WO2019119741A1 - 一种甲醇介导的半纤维素碱溶液分离方法以及一种乙醇介导的半纤维素碱溶液分离方法 - Google Patents

一种甲醇介导的半纤维素碱溶液分离方法以及一种乙醇介导的半纤维素碱溶液分离方法 Download PDF

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WO2019119741A1
WO2019119741A1 PCT/CN2018/090851 CN2018090851W WO2019119741A1 WO 2019119741 A1 WO2019119741 A1 WO 2019119741A1 CN 2018090851 W CN2018090851 W CN 2018090851W WO 2019119741 A1 WO2019119741 A1 WO 2019119741A1
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hemicellulose
alkaline solution
ethanol
methanol
solution
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PCT/CN2018/090851
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English (en)
French (fr)
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徐勇
罗京
余世袁
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南京林业大学
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Priority claimed from CN201711414868.6A external-priority patent/CN108047353A/zh
Priority claimed from CN201810200978.0A external-priority patent/CN108484798A/zh
Application filed by 南京林业大学 filed Critical 南京林业大学
Priority to US16/333,944 priority Critical patent/US20200377622A1/en
Publication of WO2019119741A1 publication Critical patent/WO2019119741A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
    • B01D21/262—Separation of sediment aided by centrifugal force or centripetal force by using a centrifuge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
    • B01D3/002—Processes specially adapted for distillation or rectification of fermented solutions by continuous methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/08—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in rotating vessels; Atomisation on rotating discs
    • B01D3/085—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in rotating vessels; Atomisation on rotating discs using a rotary evaporator
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
    • B01D9/0054—Use of anti-solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F21/00—Dissolving
    • B01F21/02—Methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/14—Hemicellulose; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D2009/0086—Processes or apparatus therefor
    • B01D2009/009—Separation of organic compounds by selective or extractive crystallisation with the aid of auxiliary substances forming complex or molecular compounds, e.g. with ureum, thioureum or metal salts

Definitions

  • the invention relates to the technical field of hemicellulose separation, in particular to a methanol-mediated hemicellulose alkali solution separation method and an ethanol-mediated hemicellulose alkali solution separation method.
  • Hemicellulose mainly refers to linear or branched-type polysaccharides with xylan or glucomannan as the main chain, which is the second largest class of lignocellulosic materials second only to cellulose. Glycan component.
  • pulp, viscose fiber, hemicellulose and xylooligosaccharide in the chemical and biological processing of lignocellulosic materials and their semi-finished products, it is necessary to use a strong alkaline solution with a mass concentration of 5% to 25%.
  • the solution must effectively separate the xylan contained therein to reuse the alkali solution, reduce water consumption and environmental pollution, and reduce production costs.
  • the existing hemicellulose alkali solution separation basically adopts the ultrafiltration method, but the conventional ultrafiltration device generally has difficulty in directly treating the hemicellulose alkali solution having such alkali concentration and high viscosity, even if diluted with water, the ultrafiltration operation will generate a large amount.
  • a low-concentration alkaline permeate containing a portion of the hemicellulose-permeable component causes a barrier to lye reuse, which ultimately results in high water consumption, membrane loss, and operating costs.
  • the invention aims at the problem that the hemicellulose alkaline solution is difficult to be efficiently separated and reused, and provides a methanol-mediated hemicellulose alkali solution separation method and an ethanol-mediated hemicellulose alkali solution separation method.
  • the invention fully utilizes the physicochemical properties of the separation and precipitation of hemicellulose dissolved in an alkaline solution by methanol, forms a hydrophobic effect by methanol, destroys the affinity effect between hemicellulose and an alkaline solution, and promotes hemicellulose from The methanol alkaline solution is efficiently separated and precipitated in situ to achieve high-efficiency separation and preparation of hemicellulose.
  • the recovery rate of hemicellulose exceeds 99%, and the residual rate of hemicellulose in methanol alkaline solution is less than 0.2%.
