CN108060190A - A kind of method using edible fungus bran production monose - Google Patents
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Abstract
本发明涉及食用菌菌糠利用开发技术领域,进一步涉及一种利用食用菌菌糠生产单糖的方法。克服现有技术存在的半纤维素含量低,木糖和葡萄糖难以分离,难以进行工业化生产的问题。本发明采用的步骤为:步骤一、酸水解:食用菌菌糠,风干粉碎,按固液比1:10~20加入质量浓度为1‑5%的稀酸溶液,100‑120℃处理30‑120min,过滤后得滤液和滤渣,滤液中木糖制备食品级木糖;步骤二、碱水解:滤渣按1:10~20固液比加入质量浓度为1‑5%的碱溶液,40‑60℃处理60‑120min后,用酸中和至中性,测定纤维素含量;步骤三、酶水解:按纤维素含量加入纤维素酶,纤维素用量为10‑20FPU/g纤维素,50℃、180rpm条件下酶解48‑72小时得酶解液,过滤得葡萄糖溶液和木质素。
The invention relates to the technical field of utilization and development of edible fungus chaff, and further relates to a method for producing monosaccharides by using edible fungus chaff. The invention overcomes the problems of low hemicellulose content, difficult separation of xylose and glucose and difficulty in industrialized production existing in the prior art. The steps adopted in the present invention are: step 1, acid hydrolysis: edible mushroom chaff, air-dried and pulverized, adding a dilute acid solution with a mass concentration of 1-5% according to a solid-to-liquid ratio of 1:10-20, and treating at 100-120°C for 30- 120min, get the filtrate and filter residue after filtration, and prepare food-grade xylose from xylose in the filtrate; Step 2, alkali hydrolysis: add the alkali solution with a mass concentration of 1-5% to the filter residue according to the solid-liquid ratio of 1:10-20, 40-60 After treating at ℃ for 60-120min, neutralize to neutral with acid, and measure the cellulose content; step 3, enzymatic hydrolysis: add cellulase according to the cellulose content, the amount of cellulose is 10-20FPU/g cellulose, 50℃, Under the condition of 180rpm, enzymolyze for 48-72 hours to obtain the enzymolyzate, and filter to obtain the glucose solution and lignin.
Description
技术领域:Technical field:
本发明涉及食用菌菌糠利用开发技术领域,进一步涉及一种利用食用菌菌糠 生产单糖的方法。The invention relates to the technical field of utilization and development of edible fungus chaff, and further relates to a method for producing monosaccharides from edible fungus chaff.
技术背景:technical background:
食用菌菌糠是以玉米芯、木屑、棉籽壳、稻草、农作物秸秆或工业废料(造 纸厂废液、醋糟、酒糟等)作为主要原料代料栽培食用菌后废弃的固体培养基。 我国目前食用菌总产量已达400~500万吨,产值300亿元以上。由此产生的菌糠 数量也非常巨大,年产量达700~900万吨。目前对菌糠的利用方法总体利用率低, 附加值不高,既造成了大量的资源浪费,又对环境造成了污染。随着食用菌产业 的快速发展,如何更加高效地处理食用废弃菌糠成为食用菌行业亟待解决的重要 课题之一。Edible fungus bran is a solid medium that is discarded after cultivating edible fungi with corncobs, sawdust, cottonseed hulls, rice straw, crop straw or industrial waste (paper mill waste, vinegar grains, distiller's grains, etc.) as the main raw material. At present, the total output of edible fungi in my country has reached 4-5 million tons, with an output value of more than 30 billion yuan. The resulting fungus chaff quantity is also very huge, with an annual output of 7 to 9 million tons. At present, the overall utilization rate of the utilization method of fungus chaff is low, and the added value is not high, which has not only caused a large amount of waste of resources, but also polluted the environment. With the rapid development of the edible fungus industry, how to deal with edible waste mushroom chaff more efficiently has become one of the important issues to be solved urgently in the edible fungus industry.
