CN103088692B - Process for the selective separation of lignin and cellulose from lignocellulosic biomass - Google Patents

Process for the selective separation of lignin and cellulose from lignocellulosic biomass Download PDF

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CN103088692B
CN103088692B CN 201310038091 CN201310038091A CN103088692B CN 103088692 B CN103088692 B CN 103088692B CN 201310038091 CN201310038091 CN 201310038091 CN 201310038091 A CN201310038091 A CN 201310038091A CN 103088692 B CN103088692 B CN 103088692B
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lignin
lignocellulosic biomass
ionic liquid
cellulose
give
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CN103088692A (en )
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王键吉
尹卫平
任运来
李欣
王晓平
黄闪闪
田广富
刘柱萍
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河南科技大学
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Abstract

从木质纤维素类生物质中选择性分离木质素和纤维素的方法,属于化工提取领域,包括以下步骤:a、木质纤维素类生物质的预处理,b、木质纤维素的溶解和生物质的降解,c、提取和分离。 Process for the selective separation of lignin and cellulose from lignocellulosic biomass, belonging to the field of chemical extraction, comprising the steps of: a, pretreatment of lignocellulosic biomass, b, the lignocellulosic biomass and dissolves degradation, c, extraction and separation. 本发明木质素的提取率达到百分之九十以上;对离子液体1-丁基-3-甲基咪唑氯盐([Bmim]Cl)的回收率也达到百分之八十以上,可达到离子液体的循环利用,降低生产成本,通过反应条件的控制,从木质纤维素类生物质中同时提取分离木质素和纤维素,在能耗方面明显降低,适合工业化的生产。 Extraction rate of lignin present invention is more than 90 percent; recovery of the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim] Cl) also reaches 80% or more, can be achieved using the ionic liquid circulation, reduce production costs, by controlling the reaction conditions, is extracted from lignocellulosic biomass simultaneously separating lignin and cellulose, significantly reduced energy consumption, suitable for industrialized production.

Description

从木质纤维轰类生物质中选择性分离木质轰和纤维轰的方法 The method of selective separation of wood fibers and H H H from lignocellulosic biomass in

技术领域 FIELD

[0001] 本发明属于化工领域提取分离技术,尤其设及从木质纤维素类生物质中选择性分离木质素和纤维素的方法。 [0001] The present invention belongs to the field of chemical extraction and separation techniques, and in particular is provided to selectively separate the cellulose and lignin from lignocellulosic biomass Method.

背景技术 Background technique

[0002] 木质素(lignin)与纤维素(cellulose)和半纤维素化emicellulose)是构成植物骨架木质纤维素的主要成分。 [0002] The lignin (Lignin) cellulose (Cellulose) and hemicellulose of emicellulose) is the main component constituting the skeleton of plant lignocellulose. 据估计,每年全世界由植物生成的木质素达1500亿吨,木质素的产量巨大、可再生、可生物降解的天然高分子化合物,由于其结构复杂、物化性质不均一、分离提取困难及易缩合等,至今尚未得到充分有效的利用。 It is estimated that each year around the world generated by the plant lignin 1,500 million tons of lignin production of large, renewable, biodegradable natural polymers, due to the complexity of its structure and physicochemical properties uniform, easy to separate and difficult to extract condensation, has not yet been fully and effectively utilized. 木质素是自然界中含量仅次于纤维素的第二丰富的可再生资源,再生速度快,是天然最丰富的芳香高聚物。 Lignin is the second most abundant renewable resource content of the nature after cellulose, the fast playback speed is the most abundant natural aromatic polymer.

[0003]木质素利用的研究已经进行了一个世纪,目前虽然出现了小规模的利用,但与它的存在数量相比,仍没有发现大规模的经济上满意的工业应用领域,从资源与环境等考虑, 从生物质等植物中提取木质素成分和分离溶解纤维素的技术,仍是特别受重视的领域,因为要实现木质素降解为大规模商业化低分子化学品的目标,必须探索出经济、环保、可行的木质素分离途径。 [0003] Lignin utilization has been a century, although currently there has been the use of small-scale, but compared with the number of its existence, still did not find satisfaction on large-scale economic industrial applications, from resources and environment and other considerations, to extract lignin from biomass, such as plant components and separate technical dissolve cellulose, is still subject to special areas of attention, because to achieve large-scale commercialization of lignin degradation of low molecular weight chemicals goal, we must explore economic, environmental, and feasible way to separate the lignin. 同时木质素的结构复杂、物理化学性质不均一,又较容易发生氧化,在受酸、碱、热的作用时,木质素结构都会发生不同程度的变化,甚至在机械处理时木质素原本结构也会发生变化。 While the structure of lignin complex, non-uniform physical and chemical properties, and more prone to oxidation, when by the action of an acid, base, heat, different changes lignin structure will occur, even when the original mechanical treatment the lignin structure It will change. 故而在提取和分离过程中木质素原有结构可能会被破坏甚至发生木质素氧化、缩合和降解等问题,试图寻求一种温和条件下,溶解和分离木质素的新途径和新方法,从而实现木质纤维素类的生物质等可再生废弃资源的充分综合利用和提取分离木质素的工业化生产,实现木质素的高值化利用。 Therefore the original structure of lignin extraction and separation process may be damaged or even lignin oxidation, degradation and condensation problems, trying to find under a mild condition, new ways and methods of dissolving and separation of lignin, in order to achieve lignocellulosic biomass waste and other renewable resources and industrial production of full utilization of lignin extraction and separation, to achieve efficient utilization of lignin.