  • Methanol evaporation in an alkaline aqueous solution and physicochemical properties of gasification, using steam (fine) distillation or gasification membrane to efficiently separate methanol alkaline solution system to obtain methanol, alkaline solution, can complete the recovery of methanol, alkaline solution
  • the residual methanol ratio is less than 0.02%.
  • the invention utilizes ethanol to effectively destroy the hydrogen bond and the hydration layer of the hemicellulose molecule in the strong alkaline solution, change the conformation of the high molecular macromolecule, thereby significantly reducing the solubility and promoting the precipitation of hemicellulose from the strong alkaline solution.
  • the technical solution adopted by the present invention is:
  • the alkaline solution is any one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate solution or a mixture thereof.
  • the hemicellulose is any one of a linear or a bulk type derived from xylan or glucomannan as a main chain or a mixture thereof.
  • the volume ratio of methanol to alkaline solution is from 1 to 4:1.
  • the method of solid-liquid separation is decantation, siphoning, overflow, filtration or centrifugation, and combinations thereof.
  • step 1) the sediment is allowed to stand for 5 to 30 minutes.
  • the recovery rate of hemicellulose exceeds 99%, and the residual ratio of hemicellulose in the alkaline solution of methanol is less than 0.5%;
  • the methanol recovery rate exceeds 98%, and the residual methanol concentration in the alkaline solution is less than 0.05%.
  • the invention also provides a method for separating and recovering hemicellulose in a strong alkaline solution in situ, comprising the following steps:
  • step (2) solid-liquid separation of the solution system prepared in step (1) by decantation, siphoning, overflow, filtration or centrifugation, respectively obtaining ethanol alkali solution supernatant and hemicellulose precipitate, hemicellulose mass recovery
  • the rate is over 90%;
  • step (1) adding an appropriate amount of ethanol solution to wash and separate the precipitate to a pH of 6.00 to 7.00 to prepare high-purity hemicellulose; combining the ethanol cleaning solution with the ethanol base of step (2)
  • the solution can be reused by distillation, rectification or gasification membrane to obtain ethanol and strong alkaline solution; the mass recovery of ethanol exceeds 92%, and the residual ethanol concentration in the strong alkaline solution is less than 0.05g/L.
  • the hemicellulose in the strongly alkaline solution refers to a linear or bulky single substance mainly composed of xylan or glucoside glycan, or a mixture of the two.
  • the amount of ethanol added is calculated from the initial volume ratio of the strongly alkaline solution, and the volume ratio of ethanol is 20% to 80%.
  • the strongly alkaline solution refers to an alkaline solution prepared by using any one of sodium hydroxide, potassium hydroxide, liquid ammonia or any combination thereof, and the solution has a pH of ⁇ 10.0.
  • the separation method of the ethanol alkali solution mixing system refers to any one of decantation, siphoning, overflow, filtration or centrifugation methods or any combination thereof.
  • the gasification separation and reuse method of the ethanol alkaline solution refers to any one of distillation, rectification, gasification membrane separation or any combination thereof; ethanol mass recovery rate exceeds 92%, strong alkaline solution
  • the residual ethanol concentration is less than 0.05 g/L.
  • the method of the invention can achieve high-efficiency separation and reuse of hemicellulose and alkaline solution, water consumption and significantly reduce power consumption and production cost; the boiling point of methanol is significantly reduced and does not form with water.
  • the boiling, the evaporation (refining) and the gasification separation of the alkaline solution are better and lower in cost, and have good practicability.
  • Rotary evaporator was used to control the vacuum degree of 100 mbar and the bottom liquid temperature of 55-64 ° C.
  • the methanol alkali solution was separated by 2 ° C water as the condensing medium.
  • the methanol mass recovery rate exceeded 98.6%, and the methanol residual mass concentration in the alkali solution. Below 0.02%, the obtained methanol solution and strong alkaline solution can be reused.
