CN102261007A - One kind of agriculture and forestry biomass cellulosic components of the whole fractionation method by the separation and preparation of fuel components and oligosaccharide alcohol - Google Patents

One kind of agriculture and forestry biomass cellulosic components of the whole fractionation method by the separation and preparation of fuel components and oligosaccharide alcohol Download PDF

Info

Publication number
CN102261007A
CN102261007A CN 201010184386 CN201010184386A CN102261007A CN 102261007 A CN102261007 A CN 102261007A CN 201010184386 CN201010184386 CN 201010184386 CN 201010184386 A CN201010184386 A CN 201010184386A CN 102261007 A CN102261007 A CN 102261007A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
cellulose
solid
forestry
crude
concentration
Prior art date
Application number
CN 201010184386
Other languages
Chinese (zh)
Other versions
CN102261007B (en )
Inventor
鲍思龙
龙亚兰
龙敏南
Original Assignee
漳州伯能生物能源有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels
    • Y02E50/17Grain bio-ethanol

Abstract

The invention discloses grading and separating of all components of forestry cellulose biomass and preparing of fuel alcohol and xylo-oligosaccharide by utilizing the separated components. The method comprises the following steps of: (a) crushing, immersing and filter pressing dry substances of the forestry cellulose biomass; (b) immersing the filter pressed solid phase part using an alkaline solution, adding an oxidizing agent, extracting and solidifying phase to form a cellulose crude product; (c) concentrating pressure filtrate through a nano-filtration membrane, adding alcohol with the final concentration of above 50% to the concentrated solution, filtering or centrifugally separating after standing to obtain precipitate and supernatant, wherein the precipitate is a hemi-cellulose crude product; and (d) adjusting the supernatant obtained in the step (c) to be acid, and filtering, separating and precipitating to obtain a lignin crude product. According to the method disclosed by the invention, the resource utilization is maximized; the independence on imported oil in our country can be reduced; the environment pollution is reduced; establishment of a new energy industry and a biological chemical industry can also be promoted; the economic growth pattern in our country is changed; and social and economic sustainable development can be realized.

Description

一种农林纤维素生物质全组份的分级分离方法及利用分离后组份制备燃料酒精和低聚木糖 One kind of agriculture and forestry biomass cellulosic components of the whole fractionation method by the separation and preparation of fuel components and oligosaccharide alcohol

技术领域 FIELD

[0001] 本发明涉及一种农林纤维素生物质全组份的分级分离方法及利用分离后组份制备燃料酒精和低聚木糖。 [0001] The present invention relates to agriculture and forestry cellulosic biomass fuel alcohol component and XOS preparation after the whole group of parts by the separation and fractionation method.

背景技术 Background technique

[0002] 天然木质纤维素是地球上最丰富的可再生资源,纤维素生物质主要包括纤维素、 半纤维素和木质素,三者按一定比例紧密地结合在一起。 [0002] Lignocellulose is naturally the most abundant renewable resource, cellulosic biomass includes cellulose, hemicellulose and lignin, a certain proportion of the three closely together. 纤维素是由许多个葡萄糖分子通过3-1,4-糖苷键连接而成的直链高聚糖,经预处理后聚合度会下降,完全水解后得到葡萄糖等六碳糖,再经酿酒酵母发酵生产燃料酒精;半纤维素是带有支链的多聚糖的总称,其结构单元包括戊糖基、己糖基、糖酸基和己酞基,其中戊糖主要为木塘和阿拉伯糖;木质素是植物界中仅次于纤维素的最丰富的有机高分子化合物,由苯丙烷单元以非线性的、随机方式连接组成的复合体,在酸的作用下难以水解的高分子无定形物质。 Cellulose is made up of many high glucose molecules by linear glycans 3-1,4- glycosidic linkages formed, after pretreatment will decrease the degree of polymerization, obtained after complete hydrolysis hexose such as glucose, and then by Saccharomyces cerevisiae production of fuel ethanol; hemicellulose is a general term polysaccharide with branched chain, which structural unit comprises a group pentose, hexose group, a hexyl group, and an acid sugar phthalidyl, wherein the pentose is mainly wood pond and arabinose; lignin is second only to cellulose in the plant kingdom most abundant organic polymer, a non-linear, randomly connected by a phenylpropane unit composed of the composite, is difficult under the action of an acid hydrolysis of the polymer of amorphous material .

[0003] 目前对纤维素生物质的利用主要强调对纤维素组份的利用,而对半纤维素和木质素组份的利用相对较少,并且没有利用生物炼制技术对纤维素生物质全组份进行分级分离,没有实现生物质全组份的资源化利用和效益的最大化。 [0003] It cellulose raw material using primarily focus on using cellulose components, and the relatively small use of hemicellulose and lignin components, and no use of biological refining cellulosic biomass technology Full the components are fractionated, not maximizing resource utilization and efficiency of the whole components of the biomass. 在利用纤维素生物质制取酒精过程中,常采用化学方法和生物方法对纤维素生物质进行降解,其产物包括葡萄糖、木糖等多种混合糖,再利用混合糖进行发酵产酒精,由于获得的产品单一,其附加值不高,经济效益较低,缺乏市场竞争力;在利用纤维素生物质制取低聚木糖过程中,通常采用一步法碱抽提,然后直接在抽提液中加酸中和,加酒精沉淀半纤维素,该方法的缺陷是半纤维素的提取率较低、碱用量大、中和时酸的用量大、半纤维素沉淀时酒精用量大,在后续的工艺过程由于采用传统的工艺技术,分离效果较差、能耗较大、成本较高。 In the use of ethanol production from cellulosic biomass process, often using chemical methods and biological methods degradation of cellulosic biomass, comprising a plurality of mixing products which sugars glucose, xylose, and then using a mixed alcohol fermentation sugars, since single product obtained, which value is not high, low economic efficiency, lack of market competitiveness; cellulosic biomass using XOS preparation process, usually one-step alkaline extraction, the extract is then directly acid was added and, hemicellulose plus ethanol precipitation, the disadvantage of this method is the extraction of hemicellulose is low, a large amount of alkali, a large amount of acid neutralized, a large amount of alcohol during precipitation of hemicellulose, in the subsequent Since the process using conventional technology, poor separation, a greater energy consumption, high cost.

发明内容 SUMMARY

[0004] 为了解决上述问题,本发明的目的在于提供了一种农林纤维素生物质全组份的分级分离方法及利用分离后组份制备燃料酒精和低聚木糖。 [0004] In order to solve the above problems, an object of the present invention to provide a cellulosic biomass FORESTRY after the whole group of parts by the separation and fractionation method for the preparation of fuel components and oligosaccharide alcohol. 本发明涉及通过生物炼制技术将农林纤维素生物质转化为燃料酒精等生物燃料以及木糖类生物基化学品。 The present invention relates to a bio-refining technology agricultural and forestry cellulose biomass into biofuels such as ethanol fuels and wood-saccharide bio-based chemicals. 生物酒精是一种无色透明、易挥发、易燃烧、不导电的液体,可按一定的比例添加到汽油中,是未来汽油的主要替代品。 Bioethanol is a colorless, transparent, volatile, flammable, non-conductive liquid, may be added to a certain percentage of gasoline, the main future gasoline substitute. 木糖是一种白色结晶粉末,易溶于水,是一种常用的化学品,可用于生产木糖醇或作为食品添加剂。 Xylose is a white crystalline powder, soluble in water, is a commonly used chemical, can be used to produce xylitol or as a food additive. 低聚木糖又称木寡糖是由2〜7个木糖分子以3-1,4糖苷键结合而成的功能性聚合糖,它可以选择性地促进肠道双歧杆菌的增殖活性,是重要的营养保健品。 XOS functional polymeric sugar oligosaccharide is known as wood 2~7 xylose molecules bonded 3-1,4 glycosidic bond, which can be selectively promoting proliferation of intestinal bifidobacteria, It is an important nutrition and health products. 本发明就是采用农林纤维素生物质,对其进行全组份的分级分离,将分离得到的各组分转化为生物燃料和高附加值生物基化学品,实现资源利用的最大化;可以减少我国对进口石油的依赖,减少对环境的污染;还可推动建立新能源工业产业和生物化工产业,改变我国经济增长的方式,实现社会和经济的可持续发展。 The present invention is the use of cellulosic biomass agriculture and forestry, its fractionation of whole components, the components will be isolated into biofuels and high value bio-based chemicals, to maximize resource utilization; country may be reduced dependence on imported oil, reduce pollution of the environment; also promote the establishment of a new energy industry and industrial bio-chemical industry, changes in the economic growth of our country and achieve sustainable social and economic development.

