CN101586136A - Method of high-efficiency pretreatment on biomass - Google Patents

Abstract

Translated fromChinese

本发明提供了一种可对木质纤维素类生物质实施绿色高效水解预处理的方法。本发明采用二步变温分段的水解方法将纤维素类生物质中的半纤维素水解成木糖及其低聚糖为主的糖类产物，完成预处理；再将预处理后的纤维素和木质素为主的固体原料加入纤维素酶，完成酶水解，以最大限度地回收糖类产物。本发明采用高温液态水为反应介质，具有廉价、环保、绿色的特点，反应条件温和，糖类产物较少降解，回收率高。采用二步变温分段水解的方法，既保证了半纤维素能够最大限度地水解获得糖产物，又进一步预处理了原料，使纤维素通过酶水解生成葡萄糖，达到环保、高效水解木质纤维素类生物质的目的。原料可以实现废物利用，促进绿色农业发展。

The invention provides a green and high-efficiency hydrolysis pretreatment method for lignocellulosic biomass. The present invention adopts a two-step temperature-variable segmental hydrolysis method to hydrolyze hemicellulose in cellulosic biomass into sugar products mainly including xylose and oligosaccharides to complete the pretreatment; then the pretreated cellulose Cellulase is added to solid raw materials mainly composed of lignin to complete enzymatic hydrolysis to maximize the recovery of sugar products. The invention adopts high-temperature liquid water as a reaction medium, has the characteristics of low cost, environmental protection and greenness, mild reaction conditions, less degradation of sugar products and high recovery rate. The two-step temperature-variable segmental hydrolysis method not only ensures that the hemicellulose can be hydrolyzed to the maximum extent to obtain sugar products, but also further pretreats the raw materials, so that the cellulose can be hydrolyzed by enzymes to generate glucose, so as to achieve environmental protection and high-efficiency hydrolysis of lignocellulose. purpose of biomass. Raw materials can realize waste utilization and promote the development of green agriculture.

Description

Translated fromChinese

一种生物质绿色高效预处理方法A green and efficient pretreatment method for biomass

技术领域technical field

本发明涉及生物化学及化工技术领域，尤其涉及一种纤维素类生物质绿色高效预处理方法及其实现设备。The invention relates to the technical fields of biochemistry and chemical industry, in particular to a green and high-efficiency pretreatment method for cellulosic biomass and equipment for its realization.

技术背景technical background

生物质是世界能源界公认的唯一可固定碳的可再生能源资源，以其生产液体燃料和化工产品有广阔前景。以生物质生产液体燃料和化工产品有两条技术路线：一是通过生物质气化获得合成气再通过化学和生化方法实现，另一条研究路线是搭建糖平台，即通过水解，将生物质中的多糖组分-纤维素和半纤维素水解获得糖类，再进一步加工、处理获得生物汽油、乙醇、丁醇、木糖醇、乙酰丙酸等能源化工产品。Biomass is recognized by the world's energy circles as the only renewable energy resource that can fix carbon, and it has broad prospects for the production of liquid fuels and chemical products. There are two technical routes for the production of liquid fuels and chemical products from biomass: one is to obtain synthesis gas through biomass gasification and then realize it through chemical and biochemical methods; the other research route is to build a sugar platform, that is, to convert biomass into The polysaccharide component-cellulose and hemicellulose are hydrolyzed to obtain sugars, which are further processed and processed to obtain energy and chemical products such as biogasoline, ethanol, butanol, xylitol, and levulinic acid.

21世纪的科技发展被称为“糖经济”或“碳水化合物经济”，将植物纤维降解为糖中间体是推动实现“糖经济”的重要基础和保证，但目前尚无可工业化的方法。木质纤维素类生物质水解是非常有潜力的技术。The development of science and technology in the 21st century is called "sugar economy" or "carbohydrate economy". The degradation of plant fibers into sugar intermediates is an important basis and guarantee to promote the realization of "sugar economy", but there is no industrialized method yet. Hydrolysis of lignocellulosic biomass is a very promising technology.

一般意义上的木质纤维素类生物质水解，指在一定温度和催化剂作用下，使其中的纤维素和半纤维素加水分解(糖化)成为单糖的过程，半纤维素水解产物为以木糖为主的五碳糖，纤维素水解产物为葡萄糖为主的六碳糖。根据所用的催化剂不同，生物质水解的方法有三种：以酸作为催化剂的稀酸水解和浓酸水解，以纤维素酶为催化剂的酶水解。In general, the hydrolysis of lignocellulosic biomass refers to the process of hydrolysis (saccharification) of cellulose and hemicellulose into monosaccharides at a certain temperature and under the action of a catalyst. The hydrolyzed product of hemicellulose is xylose The main five-carbon sugar, cellulose hydrolyzate is mainly six-carbon sugar glucose. According to the different catalysts used, there are three methods for biomass hydrolysis: dilute acid hydrolysis and concentrated acid hydrolysis using acid as a catalyst, and enzymatic hydrolysis using cellulase as a catalyst.