菌糠经过食用菌生长利用之后,其中仍富含大量的纤维素、半纤维素和木质 素,根据基质的不同,菌糠中粗纤维含量约占10‐30%,粗蛋白含量6‐13%[食药 用菌,2015,23(2):72‐75]。对这一部分可再生资源的利用研究,目前主要集 中在肥料和饲料方面。如直接以菌糠作为吸附载体接种微生物肥料,如专利 201510748273.9,这种方法只是利用了菌糠结构的疏松性作为载体进行吸附,其 本身的营养成分并没有得到利用,利用率和附加值都不高;或者对菌糠进行一定 的堆肥发酵处理,使菌糠中的大分子物质转化成小分子物质后,再接种微生物菌 剂,制备微生物肥料,如专利CN 105777231A,这类方法中菌糠经过自然发酵腐 熟,大分子物质得到了降解和利用,提高了利用率,但仍然存在自然发酵周期长,占地面积大的缺点。菌糠中大量的纤维素和半纤维素水解后生成的葡萄糖和木糖 都是可利用的单糖,其中木糖可以进一步转化成木糖醇、糠醛等工业产品;葡萄 糖可以作为发酵碳源生产各种发酵产品,把菌糠中的纤维素和半纤维素转化成单 糖,再进行进一步的开发利用,是提高菌糠附加值的一种行之有效的转化方式。 但是由于天然木质纤维素结构中的纤维素和半纤维素被包裹在木质素内部,必须 经过一定的预处理才能得到应用。专利200910086798.5采用碱水解脱除菌糠中 的木质素,之后再用酶水解的方法使纤维素和半纤维素转化为葡萄糖和木糖,提 高了菌糠的整体利用度,但碱处理在脱除木质素的同时,会水解半纤维素,使半 纤维素损失,同时残留的半纤维素在酶解时产生的木糖和纤维素水解产生的葡萄 糖混合在一起,两种单糖的性质接近,常规分离技术很难将其分开。因此再利用 受限,工业化生产很难实现。After the mushroom chaff is grown and utilized by edible fungi, it is still rich in cellulose, hemicellulose and lignin. According to different substrates, the crude fiber content in the fungus chaff accounts for about 10-30%, and the crude protein content accounts for 6-13%. [Edible and Medicinal Fungi, 2015, 23(2): 72‐75]. The research on the utilization of this part of renewable resources is currently mainly focused on fertilizer and feed. For example, microbial fertilizers are directly inoculated with fungus chaff as an adsorption carrier, such as patent 201510748273.9. This method only uses the porosity of the fungus chaff structure as a carrier for adsorption, and its own nutrients are not utilized, and the utilization rate and added value are not good. or carry out a certain composting and fermentation treatment on the chaff, so that the macromolecular substances in the chaff are converted into small molecular substances, and then inoculated with microbial agents to prepare microbial fertilizers, such as patent CN 105777231A. In this method, the chaff is passed through Natural fermentation decomposes, macromolecular substances are degraded and utilized, and the utilization rate is improved, but there are still disadvantages of long natural fermentation period and large floor area. Glucose and xylose produced by the hydrolysis of a large amount of cellulose and hemicellulose in fungal chaff are all available monosaccharides, among which xylose can be further converted into industrial products such as xylitol and furfural; glucose can be used as a carbon source for fermentation For various fermentation products, converting the cellulose and hemicellulose in the fungus chaff into monosaccharides, and then further development and utilization, is an effective conversion method to increase the added value of the fungus chaff. However, since the cellulose and hemicellulose in the natural lignocellulose structure are wrapped inside the lignin, it must be pretreated before it can be used. Patent 200910086798.5 uses alkaline hydrolysis to remove the lignin in the chaff, and then converts cellulose and hemicellulose into glucose and xylose by enzymatic hydrolysis, which improves the overall utilization of the chaff, but the alkali treatment is not effective in removing At the same time as lignin, hemicellulose will be hydrolyzed, causing the loss of hemicellulose. At the same time, the xylose produced by the enzymatic hydrolysis of the remaining hemicellulose and the glucose produced by cellulose hydrolysis are mixed together. The properties of the two monosaccharides are close. It is difficult to separate them by conventional separation techniques. Therefore, reuse is limited, and industrialized production is difficult to realize.
