WO2011082600A1 - 一种木质纤维素原料的处理方法 - Google Patents

一种木质纤维素原料的处理方法 Download PDF

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WO2011082600A1
WO2011082600A1 PCT/CN2010/077668 CN2010077668W WO2011082600A1 WO 2011082600 A1 WO2011082600 A1 WO 2011082600A1 CN 2010077668 W CN2010077668 W CN 2010077668W WO 2011082600 A1 WO2011082600 A1 WO 2011082600A1
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lignocellulosic material
added
particle size
suspension
temperature
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PCT/CN2010/077668
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English (en)
French (fr)
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俞学锋
李知洪
余明华
姚鹃
刘代武
雷锦成
李志军
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安琪酵母股份有限公司
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Priority to EP10841943.3A priority Critical patent/EP2479281B1/en
Priority to BR112012011647-9A priority patent/BR112012011647B1/pt
Priority to RU2012118496/10A priority patent/RU2518305C2/ru
Publication of WO2011082600A1 publication Critical patent/WO2011082600A1/zh
Priority to US13/445,894 priority patent/US8828187B2/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to a Chinese patent application filed on January 6, 2010, the Chinese Patent Office, the application number is 20101 0003009. X, the invention name is "a method for treating lignocellulosic raw materials" Priority is hereby incorporated by reference in its entirety.
  • the invention relates to the field of biological processing, and in particular to a method for treating a lignocellulosic material. Background technique
  • the annual agricultural waste is about 700 million tons, including wheat straw.
  • the treatment methods mainly include acid method, alkali method, steam explosion method and wet oxidation method. , organic solvent method, etc.
  • Chinese patent CN101 348804 (Beijing Forestry University) discloses a method for separating main components of low-strength steam explosion irrigation wood stems. This method requires a steam explosion device and a steam generator, and has high operational safety requirements.
  • CN1443141 (Rissor National Laboratory) reports on temperature oxidation or steam explosion, and has the same problems as the patent CN101 348804, requiring a special device for blasting.
  • Chinese patent CN101 343648 (Shanghai Jiaotong University) reported that a nano-grinder can be used to pulverize straw to 10-20 ⁇ ⁇ , which improves hydrolysis efficiency and can be replaced by chemical reagents.
  • the meter-scale pulverizer consumes a large amount of energy during the pulverization process, and the dry grinding easily causes the temperature of the motor to rise, the intermediate cooling time is long, and the production efficiency is low.
  • CN101285106 (Nanjing University of Technology) reports on the method of extracting lignin by using phosphoric acid hydrolysis and then using organic solvent, but after acid hydrolysis, neutralization, filtration and the like are also required.
  • CN101255479 (Nanjing University of Technology) reports a treatment method for high-efficiency saccharification of lignin, which adopts coarse pulverization, lye wet milling, alkali recovery and enzymatic hydrolysis steps.
  • the lye is added during the treatment and needs to be recovered by electrodialysis. Alkaline, the power consumption cost is relatively high.
  • CN101235606 (China Petroleum & Chemical Corporation) reports that a method for acid hydrolysis of lignocellulose by a circulating reactor, and a method for hydrolyzing lignocellulose by an acid method reported by CN101148458 (Graduate School of the Chinese Academy of Sciences) require special pretreatment equipment.
  • the object of the present invention is to overcome the disadvantages of the prior art by-products, high equipment requirements and high processing temperatures, and to provide a method for treating lignocellulosic raw materials.
  • a method for treating a lignocellulosic material comprising the steps of:
  • Step (2) mixing the particles obtained in the step (1) with water, and dispersing through a colloid mill to form a suspension having a particle diameter of 40-80 ⁇ m;
  • Step (3) the suspension obtained in the step (2) is homogenized by high pressure to a particle size of 10-40 ⁇ m;
  • Step (4) The suspension obtained in the step (3) is buffered with sodium acetate and an acetic acid buffer solution, and cellulase, ⁇ -glucosidase and xylanase are added thereto, and the solution is hydrolyzed for 36 to 72 hours.
  • the method of the invention coarsely pulverizes the lignocellulosic raw material, and then mixes the pulverized material with a colloid mill, finally crushes the plant cell wall under high pressure under homogenization, releases cellulose, and reduces the crystallinity of the cellulose.
  • a colloid mill In order to facilitate enzymatic hydrolysis, increase the saccharification rate of cellulose.