浓酸水解的研究始于十九世纪二十年代，指浓度在30％以上的硫酸或盐酸将生物质水解成单糖的方法。反应条件为：100℃以内，常压，2-10小时，为均相水解，一般分预处理和水解两步进行。优点是糖转化率高，无论纤维素还是半纤维素都能达到90％以上；缺点是反应速度慢，工艺复杂，生产环境恶劣，酸必须回收且费用高。主要用于处理玉米芯、麦秸等农业废弃物。The research on concentrated acid hydrolysis began in the 1920s, which refers to the method of hydrolyzing biomass into monosaccharides with sulfuric acid or hydrochloric acid with a concentration of more than 30%. The reaction conditions are: within 100°C, normal pressure, 2-10 hours, homogeneous hydrolysis, generally divided into two steps of pretreatment and hydrolysis. The advantage is that the sugar conversion rate is high, whether cellulose or hemicellulose can reach more than 90%; the disadvantage is that the reaction speed is slow, the process is complicated, the production environment is harsh, the acid must be recovered and the cost is high. It is mainly used to process agricultural waste such as corncobs and wheat straw.

酶水解始于20世纪50年代，是较新的生物质水解技术。指利用纤维素酶对生物质中的固态纤维素进行糖化进而发酵生成乙醇。在常压、45-50℃、pH为4.8左右的条件下进行，可形成单一糖类产物且产率可达90％以上，生成糖不会发生二次分解，因此越来越受到各国重视，甚至有人预测酶水解有替代酸水解的趋势。缺点是反应时间长，现有的纤维素酶酶效低、易失活、难回收，经济性差，很难实现连续性生产，同时纤维素酶的生产要消耗9％左右的生物质物料。另外，酶水解前必须进行预处理，预处理的目的是除去木质素、溶解半纤维素、破坏纤维素的晶体结构、增大纤维素酶的可接触表面，酶水解产物得率很大程度上要依赖预处理的效果。所以酶水解从纤维素酶的生产、应用到预处理的设备、操作成本都很高，工业化进程受到阻碍。Enzyme hydrolysis began in the 1950s and is a relatively new biomass hydrolysis technology. Refers to the use of cellulase to saccharify solid cellulose in biomass and then ferment to produce ethanol. Carried out under the conditions of normal pressure, 45-50°C, and a pH of about 4.8, a single sugar product can be formed with a yield of over 90%, and the sugar produced will not undergo secondary decomposition, so it has attracted more and more attention from various countries. Some even predict that enzymatic hydrolysis will replace acid hydrolysis. The disadvantage is that the reaction time is long, the existing cellulase has low enzymatic efficiency, is easy to inactivate, is difficult to recycle, has poor economic efficiency, and is difficult to realize continuous production. At the same time, the production of cellulase consumes about 9% of biomass materials. In addition, pretreatment must be carried out before enzymatic hydrolysis. The purpose of pretreatment is to remove lignin, dissolve hemicellulose, destroy the crystal structure of cellulose, and increase the accessible surface of cellulase. The yield of enzymatic hydrolyzate is largely It depends on the effect of preprocessing. Therefore, the cost of enzymatic hydrolysis from cellulase production, application to pretreatment equipment and operation is very high, and the industrialization process is hindered.

稀酸水解由法国的梅尔森斯于1856年首先提出，1898年德国人提出木材制取乙醇的商业构想，第一次世界大战和第二次世界大战期间美国和德国曾以该法建立燃料乙醇工厂，后期因木材缺乏及廉价石油的供应而停产。稀酸水解一般指用10％以内的硫酸或盐酸等无机酸为催化剂将纤维素、半纤维素水解成单糖的方法，温度100-240℃，压力大于液体饱和蒸汽压，一般高于10个大气压。优点是反应进程快，适合连续生产，酸液不用回收；缺点是所需温度和压力较高，副产物较多，反应器材质要求高。目前有两条研究路线：一是作为生物质水解的方法，二是作为酶水解最经济的预处理方法。Dilute acid hydrolysis was first proposed by Mersens of France in 1856. In 1898, the Germans proposed the commercial idea of producing ethanol from wood. During the First World War and the Second World War, the United States and Germany used this method to establish fuel The ethanol plant was later shut down due to lack of wood and the supply of cheap oil. Dilute acid hydrolysis generally refers to the method of hydrolyzing cellulose and hemicellulose into monosaccharides with inorganic acids such as sulfuric acid or hydrochloric acid within 10% as a catalyst. atmospheric pressure. The advantage is that the reaction process is fast, suitable for continuous production, and the acid solution does not need to be recovered; the disadvantage is that the required temperature and pressure are high, there are many by-products, and the requirements for the material of the reactor are high. There are currently two research routes: one is as a method of biomass hydrolysis, and the other is as the most economical pretreatment method for enzymatic hydrolysis.