发明内容 SUMMARY

[0004]本发明目的在于提供一种条件温和,工艺简单,提取率高,能从木质纤维素类生物质中选择性分离木质素和纤维素的方法。 [0004] The object of the present invention is to provide a mild conditions, simple process, extraction rate, from lignocellulosic biomass selective separation of lignin and cellulose.

[0005] 为达到上述目的,本发明的技术方案为从木质纤维素类生物质中选择性分离木质素和纤维素的方法,包括W下步骤: [0005] To achieve the above object, the technical solution of the present invention is a method for the selective separation of lignin and cellulose from lignocellulosic biomass, W comprises the steps of:

[0006]a、木质纤维素类生物质的预处理;将木质纤维素类生物质粉碎,过180目筛后,置80-110°C烘箱中干燥60-120分钟,然后膨化处理得木质纤维素类生物质颗粒备用; [0006] a, pretreated lignocellulosic biomass; lignocellulosic biomass crushing, over a 180 mesh sieve, placed in a drying oven at 80-110 ° C for 60-120 minutes, then bulked handled lignocellulosic gonadotropin spare biomass particles;

[0007]b、木质纤维素的溶解和生物质的降解:称取15-50g的离子液体1- 了基-3-甲基咪挫氯盐于50-500mL的烧瓶中,置于95-105°C油浴锅中加热溶融,揽拌离子液体并向其加入2. 5-20g木质纤维素类生物质颗粒,密封烧瓶,温度控制在90-110°C,不断揽拌加热2-3h,得粘稠状物; [0007] b, dissolution and degradation of lignocellulosic biomass: weighing 15-50g of the ionic liquid 1-chloro-3-methylimidazolium salt setback in 50-500mL flask, was placed 95-105 ° C oil-heated bath melted, stirred ionic liquid and embrace added 2. 5-20g lignocellulosic biomass particles, the flask sealed, temperature controlled at 90-110 ° C, stirred continuously embrace heating 2-3h, to obtain a viscous substance;

[0008]在上述得到的粘稠状物中边揽拌边滴加5-10%的稀盐酸,调节抑值为4. 5-4. 8,继续加热揽拌5-化,得反应浆液; [0008] In the side football viscous substance obtained as described above was added dropwise mix 5-10% dilute hydrochloric acid, adjusting the value of suppression 4. 5-48, heating was continued embrace of 5- stirred to obtain a slurry reaction.;

[0009] C、提取和分离;将反应浆液冷却至室温后,加入反应浆液体积2-8倍的去离子水, 均匀混合后转移到分液漏斗中,静置1-化后分层,得下层离子液体相和上层水相,将分离的下层离子液体相静置后抽滤,得到抽滤物I和滤液,抽滤物I于60°C的真空干燥箱中干燥,得到纤维素,滤液真空浓缩脱水后,得到离子液体;分离的上层水相静置后反复抽滤2-3次,将水蒸发浓缩得到块状浓缩物II,80°CW下真空干燥,得到木质素。 [0009] C, extraction and separation; deionized water The reaction slurry was cooled to room temperature, the reaction was added 2-8 times the volume of the slurry, mixed uniformly transferred to a separatory funnel and allowed to stand after stratification of 1- give lower ionic liquid phase and an upper aqueous phase, after separating the lower phase was allowed to stand ionic liquid filtration, suction filtration to give I and filtrate I was suction filtered in a vacuum oven of 60 ° C and dried to obtain a cellulose filtrate after dehydration and concentrated in vacuo to give an ionic liquid; after separation of the upper aqueous phase was allowed to stand suction repeated 2-3 times, water is concentrated by evaporation to give a bulk concentrate class II, and dried under vacuum at 80 ° CW, obtained lignin.

[0010] 所述的木质纤维素类生物质包括芝麻枯杆、玉米枯杆、花生壳和桃核壳。 [0010] The lignocellulosic biomass comprising sesame stem blight, stem blight of corn, peanut hulls, and Peach shell.

[0011] 所述的膨化处理压力为0. 25-0. 4Mpa,时间为30-50S。 Expanded process pressure [0011] is the 0. 25-0. 4Mpa, time 30-50S.

