CN110684204A - Method for separating wood fiber by organic acid and homologously preparing furfural - Google Patents
Method for separating wood fiber by organic acid and homologously preparing furfural Download PDFInfo
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- 150000007524 organic acids Chemical class 0.000 title claims abstract description 47
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229920002522 Wood fibre Polymers 0.000 title claims abstract description 12
- 239000002025 wood fiber Substances 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920005610 lignin Polymers 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 239000001913 cellulose Substances 0.000 claims abstract description 13
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 241000609240 Ambelania acida Species 0.000 claims description 13
- 239000010905 bagasse Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000005844 autocatalytic reaction Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000010902 straw Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 7
- 235000005985 organic acids Nutrition 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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Abstract
本发明属于生物质高效利用领域，公开了一种有机酸分离木质纤维及同源制备糠醛的方法。该方法高效分离了木质素，纤维素和半纤维素。该方法包括以下步骤：将木质纤维干燥后粉碎；木质纤维粉末与有机酸在50～120℃条件下反应10～90min；反应结束后，加入冷水终止反应；之后过滤，得到固液两部分，固体部分为纤维素，液体部分经过纯水稀释离心沉淀分离，得到高纯度木质素，液体为半纤维素水解的五碳糖。该方法高效分离木质纤维的三大组分，利用有机酸强酸且不具有氧化性的性质，生物质损失率低。溶解的半纤维素经过分离利用的有机酸加热自催化高效转化制备糠醛，而有机酸溶液经浓缩循环利用，实现了绿色循环处理工艺，为生物质高值化利用提供基础。The invention belongs to the field of efficient utilization of biomass, and discloses a method for separating wood fiber with organic acid and preparing furfural by homology. The method separates lignin, cellulose and hemicellulose with high efficiency. The method includes the following steps: drying the lignocellulose and then pulverizing it; reacting the lignocellulose powder with an organic acid at 50-120° C. for 10-90 minutes; after the reaction is completed, adding cold water to terminate the reaction; The part is cellulose, the liquid part is diluted with pure water, centrifuged and separated to obtain high-purity lignin, and the liquid is penta-carbon sugar hydrolyzed by hemicellulose. The method efficiently separates the three components of the lignocellulose, utilizes the strong acidity of organic acids and does not have oxidative properties, and has a low biomass loss rate. The dissolved hemicellulose is heated and autocatalytically converted to furfural by the separated and utilized organic acid, and the organic acid solution is concentrated and recycled to realize a green recycling process and provide a basis for the high-value utilization of biomass.
Description
技术领域technical field
本发明属于生物质高效利用领域，特别涉及一种有机酸分离木质纤维及同源制备糠醛的方法。The invention belongs to the field of high-efficiency utilization of biomass, and particularly relates to a method for separating wood fiber by organic acid and preparing furfural by homology.
背景技术Background technique
随着不可再生资源的日益消耗以及石油炼制衍生平台化学品需求的日益增加，急需开发一种可代替性的绿色能源。生物质作为一种可再生的资源具有来源广泛，储量大，环境友好等特点。生物质资源主要来源于城市垃圾，秸秆、木屑、树枝等农林废弃物，其年产量达到1700亿吨，而石油每年消耗50亿吨，煤消耗量达200亿吨，如果将这些木质纤维资源高效利用，那么将会给能源经济带来不可估量的作用。With the increasing consumption of non-renewable resources and the increasing demand for chemicals derived from petroleum refining platforms, there is an urgent need to develop an alternative green energy source. As a renewable resource, biomass has the characteristics of wide sources, large reserves and environmental friendliness. Biomass resources mainly come from urban waste, straw, wood chips, branches and other agricultural and forestry wastes. Its annual output reaches 170 billion tons, while the annual oil consumption reaches 5 billion tons and the coal consumption reaches 20 billion tons. If these wood fiber resources are efficiently utilized utilization, it will bring immeasurable effects to the energy economy.
大量的木质纤维废弃物，目前处理的方式主要是掩埋腐化，就地焚烧等，利用率很低，且是对天然可再生资源的浪费。预处理是生物质高效利用的一个关键步骤，也是整个运作过程中最昂贵的步骤之一，对后续三大组分木质素，半纤维素以及纤维素的利用都有较大的影响。A large amount of wood fiber waste, the current treatment methods are mainly burial and decay, on-site incineration, etc., the utilization rate is very low, and it is a waste of natural renewable resources. Pretreatment is a key step in the efficient utilization of biomass, and it is also one of the most expensive steps in the entire operation process. It has a great impact on the utilization of the following three components, lignin, hemicellulose and cellulose.
