CN101358218A - Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk - Google Patents

Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk Download PDF

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CN101358218A
CN101358218A CN 200810141418 CN200810141418A CN101358218A CN 101358218 A CN101358218 A CN 101358218A CN 200810141418 CN200810141418 CN 200810141418 CN 200810141418 A CN200810141418 A CN 200810141418A CN 101358218 A CN101358218 A CN 101358218A
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xylose
straw
acetone
butanol
ethanol
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CN 200810141418
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CN101358218B (en )
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王建设
王绍鹏
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王建设
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels
    • Y02E50/16Cellulosic bio-ethanol

Abstract

The invention provides a method for producing xylose co-produced with acetone, butanol and ethanol by utilizing straws. The straws are hydrated by acid to be filtered to be divided into xylose hydrolysis fluid and xylose residue; the xylose residue is zymohydrolyzed, fermented and rectified to prepare the acetone, the butanol and the ethanol; the xylose hydrolysis fluid is used for preparing the xylose. The method of producing xylose co-produced with acetone, butanol and ethanol by utilizing straws of the invention realizes the maximization of the cellulose straw substances, not only the straw resources are fully utilized to realize changing waste into valuable and the added value of products is improved to realize the economic value of the straws, but also the new raw material source and methods for the production of the acetone and the ethanol are developed and more economic benefits and social benefits are brought to the enterprises and the society.

Description

一种利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法 A method of producing xylose straw cogeneration acetone, butanol and ethanol

技术领域 FIELD

本发明属于生物化工技术领域,涉及一种利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法。 The present invention belongs to the field of bio-chemical technology, relates to a method for producing xylose straw cogeneration acetone, butanol and ethanol. 背景技术 Background technique

农作物秸杆是阳光光合作用的产物,是大宗的可再生资源,仅我国每年就 Sunshine crop straw is a product of photosynthesis, is the bulk of renewable resources, only our country each year

收获大约8亿吨,除一小部分用作饲料外,其余大部分都被白白浪费掉了。 Harvest about 800 million tons, in addition to a small portion is used as animal feed, but most of the rest have been wasted. 随着技术的发展进步,开发了利用秸秆生产木糖、木糖醇的技术,为秸秆的重新利用开辟了一条新途径。 With the development of technology, the development of the use of straw to produce xylose, xylitol technology, has opened up a new way for the re-use of straw. 但是在利用秸秆生产木糖、木糖醇的技术中还存在着一些缺点,秸秆经过酸水解、过滤后的液态部分用于生产木糖,但是过滤后的木糖渣则没有被充分地利用,有部分被用于制备乙醇,但并没有实现秸秆利用的最大化,还是存在一定资源上的浪费。 However, the use of straw in the production of xylose, xylitol art there are some shortcomings, Straw acid hydrolysis liquid portion after the filtration for the production of xylose, xylose residue after filtration but is not sufficiently utilized, part is used for production of ethanol, but did not maximize the use of straw, there is still some waste of resources.

丙酮和丁醇广泛用于有机合成塑料、树脂、油漆、医药和国防工业。 Of acetone and butanol, widely used in organic synthetic plastics, resins, paints, pharmaceuticals and defense industries. 丙酮可作为油漆、电影胶片、塑料、石油精炼脱蜡、植物油萃取、制药的溶剂和有机合成化学工业的原料。 Acetone as the starting material can be a paint, film, plastic, dewaxing petroleum refining, vegetable oil extraction, solvent and the pharmaceutical industry, synthetic organic chemistry. 丁醇除可用作溶剂外还是一种潜在的大综动力燃料, 它的燃烧值和汽油相当,是汽车用油的替代品。 In addition to the alcohol used as the solvent or a potential large mechanized propellant, and its combustion value of gasoline equivalent substitute automotive oil. 现有的丙酮、丁醇生产工艺有两种方法, 一种是石化合成法,另一种是生物发酵法。 Existing acetone, butanol production process, there are two methods, one is the petrochemical synthesis, other biological fermentation. 石化合成丙酮、丁醇的方法原料采用的是日益枯竭的石油资源,随着石油的减少石化合成法也将告终。 Petrochemical synthesis acetone, butanol feedstock used is becoming depleted oil resources, reduction with petroleum and petrochemical synthesis will be ended. 生物发酵法生采用的原料为玉米,不但成本太高,同时也给饲料行业带来了竞争压力。 Biological fermentation raw materials used for the corn, not only too expensive, but also bring competitive pressures to the feed industry. 利用玉米生产丙酮、丁醇是直接把玉米筛选、破碎、提胚、糊化、连消蒸煮等前期处理,再发酵、蒸馏生产丙酮和丁醇。 Production from corn acetone, butanol directly corn screening, crushing, pre-processing Germ, pasting, even the consumer cooking, etc., and then the fermentation, the production of acetone and butanol by distillation. 这样利用玉米发酵生产丙 Thus the use of corn fermentation prop