发明内容:Invention content:
本发明要提供一种利用食用菌菌糠生产单糖的方法,以克服现有技术存在的 半纤维素含量低,木糖和葡萄糖难以分离,难以进行工业化生产的问题。The present invention will provide a kind of method that utilizes edible mushroom chaff to produce monosaccharide, to overcome the low hemicellulose content existing in the prior art, xylose and glucose are difficult to separate, be difficult to carry out the problem of industrialized production.
为了达到本发明的目的,本发明提供的技术解决方案是:一种利用食用菌菌 糠生产单糖的方法,包括下述步骤:In order to achieve the purpose of the present invention, the technical solution provided by the present invention is: a kind of method that utilizes edible fungus chaff to produce monosaccharide, comprises the steps:
步骤一、酸水解:食用菌菌糠,风干粉碎,按固液比1:10~20加入质量浓 度为1-5%的稀酸溶液,100-120℃处理30-120min,过滤后得滤液和滤渣,滤液 中木糖制备食品级木糖;Step 1. Acid hydrolysis: Edible fungus chaff, air-dried and crushed, add a dilute acid solution with a mass concentration of 1-5% according to the solid-to-liquid ratio of 1:10-20, treat at 100-120°C for 30-120min, and obtain the filtrate and Filter residue, xylose in the filtrate prepares food-grade xylose;
步骤二、碱水解:滤渣按1:10~20固液比加入质量浓度为1-5%的碱溶液, 40-60℃处理60-120min后,用酸中和至中性,测定纤维素含量;Step 2. Alkali hydrolysis: add the alkali solution with a mass concentration of 1-5% to the filter residue at a solid-to-liquid ratio of 1:10-20, treat at 40-60°C for 60-120 minutes, neutralize with acid to neutral, and measure the cellulose content ;
步骤三、酶水解:按纤维素含量加入纤维素酶,纤维素用量为10-20FPU/g 纤维素,50℃、180rpm条件下酶解48-72小时得酶解液,过滤得葡萄糖溶液和 木质素。Step 3, enzymatic hydrolysis: add cellulase according to the cellulose content, the amount of cellulose is 10-20 FPU/g cellulose, enzymatic hydrolysis at 50°C and 180rpm for 48-72 hours to obtain an enzymatic hydrolysis solution, and filter to obtain glucose solution and wood white.
上述步骤一中稀酸溶液是硫酸或盐酸,上述滤液中木糖经过中和、浓缩、脱 色、离子交换和结晶制备食品级木糖。The dilute acid solution in the above step 1 is sulfuric acid or hydrochloric acid, and the xylose in the above-mentioned filtrate prepares food-grade xylose through neutralization, concentration, decolorization, ion exchange and crystallization.
上述步骤二中碱性溶液是氢氧化钠或氢氧化钙溶液。The alkaline solution in the above step 2 is sodium hydroxide or calcium hydroxide solution.
与现有技术相比,本发明的优点是:Compared with prior art, the advantage of the present invention is:
1、可以实现菌糠的全循环使用,实现零排放:本专利采用酸碱耦合技术对 菌糠进行水解处理,利用两步处理法将菌糠中的半纤维素和纤维素水解产生的木 糖和葡萄糖分步收集,分步利用。第一步选择合适的稀酸水解条件使菌糠里的半 纤维素得到最大程度的水解,避免了半纤维素在后续碱处理过程中的损失,从而 使木糖的收率最大化;第二步采用稀碱处理酸解原料,破坏木质素之间的酯键和 醚间,脱除部分木质素,提高纤维素的酶解率,碱处理后的纤维素原料经过纤维 素酶酶解后生成葡萄糖。酶解后的固体残留物主要为木质素,改性后可以用来生 产木质素衍生物。1. It can realize the full recycling of fungus chaff and achieve zero discharge: this patent uses acid-base coupling technology to hydrolyze the fungus chaff, and uses a two-step treatment method to hydrolyze the hemicellulose and cellulose in the fungus chaff to produce xylose Collect and utilize glucose step by step. The first step is to select the appropriate dilute acid hydrolysis conditions to maximize the hydrolysis of the hemicellulose in the fungus chaff, avoiding the loss of hemicellulose in the subsequent alkali treatment process, thereby maximizing the yield of xylose; the second The first step is to use dilute alkali to treat the acid hydrolysis raw material, destroy the ester bond and ether bond between the lignin, remove part of the lignin, and improve the enzymatic hydrolysis rate of cellulose. The cellulose raw material after alkali treatment is enzymolyzed by cellulase to form glucose. The solid residue after enzymatic hydrolysis is mainly lignin, which can be used to produce lignin derivatives after modification.