  • the homogenization is to enter the valve zone at a low flow rate under high pressure when the premixed material enters the controllable zone.
  • the flow rate suddenly increases, and its value can reach 300 m / s.
  • a corresponding large pressure drop is generated, which is formed in a very short time and a small space. Strong cavitation and eddy current, and high-speed impact with the homogenized ring, resulting in strong shear and fracture of the material particles.
  • the previously coarser suspension is processed into an ultrafine, uniform and stable liquid-solid dispersion.
  • the lignocellulosic feedstock includes straw, grass, wood, corn cob, fruit slag, and sugar cane slag.
  • the mass ratio of the particles to the water is 1 : 1 - 5
  • the dispersion time is 1-2 hours
  • the temperature is 70 - 90 °C.
  • the high pressure in step (3) is preferably a homogenous pressure of from 50 to 10,000 atmospheres, a treatment time of from 1 to 2 hours, and a temperature of from 60 to 85 °C.
  • the amount of the cellulase added in the step (4) is preferably from 10 to 60 international units per gram of the lignocellulosic material.
  • the amount of the ⁇ -glucosidase added in the step (4) is preferably 40-100 international units per gram of the lignocellulosic material.
  • the amount of the xylanase added in the step (4) is preferably 60 to 120 international units per gram of the lignocellulosic material.
  • the step of the sodium acetate and the acetic acid buffer solution is preferably 4. 8-5.
  • the enzymatic hydrolysis temperature in the step (4) is preferably 40 to 55 ° C, and the rotation speed is preferably 80 to 160 rpm.
  • the invention pulverizes the agricultural, industrial and domestic waste biomass resources such as corn stover, wheat straw, bagasse, fruit residue and wood chips into particles of different particle size range by using a blade mill, and the part of 80 ⁇ ⁇ -100 ⁇ m
  • the sample is added with a certain proportion of water, dispersed by a colloid mill, and the fineness is controlled at 40-80 ⁇ ⁇ . After pulverization, it enters the homogenizer, directly breaks the cell wall, releases lignin and hemicellulose, and reveals the cellulose crystals wrapped therein.
  • the granules, the particle size is controlled at 10-40 ⁇ ⁇ , which is beneficial to the direct hydrolysis of the cellulase, and then the sodium acetate-acetate buffer solution is added, and the pH value is controlled at 4. 8-5. 5 , and the cellulase and wood are mixed.
  • the glycanase is subjected to enzymatic hydrolysis.
  • the pulverized pulverized pulverized pulverized pulverized pulverized granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules of the granules. A partial sample of 80-100 ⁇ m was screened. In a specific embodiment, the sample is highly dispersed by mixing the sample and water in a certain ratio and transporting it to a split colloid mill. The crushed sample is obtained by shearing, grinding, and high-frequency vibration, and the particle size is 40_80 ⁇ ⁇ . .
  • the lignocellulose raw material is dispersed to a particle size of 10-40 ⁇ m, and is effectively enzymatically hydrolyzed by a mixed enzyme, and the fermentable sugar concentration in the hydrolysate can reach 148-155 g/L. , the hydrolysis rate reaches 95% _ 98%.
  • the method of the invention overcomes the defects of the prior art processing method, such as complicated by-products, high equipment requirements, high temperature and high cost, which can reduce the cost and avoid the use of chemical reagents or high temperature environment, avoiding pollution or occurrence of the environment.
  • By-products are a non-polluting and efficient treatment method that provides a practical way for the commercial production of fuel ethanol and biochemical products.
  • Figure 1 is an electron microscope scan of the straw raw material before pretreatment
  • Figure 2 is an electron microscope scan of the straw material after being dispersed by a colloid mill and a homogenizer
  • Figure 3 shows the saccharification curve of straw after treatment by different methods. detailed description:
  • the smashing of the sizing of the sizing of the sizing of the sizing of the sizing of the sizing of the sizing A partial sample of 80-100 ⁇ m was screened. The output is two tons per hour and the equipment power is 15kw.
  • the sample is highly dispersed by mixing the sample and water in a certain ratio, pumping it into a JM series split colloid mill, and obtaining the crushed sample by shearing, grinding, and high-frequency vibration, and the particle size is 40-80 ⁇ ⁇ .
