CN110551295A - Method for separating chemical components of gramineous plants and purifying lignin - Google Patents
Method for separating chemical components of gramineous plants and purifying lignin Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 99
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- 239000000126 substance Substances 0.000 title claims abstract description 27
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- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000012265 solid product Substances 0.000 claims abstract description 20
- 238000005119 centrifugation Methods 0.000 claims abstract description 17
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- 239000002994 raw material Substances 0.000 claims abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 59
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
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- 235000011054 acetic acid Nutrition 0.000 description 4
- 210000002421 cell wall Anatomy 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000002029 lignocellulosic biomass Substances 0.000 description 4
- 241001486992 Taiwanofungus camphoratus Species 0.000 description 3
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
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- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
本发明提供了一种将禾本科植物化学组分分离并将木质素提纯的方法,所述方法以禾本科植物秸秆为原料,使用酸性增溶剂溶解木质素,经过过滤、洗涤、稀释、静置和离心步骤后,得到纤维素固体产物和木质素沉淀物,沉淀物经过渗析,从而得到纯净的木质素。本发明利用一种方便回收的酸性增溶剂,便可对植物组分进行有效的分离,是一种环境友好的绿色工艺,在低温短时的条件下分离禾本科秸秆化学组分,不需要高温高压的压力容器,可节约生产成本,提高生产效率,降低能源消耗。
The invention provides a method for separating chemical components of gramineous plants and purifying lignin. The method uses gramineous plant straws as raw materials, uses an acidic solubilizer to dissolve lignin, and filters, washes, dilutes and sets aside. After the centrifugation step, a cellulose solid product and a lignin precipitate are obtained, and the precipitate is dialyzed to obtain pure lignin. The invention utilizes an easily recovered acidic solubilizer to effectively separate the plant components, and is an environment-friendly green process. The chemical components of the gramineous straw can be separated under the condition of low temperature and short time, and no high temperature is required. High-pressure pressure vessels can save production costs, improve production efficiency and reduce energy consumption.
Description
技术领域technical field
本发明涉及生物质能源技术领域,具体涉及一种将禾本科植物秸秆化学组分分离并将木质素提纯的方法。The invention relates to the technical field of biomass energy, in particular to a method for separating chemical components of gramineous plant straw and purifying lignin.
背景技术Background technique
石油、煤矿等化石燃料的过度消耗已经导致生态环境的不断恶化,并且化石燃料难以再生。木质纤维素来自于天然可再生的植物,纤维素是自然界分布最广,含量最多的一种多糖,占植物界含碳量的50%以上,是地球上储量最丰富的可再生有机能源。可以通过组分分离的方式,将分离后得到的固体纤维组分进一步开发和利用,如造纸、制造单糖、甲基纤维素、纤维素醚、多聚合纤维素等;可将得到的木质素通过嫁接或改性等手段,制作成增强剂、防垢剂、粘结剂等。因此,在开发木质纤维素,使其替代化石燃料并更大化的利用其价值方面,日益受到人们的关注。Excessive consumption of fossil fuels such as oil and coal mines has led to the continuous deterioration of the ecological environment, and fossil fuels are difficult to regenerate. Lignocellulose comes from natural and renewable plants. Cellulose is the most widely distributed and most abundant polysaccharide in nature, accounting for more than 50% of the carbon content in the plant kingdom. It is the most abundant renewable organic energy on earth. The solid fiber components obtained after separation can be further developed and utilized by means of component separation, such as papermaking, monosaccharide production, methylcellulose, cellulose ether, polymeric cellulose, etc.; the obtained lignin can be further developed and utilized. By means of grafting or modification, it can be made into a reinforcing agent, an anti-scaling agent, a binder, etc. Therefore, the development of lignocellulose to replace fossil fuels and make greater use of its value has received increasing attention.
木质纤维素是自然界中含量最丰富的生物质资源,其主要由纤维素、半纤维素和木质素组成。纤维素是由β-D-葡萄糖单元通过1-4-糖苷键连接而成的线型高分子化合物。半纤维素是细胞壁中非纤维素高聚糖的总称,由两个或两个以上的糖基组成,通常有分枝结构。木质素是由苯丙烷单元通过醚键和碳碳键连接而成的,具有三维空间结构的芳香性高聚物。木质素和半纤维素在一起,形成所谓的木质素-半纤维素复合体,填充在细胞壁的微纤丝之间,同时也存在于胞间层。Lignocellulose is the most abundant biomass resource in nature, which is mainly composed of cellulose, hemicellulose and lignin. Cellulose is a linear polymer compound composed of β-D-glucose units connected by 1-4-glycosidic bonds. Hemicellulose is a general term for non-cellulosic polysaccharides in the cell wall, consisting of two or more sugar groups, usually with a branched structure. Lignin is an aromatic high polymer with three-dimensional spatial structure, which is composed of phenylpropane units connected by ether bonds and carbon-carbon bonds. Together, lignin and hemicellulose form so-called lignin-hemicellulose complexes, which fill between the microfibrils of the cell wall and are also present in the intercellular layer.
禾本科植物秸秆生长周期短、产量大,作为农业副产品的稻草、豆秆、麦秆等是一类取之不尽的可再生天然资源。禾本科植物秸秆不仅具有可再生性,而且具有良好的生物相容性以及可生物降解性。目前稻草、豆秆、麦秆等多被用于发电、焚烧、制造乙醇等,附加值低,且对环境具有一定的破坏作用。Poaceae straw has a short growth cycle and large yield. As agricultural by-products, straw, bean straw, wheat straw, etc. are an inexhaustible renewable natural resource. Poaceae straw is not only renewable, but also has good biocompatibility and biodegradability. At present, straw, bean straw, wheat straw, etc. are mostly used for power generation, incineration, ethanol production, etc., with low added value and a certain destructive effect on the environment.
