CN107337585B - A method for preparing monophenolic compounds by microwave depolymerization of lignin - Google Patents
A method for preparing monophenolic compounds by microwave depolymerization of lignin Download PDFInfo
- Publication number
- CN107337585B CN107337585B CN201710602146.7A CN201710602146A CN107337585B CN 107337585 B CN107337585 B CN 107337585B CN 201710602146 A CN201710602146 A CN 201710602146A CN 107337585 B CN107337585 B CN 107337585B
- Authority
- CN
- China
- Prior art keywords
- lignin
- microwave
- microwave depolymerization
- reaction
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims description 34
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000004227 thermal cracking Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 17
- 239000012495 reaction gas Substances 0.000 claims abstract description 16
- 239000012159 carrier gas Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000005292 vacuum distillation Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920001732 Lignosulfonate Polymers 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021431 alpha silicon carbide Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims 2
- 238000009834 vaporization Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 5
- -1 monophenol compound Chemical class 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域technical field
本发明属于生物质能源技术领域，具体涉及一种木质素微波解聚制备单酚类化合物的方法。The invention belongs to the technical field of biomass energy, and in particular relates to a method for preparing monophenolic compounds by microwave depolymerization of lignin.
背景技术Background technique
木质素是生物质的重要组成部分之一，是地球上丰富程度仅次于纤维素的可再生碳源。目前木质素来源主要为工业木质素，为制浆造纸工业的副产物，全世界每年来自造纸业的木质素量达5000万吨以上，目前主要的利用方式还是将其直接燃烧供热，利用附加值很低，急需寻求木质素高值化利用的新途径。Lignin is one of the important components of biomass and is the second most abundant renewable carbon source on earth after cellulose. At present, the main source of lignin is industrial lignin, which is a by-product of the pulp and paper industry. The amount of lignin from the paper industry in the world reaches more than 50 million tons every year. The value of lignin is very low, and it is urgent to find a new way of high-value utilization of lignin.
木质素由于结构中既有碳链又有芳香环，且连接有甲氧基(-OCH3)、羟基(-OH)、羧基(-CO)等多种活性官能团结构，是生产芳烃、酚类化合物等高价值精细化学品的理想原料。通过热化学转化的手段可以实现木质素一定程度的降解，然而，现阶段木质素热化学转化降解存在降解效率低、炭化现象严重、转化产物得率低、产物收集困难等问题，严重制约了木质素的高效转化利用。目前多数的研究通过在高压、高温、大量氢气气氛下实现木质素的降解，但过高的成本投入和产物品质的不理想制约着技术的发展。Lignin has both carbon chains and aromatic rings in its structure, and is connected with a variety of active functional groups such as methoxy (-OCH 3 ), hydroxyl (-OH), carboxyl (-CO), etc. Ideal raw material for high-value fine chemicals such as compounds. Lignin can be degraded to a certain extent by means of thermochemical conversion. However, at the current stage, the thermochemical conversion and degradation of lignin have problems such as low degradation efficiency, serious carbonization, low yield of conversion products, and difficulty in product collection, which seriously restrict lignin. efficient conversion and utilization of nutrients. Most of the current research achieves the degradation of lignin under high pressure, high temperature, and a large amount of hydrogen atmosphere, but the high cost and unsatisfactory product quality restrict the development of technology.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种木质素微波解聚制备单酚类化合物的方法，以克服上述现有技术存在的缺陷，本发明通过改变反应气氛来大幅度提高单酚类化合物产率和收率，为木质素高效转化为单酚类化合物提供重要技术支撑。The object of the present invention is to provide a method for preparing monophenolic compounds by microwave depolymerization of lignin, in order to overcome the above-mentioned defects in the prior art, the present invention greatly improves the yield and yield of monophenolic compounds by changing the reaction atmosphere , providing important technical support for the efficient conversion of lignin into monophenolic compounds.