  • the maximum feed particle size is required to be less than 500 microns, the maximum feed temperature is less than 90 °C, the throughput is 1 ton / hour, and the equipment power is 5.9 kw.
  • High-pressure crushing The slurry pulverized by the colloid mill is pumped to a high-pressure homogenizer. Homogenization is in In the homogenizing valve, the unmixed premixed material enters the valve area at high pressure and low flow rate through the increase of the reciprocating pump. When the material enters the small gap between the controllable valve seat and the valve stem, the flow rate suddenly increased, the value can reach 300 m / s, at the same time, correspondingly to produce a huge pressure drop, in a very short time and 4 ⁇ small space to form a strong cavitation and eddy current, and The mass ring produces a high speed impact. Produces powerful shearing and breaking action on material particles.
  • the previously coarser suspension is processed into an ultrafine, uniform and stable liquid-solid phase dispersion.
  • the material removal particle size reaches 10-40 ⁇ ⁇ , which is beneficial to the saccharification process of the enzyme.
  • the maximum pressure is 100 atmospheres
  • the treatment capacity is 120 L/hour
  • the equipment power is 3.
  • Okw Example 1 The method of the present invention pretreats lignocellulosic material
  • the lignocellulosic material used in this embodiment is corn stalk, straw, wood chips, apple pomace and the like which are purchased from the surrounding area of Yichang, Hubei.
  • the lignocellulosic material is dried and shaken to remove mud.
  • the straw was separately pulverized by a pulverizer, and passed through a sieve of 10. 5 mm 0. 1 mm, 0.08 mm, and 100-80 ⁇ ⁇ of the particulate matter was collected.
  • the uniformly dispersed suspension with a particle size of 40-80 ⁇ is pumped to a high-pressure homogenizer.
  • the homogenization pressure is 50 atm
  • the treatment time is 2 hours
  • the temperature is 60 °C.
  • the high-pressure fracture of the straw cell wall is achieved. .
  • a suspension having a dispersed particle size of 10-40 ⁇ was obtained.
  • a uniformly dispersed suspension having a particle size of 10-40 ⁇ was pumped into the enzymatic hydrolysis reactor at a hydrolysis temperature of 40 ° C and a rotation speed of 80 rpm.
  • the amount of cellulase added is 10 international units per gram of lignocellulosic material
  • the amount of ⁇ -glucosidase added is Glucan cellulose raw material 40 international units, xylanase The amount added is 60 international units per gram of lignocellulosic material.
  • the content of sugar in the enzymatic hydrolysate was determined by high performance liquid phase evaporation light scattering method S, and 150 g of fermentable sugar was contained per liter of the hydrolyzate, and the cellulose hydrolysis rate was 95%.
  • the basis for its calculation is:
  • Cellulose hydrolysis rate mass of glucose obtained after enzymatic hydrolysis / (mass of cellulose contained in lignocellulosic material X 1. 1) X 100%
  • Example 2 Pretreatment of lignocellulosic material by the method of the present invention
  • the apple slag was respectively pulverized by a pulverizer, and passed through a lmm, 0.5 mm, 0.1 mm, 0. 08 mm sieve, and 100-80 ⁇ ⁇ of the particulate matter was collected.
  • the straw granules with the particle size range of 80-1 00 ⁇ ⁇ were added to the water of 1: 5, and the mixture was stirred into a colloid mill with a pump.
  • the dispersion time was 2 hours, and the treatment temperature was controlled at 90 ° C to obtain a uniform dispersed particle size. Suspension in 40-80 ⁇ .
  • the uniformly dispersed suspension with a particle size of 40-80 ⁇ is pumped to a high-pressure homogenizer with a homogenization pressure of 100 atm, a treatment time of 1 hour, and a temperature of 85 ° C to achieve high-pressure fracture of the straw cell wall. .
  • a suspension having a dispersed particle size of 10-40 ⁇ was obtained.
  • the corresponding mixed enzyme can be added to enter the enzymatic hydrolysis stage.
  • the electron microscopic observation of the particles in the suspension is shown in Fig. 2. Compared with the scanning electron micrograph before the pretreatment of the straw raw material of Fig. 1, it can be seen that the porosity of the straw is increased after the method of the present invention is treated, and the cellulose structure becomes loose. This structural change is beneficial to increase the rate of saccharification.
