulting similar; Just strength character changes slightly; And compare with the alkaline boiling of only traditional alkaline boiling or the ligno-cellulosic materials that extracts through hemicellulose before, digestion time significantly reduces.In step b), only use the white liquid of hydroxyl ion solution or sulfate process, and do not have other chemical addition agent, to keep the pulp yield lower slightly than conventional alkaline pulp-making.All these methods also can be used for by fresh ligno-cellulosic materials production quality paper pulp, and do not carry out the preextraction of hemicellulose in order to obtain than the higher pulp yield of the alkaline technology of routine.
Use technology of the present invention disclosed herein, before slurrying, can recover by about 5% of the caused pulp yield loss of preextraction hemicellulose (total 7%) with the processing of 15-20% polysulfide.Preliminary treatment when using 15% polysulfide and 0.5% sodium borohydride can realize the recovery fully of pulp yield loss (7%).The two stages modification sulfate process technology that 15% polysulfide of use recirculation is followed with the SBH of 6% polysulfide and 0.4-0.5% realizes that also 100% productive rate recovers.In addition, continuous recirculation 15% polysulfide keeps its productive rate protection efficient in technology subsequently.
Exist various additive methods to carry out the present invention.The representative universal method that is used to produce paper pulp may further comprise the steps:
A) extract organic matter in the extraction stage from ligno-cellulosic materials, wherein, the said extraction stage is single extraction or two extraction process;
B) the processing stage use the oxidizer treatment ligno-cellulosic materials, wherein, be selected from the group of forming by second extraction process, reagent-impregnated technology and first pretreating process processing stage of said;
C) the processing stage handle ligno-cellulosic materials with reductant, wherein, be selected from the group of forming by second extraction process, reagent-impregnated technology and second pretreating process processing stage of said; And subsequently
D) make ligno-cellulosic materials stand modified sulphur hydrochlorate method pulping process, to produce paper pulp.
Said method can comprise two extraction processes, in the first extraction stage, uses water extraction, in the second extraction stage or first pretreating process, extracts together with oxidant and additive, then in digester(-tor), uses anthraquinone to carry out sulfate pulping technology.In the extraction stage, can under the temperature between about 120 ℃-180 ℃, handle ligno-cellulosic materials and water.With Oxidizing and Reducing Agents, can the ligno-cellulosic materials through extraction be joined for the second extraction stage with water, and under the temperature of the rising between about 120 ℃-180 ℃, handle.With NaOH and vulcanized sodium, can the ligno-cellulosic materials through two extractions be joined digester(-tor) with water, to produce paper pulp.
The group that alkaline vulcanized sodium of the optional freedom of oxidant and polysulfide are formed, and reductant is selected from the group of being made up of sodium borohydride, sodium dithionite and in-situ hydrogen.
Said method selectively can be included in the extraction stage makes the single stage extraction process of water, then is to comprise with the pretreated two stages modification of oxidant sulfate pulping.In the extraction stage, can under the temperature between about 120 ℃-180 ℃, handle ligno-cellulosic materials and water.With Oxidizing and Reducing Agents, the processing stage of can the ligno-cellulosic materials through extraction being joined with other water, and under the temperature of the rising between about 120 ℃-180 ℃, handle.With NaOH and vulcanized sodium, can ligno-cellulosic materials be joined digester(-tor), to produce paper pulp.
Said method selectively can be the single stage oxidant pretreating process that uses polysulfide recirculation, is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose, and said method is further comprising the steps of:
A) with the ligno-cellulosic materials of oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion, and the aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is oxidized to carboxyl; And
B) handle ligno-cellulosic materials with reductant through dipping; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; Continuous subsequently digestion ligno-cellulosic materials; Make under the situation that does not have a lot of mechanical actions, ligno-cellulosic materials is separated into fiber.
Said method selectively can be two preliminary treatment of the single stage that does not have the use of polysulfide recirculation Oxidizing and Reducing Agents, is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose, and said method is further comprising the steps of:
A) with the ligno-cellulosic materials of oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion, and the aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is oxidized to carboxyl; And
B) handle ligno-cellulosic materials with reductant through dipping; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; And continuous subsequently digestion ligno-cellulosic materials; Make under the situation that does not have a lot of mechanical actions, ligno-cellulosic materials is separated into fiber.