为达到上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种木质素微波解聚制备单酚类化合物的方法，包括以下步骤：A method for preparing monophenolic compounds by microwave depolymerization of lignin, comprising the following steps:
步骤一：以质量份数计，将10份木质素与5～10份碳化硅颗粒混合均匀，置于微波解聚反应环境中；Step 1: in parts by mass, mix 10 parts of lignin and 5-10 parts of silicon carbide particles uniformly, and place them in a microwave depolymerization reaction environment;
步骤二：向微波解聚反应环境中连续通入载气和反应气的混合气，开始进行微波解聚反应；Step 2: continuously feed a mixture of carrier gas and reaction gas into the microwave depolymerization reaction environment, and start the microwave depolymerization reaction;
步骤三：将微波解聚反应生成的热裂解蒸气冷却，获得溶剂型热裂解液体；Step 3: cooling the thermal cracking vapor generated by the microwave depolymerization reaction to obtain a solvent-based thermal cracking liquid;
步骤四：将溶剂型热裂解液体进行减压蒸馏，当无蒸馏液馏出时，减压蒸馏结束，此时未蒸馏出的组分即为单酚类化合物。Step 4: The solvent-based thermal cracking liquid is subjected to vacuum distillation. When no distillate is distilled, the vacuum distillation is completed, and the components that are not distilled at this time are monophenolic compounds.
进一步地，所述的木质素为木质素磺酸盐、硫酸盐木质素、碱木质素、脱碱木质素、水解木质素或热解木质素，且木质素的粒径为0.05～0.5mm，含水率≤10％。Further, the lignin is lignosulfonate, sulfate lignin, alkali lignin, dealkalized lignin, hydrolyzed lignin or pyrolyzed lignin, and the particle size of the lignin is 0.05-0.5 mm, Moisture content≤10%.
进一步地，所述的碳化硅颗粒为纳米碳化硅颗粒、α-碳化硅颗粒或β-碳化硅颗粒，碳化硅颗粒的粒径为0.1～1.0mm。Further, the silicon carbide particles are nano-sized silicon carbide particles, α-silicon carbide particles or β-silicon carbide particles, and the particle size of the silicon carbide particles is 0.1-1.0 mm.
进一步地，步骤二中所述的混合气的流量为：每克步骤一中的木质素对应的混合气流量为10～50mL/min。Further, the flow rate of the mixed gas described in the second step is: the flow rate of the mixed gas corresponding to each gram of the lignin in the first step is 10-50 mL/min.
进一步地，所述的载气为氮气，所述的反应气为氢气与有机蒸气混合后的气体，氢气与有机蒸气的体积比为1:(10～50)，且载气与反应气的体积比为10:(1～5)。Further, the carrier gas is nitrogen, the reaction gas is a mixture of hydrogen and organic vapor, the volume ratio of hydrogen and organic vapor is 1:(10～50), and the volume of the carrier gas and the reaction gas The ratio is 10:(1～5).
进一步地，所述的有机蒸气为甲醇、乙醇、丙酮、乙醛、乙二醛、甲酸、乙醚或甲酸甲酯。Further, the organic vapor is methanol, ethanol, acetone, acetaldehyde, glyoxal, formic acid, diethyl ether or methyl formate.
进一步地，步骤二中微波解聚反应条件：微波频率为2.45GHz、微波功率为600～1200W、加热温度为500～650℃、反应时间为5～8分钟。Further, the microwave depolymerization reaction conditions in step 2: the microwave frequency is 2.45 GHz, the microwave power is 600-1200 W, the heating temperature is 500-650° C., and the reaction time is 5-8 minutes.
进一步地，步骤三中将微波解聚反应生成的热裂解蒸气在1～5℃冷凝温度下进行冷却。Further, in step 3, the thermal cracking vapor generated by the microwave depolymerization reaction is cooled at a condensation temperature of 1 to 5°C.
进一步地，步骤四中减压蒸馏温度为20～35℃，相对真空度为-0.085～-0.095Mpa。Further, in step 4, the vacuum distillation temperature is 20～35°C, and the relative vacuum degree is -0.085～-0.095Mpa.
进一步地，步骤四中减压蒸馏馏出的蒸馏液重新汽化后作为有机蒸气循环用于步骤二中。Further, the distillate obtained by distillation under reduced pressure in step 4 is re-evaporated and recycled as organic vapor in step 2.