  • the packed rectification column is used to control the vacuum degree of 100 mbar and the bottom liquid temperature of 65-70 ° C, and the methanol alkali solution is separated by distillation of 2 ° C water as a condensing medium until the methanol mass recovery exceeds 98.4%, and the residual mass of methanol in the alkali solution When the concentration is less than 0.05%, the obtained methanol solution and strong alkaline solution can be reused.
  • the hemicellulose was obtained by centrifuging the precipitate, and the recovery rate of hemicellulose was 91.4%; the ethanolic alkali solution was obtained by combining the supernatant, and the alkali recovery rate was 95%.
  • Rotary evaporator was used to control the vacuum degree of 100 mbar and the bottom liquid temperature of 60-62 ° C.
  • the ethanol alkali solution was separated by condensing medium at 18 ° C water until the mass recovery of ethanol exceeded 96.2%, and the residual mass concentration of ethanol in the alkali solution Below 0.03%, the obtained ethanol solution and strong alkaline solution can be reused.
  • the ethanolic alkali solution was obtained by combining the supernatants, and the alkali recovery rate was 98%.
  • the packed rectification column is used to control the vacuum degree of 100 mbar and the bottom liquid temperature of 68-70 ° C, and the ethanol alkali solution is separated by condensing medium distillation at 18 ° C water until the mass recovery rate of ethanol exceeds 95%, and the residual quality of ethanol in the alkali solution When the concentration is less than 0.04%, the obtained ethanol solution and strong alkaline solution can be reused.
  • the hemicellulose was obtained by centrifuging the precipitate, and the recovery rate of hemicellulose was 91.4%; the ethanolic alkali solution was obtained by combining the supernatant, and the alkali recovery rate was 95%.
