WO2023123805A1 - 一种利用玉米秸秆制备精制木糖及可发酵糖的系统和方法 - Google Patents

一种利用玉米秸秆制备精制木糖及可发酵糖的系统和方法 Download PDF

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WO2023123805A1
WO2023123805A1 PCT/CN2022/092088 CN2022092088W WO2023123805A1 WO 2023123805 A1 WO2023123805 A1 WO 2023123805A1 CN 2022092088 W CN2022092088 W CN 2022092088W WO 2023123805 A1 WO2023123805 A1 WO 2023123805A1
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tank
corn stalks
xylose
fermentable sugar
decolorization
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PCT/CN2022/092088
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English (en)
French (fr)
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李勉
严良聪
胡昌辉
杨铭乾
罗家星
杨武龙
甄妮
曾方明
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浙江华康药业股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • 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

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  • the invention belongs to the technical field of sugar alcohol preparation, in particular to a system and method for preparing refined xylose and fermentable sugar by using corn stalks.
  • the process of using hemicellulose in agricultural waste to extract xylose and fermentable sugar in the fields of food and chemical industry is mainly to directly treat agricultural waste with sulfuric acid, hydrolyze the hemicellulose component to obtain xylose, and then hydrolyze Wherein the cellulose component obtains a fermentable glucose solution.
  • the patent of Publication No. CN112661975A handles bamboo scraps with sulfuric acid, then separates xylose from the hydrolyzate.
  • sulfuric acid is used directly to treat agricultural waste. In order to hydrolyze hemicellulose into xylose as much as possible, a relatively high concentration of sulfuric acid is often added.
  • xylose will be converted into other substances such as furfural, and on the other hand, more Impurities such as cellulose, lignin and colloids in plant cell walls add difficulties and costs to the subsequent separation and extraction process of xylose.
  • the patent of notification number CN102584907B uses corn stalks as raw materials to produce xylose and arabinose, using four ion exchanges.
  • auxiliary methods to treat agricultural waste such as the patent of notification number CN104498640B, which first soaks in dilute acid for 2 to 10 hours, and then performs steam explosion hydrolysis to obtain xylose hydrolyzate.
  • notification number CN104498640B also mentions the method of extracting hemicellulose by combined alkali-acid treatment of corncobs, the concentration of the alkali solution used is 0.8% to 5% (mass fraction), and the primary extraction rate of hemicellulose is the highest was 52%.
  • the existing technology directly treats agricultural waste with sulfuric acid. Due to the high concentration of sulfuric acid used, on the one hand, part of the xylose will be converted into other substances such as furfural, which will reduce the yield of xylose. On the other hand, it will introduce lignin and plant cell wall Impurities such as colloids are not conducive to the subsequent separation, extraction and utilization of xylose.
  • auxiliary treatment by methods such as steam explosion requires high temperature and high pressure, large energy consumption, and high cost.
  • the technical problem to be solved by the present invention is to provide a system and method for preparing refined xylose and fermentable sugar from corn stalks, so as to maximize the extraction of xylose and glucose from corn stalks under low-cost process treatment .
  • the present invention is achieved by providing a system for preparing refined xylose and fermentable sugar from corn stalks, including a premixing tank for premixing straw powder and water connected through an intermediate pipeline, and a tank for dilute alkali treatment of straw powder.
  • Decolorization tank for decolorization of hydrolyzate, post-decolorization tank for storing decolorization solution, ion exchange device for ion exchange and impurity removal of decolorization solution, post-transaction tank for temporary storage of separation liquid, and concentration of ion exchange liquid
  • the ion exchange device includes single-connected anion exchange columns and cation exchange columns.
  • the type of resin used in the anion exchange column is D301-FD
  • the type of resin used in the cation exchange column is D001-F.
  • the present invention is achieved by providing a method for preparing refined xylose and fermentable sugar using corn stalks, which uses the system for preparing refined xylose and fermentable sugar using corn stalks as described above, the method comprising follows the steps below:
  • Step 1 Process the corn stalks into powder with a pulverizer, and then dry them to obtain the absolute dry powdered corn stalks.
  • the size of the powder particles is 60 mesh to 300 mesh.