酶水解是当前公认的生物质水解主流技术，但面临着缺乏高效预处理方法、纤维素酶成本居高不下等难点。高温液态水法是近年来倍受关注的预处理方法，高温液态水水解(HotLiquid Water)又称自动水解(Autohydrolysis)，是指在一定温度下和大于该温度饱和蒸汽压的条件下，使水保持液体状态来水解生物质中的半纤维素。其原理是在高温高压下，水会解离出H⁺和OH^-，具备酸碱自催化功能，从而完成半纤维素的水解。该法的优点是无需催化剂，成本低廉，糖类产物回收率高。Enzyme hydrolysis is currently recognized as the mainstream technology for biomass hydrolysis, but it faces difficulties such as the lack of efficient pretreatment methods and the high cost of cellulase. The high-temperature liquid water method is a pretreatment method that has attracted much attention in recent years. The high-temperature liquid water hydrolysis (Hot Liquid Water) is also called autohydrolysis (Autohydrolysis). Maintain liquid state to hydrolyze hemicellulose in biomass. The principle is that under high temperature and high pressure, water will dissociate into H⁺ and OH^- , which has the function of acid-base self-catalysis, thereby completing the hydrolysis of hemicellulose. The advantage of this method is that no catalyst is needed, the cost is low, and the recovery rate of sugar products is high.

在生物质高温液态水水解研究领域，Appell课题组最先在350℃和CO气氛下以Na₂CO₃为催化剂在高温高压液态热水中将木片水解成重油，此后人们对这种方法的研究不断深入，主要集中在催化剂的选择和反应机理的探讨。Boocock以Ni为催化剂，Tomoaki课题组以碱和Ni为催化剂分别对木材或纤维素水解进行了研究。近年米G.Garrote课题组研究高温液态水制取低聚木糖，分别以大麦壳、玉米芯、桉树、稻壳等为原料，在158℃发现产物中90％以上的木聚糖可水解为低聚糖，其中大麦壳效果最好，低聚木糖得率达到原料总量的27.1％，产物中低聚糖是单糖的4倍，且糠醛等降解产物极少。Sasaki等将高压液态热水进一步升高温度和压力得到超临界水，不加任何催化剂对纤维素进行水解。2000年以来，近临界水走入了研究者的视界，日本林业和林产品研究所的Masahiro等研究了310-320℃木材粉末在近临界水中的水解行为，发现70-90％的原料可转化为水溶性物质，且产物中以单糖和低聚糖为主。In the field of biomass high-temperature liquid water hydrolysis research, the Appell research group first used Na₂ CO₃ as a catalyst to hydrolyze wood chips into heavy oil in high-temperature, high-pressure liquid hot water at 350°C and a CO atmosphere. Continue to deepen, mainly focus on the selection of catalysts and the discussion of the reaction mechanism. Boocock used Ni as a catalyst, and Tomoaki's research group used alkali and Ni as catalysts to study the hydrolysis of wood or cellulose, respectively. In recent years, Mi G.Garrote's research group has studied the preparation of xylo-oligosaccharides from high-temperature liquid water, using barley husks, corncobs, eucalyptus, rice husks, etc. as raw materials, and found that more than 90% of the xylans in the products can be hydrolyzed at 158°C. Oligosaccharides, of which barley husk has the best effect, the yield of xylooligosaccharides reaches 27.1% of the total raw materials, oligosaccharides in the product are 4 times that of monosaccharides, and the degradation products such as furfural are very few. Sasaki et al further raised the temperature and pressure of high-pressure liquid hot water to obtain supercritical water, and hydrolyzed cellulose without adding any catalyst. Since 2000, near-critical water has entered the field of vision of researchers. Masahiro et al. from the Japan Institute of Forestry and Forest Products studied the hydrolysis behavior of wood powder at 310-320°C in near-critical water, and found that 70-90% of the raw materials can be converted It is a water-soluble substance, and the products are mainly monosaccharides and oligosaccharides.

国内浙江大学国家能源清洁利用重点实验室王树荣课题组曾以此法水解白松、速生杨和玉米秸秆，并进行了对比，将此作为二步超低酸水解工艺的第一步。浙江大学吕秀阳课题组就生物质近临界水制取乙酰丙酸等化工产品及其反应动力学进行了研究。Domestic Zhejiang University National Key Laboratory of Energy Clean Utilization Wang Shurong's research group has used this method to hydrolyze white pine, fast-growing poplar and corn straw, and compared them, using this as the first step of the two-step ultra-low acid hydrolysis process. Lv Xiuyang's research group from Zhejiang University conducted research on the production of chemical products such as levulinic acid from biomass near critical water and its reaction kinetics.

中科院广州能源所生物质能中心生化转化实验室自2006年开始进行该工艺的研究，将高温液态水法作为酶水解的预处理方法，探寻生物质高效产糖的新途径，提出生物质高温液态水二段变温预处理工艺，以实现高效糖平台的搭建。The Biochemical Transformation Laboratory of the Biomass Energy Center of the Guangzhou Institute of Energy, Chinese Academy of Sciences has been conducting research on this process since 2006. The high-temperature liquid water method is used as a pretreatment method for enzymatic hydrolysis to explore new ways to efficiently produce sugar from biomass. The second-stage variable temperature pretreatment process of water is used to realize the construction of high-efficiency sugar platform.