专利(CN104404803B)公开了一种秸秆组分分离及秸秆组分利用的方法,该发明方法通过对秸秆蒸汽爆破处理,将半纤维素首先分离出来,然后对提取半纤维素后的剩余料再次蒸汽爆破处理,实现纤维素和木质素的分离。此工艺虽然可以有效的避免化学处理的二次污染问题,但该方法对参数的精确性具有很高的要求,实际应用到生产的工艺参数必须与实验室设备一致,才能保证参数的可用性,否则只能停留在实验室阶段,因此,该方法可能会制约实现工业化应用。The patent (CN104404803B) discloses a method for the separation of straw components and the utilization of straw components. The inventive method first separates the hemicellulose through steam explosion treatment of the straw, and then steams the remaining material after extracting the hemicellulose again. Blasting treatment to achieve separation of cellulose and lignin. Although this process can effectively avoid the problem of secondary pollution caused by chemical treatment, this method has high requirements on the accuracy of parameters, and the process parameters actually applied to production must be consistent with laboratory equipment to ensure the availability of parameters. It can only stay in the laboratory stage, therefore, this method may restrict the realization of industrial application.
专利(CN104987429B)公开了一种牛樟芝化合物组分分离的提取方法,以牛樟芝子实体粉或菌丝体为原料,采用酶解、超临界CO2萃取、离子交换色谱、膜分离超滤和层析法纯化相结合的技术实现牛樟芝化合物组分的分离提取。该方法虽然可以得到的分离物纯度较高,但其采用的方法需要很大的成本,对于普通植物的组分分离可能并不是一种合适的方法。Patent (CN104987429B) discloses a kind of extraction method of Antrodia camphorata compound component separation, takes Antrodia camphorata fruit body powder or mycelium as raw material, adopts enzymolysis, supercritical CO 2 extraction, ion exchange chromatography, membrane separation ultrafiltration and chromatography The separation and extraction of Antrodia camphorata compound components can be realized by the technology combined with the purification method. Although this method can obtain a higher purity of the isolate, the method adopted requires a lot of cost, and may not be a suitable method for the separation of common plant components.
专利(CN105484083B)公开了一种木质纤维素组分分离的工艺,该工艺通过辐照预处理生物质,耦合低沸点四氢呋喃或者高沸点γ-内戊酯反应,一次过滤得纤维素组分,滤液经回收四氢呋喃,或加入饱和NaCl溶液分相沉淀木质素,二次过滤,残渣为木质素组分,二次滤液干燥为半纤维素组分。该方法采用的辐照预处理具有一定的辐射性,对于人体存在着一定的安全隐患,其使用的四氢呋喃对人体也存在着一定的致癌风险,因此,可能对人体健康而言,并不是一种很友好的工艺方法。Patent (CN105484083B) discloses a process for the separation of lignocellulose components. The process pretreats biomass by irradiation, couples low-boiling tetrahydrofuran or high-boiling γ-lactate reaction, and obtains cellulose components by one-time filtration. After recovering tetrahydrofuran, or adding saturated NaCl solution, the lignin is phase-separated and precipitated, and filtered for a second time. The residue is a lignin component, and the secondary filtrate is dried to obtain a hemicellulose component. The irradiation pretreatment used in this method has certain radioactivity, which poses certain safety hazards to the human body, and the tetrahydrofuran used in the method also has a certain carcinogenic risk to the human body. Very friendly crafting method.
专利(CN106061891B)公开了一种利用混合酸将植物中木质素脱除的工艺。该工艺涉及将用选自乙酸、甲酸、丙酸、丁酸或这些酸的混合物、优选乙酸与甲酸的混合物的有机酸的溶液浸渍的植物物质脱木素的系统,含有所述植物物质和包含过氧化氢与至少一种磷添加剂的过氧化氢组合物,该系统用于用选自乙酸、甲酸、丙酸、丁酸或这些酸的混合物、优选乙酸与甲酸的混合物的有机酸的溶液浸渍的植物物质的脱木素。该方法需要的混合酸种类较多,且使用了磷作为添加剂,容易造成化学试剂的二次污染问题,可能并不是一种环境友好的工艺方法。The patent (CN106061891B) discloses a process for removing lignin from plants by using mixed acid. The process involves a system for delignifying plant matter impregnated with a solution of an organic acid selected from acetic acid, formic acid, propionic acid, butyric acid or a mixture of these acids, preferably a mixture of acetic acid and formic acid, containing said plant matter and comprising Hydrogen peroxide composition with at least one phosphorus additive for impregnation with a solution of an organic acid selected from acetic acid, formic acid, propionic acid, butyric acid or mixtures of these acids, preferably a mixture of acetic acid and formic acid delignification of plant matter. This method requires many types of mixed acids, and uses phosphorus as an additive, which is likely to cause secondary pollution of chemical reagents, and may not be an environmentally friendly process method.
专利(CN105861592B)公开了一种预处理木质纤维素类生物质的方法,该方法以粒度为0.5~2mm的木质纤维素类生物质为原料,采用固体碱为催化剂在水热环境下对木质纤维素类生物质进行预处理,打破木质纤维素致密结构,催化木质纤维素中木质素的剥离降解、半纤维素的溶出分离。该方法所用的固体碱制备方法较为复杂,对原料的要求也较高,需要先将原料预处理使其粒度变小,这种方式可能会导致生产成本增加。Patent (CN105861592B) discloses a method for pretreating lignocellulosic biomass. The method uses lignocellulosic biomass with a particle size of 0.5 to 2 mm as raw material, and uses solid alkali as catalyst to treat lignocellulosic biomass in a hydrothermal environment. The lignocellulosic biomass is pretreated to break the dense structure of lignocellulose and catalyze the stripping and degradation of lignin in lignocellulose and the dissolution and separation of hemicellulose. The preparation method of the solid base used in this method is relatively complicated, and the requirements for raw materials are also high. The raw materials need to be pretreated to make the particle size smaller, which may lead to increased production costs.