  • Rotary evaporator was used to control the vacuum degree of 100 mbar and the bottom liquid temperature of 60-62 ° C.
  • the ethanol alkali solution was separated by condensing medium at 18 ° C water until the mass recovery of ethanol exceeded 96.2%, and the residual mass concentration of ethanol in the alkali solution Below 0.03%, the obtained ethanol solution and strong alkaline solution can be reused.
  • the ethanolic alkali solution was obtained by combining the supernatants, and the alkali recovery rate was 98%.
  • the packed rectification column is used to control the vacuum degree of 100 mbar and the bottom liquid temperature of 68-70 ° C, and the ethanol alkali solution is separated by condensing medium distillation at 18 ° C water until the mass recovery rate of ethanol exceeds 95%, and the residual quality of ethanol in the alkali solution When the concentration is less than 0.04%, the obtained ethanol solution and strong alkaline solution can be reused.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

本发明公开了一种甲醇介导的半纤维素碱溶液分离方法以及乙醇介导的半纤维素碱溶液分离方法，向溶解半纤维素的碱性溶液中加入甲醇/乙醇充分混匀，通过甲醇/乙醇介导的疏水作用破坏半纤维素与碱性溶液间形成的水化层作用，使半纤维素从溶液体系中析出，并经沉降、离心或过滤分离得到半纤维素沉淀物与碱性甲醇/乙醇溶液；利用碱性条件对甲醇/乙醇与水蒸发和气化分离的促进作用，采用减压蒸(精)馏或气化膜分离甲醇/乙醇与碱性溶液，所制得的碱性溶液、甲醇/乙醇再回用于溶解半纤维素及分离。通过本方法的强碱性溶液、甲醇/乙醇的完全回用，实现碱溶解与分离半纤维素的高效、清洁和节约化生产，碱溶解半纤维素的分离与回收效率超过99％。

Description

一种甲醇介导的半纤维素碱溶液分离方法以及一种乙醇介导的半纤维素碱溶液分离方法
本申请要求于2017年12月20日提交中国专利局、申请号为CN201711414868.6、发明名称为“一种原位分离和回收强碱性溶液中半纤维素的方法”的中国专利申请，以及于2018年03月12日提交中国专利局、申请号为CN201810200978.0、发明名称为“一种甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及半纤维素分离技术领域，尤其涉及一种甲醇介导的半纤维素碱溶液分离方法以及一种乙醇介导的半纤维素碱溶液分离方法。
背景技术
半纤维素主要是指以木聚糖或葡甘聚糖为主链的线性或带有支链的体型高聚糖类物质，它是木质纤维原料中仅次于纤维素的第二大类高聚糖组分。在木质纤维原料及其半成品的化学和生物等加工制备纸浆、粘胶纤维、半纤维素以及低聚木糖等产品的生产过程中，需要使用质量浓度为5％～25％的强碱性溶液，如氢氧化钠、氢氧化钾、液氮等处理从原料中溶解、分离出木聚糖、甘露聚糖半纤维素组分，因而会生成大量富含半纤维素的高粘度、强碱性溶液，必须有效分离出其中所含有的木聚糖以回用碱溶液，减少水耗和环境污染，降低生产成本。现有的半纤维素碱溶液分离基本上都采用超滤方法，但是常规超滤装置一般难以直接处理如此碱浓度和高粘度的半纤维素碱溶液，即便加水稀释后超滤操作也会产生大量含有部分半纤维素透过组分的低浓碱性透过液，造成碱液回用的障碍，最终造成生产的水耗、膜损耗和运行成本高昂。