Said method selectively can be use polysulfide recirculation with oxidant then with two stage pretreating process of reductant, be used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose, said method is further comprising the steps of:
A) with the ligno-cellulosic materials of oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion, and the aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is oxidized to carboxyl; And
B) handle ligno-cellulosic materials with reductant through dipping; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; And continuous subsequently digestion ligno-cellulosic materials; Make under the situation that does not have a lot of mechanical actions, ligno-cellulosic materials is separated into fiber.
Said method can be carried out being lower than under 180 ℃ the temperature, and step a) can be carried out under the 7.0-13.0 in temperature between 120 ℃-180 ℃ and pH, and step b) can be carried out under the temperature between 80 ℃-180 ℃.Other additive can in step a) and step b) one or both of, be added, to improve resulting pulp yield.The said other optional freedom of additive is the group of anthraquinone, anthraquinone derivative and reductant composition for example.Said reductant is selected from by lithium aluminium hydride reduction, alkali metal borohydride, alkali metal dithionite, the amalgam of alkali-metal, diisobutylaluminium hydride, oxalic acid, formic acid and/or the group formed at the hydrogen that the hydroxyl ion solution for example exists in the white liquid of sulfate process.Can a part be back to the extraction stage from the extract recirculation of extracting the stage, be used to improve the sugared content of extract.Though preferred embodiment comprise water and/or steam extraction technology, extraction process is not limited to water or steam.In second pretreating process, use or do not use anthraquinone and derivative thereof, can use the white liquid of the sulfate process that contains polysulfide and reductant to handle ligno-cellulosic materials, and second pretreating process can be lower than under 150 ℃ the temperature maintenance at least 30 minutes.
The above detailed description of preferred implementation, embodiment and accompanying drawing is only presented for purposes of illustration, be not intended to limit scope of the present invention and spirit, and scope of the present invention is defined by accompanying claims with spirit.Those skilled in the art recognize that, under the situation that does not depart from scope of the present invention and spirit, can carry out various deformation disclosed in this manual the present invention.

Claims (49)

1. the method for the ligno-cellulosic materials protected from degradation of protection preextraction hemicellulose in alkaline pulp-making technology, said method comprises:
A) water or steam extract organic matter from ligno-cellulosic materials;
B) with Oxidizing and Reducing Agents or the said ligno-cellulosic materials of additive treating, wherein, said processing comprises that also second extracts; And
C) in digester(-tor), make said ligno-cellulosic materials stand sulfate pulping technology.
2. method according to claim 1, wherein, said extraction also is included in and handles said ligno-cellulosic materials and water under the temperature between about 120 ℃-180 ℃.
3. method according to claim 2 wherein, with said oxidant and said reductant, will join said second with water through the said ligno-cellulosic materials that extracts and extract, and under the temperature of the rising between about 120 ℃-180 ℃, handle.
4. method according to claim 3 wherein, with NaOH and vulcanized sodium, will join said digester(-tor) with water through the said ligno-cellulosic materials of two extractions, to produce paper pulp.
5. method according to claim 4, wherein, said oxidant is selected from the group of being made up of polysulfide, and said reductant is selected from the group of being made up of sodium borohydride, sodium dithionite and in-situ hydrogen.
6. the method for the ligno-cellulosic materials protected from degradation of protection preextraction hemicellulose in alkaline pulp-making technology, said method comprises:
A) water or steam extract organic matter from ligno-cellulosic materials;
B) handle said ligno-cellulosic materials with Oxidizing and Reducing Agents; And
C) in digester(-tor), make said ligno-cellulosic materials stand sulfate pulping technology, to produce paper pulp.
7. method according to claim 6, wherein, said extraction also is included in and handles said ligno-cellulosic materials and water under the temperature between about 120 ℃-180 ℃.
8. method according to claim 7, wherein, said processing also comprises with said oxidant and said reductant, and other water is added said ligno-cellulosic materials, and under the temperature of the rising between about 120 ℃-180 ℃, further handles.
9. method according to claim 8 wherein, with NaOH and vulcanized sodium, joins said digester(-tor) with treated ligno-cellulosic materials, to produce paper pulp.
10. method according to claim 9, wherein, said oxidant is selected from the group of being made up of polysulfide, and said reductant is selected from the group of being made up of sodium borohydride, sodium dithionite and in-situ hydrogen.
11. the method for the ligno-cellulosic materials protected from degradation of protection preextraction hemicellulose in alkaline pulp-making technology, said method comprises:
A) water or steam extract organic matter from ligno-cellulosic materials;
B) with the said ligno-cellulosic materials of oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion;
C) handle said ligno-cellulosic materials with reductant through dipping; And
D) in digester(-tor), make said ligno-cellulosic materials stand sulfate pulping technology,, make said ligno-cellulosic materials be separated into fiber to produce paper pulp.