[0012] 本发明的有益效果: [0012] Advantageous effects of the invention:

[0013] 1)本发明所提供的从木质纤维素类生物质中选择性分离木质素和纤维素的方法,将生物质过180目筛后,进行膨化处理,解除枯杆、玉米杆、花生壳和核桃壳中木质素对纤维素和半纤维素的包裹W及致密的纤维素结晶区结构,使原料的物理结构发生变化,增加木质纤维素粉末溶解的有效比表面积,促进木质纤维类生物质的降解和木质素的溶解; After [0013] 1) a method for selectively separating the cellulose and lignin from lignocellulosic biomass is provided in the present invention, the biomass through the 180 mesh sieve, puffing process, releasing dry stalk, corn stalk, peanut shell and walnut shell lignin and cellulose and hemicellulose package W dense crystalline regions of the cellulose structure, so that changes in the physical structure of the material, increasing the effective surface area of ​​the powder was dissolved lignocellulose, promotion of lignocellulosic Biomass lignin degradation and dissolution of the substance;

[0014] 2)该发明W1- 了基-3-甲基咪挫氯盐(出mim]Cl)离子液体与膨化的木质纤维素在95-105°C下揽拌2-3小时进行处理,通过降低纤维素的聚合度、结晶度,破坏木质素与半纤维素的结合层,脱去木质素,增加木质纤维素类生物质粉末溶解的有效比表面积等,提高了木质素的提取率,使木质素提取率达到百分之九十W上; [0014] 2) The invention W1- a setback-3-methylimidazolium chloride (a mim] Cl) ionic liquid to the lignocellulosic puffed embrace stirred at 95-105 ° C 2-3 hours treatment, by reducing the degree of polymerization of cellulose crystallinity, hemicellulose and lignin destruction bonding layer, delignified, increasing the effective surface area lignocellulosic biomass powder was dissolved and the like, to improve the extraction rate of lignin, lignin extraction rate on ninety percent W;

[0015] 3)本发明中对离子液体的回收率达到百分之八十W上,可达到离子液体的循环利用,降低生产成本,通过反应条件的控制,从木质纤维素类生物质中同时提取和分离出木质素和纤维素,在能耗方面明显降低,适合工业化的生产; [0015] 3) of the present invention on the recovery of the ionic liquid reaches eighty percent of W, up to recycle the ionic liquid, to reduce production costs, by controlling the reaction conditions, while from lignocellulosic biomass extraction and separation of lignin and cellulose, significantly reduced energy consumption, suitable for industrialized production;

[0016] 4)基于前期对草本/木本、坚果等不同生物质材料中木质素的含量分析W玉米枯杆、芝麻枯杆、花生壳、桃核壳为材料,W及通过该法进行试验和测试,该法也可对此类木质纤维素类植物和农产品的下脚料进行木质素和纤维素的选择性分离。 [0016] 4) based on the content of the pre-herbaceous / woody biomass material nuts different lignin Analysis W maize stem blight, stem blight sesame, peanut shells, peach stone materials for the shell, and W were tested by this method and testing, the method can also be selective separation of lignin and cellulose such lignocellulosic waste and agricultural plants.

附图说明 BRIEF DESCRIPTION

[0017] 图1为从芝麻枯杆中分离抽滤物I纤维素的红外图谱; [0017] Figure 1 is an infrared spectrum separate from the cellulose I was suction filtered dry sesame rod;

[001引图2为木质素标准品的红外图谱; [001] Figure 2 is an infrared spectrum cited standards of lignin;

[0019]图3为从芝麻枯杆中分离浓缩物II木质素的红外图谱; [0019] FIG. 3 is a II concentrate was separated from the IR spectra of lignin dry sesame rod;

[0020] 图4为从玉米枯杆中分离浓缩物II木质素的红外图谱; [0020] FIG. 4 is a lignin-II concentrate was separated from the corn dry IR spectra rod;

[0021] 图5为从花生壳中分离浓缩物II木质素的红外图谱; [0021] FIG. 5 is a concentrate was separated from the IR spectra of lignin II Peanut Shell;

[0022] 图6为从核桃壳中分离浓缩物II木质素的红外图谱。 [0022] FIG. 6 is a concentrate was separated from the IR spectra of lignin II walnut shell.

具体实施方式 detailed description

[0023] 下面结合附图和实施例对本发明作进一步详细说明。 Drawings and embodiments of the present invention will be further described in detail [0023] below in conjunction.