  • a uniformly dispersed suspension having a particle size of 10-40 ⁇ was pumped into the hydrolysis reaction vessel at a hydrolysis temperature of 55 ° C and a rotation speed of 160 rpm.
  • the amount of cellulase added is 60 international units per gram of lignocellulosic material
  • the amount of ⁇ -glucosidase added is 100 units of lignocellulosic raw material
  • the amount of xylanase added is 120 international units per gram of lignocellulosic material
  • enzymatically hydrolyzed for 72 hours and the sugar in the enzymatic hydrolyzate is determined by high performance liquid phase evaporation light scattering method S method.
  • Content 160 grams per liter of hydrolysate Fermented sugar, the cellulose hydrolysis rate was 98%. The basis for its calculation is:
  • Cellulose hydrolysis rate mass of glucose obtained after enzymatic hydrolysis / (mass quality of cellulose contained in lignocellulosic material X 1. 1) 100%
  • Example 3 Comparison of pretreatment of lignocellulosic material with other methods of the method of the present invention
  • the sodium hydroxide having a volume fraction of 1.0% was put into the reaction vessel at a ratio of lignocellulose raw material to water of 1:3, and treated at 70-90 ° C for 2.5 hours, followed by suction filtration. The filtrate was adjusted to pH neutral. The alkali treated lignocellulose is obtained. After drying at room temperature, it is hydrolyzed by enzymatic hydrolysis. The content of sugar in the enzymatic hydrolysate was determined by high performance liquid phase evaporative light scattering method.
  • Method 3 Steam Blasting
  • the lignin is added to the blasting kettle at a weight ratio of 1:1, and steam is introduced to a pressure of 0. 8MP097382a-l. 8 MP097382a, and the reaction is 8 _15 min.
  • the pneumatic valve is controlled to instantaneously release pressure, and the raw material is separated into the receiving container by the cyclone under the action of the pressure difference.