[0005] 为达到上述的目的,本发明采用如下技术方案:[0006] 一种农林纤维素生物质全组份的分级分离方法,包括如下步骤: [0005] To achieve the above object, the present invention adopts the following technical solution: [0006] Agriculture and Forestry parts of one whole group cellulosic biomass fractionation method, comprising the steps of:

[0007] a)农林纤维素生物质的新鲜物质或干物质(购于福建省漳州糖厂)的粉碎、浸泡和压滤; [0007] a) fresh or dry substance FORESTRY cellulosic biomass (available from Zhangzhou sugar) pulverized and soaked filter press;

[0008] b)压滤后的固相部分用碱液浸泡,加入氧化剂,先在中温下抽提,二次压滤后得到二次液相和二次固相两部分;二次固相部分继续浸泡于碱液中,在高温下抽提,三次压滤后得到的三次固相和三次液相两部分;其中三次固相主要成份为纤维素粗品,三次液相主要成份为半纤维素和降解木质素混合液;在中温碱处理过程中加入氧化剂,能加速木质素的分解,使木质纤维素的物理结构解离,有利于半纤维素组份与木质素组份进入碱溶液,为纤维素生物质中三个组份的完全分离奠定基础。 [0008] b) the solid phase portion of the filter press after soaking with lye, adding an oxidizing agent, the first extraction in the temperature, after the second filter press to obtain a secondary liquid phase and a solid phase two secondary portion; second solid phase portion continue soaked in lye, extraction at elevated temperature, after three filter press to give a solid cubic phase two and three portions; wherein the three main ingredients of the solid phase crude cellulose, the main component of the three phase hemicellulose and degradation of lignin mixture; adding an oxidizing agent in the temperature during the alkali treatment, can accelerate the decomposition of lignin to make the physical structure of the dissociated lignocellulosic conducive component parts of hemicellulose and lignin into the group of the alkali solution, the fiber Su biomass three components completely separate basis.

[0009] c)合并中温碱氧化抽提与高温碱抽提的液相压滤液(包括二次液相和三次液相),经纳滤膜(汇通/海德能/陶氏等商家提供)将压滤液浓缩,在浓缩液中加入终浓度为50%以上的酒精,静止后过滤或离心分离,得到沉淀物和上清液;沉淀物就为半纤维素粗品; [0009] c) the liquid pressure in the combined filtrate was extracted with hot alkaline oxidizing temperature alkaline extraction (including a secondary liquid phase and three phase), provide a nanofiltration membrane (Remittance / Hyde / Dow and other merchant) the the filtrate was concentrated under pressure, final concentration of 50% or more of alcohol in the concentrate, stopping after filtration or centrifugation, to obtain a precipitate and supernatant; hemicellulose to precipitate crude product;

[0010] d)将步骤C)中得到的上清液调至酸性,静止后过滤或离心分离,沉淀则为木质素粗品。 The supernatant was adjusted to acidic, the static filtration or centrifugation [0010] d) The step C) obtained in the separation, the lignin was precipitated crude product.

[0011 ] 所述的碱液采用浓度为1 %〜7%的NaOH,KOH, Na2CO3中的一种;所述的氧化剂采用浓度为1 %〜5 %的O3、H2O2, KMnO4中的一种。 [0011] The use of lye concentration of 1% ~ 7% of NaOH, KOH, Na2CO3 one kind of; the oxidizing agent using a concentration of 1% ~ 5% of O3, one kind of H2O2, KMnO4 in.

[0012] 所述的中温抽提采用温度为40〜60°C条件下抽提2〜4小时;所述的高温抽提采用温度为100〜160°C条件下抽提至少1小时以上。 [0012] The extraction temperature employed in the extraction of 2 ~ 4 hours at a temperature of 40~60 ° C condition; the extraction temperature employed extraction temperature is at least 1 hour at 100~160 ° C conditions.

[0013] 所述的步骤C)中压滤液浓缩至5倍以上,直到半纤维素与木质素固型物浓度达10%以上,碱液回收80%以上;且步骤C)和步骤d)中的静止时间均为1〜5小时;步骤d) 中调节酸性至PH为3〜4。 The filtrate was [0013] according to step C) is concentrated to a pressure more than 5 times, until the hemicellulose and lignin-curing concentration of more than 10%, 80% or more lye recovery; and step C) and step d) rest times are 1 ~ 5 hours; acidity adjusting step d) to a PH of 3 to 4.

[0014] 所述的分离得到的纤维素粗品一方面用于制备纤维素酶或半纤维素酶,另一方面利用纤维素酶将纤维素粗品降解为葡萄糖,经酵母发酵后生产酒精;分离得到的半纤维素粗品利用半纤维素酶将其降解为木糖和低聚木糖化学品,经分离提纯后作为食品添加剂或生产木糖醇的原料;分离得到的木质素作为分散剂、吸附剂/解吸剂、石油回收助剂、浙青乳化剂,利用木质素能制造可降解、可再生的聚合物。 Separation [0014] The obtained crude cellulose aspect for preparing a cellulase or hemicellulase, cellulase enzymes other hand, crude degrade cellulose to glucose, after yeast fermentation to produce alcohol; isolated the crude hemicellulose using hemicellulase be degraded to xylose and xylo-oligosaccharide which chemicals, after separation and purification as the starting material for producing xylitol or food additive; isolated lignin as a dispersant, the adsorbent / desorbent, the oil recovery aids, emulsifiers Zhejiang green, lignin can be manufactured using biodegradable, renewable polymer.

[0015] 一种利用分离后组份制备燃料酒精,所述的分离得到的纤维素粗品一方面用于制备纤维素酶或半纤维素酶,另一方面利用纤维素酶将纤维素粗品降解为葡萄糖,经酵母发酵后生产酒精;所述的纤维素酶或半纤维素酶的制备方法为:将所述的纤维素粗品,采用固态发酵制曲的方法,分别接种产纤维素酶菌株或产半纤维素酶菌株,固态发酵培养3天后收获纤维素酶或半纤维素酶。 [0015] A component prepared by the separation after the alcohol fuel, separating the resulting crude cellulose aspect for preparing a cellulase or hemicellulase, cellulase enzymes other hand, crude cellulose degradation glucose, after yeast fermentation to produce alcohol; the cellulase or hemicellulase preparation method is as follows: the crude cellulose, solid state fermentation of koji were inoculated producing cellulase producing strain or hemicellulase strain solid fermentation harvested after 3 days of cellulase or hemicellulase.

[0016] 所述的产纤维素酶菌株采用灰绿曲霉或青霉这2种真菌中的一种;产半纤维素酶菌株采用黑曲霉或木霉这2种真菌中的一种。 [0016] The use of the cellulase-producing strains of Aspergillus or Penicillium glaucum one of these two kinds of fungi; hemicellulase producing strain of Aspergillus niger or Trichoderma uses a two kinds of fungi.

[0017] 所述的纤维素粗品与纤维素酶与按5 : 1-1 : 1比例混合,添加适量的水,使固液比为1 : 10,在50°C酶解12小时以上得到纤维素酶解后的糖化液,纤维素酶解后的糖化液经纳滤膜浓缩至糖浓度15%以上;浓缩后的糖化液直接用于发酵产酒精。 [0017] The cellulose crude cellulase and 5: 1 to 1: 1 ratio, the amount of water added, solid-liquid ratio of 1: 10, to give the fibers above 50 ° C 12 hours hydrolysis after the saccharification liquid enzymatic factors, enzymatic saccharification of cellulose solution after nanofiltration was concentrated to a sugar concentration above 15%; concentrated saccharified solution was used directly after fermentation alcohol.

[0018] 一种利用分离后组份制备低聚木糖:所述的分离得到的半纤维素粗品与半纤维素酶按5 : 1-1 : 1的比例混合后,添加半纤维素粗品5〜6倍重量体积的水,在60°C反应5〜16小时,加入活性炭脱色剂进行脱色,然后通过过滤除去固体杂质;将脱色过滤后的糖化液通过离子交换树脂脱盐,然后进行膜浓缩;将脱色和脱盐后的糖化液浓缩至15%以上后进行喷雾干燥制成粉末状低聚木糖或通过纳滤膜浓缩为高浓度的低聚木糖液。 XOS preparation after the component [0018] utilizing isolated: hemicellulose of the crude product isolated by the hemicellulase 5: 1 to 1: 1 mixing ratio after the addition of the crude hemicellulose 5 ~ 6 times the weight volume of water, reacted at 60 ° C 5~16 hours, decolorizing charcoal was added bleaching agent and then removing the solid impurities by filtration; saccharified solution decolorized after the ion-exchange resin was filtered through a desalting and then subjected to membrane concentration; after the spray decolorized and desalted saccharified solution was concentrated to 15% or more powdered dried through a nanofiltration membrane or XOS concentrated to a high concentration xylooligosaccharide solution.