  • Step 2 After mixing the absolute dry powdered corn stalks and process water in a certain proportion, adjust the NaOH concentration in the system to 0.1% to 0.4% with 30% concentrated lye, and conduct alkali treatment for 1.2 hours at a temperature of 85°C to 125°C ⁇ 2.0h; then the straw residue and centrifugal supernatant are obtained through centrifugation, and the supernatant enters the lignin extraction process.
  • Step 3 Mix the straw residue with 1.0% to 2.5% of dilute H 2 SO 4 in a certain proportion, acidify at 130°C to 160°C for 30min to 50min, then perform centrifugation to obtain the hydrolyzate and acidolysis residue, acidify After the residue is subjected to enzymatic hydrolysis treatment with cellulase, glucose liquid which can be used for fermentation is obtained.
  • Step 4 After adjusting the hydrolyzed solution with an alkaline substance to a pH value of 3.0-5.0, decolorization, separation, concentration and crystallization are successively performed to obtain crystalline xylose.
  • the system and method for preparing refined xylose and fermentable sugar from corn stalks of the present invention avoids directly hydrolyzing corn stalks with sulfuric acid, and uses dilute alkali-dilute acid to jointly treat corn stalks, that is, through alkali pretreatment
  • the treatment first removes impurities such as lignin that is easily hydrolyzed in corn stalks and colloids in plant cell walls, and at the same time basically retains the xylose unit components in corn stalk hemicellulose, and then performs dilute acid hydrolysis to convert the Hemicellulose is hydrolyzed into xylose with a conversion rate of 75.78%.
  • a relatively clear hydrolyzate with less impurities and easy separation of xylose and acidolysis residue with high cellulose components is obtained.
  • the conductivity of the hydrolyzate is only 2522 ⁇ s /cm, after the acid hydrolysis residue undergoes enzymatic hydrolysis of cellulose, a glucose solution with a glucose concentration > 146g/L is obtained, which can be used for fermentation to prepare high value-added products such as cellulosic ethanol.
  • Both dilute alkali and dilute acid treatment are in place in one step, no multi-stage treatment is required, and the process is simplified, and the concentration of dilute alkali used is only 0.25wt%, and the concentration of dilute sulfuric acid is 2%, which is higher than that of alkali-acid in the patent of notification number CN104498640B.
  • the concentration of the used alkali solution is 0.8wt% to 5wt%, and the highest extraction rate of hemicellulose is 52%)
  • the alkali solution concentration is lower, and the hemicellulose
  • the primary extraction rate is 23.78% higher.
  • the invention also has the characteristics of simple process, cost saving and the like.
  • Fig. 1 is the principle schematic diagram of the system for preparing refined xylose and fermentable sugar by using corn stalks in the present invention
  • Fig. 2 is a schematic process flow diagram of the system and method for preparing refined xylose and fermentable sugar by utilizing corn stalks in the present invention
  • Fig. 3 is the corresponding curve of enzymolysis glucose concentration and enzymolysis time in Example 4 of the present invention.
  • Fig. 1 the preferred embodiment of the system of dilute alkali-dilute acid joint treatment corn stalk extracting xylose of the present invention
  • the arrow in the figure shows the materials in the system (such as corn stalk powder, process water, feed liquid, Flow direction of Ca(OH) 2 , concentrated acid solution, concentrated alkali solution, activated carbon, waste carbon, hydrolyzate, acidolysis residue, etc.).
  • the system includes a premix tank 1 for premixing straw powder and water, an alkali treatment tank 2 for dilute alkali treatment of straw powder, and an acid hydrolysis tank for acid hydrolysis of straw residues after alkali treatment, which are connected through intermediate pipelines 3.
  • Enzymolysis tank 18 for enzymolysis of acidolysis residue after acid treatment neutralization tank 4 for neutralization of hydrolyzate, decolorization tank 5 for decolorization of hydrolyzate after neutralization, storage tank for decolorization
  • Post-decolorization tank 6 ion exchange device 7 for ion exchange and impurity removal of decolorization liquid, post-transaction tank 8 for temporary storage of separation liquid, evaporator for concentration of ion exchange liquid 9, crystallization of concentrated liquid
  • the first centrifuge 11 and the second centrifuge 12 are respectively arranged on the intermediate pipeline between the alkali treatment tank 2 and the acidolysis tank 3, between the acidolysis tank 3 and the neutralization tank 4 for solidifying the hydrolyzate.