[0024] 实施例1; [0024] Example 1;

[0025] 从木质纤维素类生物质中选择性分离木质素和纤维素的方法,包括W下步骤: [0025] A method for the selective separation of lignin and cellulose from lignocellulosic biomass, W comprises the steps of:

[0026]a、木质纤维素类生物质的预处理:将芝麻枯杆粉碎,过180目筛后,置105°C烘箱中干燥60分钟,然后膨化处理得芝麻枯杆颗粒备用; [0026] a, pretreated lignocellulosic biomass: Sesame dry grinding rod, through the 180 mesh sieve, placed in drying oven at 105 ° C for 60 minutes and then extruded rod handled dry particles sesame standby;

[0027]b、木质纤维素的溶解和生物质的降解:称取15g的离子液体1- 了基-3-甲基咪挫氯盐于50mL的烧瓶中,置于104°C油浴锅中加热溶融,揽拌离子液体并向其加入2. 5g芝麻枯杆颗粒,密封烧瓶,温度控制在90°C,不断揽拌加热化,得粘稠状物; [0027] b, dissolution and degradation of lignocellulosic biomass: Weigh 15g of the ionic liquid 1-chloro-3-methylimidazolium salt setback in 50mL flask, placed in an oil bath of 104 ° C heat-melted, mixed with the ionic liquid and embrace added 2. 5g of sesame dry particles lever, the flask sealed, temperature controlled at 90 ° C, stirred continuously embrace of heating to give a viscous substance;

[0028] 在上述得到的粘稠状物中边揽拌边滴加10%的稀盐酸,调节抑值为4. 5,继续加热揽拌化,得反应浆液; [0028] In the viscous substance obtained as described above embrace the edge stirred added dropwise a 10% diluted hydrochloric acid, adjusted suppression value 4.5, and heating was continued embrace of mixed to obtain a slurry reaction;

[0029] C、提取和分离;将反应浆液冷却至室温后,加入反应浆液体积5倍的去离子水,均匀混合后转移到分液漏斗中,静置化后分层,得下层离子液体相和上层水相,将分离的下层离子液体相静置后抽滤,得到抽滤物I和滤液,抽滤物I于60°C的真空干燥箱中干燥, 得到纤维素,滤液真空浓缩脱水后,得到离子液体12. 8g;分离的上层水相静置后反复抽滤2-3次,将水蒸发浓缩得到块状浓缩物II,80°CW下真空干燥,得到木质素0. 612g。 [0029] C, extraction and separation; deionized water The reaction slurry was cooled to room temperature, the reaction was added 5 times the volume of the slurry, mixed uniformly transferred to a separatory funnel and, after standing stratified give lower ionic liquid phase after the upper aqueous phase and the separated ionic liquid phase was allowed to stand lower suction, suction filtered to give I and filtrate I was suction filtered in a vacuum oven of 60 ° C and dried to obtain a cellulose, the filtrate was concentrated under vacuum dehydration , ionic liquid 12. 8g; separated upper aqueous phase left after suction filtration is repeated 2-3 times, water is concentrated by evaporation to give a bulk concentrate class II, and dried under vacuum at 80 ° CW, lignin give 0. 612g. 所述的膨化处理压力为0. 25Mpa,时间为30s。 The treatment pressure is puffed 0. 25Mpa, time of 30s.

[0030] 图1、图3为抽滤物I和浓缩物II的红外图谱,图2为木质素标准品的标准图谱,分别准确称取2.0mg真空干燥后的抽滤物I、浓缩物II和木质素标准品,再加入约150mg漠化钟,放入压片机的样品槽中,压成均匀透明薄膜,进行FT-IR红外光谱测定。 [0030] FIG 1, FIG 3 is a concentrate suction filtered I and II of the infrared spectrum, FIG. 2 is a standard pattern of lignin standards were precisely weighed after suction filtration was taken 2.0mg I dried in vacuo concentrate II standards and lignin, then add about 150mg desertification bell, into the sample vessel tableting machine, pressed into a uniform transparent film, the infrared spectrum was measured FT-IR.

[0031] 从图2和图3的红外分析图谱可W看出,分离的芝麻杆木质素与标准木质素图谱比较,其中芳香族化合物环内碳原子间伸缩振动引起的环的骨架振动特征吸收峰在1630. 01 (s)cm-i,1509. 79 (s)cm-i,1463. 55(m)cm-i,1422. 85(m)cm-i,805. 23(w)cm-i为芳环上S取代吸收;酪哲基的C-0伸缩振动吸收在1261. 36 (br.)cm4;芳环上的烷氧基吸收在1125.21-1035.35cnfi为一宽和强的吸收带。 [0031] W can be seen from the analysis of the infrared spectrum of FIG. 2 and FIG. 3, comparing the separate lignin standard sesame lignin rod pattern, the ring skeleton vibration characteristics between the aromatic compound wherein the ring carbon atoms stretching vibration absorption caused peak at 1630. 01 (s) cm-i, 1509. 79 (s) cm-i, 1463. 55 (m) cm-i, 1422. 85 (m) cm-i, 805. 23 (w) cm- S i is substituted on the aromatic ring absorbent; C-0 stretching vibration absorption in casein Zenith 1261. 36 cm4 (br.); an alkoxy group on the aromatic ring is a 1125.21-1035.35cnfi absorption and strong absorption band width. 与木质素不同,芝麻杆木质素的吸收峰为1735. 53cnTi,经红外分析在酬基吸收官能团区,故该木质素中含有酬基。 Different lignin, lignin absorption sesame rod is 1735. 53cnTi, by infrared absorption analysis functionality group pay zone, so that the lignin-containing group reward.