与现有技术相比，本发明具有以下有益的技术效果：Compared with the prior art, the present invention has the following beneficial technical effects:
本发明提出的木质素微波解聚制备单酚类化合物的方法，实现了木质素的快速高效解聚，使得木质素解聚制备单酚类化合物达到了理论的得率，大幅度提高了木质素的利用率和利用价值，具体优点如下：The method for preparing monophenolic compounds by microwave depolymerization of lignin proposed in the present invention realizes the rapid and efficient depolymerization of lignin, makes the monophenolic compounds prepared by depolymerization of lignin reach the theoretical yield, and greatly improves the lignin The utilization rate and value of utilization, the specific advantages are as follows:
(1)传统解聚反应通常只加入载气如氮气进行，导致木质素的热转化效率很低，并且木质素转化过程中生成的单酚类化合物中间体在冷凝过程中容易二次缩聚生成焦油状物质无法使用，此外，传统使用氮气为载气反应生成的液体产物由于黏度大流动性差往往粘附在反应器壁上无法很好的收集到。本发明创新性的提出了将载气与反应气进行混合，反应气一方面很好的阻止了解聚生成的单酚类中间体的二次缩聚，另一方面作为溶剂将反应生成的单酚类化合物携带出反应体系，收集效率大幅度提高。(1) The traditional depolymerization reaction is usually only carried out by adding a carrier gas such as nitrogen, resulting in a very low thermal conversion efficiency of lignin, and the monophenolic compound intermediates generated during the lignin conversion process are prone to secondary polycondensation during the condensation process to form tar In addition, the liquid products produced by the traditional reaction using nitrogen as the carrier gas often adhere to the reactor wall and cannot be collected well due to the high viscosity and poor fluidity. The present invention innovatively proposes to mix the carrier gas and the reaction gas. On the one hand, the reaction gas can well prevent the secondary polycondensation of the monophenols intermediates generated by depolymerization, and on the other hand, it acts as a solvent for the monophenols generated by the reaction. The compound is carried out of the reaction system, and the collection efficiency is greatly improved.
(2)本发明提出了在微波解聚过程中通入载气和反应气的混合气，来提高木质素解聚为单酚类化合物的得率；其中，氮气作为载气主要起到保护气的作用，反应气为氢气和有机蒸气混合后的气体，反应气中氢气的体积比例比较小，主要作用是降低木质素中的醚键和碳碳键断裂的活化能，辅助断键；反应气中有机蒸气为沸点较低的小分子有机物，主要作用是当木质素中的醚键、碳碳键断裂时，这些小分子有机蒸气能够迅速嫁接到断键的两端，如甲醇中的甲基和羟基分别嫁接到断键的两端，以防止断裂的键进行二次缩聚，从而大幅度提高木质素微波解聚生成单酚类化合物的效率和转化率。(2) The present invention proposes to introduce a mixture of carrier gas and reaction gas into the microwave depolymerization process to improve the yield of lignin depolymerization into monophenolic compounds; wherein nitrogen as the carrier gas mainly acts as a protective gas The reaction gas is a mixture of hydrogen and organic vapor, and the volume ratio of hydrogen in the reaction gas is relatively small. The main function is to reduce the activation energy of the breaking of ether bonds and carbon-carbon bonds in lignin, and assist in breaking bonds; The reaction gas Medium organic vapor is a small molecule organic matter with a lower boiling point. The main function is that when the ether bond and carbon-carbon bond in lignin are broken, these small molecular organic vapor can be quickly grafted to both ends of the broken bond, such as methyl in methanol. and hydroxyl groups were grafted to both ends of the broken bonds to prevent the broken bonds from undergoing secondary polycondensation, thereby greatly improving the efficiency and conversion rate of lignin microwave depolymerization to generate monophenolic compounds.
(3)本发明将反应气中的有机蒸气在冷凝过程中重新收集后，经过减压蒸馏回收，重新气化循环利用作为反应气中的有机蒸气，大幅度提高了有机蒸气参与反应的效率，并且无废液排放，工艺清洁环保。(3) the present invention re-collects the organic vapor in the reaction gas in the condensation process, recovers through reduced pressure distillation, and re-gasifies and recycles the organic vapor as the reaction gas, greatly improving the efficiency of the organic vapor participating in the reaction, And there is no waste liquid discharge, and the process is clean and environmentally friendly.