[0019] 本发明的有益效果是:本发明建立了成熟的生物炼制技术对纤维素生物质进行分级分离和高效转化,将纤维素生物质中的三种组分进行分级分离提纯得到纤维素、半纤维素、木质素组份;然后充分应用各个组分,来制取生物燃料和生物基化学品:首先从纤维素生物质中分离获得纤维素,利用纤维素酶将纤维素降解为葡萄糖,经酵母发酵后生产酒精; 利用半纤维素酶将木聚糖降解为木糖和低聚木糖等化学品,经分离提纯后作为食品添加剂或生产木糖醇的原料;木质素可作为分散剂、吸附剂/解吸剂、石油回收助剂、浙青乳化剂, 利用木质素能制造可降解、可再生的聚合物。 [0019] Advantageous effects of the present invention are: the present invention established a mature technology biorefinery cellulosic biomass fractionation and conversion efficiency, three components of the cellulosic biomass were fractionated to obtain purified cellulose , hemicellulose, lignin component groups; and full application of the individual components, to the preparation of biofuels and biochemicals: firstly isolated cellulose from cellulosic biomass, to the degradation of cellulose to glucose with cellulase enzymes , after yeast fermentation to produce alcohol; using hemicellulase degrading xylan to xylose and xylo-oligosaccharide and other chemicals, after separation and purification as the starting material for producing xylitol or food additive; lignin as a dispersant agent, adsorbent / desorbent, the oil recovery aids, emulsifiers Zhejiang green, lignin can be manufactured using biodegradable, renewable polymer. 在半纤维素分级分离中采用两步法提取,先中温氧化提取,后高温提取,可大幅度提高半纤维素的提取率,实际提取率可达理论提取率的95%以上。 Extracting two-step method, the first extraction temperature oxidation, high temperature extraction, the extraction rate may greatly improve the hemicellulose, the actual extraction rate of 95% of the theoretical extraction rate employed in the fractionation of hemicellulose. 在半纤维素抽提过程中,采用中温-高温-中温的处理程序,可以提高工艺过程的热利用效率。 Hemicellulose extraction process, using the medium temperature - high temperature - high temperature in the handler, can improve the heat efficiency of the process. 将现代膜分离技术运用于碱液回收、糖化液组份分离、糖化液浓缩、酒精脱水等工艺过程,可大幅度降低生产过程的能耗和成本。 The technology used in modern membrane separation lye recovery group saccharified liquid parts separated, concentrated saccharified solution, alcohol dehydration and other processes, can significantly reduce energy consumption and cost of the production process.

[0020] 综上所述,本发明的技术方案能实现对纤维素生物质全组份的最大资源化利用, 大幅度提高生产品的附加值,提升生物质产业的经济效益,避免资源浪费。 [0020] In summary, the technical solution of the present invention can achieve the full component of cellulosic biomass maximum resource utilization, greatly improving the added value of raw products to enhance economic efficiency biomass industry, to avoid waste of resources. 同时可引导经济结构调整和产业发展模式的改变。 Meanwhile bootable alter the structure adjustment and development mode of economic sectors. 本发明整合了生物酶催化法与化学处理方法,将两者的优点结合在一起,可以大大减少对环境的污染,大幅度提高生产效率。 The present invention integrates the biological and chemical treatment methods enzymatic methods, combining the advantages of both, can greatly reduce environmental pollution, greatly improve production efficiency. 且大幅度提高整个产业链的经济效益,比单独生产纤维素酒精的经济效益提高10倍以上,为规模开发利用纤维素生物质提供了一条可行途径。 And greatly improve the economic efficiency of the whole industry chain, increased more than 10 times higher than the economic benefits alone cellulosic ethanol production, providing a feasible way for large-scale development and utilization of cellulosic biomass.

附图说明 BRIEF DESCRIPTION

[0021] 图1是本发明的工艺路线图。 [0021] FIG. 1 is a process route of the present invention of FIG. 具体实施方式 detailed description

[0022] 下面结合附图1对本发明作进一步详细的说明。 [0022] Next, one pair of the present invention will be further described in detail accompanying drawings binding.

[0023] 实施例1 [0023] Example 1

[0024] 本实施例所采用的一种农林纤维素生物质全组份的分级分离方法,包括如下步骤: [0024] The whole set of parts of one embodiment of the present agriculture and forestry cellulosic biomass embodiment employed fractionation method, comprising the steps of:

[0025] 1、农林纤维素生物质的鲜物质或干物质经粉碎后,先以清水浸泡,然后压滤; [0025] 1, fresh or dry substance FORESTRY cellulosic biomass after grinding, first soaked with water, and then filter press;

[0026] 2、将经过1处理后的固相部分以浓度为1 %的NaOH碱液浸泡,固液比为1 : IO(WN)左右,加入浓度为5%的O3氧化剂,先在中温60°C下抽提2小时,二次压滤后得到二次液相和二次固相两部分;二次固相部分继续浸泡于的NaOH碱液中,固液比为1 : IO(WN)左右,在高温80°C下抽提至少1小时以上,三次压滤后得到的三次固相和三次液相两部分;其中三次固相部分主要为纤维素粗品,三次液相主要成份为半纤维素和降解木质素混合液。 [0026] 2, after the solid phase portion processed at a concentration of 1% NaOH alkaline soaking liquid ratio of 1: IO (WN) or so, added at a concentration of 5% O3 oxidant, the temperature to 60 extracted for 2 hours at ° C, after the second filter press to obtain a secondary liquid phase and a solid phase two secondary part; of NaOH lye soaking, secondary solid phase portion in the solid-liquid ratio of 1: IO (WN) about, extraction at elevated temperature at least 80 ° C for 1 hour, three times a filter press to give a solid phase and three phase two parts; solid phase portion wherein the three main crude cellulose, the three main ingredients of hemicelluloses liquid hormone and degradation of lignin mixture.

[0027] 3、合并中温碱氧化抽提与高温碱抽提的液相压滤液(包括二次液相和三次液相),经纳滤膜将压滤液浓缩5倍以上,直到半纤维素与木质素固型物浓度达10%以上,碱液回收80%以上;在浓缩液中加入终浓度为50%以上的酒精,静止1〜5小时后过滤或离心分离,得到沉淀物和上清液;沉淀物即为半纤维素粗品; [0027] 3, the combined pressure-temperature alkaline oxidizing liquid extraction with hot alkali extraction filtrate (including the cubic phase and the second liquid), the pressure by nanofiltration the filtrate was concentrated more than 5 times, until the hemicellulose and lignin type solid concentration of more than 10%, 80% or more lye recovery; a final concentration of 50% or more of alcohol in the concentrate, still ~ 5 h after filtration or centrifugation, to obtain a precipitate and supernatant ; precipitate the hemicellulose is the crude product;

[0028] 4、将步骤3中得到的上清液调至酸性pH 3〜4,静止1〜5小时后过滤或离心分离,沉淀则为木质素粗品。 [0028] 4, the supernatant was adjusted to an acidic pH of 3 to 4 obtained in step 3, ~ 5 hours after static filtration or centrifugation, a crude lignin was precipitated. 分离得到的木质素作为分散剂、吸附剂/解吸剂、石油回收助剂、 浙青乳化剂,利用木质素能制造可降解、可再生的聚合物。 Isolated lignin as a dispersant, the adsorbent / desorbent, the oil recovery aids, emulsifiers Zhejiang Green, lignin can be manufactured using biodegradable, renewable polymer.