2、本发明通过对菌糠进行酸碱耦合预处理,所采用的工艺条件温和,纤维 素及半纤维素损失小,可以同时生产木糖、葡萄糖和木质素,实现纤维素、半纤 维素和木质素的分级利用,提高其附加值;使其再利用变得简单可行,可实现大 规模的工业化生产,使得食用废弃菌糠的高效处理成为现实。2. The present invention carries out acid-base coupling pretreatment on the fungus chaff, the process conditions adopted are mild, the loss of cellulose and hemicellulose is small, xylose, glucose and lignin can be produced simultaneously, and cellulose, hemicellulose and The graded utilization of lignin improves its added value; makes its reuse simple and feasible, realizes large-scale industrial production, and makes the efficient treatment of edible waste fungus chaff a reality.
3、环境污染小:在本发明的制备过程中,稀酸水解后直接采用稀碱中和, 大大降低酸的排放,减少对环境的污染。3. Small environmental pollution: In the preparation process of the present invention, dilute acid is directly used for neutralization after hydrolysis, which greatly reduces acid discharge and reduces environmental pollution.
附图说明:Description of drawings:
图1是本发明的工艺流程图。Fig. 1 is a process flow diagram of the present invention.
具体实施方式:Detailed ways:
本发明提供一种利用食用菌菌糠生产单糖的方法,具体为利用两步预处理的 方法分步水解半纤维素和纤维素得到木糖和葡萄糖的方法。The invention provides a method for producing monosaccharides by using edible mushroom chaff, specifically a method for obtaining xylose and glucose by hydrolyzing hemicellulose and cellulose step by step through a two-step pretreatment method.
下面将通过具体实施例对本发明进行详细地说明。The present invention will be described in detail below through specific examples.
实施例1:Example 1:
步骤一,酸水解:将平茹、鸡腿菇、金针茹等各种食用菌菌糠,风干后粉 碎至10目左右,按固液比1:10加入质量浓度为5%的硫酸溶液中,100℃处理 30min,过滤后得滤液和液渣;Step 1, acid hydrolysis: air-dry and crush the bran of various edible fungi such as Pingru, Coprinus comatus, and Golden Needle to about 10 mesh. ℃ for 30 minutes, after filtration, the filtrate and liquid residue were obtained;
测定滤液中木糖的含量为13g/L左右,半纤维素的转化率可达到92%以上。 滤液经过中和、浓缩、脱色、离子交换和结晶制备食品级木糖,木糖的产量可达 到100g/kg菌糠,还可进一步生产木糖醇及糠醛等产品。The content of xylose in the measured filtrate is about 13g/L, and the conversion rate of hemicellulose can reach more than 92%. The filtrate is neutralized, concentrated, decolorized, ion-exchanged and crystallized to prepare food-grade xylose. The xylose output can reach 100g/kg fungus chaff, and further products such as xylitol and furfural can be produced.