具体实施方式Detailed ways
下面对本发明的实施方式做进一步详细描述：Embodiments of the present invention are described in further detail below:
针对目前木质素热转化过程中单酚类化合物中间体二次缩聚现象严重、转化为单酚类化合物效率和产率低、生成的单酚类化合物黏度大易在管壁沉积导致收集困难等问题，本发明提出一种木质素微波解聚制备单酚类化合物的方法，包括以下步骤：In view of the serious secondary polycondensation phenomenon of monophenolic compound intermediates in the current thermal conversion process of lignin, the conversion efficiency and yield of monophenolic compounds are low, and the viscosity of the generated monophenolic compounds is easy to deposit on the tube wall, resulting in difficulty in collection and so on. The present invention proposes a method for preparing monophenolic compounds by microwave depolymerization of lignin, comprising the following steps:
(1)将10质量份的木质素与(5～10)质量份的碳化硅颗粒混合均匀，置于微波解聚反应环境中。所述的木质素为木质素磺酸盐、硫酸盐木质素、碱木质素、脱碱木质素、水解木质素或热解木质素，粒径为0.05～0.5mm，含水率≤10％；所述的碳化硅为纳米碳化硅、α-碳化硅或β-碳化硅，粒径为0.1～1.0mm。(1) Mix 10 parts by mass of lignin and (5-10) parts by mass of silicon carbide particles uniformly, and place in a microwave depolymerization reaction environment. The lignin is lignosulfonate, sulfate lignin, alkali lignin, dealkalized lignin, hydrolyzed lignin or pyrolyzed lignin, the particle size is 0.05-0.5 mm, and the moisture content is less than or equal to 10%; The silicon carbide is nano-silicon carbide, α-silicon carbide or β-silicon carbide, and the particle size is 0.1-1.0 mm.
(2)微波反应环境中连续通入载气和反应气的混合气，开始进行微波解聚反应。所述的混合气的流量为：每克木质素对应的混合气流量为10～50mL/min；所述的载气为氮气，载气与反应气的体积比为10:(1～5)；所述的反应气为氢气与有机蒸气混合后的气体，氢气与有机蒸气的体积比为1:(10～50)，其中，有机蒸气为甲醇、乙醇、丙酮、乙醛、乙二醛、甲酸、乙醚、甲酸甲酯中的一种。所述的微波解聚反应条件为微波频率2.45GHz、微波功率600～1200W、加热温度500～650℃、反应时间5～8分钟。(2) The mixed gas of the carrier gas and the reaction gas is continuously introduced into the microwave reaction environment to start the microwave depolymerization reaction. The flow rate of the mixed gas is as follows: the flow rate of the mixed gas corresponding to each gram of lignin is 10-50 mL/min; the carrier gas is nitrogen, and the volume ratio of the carrier gas to the reaction gas is 10: (1-5); Described reaction gas is the gas after hydrogen and organic steam are mixed, the volume ratio of hydrogen and organic steam is 1: (10～50), wherein, organic steam is methanol, ethanol, acetone, acetaldehyde, glyoxal, formic acid , one of ether and methyl formate. The microwave depolymerization reaction conditions are microwave frequency 2.45GHz, microwave power 600-1200W, heating temperature 500-650°C, and reaction time 5-8 minutes.
(3)微波解聚生成的热裂解蒸气在1～5℃冷凝温度下进行冷却，获得溶剂型热裂解液体。(3) The thermal cracking vapor generated by microwave depolymerization is cooled at a condensation temperature of 1 to 5° C. to obtain a solvent-based thermal cracking liquid.
(4)将溶剂型热裂解液体进行减压蒸馏，减压蒸馏温度20～35℃，相对真空度-0.085～-0.095Mpa，当无蒸馏液馏出时，减压蒸馏结束，此时未蒸馏出的组分即为单酚类化合物。(4) The solvent-based thermal cracking liquid is subjected to vacuum distillation, the vacuum distillation temperature is 20～35 ℃, and the relative vacuum degree is -0.085～-0.095Mpa. When no distillate is distilled out, the vacuum distillation ends, and no distillation is performed at this time. The resulting components are monophenolic compounds.