酮和丁醇的方法的成本较高。 Butanol, ketones and high cost method. 发明内容 SUMMARY

本发明的目的是提供一种利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 实现了资源利用最大化。 Object of the present invention is to provide a straw producing xylose cogeneration acetone, butanol and ethanol, to achieve the maximum utilization of resources.

为实现上述目的,本发明采用以下技术方案: 一种利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法,秸秆粉碎用热水浸泡后加入稀酸进行水解,过滤分为木糖水解液和木糖渣,木糖水解液经蒸发、脱色、过滤、离子交换、浓縮和 To achieve the above object, the present invention employs the following technical solutions: A straw producing xylose cogeneration acetone, butanol and ethanol, soaked in hot water after the straw chopping dilute acid is added for hydrolysis, and the hydrolyzate was filtered into xylose xylose residue, xylose evaporated hydrolyzate, bleaching, filtration, ion-exchange, concentration, and

结晶生产木糖,向木糖渣中加入35〜6(TC的热水,木糖渣与热水的重量比为1: 3〜6,加入碱性物质调PH值为4〜7,再分批加入纤维素酶,每克木糖渣加入200〜600ncu纤维素酶,然后在40〜55"C下连续酶解60〜120小时;酶解完毕膜分离过滤分为分解液和滤渣,滤渣返回继续酶解;向分离液中加入氮源类物质,调整分离液中糖的质量百分比浓度为4〜6%,然后在120〜15(TC下进行蒸煮杀菌30〜45分钟,冷却至35〜4rC后送入发酵罐,接种菌种,在34〜39°C 下厌氧发酵36〜72小时;发酵液进行精馏分出丙酮、丁醇和乙醇。 所述秸秆粉碎后用60〜9(TC热水浸泡1〜3小时。 Production crystalline xylose, xylose was added to the slag 35~6 (TC hot water, the hot water Xylose Residue weight ratio of 1: 3 ~ 6, a basic substance is added to adjust PH value 4~7, subdivision batch addition of cellulase per gram cellulose 200~600ncu xylose residue added, followed by continuous hydrolysis at 40~55 "C 60~120 hours; complete hydrolysis decomposition liquid into the membrane separation filter and residues, residues return continue hydrolysis; nitrogen species added to the separated liquid, adjusting the mass concentration of sugar in the separating liquid is 4 ~ 6%, and then subjected to retort sterilization (under 120~15 TC 30~45 minutes, cooled to 35~4rC into the fermenter, inoculated with bacteria, anaerobic fermentation at 34~39 ° C 36~72 hours; fermentation broth separated distillation of acetone, butanol and ethanol after the straw chopping with 60~9 (TC heat. water soak 1 ~ 3 hours.

所述稀酸为质量百分比浓度为0. 3〜6%的稀硫酸或稀盐酸,稀酸的加入量为秸秆重量的5〜8倍。 The dilute acid is a mass concentration of 0. 3 ~ 6% dilute sulfuric acid or dilute hydrochloric acid, dilute acid is added in an amount of 5 ~ 8 times the weight of the straw.