发明内容
本发明针对半纤维素碱性溶液难以高效分离与回用的问题，供一种甲醇介导的半纤维素碱溶液分离方法以及一种乙醇介导的半纤维素碱溶液分离方法。
本发明充分利用甲醇对溶解于碱性溶液中半纤维素分离与沉淀的物化特性，以甲醇介导形成疏水效应，破坏半纤维素与碱性溶液之间的亲和效应，促使半纤维素从甲醇碱性溶液高效分离并原位沉淀析出，以实现半纤维素的高效分离与制备，半纤维素的回收率超过99％，甲醇碱性溶液中半纤维素的残留率低于0.2％；利甲醇在碱性水溶液中的蒸发与气化的物化特性，采用蒸(精)馏或气化膜以高效分离甲醇碱性溶液体系分别制得甲醇、碱性溶液，可完成回收甲醇，碱性溶液中甲醇残留率低于0.02％。
本发明利用乙醇有效破坏半纤维素分子在强碱性溶液中的氢键及水化层、改变高聚糖大分子的构象，进而显著降低其溶解度，促进半纤维素从强碱性溶液中沉淀析出以实现其原位高效分离；同时，利用高浓度碱对乙醇/水体系萃取蒸馏性能的提升作用，采用蒸馏、精馏或气化膜技术高效分离乙醇、碱溶液，进而提高它们回用的质量性能，最终实现半纤维素强碱性溶液的简单、快速和高效分离与回收，显著提高强碱法溶解分离制备半纤维素生产体系的经济效益和环境效益。
为了解决上述技术问题，本发明采用的技术方案是：
一种甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，包括以下步骤：
1)向溶解半纤维素的碱性溶液中加入甲醇，充分搅拌混匀，静置沉降；
2)固液分离步骤1)的体系，得到上清液为甲醇碱性溶液，沉淀物为半纤维素；
3)采用蒸馏或精馏或气化膜分离甲醇碱性溶液分别得到甲醇、碱性溶液；
4)分离得到的碱性溶液、甲醇，再回用于半纤维素溶解与分离制备。
优选的，所述碱性溶液为氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾溶液中的任意一种或它们的混合液。
优选的，所述半纤维素为来自于木聚糖或葡甘聚糖为主链的线性或体型中的任意一种或它们的混合。
优选的，步骤1)中，甲醇与碱性溶液体积比为1～4：1。
优选的，步骤2)中，固液分离的方法为倾析、虹吸、溢流、过滤或 离心以及它们的组合。
优选的，步骤1)中，静置沉降5～30分钟。
优选的，步骤2)中，半纤维素回收得率超过99％，甲醇碱性溶液中半纤维素的残留率低于0.5％；
优选的，步骤3)中，甲醇回收率超过98％，碱性溶液中残留的甲醇浓度低于0.05％。
本发明还提供了一种原位分离和回收强碱性溶液中半纤维素的方法，包括下面步骤：
(1)在充分搅拌条件下，按溶液的初始体积比，向含有半纤维素的强碱性溶液中匀速加入20％～80％乙醇，混合均匀后于室温条件下静置15～150min，使半纤维素从强碱性溶液体系中原位沉淀析出；
(2)采用倾析、虹吸、溢流、过滤或离心方法对步骤(1)制备的溶液体系进行固液分离，分别得到乙醇碱溶液上清液和半纤维素沉淀物，半纤维素质量回收率超过90％；
(3)可按照步骤(1)的乙醇体积浓度，加入适量的乙醇溶液清洗和分离沉淀物至pH值6.00～7.00以制备高纯度半纤维素；合并乙醇清洗液与步骤(2)的乙醇碱溶液，采用蒸馏、精馏或气化膜分离得到乙醇、强碱性溶液即可回用；乙醇质量回收率超过92％，强碱性溶液中残留的乙醇浓度低于0.05g/L。
优选的，所述强碱性溶液中的半纤维素是指以木聚糖或葡苷聚糖为主链的线性或体型的单一物质或者它们两者的混合物。
优选的，加入乙醇量以其与强碱性溶液初始体积比计算，乙醇的体积比为20％～80％。
优选的，所述的强碱性溶液是指采用氢氧化钠、氢氧化钾、液氨其中任意一种物质或它们的任意组合所配制的碱性溶液，溶液pH≥10.0。
优选的，乙醇碱溶液混合体系的分离方法是指倾析、虹吸、溢流、过滤或离心方法的任意一种方法或它们的任意组合方法。
优选的，所述乙醇碱性溶液的气化分离回用方法是指蒸馏、精馏、气化膜分离的任意一种方法或者它们的任意组合；乙醇质量回收率超过92％，强碱性溶液中残留乙醇浓度低于0.05g/L。
与现有技术相比，采用本发明方法可以实现半纤维素与碱性溶液的高效分离与回用，无水耗且显著降低电耗和生产成本；甲醇的沸点显著降低且不与水形成共沸物，与碱性溶液的蒸发(精馏)与气化分离的效果更好且成本更低，具有很好的实用性。
具体实施方式
下面结合实施例对本发明进一步说明。
实施例1