专利(CN105854907B)公开了一种秸秆组分分离制备超低粘度羧甲基纤维素的方法,该方法先采用酸法水解秸秆半纤维素获得可发酵单糖,然后采用有机溶剂法提取秸秆木质素获得高活性木质素,再采用碱性氧化法精制纤维素,最后对秸秆纤维素进行醚化改性制备羧甲基纤维素。该工艺分为四个阶段,较为繁琐,每一个阶段都使用了化学药品,该工艺可能会造成化学药品二次污染。Patent (CN105854907B) discloses a method for separating and preparing ultra-low viscosity carboxymethyl cellulose from straw components. The method first adopts acid method to hydrolyze straw hemicellulose to obtain fermentable monosaccharide, and then adopts organic solvent method to extract straw lignin High activity lignin is obtained, cellulose is purified by alkaline oxidation method, and finally carboxymethyl cellulose is prepared by etherification modification of straw cellulose. The process is divided into four stages, which are relatively cumbersome, and chemicals are used in each stage, which may cause secondary pollution of chemicals.
现有的禾本植物化学组分分离技术较为复杂,实验条件要求比较高,且容易造成二次污染。因此,如何实现在最佳条件下可以最大效率的对植物组分分离是生物质能源应用范围的重要研究方向。The existing gramineous plant chemical component separation technology is relatively complex, the experimental conditions are relatively high, and it is easy to cause secondary pollution. Therefore, how to realize the separation of plant components with maximum efficiency under optimal conditions is an important research direction in the application range of biomass energy.
发明内容SUMMARY OF THE INVENTION
本发明的主要目的在于提供了一种将禾本科植物秸秆化学组分分离的方法,该方法使用酸性增溶剂,可高效分离禾本科植物秸秆细胞壁化学组分组分,酸性增溶剂可重复利用、操作工艺简单、减少时间成本、降低能源消耗、节约成本,可以减少化学药品对环境的污染以及反应时间长和反应温度高带来的成本增加的现象。The main purpose of the present invention is to provide a method for separating chemical components of gramineous plant straws. The method uses an acidic solubilizer, which can efficiently separate the chemical components of gramineous plant straws cell wall, and the acidic solubilizer can be reused and operated. The process is simple, the time cost is reduced, the energy consumption is reduced, and the cost is saved, which can reduce the pollution of chemicals to the environment and the phenomenon of cost increase caused by long reaction time and high reaction temperature.
本发明的另一个目的是提供了经上述方法制得的木质素的提纯方法,该方法经稀释、静置、离心、渗析等常规实验方法,制得纯净木质素,以达到高效利用生物质资源的目的。Another object of the present invention is to provide a method for purifying the lignin obtained by the above method. This method uses conventional experimental methods such as dilution, standing, centrifugation, and dialysis to obtain pure lignin, so as to achieve efficient utilization of biomass resources. the goal of.
一种将禾本科植物秸秆化学组分分离并将木质素提纯的方法,包括以下步骤:A method for separating chemical components of gramineous plant straw and purifying lignin, comprising the following steps:
(1)粉碎:挑选晒干的禾本科植物秸秆,利用粉碎机粉碎,制得禾本科植物秸秆碎渣,备用。(1) Pulverization: Select sun-dried grass stalks and pulverize them with a pulverizer to obtain slag of grass stalks for use.
(2)酸解:称取步骤(1)所制备的禾本科植物秸秆碎渣,酸性增溶剂和去离子水,将禾本科植物秸秆碎渣放入多孔圆底烧瓶中,酸性增溶剂和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热到设定温度后,将锥形瓶内酸性增溶剂溶液加入多孔圆底烧瓶,继续搅拌,设定反应时间,反应结束时在多孔圆底烧瓶添加与反应原料总重等重的去离子水,制得纤维悬浮液,备用。(2) Acid hydrolysis: Weigh the gramineous plant straw scraps prepared in step (1), the acidic solubilizer and deionized water, put the gramineous plant straw scraps into a porous round-bottomed flask, and the acidic solubilizer and deionized water Put the ionized water into the conical flask and stir it evenly. Put the porous round-bottomed flask and the conical flask into the water bath at the same time, and fix it with a test tube holder. After heating to the set temperature in the water bath, the acid in the conical The solubilizer solution was added to the porous round-bottomed flask, continued stirring, and the reaction time was set. At the end of the reaction, deionized water equal to the total weight of the reaction raw materials was added to the porous round-bottomed flask to prepare a fiber suspension for use.
将酸性增溶剂溶液和禾本科植物秸秆碎渣分开同时加热至设定温度后再混合在一起,可以准确的探究在该温度下酸性增溶剂对植物组分分离的效果。为避免转速对反应产生的影响,所有反应均在同一转速下进行。The acidic solubilizer solution and the gramineous plant straw residue were separated and heated to a set temperature and then mixed together. The effect of the acidic solubilizer on the separation of plant components at this temperature can be accurately explored. In order to avoid the influence of rotation speed on the reaction, all reactions were carried out at the same rotation speed.
加入去离子水可以使温度迅速降低,从而达不到反应所需的温度,该做法可确保反应时间的准确性。The addition of deionized water can quickly reduce the temperature to the temperature required for the reaction, which ensures the accuracy of the reaction time.
(3)过滤:过滤步骤(2)所得的纤维悬浮液,分离得到含纤维素的固体产物和溶解有木质素的滤液,备用。(3) Filtration: Filtration of the fiber suspension obtained in step (2), separation to obtain a cellulose-containing solid product and a filtrate in which lignin is dissolved, for subsequent use.
(4)洗涤:用去离子水洗涤步骤(3)所制得的固体产物,收集洗涤下来的废液。(4) Washing: the solid product obtained in step (3) is washed with deionized water, and the washed waste liquid is collected.