  • Liquid separation, a plate and frame filter press 13 is provided on the intermediate pipeline between the decolorizing tank 5 and the decolorizing tank 6 to remove activated carbon impurities in the decolorizing liquid.
  • a third centrifuge 14 is provided on the intermediate pipeline behind the crystallization tank 10 for separating the crystallized sugar from the mother liquor after crystallization tank crystallization, and then obtaining crystal xylose.
  • the system is also equipped with a concentrated alkali tank 15 and a concentrated acid tank 16 which are sequentially connected to the alkali treatment tank 2 and the acid hydrolysis tank 3, and the decolorization tank 5 is connected to a carbon distribution tank 17 for dissolving activated carbon.
  • the ion exchange device 7 includes a single-connected anion exchange column 71 and a cation exchange column 72 .
  • the resin model used by the anion exchange column 71 is D301-FD
  • the resin model used by the cation exchange column 72 is D001-F.
  • the present invention also discloses a method for preparing refined xylose and fermentable sugar by using corn stalks, which uses the system for preparing refined xylose and fermentable sugar by using corn stalks as described above. Said method comprises the steps:
  • Step 1 Raw material screening: The raw material used in the present invention is corn stalks with a moisture content of about 10%. The components are determined as shown in Table 1.
  • Step 2 Raw material pretreatment: first process the corn stalks into powder with a pulverizer, and the size of the powder particles is 60 mesh to 300 mesh, and then put them in a blast drying oven and dry them at 45°C for 24 hours
  • the water content is basically 0, that is, it is made into dry powdered corn stalks.
  • Step 3 Alkali treatment: After mixing the absolute dry powdered corn stalks and process water in a certain proportion, adjust the NaOH concentration in the system to 0.1% to 0.4% with 30% concentrated lye, at a temperature of 85°C to 125°C, the alkali Treat for 1.2h to 2.0h, and then obtain straw residue and centrifugal supernatant through the first centrifugation. The centrifugal supernatant enters the lignin extraction process.
  • Step 4 acid hydrolysis: mix the straw residue with 1.0% to 2.5% dilute H 2 SO 4 in a certain proportion, acidify at 130°C to 160°C for 30min to 50min, and then perform a second centrifugation to obtain the hydrolyzate and Acid hydrolysis residue.
  • the acid hydrolysis residue is subjected to enzymatic hydrolysis treatment with cellulase to obtain glucose liquid which can be used for fermentation.
  • Step 5 neutralization: adjust the pH value of the hydrolyzate to 3.0-5.0 with alkaline substance Ca(OH) 2 .
  • Step 6 Refining: the neutralized hydrolyzate is subjected to decolorization, separation, concentration and crystallization in sequence, and then centrifuged for the third time to obtain crystalline xylose and mother liquor.
  • Activated carbon is used during the decolorization treatment, and the consumption of activated carbon is 0.5% of the volume of the hydrolyzed solution.
  • concentration treatment the refraction of the concentrated solution is more than 70%, and then the temperature-lowering crystallization treatment is carried out.
  • the mother liquor is used for re-concentration and recycling.
  • Embodiment 1 alkali treatment
  • the present embodiment has carried out 29 groups of experiments altogether, and concrete experimental plan and experimental result are as shown in table 3, and the optimal condition that draws optimal experimental group is: hemicellulose content is the highest 23.2%, and optimal pretreatment condition is : 0.25% concentration of NaOH solution, 1:10 solid-liquid ratio, 105 °C for 1.2h. Under this optimal condition, theoretically 100g of dry corn stalks (containing about 21.5g of xylose and 38.7g of glucose) will leave 78.08g of straw residue after alkali treatment (about 18.1g of xylose and 35.4g of glucose). The components of the straw residue after alkali treatment were determined, and the test results in Table 2 were obtained.
  • Embodiment 2 acid hydrolysis
  • the acid hydrolysis experiment was carried out on the corn stalk residue after being treated with the optimal alkali treatment conditions.
  • the acid concentration was 2%
  • the maximum xylose yield was 80.64%.
  • the hemicellulose content in the acid hydrolysis residue was 3.51%, and the cellulose The content is 64.70%.
  • reaction conditions solid-to-liquid ratio 1:8, reaction temperature 125°C, reaction time 140min.