所述水解时温度为100〜130。 When the hydrolysis temperature is 100-130. C,水解时压力为0. 1〜0. 3MPa,水解时间为3〜 8小时。 C, de hydrolysis pressure is 0. 1~0. 3MPa, hydrolysis time 3 ~ 8 hours.

所述菌种为丙酮丁醇梭菌、丙酮丁酸杆菌、糖丁酸梭菌或巴氏芽孢梭菌。 The strain is a Clostridium acetobutylicum, Bacillus butyric acetone, Clostridium saccharobutylicum or Clostridium pasteurianum.

所述氮源类物质为硫酸铵、硫酸氢铵、氯化铵、豆粕、棉籽粕、花生粕、 玉米或菜籽粕,氮源类物质的加入量为分解液重量的1〜5°/0。 The nitrogen source substances as ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, soybean meal, cottonseed meal, peanut meal, corn meal or added amount of the nitrogen source substances is decomposed by weight solution of 1~5 ° / 0 .

所述碱性物质为氢氧化钙、碳酸钙、碳酸钠、氢氧化钠、碳酸钾或氢氧化钾。 Said alkaline substance is calcium hydroxide, calcium carbonate, sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.

所述精馏工序前先进行粗馏。 First the crude distillation before the distillation step.

所述酶解时使用酶解发生器。 Enzymatic hydrolysis using said generator.

所述秸秆为玉米秸秆、小麦秸秆、高粱秸秆、向日葵秸秆、稻草、玉米芯、 甘蔗渣、花生壳或棉籽壳中的一种或多种。 The straw as corn stover, wheat straw, sorghum straw, sunflower stalks, one or more of straw, corn cobs, sugar cane bagasse, peanut hulls or cotton seed hulls in.

本发明所使用的原料是秸秆类物质,秸秆类物质主要是由半纤维素、纤维素和木质素三种成分组成,半纤维素物质主要组成成分是木聚糖,半纤维素物质不易被纤维素酶水解,而纤维素主要组成成分是己聚糖,纤维素又不易被稀酸水解。 Material used in the present invention is a substance straw, straw material is mainly composed of hemicellulose, cellulose and lignin three components, the main component of the hemicellulose is xylan materials, hemicellulose fiber material is not easily luciferase hydrolysis, the main component of the cellulose polysaccharide is hexyl, dilute acid hydrolysis of cellulose without easily. 为了充分地利用纤维素秸秆类物质,本发明先用热水浸泡秸秆,去掉原料中的果胶和单宁等妨碍水解的物质,然后利用稀酸使半纤维素水解转化为戊糖,戊糖是生产木糖、木糖醇或糠醛的很好的原料;而在同等条件下半纤维素酸水解速度是纤维素酸水解速度的100倍,不易被酸水解的纤维素则用少量的纤维素酶水解生成单糖一葡萄糖,这样不但降低了纤维素酶的用量,也大大提高了纤维素的利用率,葡萄糖中加入菌种发酵获得丙酮、丁醇和乙醇的混合物,精馏将混合物分离。 In order to fully utilize the cellulose-based material straw, soaked with hot water according to the present invention, the straw, and remove the pectin starting material tannin substances hinder hydrolysis, then hydrolyzed using dilute acid hemicellulose into pentoses, pentose production is xylose, xylitol or furfural good material; and under the same conditions of acid hydrolysis of hemicellulose 100 times faster than the speed of acid hydrolysis of cellulose, the cellulose is not easily the acid hydrolysis of cellulose with a small amount of enzymatic hydrolysis of a monosaccharide glucose, not only reduces the amount of such cellulase, but also greatly improves the utilization of cellulose, glucose was added to the mixture obtained by fermentation of strains of acetone, butanol and ethanol, the distillation mixture. 本发明利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法实现了纤维素秸秆类物质利用的最大化,不但充分地利用秸杆资源,实现了变废为宝,提高了产品的附加值,实现了其经济价值,同时也为丙酮、丁醇的生产开辟了新的原料资源和方法,为企业和社会带来了更多的经济效益和社会效益。 The present invention utilizes straw to produce xylose cogeneration acetone, butanol and ethanol to achieve maximum utilization of cellulosic materials straw, straw only full use of resources to achieve turning waste, increase the added value of products, It achieved its economic value, but also opened up a new raw material resources and methods as acetone, butanol production, business and society to bring more economic and social benefits.