(5)稀释:将步骤(3)所得的滤液和步骤(4)所得的废液混合制得混合液,并用去离子水稀释混合液,稀释至酸性增溶剂浓度低于其临界胶束浓度。(5) Dilution: the filtrate obtained in step (3) and the waste liquid obtained in step (4) are mixed to obtain a mixed solution, and the mixed solution is diluted with deionized water until the acid solubilizer concentration is lower than its critical micelle concentration.
木质素溶于酸中,当酸浓低至其临界胶束浓度时,木质素会从酸溶液中析出而形成沉淀。Lignin is soluble in acid, and when the acid concentration is as low as its critical micelle concentration, lignin will precipitate out of the acid solution to form a precipitate.
(6)静置:静置步骤(5)中所得的混合液,直至上层上清液和下层沉淀物分离。(6) Standing: the mixed solution obtained in step (5) is left standing until the supernatant of the upper layer and the sediment of the lower layer are separated.
(7)离心:吸掉步骤(6)中所得的上清液,将下层沉淀物离心,去掉多余水分。(7) Centrifugation: the supernatant liquid obtained in step (6) was sucked off, and the lower sediment was centrifuged to remove excess water.
离心主要是将木质素与水分离,在去除水分的同时,溶解在水中的酸性增溶剂和单糖类小分子物质也一同去除。Centrifugation mainly separates lignin from water. While removing water, acidic solubilizers and monosaccharide small molecules dissolved in water are also removed together.
(8)渗析:将步骤(7)中离心后的沉淀物转移至半透膜袋中,将半透膜袋放入去离子水里渗析。(8) Dialysis: transfer the sediment after centrifugation in step (7) into a semipermeable membrane bag, and put the semipermeable membrane bag into deionized water for dialysis.
附着在木质素上的酸性增溶剂和单糖类小分子通过半透膜转移到去离子水中,半透膜中会保留下木质素大分子。The acidic solubilizers and small monosaccharide molecules attached to the lignin are transferred to deionized water through the semipermeable membrane, and the lignin macromolecules are retained in the semipermeable membrane.
(9)干燥:步骤(8)渗析完成后,将沉淀物离心,去除水分,并冷冻干燥,得到纯净木质素。(9) Drying: after the dialysis in step (8) is completed, the precipitate is centrifuged to remove moisture, and freeze-dried to obtain pure lignin.
再次离心去除水分,可以减少木质素后期的干燥时间。Centrifuging again to remove water can reduce the drying time of the lignin later.
作为优选,步骤(1)中所述的禾本科植物为小麦、玉米、大豆、水稻、大麦、高粱、燕麦、甘蔗中的任意一种。Preferably, the grass plant described in step (1) is any one of wheat, corn, soybean, rice, barley, sorghum, oat, and sugarcane.
作为优选,步骤(2)中所述酸性增溶剂成分为对甲苯磺酸,所述对甲苯磺酸在实验总重量中质量百分比浓度为30%-60%。Preferably, the acidic solubilizer component in step (2) is p-toluenesulfonic acid, and the mass percent concentration of the p-toluenesulfonic acid in the total experimental weight is 30%-60%.
作为优选,步骤(2)中所述设定温度为60-80℃,所述反应时间为15-60min。Preferably, the set temperature in step (2) is 60-80° C., and the reaction time is 15-60 min.
作为优选,步骤(3)中所述的过滤采用真空过滤,所述真空过滤采用布氏漏斗与抽吸瓶、真空泵依次连接。Preferably, the filtration described in the step (3) adopts vacuum filtration, and the vacuum filtration adopts a Buchner funnel to be connected to a suction bottle and a vacuum pump in sequence.
其中,布氏漏斗与抽吸瓶、真空泵依次连接,可以加快过滤速度。Among them, the Buchner funnel is connected with the suction bottle and the vacuum pump in turn, which can speed up the filtration speed.
作为优选,步骤(4)中所述的洗涤使用去离子水将固体产物洗涤至中性。Preferably, the washing described in step (4) uses deionized water to wash the solid product to neutrality.
将固体产物洗涤到中性可以确保固体产物上不会附着酸性增溶剂,在洗涤的过程中,固体产物上的单糖类小分子物质会溶解在水中而脱除,因此可得到纯净的固体产物。Washing the solid product to neutrality can ensure that no acidic solubilizer is attached to the solid product. During the washing process, the small monosaccharide substances on the solid product will be dissolved in water and removed, so a pure solid product can be obtained. .
作为优选,步骤(5)中所述临界胶束浓度为1%。Preferably, the critical micelle concentration in step (5) is 1%.
作为优选,步骤(6)中所述的混合液静置时间为24h。Preferably, the mixture standing time described in step (6) is 24h.
作为优选,步骤(8)中所述的放入去离子水中渗析,具体是每12小时测一次去离子水的电导率,并更换去离子水,直至电导率小于0.1。Preferably, the dialysis in deionized water described in the step (8) is to measure the conductivity of the deionized water every 12 hours, and replace the deionized water until the conductivity is less than 0.1.
酸性增溶剂和单糖类小分子物质溶解在水中,会产生电导率,通过比较纯水电导率与渗析的水的电导率,可以有效的得知渗析的速度和反应的终点。Acidic solubilizers and monosaccharide small molecules dissolved in water will generate electrical conductivity. By comparing the electrical conductivity of pure water with the electrical conductivity of dialysis water, the speed of dialysis and the end point of the reaction can be effectively known.
作为优选,步骤(7)和步骤(9)中所述的离心条件是20℃下,转速是8000r/min,离心10min。Preferably, the centrifugation conditions described in step (7) and step (9) are at 20° C., the rotation speed is 8000 r/min, and the centrifugation is performed for 10 min.