  • the hemicellulose content of corn stalks is 21.50%, and the average hemicellulose content in the straw residue after alkali treatment is 23.25%.
  • reaction conditions 2% H 2 SO 4 , reaction temperature 125° C., reaction time 140 min.
  • the hemicellulose content in corn stalks is 21.50%, and the average hemicellulose content in alkali-treated straw residues is 23.25%.
  • xylose crystals are obtained, and the purity of xylose is above 99.5%. Based on the xylose content in the hydrolyzate, the yield of crystal xylose is 26.5%. Throughout the refining process, the xylose crystallization mother liquor will be repeatedly concentrated and crystallized for use.
  • the decolorization and separation process will cause some loss of xylose.
  • the embodiment of the present invention uses one separation to reduce the xylose loss rate. Nearly 1% (xylose loss ⁇ 16.2%).
  • Embodiment 4 Acid hydrolysis residue prepares glucose
  • the acid hydrolysis residue obtained after dilute alkali-dilute acid treatment is added to Novozymes Ctec2 cellulase for enzymolysis.
  • the glucose concentration of 20% dry basis enzymatic hydrolysis can reach 146g/L, and the concentration of 25% dry basis enzymatic hydrolysis glucose can reach 177g/L, the corresponding curve of enzymolysis glucose concentration and enzymolysis time as shown in Figure 3 was obtained.
  • the test parameters for preparing enzymatic glucose are disclosed as follows: 20% dry basis, glucose concentration 120g/L; 25% dry basis, glucose concentration 140g/L. Therefore, the comparison of the test data shows that the glucose concentration prepared by the method of the present invention is nearly 20% higher than that of the prior art method.

Abstract