[0029] 纤维素酶与半纤维素酶的制备 Preparation cellulase hemicellulase [0029]

[0030] 将分离得到的固相纤维素粗品浸泡于40°C温水中,加入适量的盐酸,调节pH值至近中性。 [0030] The isolated crude solid cellulose soaked in warm 40 ° C, the appropriate amount of hydrochloric acid was added to adjust the pH to near neutral. 取其中一部分用于制备纤维素酶和半纤维素酶,另一部分作为糖化的原料。 Wherein a portion taken for the preparation of cellulases and hemicellulases, as another part of the feed saccharified. 纤维素酶和半纤维素酶的制备采取固态发酵制曲的方法进行,以灰绿曲霉为产纤维素酶菌株, 以黑曲霉作为产半纤维素酶菌株,在固相纤维素粗品中添加一定比例(干重5 : 1)的麸皮或豆饼作为营养组份,并添加一定比例的水(固液比约为3 : 1),接种产纤维素酶菌株或产半纤维素酶菌株,在适宜的条件下培养3天左右,得到固态纤维素酶或固态半纤维素酶。 Preparation of cellulases and hemicellulases method of solid state fermentation to take koji be, as Aspergillus glaucus cellulase producing strain, Aspergillus niger strain as a hemicellulase production, adding a certain solid phase crude cellulose ratio (dry weight of 5: 1) as a cake or bran component nutrition group, and add a certain proportion of water (solid-liquid ratio of about 3: 1), vaccination strains producing cellulase or hemicellulase producing strains, in culturing under suitable conditions for about 3 days to give a solid cellulase or hemicellulase solid.

[0031] 利用分离后组分进行纤维素糖化与发酵制酒精 After the [0031] components were separated by using a cellulose saccharification and fermentation alcohol

[0032] 将分离得到的固态纤维素粗品与固态纤维素酶按5 : 1的比例混合,添加适量的水,使固液比为1 : 10,在50°C酶解12小时以上,所得的糖化液经纳滤膜浓缩至糖浓度15%以上。 [0032] The cellulose isolated solid and the solid obtained crude cellulase 5: 1 ratio, the amount of water added, solid-liquid ratio of 1: 10, more than 50 ° C hydrolysis for 12 hours the resulting saccharified solution was concentrated by nanofiltration to a concentration of more than 15% sugar. 在浓缩后的糖化液中添加适量的豆饼作为氮营养组份,并添加无机盐组份,包括钾、钠、钙、镁、硫;并调节PH值至中性,装入发酵罐进行灭菌处理,降温后按10% (ν/ν)接种量接入酒精酵母,发酵结束(50h以上)后,先对发酵液进行蒸馏得到95%左右的酒精,然后再通过膜脱水分离技术得到无水酒精,作为燃料用途。 Saccharified solution in the appropriate amount of the concentrated soybean nutrition group as a nitrogen component, and inorganic salt components, including potassium, sodium, calcium, magnesium, sulfur; and adjust the PH to neutral, charged sterilized fermenter after the treatment, according to 10% (ν / ν) inoculum access alcohol yeast after cooling, the end of fermentation (5Oh above), to obtain a fermentation broth is subjected to distillation of about 95% alcohol, then the obtained anhydrous by dehydration of the membrane separation technique alcohol, use as a fuel.

[0033] 利用分离后组分制备低聚木糖 After [0033] was prepared using the separate components xylooligosaccharides

[0034] 对半纤维素粗品常温下洗脱至pH近中性(pH = 7左右),除去残留碱液,收集固相部分,加入5倍重量体积的水,按5 : 1的比例加入木聚糖酶进行糖化分解,在恒温(60°C) 水浴反应5〜16小时;半纤维素糖化液的主要包括木糖、低聚木糖等,将酶解液导入脱色罐,加入活性炭脱色剂进行脱色,然后通过过滤(板框压滤等)除去固体杂质;将脱色过滤后的糖化液通过离子交换树脂脱盐,待达到低聚木糖的各项指标(QB-TJ984-2008_低聚木糖)浅黄色澄清透明液体,投射比> 60%后进行膜浓缩;将脱色和脱盐后的糖化液浓缩至15%以上后进行喷雾干燥制成低聚木糖粉末)(0S2-7 ^ 70(以干基计),M)S2-5 ^ 50% (以干基计),或通过纳滤膜浓缩为高浓度的低聚木糖液M)S2-7彡70 (以干基计), X0S2-5 ^ 50% (以干基计)。 [0034] The crude hemicellulose eluted at room temperature to a pH near neutral (pH = about 7), to remove the residual alkali, the solid phase portion was collected, added to 5 times the weight volume of water, 5: 1 ratio was added Wood glycanase saccharification decomposed at a constant temperature (60 ° C) bath for 5~16 hours; saccharification of hemicellulose include xylose solution, like XOS, the enzyme was introduced into bleaching tank, adding activated carbon bleaching agent the indicators decolored saccharified solution was filtered through a desalting ion exchange resin, to be achieved XOS (QB-TJ984-2008_ oligomerization wood; was decolorized and solid impurities removed by filtration (plate and frame filter press) sugar) as a pale yellow clear transparent liquid, the throw ratio> 60% after the membrane-concentrated; decolorized and desalted saccharified solution was concentrated to 15% or more spray-dried powder made XOS) (0S2-7 ^ 70 ( dry basis), M) S2-5 ^ 50% (dry basis), or by nanofiltration was concentrated to a high concentration solution xylooligosaccharides M) S2-7 San 70 (dry basis), X0S2-5 ^ 50% (dry basis).

[0035] 实施例2 [0035] Example 2

[0036] 本实施例所采用的一种农林纤维素生物质全组份的分级分离方法,包括如下步骤: [0036] This whole set of parts of one embodiment of agriculture and forestry cellulosic biomass fractionation method employed in embodiment, comprising the steps of:

[0037] 1、农林纤维素生物质干物质经粉碎后,先以清水浸泡,然后压滤; [0037] 1, agriculture and forestry cellulose biomass after dry pulverization, the first soaked with water, and then filter press;

[0038] 2、将经过1处理后的固相部分以浓度为7%的KOH碱液浸泡,固液比为1 : IO(WN) 左右,加入浓度为5%的H2O2氧化剂,先在中温60°C下抽提2〜4小时,二次压滤后得到二次液相和二次固相两部分;二次固相部分继续浸泡于的KOH碱液中,固液比为1 : IO(WN) 左右,在高温140°C下抽提至少1小时以上,三次压滤后得到的三次固相和三次液相两部分;其中三次固相部分主要为纤维素粗品,三次液相主要成份为半纤维素和降解木质素混合液。 [0038] 2, after the solid phase portion processed at a concentration of 7% KOH alkaline soaking liquid ratio of 1: IO (WN) or so, added at a concentration of 5% H2O2 oxidant, the temperature to 60 2 ~ 4 hours extraction ° C, after the second filter press to obtain a secondary liquid phase and a solid phase two secondary part; of KOH alkaline soaking, secondary solid phase portion in the solid-liquid ratio of 1: IO ( ) about WN, at the extraction temperature at least 140 ° C for 1 hour, three times a filter press to obtain a solid phase and three phase two parts; solid phase portion wherein the three main crude cellulose, the three main ingredients of the liquid phase hemicellulose and lignin degradation mixture.

[0039] 3、合并中温碱氧化抽提与高温碱抽提的液相压滤液(包括二次液相和三次液相),经纳滤膜将压滤液浓缩5倍以上,直到半纤维素与木质素固型物浓度达10%以上,碱液回收80%以上;在浓缩液中加入终浓度为50%以上的酒精,静止5小时后过滤或离心分离,得到沉淀物和上清液;沉淀物即为半纤维素粗品; [0039] 3, the combined pressure-temperature alkaline oxidizing liquid extraction with hot alkali extraction filtrate (including the cubic phase and the second liquid), the pressure by nanofiltration the filtrate was concentrated more than 5 times, until the hemicellulose and lignin type solid concentration of more than 10%, 80% or more lye recovery; a final concentration of 50% or more of alcohol in the concentrate, after 5 hours the stationary filtration or centrifugation, to obtain a precipitate and a supernatant; precipitation The crude product is the hemicellulose;

[0040] 4、将步骤3中得到的上清液调至酸性pH 3〜4,静止5小时后过滤或离心分离,沉淀则为木质素粗品。 [0040] 4, the supernatant was adjusted to an acidic pH of 3 to 4 obtained in step 3, 5 hours after the stationary filtration or centrifugation, a crude lignin was precipitated. 分离得到的木质素作为分散剂、吸附剂/解吸剂、石油回收助剂、浙青乳化剂,利用木质素能制造可降解、可再生的聚合物。 Isolated lignin as a dispersant, the adsorbent / desorbent, the oil recovery aids, emulsifiers Zhejiang Green, lignin can be manufactured using biodegradable, renewable polymer.