具体实施方式 detailed description

实施例i:将玉米芯粉碎后用9crc热水浸泡i小时,然后加入质量百分比 Example i: After soaking 9crc pulverized corncob hot i h, followed by addition of mass percent

浓度为0. 3%的稀硫酸进行水解,稀硫酸加入量为玉米芯重量的8倍,水解时温度为IO(TC,水解时压力为0. lMPa,水解时间为8小时,过滤分为木糖水解液和木糖渣,木糖水解液经蒸发、脱色、过滤、离子交换、浓縮和结晶生产木糖; 向木糖渣中加入35'C的热水,木糖渣与热水的重量比为1: 6,加入氢氧化钙调PH值为4,再分批加入纤维素酶,每克木糖渣加入200ncu纤维素酶,然后送入酶解发生器在4(TC下连续酶解120小时;酶解完毕膜分离过滤分为分解液和滤渣,滤渣返回继续酶解;向分离液中加入硫酸铵,硫酸铵的加入量为分解液重量的1%,浓縮调整分离液中糖的质量百分比浓度为6%,然后在120。C下进行蒸煮杀菌45分钟,冷却至35t:后送入发酵罐,接种丙酮丁醇梭菌菌种,在34°C 下厌氧发酵72小时;发酵液先进行粗馏再进行精馏分出丙酮、丁醇和乙醇,丙酮、丁醇、 At a concentration of 0.3% dilute sulfuric acid hydrolysis, dilute sulfuric acid is added in an amount of 8 times the weight of the core of the corn, the hydrolysis temperature is IO (TC, 0. lMPa pressure hydrolysis, the hydrolysis time is 8 hours, filtered into wood xylose residue hydrolyzate and sugar, xylose evaporated hydrolyzate, bleaching, filtration, ion-exchange, concentration and crystallization of xylose production; 35'C hot water was added to the residue xylose, xylose slag and hot water a weight ratio of 1: 6, of calcium hydroxide was added to adjust PH value of 4, was added portionwise cellulase per g of xylose residue was added 200ncu cellulase enzyme then fed generator (continuous enzyme under the TC 4 Solutions of 120 hours; complete hydrolysis decomposition liquid into the membrane separation and filtration residue, returns to continue hydrolysis residues; ammonium sulfate was added to the separated liquid, the amount of ammonium sulfate is added to the decomposition solution of 1% by weight, adjustment of the separation liquid concentrate sugar mass concentration of 6%, followed by retort sterilization at at 120.C for 45 minutes and cooled to 35t: rear into the fermenter, inoculated with C. acetobutylicum strains, anaerobic fermentation at 34 ° C 72 hours ; broth then evaporated to rough-distillation separation of acetone, butanol and ethanol, acetone, butanol, 醇的质量比为27: 62.2: 10.1。 Alcohol mass ratio was 27: 62.2: 10.1.