在反应罐中加入300mL半纤维素强碱性溶液(pH11.0，半纤维素质量浓度3.0％，氢氧化钠质量浓度17％)，匀速流加750mL甲醇至混合均匀，在室温条件下静置15min至沉淀完全。采用管式离心机于9000g离心力条件下离心分离剩余溶液5min得到沉淀物，采用200mL的70％甲醇溶液分2次洗涤沉淀物即得到半纤维素，半纤维的回收率达到99.2％；离心上清液为甲醇碱溶液，碱回收率达到98％。采用旋转蒸发仪，控制真空度100mbar和釜底料液温度55～64℃，以2℃水为冷凝介质精馏分离甲醇碱溶液，至甲醇质量回收率超过98.6％，碱溶液中甲醇残余质量浓度低于0.02％，所得到的甲醇溶液、强碱性溶液即可回用。
实施例2
在锥底不锈钢反应罐中加入10L半纤维素强碱性溶液(pH13.8，半纤维素质量浓度4.0％，氢氧化钠质量浓度20％)，启动机械搅拌装置，匀速流加30L甲醇至混合均匀，在室温条件下静置30min至沉淀完全。采用管式离心机于9000g离心力条件下离心分离剩余溶液10min得到沉淀物，以6L的70％浓度甲酸溶液分2次洗涤沉淀物即得半纤维素，半纤维素回收率达到99.1％；离心上清液得甲醇碱溶液，碱回收率达到98％。采用填料精馏塔，控制真空度100mbar和釜底料液温度65～70℃，以2℃水为冷凝介质精馏分离甲醇碱溶液，至甲醇质量回收率超过98.4％，碱溶液中甲醇残余质量浓度低于0.05％，所得到的甲醇溶液、强碱性溶液即可回用。
对比例1
在反应罐中加入300mL半纤维素强碱性溶液(pH11.0，半纤维素质量浓度3.0％，氢氧化钠质量浓度17％)，启动机械搅拌装置，匀速流加 300mL乙醇至混合均匀，在室温条件下静置30min至沉淀完全。利用吸管吸取上清液A至400mL，采用管式离心机于5844g离心力条件下离心分离剩余溶液60min得到沉淀物，以500mL乙醇溶液(乙醇与水初始体积比80％：20％)分两次洗涤、离心沉淀物得半纤维素，半纤维素回收率达91.4％；合并离心上清液得乙醇碱溶液，碱回收率达到95％。采用旋转蒸发仪，控制真空度100mbar和釜底料液温度60～62℃，以18℃水为冷凝介质精馏分离乙醇碱溶液，至乙醇质量回收率超过96.2％，碱溶液中乙醇残余质量浓度低于0.03％，所得到的乙醇溶液、强碱性溶液即可回用。
对比例2
在锥底不锈钢反应罐中加入10L半纤维素强碱性溶液(pH13.8，半纤维素质量浓度4.0％，氢氧化钠质量浓度20％)，启动机械搅拌装置，匀速流加8L乙醇至混合均匀，在室温条件下静置20min至沉淀完全。以虹吸管吸取上清液A至12～12.5L，采用管式离心机于5844g离心力条件下离心分离剩余溶液10min得到沉淀物，以2L乙醇溶液(乙醇与水初始体积比80％:20％)分两次洗涤、离心沉淀物得半纤维素，半纤维素回收率达92.6％；合并离心上清液得乙醇碱溶液，碱回收率达到98％。采用填料精馏塔，控制真空度100mbar和釜底料液温度68～70℃，以18℃水为冷凝介质精馏分离乙醇碱溶液，至乙醇质量回收率超过95％，碱溶液中乙醇残余质量浓度低于0.04％，所得到的乙醇溶液、强碱性溶液即可回用。
实施例3
在反应罐中加入300mL半纤维素强碱性溶液(pH11.0，半纤维素质量浓度3.0％，氢氧化钠质量浓度17％)，启动机械搅拌装置，匀速流加300mL乙醇至混合均匀，在室温条件下静置30min至沉淀完全。利用吸管吸取上清液A至400mL，采用管式离心机于5844g离心力条件下离心分离剩余溶液60min得到沉淀物，以500mL乙醇溶液(乙醇与水初始体积比80％:20％)分两次洗涤、离心沉淀物得半纤维素，半纤维素回收率达91.4％；合并离心上清液得乙醇碱溶液，碱回收率达到95％。采用旋转蒸发仪，控制真空度100mbar和釜底料液温度60～62℃，以18℃水为冷凝介质精馏分离乙醇碱溶液，至乙醇质量回收率超过96.2％，碱溶液中乙醇残余质量浓度低于0.03％，所得到的乙醇溶液、强碱性溶液即可回用。
实施例4
在锥底不锈钢反应罐中加入10L半纤维素强碱性溶液(pH13.8，半纤维素质量浓度4.0％，氢氧化钠质量浓度20％)，启动机械搅拌装置，匀速流加8L乙醇至混合均匀，在室温条件下静置20min至沉淀完全。以虹吸管吸取上清液A至12～12.5L，采用管式离心机于5844g离心力条件下离心分离剩余溶液10min得到沉淀物，以2L乙醇溶液(乙醇与水初始体积比80％:20％)分两次洗涤、离心沉淀物得半纤维素，半纤维素回收率达92.6％；合并离心上清液得乙醇碱溶液，碱回收率达到98％。采用填料精馏塔，控制真空度100mbar和釜底料液温度68～70℃，以18℃水为冷凝介质精馏分离乙醇碱溶液，至乙醇质量回收率超过95％，碱溶液中乙醇残余质量浓度低于0.04％，所得到的乙醇溶液、强碱性溶液即可回用。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (14)