木质纤维是一种天然的三维网状的高分子聚合物，其中木质素是一种粘合剂，起着保护和支撑作用。因此，去木质化是整个预处理关键一步。木质纤维预处理方法很多，可划分为物理法、化学法、生物法以及他们相结合的方法。但是大多处预处理方法的处理时间较长，温度较高，能量输入大，使得操作运行成本较高，且会对设备造成一定的腐蚀，这也就限制了生物质资源的大规模应用。因此急需开发一种绿色、循环经济的新型溶剂，对木质纤维进行有效的处理分离。Lignin is a natural three-dimensional network of high-molecular polymers, in which lignin is a binder, which plays a protective and supportive role. Therefore, delignification is a key step in the whole pretreatment. There are many pretreatment methods for lignocellulose, which can be divided into physical methods, chemical methods, biological methods and their combined methods. However, most of the pretreatment methods have long processing time, high temperature and large energy input, which make the operation cost high and cause certain corrosion to the equipment, which also limits the large-scale application of biomass resources. Therefore, there is an urgent need to develop a new type of solvent with green and circular economy to effectively treat and separate wood fibers.
发明内容SUMMARY OF THE INVENTION
为了克服现有木质纤维素生物质分离技术中存在过程处理时间较长，产生大量废酸废碱带来环境污染、运行成本较高的缺点和不足，以及生物质分离半纤维素制备糠醛的低效能，本发明的首要目的在于提供一种有机酸分离木质纤维及同源制备糠醛的方法；该方法是破坏木质纤维的三维网状结构，从而高效分离纤维素、木质素，为高值化利用提供基础，半纤维素经同源有机酸加热的简单工艺制备高纯糠醛；具有操作温度较低、处理时间很短、能够实现快速的去木质化，而且有机酸试剂廉价、循环可再生，具有极大的应用价值，市场情景可观。In order to overcome the shortcomings and deficiencies of the existing lignocellulosic biomass separation technology, which has a long process processing time, a large amount of waste acid and waste alkali, environmental pollution, and high operating costs, and the low cost of biomass separation hemicellulose to prepare furfural The primary purpose of the present invention is to provide a method for separating lignocellulose with organic acid and preparing furfural by homology; the method is to destroy the three-dimensional network structure of lignofiber, thereby efficiently separating cellulose and lignin, which is a high-value utilization Provides a basis for the preparation of high-purity furfural by a simple process of heating hemicellulose by homologous organic acids; it has the advantages of low operating temperature, short treatment time, rapid delignification, cheap organic acid reagents, and recyclable regeneration. Great application value and considerable market scenarios.
本发明目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种有机酸分离木质纤维及同源制备糠醛的方法，包括以下操作步骤：将木质纤维干燥后，粉碎待用；向木质纤维粉末中加入有机酸，有机酸和木质纤维粉末的液固比按照(8～30)mL：1g，采用油浴加热法处理木质纤维粉末，于50～120℃下搅拌反应10～90min，反应结束后加入冷水稀释终止反应；将反应体系在室温条件下进行真空分离，得到固液两部分，固体部分为纤维素；液体部分经过纯水稀释离心沉淀分离，得到沉淀为纯度90％以上的木质素，上清液为半纤维素水解的五碳糖。A method for separating lignocellulose and homologous preparation of furfural by organic acid, comprising the following operation steps: after drying the lignocellulose, pulverizing it for use; adding an organic acid to the lignocellulose powder, and the liquid-solid ratio of the organic acid and the lignocellulose powder is as follows: (8～30)mL: 1g, use oil bath heating method to treat lignocellulosic powder, stir the reaction at 50～120℃ for 10～90min, add cold water after the reaction to dilute to terminate the reaction; carry out vacuum separation of the reaction system at room temperature , to obtain two parts of solid and liquid, the solid part is cellulose; the liquid part is diluted with pure water, centrifuged and separated to obtain lignin with a purity of more than 90%, and the supernatant is penta-carbon sugar hydrolyzed by hemicellulose.
所述木质纤维为秸秆、蔗渣、玉米芯、木屑和稻草中的一种以上。The wood fiber is one or more of straw, bagasse, corncob, sawdust and straw.
所述有机酸为质量浓度分数为50～85％的溶液，具体为顺丁烯二酸、甲酸、乙酸、对甲苯磺酸、草酸和磷酸中的一种以上。The organic acid is a solution with a mass concentration fraction of 50-85%, specifically one or more of maleic acid, formic acid, acetic acid, p-toluenesulfonic acid, oxalic acid and phosphoric acid.