本发明涉及一种利用玉米秸秆制备精制木糖及可发酵糖的系统，包括通过中间管道相连通的预混罐、碱处理罐、酸解罐、酶解罐、中和罐、脱色罐、脱色后罐、离子交换装置、离交后罐、蒸发器、结晶罐以及设置在各中间管道上的多个输料泵和多个阀门，还设置第一离心机、第二离心机和第三离心机。所述系统还配套有浓碱罐、浓酸罐依次连接碱处理罐和酸解罐，脱色罐连接有配炭罐用以溶解活性炭。本发明还公开一种使用该系统进行利用玉米秸秆制备精制木糖及可发酵糖的方法。本发明稀碱和稀酸处理均是一步到位，不需要多级处理，简化工序，具有工艺简单，节约成本等特点。

Description

一种利用玉米秸秆制备精制木糖及可发酵糖的系统和方法 技术领域
本发明属于糖醇制备技术领域，特别涉及一种利用玉米秸秆制备精制木糖及可发酵糖的系统和方法。
背景技术
目前在食品、化工等领域利用农业废弃物中的半纤维素提取木糖和可发酵糖的工艺主要是以硫酸直接处理农业废弃物，水解其中的半纤维素组分来得到木糖，然后水解其中纤维素组分得到可发酵的葡萄糖液。如公开号CN112661975A的专利以硫酸来处理竹材碎料，然后从水解液中分离出木糖。然而直接以硫酸来处理农业废弃物，为尽可能水解半纤维素为木糖，往往加入比较高浓度的硫酸，这一方面会使部分木糖转化为糠醛等其他物质，另一方面会引入更多纤维素和木质素及植物细胞壁中的胶体等杂质，为后续木糖的分离提取工艺增加困难及成本。如公告号CN102584907B的专利以玉米秸秆为原料生产木糖和阿拉伯糖的方法，采用四次离子交换。除了直接以硫酸水解外，还有借助一些其他辅助方法来处理农业废弃物，如公告号CN104498640B的专利，先采用稀酸浸泡2～10小时，随后进行汽爆水解处理，得到木糖水解液。然而采用汽爆处理，一般需要高温高压，能量消耗大，成本较高。公告号CN104498640B的专利中也有提及用碱-酸联合处理玉米芯来提取半纤维素的方法，其所用的碱溶液浓度为0.8％～5％(质量分数)，半纤维素的一次提取率最高为52％。
现有技术直接以硫酸处理农业废弃物，由于所用硫酸浓度较高，一方面会使部分木糖转化为糠醛等其他物质，降低木糖产率，另一方面会引入木质素及植物细胞壁中的胶体等杂质，不利于后续木糖的分离提取及利用。另外，借助汽爆等方法来辅助处理，需要高温高压，能量消耗大，成本较高。
发明内容
本发明所要解决的技术问题在于，提供一种利用玉米秸秆制备精制木糖及可发酵糖的系统和方法，尽可能地在低成本的工艺处理下最大化地从玉米秸秆中提取木糖及葡萄糖。
本发明是这样实现的，提供利用玉米秸秆制备精制木糖及可发酵糖的系统，包括通过中间管道相连通的用于秸秆粉末与水预混的预混罐、用于稀碱处理秸秆粉末的碱处理罐、用于碱处理后秸秆残渣酸水解的酸解罐、用于酸处理后酸解残渣酶解的酶解罐、用于水解液中和反应的中和罐、用于中和后水解液脱色的脱色罐、用于储存脱色液的脱色后罐、用于脱色液离子交换除杂的离子交换装置、用于暂存离交液的离交后罐、用于离子交换液浓缩的蒸发器、用于浓缩液结晶的结晶罐以及设置在各中间管道上的多个输料泵和多个阀门，在所述碱处理 罐和酸解罐之间、酸解罐与中和罐之间的中间管道上分别设置第一离心机和第二离心机用于进行水解液的固液分离，在脱色罐与脱色后罐之间的中间管道上设置有板框压滤机用于除去脱色液中的活性炭杂质，在结晶罐之后的中间管道上设置有第三离心机用于结晶罐结晶后的晶体糖与母液的分离，进而得到晶体木糖；所述系统还配套有浓碱罐、浓酸罐依次连接碱处理罐和酸解罐，脱色罐连接有配炭罐用以溶解活性炭。
进一步地，所述离子交换装置包括单联的阴离子交换柱和阳离子交换柱。
进一步地，所述阴离子交换柱使用的树脂型号为D301-FD，阳离子交换柱使用的树脂型号为D001-F。
本发明是这样实现的，提供一种利用玉米秸秆制备精制木糖及可发酵糖的方法，其使用了如前所述的利用玉米秸秆制备精制木糖及可发酵糖的系统，所述方法包括如下步骤：
步骤一、将玉米秸秆用粉碎机处理成粉状，然后干燥后得到绝干粉状玉米秸秆，粉状颗粒的尺寸在60目～300目。
步骤二、将绝干粉状玉米秸秆与工艺水按一定比例混合后，并用30％浓碱液调节体系中NaOH浓度为0.1％～0.4％，在85℃～125℃温度下，碱处理1.2h～2.0h；然后经离心分离得到秸秆残渣和离心清液，离心清液进入木质素提取工序。