实施例2:将玉米秸秆、小麦秸秆和高粱秸秆混合粉碎后用8CTC热水浸泡2 小时,然后加入质量百分比浓度为3%的稀盐酸进行水解,稀盐酸加入量为玉米秸秆、小麦秸秆和高粱秸秆总重量的7倍,水解时温度为120°C,水解时压力为0.2MPa,水解时间为5小时,过滤分为木糖水解液和木糖渣,木糖水解液经蒸发、脱色、过滤、离子交换、浓縮和结晶生产木糖;向木糖渣中加入45。 Example 2: The corn stover, wheat straw and sorghum straw after mixing pulverized 8CTC hot water soak 2 hours, and then the mass concentration of 3% dilute hydrochloric acid hydrolysis, dilute hydrochloric acid was added in an amount of corn stover, wheat straw and sorghum 7 times the total weight of the straw, when the hydrolysis temperature is 120 ° C, pressure was 0.2MPa hydrolysis, the hydrolysis time was 5 hours, filtered into xylose and xylose residue hydrolyzate, hydrolyzate was evaporated xylose, bleaching, filtration , ion exchange, concentration and crystallization of xylose production; 45 was added to the xylose residue. C的热水,木糖渣与热水的重量比为1: 5.5,加入碳酸钙调PH值为5,再分批加入纤维素酶,每克木糖渣加入400ncu纤维素酶,然后送入酶解发生器在5CTC下连续酶解90小时;酶解完毕膜分离过滤分为分解液和滤渣,滤渣返回继续酶解;向分离液中加入硫酸氢铵,硫酸氢铵的加入量为分解液重量的3%,浓縮调整分离液中糖的质量百分比浓度为5%,然后在14(TC下进行蒸煮杀菌40分钟,冷却至38'C后送入发酵罐,接种糖丁酸梭菌菌种,在37。C下厌氧发酵50小时;发酵液先进行粗馏再进行精馏分出丙酮、丁醇和乙醇,丙酮、丁醇、乙醇的质量比为28: 61: 10.1。 C hot water, the weight ratio of the hot slag and xylose was 1: 5.5, calcium carbonate was added to adjust PH value of 5, then added portionwise cellulase per gram cellulose 400ncu Xylose Residue added, and then into in continuous enzymatic hydrolysis generator 5CTC 90 hours; complete hydrolysis decomposition liquid into the membrane separation and filtration residue, returns to continue hydrolysis residues; ammonium bisulfate was added to the separated liquid was added an amount of ammonium bisulfate solution is decomposed 3% by weight of the concentrated mass percentage to adjust the concentration of sugar in the separating liquid is 5%, then subjected to retort sterilization at (the TC 14 40 minutes into the fermenter after cooling to 38'C, inoculated bacterium Clostridium saccharobutylicum species, anaerobic fermentation 50 hours at 37.C; broth then evaporated to rough-distillation separation of acetone, butanol and ethanol, acetone, butanol, ethanol mass ratio of 28: 61: 10.1.

实施例3:将花生壳和棉籽壳混合粉碎后用6(TC热水浸泡3小时,然后加入质量百分比浓度为6%的稀硫酸进行水解,稀硫酸加入量为花生壳和棉籽壳总重量的5倍,水解时温度为13(TC,水解时压力为0.3MPa,水解时间为3小时, 过滤分为木糖水解液和木糖渣,木糖水解液经蒸发、脱色、过滤、离子交换、 浓縮和结晶生产木糖;向木糖渣中加入6(TC的热水,木糖渣与热水的重量比为1: 3,加入氢氧化钠调PH值为7,再分批加入纤维素酶,每克木糖渣加入500ncu 纤维素酶,然后送入酶解发生器在55X:下连续酶解60小时;酶解完毕膜分离过 Example 3: A mixed cotton seed hulls, and peanut shell pulverized by hydrolysis (TC soaked in hot water for 3 hours and then added to the mass concentration of 6% dilute sulfuric acid 6, dilute sulfuric acid is added in an amount of peanut hulls and cotton hulls total weight 5 times, the hydrolysis temperature 13 (TC, pressure was 0.3MPa hydrolysis, hydrolysis for 3 hours, filtered into xylose and xylose residue hydrolyzate, hydrolyzate was evaporated xylose, bleaching, filtration, ion exchange, concentration and crystallization of xylose production; xylose was added to the slag 6 (TC hot water, the weight ratio of xylose slag and water is 1: 3, was added sodium hydroxide PH value of 7, then added portionwise fibers luciferase, was added per g of xylose residue 500ncu cellulase enzyme then fed generator 55X: continuous hydrolysis 60 hours; complete hydrolysis over a membrane separation