所述搅拌反应的时间为10～90min。The time of the stirring reaction is 10-90 min.
所述加入冷水稀释终止反应中使用的冷水的量按照每2g木质纤维粉末使用20～40mL冷水。The amount of cold water used in the dilution termination reaction by adding cold water is 20-40 mL of cold water per 2 g of lignocellulosic powder.
所述液体部分经过纯水稀释离心沉淀分离具体按照以下步骤：将液体部分稀释至酸的质量分数为2～10％，转入离心机中于3000～8000r离心5-15min，得到的沉淀即为木质素，冷冻干燥备用；对所得上清液加热升温至100℃，利用有机酸为催化剂进行自催化，制备糠醛，之后对溶液进行旋蒸浓缩，得到有机酸溶液进行循环利用。The liquid part is diluted with pure water, centrifuged and separated according to the following steps: the liquid part is diluted to an acid mass fraction of 2-10%, transferred to a centrifuge and centrifuged at 3000-8000r for 5-15min, and the obtained precipitate is lignin, freeze-drying for later use; heating the obtained supernatant to 100° C., using organic acid as a catalyst for autocatalysis to prepare furfural, and then performing rotary evaporation and concentration on the solution to obtain an organic acid solution for recycling.
本发明相对于现有技术具有如下的优点及效果：Compared with the prior art, the present invention has the following advantages and effects:
(1)本发明创造性地利用有机酸的性质处理分离木质纤维，实验过程简单，操作方便，有机酸水溶液廉价绿色可循环，可实现高效地实现去木质化过程，其处理效果与传统碱法纸浆在150℃，处理2h相当，极大地降低了处理分离成本，具有极高的应用价值，市场前景广阔。(1) The present invention creatively utilizes the properties of organic acids to process and separate wood fibers, the experimental process is simple, the operation is convenient, the organic acid aqueous solution is cheap, green, and recyclable, and the process of delignification can be efficiently realized, and its treatment effect is similar to that of traditional alkaline pulp. At 150°C, the treatment is equivalent to 2h, which greatly reduces the cost of treatment and separation, and has extremely high application value and broad market prospects.
(2)基于有机酸处理得到的木质素纯度较高，90％以上的木质素去除，增加了纤维素酶对纤维素的可及性，大大增加了后续的酶解效率。(2) The lignin obtained by the organic acid treatment is of high purity, and more than 90% of the lignin is removed, which increases the accessibility of cellulase to cellulose and greatly increases the subsequent enzymatic hydrolysis efficiency.
(3)本发明方法高效分离木质纤维的三大组分，利用有机酸强酸且不具有氧化性的性质，生物质损失率低；溶解的半纤维素经过分离利用的有机酸加热自催化高效转化制备糠醛，而有机酸溶液经浓缩循环利用，实现了绿色循环处理工艺，为生物质高值化利用提供基础。(3) The method of the present invention efficiently separates the three major components of lignocellulose, utilizes organic acids that are strong acid and does not have oxidative properties, and has low biomass loss rate; dissolved hemicellulose is heated and efficiently converted by organic acids separated and utilized by autocatalysis Furfural is prepared, and the organic acid solution is concentrated and recycled to realize a green recycling process and provide a basis for high-value utilization of biomass.
附图说明Description of drawings
图1为蔗渣经过本发明方法处理分离前后的显微图，其中(a)为未经有机酸处理的蔗渣纤维的显微图，(b)为经过有机酸处理的蔗渣纤维的显微图。Figure 1 is a micrograph of bagasse before and after separation by the method of the present invention, wherein (a) is a micrograph of bagasse fiber without organic acid treatment, and (b) is a micrograph of bagasse fiber treated with organic acid.
图2为蔗渣经过本发明方法处理分离前后的FTI R图谱分析。Fig. 2 is the FTI R spectrum analysis of bagasse before and after treatment and separation by the method of the present invention.
具体实施方法Specific implementation method
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be described in further detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.