  • the raw material is cooled to obtain a filter residue. After drying at room temperature, it was hydrolyzed by the enzymatic hydrolysis method of Example 5.
  • the content of sugar in the enzymatic hydrolysate was determined by high performance liquid phase evaporation light scattering method S.
  • Example 1 and Example 2 were saccharified as required, and compared with the straw saccharification effect after the acid method, the alkali method, and the steam explosion method, and the results are shown in Fig. 3.
  • the results show that the saccharification effect after the treatment by the method of the invention is better than that of the other four treatment methods, and the sugar concentration can reach about 150 g/L.
  • the above is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. These improvements and retouchings should also be considered. It is the scope of protection of the present invention.

Description

一种木质纤維素原料的处理方法 本申请要求于 2010 年 1 月 6 日提交中国专利局、 申请号为 20101 0003009. X , 发明名称为 "一种木质纤维素原料的处理方法" 的中国专利 申请的优先权， 其全部内容通过引用结合在本申请中。 技术领域
本发明涉及生物加工领域， 具体涉及一种木质纤维素原料的处理方法。 背景技术
随着石油资源的日益减少， 粮食的日益紧张， 以及对乙醇、 丁醇等为主的 液体燃料和其他生物质化工产品如乳酸、丁二酸等的巨大需求，促使以木质纤 维素为原料生产可发酵的糖，然后生物转化为生物化工产品的研究与开发成为 中国、 美国等世界耗能大国的科学界和产业界的热点。
我国是一个农业大国， 每年形成的农业废弃物约有 7亿 t , 其中麦草秸秆
1. 1亿 t， 稻草秸秆 1. 8亿 t， 棉秸 1 300万 t， 大豆秸秆 1500万 t， 其中麦草 秸秆产量约占秸秆总量的约 18%。 除少数秸秆被作为牲畜饲料、 农家肥和农村 燃料外， 大多数秸秆被堆放或直接焚烧， 不仅造成生物质资源的巨大浪费， 也 带来严重的环境污染问题。 利用这些农村秸秆发展纤维素乙醇和生物化工产 品， 足以解决我国面临的能源危机， 同时可以为生物化工发展提供原料。
但纤维素用酶法进行糖化处理前， 由于木质纤维素的特殊结构， 需要特殊 预处理， 将结晶纤维素结构变得疏松， 处理方法主要有酸法、 碱法、 蒸汽爆破 法、 湿氧化法、 有机溶剂法等。
如中国专利 CN101 348804 (北京林业大学）公开了一种低强度蒸汽爆破灌 木茎秆分离主要成份的方法。该方法需要蒸汽爆破装置及蒸汽发生器，操作安 全要求高。 CN1443141 (里索国家实验室）报道了温法氧化或蒸汽爆破， 存在 和专利 CN101 348804相同的问题， 需要爆破专用装置。
中国专利 CN101 343648 (上海交通大学）报道了一种利用纳米粉碎机， 可 以将秸秆粉碎到 10-20 μ ηι, 提高水解效率， 可以替代化学试剂法处理， 但纳 米尺度的粉碎机在粉碎过程中需要消耗大量的能量，而且干磨容易导致电机温 度升高， 中间冷却时间长， 生产效率低。
CN101285106 (南京工业大学）报道利用磷酸水解， 然后利用有机溶剂萃取 木质素的方法， 但酸法水解后还需要中和、 过滤等处理过程。
CN101255479 (南京工业大学）报道一种将木质素高效糖化的处理方法， 采用粗粉碎、 碱液湿磨、 碱回收和酶解步骤， 其处理过程中添加了碱液， 并需 要利用电渗析方法回收碱液， 电耗成本相对较高。