[0041] 纤维素酶与半纤维素酶的制备 Preparation cellulase hemicellulase [0041]

[0042] 将分离得到的固相纤维素粗品浸泡于60°C温水中,加入适量的硫酸,调节pH值至近中性。 [0042] The isolated crude solid cellulose was immersed in 60 ° C warm water, adding an appropriate amount of sulfuric acid to adjust the pH to near neutral. 取其中一部分用于制备纤维素酶和半纤维素酶,另一部分作为糖化的原料。 Wherein a portion taken for the preparation of cellulases and hemicellulases, as another part of the feed saccharified. 纤维素酶和半纤维素酶的制备采取固态发酵制曲的方法进行,以青霉为产纤维素酶菌株,以木霉作为产半纤维素酶菌株,在固相纤维素粗品中添加一定比例(干重51 : 1)的麸皮或豆饼作为营养组份,并添加一定比例的水(固液比约为3 : 1),接种产纤维素酶菌株或产半纤维素酶菌株,在适宜的条件下培养3天左右,得到固态纤维素酶或固态半纤维素酶。 Preparation of cellulases and hemicellulases taken solid koji fermentation is performed, as cellulase-producing Penicillium strain, to yield a hemicellulase as Trichoderma strains, certain proportion of cellulose in the solid phase crude (dry weight 51: 1) as a cake or bran component nutrition group, and add a certain proportion of water (solid-liquid ratio of about 3: 1), vaccination strains producing cellulase or hemicellulase producing strain, in a suitable cultured under conditions of about 3 days to obtain a solid cellulase or hemicellulase solid.

[0043] 利用分离后组分进行纤维素糖化与发酵制酒精 After the [0043] components were separated by using a cellulose saccharification and fermentation alcohol

[0044] 将分离得到的固态纤维素粗品与固态纤维素酶按1 : 1的比例混合,添加适量的水,使固液比为1 : 10,在50°C酶解12小时以上,所得的糖化液经纳滤膜浓缩至糖浓度15%以上。 [0044] The solid crude cellulose obtained by separating a solid-state cellulase: 1 ratio, the amount of water added, solid-liquid ratio of 1: 10, more than 50 ° C hydrolysis for 12 hours the resulting saccharified solution was concentrated by nanofiltration to a concentration of more than 15% sugar. 在浓缩后的糖化液中添加适量的豆饼作为氮营养组份,并添加无机盐组份,包括钾、钠、钙、镁;并调节PH值至中性,装入发酵罐进行灭菌处理,降温后按10% (ν/ν)接种量接入酒精酵母,发酵结束(50h以上)后,先对发酵液进行蒸馏得到95%左右的酒精,然后再通过膜脱水分离技术得到无水酒精,作为燃料用途。 Appropriate amount of soybean in the concentrated saccharified solution as a component of nitrogen nutrition group, and adding an inorganic salt components, including potassium, sodium, calcium, magnesium; and adjust the PH to neutral, charged fermentor sterilization treatment, press 10% (ν / ν) access alcohol yeast inoculum after cooling, the end of fermentation (5Oh above), to obtain a fermentation broth is subjected to distillation of about 95% alcohol, and then obtained by the ethanol dehydration membrane separation technique, The use as a fuel.

[0045] 利用分离后组分制备低聚木糖 After [0045] was prepared using the separate components xylooligosaccharides

[0046] 对半纤维素粗品常温下洗脱至pH近中性(pH = 7左右),除去残留碱液,收集固相部分,加入5〜10倍重量体积的水,按1 : 1的比例加入木聚糖酶进行糖化分解,在恒温(600C )水浴反应5〜16小时;半纤维素糖化液的主要包括木糖、低聚木糖等,将酶解液导入脱色罐,加入活性炭脱色剂进行脱色,然后通过过滤(板框压滤等)除去固体杂质;将脱色过滤后的糖化液通过离子交换树脂脱盐,待达到低聚木糖的各项指标(QB-T-2984-2008_ 低聚木糖)浅黄色澄清透明液体,投射比> 60%后进行膜浓缩;将脱色和脱盐后的糖化液浓缩至15%以上后进行喷雾干燥制成低聚木糖粉末)(0S2-7 ^ 70(以干基计), X0S2-5 ^50% (以干基计),或通过纳滤膜浓缩为高浓度的低聚木糖液)(0S2-7彡70(以干基计),X0S2-5 ^ 50% (以干基计)。 [0046] The crude hemicellulose eluted at room temperature to a pH near neutral (pH = about 7), to remove the residual alkali, the solid phase portion was collected, added to 5 to 10 times the weight volume of water, 1: 1 ratio xylanase added saccharification decomposition reaction at a constant temperature water bath (600C) 5~16 hours; saccharification of hemicellulose include xylose solution, like XOS, the enzyme was introduced into bleaching tank, adding activated carbon bleaching agent decolorized and then removing the solid impurities by filtration (plate and frame filter press); decolored the saccharified solution was filtered through a desalting ion exchange resin, the targets to be achieved XOS (QB-T-2984-2008_ oligo after the spray-saccharified solution decolored and desalted and concentrated to more than 15% of dried powder made XOS) (0S2-7 ^ 70; xylose) as a pale yellow clear transparent liquid, the throw ratio> 60% for the membrane and concentrated (dry basis), X0S2-5 ^ 50% (dry basis), or by nanofiltration was concentrated to a high concentration xylooligosaccharide solution) (0S2-7 San 70 (dry basis), X0S2 -5 ^ 50% (dry basis).

[0047] 实施例3 [0047] Example 3

[0048] 本实施例所采用的一种农林纤维素生物质全组份的分级分离方法,包括如下步骤: [0048] The whole set of parts of one embodiment of the present agriculture and forestry cellulosic biomass embodiment employed fractionation method, comprising the steps of:

[0049] 1、农林纤维素生物质干物质经粉碎后,先以清水浸泡,然后压滤; [0049] 1, agriculture and forestry cellulose biomass after dry pulverization, the first soaked with water, and then filter press;

[0050] 2、将经过1处理后的固相部分以浓度为4 %的Na2CO3碱液浸泡,固液比为1 : 10 (W/V)左右,加入浓度为4%的KMnO4氧化剂,先在中温50°C下抽提3小时,二次压滤后得到二次液相和二次固相两部分;二次固相部分继续浸泡于浓度为4%的Na2CO3中,固液比为1 : IO(WN)左右,在高温100°C下抽提至少1小时以上,三次压滤后得到的三次固相和三次液相两部分;其中三次固相部分主要为纤维素粗品,三次液相主要成份为半纤维素和降解木质素混合液。 [0050] 2, the solid phase portion through an after treatment at a concentration of 4% Na2CO3 alkali soaking liquid ratio of 1: 10 (W / V) or so, was added KMnO4 concentration of 4% of an oxidizing agent, in the first extraction medium temperature 50 ° C 3 hours, to give the secondary filter press a secondary solid phase and a liquid phase of the secondary two parts; solid phase portion of the secondary soaking, in a concentration of 4% Na2CO3 solid-liquid ratio of 1: IO (WN) or so, extraction at high temperatures above 100 ° C for at least 1 hour, three times a filter press to give a solid phase and three phase two parts; solid phase portion wherein the three main crude cellulose, liquid phase mainly three component of hemicellulose and lignin degradation mixture. [0051] 3、合并中温碱氧化抽提与高温碱抽提的液相压滤液(包括二次液相和三次液相),经纳滤膜将压滤液浓缩5倍以上,直到半纤维素与木质素固型物浓度达10%以上,碱液回收80%以上;在浓缩液中加入终浓度为50%以上的酒精,静止3小时后过滤或离心分离,得到沉淀物和上清液;沉淀物即为半纤维素粗品; [0051] 3, the combined pressure-temperature alkaline oxidizing liquid extraction with hot alkali extraction filtrate (including the cubic phase and the second liquid), the pressure by nanofiltration the filtrate was concentrated more than 5 times, until the hemicellulose and lignin type solid concentration of more than 10%, 80% or more lye recovery; a final concentration of 50% or more of alcohol in the concentrate, still three hours after filtration or centrifugation, to obtain a precipitate and a supernatant; precipitation The crude product is the hemicellulose;

[0052] 4、将步骤3中得到的上清液调至酸性pH 3〜4,静止3小时后过滤或离心分离,沉淀则为木质素粗品。 [0052] 4, the supernatant was adjusted to an acidic pH of 3 to 4 obtained in step 3, still three hours after filtration or centrifugation, a crude lignin was precipitated. 分离得到的木质素作为分散剂、吸附剂/解吸剂、石油回收助剂、浙青乳化剂,利用木质素能制造可降解、可再生的聚合物。 Isolated lignin as a dispersant, the adsorbent / desorbent, the oil recovery aids, emulsifiers Zhejiang Green, lignin can be manufactured using biodegradable, renewable polymer.