滤分为分解液和滤渣,滤渣返回继续酶解;向分离液中加入玉米,玉米的加入量为分解液重量的2%,加水调整分离液中糖的质量百分比浓度为4%,然后在150 。 Decomposition liquid into filtrate and filter cake, the filter cake continues to return to enzymatic hydrolysis; corn added to the separated liquid in an amount of 2% corn by weight of the decomposition solution, adding water to adjust the mass concentration of sugar in the separating liquid is 4%, then 150 . C下进行蒸煮杀菌30分钟,冷却至4rc后送入发酵罐,接种丙酮丁醇梭菌菌种, 在39。 C retort sterilization carried out for 30 minutes and cooled to 4rc into the fermenter, inoculated with C. acetobutylicum strains, at 39. C下厌氧发酵36小时;发酵液先进行粗馏再进行精馏分出丙酮、丁醇和乙醇,丙酮、丁醇、乙醇的质量比为27.4: 62: 10.1。 C under anaerobic fermentation 36 hours; the crude fermentation broth to be distilled further distillation separation of acetone, butanol and ethanol, acetone, butanol, ethanol mass ratio of 27.4: 62: 10.1.

实施例4:将甘蔗渣和稻草混合粉碎后用7(TC热水浸泡2. 5小时,然后加入质量百分比浓度为5%的稀盐酸进行水解,稀盐酸加入量为甘蔗渣和稻草总重量的6倍,水解时温度为11(TC,水解时压力为0. 15MPa,水解时间为6小时, 过滤分为木糖水解液和木糖渣,木糖水解液经蒸发、脱色、过滤、离子交换、 浓縮和结晶生产木糖;向木糖渣中加入5(TC的热水,木糖渣与热水的重量比为1: 4,加入碳酸钠调PH值为6,再分批加入纤维素酶,每克木糖渣加入600ncu 纤维素酶,然后送入酶解发生器在45-C下连续酶解100小时;酶解完毕膜分离过滤分为分解液和滤渣,滤渣返回继续酶解;向分离液中加入豆粕,豆粕的加入量为分解液重量的5%,调整分离液中糖的质量百分比浓度为5%,然后在130 。C下进行蒸煮杀菌35分钟,冷却至4(TC后送入发酵罐,接种巴氏芽孢梭菌菌种, 在38。C下厌氧 Example 4: The bagasse and straw mixed with pulverized 7 (TC 2.5 hours water soak and then the mass concentration of 5% dilute hydrochloric acid hydrolysis, dilute hydrochloric acid was added in an amount of bagasse and straw on the total weight of 6 times, the hydrolysis temperature 11 (TC, pressure hydrolysis is 0. 15MPa, the hydrolysis time was 6 hours, filtered into xylose and xylose residue hydrolyzate, hydrolyzate was evaporated xylose, bleaching, filtration, ion exchange , and concentrated to produce a crystalline xylose; xylose was added to the slag 5 (TC hot water, the weight ratio of the hot slag and xylose was 1: 4, sodium carbonate was added to adjust PH value of 6, then added portionwise fibers luciferase, was added per g of xylose residue 600ncu cellulase, and then continuously fed to the generator enzymatic hydrolysis at 45-C 100 hours; complete hydrolysis decomposition liquid into the membrane separation and filtration residue, returns to continue hydrolysis residues ; amount added soybean meal, soybean meal is an exploded separated liquid to 5% by weight of the solution, adjusting the separated liquid sugar mass concentration of 5%, followed by retort sterilization at 130 .C 35 min, cooled to 4 (TC into the fermenter, inoculated with Clostridium pasteurianum species, anaerobic at 38.C 发酵60小时;发酵液先进行粗馏再进行精馏分出丙酮、丁醇和乙醇,丙酮、丁醇、乙醇的质量比为28.2: 61: 10。 60 hours of fermentation; fermentation was then evaporated to a crude distillation for the separation of acetone, butanol and ethanol, acetone, butanol, ethanol mass ratio of 28.2: 61: 10.