  1. 一种甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于，包括以下步骤：
    1)向溶解半纤维素的碱性溶液中加入甲醇，充分搅拌混匀，静置沉降；
    2)固液分离步骤1)的体系，得到上清液为甲醇碱性溶液，沉淀物为半纤维素；
    3)采用蒸馏或精馏或气化膜分离甲醇碱性溶液分别得到甲醇、碱性溶液；
    4)分离得到的碱性溶液、甲醇，再回用于半纤维素溶解与分离制备。
  2. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：所述碱性溶液为氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾溶液中的任意一种或它们的混合液。
  3. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：所述半纤维素为来自于木聚糖或葡甘聚糖为主链的线性或体型中的任意一种或它们的混合。
  4. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：步骤1)中，甲醇与碱性溶液体积比为1～4：1。
  5. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：步骤2)中，固液分离的方法为倾析、虹吸、溢流、过滤或离心以及它们的组合。
  6. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：步骤1)中，静置沉降5～30分钟。
  7. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：步骤2)中，半纤维素回收得率超过99％，甲醇碱性溶液中半纤维素的残留率低于0.5％；
  8. 根据权利要求1所述甲醇介导疏水高效分离与回用碱性溶液及其溶解半纤维素的方法，其特征在于：步骤3)中，甲醇回收率超过98％， 碱性溶液中残留的甲醇浓度低于0.05％。
  9. 一种原位分离和回收强碱性溶液中半纤维素的方法，其特征在于，包括下面步骤：
    (1)在充分搅拌条件下，按溶液的初始体积比，向含有半纤维素的强碱性溶液中匀速加入20％～80％乙醇，混合均匀后于室温条件下静置15～150min，使半纤维素从强碱性溶液体系中原位沉淀析出；
    (2)采用倾析、虹吸、溢流、过滤或离心方法对步骤(1)制备的溶液体系进行固液分离，分别得到乙醇碱溶液上清液和半纤维素沉淀物，半纤维素质量回收率超过90％；
    (3)可按照步骤(1)的乙醇体积浓度，加入适量的乙醇溶液清洗和分离沉淀物至pH值6.00～7.00以制备高纯度半纤维素；合并乙醇清洗液与步骤(2)的乙醇碱溶液，采用蒸馏、精馏或气化膜分离得到乙醇、强碱性溶液即可回用；乙醇质量回收率超过92％，强碱性溶液中残留的乙醇浓度低于0.05g/L。
  10. 根据权利要求9所述原位分离和回收强碱性溶液中半纤维素的方法，其特征在于：所述强碱性溶液中的半纤维素是指以木聚糖或葡苷聚糖为主链的线性或体型的单一物质或者它们两者的混合物。
  11. 根据权利要求9所述原位分离和回收强碱性溶液中半纤维素的方法，其特征在于：加入乙醇量以其与强碱性溶液初始体积比计算，乙醇的体积比为20％～80％。
  12. 根据权利要求9所述原位分离和回收强碱性溶液中半纤维素的方法，其特征在于：所述的强碱性溶液是指采用氢氧化钠、氢氧化钾、液氨其中任意一种物质或它们的任意组合所配制的碱性溶液，溶液pH≥10.0。
  13. 根据权利要求9所述原位分离和回收强碱性溶液中半纤维素的方法，其特征在于：乙醇碱溶液混合体系的分离方法是指倾析、虹吸、溢流、过滤或离心方法的任意一种方法或它们的任意组合方法。
  14. 根据权利要求9所述原位分离和回收强碱性溶液中半纤维素的方法，其特征在于：所述乙醇碱性溶液的气化分离回用方法是指蒸馏、精馏、气化膜分离的任意一种方法或者它们的任意组合；乙醇质量回收率超过92％，强碱性溶液中残留乙醇浓度低于0.05g/L。
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