[0053] 纤维素酶与半纤维素酶的制备 Preparation cellulase hemicellulase [0053]

[0054] 将分离得到的固相纤维素粗品浸泡于50°C温水中,加入适量的盐酸,调节pH值至近中性。 [0054] The isolated crude solid cellulose was immersed in 50 ° C warm water, adding an appropriate amount of hydrochloric acid to adjust the pH to near neutral. 取其中一部分用于制备纤维素酶和半纤维素酶,另一部分作为糖化的原料。 Wherein a portion taken for the preparation of cellulases and hemicellulases, as another part of the feed saccharified. 纤维素酶和半纤维素酶的制备采取固态发酵制曲的方法进行,以青霉作为产纤维素酶菌株,以黑曲霉作为产半纤维素酶菌株,在固相纤维素粗品中添加一定比例(干重3 : 1)的麸皮或豆饼作为营养组份,并添加一定比例的水(固液比约为3 : 1),接种产纤维素酶菌株或产半纤维素酶菌株,在适宜的条件下培养3天左右,得到固态纤维素酶或固态半纤维素酶。 Preparation of cellulases and hemicellulases method of solid state fermentation to take koji is, as cellulase-producing Penicillium strains as Aspergillus niger strain producing a hemicellulase, certain proportion of cellulose in the solid phase crude (dry weight 3: 1) as bran or soybean nutrition group component, and water (solid-liquid ratio of about 3: 1) a proportion of inoculated strains producing cellulase or hemicellulase producing strain, in a suitable cultured under conditions of about 3 days to obtain a solid cellulase or hemicellulase solid.

[0055] 利用分离后组分进行纤维素糖化与发酵制酒精 After the [0055] components were separated using saccharification and fermentation alcohol

[0056] 将分离得到的固态纤维素粗品与固态纤维素酶按3 : 1的比例混合,添加适量的水,使固液比为1 : 10,在50°C酶解12小时以上,所得的糖化液经纳滤膜浓缩至糖浓度15%以上。 [0056] The solid crude cellulose obtained by separating the solid Cellulase 3: 1 ratio, the amount of water added, solid-liquid ratio of 1: 10, more than 50 ° C hydrolysis for 12 hours the resulting saccharified solution was concentrated by nanofiltration to a concentration of more than 15% sugar. 在浓缩后的糖化液中添加适量的豆饼作为氮营养组份,并添加无机盐组份,包括钾、钠、钙、镁;并调节PH值至中性,装入发酵罐进行灭菌处理,降温后按10% (ν/ν)接种量接入酒精酵母,发酵结束(50h以上)后,先对发酵液进行蒸馏得到95%左右的酒精,然后再通过膜脱水分离技术得到无水酒精,作为燃料用途。 Appropriate amount of soybean in the concentrated saccharified solution as a component of nitrogen nutrition group, and adding an inorganic salt components, including potassium, sodium, calcium, magnesium; and adjust the PH to neutral, charged fermentor sterilization treatment, press 10% (ν / ν) access alcohol yeast inoculum after cooling, the end of fermentation (5Oh above), to obtain a fermentation broth is subjected to distillation of about 95% alcohol, and then obtained by the ethanol dehydration membrane separation technique, The use as a fuel.

[0057] 利用分离后组分制备低聚木糖 After [0057] was prepared using the separate components xylooligosaccharides

[0058] 对半纤维素粗品常温下洗脱至pH近中性(pH = 7左右),除去残留碱液,收集固相部分,加入5〜10倍重量体积的水,按3 : 1的比例加入木聚糖酶进行糖化分解,在恒温(600C )水浴反应5〜16小时;半纤维素糖化液的主要包括木糖、低聚木糖等,将酶解液导入脱色罐,加入活性炭脱色剂进行脱色,然后通过过滤(板框压滤等)除去固体杂质;将脱色过滤后的糖化液通过离子交换树脂脱盐,待达到低聚木糖的各项指标(QB-TJ984-2008_ 低聚木糖)浅黄色澄清透明液体,投射比> 60%后进行膜浓缩;将脱色和脱盐后的糖化液浓缩至15%以上后进行喷雾干燥制成低聚木糖粉末)(0S2-7 ^ 70(以干基计), X0S2-5 ^50% (以干基计),或通过纳滤膜浓缩为高浓度的低聚木糖液)(0S2-7彡70(以干基计),X0S2-5 ^ 50% (以干基计)。 [0058] The crude hemicellulose eluted at room temperature to a pH near neutral (pH = about 7), to remove the residual alkali, the solid phase portion was collected, added to 5 to 10 times the weight volume of water, a 3: 1 ratio xylanase added saccharification decomposition reaction at a constant temperature water bath (600C) 5~16 hours; saccharification of hemicellulose include xylose solution, like XOS, the enzyme was introduced into bleaching tank, adding activated carbon bleaching agent the indicators decolored saccharified solution was filtered through a desalting ion exchange resin, to be achieved XOS (QB-TJ984-2008_ xylooligosaccharides; decolorized, and then removing the solid impurities by filtration (plate and frame filter press) ) as a pale yellow clear transparent liquid, the throw ratio> 60% after the membrane-concentrated; decolorized and desalted saccharified solution was concentrated to 15% or more spray-dried powder made XOS) (0S2-7 ^ 70 (in dry basis), X0S2-5 ^ 50% (dry basis), concentrated to a high concentration or a xylooligosaccharide solution through a nanofiltration membrane) (0S2-7 San 70 (dry basis), X0S2-5 ^ 50% (dry basis).

[0059] 本发明的各个实施例开创了全新的纤维素生物质利用理念:全组份分离工艺与全组分利用工艺;发明了全新的分离技术,在以碱法预处理的基础上,通过添加氧化剂和辅助剂,通过增加高温提取步骤,促进纤维素生物质组份的相互分离;其次应用膜分离技术对碱实现回收,对半纤维素和木质素提取组份实现浓缩;再是发明了固态发酵技术制备特异的纤维素酶,利用纤维素酶对纤维素组份进行糖化分解,糖化液经膜浓缩至15%以上的糖浓度后进行发酵产酒精,发酵液经蒸馏和膜脱水,产品为无水酒精;发明了固态发酵技术制备特异的半纤维素酶,利用半纤维素酶对木聚糖进行糖化,糖化液经膜分离与浓缩、脱盐、脱色和喷雾干燥,获得低聚木糖产品。 [0059] The various embodiments of the present invention utilizing the concept of creating a new cellulosic biomass: All components of the whole separation process using a process component; invention, a new separation technique, on the basis of alkaline pretreatment to by adding an oxidizing agent and adjuvant, by adding a high temperature extraction steps to promote parts of cellulosic biomass are separated from each group; followed by application of membrane technology to achieve recovery of alkali, hemicellulose and lignin extraction parts concentrated achieved group; the invention is further preparation of solid state fermentation technique specific cellulase parts of cellulose with cellulase enzymes decomposing saccharified group, for alcoholic fermentation saccharification was concentrated to more than 15% of the sugar concentration through the membrane, the fermentation broth by distillation and membrane dehydration, the product is ethanol; specific disclosure of the preparation of solid state fermentation technique hemicellulase, xylanase for saccharification, saccharification and separation membrane was dried and concentrated, desalted and decolorized using hemicellulase spray drying to obtain xylooligosaccharide product.