CN101235606 (中国石油化工股份有限公司）报道利用循环反应器酸水解 木质纤维素的方法， 和 CN101148458 (中国科学院研究生院）报道的利用酸法 水解木质纤维素的方法， 都需要特殊的预处理设备。
因此， 目前急需寻找一种廉价、 无环境污染， 不需要高温条件的， 也无需 酸、 碱的生产能力大的处理方法。 发明内容
本发明目的在于克服现有技术副产物复杂、设备要求高、处理温度高的不 足， 提供一种木质纤维素原料的处理方法。
本发明是通过以下技术方案实现的：
一种木质纤维素原料的处理方法， 包括如下步骤：
步骤（1)： 将木质纤维素原料粉碎后过筛，取粒径为 0. 08匪- 0. 1匪的颗粒 备用；
步骤（2)：将步骤（1)所得颗粒和水混合， 经胶体磨分散形成颗粒粒径为 40-80 μ ηι的悬浮液；
步骤（3)：将步骤（2)所得悬浮液经高压均质至颗粒粒径为 10-40 μ m;
步骤（4)： 将步骤（3)所得悬浮液用醋酸钠及醋酸緩沖溶液緩沖，添加纤维 素酶、 β -葡萄糖苷酶和木聚糖酶， 酶解 36-72小时。
本发明所述方法将木质纤维素原料进行粗粉碎，然后利用胶体磨对粉碎物 料进行混合， 最后在均质作用下使植物细胞壁在高压下破碎， 释放出纤维素， 减小纤维素的结晶度， 以利于进行酶解， 提高纤维素的糖化率。
所述均质是将预混物料在高压下以低流速进入阀区，当物料进入可控制的 阀座与阀杆之间的微小缝隙时， 流速突然增加， 其值可达 300米 /秒， 与此同 时，相应的产生巨大的压降，在极短的时间及 ^艮小的空间内形成强烈的空穴效 应和涡流作用， 并与均质环产生高速撞击，对物料颗粒产生强大的剪切和破碎 作用。 通过上述作用， 使原先较粗大的悬浮液加工呈超微细的， 均匀的稳定的 液一固相分散物。
所述木质纤维素原料包括秸秆类、 草类、 木材类、 玉米芯、 水果渣、 甘蔗 渣。
步骤（2)中优选所述颗粒和水质量比在 1 : 1_ 5 , 分散时间 1-2小时， 温 度为 70_90 °C。
步骤（3)所述高压优选均质的压力在 50-1 00大气压， 处理时间 1-2小时， 温度为 60- 85 °C。
步骤（4 )所述纤维素酶的添加量优选为每克木质纤维素原料 10-60个国 际单位。
步骤（ 4 )所述 β -葡萄糖苷酶的添加量优选为每克木质纤维素原料 40-100 个国际单位。
步骤（ 4 )所述木聚糖酶的添加量优选为每克木质纤维素原料 60-120个国 际单位。
步骤（ 4 )所述醋酸钠及醋酸緩沖溶液 ρΗ值优选为 4. 8-5. 8。
步骤（4 )所述酶解温度优选为 40_55 °C , 转速优选为 80_160rpm。
本发明将玉米秸秆、 麦秆、 甘蔗渣、 水果渣、 木屑等农业、 工业及生活废 弃的生物质资源用叶片式粉碎机粉碎成不同粒度范围的颗粒， 将 80 μ ηι-100 μ m的部分样品加入一定比例的水， 用胶体磨分散， 细度控制在 40-80 μ ηι, 粉碎 后进入均制机， 直接将细胞壁破碎， 释放木质素和半纤维素， 露出包裹在里面 的纤维素晶体颗粒， 粒度控制在 10-40 μ ηι, 有利于纤维素酶的直接水解， 然 后加入醋酸钠-醋酸緩沖溶液样品， ρΗ值控制在 4. 8-5. 5 , 再加混合纤维素酶 和木聚糖酶， 进行酶解。
在具体实施方式中样品的粉碎用粉碎机将木质纤维素类样品粉碎成不同 粒度范围的颗粒，粉碎后用目筛筛出需要的不同尺寸范围的样品，得到已过目 0. 08mm-0. lmm目筛 80-100 μ m的部分样品。 在具体实施方式中样品的高度分散是将样品和水按照一定比例混合，输送 到分体式胶体磨中， 通过剪切、 研磨、 高频震动获得破碎后的样品， 除料粒径 在 40_80 μ ηι。
按照本发明所述方法， 木质纤维素原料分散至粒径为 10-40 μ ηι后， 在混 合酶的作用下进行有效的酶解， 酶解液中可发酵糖浓度可达到 148-155g/L , 水解率达到 95%_98%。
本发明所述方法克服了现有技术的处理方法副产物复杂，设备要求高， 温 度高， 成本大的缺陷， 既可减少成本又可避免使用化学试剂或高温环境， 避免 对环境产生污染或产生副产物，是一种无污染而且高效的处理方法， 为燃料乙 醇和生物化工产品的商业化生产提供了一种切实可行的途径。 附图说明：
图 1为秸秆原料预处理前的电镜扫描图；
图 2为秸秆原料经过胶体磨和均质机分散后的电镜扫描图；
图 3为不同方法处理后秸秆的糖化曲线。 具体实施方式：
下面结合实施例， 进一步阐述本发明：
具体实施方式对本发明技术方案的实施， 给出了详细的实施方式和过程， 但本发明的保护范围不限于下述的实施例。下列实施例中未注明具体条件的实 验方法， 通常按照常规条件或按照制造厂商所建议的条件。
在具体实施方式中样品的粉碎用粉碎机将木质纤维素类样品粉碎成不同 粒度范围的颗粒，粉碎后用目筛筛出需要的不同尺寸范围的样品，得到已过目 0. 08mm- 0. lmm目筛 80-100 μ m的部分样品。产量每小时两吨，设备功率为 15kw。