以上以具体实施例来说明本发明的技术方案,但并非是对本发明的技术方案的限制,本领域技术人员应该理解,依然可以对发明进行修改或等同替换, 而不脱离本发明的精神和范围的任何修改或局部替换,其均应涵盖在本发明的保护范围之中。 Above to the specific embodiments described aspect of the present invention, but not to limit the technical solution of the present invention, those skilled in the art will appreciate, modifications may be made to the invention, or equivalent replacements without departing from the spirit and scope of the invention any modifications or partial replacement, which should fall in the protection scope of the present invention.

Claims (10)

  1. 1、一种利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法,秸秆粉碎用热水浸泡后加入稀酸进行水解,过滤分为木糖水解液和木糖渣,木糖水解液经蒸发、脱色、过滤、离子交换、浓缩和结晶生产木糖,其特征在于:向木糖渣中加入35~60℃的热水,木糖渣与热水的重量比为1∶3~6,加入碱性物质调PH值为4~7,再分批加入纤维素酶,每克木糖渣加入200~600ncu纤维素酶,然后在40~55℃下连续酶解60~120小时;酶解完毕膜分离过滤分为分解液和滤渣,滤渣返回继续酶解;向分离液中加入氮源类物质,调整分离液中糖的质量百分比浓度为4~6%,然后在120~150℃下进行蒸煮杀菌30~45分钟,冷却至35~41℃后送入发酵罐,接种菌种,在34~39℃下厌氧发酵36~72小时;发酵液进行精馏分出丙酮、丁醇和乙醇。 1, the production of xylose-utilizing straw cogeneration acetone, butanol and ethanol, soaked in hot water after the straw chopping dilute acid is added for hydrolysis, the hydrolyzate was filtered into xylose and xylose residue, xylose hydrolyzate was evaporated , bleaching, filtration, ion-exchange, concentration and crystallization of xylose production, characterized in that: hot water 35 ~ 60 ℃ xylose was added to the residue, the weight ratio of water to slag and xylose 1:3 to 6, was added basic substance adjust PH value of 4 to 7, and then added portionwise cellulase enzyme per gram of xylose residue was added 200 ~ 600ncu cellulase enzyme and then continuously at 40 ~ 55 ℃ 60 ~ 120 hours; complete hydrolysis separation into membrane filtration residue and the decomposing fluid, to return to continue digestion residues; nitrogen species added to the separated liquid, adjusting the mass concentration of sugar in the separating liquid is 4 to 6%, and then subjected to retort at 120 ~ 150 ℃ sterilization for 30 to 45 minutes and, after cooling to 35 ~ 41 ℃ into the fermenter, inoculated with bacteria, 34 ~ 39 ℃ fermentation in 36 to 72 hours under anaerobic; separated fermentation broth distillation of acetone, butanol and ethanol.
  2. 2、 如权利要求1所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 其特征在于:所述秸秆粉碎后用60〜90'C热水浸泡1〜3小时。 2, the use of straw as claimed in production of xylose in claim 1 cogeneration acetone, butanol and ethanol, characterized in that: after the straw chopping hot water soaking 60~90'C 1~3 hours.
  3. 3、 如权利要求2所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 其特征在于:所述稀酸为质量百分比浓度为0.3〜6%的稀硫酸或稀盐酸,稀酸的加入量为秸秆重量的5〜8倍。 3, the use of straw as claimed in xylose production claim 2 cogeneration acetone, butanol and ethanol, characterized in that: said dilute acid is a mass concentration of 0.3~6% dilute sulfuric acid or dilute hydrochloric acid, dilute added in an amount of 5 ~ 8 times the weight of the straw.
  4. 4、 如权利要求3所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 其特征在于:所述水解时温度为100〜130°C,水解时压力为0. 1〜0. 3MPa,水解时间为3〜8小时。 4, the use of straw as claimed in xylose production claim 3 cogeneration acetone, butanol and ethanol, wherein: when the hydrolysis temperature is 100~130 ° C, a pressure of 0.5 1~0 hydrolysis. 3MPa, hydrolysis time is 3~8 hours.