有益效果beneficial effect
1.本发明所述方法实现了仅利用一种方便回收的酸性增溶剂,便可对植物组分进行有效的分离,是一种环境友好的绿色工艺,有效避免了传统工艺在化学试剂的回收上成本投入太大的弊端,并摆脱了组分分离工艺对多种化学试剂共同作用依赖问题。1. The method of the present invention realizes that only a kind of acid solubilizer for convenient recovery can be used to effectively separate plant components, which is a kind of environmentally friendly green technology, which effectively avoids the recovery of chemical reagents in traditional technology. It has the disadvantage of too much cost investment, and gets rid of the problem of dependence on the joint action of multiple chemical reagents in the component separation process.
2.本发明所述方法在低温短时的条件下分离禾本科植物组分,不需要高温高压的压力容器,可节约生产成本,提高生产效率,降低能源消耗,低温的操作条件还可有效避免烫伤等安全事故的发生。2. The method of the present invention separates the grass components under low temperature and short time conditions, does not require high temperature and high pressure pressure vessels, can save production costs, improve production efficiency, reduce energy consumption, and low temperature operating conditions can also be effectively avoided. The occurrence of safety accidents such as burns.
3.由于在低温环境下分离化学组分,对纤维素与半纤维素的降解程度较低,因此得到的固体纤维组分的得率高,另外得到的木质素缩聚程度低,较好的保留了木质素的原始大分子结构。3. Due to the separation of chemical components in a low temperature environment, the degradation degree of cellulose and hemicellulose is low, so the yield of solid fiber components obtained is high, and the obtained lignin has a low degree of polycondensation and better retention. The original macromolecular structure of lignin.
4.本发明所述方法得到的固体纤维产物可以较好的保存其原始形态,可进一步用于制造纸张,为制浆造纸行业提供了一种新型的制浆思路,也可以用于生物质能源行业,将固体纤维产物酶解成单糖,再经发酵变成生物乙醇或生物质柴油等。4. The solid fiber product obtained by the method of the present invention can better preserve its original form, and can be further used to manufacture paper, which provides a new type of pulping idea for the pulp and paper industry, and can also be used for biomass energy. In the industry, the solid fiber products are enzymatically hydrolyzed into monosaccharides, and then fermented into bioethanol or biomass diesel.
上述内容仅是本发明技术方案的概述,为了更清楚的了解本发明的技术手段,下面结合附图对本发明作进一步的描述。The above content is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly, the present invention will be further described below with reference to the accompanying drawings.
附图说明Description of drawings
图1为本发明的工艺流程图;Fig. 1 is the process flow diagram of the present invention;
图2为本发明所制得的固体产物在40倍显微镜下的形态;Fig. 2 is the morphology of the solid product prepared by the present invention under a 40-fold microscope;
图3为本发明得的木质素分子量分布曲线图。Fig. 3 is the molecular weight distribution curve diagram of lignin obtained by the present invention.
具体实施方式Detailed ways
本发明公开了一种禾本科植物细胞壁化学组分分离并将木质素提纯的方法,在低温短时的条件下,使用酸性增溶剂溶解木质素,令木质素随酸性增溶剂一起脱离固体产物。根据木质素溶于酸而不溶于水的性质,通过将含有酸性增溶剂和木质素的滤液进行稀释,当酸性增溶剂浓度低于临界胶束浓度时,木质素会脱离酸性增溶剂而形成沉淀。得到的木质素通过简单的渗析作用,即可将附着在木质素上的酸性增溶剂和单糖类小分子物质等去除,从而得到纯净的木质素。而固体产物可保留较好的纤维形态,不仅可用于制作纸张,还可用于水解得到可发酵单糖等。The invention discloses a method for separating chemical components of a gramineous plant cell wall and purifying lignin. Under the condition of low temperature and short time, an acidic solubilizer is used to dissolve the lignin, so that the lignin is separated from the solid product together with the acidic solubilizer. According to the property of lignin soluble in acid but not soluble in water, by diluting the filtrate containing acid solubilizer and lignin, when the acid solubilizer concentration is lower than the critical micelle concentration, the lignin will be separated from the acid solubilizer and form a precipitate . The obtained lignin can remove the acidic solubilizer and monosaccharide small molecular substances attached to the lignin by simple dialysis, thereby obtaining pure lignin. The solid product can retain a good fiber form, and can not only be used to make paper, but also be used for hydrolysis to obtain fermentable monosaccharides.
为了理解本发明,下面结合实施例对本发明作进一步说明。In order to understand the present invention, the present invention will be further described below with reference to the examples.
其中禾本科植物为小麦、玉米、大豆、水稻、大麦、高粱、燕麦、甘蔗中的任意一种,具体实施例中我们选用了水稻秸秆为例进行说明。Wherein, the grasses are any one of wheat, corn, soybean, rice, barley, sorghum, oat, and sugarcane. In the specific embodiment, we use rice straw as an example to illustrate.
为考察不同工艺条件对固体产物得率和木质素脱除率的影响,我们设置了不同的考察条件,包括不同的酸性增溶剂浓度,不同的反应温度,不同的反应时间,具体实施例如下所示:In order to investigate the influence of different process conditions on the solid product yield and lignin removal rate, we set up different investigation conditions, including different concentrations of acidic solubilizers, different reaction temperatures, and different reaction times. Specific examples are as follows. Show:
实施例1:Example 1:
实验总重量为200g,其中原料重与总重量比例为1:10。The total weight of the experiment is 200g, and the ratio of raw material weight to total weight is 1:10.