通过中华人民共和国国家知识产权局网站进行专利查询，目前国内有关木质纤维素类生物质水解方面相关专利如下：Through the patent query on the website of the State Intellectual Property Office of the People's Republic of China, the current domestic patents related to the hydrolysis of lignocellulosic biomass are as follows:

(1)由生物质水解制备还原性单糖的方法.公开(公告)号：CN1432574；(1) Method for preparing reducing monosaccharides by hydrolysis of biomass. Publication (announcement) number: CN1432574;

(2)半纤维素浓酸预处理常压水解技术，公开(公告)号：CN1327972；(2) Atmospheric pressure hydrolysis technology for hemicellulose concentrated acid pretreatment, publication (announcement) number: CN1327972;

(3)一种酸水解植物纤维素的方法.公开(公告)号：CN1109100；(3) A method for acid hydrolyzing plant cellulose. Publication (announcement) number: CN1109100;

(4)一种生物质预处理的方法，公开(公告)号：CN1824782；(4) A method for biomass pretreatment, publication (announcement) number: CN1824782;

(5)生物质超低酸水解制取液体燃料装置，公开(公告)号：CN1624076；(5) Biomass ultra-low acid hydrolysis to produce liquid fuel device, publication (announcement) number: CN1624076;

(6)从纤维素生物质获得产物糖流的方法，申请号/专利号：200580031101；(6) Method for obtaining product sugar stream from cellulosic biomass, application number/patent number: 200580031101;

(7)将纤维素材料转化成乙醇的方法和设备，公开(公告)号：CN101268121A；(7) Method and equipment for converting cellulose materials into ethanol, publication (announcement) number: CN101268121A;

从以上专利情况看，专利(1)-(5)皆酸水解技术，专利(6)重在糖类产物的分离回收，与本项目较相关的只有专利(7)“将纤维素材料转化成乙醇的方法和设备”，该专利申请人为丹麦霍尔姆克里斯藤森生物系统公司，公开了一种水热预处理再酶解糖化的方法，但并未提及预处理工艺的细节，本发明提出两步分段变温高温液态水水解工艺，与其有本质不同。Judging from the above patents, patents (1)-(5) are all acid hydrolysis technologies, and patent (6) focuses on the separation and recovery of sugar products. Only patent (7) "converting cellulose materials into Method and equipment for ethanol", the patent applicant is Holm Christensen Biosystems, Denmark, which discloses a method of hydrothermal pretreatment followed by enzymatic hydrolysis and saccharification, but does not mention the details of the pretreatment process. The present invention The proposed two-step segmental variable temperature high temperature liquid water hydrolysis process is essentially different from it.

发明内容Contents of the invention

本发明的目的在于提供一种可对木质纤维素类生物质实施绿色高效水解预处理的方法，以提高糖得率，搭建高效生物质糖平台，为生物质基能源和化工产品的工业化生产做好铺垫。The purpose of the present invention is to provide a green and high-efficiency hydrolysis pretreatment method for lignocellulosic biomass, so as to increase the sugar yield, build a high-efficiency biomass sugar platform, and make a contribution to the industrial production of biomass-based energy and chemical products. Good foreshadowing.

为达到上述目的，本发明采取了以下的技术方案：To achieve the above object, the present invention has taken the following technical solutions:

本发明采用二步变温分段的水解方法将纤维素类生物质中的半纤维素水解成木糖及其低聚糖为主的糖类产物，完成预处理；再将预处理后的纤维素和木质素为主的固体原料加入纤维素酶，将纤维素水解成葡萄糖为主的液体产物，完成酶水解，以最大限度地回收糖类产物。The present invention adopts a two-step temperature-variable segmental hydrolysis method to hydrolyze hemicellulose in cellulosic biomass into sugar products mainly including xylose and oligosaccharides to complete the pretreatment; then the pretreated cellulose Cellulase is added to the solid raw material mainly composed of lignin to hydrolyze the cellulose into a liquid product mainly composed of glucose, and the enzymatic hydrolysis is completed to maximize the recovery of sugar products.

本发明的具体步骤为：Concrete steps of the present invention are:

1)将粒度在0.5-2mm之间的木质纤维素类生物质原料，按质量比1∶5-1∶20的比例加入水，在高压反应器内(高压反应器的压力范围为2-10MPa)，在160-200℃的高温液态水环境下反应10-60min，固液分离，完成第一步水解；第一步水解液体产物为木糖、低聚木糖等五碳糖为主的水解液，固体产物以纤维素和木质素为主要组分。1) Add water to the lignocellulosic biomass raw material with a particle size between 0.5-2mm in a mass ratio of 1:5-1:20, and put it in a high-pressure reactor (the pressure range of the high-pressure reactor is 2-10MPa ), react in a high-temperature liquid water environment at 160-200°C for 10-60min, separate solid and liquid, and complete the first step of hydrolysis; the liquid product of the first step is hydrolysis of five-carbon sugars such as xylose and xylooligosaccharides Liquid and solid products are mainly composed of cellulose and lignin.