在具体实施方式中样品的高度分散是将样品和水按照一定比例混合，泵输 送到 JM系列分体式胶体磨中， 通过剪切、 研磨、 高频震动获得破碎后的样品， 除料粒径在 40-80 μ ηι。 要求最大进料颗粒尺寸小于 500微米， 最高进料温度 小于 90 °C , 产量： 1吨 /小时， 设备功率为 5. 5kw。
高压破碎： 将经过胶体磨粉碎后的浆体用泵输送到高压均质机。 均质是在 均质阀内进行的， 未经均质的预混物料， 通过往复泵的增加， 以高压和低流速 进入阀区，当物料进入可控制的阀座与阀杆之间的微小缝隙时，流速突然增加， 其值可达 300米 /秒， 与此同时， 相应的要产生巨大的压降， 在极短的时间及 4艮小的空间内形成强烈的空穴效应和涡流作用， 并与均质环产生高速撞击。对 物料颗粒产生强大的剪切和破碎作用。通过上述作用，使原先较粗大的悬浮液 加工呈超微细的， 均匀的稳定的液-固相分散物。 除料粒径达到 10-40 μ ηι, 利 于酶的糖化过程。 最大压力为 100大气压， 处理量为 120L/小时， 设备功率为 3. Okw 实施例 1: 本发明所述方法预处理木质纤维素原料
本实施例使用的木质纤维素原料是从湖北宜昌周边地区采购的玉米秸秆、 麦秆、 木屑、 苹果渣等。 将木质纤维素原料晾干震动除泥。
1、 粗粉碎
将秸秆分别用粉碎机粉碎， 过 1 0. 5mm 0. 1mm, 0. 08mm 筛子， 收集 100-80 μ ηι上颗粒物。
2、 快速分散
将其中粒径范围为 80-1 00 μ ηι的秸秆颗粒加入 1 : 1的水， 搅勾后用泵打 入胶体磨， 分散时间 1 小时， 处理温度控制在 70 °C , 得到分散均匀的粒度在 40-80 μ ηι的悬浮液。
3、 高压均质
将分散均匀的粒度在 40-80 μ ηι的悬浮液， 利用泵输送到高压均质机中， 均质压力在 50大气压， 处理时间 2小时， 温度在 60 °C , 实现了秸秆细胞壁的 高压破碎。 得到分散粒度在 10-40 μ ηι的悬浮液。 待降温至 5 (TC左右， 即可加 入相应的混合酶， 进入酶解阶段。
4、 酶解
将分散均匀的粒度在 10-40 μ ηι的悬浮液， 利用泵输送到酶解反应釜中， 酶解温度为 40 °C , 转速为 80rpm。 添加纤维素酶和 β _葡萄糖苷酶， 纤维素酶 和和 β _葡萄糖苷酶， 纤维素酶的添加量为每克木质纤维素原料 10 个国际单 位， β -葡萄糖苷酶的添加量为每克木质纤维素原料 40个国际单位，木聚糖酶 的添加量为每克木质纤维素原料 60个国际单位。酶解 36小时， 用高效液相蒸 发光散射法 S 法测定酶解液中糖的含量， 每升酶解液中含 150克的可发酵糖， 得到纤维素水解率为 95%。 其计算依据为：
纤维素水解率 = 酶解后所得葡萄糖的质量 / (木质纤维素原料含有的纤维 素质量 X 1. 1) X 100% 实施例 2: 本发明所述方法预处理木质纤维素原料
1、 粗粉碎
将苹果渣分别用粉碎机粉碎， 过 lmm、 0. 5mm, 0. 1mm, 0. 08mm筛子， 收集 100-80 μ ηι上颗粒物。
2、 快速分散
将其中粒径范围为 80-1 00 μ ηι的秸秆颗粒加入 1 : 5的水， 搅勾后用泵打 入胶体磨， 分散时间 2小时， 处理温度控制在 90 °C , 得到分散均匀的粒度在 40-80 μ ηι的悬浮液。
3、 高压均质
将分散均匀的粒度在 40-80 μ ηι的悬浮液， 利用泵输送到高压均质机中， 均质 压力在 100大气压， 处理时间 1小时， 温度在 85 °C , 实现了秸秆细胞壁的高 压破碎。 得到分散粒度在 10-40 μ ηι的悬浮液。 待降温后， 即可加入相应的混 合酶， 进入酶解阶段。 取悬浮液中的颗粒电镜观察， 见图 2 ; 与图 1的秸秆原 料预处理前的扫描电镜图形成对比，可看出本发明所述方法处理后秸秆空隙率 增加， 纤维素结构变得疏松， 这种结构改变有利于提高糖化率。
4、 酶解
将分散均匀的粒度在 10-40 μ ηι的悬浮液， 利用泵输送到酶解反应釜中， 酶解温度为 55 °C , 转速为 160rpm。 添加纤维素酶和 β _葡萄糖苷酶， 纤维素酶 和和 β _葡萄糖苷酶， 纤维素酶的添加量为每克木质纤维素原料 60 个国际单 位， β -葡萄糖苷酶的添加量为每克木质纤维素原料 100个国际单位， 木聚糖 酶的添加量为每克木质纤维素原料 120个国际单位， 酶解 72小时， 用高效液 相蒸发光散射法 S 法测定酶解液中糖的含量， 每升酶解液中含 160克的可发 酵糖， 得到纤维素水解率为 98%。 其计算依据为：