(1)粉碎:挑选晒干的禾本科植物秸秆,利用粉碎机粉碎,制得禾本科植物秸秆碎渣,备用;(1) pulverization: select sun-dried grass stalks, and pulverize with a pulverizer to obtain slag of grass stalks, for subsequent use;
(2)酸解:称取20g的禾本科植物秸秆碎渣,60g对甲苯磺酸和120g去离子水,其中对甲苯磺酸占总重量的30%,禾本科植物秸秆碎渣放入多孔圆底烧瓶中,对甲苯磺酸和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热至80℃,将锥形瓶内对甲苯磺酸溶液加入多孔圆底烧瓶,继续搅拌30min,反应结束,在多孔圆底烧瓶添加200g去离子水,制得纤维悬浮液,备用;(2) acidolysis: take by weighing 20g of gramineous plant straw scraps, 60g p-toluenesulfonic acid and 120g deionized water, wherein p-toluenesulfonic acid accounts for 30% of the total weight, and the gramineous plant straw scraps are put into a porous circle In the bottom flask, put p-toluenesulfonic acid and deionized water into the conical flask and stir evenly, put the porous round bottom flask and the conical flask into the water bath at the same time, fix it with a test tube holder, and heat it to 80 in the water bath. ℃, the p-toluenesulfonic acid solution in the conical flask was added to the porous round-bottom flask, and the stirring was continued for 30 min. After the reaction was completed, 200 g of deionized water was added to the porous round-bottom flask to prepare a fiber suspension for use;
(3)过滤:采用布式漏斗过滤步骤(2)所得的纤维悬浮液,分离得到含纤维素的固体产物和溶解木质素的滤液,备用;(3) filter: adopt cloth funnel to filter the fiber suspension of step (2) gained, separate and obtain the filtrate containing cellulose-containing solid product and dissolving lignin, for subsequent use;
(4)洗涤:用去离子水洗涤步骤(3)所制得的固体产物,将固体产物洗涤至中性,收集洗涤下来的废液;(4) washing: the solid product obtained in step (3) is washed with deionized water, the solid product is washed to neutrality, and the washed waste liquid is collected;
(5)稀释:将步骤(3)所得的滤液和步骤(4)所得的废液混合得混合液,并用去离子水稀释混合液,稀释至对甲苯磺酸浓度低于1%;(5) dilution: the filtrate obtained in step (3) and the waste liquid obtained in step (4) are mixed to obtain a mixed solution, and the mixed solution is diluted with deionized water, and diluted to a p-toluenesulfonic acid concentration lower than 1%;
(6)静置:静置步骤(5)中所得的混合液24h,至上层上清液和下层沉淀物分离;(6) leave standstill: stand the mixed solution gained in the standstill step (5) for 24h, to separate the supernatant of the upper layer and the sediment of the lower layer;
(7)离心:吸掉步骤(6)中所得的的上清液,将下层沉淀物在20℃离心10min,去掉多余水分;(7) Centrifugation: suction off the supernatant liquid obtained in step (6), and centrifuge the lower sediment at 20° C. for 10 min to remove excess water;
(8)渗析:将步骤(7)中离心后的沉淀物转移至半透膜袋中,将半透膜袋放入纯水里渗析,每12小时测一次去离子水的电导率,并更换去离子水,直至电导率小于0.1;(8) Dialysis: transfer the sediment after centrifugation in step (7) into a semi-permeable membrane bag, put the semi-permeable membrane bag into pure water for dialysis, measure the conductivity of deionized water every 12 hours, and replace Deionized water until the conductivity is less than 0.1;
(9)干燥:步骤(8)渗析完成后,将沉淀物在20℃下,转速8000r/min,离心10min,去除水分,并冷冻干燥,得到纯净木质素。(9) Drying: After the dialysis in step (8) is completed, the precipitate is centrifuged for 10 min at 20° C. at a rotational speed of 8000 r/min to remove moisture, and freeze-dried to obtain pure lignin.
分离结束后,得到固体纤维和纯净木质素,其中固体纤维产物得率为64.46%,木质素脱除率达33%。After the separation, solid fiber and pure lignin were obtained, wherein the yield of solid fiber product was 64.46%, and the lignin removal rate was 33%.
实施例2:Example 2:
实验总重量为200g,其中原料重与总重量比例为1:10。The total weight of the experiment is 200g, and the ratio of raw material weight to total weight is 1:10.
(1)粉碎:方法同实施例1;(1) pulverizing: the method is the same as in Example 1;
(2)酸解:称取20g的禾本科植物秸秆碎渣,90g对甲苯磺酸和90g去离子水,其中对甲苯磺酸占总重量的45%,禾本科植物秸秆碎渣放入多孔圆底烧瓶中,对甲苯磺酸和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热至80℃,将锥形瓶内对甲苯磺酸溶液加入多孔圆底烧瓶,继续搅拌15min,反应结束,在多孔圆底烧瓶添加200g去离子水,制得纤维悬浮液,备用;(2) acidolysis: take by weighing 20g of gramineous plant straw scraps, 90g p-toluenesulfonic acid and 90g deionized water, wherein p-toluenesulfonic acid accounts for 45% of the total weight, and the gramineous plant straw scraps are put into a porous circle In the bottom flask, put p-toluenesulfonic acid and deionized water into the conical flask and stir evenly, put the porous round bottom flask and the conical flask into the water bath at the same time, fix it with a test tube rack, and heat it to 80 in the water bath. ℃, the p-toluenesulfonic acid solution in the conical flask was added to the porous round-bottom flask, and the stirring was continued for 15 min. After the reaction was completed, 200 g of deionized water was added to the porous round-bottom flask to prepare a fiber suspension for use;
(3)过滤:方法同实施例1;(3) filtering: the method is the same as in Example 1;
(4)洗涤:方法同实施例1;(4) washing: the method is the same as in Example 1;
(5)稀释:方法同实施例1;(5) dilution: method is with embodiment 1;
(6)静置:方法同实施例1;(6) leave standstill: method is with embodiment 1;
(7)离心:方法同实施例1;(7) Centrifugation: the method is the same as in Example 1;
(8)渗析:方法同实施例1;(8) Dialysis: the method is the same as in Example 1;
(9)干燥:方法同实施例1。(9) Drying: the method is the same as that of Example 1.