12. method according to claim 11, wherein, said being immersed under the temperature that is lower than 180 ℃ carried out.
13. method according to claim 11, wherein, the said pH of being immersed in carries out under the 7.0-13.0.
14. method according to claim 11 wherein, in said dipping or said processing, also comprises the adding additive, to improve the productive rate of gained paper pulp.
16. method according to claim 14, wherein, said additive is selected from the group of being made up of anthraquinone, anthraquinone derivative and reductant.
17. method according to claim 11; Wherein, said reductant is selected from by lithium aluminium hydride reduction, alkali metal borohydride, alkali metal dithionite, the amalgam of alkali-metal, diisobutylaluminium hydride, oxalic acid, formic acid and/or the group formed at the hydrogen that the hydroxyl ion solution for example exists in the white liquid of sulfate process.
18. method according to claim 11 wherein, will be returned from a part of aqueous extract recirculation of said extraction, be used to improve the sugared content of said extract.
19. method according to claim 11, wherein, said processing is carried out under the temperature between 80 ℃-180 ℃.
20. method according to claim 11 wherein, will contain the polysulfide ion solution and from said dipping, take out and deliver to the polysulfide storage tank, be used for recirculation.
21. the method for the ligno-cellulosic materials protected from degradation of protection preextraction hemicellulose in alkaline pulp-making technology, said method comprises:
A) water or steam extract organic matter from ligno-cellulosic materials;
B) the said ligno-cellulosic materials that extracts hemicellulose with first oxidizer treatment is as first preliminary treatment, and wherein, said oxidant is the aqueous solution that contains the polysulfide ion;
C) handle said ligno-cellulosic materials as second preliminary treatment with second Oxidizing and Reducing Agents; And
D) in digester(-tor), make said ligno-cellulosic materials stand sulfate pulping technology, to produce paper pulp.
22. method according to claim 21, wherein, said first preliminary treatment is carried out being lower than under 180 ℃ the temperature.
23. method according to claim 21, wherein, said first preliminary treatment is to carry out under the 7.0-13.0 at pH.
24. method according to claim 21 wherein, in said first preliminary treatment or said second preliminary treatment, also comprises the adding additive, to improve resulting pulp yield.
25. method according to claim 24, wherein, said additive is selected from the group of being made up of anthraquinone, anthraquinone derivative and reductant.
26. method according to claim 21; Wherein, said reductant is selected from by lithium aluminium hydride reduction, alkali metal borohydride, alkali metal dithionite, the amalgam of alkali-metal, diisobutylaluminium hydride, oxalic acid, formic acid and/or the group formed at the hydrogen that the hydroxyl ion solution for example exists in the white liquid of sulfate process.
27. method according to claim 21 wherein, will be returned from a part of aqueous extract recirculation of said extraction, be used to improve the sugared content of said extract.
28. method according to claim 21 wherein, will contain the polysulfide ion solution and from said first preliminary treatment, take out and deliver to the polysulfide storage tank, be used for recirculation.
29. method according to claim 21, wherein, said first preliminary treatment is carried out under the temperature between 80 ℃-180 ℃.
30. method according to claim 21 wherein, in said second preliminary treatment, is handled said ligno-cellulosic materials with the white liquid of sulfate process that contains polysulfide and reductant.
31. method according to claim 30, wherein, said second preliminary treatment was carried out 30 minutes being lower than under 150 ℃ the temperature at least.
32. a system that is used in the ligno-cellulosic materials protected from degradation of alkaline pulp-making technology protection preextraction hemicellulose, said system comprises:
A) be used for the device of water extraction, discharge organic matter from said ligno-cellulosic materials at this device that is used for water extraction;
B) be used to the device handling or flood, this be used for handling or the device that floods Oxidizing and Reducing Agents is joined said in the ligno-cellulosic materials of preextraction, the organic matter that extracts with compensation; And
C) digester(-tor) is separated into fiber with said ligno-cellulosic materials in this digester(-tor), to produce paper pulp.
33. a method that is used to produce paper pulp said method comprising the steps of:
A) from ligno-cellulosic materials, extract hemicellulosic materials;
B) through being selected from the technology of the group of forming by extraction process, reagent-impregnated technology and first pretreating process, with the said ligno-cellulosic materials of oxidizer treatment;
C) through being selected from the technology of the group of forming by extraction process, reagent-impregnated technology and second pretreating process, handle said ligno-cellulosic materials with reductant; And subsequently
D) make said ligno-cellulosic materials stand modified sulphur hydrochlorate method pulping process, to produce paper pulp.