Claims (9)

  1. 1. 一种农林纤维素生物质全组份的分级分离方法,其特征在于包括如下步骤:a)农林纤维素生物质的干物质的先经粉碎、清水浸泡和压滤;b)压滤后的固相部分用碱液浸泡,加入氧化剂,先在中温下抽提,二次压滤后得到二次液相和二次固相两部分;二次固相部分继续浸泡于碱液中,在高温下抽提,三次压滤后得到的三次固相和三次液相两部分;其中三次固相主要成份为纤维素粗品,三次液相主要成份为半纤维素和降解木质素混合液;c)合并中温碱氧化抽提与高温碱抽提的液相压滤液,经纳滤膜将压滤液浓缩,在浓缩液中加入终浓度为50%以上的酒精,静止后过滤或离心分离,得到沉淀物和上清液;沉淀物就为半纤维素粗品;d)将步骤c)中得到的上清液调至酸性,静止后过滤或离心分离,沉淀则为木质素粗PΡΠ O A whole group of agriculture and forestry cellulosic biomass parts fractionation method, characterized by comprising the steps of: a) first crushed, soaked with water and dry filter press agroforestry cellulosic biomass; b) the filter press the solid phase portion soaked with lye, adding an oxidizing agent, the first extraction in the temperature, after the second filter press to obtain a secondary liquid phase and a solid phase two secondary portion; second solid phase portion in the soaking, lye, in the extraction temperature, the three filter press to obtain a solid phase and three cubic liquid two portions; wherein the three main ingredients of the solid phase crude cellulose, the main component of the three phase hemicellulose and lignin degradation and a mixture; c) the combined alkaline oxidizing medium temperature pressure liquid filtrate was extracted with hot alkaline extraction, dried nanofiltration the filtrate was concentrated under pressure, ethanol was added to a final concentration of 50% or more concentrated solution, the stationary after filtration or centrifugation, to obtain a precipitate and a supernatant; hemicellulose to precipitate crude product; D) in step c) is obtained supernatant was adjusted to acidic, stopping after filtration or centrifugation, a crude lignin was precipitated PΡΠ O
  2. 2.如权利要求1所述的一种农林纤维素生物质全组份的分离方法,其特征在于:所述的农林纤维素生物质采用秸秆、蔗渣、芒草、林业加工废弃物。 2. The whole method of separating components of agriculture and forestry cellulosic biomass according to claim 1, wherein: said cellulosic biomass agriculture and forestry use straw, bagasse, miscanthus, forestry processing waste.
  3. 3.如权利要求1所述的一种农林纤维素生物质全组份的分离方法,其特征在于:所述的碱液采用浓度为〜7%的NaOH,KOH, Na2CO3中的一种;所述的氧化剂采用浓度为1 % 〜5 % 的H2O2, O3> KMnO4 中的一种。 3 parts of a whole set of one FORESTRY cellulosic biomass separation method according to claim 1, wherein: the concentration of the lye employed ~ 7% of NaOH, KOH, Na2CO3 of one; the said oxidizing agent is employed at a concentration of 1% ~ 5% of H2O2, O3> one kind of KMnO4.
  4. 4.如权利要求1所述的一种农林纤维素生物质全组份的分离方法,其特征在于:所述的中温抽提采用温度为40〜60°C条件下抽提2〜4小时;所述的高温抽提采用温度为100〜160°C条件下抽提至少1小时以上。 4. The whole method of separating components of agriculture and forestry cellulosic biomass according to claim 1, wherein: the extraction temperature employed in the extraction of 2 ~ 4 hours at a temperature of 40~60 ° C condition; the high temperature extraction using the extraction temperature is at least 1 hour at 100~160 ° C conditions.
  5. 5.如权利要求1所述的一种农林纤维素生物质全组份的分离方法,其特征在于:所述的步骤c)中压滤液浓缩至5倍以上,直到半纤维素与木质素固型物浓度达10%以上,碱液回收80%以上;且步骤c)和步骤d)中的静止时间均为1〜5小时;步骤d)中调节酸性至pH为3〜4。 5. The overall method for separating parts FORESTRY cellulosic biomass according to claim 1, wherein: said step c), the filtrate was concentrated under pressure to more than 5 times, until the solid lignin and hemicellulose Form concentration of 10% or more, 80% or more lye recovery; and step c) and step d) are still time ~ 5 hours; step d) adjusting the acidity to pH ~ 4.
  6. 6. 一种利用权利要求1分离后组份制备燃料酒精,其特征在于:所述的分离得到的纤维素粗品一方面用于制备纤维素酶或半纤维素酶,另一方面利用纤维素酶将纤维素粗品降解为葡萄糖,经酵母发酵后生产酒精;所述的纤维素酶或半纤维素酶的制备方法为:将所述的纤维素粗品,采用固态发酵制曲的方法,分别接种产纤维素酶菌株或产半纤维素酶菌株,固态发酵培养3天后收获纤维素酶或半纤维素酶。 Group 6. utilizing separate parts according to claim 1 prepared fuel alcohol, wherein: separating the obtained crude cellulose aspect for preparing a cellulase or hemicellulase, cellulase enzymes other hand, the crude product degradation of cellulose to glucose by the yeast fermentation to produce alcohol; the cellulase or hemicellulase preparation method is as follows: the crude cellulose, solid state fermentation of the koji, production were inoculated strains producing cellulases or hemicellulases strain solid fermentation harvested after 3 days of cellulase or hemicellulase.
  7. 7.如权利要求6所述的利用分离后组份制备燃料酒精,其特征在于:所述的产纤维素酶菌株采用灰绿曲霉或青霉这2种真菌中的一种;产半纤维素酶菌株采用黑曲霉或木霉这2种真菌中的一种。 7. The use according to claim 6 separated after the production of fuel alcohol component, wherein: said producing cellulase using a strain of Aspergillus or Penicillium glaucum one of these two kinds of fungi; Yield hemicellulose enzyme uses a strain of Aspergillus niger or Trichoderma these two fungi.
  8. 8.如权利要求6或7所述的利用分离后组份制备燃料酒精,其特征在于:所述的纤维素粗品与纤维素酶与按5 : 1-1 : 1比例混合,添加适量的水,使固液比为1 : 10,在50°C 酶解12小时以上得到纤维素酶解后的糖化液,纤维素酶解后的糖化液经纳滤膜浓缩至糖浓度15%以上;浓缩后的糖化液直接用于发酵产酒精。 8. The use of the separator 6 or claim 7, the production of fuel alcohol component, wherein: said crude cellulose with cellulase and 5: 1 to 1: 1 ratio, the amount of water added , solid-liquid ratio of 1: 10, the saccharified solution obtained after hydrolysis of cellulose hydrolysis above 50 ° C for 12 hours saccharified solution by nanofiltration after the hydrolysis of cellulose to glucose concentration was concentrated more than 15%; concentration after the saccharification liquid was used directly in the alcohol fermentation.
  9. 9. 一种利用权利要求1分离后组份制备低聚木糖,其特征在于:所述的分离得到的半纤维素粗品与半纤维素酶按5 : 1-1 : 1的比例混合后,添加半纤维素粗品5〜6倍重量体积的水,在60°C反应5〜16小时,加入活性炭脱色剂进行脱色,然后通过过滤除去固体杂质;将脱色过滤后的糖化液通过离子交换树脂脱盐,然后进行膜浓缩;将脱色和脱盐后的糖化液浓缩至15%以上后进行喷雾干燥制成粉末状低聚木糖或通过纳滤膜浓缩为高浓度的低聚木糖液。 A use as claimed in claim 1 separated components XOS preparation, characterized in that: the separated crude hemicellulose with hemicellulases 5: 1-1: 1 ratio mixed, the crude hemicellulose added 5 to 6 times the weight volume of water, reacted at 60 ° C 5~16 hours, decolorizing charcoal was added bleaching agent and then removing the solid impurities by filtration; saccharified solution decolorized after the desalting was filtered through an ion exchange resin followed by membrane concentration; the saccharified solution decolored and desalted concentrated to more than 15% was spray-dried powdered XOS or by nanofiltration was concentrated to a high concentration xylooligosaccharide solution.
CN 201010184386 2010-05-26 2010-05-26 Method for grading and separating all components of forestry cellulose biomass and preparing fuel alcohol and xylo-oligosaccharide by utilizing separated components CN102261007B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010184386 CN102261007B (en) 2010-05-26 2010-05-26 Method for grading and separating all components of forestry cellulose biomass and preparing fuel alcohol and xylo-oligosaccharide by utilizing separated components

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010184386 CN102261007B (en) 2010-05-26 2010-05-26 Method for grading and separating all components of forestry cellulose biomass and preparing fuel alcohol and xylo-oligosaccharide by utilizing separated components

Publications (2)

Publication Number Publication Date
CN102261007A true true CN102261007A (en) 2011-11-30
CN102261007B CN102261007B (en) 2013-05-15

Family

ID=45007825

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010184386 CN102261007B (en) 2010-05-26 2010-05-26 Method for grading and separating all components of forestry cellulose biomass and preparing fuel alcohol and xylo-oligosaccharide by utilizing separated components

Country Status (1)