纤维素水解率 = 酶解后所得葡萄糖的质量 / (木质纤维素原料含有的纤维 素质量 X 1. 1) 100% 实施例 3: 本发明所述方法预处理木质纤维素原料与其他方法的比较
方法 1 : 酸法处理
将体积分数为 4%的稀硫酸，木质纤维素原料和水的比例为 1： 3投入反应 釜中， 在 140-160 °C下处理 10-30min。 然后抽滤， 调整 pH值为中性， 即得到 酸法处理的木质纤维素。 室温晾干后， 采用酶解方法水解。 用高效液相蒸发光 散射法 S 法测定酶解液中糖的含量 。 方法 2: 碱法处理
将体积分数为 1. 0%的氢氧化钠， 以木质纤维素原料和水的比例为 1 : 3 比投入反应釜中， 在 70-90 °C下处理 2. 5h后抽滤。 滤液调整 pH值为中性。 得 到碱法处理的木质纤维素。 室温晾干后， 酶解方法水解。 用高效液相蒸发光散 射法 S 法测定酶解液中糖的含量 。 方法 3: 蒸汽爆破法处理
将木质纤维素原料和水按重量比 1 : 1投入爆破釜中， 通入蒸汽， 升压至 0. 8MP097382a-l. 8 MP097382a , 反应 8 _15min。 控制气动阀瞬间泄压， 在压 差作用下， 使原料通过旋风分离进入接收容器中。 原料冷却， 得到滤渣。 室温 晾干后， 采用实例 5 的酶解方法水解。 用高效液相蒸发光散射法 S 法测定酶 解液中糖的含量 。 将实施例 1和实施例 2处理的秸秆按要求进行糖化， 与酸法、 碱法、 蒸汽 爆破法处理后的秸秆糖化效果进行比较， 结果见图 3。 结果显示， 本发明所述 方法处理后的糖化效果优于其他四种处理方法的糖化效果， 糖浓度可以达到 150g/L左右。 以上仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术 人员来说， 在不脱离本发明原理的前提下， 还可以做出若干改进和润饰， 这些 改进和润饰也应视为本发明的保护范围。

Claims

权 利 要 求
1、 一种木质纤维素原料的处理方法， 包括如下步骤：
步骤 1: 将木质纤维素原料粉碎后过筛， 取粒径为 0. 08mm-0. lmm的颗粒 备用；
步骤 2:将步骤 1所得颗粒和水混合，经胶体磨分散形成颗粒粒径为 40-80 μ ηι的悬浮液；
步骤 3:将步骤 2所得悬浮液经高压均质至颗粒粒径为 10-40 μ ηι;
步骤 4: 将步骤 3所得悬浮液用醋酸钠及醋酸緩沖溶液緩沖， 添加纤维素 酶、 β -葡萄糖苷酶和木聚糖酶， 酶解 36-72小时。
2、 根据权利要求 1所述的处理方法， 其特征在于： 所述木质纤维素原料 包括秸秆类、 草类、 木材类、 玉米芯、 水果渣、 甘蔗渣。
3、 根据权利要求 1所述的处理方法， 其特征在于： 步骤 2中所述颗粒和 水的质量比在 1 : 1- 5 , 分散时间 1-2小时， 温度为 70_90 °C。
4、 根据权利要求 1所述的处理方法， 其特征在于： 步骤 3所述高压均质 的压力在 50-100大气压， 处理时间 1-2小时， 温度为 60-85 °C。
5、 根据权利要求 1所述的处理方法， 其特征在于： 步骤 4所述纤维素酶 的添加量为每克木质纤维素原料 10-60个国际单位。
6、根据权利要求 1所述的处理方法， 其特征在于： 步骤 4所述 β -葡萄糖 苷酶的添加量为每克木质纤维素原料 40-100个国际单位。
7、 根据权利要求 1所述的处理方法， 其特征在于： 步骤 4所述木聚糖酶 的添加量为每克木质纤维素原料 60-120个国际单位。
8、 根据权利要求 1所述的处理方法， 其特征在于： 步骤 4所述醋酸钠及 醋酸緩沖溶液 ρΗ值为 4. 8-5. 8。
9、 根据权利要求 1所述的处理方法， 其特征在于： 步骤 4所述酶解温度 为 40- 55 °C , 转速为 80- 160rpm。
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US8828187B2 (en) 2014-09-09
RU2518305C2 (ru) 2014-06-10
BR112012011647A2 (pt) 2015-09-29
EP2479281A4 (en) 2016-11-23
US20120193049A1 (en) 2012-08-02
RU2012118496A (ru) 2013-11-10
EP2479281B1 (en) 2018-08-15
BR112012011647B1 (pt) 2018-12-26
EP2479281A1 (en) 2012-07-25
CN102115994B (zh) 2012-08-29

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