[0032] 基于前期对草本/木本、坚果等不同生物质材料中木质素的含量分析W玉米枯杆、芝麻枯杆、花生壳、桃核壳为材料,利用国标法分别测出它们的木质素的含量,为生物质能源植物的开发利用提供科学依据。 [0032] Based on the content of the pre-herbaceous / woody biomass material nuts different lignin Analysis W maize stem blight, stem blight sesame, peanut shells, peach pit shell of material, were measured by using the GB method thereof wood pigment content, provide a scientific basis for the development and utilization of biomass energy plants. 测得的上述不同木质纤维素其中的木质素含量如下表所示: Wherein these different lignocellulosic lignin content measured as follows:

[0033] [0033]

Figure CN103088692BD00051

[0034] 进而计算出出mim]Cl对木质素的提取率:; [0034] Further the calculated mim] Cl extraction rate of lignin:;

[00巧] [00 clever]

Figure CN103088692BD00052

[0036] [Bmim]Cl的回收率; [0036] [Bmim] Cl recovery;

[0037] [0037]

Figure CN103088692BD00053

[003引实施例2; [Example 2 Primer 003;

[0039] 从木质纤维素类生物质中选择性分离木质素和纤维素的方法,包括W下步骤: [0039] A method for the selective separation of lignin and cellulose from lignocellulosic biomass, W comprises the steps of:

[0040]a、木质纤维素类生物质的预处理:将玉米枯杆粉碎,过180目筛后,置80°C烘箱中干燥60分钟,然后膨化处理得玉米枯杆颗粒备用; [0040] a, pretreated lignocellulosic biomass: corn dry grinding rod, over a 180 mesh sieve, placed in a drying oven at 80 ° C for 60 minutes and then extruded corn handled dry particles spare rod;

[0041]b、木质纤维素的溶解和生物质的降解:称取15g的离子液体1-了基-3-甲基咪挫氯盐于100血的烧瓶中,置于95°C油浴锅中加热溶融,揽拌离子液体并向其加入2. 5g玉米枯杆颗粒,密封烧瓶,温度控制在1l〇°C,不断揽拌加热化,得粘稠状物; [0041] b, dissolution and degradation of lignocellulosic biomass: Weigh 15g of the ionic liquid 1-chloro-3-methylimidazolium salt in a flask setback 100 in the blood, placed in an oil bath at 95 ° C pot heating melted, stirred ionic liquid and embrace added 2. 5g dry corn stem particles, the flask sealed, temperature controlled at 1l〇 ° C, stirred continuously embrace of heating to give a viscous substance;

[0042] 在上述得到的粘稠状物中边揽拌边滴加5%的稀盐酸,调节抑值为4. 8,继续加热揽拌化,得反应浆液; [0042] In the viscous substance obtained as described above embrace the edge stirred added dropwise a 5% dilute hydrochloric acid, adjusting the suppression value 4.8, and heating was continued embrace of mixed to obtain a slurry reaction;

[0043]c、提取和分离;将反应浆液冷却至室温后,加入反应浆液体积2倍的去离子水,均匀混合后转移到分液漏斗中,静置化后分层,得下层离子液体相和上层水相,将分离的下层离子液体相静置后抽滤,得到抽滤物I和滤液,抽滤物I于60°C的真空干燥箱中干燥, 得到纤维素,滤液真空浓缩脱水后,得到离子液体12. 7g;分离的上层水相静置后反复抽滤2-3次,将水蒸发浓缩得到块状浓缩物II,80°CW下真空干燥,得到木质素0. 34g。 [0043] c, extraction and separation; deionized water The reaction slurry was cooled to room temperature, the reaction was added 2 times the volume of the slurry, mixed uniformly transferred to a separatory funnel and, after standing stratified give lower ionic liquid phase after the upper aqueous phase and the separated ionic liquid phase was allowed to stand lower suction, suction filtered to give I and filtrate I was suction filtered in a vacuum oven of 60 ° C and dried to obtain a cellulose, the filtrate was concentrated under vacuum dehydration , ionic liquid 12. 7g; separated upper aqueous phase left after suction filtration is repeated 2-3 times, water is concentrated by evaporation to give a bulk concentrate class II, and dried under vacuum at 80 ° CW, lignin give 0. 34g. 所述的膨化处理压力为0. 4Mpa,时间为50s。 The treatment pressure is puffed 0. 4Mpa, time of 50s.