步骤三、将秸秆残渣与1.0％～2.5％的稀H 2SO 4按一定比例混合，在130℃～160℃下酸解30min～50min，然后进行离心分离得到水解液和酸解残渣，酸解残渣经过纤维素酶的酶解处理后得到可用于发酵的葡萄糖液。
步骤四、用碱性物质调节水解液至pH值为3.0～5.0后，依次采取脱色、离交、浓缩、结晶处理后得到晶体木糖。
与现有技术相比，本发明的利用玉米秸秆制备精制木糖及可发酵糖的系统和方法，避免直接以硫酸来水解玉米秸秆，采用稀碱-稀酸联合处理玉米秸秆，即通过碱预处理先去除玉米秸秆中易水解的木质素及植物细胞壁中的胶体等杂质，同时使玉米秸秆半纤维素中的木糖单元成分基本保留，然后进行稀酸水解，将玉米秸秆半纤维素中的半纤维素水解成木糖，转化率达75.78％，同时得到比较澄清、杂质较少、易于分离出木糖的水解液和纤维素组分高的酸解残渣，水解液的电导率仅有2522μs/cm，酸解残渣经过纤维素酶解后，得到了葡萄糖浓度＞146g/L的葡萄糖液，可用于发酵制备纤维素乙醇等高附加值产品。
在水解液后续精制提取木糖工艺中，只采用一次离交，离交时水解液与阴阳树脂的体积比均约为20:1。比公告号CN102584907B的专利以玉米秸秆为原料生产木糖和阿拉伯糖的方法中采用的四组阴阳离子交换树脂净化相比，节约后续分离提纯木糖产品的时间和成本，并 且不会增加精制工序中木糖的损失。
稀碱和稀酸处理均是一步到位，不需要多级处理，简化工序，且所用的稀碱浓度仅为0.25wt％，稀硫酸浓度为2％，比公告号CN104498640B的专利中用碱-酸来联合处理玉米芯来提取半纤维素的方法中(所用的碱溶液浓度为0.8wt％～5wt％，半纤维素的一次提取率最高为52％)的碱溶液浓度更低，且半纤维素的一次提取率高出23.78％。本发明还具有工艺简单，节约成本等特点。
附图说明
图1为本发明利用玉米秸秆制备精制木糖及可发酵糖的系统的原理示意图；
图2为本发明利用玉米秸秆制备精制木糖及可发酵糖的系统和方法的工艺流程示意图；
图3为本发明实施例4的酶解葡萄糖浓度与酶解时间的对应曲线。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参照图1所示，本发明稀碱-稀酸联合处理玉米秸秆提取木糖的系统的较佳实施例，图中箭头所示为系统中物料(如玉米秸秆粉末、工艺水、料液、Ca(OH) 2、浓酸液、浓碱液、活性炭、废炭、水解液、酸解残渣等)的流动方向。
所述系统包括通过中间管道相连通的用于秸秆粉末与水预混的预混罐1、用于稀碱处理秸秆粉末的碱处理罐2、用于碱处理后秸秆残渣酸水解的酸解罐3、用于酸处理后酸解残渣酶解的酶解罐18、用于水解液中和反应的中和罐4、用于中和后水解液脱色的脱色罐5、用于储存脱色液的脱色后罐6、用于脱色液离子交换除杂的离子交换装置7、用于暂存离交液的离交后罐8、用于离子交换液浓缩的蒸发器9、用于浓缩液结晶的结晶罐10以及设置在各中间管道上的多个输料泵和多个阀门。
在所述碱处理罐2和酸解罐3之间、酸解罐3与中和罐4之间的中间管道上分别设置第一离心机11和第二离心机12用于进行水解液的固液分离，在脱色罐5与脱色后罐6之间的中间管道上设置有板框压滤机13用于除去脱色液中的活性炭杂质。在结晶罐10之后的中间管道上设置有第三离心机14用于结晶罐结晶后的晶体糖与母液的分离，进而得到晶体木糖。所述系统还配套有浓碱罐15、浓酸罐16依次连接碱处理罐2和酸解罐3，脱色罐5连接有配炭罐17用以溶解活性炭。
所述离子交换装置7包括单联的阴离子交换柱71和阳离子交换柱72。所述阴离子交换 柱71使用的树脂型号为D301-FD，阳离子交换柱72使用的树脂型号为D001-F。
请参照图2所示，本发明还公开一种利用玉米秸秆制备精制木糖及可发酵糖的方法，其使用了如前所述的利用玉米秸秆制备精制木糖及可发酵糖的系统，所述方法包括如下步骤：
步骤一、原料筛选：本发明所用原料为玉米秸秆，水份含量约为10％，组分测定如表1所示。
表1本发明所用玉米秸秆的组分测定结果
秸秆组分 纤维素 半纤维素 木质素及其他
比例 36％～41％ 19％～24％ 35％～45％
步骤二、原料预处理：先将玉米秸秆用粉碎机处理成粉状，粉状颗粒的尺寸在60目～300目，然后放到鼓风式干燥箱中，在45℃下进行干燥，干燥24h左右，含水量基本上为0，即制成绝干粉状玉米秸秆。