2)液体产物收集完毕，在高压反应器内(高压反应器的压力范围为2-10MPa)将第一步水解的固体产物第二次按质量比1∶5-1∶20的比例加水，升温至200-260℃，反应0-30min，固液分离，冷却，此时的液体产物主要为少量葡萄糖、液态低聚葡糖和糠醛类副产物，固体产物为预处理好的纤维素和木质素为主的酶解原料。2) After the liquid product is collected, in the high pressure reactor (the pressure range of the high pressure reactor is 2-10MPa), the solid product hydrolyzed in the first step is added with water in the ratio of 1:5-1:20 by mass ratio for the second time, and the temperature is raised to 200-260°C, react for 0-30min, separate solid and liquid, and cool. At this time, the liquid products are mainly a small amount of glucose, liquid oligoglucose and furfural by-products, and the solid products are pretreated cellulose and lignin. The main enzymatic raw material.

3)将步骤2)得到的固体产物按照每克原料干重加入8-30FPU的纤维素酶，在PH值4.0-5.5，温度在37℃至55℃及搅拌下，水解至葡萄糖浓度不再升高，将液体取出，完成酶解；酶解液主要成分是葡萄糖，固体残渣主要组分是木质素。3) Add 8-30 FPU cellulase to the solid product obtained in step 2) according to the dry weight of each gram of raw material, and hydrolyze it at a pH value of 4.0-5.5 at a temperature of 37°C to 55°C under stirring until the glucose concentration does not rise any more High, take out the liquid and complete the enzymatic hydrolysis; the main component of the enzymatic hydrolysis solution is glucose, and the main component of the solid residue is lignin.

4)将步骤1)、步骤2)水解液体产物和步骤3)的酶解产物合并得到木质纤维素类生物质水解产物，可用于微生物发酵制取乙醇，或通过生化或化工过程制取丁醇、烃类等能源化工产品；因固体残渣为生物质中热值最高的木质素，可用于燃烧作为工艺热源或用做制取其他化工产品的原料。通过以上二步变温预处理和后续酶解，将木质纤维素中的多糖组份-半纤维素和纤维素分别水解成木糖和葡萄糖及其相应液态低聚糖为主的液体产物。4) Combine step 1), step 2) hydrolyzed liquid product and step 3) enzymatic hydrolyzate to obtain lignocellulosic biomass hydrolyzate, which can be used to produce ethanol by microbial fermentation, or produce butanol through biochemical or chemical processes , hydrocarbons and other energy chemical products; because the solid residue is lignin with the highest calorific value in biomass, it can be used for combustion as a process heat source or as a raw material for the production of other chemical products. Through the above two-step variable temperature pretreatment and subsequent enzymatic hydrolysis, the polysaccharide components in lignocellulose—hemicellulose and cellulose—are hydrolyzed into xylose, glucose and their corresponding liquid oligosaccharide-based liquid products respectively.

实现本工艺的设备包括以间歇、渗滤和连续的高压反应器为主体的系统装置。The equipment for realizing this process includes system devices mainly consisting of intermittent, percolation and continuous high-pressure reactors.

所述木质纤维素类生物质原料包括含有纤维素和半纤维素的植物类物质，包括木屑等林业废弃物，秸秆等农业废弃物，甘蔗渣等糖(酒)厂加工废弃物，以及速生林、象草等纤维素类能源植物。The lignocellulosic biomass raw material includes plant matter containing cellulose and hemicellulose, including forestry waste such as sawdust, agricultural waste such as straw, sugar (wine) factory processing waste such as bagasse, and fast-growing forest , Elephant grass and other cellulosic energy plants.

本发明的特点和技术效果是：Features and technical effects of the present invention are:

1.采用高温液态水为反应介质，具有廉价、环保、绿色的特点，反应条件温和，糖类产物较少降解，回收率高。1. High-temperature liquid water is used as the reaction medium, which is cheap, environmentally friendly, and green. The reaction conditions are mild, the sugar products are less degraded, and the recovery rate is high.

2.采用二步变温分段水解的方法，先以较低的温度水解半纤维素为相应的单糖及低聚糖及少量乙酸、糠醛等产物，再以较高温度对原料进行二次升温预处理，既保证了半纤维素能够最大限度地水解获得糖产物，又进一步预处理了原料，使纤维素酶能将其高效水解生成葡萄糖，达到环保、高效水解木质纤维素类生物质的目的。2. Adopt the method of two-step variable temperature segmental hydrolysis, firstly hydrolyze hemicellulose at a lower temperature to produce corresponding monosaccharides and oligosaccharides and a small amount of acetic acid, furfural and other products, and then heat up the raw materials for a second time at a higher temperature Pretreatment not only ensures that hemicellulose can be hydrolyzed to the maximum to obtain sugar products, but also further pretreats raw materials so that cellulase can efficiently hydrolyze it to generate glucose, achieving the purpose of environmental protection and efficient hydrolysis of lignocellulosic biomass .