[0044] 经计算得出mim]Cl对木质素的提取率93. 79%,出mim]Cl的回收率84. 67%。 [0044] was calculated mim] Cl lignin extraction rate of 93.79%, a recovery mim] Cl is 84.67%. 图4 为从玉米枯杆中提取的浓缩物II木质素的红外图谱,从图4可W看出,玉米枯杆木质素的芳香族化合物环内碳原子间伸缩振动引起的环的骨架振动特征吸收峰在1653.34 (s)cnTi, 1500. 91. (s)cm-i,酪哲基的C-0伸缩振动吸收在1119. 20. (br. )cm-i;芳环上取代基吸收在790. 67畑1一1。 4 is extracted from the corn dry rod IR spectra lignin concentrate II, W can be seen from Figure 4, between the aromatic compound maize stem blight lignin skeleton stretching vibration of the ring carbon atoms of the ring caused by the characteristic vibration an absorption peak at 1653.34 (s) cnTi, 1500. 91. (s) cm-i, C-0 stretching vibration absorption in casein Zenith 1119. 20. cm-i (br.); substituent group on the aromatic ring absorption at 790 67 Hata 1-1.

[004引实施例3; [Example 3 lead 004;

[0046] 从木质纤维素类生物质中选择性分离木质素和纤维素的方法,包括W下步骤: [0046] A method for the selective separation of lignin and cellulose from lignocellulosic biomass, W comprises the steps of:

[0047]a、木质纤维素类生物质的预处理;将花生壳粉碎,过180目筛后,置110°C烘箱中干燥90分钟,然后膨化处理得花生壳颗粒备用; [0047] a, pretreated lignocellulosic raw material; the pulverized peanut shell, over 180 mesh sieve, placed in drying oven at 110 ° C for 90 minutes and then expanded spare handled peanut shell particles;

[0048]b、木质纤维素的溶解和生物质的降解:称取50g的离子液体1-了基-3-甲基咪挫氯盐于500mL的烧瓶中,置于110°C油浴锅中加热溶融,揽拌离子液体并向其加入20g花生壳颗粒,密封烧瓶,温度控制在9(TC,不断揽拌加热2.化,得粘稠状物; [0048] b, dissolution and degradation of lignocellulosic biomass: Weigh 50g of the ionic liquid 1-chloro-3-methylimidazolium salt setback in 500mL flask, placed in an oil bath of 110 ° C heat-melted, mixed with the ionic liquid and embrace 20g peanut shell particles are added, the flask sealed, temperature controlled at 9 (TC, 2. heating of continuously embrace stirred to obtain a viscous substance;

[0049] 在上述得到的粘稠状物中边揽拌边滴加8%的稀盐酸,调节抑值为4. 5,继续加热揽拌化,得反应浆液; [0049] In the viscous substance obtained as described above was added dropwise edge stirred embrace 8% dilute hydrochloric acid, adjusting the suppression value 4.5, and heating was continued embrace of mixed to obtain a slurry reaction;

[0050] t提取和分离;将反应浆液冷却至室温后,加入反应浆液体积6倍的去离子水,均匀混合后转移到分液漏斗中,静置Ih后分层,得下层离子液体相和上层水相,将分离的下层离子液体相静置后抽滤,得到抽滤物I和滤液,抽滤物I于60°C的真空干燥箱中干燥,得到纤维素,滤液真空浓缩脱水后,得到离子液体42. 02g;分离的上层水相静置后反复抽滤2-3次,将水蒸发浓缩得到块状浓缩物II,80°CW下真空干燥,得到木质素3. 39g。 [0050] t extraction and separation; The reaction slurry was cooled to room temperature, the reaction was added deionized water 6 times the volume of the slurry, mixed uniformly transferred to a separatory funnel and allowed to stand Ih stratification, and have a lower ionic liquid phase the upper aqueous phase was separated ionic liquid phase was allowed to stand lower suction, suction filtered to give I and filtrate I was suction filtered in a vacuum oven of 60 ° C and dried to obtain a cellulose filtrate was concentrated in vacuo and dehydrated, ionic liquid 42. 02g; separated upper aqueous phase left after suction filtration is repeated 2-3 times, water is concentrated by evaporation to give a bulk concentrate class II, and dried under vacuum at 80 ° CW, lignin give 3. 39g. 所述的膨化处理压力为0. 3Mpa,时间为40s。 The treatment pressure is puffed 0. 3Mpa, time of 40s.