分离结束后,得到固体纤维和纯净木质素,其中固体纤维产物得率为62.55%,木质素脱除率达37%。After the separation, solid fiber and pure lignin were obtained, wherein the yield of solid fiber product was 62.55%, and the lignin removal rate was 37%.
实施例3:Example 3:
实验总重量为200g,其中原料重与总重量比例为1:10。The total weight of the experiment is 200g, and the ratio of raw material weight to total weight is 1:10.
(1)粉碎:方法同实施例1;(1) pulverizing: the method is the same as in Example 1;
(2)酸解:称取20g的禾本科植物秸秆碎渣,120g对甲苯磺酸和60g去离子水,其中对甲苯磺酸占总重量的60%,禾本科植物秸秆碎渣放入多孔圆底烧瓶中,对甲苯磺酸和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热至60℃,将锥形瓶内对甲苯磺酸溶液加入多孔圆底烧瓶,继续搅拌30min,反应结束,在多孔圆底烧瓶添加200g去离子水,制得纤维悬浮液,备用;(2) acidolysis: take by weighing 20g of gramineous plant straw scraps, 120g p-toluenesulfonic acid and 60g deionized water, wherein p-toluenesulfonic acid accounts for 60% of the total weight, and the gramineous plant straw scraps are put into the porous circle In the bottom flask, put p-toluenesulfonic acid and deionized water into the conical flask and stir evenly, put the porous round bottom flask and the conical flask into the water bath at the same time, fix it with a test tube rack, and heat it to 60 in the water bath. ℃, the p-toluenesulfonic acid solution in the conical flask was added to the porous round-bottom flask, and the stirring was continued for 30 min. After the reaction was completed, 200 g of deionized water was added to the porous round-bottom flask to prepare a fiber suspension for use;
(3)过滤:方法同实施例1;(3) filtering: the method is the same as in Example 1;
(4)洗涤:方法同实施例1;(4) washing: the method is the same as in Example 1;
(5)稀释:方法同实施例1;(5) dilution: method is with embodiment 1;
(6)静置:方法同实施例1;(6) leave standstill: method is with embodiment 1;
(7)离心:方法同实施例1;(7) Centrifugation: the method is the same as in Example 1;
(8)渗析:方法同实施例1;(8) Dialysis: the method is the same as in Example 1;
(9)干燥:方法同实施例1。(9) Drying: the method is the same as that of Example 1.
分离结束后,得到固体纤维和纯净木质素,其中固体纤维产物得率为65.04%,木质素脱除率达30%。After the separation, solid fiber and pure lignin were obtained, wherein the yield of solid fiber product was 65.04%, and the removal rate of lignin reached 30%.
实施例4:Example 4:
实验总重量为200g,其中原料重与总重量比例为1:10。The total weight of the experiment is 200g, and the ratio of raw material weight to total weight is 1:10.
(1)粉碎:方法同实施例1;(1) pulverizing: the method is the same as in Example 1;
(2)酸解:称取20g的禾本科植物秸秆碎渣,120g对甲苯磺酸和60g去离子水,其中对甲苯磺酸占总重量的60%,禾本科植物秸秆碎渣放入多孔圆底烧瓶中,对甲苯磺酸和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热至80℃,将锥形瓶内对甲苯磺酸溶液加入多孔圆底烧瓶,继续搅拌45min,反应结束,在多孔圆底烧瓶添加200g去离子水,制得纤维悬浮液,备用;(2) acidolysis: take by weighing 20g of gramineous plant straw scraps, 120g p-toluenesulfonic acid and 60g deionized water, wherein p-toluenesulfonic acid accounts for 60% of the total weight, and the gramineous plant straw scraps are put into the porous circle In the bottom flask, put p-toluenesulfonic acid and deionized water into the conical flask and stir evenly, put the porous round bottom flask and the conical flask into the water bath at the same time, fix it with a test tube holder, and heat it to 80 in the water bath. ℃, add the p-toluenesulfonic acid solution in the conical flask to the porous round-bottomed flask, continue to stir for 45 min, the reaction is over, add 200 g of deionized water to the porous round-bottomed flask to prepare a fiber suspension for use;
(3)过滤:方法同实施例1;(3) filtering: the method is the same as in Example 1;
(4)洗涤:方法同实施例1;(4) washing: the method is the same as in Example 1;
(5)稀释:方法同实施例1;(5) dilution: method is with embodiment 1;
(6)静置:方法同实施例1;(6) leave standstill: method is with embodiment 1;
(7)离心:方法同实施例1;(7) Centrifugation: the method is the same as in Example 1;
(8)渗析:方法同实施例1;(8) Dialysis: the method is the same as in Example 1;
(9)干燥:方法同实施例1。(9) Drying: the method is the same as that of Example 1.
分离结束后,得到固体纤维和纯净木质素,其中固体纤维产物得率为55.65%,木质素脱除率达45%。After the separation, solid fibers and pure lignin were obtained, wherein the yield of solid fibers was 55.65%, and the removal rate of lignin reached 45%.
实施例5:Example 5:
实验总重量为200g,其中原料重与总重量比例为1:10。The total weight of the experiment is 200g, and the ratio of raw material weight to total weight is 1:10.