3.原料的木质纤维素类生物质原料包括含有纤维素和半纤维素的植物类物质，包括木屑等林业废弃物，秸秆等农业废弃物，甘蔗渣等糖(酒)厂加工废弃物，以及速生林、象草等纤维素类能源植物。可以实现废物利用，促进绿色农业发展。3. The lignocellulosic biomass raw material of the raw material includes plant matter containing cellulose and hemicellulose, including forestry waste such as sawdust, agricultural waste such as straw, sugar (wine) factory processing waste such as bagasse, and Cellulose energy plants such as fast-growing forests and elephant grasses. It can realize waste utilization and promote the development of green agriculture.

附图说明Description of drawings

图1是本发明方法流程图。Fig. 1 is a flow chart of the method of the present invention.

具体实施方式Detailed ways

下面结合附图和实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

如图1所示，将生物质原料粉碎，使其粒度在0.5-2mm之间，按质量比1∶5-1∶20的比例加入去离子水，装入压力范围为2-10MPa的高压反应器内，在160-200℃的高温液态水环境下处理10-60min，收集液体产物，完成第一步水解，获得第一步水解液体产物和固体产物。将其快速实现固液分离，液体产物为木糖等五碳糖为主的水解液，固体产物以纤维素和木质素为主要组分。将第一步固体产物第二次以质量比1∶5-1∶20的比例加入水，在压力范围为2-10MPa的高压反应器中升温至200-260℃，反应0-30min，取出固体产物和第二步水解液体产物，固液分离，冷却，此时的固体产物为预处理好的纤维素和木质素为主的酶解原料。第二步水解固体产物按照每克原料干重加入8-30FPU的纤维素酶，在PH值4.0-5.5，温度为37℃至55℃及搅拌的条件下，水解至葡萄糖浓度不再升高，固液分离，获得酶解液体产物和固体残渣，完成酶解。酶解液主要成分是葡萄糖，酶解残渣主要组分是木质素。通过以上二步变温预处理和后续酶解，将木质纤维素中的多糖组份-半纤维素和纤维素分别水解成木糖和葡萄糖及其相应液态低聚糖为主的液体产物。将第一步、第二步水解液体产物和酶解产物用于微生物发酵制取乙醇，或通过生化或化工过程制取丁醇、烃类等能源化工产品；因固体残渣为生物质中热值最高的木质素，可用于燃烧作为工艺热源或用做制取其他化工产品的原料。As shown in Figure 1, the biomass raw material is crushed so that the particle size is between 0.5-2mm, and deionized water is added in a ratio of 1:5-1:20 by mass, and a high-pressure reaction with a pressure range of 2-10MPa is installed. In the container, treat in a high-temperature liquid water environment at 160-200°C for 10-60 minutes, collect the liquid product, complete the first step of hydrolysis, and obtain the first step of hydrolysis liquid product and solid product. The solid-liquid separation is quickly realized. The liquid product is a hydrolyzate mainly composed of five-carbon sugars such as xylose, and the solid product is mainly composed of cellulose and lignin. Add water to the solid product of the first step for the second time at a mass ratio of 1:5-1:20, raise the temperature to 200-260°C in a high-pressure reactor with a pressure range of 2-10MPa, react for 0-30min, and take out the solid The product and the liquid product of the second step of hydrolysis, solid-liquid separation, cooling, the solid product at this time is the pretreated cellulose and lignin-based enzymatic raw materials. The second step is to hydrolyze the solid product by adding 8-30 FPU cellulase per gram of raw material dry weight, and hydrolyze it until the glucose concentration no longer increases at a pH value of 4.0-5.5, a temperature of 37°C to 55°C, and stirring. Solid-liquid separation to obtain enzymatic hydrolysis liquid products and solid residues to complete enzymatic hydrolysis. The main component of the enzymolysis solution is glucose, and the main component of the enzymolysis residue is lignin. Through the above two-step variable temperature pretreatment and subsequent enzymatic hydrolysis, the polysaccharide components in lignocellulose—hemicellulose and cellulose—are hydrolyzed into xylose, glucose and their corresponding liquid oligosaccharide-based liquid products respectively. Use the first and second hydrolysis liquid products and enzymatic hydrolysis products for microbial fermentation to produce ethanol, or produce butanol, hydrocarbons and other energy and chemical products through biochemical or chemical processes; because the solid residue is the calorific value of biomass The highest lignin can be burned as a process heat source or used as a raw material for the production of other chemical products.