Country Link
CN (1) CN102261007B (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103554274A (en) * 2013-10-21 2014-02-05 昆明理工大学 Preparation method of bagasse pith oxidized cellulose
CN103896992A (en) * 2014-04-17 2014-07-02 齐鲁工业大学 Method for preparing oligosaccharides from lignocellulosic hydrolyzate
CN103924468A (en) * 2014-05-16 2014-07-16 长春工业大学 Separation method of lignocellulose raw material ingredients
CN104109722A (en) * 2014-07-01 2014-10-22 丽水学院 Preparation method for xylo-oligosaccharide
CN104136466A (en) * 2011-12-30 2014-11-05 麦兰特公司 Integrated biorefinery
CN104131050A (en) * 2014-07-31 2014-11-05 江南大学 Efficient combined preprocessing method for straws
CN104357513A (en) * 2014-11-07 2015-02-18 宜宾雅泰生物科技有限公司 Electrodialysis process for preparing food-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor
CN104357515A (en) * 2014-11-07 2015-02-18 宜宾雅泰生物科技有限公司 Method for preparing feed-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor
CN104357516A (en) * 2014-11-07 2015-02-18 宜宾雅泰生物科技有限公司 Process for producing food-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor
CN104428421A (en) * 2012-07-13 2015-03-18 亲切消费者有限公司 Process for using tobacco
CN105113307A (en) * 2015-07-23 2015-12-02 华南理工大学 Pulping method via pre-extraction of bagasse easily soluble hemicelluloses, and product obtained via pulping method
CN105154986A (en) * 2015-08-04 2015-12-16 江南大学 Comprehensive cotton stalk base utilization method through combinations of alkali pretreatment, low pressure steam explosion and bio-enzyme treatment
CN105297511A (en) * 2015-11-26 2016-02-03 山东福田药业有限公司 Separation method of organic constituent in agricultural waste
CN105316366A (en) * 2015-10-20 2016-02-10 陈国章 Production method for comprehensively utilizing biological straw
CN105672012A (en) * 2016-01-27 2016-06-15 安徽格义循环经济产业园有限公司 Method for simultaneously extracting hemicellulose, cellulose and lignin from biomass material
CN106192514A (en) * 2016-07-26 2016-12-07 长春博纳士环保科技有限公司 Efficient separating purifying technique for lignin, hemi-cellulose and cellulose

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101016703A (en) * 2007-03-08 2007-08-15 上海交通大学 Method of producing cellulose, lignin and xylose by biomass material
CN101143881A (en) * 2007-10-11 2008-03-19 孔延华 Method for synchronously extracting hemicellulose, cellulose and lignin and reclaiming phenolic acid compounds
US20090308383A1 (en) * 2008-06-10 2009-12-17 Andritz Inc. Apparatus and method for hydrolysis of cellulosic material in a multi-step process to produce c5 and c6 sugars using a single vessel
CN101643796A (en) * 2009-08-28 2010-02-10 上海中科清洁能源技术发展中心 Method for utilizing straw biomass by grades

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101016703A (en) * 2007-03-08 2007-08-15 上海交通大学 Method of producing cellulose, lignin and xylose by biomass material
CN101143881A (en) * 2007-10-11 2008-03-19 孔延华 Method for synchronously extracting hemicellulose, cellulose and lignin and reclaiming phenolic acid compounds
US20090308383A1 (en) * 2008-06-10 2009-12-17 Andritz Inc. Apparatus and method for hydrolysis of cellulosic material in a multi-step process to produce c5 and c6 sugars using a single vessel
CN101643796A (en) * 2009-08-28 2010-02-10 上海中科清洁能源技术发展中心 Method for utilizing straw biomass by grades

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104136466A (en) * 2011-12-30 2014-11-05 麦兰特公司 Integrated biorefinery
CN104428421A (en) * 2012-07-13 2015-03-18 亲切消费者有限公司 Process for using tobacco
CN103554274A (en) * 2013-10-21 2014-02-05 昆明理工大学 Preparation method of bagasse pith oxidized cellulose
CN103896992A (en) * 2014-04-17 2014-07-02 齐鲁工业大学 Method for preparing oligosaccharides from lignocellulosic hydrolyzate
CN103896992B (en) * 2014-04-17 2016-05-25 齐鲁工业大学 A method of preparing oligosaccharides from lignocellulosic hydrolyzate
CN103924468A (en) * 2014-05-16 2014-07-16 长春工业大学 Separation method of lignocellulose raw material ingredients
CN104109722B (en) * 2014-07-01 2016-03-30 丽水学院 A method for the preparation of xylooligosaccharides
CN104109722A (en) * 2014-07-01 2014-10-22 丽水学院 Preparation method for xylo-oligosaccharide
CN104131050A (en) * 2014-07-31 2014-11-05 江南大学 Efficient combined preprocessing method for straws
CN104357513A (en) * 2014-11-07 2015-02-18 宜宾雅泰生物科技有限公司 Electrodialysis process for preparing food-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor
CN104357515A (en) * 2014-11-07 2015-02-18 宜宾雅泰生物科技有限公司 Method for preparing feed-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor
CN104357516A (en) * 2014-11-07 2015-02-18 宜宾雅泰生物科技有限公司 Process for producing food-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor
CN105113307A (en) * 2015-07-23 2015-12-02 华南理工大学 Pulping method via pre-extraction of bagasse easily soluble hemicelluloses, and product obtained via pulping method
CN105154986A (en) * 2015-08-04 2015-12-16 江南大学 Comprehensive cotton stalk base utilization method through combinations of alkali pretreatment, low pressure steam explosion and bio-enzyme treatment
CN105316366A (en) * 2015-10-20 2016-02-10 陈国章 Production method for comprehensively utilizing biological straw
CN105297511A (en) * 2015-11-26 2016-02-03 山东福田药业有限公司 Separation method of organic constituent in agricultural waste
CN105672012A (en) * 2016-01-27 2016-06-15 安徽格义循环经济产业园有限公司 Method for simultaneously extracting hemicellulose, cellulose and lignin from biomass material
CN106192514A (en) * 2016-07-26 2016-12-07 长春博纳士环保科技有限公司 Efficient separating purifying technique for lignin, hemi-cellulose and cellulose

Also Published As

Publication number Publication date Type
CN102261007B (en) 2013-05-15 grant

Similar Documents

Publication Publication Date Title
Binod et al. Bioethanol production from rice straw: an overview
Li et al. Simultaneous saccharification and fermentation of lignocellulosic residues pretreated with phosphoric acid–acetone for bioethanol production
Cara et al. Conversion of olive tree biomass into fermentable sugars by dilute acid pretreatment and enzymatic saccharification
Romaní et al. Bioethanol production from hydrothermally pretreated Eucalyptus globulus wood
US20080032344A1 (en) Process for recovery of holocellulose and near-native lignin from biomass
US20090011473A1 (en) Saccharifying cellulose
US20080044877A1 (en) Process for Producing Ethanol
Zhang et al. Ethanol production from high dry matter corncob using fed-batch simultaneous saccharification and fermentation after combined pretreatment
Chen et al. Key technologies for bioethanol production from lignocellulose
Wan et al. Liquid hot water and alkaline pretreatment of soybean straw for improving cellulose digestibility
Eliana et al. Effects of the pretreatment method on enzymatic hydrolysis and ethanol fermentability of the cellulosic fraction from elephant grass
CN101285106A (en) Process for preparing multicomponent liquid glucose and lignose while effectively hydrolyzing lignocellulosic biomass
CN102061323A (en) Comprehensive utilization process of wood cellulose
WO2009060126A1 (en) Process for preparing a sugar product
WO2010015404A1 (en) Process for the production of sugars from biomass
CN101628920A (en) Comprehensive utilization method of corn cob
CN101492700A (en) Intensive processing method for stalk articles or agricultural castoff
WO2009063138A2 (en) Method for producing lipid
Zhuang et al. Liquid hot water pretreatment of lignocellulosic biomass for bioethanol production accompanying with high valuable products
CN101586136A (en) Method of high-efficiency pretreatment on biomass
CN102051383A (en) Method for treating lignocellulose raw material through steam explosion and producing biogas, cellulose and lignin simultaneously
Teng et al. Production of xylooligosaccharides from the steam explosion liquor of corncobs coupled with enzymatic hydrolysis using a thermostable xylanase
Zhao et al. Enzymatic hydrolysis and simultaneous saccharification and fermentation of alkali/peracetic acid-pretreated sugarcane bagasse for ethanol and 2, 3-butanediol production
JP2009189291A (en) Saccharifying method for cellulose-containing biomass
CN1425773A (en) Process for preparing oligosaccharide and trans-ferulaic acid

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 363900 ZHANGZHOU, FUJIAN PROVINCE TO: 361000 XIAMEN, FUJIAN PROVINCE

C41 Transfer of patent application or patent right or utility model
ASS Succession or assignment of patent right

Owner name: CHEN FANGHE

Free format text: FORMER OWNER: ZHANGZHOU BONENG BIOLOGICAL ENERGY CO., LTD.

Effective date: 20140613

CF01