(1)粉碎:方法同实施例1;(1) pulverizing: the method is the same as in Example 1;
(2)酸解:称取20g的禾本科植物秸秆碎渣,90g对甲苯磺酸和90g去离子水,其中对甲苯磺酸占总重量的45%,禾本科植物秸秆碎渣放入多孔圆底烧瓶中,对甲苯磺酸和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热至70℃,将锥形瓶内对甲苯磺酸溶液加入多孔圆底烧瓶,继续搅拌60min,反应结束,在多孔圆底烧瓶添加200g去离子水,制得纤维悬浮液,备用;(2) acidolysis: take by weighing 20g of gramineous plant straw scraps, 90g p-toluenesulfonic acid and 90g deionized water, wherein p-toluenesulfonic acid accounts for 45% of the total weight, and the gramineous plant straw scraps are put into a porous circle In the bottom flask, put p-toluenesulfonic acid and deionized water into the conical flask and stir evenly, put the porous round bottom flask and the conical flask into the water bath at the same time, fix it with a test tube holder, and heat it to 70 in the water bath. ℃, add the p-toluenesulfonic acid solution in the conical flask to the porous round-bottomed flask, continue to stir for 60 min, the reaction is over, add 200 g of deionized water to the porous round-bottomed flask, and prepare a fiber suspension for use;
(3)过滤:方法同实施例1;(3) filtering: the method is the same as in Example 1;
(4)洗涤:方法同实施例1;(4) washing: the method is the same as in Example 1;
(5)稀释:方法同实施例1;(5) dilution: method is with embodiment 1;
(6)静置:方法同实施例1;(6) leave standstill: method is with embodiment 1;
(7)离心:方法同实施例1;(7) Centrifugation: the method is the same as in Example 1;
(8)渗析:方法同实施例1;(8) Dialysis: the method is the same as in Example 1;
(9)干燥:方法同实施例1。(9) Drying: the method is the same as that of Example 1.
分离结束后,得到固体纤维和纯净木质素,其中固体纤维产物得率为59.98%,木质素脱除率达40%。After the separation, solid fiber and pure lignin were obtained, wherein the yield of solid fiber product was 59.98%, and the removal rate of lignin reached 40%.
实施例6:Example 6:
实验总重量为200g,其中原料重与总重量比例为1:10。The total weight of the experiment is 200g, and the ratio of raw material weight to total weight is 1:10.
(1)粉碎:方法同实施例1;(1) pulverizing: the method is the same as in Example 1;
(2)酸解:称取20g的禾本科植物秸秆碎渣,90g对甲苯磺酸和90g去离子水,其中对甲苯磺酸占总重量的45%,禾本科植物秸秆碎渣放入多孔圆底烧瓶中,对甲苯磺酸和去离子水放入锥形瓶中并搅拌均匀,把多孔圆底烧瓶和锥形瓶同时放入水浴锅中,并用试管架固定,在水浴锅中加热至80℃,将锥形瓶内对甲苯磺酸溶液加入多孔圆底烧瓶,继续搅拌60min,反应结束,在多孔圆底烧瓶添加200g去离子水,制得纤维悬浮液,备用;(2) acidolysis: take 20g of gramineous plant straw scraps, 90g p-toluenesulfonic acid and 90g deionized water, wherein p-toluenesulfonic acid accounts for 45% of the total weight, and the gramineous plant straw scraps are put into the porous circle In the bottom flask, put p-toluenesulfonic acid and deionized water into the conical flask and stir evenly, put the porous round bottom flask and the conical flask into the water bath at the same time, fix it with a test tube holder, and heat it to 80 in the water bath. ℃, add the p-toluenesulfonic acid solution in the conical flask to the porous round-bottomed flask, continue to stir for 60min, the reaction is over, add 200 g of deionized water to the porous round-bottomed flask, and prepare a fiber suspension for use;
(3)过滤:方法同实施例1;(3) filtering: the method is the same as in Example 1;
(4)洗涤:方法同实施例1;(4) washing: the method is the same as in Example 1;
(5)稀释:方法同实施例1;(5) dilution: method is with embodiment 1;
(6)静置:方法同实施例1;(6) leave standstill: method is with embodiment 1;
(7)离心:方法同实施例1;(7) Centrifugation: the method is the same as in Example 1;
(8)渗析:方法同实施例1;(8) Dialysis: the method is the same as in Example 1;
(9)干燥:方法同实施例1。(9) Drying: the method is the same as that of Example 1.
分离结束后,得到固体纤维和纯净木质素,其中固体纤维产物得率为51.28%,木质素脱除率达42%。After the separation, solid fiber and pure lignin were obtained, wherein the yield of solid fiber product was 51.28%, and the lignin removal rate was 42%.
不同实验条件所得的结果如表1所示,不同实施例所得固体纤维产物得率和木质素脱除率的结果。The results obtained under different experimental conditions are shown in Table 1, and the results of the solid fiber product yield and lignin removal rate obtained in different embodiments.
表1Table 1
通过实验结果分析,我们可以发现,随着对甲苯磺酸浓度升高,反应时间增长,反应温度升高,木质素的脱除率也升高。Through the analysis of the experimental results, we can find that with the increase of p-toluenesulfonic acid concentration, the reaction time increases, the reaction temperature increases, and the removal rate of lignin also increases.
如图2所示,通过显微镜观察固体产物的形态,结果发现,固体产物能够较好的保留其纤维形态,可用于进一步制造纸张或其他化学品。As shown in Figure 2, the morphology of the solid product was observed through a microscope, and it was found that the solid product could well retain its fiber morphology and could be used to further manufacture paper or other chemicals.
图3为经GPC分析得到的木质素分子量分布曲线图,由图中曲线可知,木质素分子量分布较广,未出现大分子木质素缩聚的情况,较好的保留了各个分子量的木质素。Figure 3 shows the molecular weight distribution curve of lignin obtained by GPC analysis. From the curve in the figure, it can be seen that the molecular weight distribution of lignin is wide, and no polycondensation of macromolecular lignin occurs, and lignin of various molecular weights is well preserved.
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何的简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。The above are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Technical personnel, within the scope of the technical solution of the present invention, can make some changes or modifications to equivalent examples of equivalent changes by using the technical content disclosed above, but any content that does not depart from the technical solution of the present invention, according to the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments by the technical essence of the invention still fall within the scope of the technical solutions of the present invention.
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CN113598195A (en) * | 2021-08-06 | 2021-11-05 | 南京林业大学 | Application of small molecular lignin as plant growth regulator |
CN113598195B (en) * | 2021-08-06 | 2022-06-03 | 南京林业大学 | Application of small molecular lignin as plant growth regulator |
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