实施例1：Example 1:

以桉木为水解原料，将其粉碎筛分，以0.5-2mm桉木屑为原料，按液固比20∶1的质量比加水，投料入高压反应釜中，密闭反应系统，在搅拌转速500r/min，压力2Mpa的条件下，160℃反应60min，或压力4Mpa、180℃反应20min，或压力4Mpa200℃反应10min，以获得木糖及其低聚糖产物的最高值，将液体产物冷却收集，完成第一步预处理；迅速向釜内打入常温去离子水，液固比20∶1；加热至200℃、压力4Mpa下将液体产物保温30min收集、或加热至240℃将液体产物保温20min收集，或加热至260℃、将液体产物立刻冷却收集；釜内加水，待固体产物冷却至室温，取出，完成第二步预处理；冷却后的固体产物为经过二步变温预处理的产物，将其作为酶水解原料，进行纤维素酶水解，酶解条件为：pH 4.0，温度50℃，液固比20∶1，加酶量为8FPU/g，酶水解时间72小时。经过以上二步预处理，原料中的木聚糖转化率均可达到100％，第一步预处理液体产物中木糖和低聚木糖回收率在85％到92％之间；第二步变温处理后，葡聚糖有6％到17％的转化，糖回收率在5％到10％之间，经过两步变温预处理后的原料，葡聚糖酶解率为85％到95％，桉木中总糖(木聚糖和葡聚糖)回收率在80％到97％之间。同时选择液固比5∶1和10∶1进行试验，发现结果相近，产物中糖类产物浓度有所提高。Use eucalyptus as the raw material for hydrolysis, crush and sieve it, use 0.5-2mm eucalyptus wood chips as the raw material, add water according to the mass ratio of liquid to solid ratio of 20:1, feed the material into the high-pressure reactor, close the reaction system, and stir at a speed of 500r/ Min, under the condition of pressure 2Mpa, react at 160°C for 60min, or at 4Mpa at 180°C for 20min, or at 4Mpa at 200°C for 10min, to obtain the highest value of xylose and its oligosaccharide products, cool and collect the liquid product, and complete The first step of pretreatment: quickly pour deionized water at room temperature into the kettle, with a liquid-solid ratio of 20:1; heat to 200°C and keep the liquid product at a pressure of 4Mpa for 30 minutes to collect, or heat to 240°C to keep the liquid product for 20 minutes to collect , or heated to 260°C, cooling and collecting the liquid product immediately; add water to the kettle, wait for the solid product to cool to room temperature, take it out, and complete the second step of pretreatment; the cooled solid product is the product of the two-step temperature-varying pretreatment, and the As raw material for enzymatic hydrolysis, cellulosic hydrolysis is carried out under the conditions of enzymatic hydrolysis: pH 4.0, temperature 50°C, liquid-solid ratio 20:1, enzyme amount 8 FPU/g, and enzymatic hydrolysis time 72 hours. After the above two steps of pretreatment, the conversion rate of xylan in the raw material can reach 100%, and the recovery rate of xylose and xylooligosaccharides in the liquid product of the first step pretreatment is between 85% and 92%; the second step After variable temperature treatment, the conversion of dextran is 6% to 17%, the sugar recovery rate is between 5% and 10%, and the enzymatic hydrolysis rate of dextran is 85% to 95% after two-step variable temperature pretreatment , the recovery of total sugars (xylan and glucan) in eucalyptus was between 80% and 97%. At the same time, liquid-solid ratios of 5:1 and 10:1 were selected for testing, and the results were found to be similar, and the concentration of sugar products in the product was increased.

实施例2：Example 2:

以桉木为水解原料，将其粉碎筛分，以0.5-2mm桉木屑为原料，按液固比5∶1的质量比加水，放入高压反应系统中，密闭反应系统，加热至180℃，在压力10Mpa的条件下，反应20min，将液体产物冷却收集，完成第一步预处理；迅速向釜内打入常温去离子水，液固比5∶1，加热至200℃反应20min，立刻将液体产物冷却放出，反应器内加水，待固体产物冷却至室温，取出，完成第二步预处理；冷却后的固体产物为经过二步变温预处理的产物，将其作为酶水解原料，进行纤维素酶水解，酶解条件为：pH 5.5，温度为37℃，液固比5∶1，加酶量30FPU/g，酶水解时间72小时。经过以上二步预处理，原料中的木聚糖转化率达到100％，第一步预处理液体产物中木糖和低聚木糖回收率达91.68％；第二步变温处理后，葡聚糖有8.46％转化，糖回收率5.20％，经过两步变温预处理后的原料，葡聚糖酶解率为89.94％，桉木中总糖(木聚糖和葡聚糖)回收率达96.63％。Use eucalyptus as the raw material for hydrolysis, crush and sieve it, use 0.5-2mm eucalyptus wood chips as the raw material, add water at a mass ratio of liquid to solid 5:1, put it into a high-pressure reaction system, seal the reaction system, and heat it to 180°C. Under the condition of a pressure of 10Mpa, react for 20 minutes, cool and collect the liquid product, and complete the first step of pretreatment; quickly pour deionized water at room temperature into the kettle, with a liquid-solid ratio of 5:1, heat to 200°C for 20 minutes, and immediately The liquid product is cooled and released, and water is added to the reactor. After the solid product is cooled to room temperature, it is taken out to complete the second step of pretreatment; the cooled solid product is the product that has undergone the second step of variable temperature pretreatment, and it is used as the raw material for enzymatic hydrolysis. Enzyme hydrolysis, enzymatic hydrolysis conditions: pH 5.5, temperature 37°C, liquid-solid ratio 5:1, enzyme amount 30FPU/g, enzymatic hydrolysis time 72 hours. After the above two steps of pretreatment, the conversion rate of xylan in the raw material reaches 100%, and the recovery rate of xylose and xylooligosaccharides in the liquid product of the first step pretreatment reaches 91.68%; after the second step of variable temperature treatment, the dextran There is 8.46% conversion, the sugar recovery rate is 5.20%, the raw material after two-step variable temperature pretreatment, the enzymatic hydrolysis rate of glucan is 89.94%, and the recovery rate of total sugar (xylan and glucan) in Eucalyptus wood reaches 96.63% .