步骤二,碱水解:滤渣按1:10固液比加入质量浓度为5%的氢氧化钠溶液 中,60℃处理60min后,用酸中和至中性,测定纤维素的含量;Step 2, alkali hydrolysis: add the filter residue to a sodium hydroxide solution with a mass concentration of 5% at a solid-to-liquid ratio of 1:10, treat at 60°C for 60 minutes, neutralize with acid to neutral, and measure the cellulose content;
步骤三,酶水解:按纤维素含量加入商品纤维素酶(CTec2,丹麦 诺维信酶制剂公司生产),用量为20FPU/g纤维素,50℃、180rpm条件下酶解 48小时得酶解液,酶解液经过滤后得滤液和滤渣,滤液为葡萄糖溶液,其产量 经测定可达40g/L酶解液,经过稀释后可以用来作为培养各种微生物的碳源;滤 渣主要成分为木质素,经过改性可以生产各种木质素衍生物。Step 3, enzymatic hydrolysis: add commercial cellulase ( CTec2, produced by Danish Novozymes Enzyme Preparation Company), the dosage is 20FPU/g cellulose, and the enzymolysis solution is obtained by enzymolysis at 50°C and 180rpm for 48 hours, and the filtrate and filter residue are obtained after the enzymolysis solution is filtered, and the filtrate is glucose solution , its output can reach 40g/L enzymatic hydrolysis solution, which can be used as a carbon source for cultivating various microorganisms after dilution; the main component of the filter residue is lignin, which can be modified to produce various lignin derivatives.
实施例2:Example 2:
步骤一,酸水解:将平茹、鸡腿菇、金针茹等各种食用菌菌糠,风干后粉 碎至10目左右,按固液比1:15加入质量浓度为2%的硫酸溶液中,120℃处理 60min,过滤后得滤液和液渣;测定滤液中木糖的含量为9g/L左右,半纤维素的 转化率可达到90%。滤液经过中和、浓缩、脱色、离子交换和结晶制备食品级木 糖,木糖的产量可达到98g/kg菌糠。Step 1, acid hydrolysis: air-dry and crush the bran of various edible fungi such as Pingru, Coprinus comatus, and Flammulina to about 10 meshes, and add them to a sulfuric acid solution with a mass concentration of 2% according to a solid-to-liquid ratio of 1:15, 120 ℃ for 60 minutes, after filtration, the filtrate and liquid residue were obtained; the content of xylose in the filtrate was determined to be about 9g/L, and the conversion rate of hemicellulose could reach 90%. The filtrate prepares food-grade xylose through neutralization, concentration, decolorization, ion exchange and crystallization, and the output of xylose can reach 98g/kg bacterium chaff.
步骤二,碱水解:滤渣按1:15固液比加入质量浓度为2%的氢氧化钠溶液 中,60℃处理100min,用酸中和至中性,测定纤维素的含量;Step 2, alkali hydrolysis: add the filter residue to a sodium hydroxide solution with a mass concentration of 2% at a solid-to-liquid ratio of 1:15, treat at 60°C for 100 minutes, neutralize with acid to neutral, and measure the cellulose content;
步骤三,酶水解:按纤维素含量加入商品纤维素酶(CTec2,丹麦诺 维信酶制剂公司生产),用量为10FPU/g纤维素,50℃、180rpm条件下酶解60 小时得酶解液,酶解液经过滤后得滤液和滤渣,滤液为葡萄糖溶液,其产量经测 定可达25g/L酶解液。Step 3, enzymatic hydrolysis: add commercial cellulase ( CTec2, produced by Danish Novozymes Enzyme Preparation Company), the dosage is 10FPU/g cellulose, the enzymolysis solution is obtained by enzymolysis at 50°C and 180rpm for 60 hours, the enzymolysis solution is filtered to obtain filtrate and filter residue, and the filtrate is glucose solution , and its yield has been determined to reach 25g/L enzymatic hydrolyzate.
实施例3:Example 3:
步骤一,酸水解:将平茹、鸡腿菇、金针茹等各种食用菌菌糠,风干后粉 碎至10目左右,按固液比1:20加入质量浓度为5%的硫酸溶液中,100℃处理 120min,过滤后得滤液和液渣;Step 1, acid hydrolysis: air-dry and crush the bran of various edible fungi such as Pingru, Coprinus comatus, and Golden Needle to about 10 mesh. ℃ treatment for 120min, after filtration, the filtrate and liquid residue were obtained;
测定滤液中木糖的含量为7g/L左右,半纤维素的转化率可达到89%。滤液经过中和、 浓缩、脱色、离子交换和结晶制备食品级木糖,木糖的产量可达到97g/kg菌糠。The content of xylose in the measured filtrate is about 7g/L, and the conversion rate of hemicellulose can reach 89%. The filtrate is neutralized, concentrated, decolorized, ion-exchanged and crystallized to prepare food-grade xylose, and the yield of xylose can reach 97g/kg fungus chaff.