34. method according to claim 33 wherein, in extraction process, is handled said ligno-cellulosic materials under the temperature between about 120 ℃-180 ℃.
35. method according to claim 34, wherein, said oxidant is selected from the group of being made up of polysulfide.
36. method according to claim 35; Wherein, said reductant is selected from by lithium aluminium hydride reduction, alkali metal borohydride, alkali metal dithionite, the amalgam of alkali-metal, diisobutylaluminium hydride, oxalic acid, formic acid and/or the group formed at the hydrogen that the hydroxyl ion solution for example exists in the white liquid of sulfate process.
37. method according to claim 36; Wherein, Said method is included in the first extraction stage and uses water extraction; In the second extraction stage or first pretreating process, extract together, then in digester(-tor), carry out two extraction processes of modified sulphur hydrochlorate method pulping process with anthraquinone with oxidant and additive.
38. method according to claim 36, wherein, said method comprises it then being the single stage extraction process that comprises with the pretreated two stages modification of oxidant sulfate pulping.
39. method according to claim 36, wherein, said method is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose for using the single stage oxidant pretreating process of polysulfide recirculation.
40. according to the described method of claim 39, said method is further comprising the steps of:
A) with the ligno-cellulosic materials of said oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion, and the aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is oxidized to carboxyl;
B) handle said ligno-cellulosic materials with reductant through dipping; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; And the continuous subsequently said ligno-cellulosic materials of digestion; Make and under the situation that does not have a lot of mechanical actions, said ligno-cellulosic materials is separated into fiber.
41. according to the described method of claim 40, said method comprises that also adding is selected from the other additive of the group of being made up of anthraquinone, anthraquinone derivative and reductant.
42. according to the described method of claim 41, wherein, will be back to said extraction process, be used to improve the sugared content of said hemicellulosic materials from a part of aqueous extract recirculation of said extraction process.
43. method according to claim 36, wherein, said method with two preliminary treatment of single stage that Oxidizing and Reducing Agents carries out, is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose for there not being polysulfide recirculation.
44. according to the described method of claim 43, said method is further comprising the steps of:
A) with the ligno-cellulosic materials of said oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion, and the aldehyde end group of the ligno-cellulosic materials of said thus extraction hemicellulose is oxidized to carboxyl;
B) handle said ligno-cellulosic materials with reductant through dipping; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; And the continuous subsequently said ligno-cellulosic materials of digestion; Make and under the situation that does not have a lot of mechanical actions, said ligno-cellulosic materials is separated into fiber.
45. according to the described method of claim 44, said method comprises that also adding is selected from the other additive of the group of being made up of anthraquinone, anthraquinone derivative and reductant.
46. according to the described method of claim 45, wherein, will be back to said extraction process, be used to improve the sugared content of said hemicellulosic materials from a part of aqueous extract recirculation of said extraction process.
47. method according to claim 36, wherein, said technology with the two stage pretreating process that oxidant then carries out with reductant, is used to make the ligno-cellulosic materials alkaline pulp-making of preextraction hemicellulose for using polysulfide recirculation.
48. according to the described method of claim 47, said method is further comprising the steps of:
A) with the ligno-cellulosic materials of said oxidant dipping extraction hemicellulose, wherein, said oxidant is the aqueous solution that contains the polysulfide ion, and the aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is oxidized to carboxyl;
B) handle said ligno-cellulosic materials with reductant through dipping; The aldehyde end group that extracts the ligno-cellulosic materials of hemicellulose thus is reduced to sugar alcohol or sulfo-sugar alcohol; And the continuous subsequently said ligno-cellulosic materials of digestion; Make and under the situation that does not have a lot of mechanical actions, said ligno-cellulosic materials is separated into fiber.
49. according to the described method of claim 48, said method comprises that also adding is selected from the other additive of the group of being made up of anthraquinone, anthraquinone derivative and reductant.
50. according to the described method of claim 49, wherein, will be back to said extraction process, be used to improve the sugared content of said hemicellulosic materials from a part of aqueous extract recirculation of said extraction process.
CN2010800154207A 2009-04-02 2010-04-02 Pulping process for quality protection including methods for hemicellulose extraction and treatment of hemicellulose -extracted lignocellulosic materials Pending CN102388177A (en)

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