实施例中的原料均可通过市售得到；除非特别说明，本发明所采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The raw materials in the examples are all commercially available; unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
实施例1Example 1
称取2g 40-60目秸秆于烧杯中，加入质量浓度为75％的对甲苯磺酸水溶液16mL，在50℃下，油浴反应10min，反应结束后加入20mL去离子水后，将反应体系在室温条件下进行真空分离，得到固液两部分，固体部分经过蒸馏水多次洗涤至中性，经冷冻干燥后获得纤维素，置于干燥箱中备用。收集液体部分，记录体积，稀释至2％，5000r下离心5min，得到沉淀为木质素；所得上清液加热升温至100℃，利用有机酸为催化剂进行自催化，制备糠醛，之后对溶液进行旋蒸浓缩，得到有机酸溶液进行循环利用。Weigh 2 g of 40-60 mesh straw into a beaker, add 16 mL of p-toluenesulfonic acid aqueous solution with a mass concentration of 75%, and react at 50 ° C in an oil bath for 10 min. After the reaction is completed, add 20 mL of deionized water, and put the reaction system in Vacuum separation is carried out at room temperature to obtain two parts of solid and liquid. The solid part is washed with distilled water for many times to neutrality, and cellulose is obtained after freeze drying, which is placed in a drying box for use. Collect the liquid part, record the volume, dilute to 2%, centrifuge at 5000 r for 5 min, and obtain the precipitate as lignin; the obtained supernatant is heated to 100 ° C, and the organic acid is used as a catalyst for autocatalysis to prepare furfural, and then the solution is rotated. Evaporate and concentrate to obtain organic acid solution for recycling.
实施例2Example 2
称取2g 40-60目秸秆于烧杯中，加入质量浓度为65％的磷酸水溶液30mL，在80℃下油浴反应60min，反应结束后加入25mL去离子水后，将反应体系在室温条件下进行真空分离，得到固液两部分，固体部分经过蒸馏水多次洗涤至中性，经冷冻干燥后获得纤维素，置于干燥箱中备用。收集液体部分，记录体积，稀释至5％，3000r下离心15min，得到沉淀为木质素；所得上清液加热升温至100℃，利用有机酸为催化剂进行自催化，制备糠醛，之后对溶液进行旋蒸浓缩，得到有机酸溶液进行循环利用。Weigh 2 g of 40-60 mesh straw into a beaker, add 30 mL of phosphoric acid aqueous solution with a mass concentration of 65%, and react in an oil bath at 80 ° C for 60 min. After the reaction is completed, add 25 mL of deionized water, and carry out the reaction system at room temperature. Vacuum separation to obtain two parts of solid and liquid, the solid part is washed with distilled water for many times until neutral, and freeze-dried to obtain cellulose, which is placed in a drying box for use. Collect the liquid part, record the volume, dilute to 5%, and centrifuge at 3000 r for 15 min to obtain the precipitation as lignin; the obtained supernatant is heated to 100 ° C, and the organic acid is used as a catalyst for autocatalysis to prepare furfural, and then the solution is rotated. Evaporate and concentrate to obtain organic acid solution for recycling.
实施例3Example 3
称取2g 40-60目甘蔗渣于烧杯中，加入质量浓度为60％的顺丁烯二酸水溶液40mL，在100℃下油浴反应70min，反应结束后加入30mL去离子水后，将反应体系在室温条件下进行真空分离，得到固液两部分，固体部分经过蒸馏水多次洗涤至中性，经冷冻干燥后获得纤维素，置于干燥箱中备用。收集液体部分，记录体积，稀释至7％，8000r下离心5min，得到沉淀为木质素；所得上清液加热升温至100℃，利用有机酸为催化剂进行自催化，制备糠醛，之后对溶液进行旋蒸浓缩，得到有机酸溶液进行循环利用。Weigh 2 g of 40-60 mesh bagasse into a beaker, add 40 mL of an aqueous solution of maleic acid with a mass concentration of 60%, react in an oil bath at 100 ° C for 70 min, and add 30 mL of deionized water after the reaction is completed. Vacuum separation is carried out at room temperature to obtain two parts of solid and liquid. The solid part is washed with distilled water for many times until neutral, and freeze-dried to obtain cellulose, which is placed in a drying box for use. Collect the liquid part, record the volume, dilute to 7%, centrifuge at 8000 r for 5 min, and obtain the precipitate as lignin; the obtained supernatant is heated to 100 ° C, and the organic acid is used as a catalyst for autocatalysis to prepare furfural, and then the solution is rotated. Evaporate and concentrate to obtain organic acid solution for recycling.
蔗渣经过本发明方法处理分离前后的显微图如图1所示，从图中可以看出，未经有机酸处理的蔗渣纤维束排列有序，结构紧密，表面光滑平整；经过有机酸处理后，由于木质素和半纤维素的降解溶出，纤维素表面变得粗糙不平，出现许多沟壑孔洞，暴露出内部的纤维束。The micrographs of bagasse before and after separation by the method of the present invention are shown in Figure 1. As can be seen from the figure, the bagasse fiber bundles without organic acid treatment are arranged in an orderly manner, with compact structure and smooth surface; , due to the degradation and dissolution of lignin and hemicellulose, the surface of cellulose becomes rough and uneven, and many gullies and holes appear, exposing the inner fiber bundles.