步骤三、碱处理：将绝干粉状玉米秸秆与工艺水按一定比例混合后，并用30％浓碱液调节体系中NaOH浓度为0.1％～0.4％，在85℃～125℃温度下，碱处理1.2h～2.0h，然后经第一次离心分离得到秸秆残渣和离心清液。离心清液进入木质素提取工序。
步骤四、酸水解：将秸秆残渣与1.0％～2.5％的稀H 2SO 4按一定比例混合，在130℃～160℃下酸解30min～50min，然后进行第二次离心分离得到水解液和酸解残渣。酸解残渣经过纤维素酶的酶解处理后得到可用于发酵的葡萄糖液。
步骤五、中和：用碱性物质Ca(OH) 2调节水解液pH值至3.0～5.0。
步骤六、精制：对中和后的水解液，依次采取脱色、离交、浓缩、结晶处理后进行第三次离心分离得到晶体木糖和母液。脱色处理时使用活性炭，活性炭的使用量为水解液体积的0.5％。浓缩处理时浓缩液的折光≥70％，随后进行降温结晶处理。母液用于再浓缩回收利用。
下面结合具体实施例进一步说明本发明的利用玉米秸秆制备精制木糖及可发酵糖的方法。
实施例1碱处理
本实施例共进行了29组实验，具体实验方案和实验结果如表3所示，并得出最优实验组的最佳条件是：半纤维素含量最高为23.2％，最佳预处理条件为：0.25％浓度NaOH溶液下，1:10固液比，105℃下保温1.2h。在此最佳条件下，理论上100g绝干玉米秸秆(约含木糖21.5g，葡萄糖38.7g)，经过碱处理，剩余秸秆残渣78.08g(约含木糖18.1g，葡萄糖35.4g)。测定碱处理后秸秆残渣的组分，得到表2的测试结果。
表2碱处理最佳条件下秸秆残渣的组分结果
秸秆残渣 纤维素 半纤维素 木质素及其他
比例 45.3％ 23.2％ 31.5％
表3碱处理条件实验方案
Figure PCTCN2022092088-appb-000001
实施例2酸水解
本实施例将碱处理过的玉米秸秆残渣进行10组酸水解实验，具体实施方案和实验结果数据分别如表4和表5所示。
经最优碱处理条件处理后玉米秸秆残渣进行酸水解实验，当酸的浓度为2％时，木糖得率最大为80.64％，此时酸解残渣中半纤维素含量为3.51％，纤维素含量为64.70％。
表4碱处理过的玉米秸秆残渣的酸水解结果
Figure PCTCN2022092088-appb-000002
其余反应条件:固液比1:8、反应温度125℃，反应时间140min。玉米秸秆半纤维素含量21.50％，碱处理后的秸秆残渣中半纤维素含量均值23.25％。
从表5的数据中可以看到，当固液比增加到1:9时，木糖得率基本已达到最大为82.11％； 固液比从1:9继续增加至1:10，1:11时，木糖得率基本在82.2％左右，增加不明显。再进一步将固液比增加至1:12时，木糖得率出现下降趋势。纤维素组分提升至65％～66％。
表5玉米秸秆固液比反应条件优化结果
Figure PCTCN2022092088-appb-000003
其余反应条件：2％的H 2SO 4，反应温度125℃，反应时间140min。玉米秸秆中半纤维素含量21.50％，碱处理后的秸秆残渣中半纤维素含量均值23.25％。
总的稀碱-稀酸联合处理工艺下，以玉米秸秆为原料，水解液中的木糖得率约为75.78％，现有技术的木糖得率最大52％，比现有技术高23.78％。
实施例3精制木糖制备
本实施例将水解液依次经过中和、脱色、一次离交、浓缩结晶工艺后，得到木糖晶体，木糖纯度在99.5％以上。以水解液中的木糖含量为基数，晶体木糖的收率为26.5％。整个精制过程，木糖结晶母液将会重复浓缩结晶利用。
脱色和离交工序会使木糖有所损失，相比于现有技术采用的四次离交(木糖损失率＞17％)，本发明实施例采用一次离交使木糖损失率降低了近1％(木糖损失率为＜16.2％)。
与现有的采用四次离交的精制工序相比，由于之前的碱处理已去除大部分易水解的非木糖杂质，采用一次离交(水解液与阴阳树脂的体积比均约为20:1)即可将脱色液的电导率由6525μs/cm降为6.5μs/cm(表6)，节约时间和成本，并且降低了木糖的损失。相应的各精制阶段参数如表6所示。
表6玉米秸秆水解液提取木糖晶体各精制工序参数
Figure PCTCN2022092088-appb-000004