[0051] 经计算得出mim]Cl对木质素的提取率93. 49%,出mim]Cl的回收率84. 04%。 [0051] was calculated mim] Cl lignin extraction rate of 93.49%, a recovery mim] Cl is 84.04%. 图5 为从花生壳中提取的浓缩物II木质素的红外图谱,从图5可W看出,其中花生壳中的木质素的芳香族化合物环内碳原子间伸缩振动引起的环的骨架振动特征吸收峰在1616.62(S) cm-i,1501. 72(S)cm-哺1463. 37 (m)cm-1酪哲基的C-0 伸缩振动吸收在1266. 39cm-哺1084. 86 (br. )cm-i。 5 is extracted from the peanut shell IR spectra lignin concentrate II, W can be seen from Figure 5, wherein between the inner shell peanut aromatic compounds lignin skeleton stretching vibration of the ring carbon atoms of the ring due to vibration characteristic absorption peak at 1616.62 (S) cm-i, 1501. 72 (S) cm- feeding 1463. 37 (m) cm-1 C-0 stretching vibration absorption in casein Zenith 1266. 39cm- feeding 1084. 86 (br .) cm-i.

[005引实施例4; [Example 4 lead 005;

[0053] 从木质纤维素类生物质中选择性分离木质素和纤维素的方法,包括W下步骤: [0053] A method for the selective separation of lignin and cellulose from lignocellulosic biomass, W comprises the steps of:

[0054]a、木质纤维素类生物质的预处理;将核桃壳粉碎,过180目筛后,置90°C烘箱中干燥120分钟,然后膨化处理得核桃壳颗粒备用; [0054] a, pretreated lignocellulosic biomass; crushed walnut shells, over a 180 mesh sieve, dried in an oven set to 90 ° C for 120 minutes and then expanded spare handled walnut shell particles;

[0055]b、木质纤维素的溶解和生物质的降解:称取30g的离子液体1-了基-3-甲基咪挫氯盐于250mL的烧瓶中,置于110°C油浴锅中加热溶融,揽拌离子液体并向其加入lOg核桃壳颗粒,密封烧瓶,温度控制在l〇〇°C,不断揽拌加热化,得粘稠状物; [0055] b, dissolution and degradation of lignocellulosic biomass: Weigh 30g of the ionic liquid 1-chloro-3-methylimidazolium salt setback in 250mL flask, placed in an oil bath of 110 ° C heat-melted, mixed with the ionic liquid and embrace lOg walnut shell particles added, the flask sealed, temperature controlled at l〇〇 ° C, stirred continuously embrace of heating to give a viscous substance;

[0056]在上述得到的粘稠状物中边揽拌边滴加10%的稀盐酸,调节抑值为4. 8,继续加热揽拌化,得反应浆液; [0056] In the viscous substance obtained as described above embrace the edge stirred added dropwise a 10% diluted hydrochloric acid, adjusted suppression value 4.8, and heating was continued embrace of mixed to obtain a slurry reaction;

[0057] C、提取和分离;将反应浆液冷却至室温后,加入反应浆液体积8倍的去离子水,均匀混合后转移到分液漏斗中,静置化后分层,得下层离子液体相和上层水相,将分离的下层离子液体相静置后抽滤,得到抽滤物I和滤液,抽滤物I于60°C的真空干燥箱中干燥, 得到纤维素,滤液真空浓缩脱水后,得到离子液体26.Ig;分离的上层水相静置后反复抽滤2-3次,将水蒸发浓缩得到块状浓缩物II,80°CW下真空干燥,得到木质素2. 63g。 [0057] C, extraction and separation; deionized water The reaction slurry was cooled to room temperature, the reaction slurry was added 8 times the volume, mixed uniformly transferred to a separatory funnel and, after standing stratified give lower ionic liquid phase after the upper aqueous phase and the separated ionic liquid phase was allowed to stand lower suction, suction filtered to give I and filtrate I was suction filtered in a vacuum oven of 60 ° C and dried to obtain a cellulose, the filtrate was concentrated under vacuum dehydration , ionic liquid 26.Ig; suction filtration repeated 2-3 times the upper aqueous phase separated after standing, the water is evaporated and concentrated to give a bulk concentrate class II, and dried under vacuum at 80 ° CW, lignin give 2. 63g. 所述的膨化处理压力为0. 25Mpa,时间为50s。 The treatment pressure is puffed 0. 25Mpa, time of 50s. 经计算得[Bmim]Cl对木质素的提取率91. 67%,[Bmim] Cl的回收率87. 00%。 It was calculated [Bmim] Cl lignin extraction rate of 91.67%, the recovery rate [Bmim] Cl of 87.00%. 图6为从核桃壳中提取的浓缩物II木质素的红外图谱,从图6可W看出,核桃壳中木质素的芳香族化合物环内碳原子间伸缩振动引起的环的骨架振动特征吸收峰在1616. 60 (s)cm-i,1500. 72 (s)cm-i和1456. 98(m)cm-i。 6 is extracted from the concentrate II walnut shell lignin IR spectra, W can be seen from Figure 6, the ring skeleton vibration characteristics between the aromatic compound walnut shell ring carbon atoms in the lignin due to the stretching vibration absorption peak (s) cm-i, 1500. 72 (s) cm-i and 1456. 98 (m) cm-i at 1616.60. 芳环上酪哲基C-0 伸缩振动吸收在1112. 43 (br. )cm-i,芳环上取代基吸收在832. 15畑1一1。 Aromatic ring casein Zenith C-0 stretching vibration absorption in 1112. 43 (br.) Cm-i, a substituent taken up in a 1 1 832.15 Hata on the aromatic ring.