蔗渣经过本发明方法处理分离前后的FTI R图谱分析如图2所示，蔗渣组分的结构变化可通过FTI R图谱分析。1734cm-1是蔗渣原料中半纤维素的羰基特征吸收峰，此峰强度经过预处理后几乎消失，表明处理分离过程中半纤维素水脱除。1513cm-1是蔗渣原料木质素芳环特征吸收峰，经过预处理分离后，此峰强度变得微弱，说明经有机酸处理后，木质素脱除效果良好。The FTI R spectrum analysis of bagasse before and after treatment and separation by the method of the present invention is shown in Figure 2, and the structural changes of the bagasse components can be analyzed by the FTI R spectrum. 1734cm -1 is the characteristic absorption peak of carbonyl group of hemicellulose in bagasse raw material. The intensity of this peak almost disappears after pretreatment, indicating that the water of hemicellulose is removed during the separation process. 1513cm -1 is the characteristic absorption peak of the lignin aromatic ring of the bagasse raw material. After pretreatment and separation, the intensity of this peak becomes weak, indicating that the lignin removal effect is good after the organic acid treatment.
实施例4Example 4
称取2g 40-60目稻草于烧杯中，加入质量浓度为55％的草酸水溶液50mL，在110℃下油浴反应80min，反应结束后加入35mL去离子水后，将反应体系在室温条件下进行真空分离，得到固液两部分，固体部分经过蒸馏水多次洗涤至中性，经冷冻干燥后获得纤维素，置于干燥箱中备用。收集液体部分，记录体积，稀释至8％，5000r下离心10min，得到沉淀为木质素；所得上清液加热升温至100℃，利用有机酸为催化剂进行自催化，制备糠醛，之后对溶液进行旋蒸浓缩，得到有机酸溶液进行循环利用。Weigh 2g of 40-60 mesh straw into a beaker, add 50mL of oxalic acid aqueous solution with a mass concentration of 55%, react in an oil bath at 110°C for 80min, add 35mL of deionized water after the reaction, and carry out the reaction system at room temperature. Vacuum separation to obtain two parts of solid and liquid, the solid part is washed with distilled water for many times until neutral, and freeze-dried to obtain cellulose, which is placed in a drying box for use. Collect the liquid part, record the volume, dilute to 8%, and centrifuge at 5000r for 10min to obtain the precipitate as lignin; the obtained supernatant is heated to 100°C, and the organic acid is used as a catalyst for autocatalysis to prepare furfural, and then the solution is rotated. Evaporate and concentrate to obtain organic acid solution for recycling.
实施例5Example 5
称取2g 40-60目木屑于烧杯中，加入质量浓度为55％的乙酸水溶液60mL，在120℃下油浴反应90min，反应结束后加入40mL去离子水后，将反应体系在室温条件下进行真空分离，得到固液两部分，固体部分经过蒸馏水多次洗涤至中性，经冷冻干燥后获得纤维素，置于干燥箱中备用。收集液体部分，记录体积，稀释至10％，5000r下离心15min，得到沉淀为木质素；所得上清液加热升温至100℃，利用有机酸为催化剂进行自催化，制备糠醛，之后对溶液进行旋蒸浓缩，得到有机酸溶液进行循环利用。Weigh 2g of 40-60 mesh sawdust in a beaker, add 60 mL of acetic acid aqueous solution with a mass concentration of 55%, react in an oil bath at 120 ° C for 90 min, add 40 mL of deionized water after the reaction, and carry out the reaction system at room temperature. Vacuum separation to obtain two parts of solid and liquid, the solid part is washed with distilled water for many times until neutral, and freeze-dried to obtain cellulose, which is placed in a drying box for use. Collect the liquid part, record the volume, dilute to 10%, and centrifuge at 5000r for 15min to obtain the precipitate as lignin; the obtained supernatant is heated to 100°C, and the organic acid is used as a catalyst for autocatalysis to prepare furfural, and then the solution is rotated. Evaporate and concentrate to obtain organic acid solution for recycling.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.
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| CN116374990A (en) * | 2023-03-08 | 2023-07-04 | 华南理工大学 | Method for Pretreating Lignocellulosic Biomass with Formic Acid to Prepare Powder/Block Biomass Grade Porous Carbon |
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