实施例4酸解残渣制备葡萄糖
经过稀碱-稀酸处理后得到的酸解残渣，加入诺维信Ctec2纤维素酶进行酶解，20％干基酶解葡萄糖浓度可以达到146g/L，25％干基酶解葡萄糖浓度可以达到177g/L，得到如图3所 示的酶解葡萄糖浓度与酶解时间的对应曲线。在公开号CN112522347A的专利中，公开制备酶解葡萄糖的试验参数是：20％干基，葡萄糖浓度120g/L；25％干基，葡萄糖浓度140g/L。因此，两者试验数据对比可知，本发明的方法比现有技术的方法制备的葡萄糖浓度提升了近20％。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种利用玉米秸秆制备精制木糖及可发酵糖的系统，其特征在于，包括通过中间管道相连通的用于秸秆粉末与水预混的预混罐、用于稀碱处理秸秆粉末的碱处理罐、用于碱处理后秸秆残渣酸水解的酸解罐、用于酸处理后酸解残渣酶解的酶解罐、用于水解液中和反应的中和罐、用于中和后水解液脱色的脱色罐、用于储存脱色液的脱色后罐、用于脱色液离子交换除杂的离子交换装置、用于暂存离交液的离交后罐、用于离子交换液浓缩的蒸发器、用于浓缩液结晶的结晶罐以及设置在各中间管道上的多个输料泵和多个阀门，在所述碱处理罐和酸解罐之间、酸解罐与中和罐之间的中间管道上分别设置第一离心机和第二离心机用于进行水解液的固液分离，在脱色罐与脱色后罐之间的中间管道上设置有板框压滤机用于除去脱色液中的活性炭杂质，在结晶罐之后的中间管道上设置有第三离心机用于结晶罐结晶后的晶体糖与母液的分离，进而得到晶体木糖；所述系统还配套有浓碱罐、浓酸罐依次连接碱处理罐和酸解罐，脱色罐连接有配炭罐用以溶解活性炭。
  2. 如权利要求1所述的利用玉米秸秆制备精制木糖及可发酵糖的系统，其特征在于，所述离子交换装置包括单联的阴离子交换柱和阳离子交换柱。
  3. 如权利要求2所述的利用玉米秸秆制备精制木糖及可发酵糖的系统，其特征在于，所述阴离子交换柱使用的树脂型号为D301-FD，阳离子交换柱使用的树脂型号为D001-F。
  4. 一种利用玉米秸秆制备精制木糖及可发酵糖的方法，其特征在于，其使用了如权利要求1或2或3所述的利用玉米秸秆制备精制木糖及可发酵糖的系统，所述方法包括如下步骤：
    步骤一、将玉米秸秆用粉碎机处理成粉状，然后干燥后得到绝干粉状玉米秸秆，粉状颗粒的尺寸在60目～300目；
    步骤二、将绝干粉状玉米秸秆与工艺水按一定比例混合后，并用30％浓碱液调节体系中NaOH浓度为0.1％～0.4％，在85℃～125℃温度下，碱处理1.2h～2.0h；然后经离心分离得到秸秆残渣和离心清液，离心清液进入木质素提取工序；
    步骤三、将秸秆残渣与1.0％～2.5％的稀H 2SO 4按一定比例混合，在130℃～160℃下酸解30min～50min，然后进行离心分离得到水解液和酸解残渣，酸解残渣经过纤维素酶的酶解处理后得到可用于发酵的葡萄糖液；
    步骤四、用碱性物质调节水解液至pH值为3.0～5.0后，依次采取脱色、离交、浓缩、结晶处理后得到晶体木糖。
  5. 如权利要求4所述的利用玉米秸秆制备精制木糖及可发酵糖的方法，其特征在于，在步骤一中，所使用的玉米秸秆的组分包括纤维素36％～41％，半纤维素19％～24％，木质素及其他35％～45％。
  6. 如权利要求4所述的利用玉米秸秆制备精制木糖及可发酵糖的方法，其特征在于，在 步骤一中，对粉状的玉米秸秆进行干燥方法是：将粉状的玉米秸秆放到鼓风式干燥箱中，在45℃下进行干燥，干燥24h，使得粉状的玉米秸秆的含水量为0。
  7. 如权利要求4所述的利用玉米秸秆制备精制木糖及可发酵糖的方法，其特征在于，在步骤四中，所述碱性物质为Ca(OH) 2。
  8. 如权利要求4所述的利用玉米秸秆制备精制木糖及可发酵糖的方法，其特征在于，在步骤四中，脱色处理时使用活性炭，活性炭的使用量为水解液体积的0.5％。
  9. 如权利要求4所述的利用玉米秸秆制备精制木糖及可发酵糖的方法，其特征在于，在步骤四中，浓缩处理时浓缩液的折光≥70％，随后进行降温结晶处理。
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