Claims (2)

  1. 1. 从木质纤维素类生物质中选择性分离木质素和纤维素的方法,包括对木质纤维素类生物质预处理的步骤,W及木质纤维素溶解和生物质降解的步骤,具体为: a、 木质纤维素类生物质的预处理;将木质纤维素类生物质粉碎,过180目筛后,置80-110°C烘箱中干燥60-120分钟,然后在0. 25-0. 4MI^a的压力下膨化处理30-50s,得木质纤维素类生物质颗粒备用; b、 木质纤维素的溶解和生物质的降解:称取15-50g的离子液体1-了基-3-甲基咪挫氯盐于50-500ml的烧瓶中,置于95-105°C油浴锅中加热溶融,揽拌离子液体并向其加入2. 5-20g木质纤维素类生物质颗粒,密封烧瓶,温度控制在90-110°C,不断揽拌加热2-化,得粘稠状物;在上述得到的粘稠状物中边揽拌边滴加5-10%的稀盐酸,调节抑值为4. 5 -4. 8,继续加热揽拌5 -化,得反应浆浓; 其特征在于;还包括W下步骤: C、提取和分离 A method from lignocellulosic biomass selectively separating lignin and cellulose, comprising the step of lignocellulosic biomass pretreatment, W, and the step of lignocellulosic biomass degradation and dissolution, specifically: a, pretreated lignocellulosic raw material; lignocellulosic biomass crushing, over a 180 mesh sieve, placed in a drying oven at 80-110 ° C for 60-120 minutes, and then 0. 25-0 4MI. ^ a pressure of expanding treatment of 30-50s, have lignocellulosic biomass particles standby; dissolution and degradation of biomass, b, the lignocellulosic: weighing 15-50g the ionic liquid 1-methyl-3- chloride in imidazole group fell 50-500ml flask, sealed flask was placed in an oil bath of 95-105 ° C heat-melted, mixed with the ionic liquid and embrace added 2. 5-20g lignocellulosic biomass particles, , temperature controlled at 90-110 ° C, stirred continuously embrace heating of 2- afford a viscous substance; the viscous substance obtained as described above was added dropwise edge stirred embrace 5-10% dilute hydrochloric acid, adjusting the value of the suppression For 4. 5-48, heating was continued embrace stirred 5 - of, concentrated to give a reaction slurry; wherein; W further comprises the steps of: C, extraction and separation ;将反应浆液冷却至室温后,加入反应浆液体积2-8倍的去离子水,均匀混合后转移到分液漏斗中,采用静置分层的方法使其分为下层离子液体相和上层水相, 静置时间为1-化;将分离的下层离子液体相静置后抽滤,得到抽滤物I和滤液,抽滤物I 于60°C的真空干燥箱中干燥,得到纤维素,滤液真空浓缩脱水后,得到离子液体;分离的上层水相静置后反复抽滤2-3次,将水蒸发浓缩得到块状浓缩物n,8(TCW下真空干燥,得到木质素。 ; Methods reaction slurry was cooled to room temperature, the reaction slurry was added 2-8 times the volume of deionized water, transferred to a separatory funnel and mixed uniformly using hierarchical standing to separate into a lower ionic liquid phase and an upper aqueous phase, of standing time is 1; the separated ionic liquid phase was allowed to stand lower suction, suction filtered to give I and filtrate I was suction filtered and dried in a vacuum oven of 60 ° C to give cellulose, after dehydration filtrate was concentrated in vacuo, to give the ionic liquid; after separation of the upper aqueous phase was allowed to stand suction repeated 2-3 times, and the aqueous concentrate was concentrated by evaporation to give a bulk n, 8 (TCW dried under vacuum to give the lignin.
  2. 2. 根据权利要求1所述的从木质纤维素类生物质中选择性分离木质素和纤维素的方法,其特征在于;所述的木质纤维素类生物质包括芝麻枯杆、玉米枯杆、花生壳和桃核壳。 The process for the selective separation of lignin and cellulose from lignocellulosic biomass according to claim 1, characterized in that; said lignocellulosic biomass comprises sesame stem blight, corn dry rod, Peach shell and peanut shells.
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