步骤二,碱水解:滤渣按1:20固液比加入质量浓度为5%的氢氧化钠溶液 中,60℃处理60min后,用酸中和至中性,测定纤维素的含量;Step 2, alkali hydrolysis: add the filter residue to a sodium hydroxide solution with a mass concentration of 5% at a solid-to-liquid ratio of 1:20, treat at 60°C for 60 minutes, neutralize with acid to neutral, and measure the cellulose content;
步骤三,酶水解:按纤维素含量加入商品纤维素酶(CTec2,丹麦诺 维信酶制剂公司生产),用量为15FPU/g纤维素,50℃、180rpm条件下酶解72 小时得酶解液,酶解液经过滤后得滤液和滤渣,滤液为葡萄糖溶液,其产量经测 定可达18g/L酶解液。Step 3, enzymatic hydrolysis: add commercial cellulase ( CTec2, produced by Danish Novozymes Enzyme Preparation Company), the dosage is 15FPU/g cellulose, and the enzymolysis solution is obtained by enzymolysis at 50°C and 180rpm for 72 hours, and the filtrate and filter residue are obtained after the enzymolysis solution is filtered, and the filtrate is glucose solution , and its output has been determined to reach 18g/L enzymatic hydrolyzate.
上述实施例1为最佳实施例。Above-mentioned embodiment 1 is the best embodiment.
Claims (3)
- A kind of 1. method using edible fungus bran production monose, it is characterised in that:Comprise the following steps:Step 1: sour water solution:Edible fungus bran is air-dried and crushed, by solid-to-liquid ratio 1:10~20 add in mass concentration as the dilute of 1-5% Acid solution, 100-120 DEG C of processing 30-120min, obtains filtrate and filter residue after filtering, xylose prepares food-grade xylose in filtrate;Step 2: basic hydrolysis:Filter residue presses 1:10~20 solid-to-liquid ratios add in the aqueous slkali that mass concentration is 1-5%, 40-60 DEG C of processing After 60-120min, neutrality is neutralized to acid, measures content of cellulose;Step 3: enzyme hydrolysis:By content of cellulose add in cellulase, cellulose dosage be 10-20FPU/g celluloses, 50 DEG C, Enzymolysis liquid is obtained when enzymolysis 48-72 is small under the conditions of 180rpm, filters to obtain glucose solution and lignin.
- 2. a kind of method using edible fungus bran production monose according to claim 1, it is characterised in that:Above-mentioned steps Dilute acid soln is sulfuric acid or hydrochloric acid in one, in above-mentioned filtrate xylose by neutralizing, it is prepared by concentration, decoloration, ion exchange and crystallization Food-grade xylose.
- 3. a kind of method using edible fungus bran production monose according to claim 1 or 2, it is characterised in that:It is above-mentioned Step 2 neutral and alkali solution is sodium hydroxide or calcium hydroxide solution.
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| CN110204381A (en) * | 2019-07-15 | 2019-09-06 | 绥化学院 | A kind of method that modified auricuralia auricular bran prepares biological organic complex fertilizer |
| CN110714041A (en) * | 2019-11-19 | 2020-01-21 | 云南省烟草农业科学研究院 | Method for efficiently and directly producing glucose by using waste tobacco stems |
| CN116851407A (en) * | 2023-07-26 | 2023-10-10 | 泸州老窖股份有限公司 | A method and system for processing distiller's grains |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110204381A (en) * | 2019-07-15 | 2019-09-06 | 绥化学院 | A kind of method that modified auricuralia auricular bran prepares biological organic complex fertilizer |
| CN110714041A (en) * | 2019-11-19 | 2020-01-21 | 云南省烟草农业科学研究院 | Method for efficiently and directly producing glucose by using waste tobacco stems |
| CN116851407A (en) * | 2023-07-26 | 2023-10-10 | 泸州老窖股份有限公司 | A method and system for processing distiller's grains |
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