  5. 5、 如权利要求1至4任一项所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法,其特征在于:所述菌种为丙酮丁醇梭菌、丙酮丁酸杆菌、糖丁酸梭菌或巴氏芽孢梭菌。 5, the use of straw as claimed in xylose production cogeneration acetone, butanol and ethanol according to any one of claims 4, wherein: said strain is Clostridium acetobutylicum, Bacillus acetone butyric acid, sugar Clostridium butyricum or Clostridium Pap.
  6. 6、 如权利要求5所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 其特征在于:所述氮源类物质为硫酸铵、硫酸氢铵、氯化铵、豆粕、棉籽粕、 花生粕、玉米或菜籽粕,氮源类物质的加入量为分解液重量的1〜5%。 6, the use of straw as claimed in producing xylose according to claim 5 cogeneration of acetone, butanol and ethanol, characterized in that: the nitrogen source substances as ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, soybean meal, cottonseed meal , peanut meal, corn meal or added amount of the nitrogen species is ~ 5% by weight of the decomposing fluid.
  7. 7、 如权利要求6所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 其特征在于:所述碱性物质为氢氧化钙、碳酸钙、碳酸钠、氢氧化钠、碳酸钾或氢氧化钾。 7, the use of straw as claimed in production of xylose claim 6 cogeneration acetone, butanol and ethanol, characterized in that: said alkaline substance is calcium hydroxide, calcium carbonate, sodium carbonate, sodium hydroxide, potassium or potassium hydroxide.
  8. 8、 如权利要求7所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法,其特征在于:所述精馏工序前先进行粗馏。 8, the use of straw as claimed in xylose production cogeneration claim 7 acetone, butanol and ethanol, characterized in that: prior to said first distillation crude distillation step.
  9. 9、 如权利要求8所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法, 其特征在于:所述酶解时使用酶解发生器。 9, the use of straw as claimed in xylose production claim 8 cogeneration acetone, butanol and ethanol, characterized in that: said generator using enzymatic hydrolysis.
  10. 10、 如权利要求9所述的利用秸秆生产木糖联产丙酮、丁醇和乙醇的方法,其特征在于:所述秸秆为玉米秸秆、小麦秸秆、高粱秸秆、向日葵秸秆、稻草、 玉米芯、甘蔗渣、花生壳或棉籽壳中的一种或多种。 10, the use of straw as claimed in xylose production cogeneration claim 9 acetone, butanol and ethanol, characterized in that: the straw as corn stover, wheat straw, sorghum straw, sunflower stalks, straw, corn cobs, sugar cane one or more slag, peanut hulls or cotton seed hulls in.
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CN101597625B (en) 2009-07-23 2012-08-29 南京林业大学 Method for preparing fuel ethanol by low-energy consumption wood raw material
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CN101942382B (en) 2009-07-06 2014-01-15 中国科学院过程工程研究所 Device and method for producing butanol by fermenting straw dilute acid hydrolyzed pentaglucose
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US9309577B2 (en) 2011-01-28 2016-04-12 Institute Of Process Engineering, Chinese Academy Of Sciences Process for producing bio-based product from straw hemicellulose and fully utilizing the components thereof
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CN102876736A (en) * 2012-07-25 2013-01-16 中国科学院成都生物研究所 Method for producing acetone, ethanol and butanol by taking straw as raw material
CN103320548A (en) * 2013-06-24 2013-09-25 稼禾生物股份有限公司 Method for preparing xylooligosaccharide and cellulose by using crop straws
CN103757072A (en) * 2014-01-10 2014-04-30 杭州师范大学 Method for preparing xylan and xylo-oligosaccharide from rice straw
CN104178528A (en) * 2014-09-18 2014-12-03 苏州新协力环保科技有限公司 Method for making alcohol from straws
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