以上实施例证明，通过以上所述两步变温预处理，可实现生物质中半纤维素和纤维素的高效转化，结合纤维素酶水解，该工艺较好地回收了糖类产物。The above examples prove that through the above-mentioned two-step temperature-variable pretreatment, efficient conversion of hemicellulose and cellulose in biomass can be realized, combined with cellulase hydrolysis, this process can recover sugar products well.

Claims (2)

Translated fromChinese

1.一种生物质绿色高效预处理方法，采用木质纤维素类生物质为原料，其特征在于由以下步骤组成：1. A green and efficient pretreatment method for biomass, using lignocellulosic biomass as raw material, is characterized in that it consists of the following steps:1)将粒度在0.5-2mm之间的木质纤维素类生物质原料，按质量比1∶5-1∶20的比例加入水，在高压反应器内，在160-200℃的高温液态水环境下反应10-60min，固液分离，完成第一步水解；液体产物为木糖等五碳糖及其低聚糖为主的水解液，固体产物以纤维素和木质素为主要组分；1) Add lignocellulosic biomass raw materials with a particle size of 0.5-2mm to water at a mass ratio of 1:5-1:20, and in a high-pressure reactor, in a high-temperature liquid water environment of 160-200°C React for 10-60 minutes, separate solid and liquid, and complete the first step of hydrolysis; the liquid product is a hydrolyzate mainly composed of five-carbon sugars such as xylose and its oligosaccharides, and the solid product is mainly composed of cellulose and lignin;2)液体产物收集完毕，在高压反应器内将固体产物第二次按质量比1∶5-1∶20的比例加水，升温至200-260℃，反应0-30min，固液分离、冷却，此时的液体产物主要为少量葡萄糖、液态低聚葡糖及糠醛类副产物，固体产物为预处理好的纤维素和木质素为主的酶解原料；2) After the liquid product is collected, add water to the solid product in the high-pressure reactor for the second time according to the mass ratio of 1:5-1:20, raise the temperature to 200-260°C, react for 0-30min, separate the solid and liquid, and cool. At this time, the liquid products are mainly a small amount of glucose, liquid oligosaccharides and furfural by-products, and the solid products are pretreated cellulose and lignin-based enzymatic raw materials;3)将步骤2)得到的固体产物按照每克原料干重加入8-30FPU的纤维素酶，在PH值4.0-5.5，温度37℃至55℃及搅拌下，水解至葡萄糖浓度不再升高，将液体取出，完成酶解；酶解液主要成分是葡萄糖，固体残渣主要组分是木质素；3) Add 8-30 FPU cellulase to the solid product obtained in step 2) according to the dry weight of each gram of raw material, and hydrolyze it at a pH value of 4.0-5.5 at a temperature of 37°C to 55°C under stirring until the glucose concentration no longer increases , take out the liquid, and complete the enzymolysis; the main component of the enzymolysis solution is glucose, and the main component of the solid residue is lignin;4)将步骤1)、步骤2)水解液体产物和步骤3)的酶解产物合并得到木质纤维素类生物质水解产物。4) Combining step 1), step 2) hydrolyzed liquid product and step 3) enzymatic hydrolyzate to obtain lignocellulosic biomass hydrolyzate.2、根据权利要求1所述的生物质绿色高效预处理方法，其特征在于所述步骤1)和步骤2)中高压反应器的压力范围为2-10MPa，使对应反应温度下的高温水保持在液体状态，即反应器内压力在该温度下水的饱和蒸汽压以上。2. The green and high-efficiency pretreatment method for biomass according to claim 1, characterized in that the pressure range of the high-pressure reactor in the step 1) and step 2) is 2-10MPa, so that the high-temperature water under the corresponding reaction temperature is maintained In the liquid state, that is, the pressure in the reactor is above the saturated vapor pressure of water at this temperature.

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