(5)上述蒸馏出的馏出液重新汽化后循环用于步骤(2)中的有机蒸气。(5) The above-mentioned distillate is re-vaporized and recycled for the organic vapor in step (2).
下面结合实施例对本发明做进一步详细描述：Below in conjunction with embodiment, the present invention is described in further detail:
实施例1Example 1
以碱木质素原料为例介绍本发明的实施过程如下：Taking the alkali lignin raw material as an example to introduce the implementation process of the present invention as follows:
将10g碱木质素(粒径0.2～0.5mm，含水率8％)与5g的纳米碳化硅颗粒(粒径0.1～0.45mm)混合均匀，进行微波解聚反应。微波解聚反应中连续通入100mL/min氮气、1mL/min氢气和10mL/min甲醇的混合气，开始进行微波解聚反应，微波解聚反应条件为微波频率2.45GHz、微波功率600W、加热温度500℃、反应时间8分钟。微波解聚生成的热裂解蒸气在1℃冷凝温度下进行冷却，获得溶剂型热裂解液体。将溶剂型热裂解液体进行减压蒸馏，减压蒸馏温度20℃，相对真空度-0.085Mpa，当无蒸馏液馏出时，减压蒸馏结束，此时未蒸馏出的组分即为单酚类化合物。经称重，单酚类化合物为7.6g，产率达到76％；分子量测定范围集中在95～179Da，说明产物主要为单酚类化合物。10 g of alkali lignin (particle size 0.2-0.5 mm, moisture content 8%) and 5 g of nano-silicon carbide particles (particle size 0.1-0.45 mm) were mixed uniformly to carry out microwave depolymerization reaction. In the microwave depolymerization reaction, a mixture of 100 mL/min nitrogen, 1 mL/min hydrogen and 10 mL/min methanol was continuously introduced to start the microwave depolymerization reaction. The microwave depolymerization reaction conditions were microwave frequency 2.45 GHz, microwave power 600 W, and heating temperature. 500°C, reaction time 8 minutes. The thermal cracking vapor generated by microwave depolymerization is cooled at a condensation temperature of 1 °C to obtain a solvent-based thermal cracking liquid. The solvent-based thermal cracking liquid is subjected to vacuum distillation, the vacuum distillation temperature is 20 ° C, and the relative vacuum degree is -0.085Mpa. When no distillate is distilled, the vacuum distillation is completed, and the component that is not distilled at this time is monophenol. class compounds. After weighing, the monophenolic compound was 7.6 g, and the yield reached 76%; the molecular weight determination range was concentrated in 95-179Da, indicating that the product was mainly monophenolic compound.
实施例2Example 2
以热解木质素原料为例介绍本发明的实施过程如下：Taking the pyrolysis lignin raw material as an example to introduce the implementation process of the present invention as follows:
将10g热解木质素(粒径0.05～0.1mm，含水率3％)与10g的α-碳化硅颗粒(粒径0.45～1.0mm)混合均匀，进行微波解聚反应。微波解聚反应中连续通入300mL/min氮气、3mL/min氢气和150mL/min乙醛的混合气，开始进行微波解聚反应，微波解聚反应条件为微波频率2.45GHz、微波功率1200W、加热温度650℃、反应时间5分钟。微波解聚生成的热裂解蒸气在5℃冷凝温度下进行冷却，获得溶剂型热裂解液体。将溶剂型热裂解液体进行减压蒸馏，减压蒸馏温度35℃，相对真空度-0.095Mpa，当无蒸馏液馏出时，减压蒸馏结束，此时未蒸馏出的组分即为单酚类化合物。经称重，单酚类化合物为6.8g，产率达到68％；分子量测定范围集中在95～131Da，说明产物主要为单酚类化合物。Mix 10 g of pyrolyzed lignin (particle size 0.05-0.1 mm, moisture content 3%) and 10 g of α-silicon carbide particles (particle size 0.45-1.0 mm) to conduct microwave depolymerization reaction. In the microwave depolymerization reaction, a mixture of 300 mL/min nitrogen, 3 mL/min hydrogen and 150 mL/min acetaldehyde was continuously introduced to start the microwave depolymerization reaction. The microwave depolymerization reaction conditions were microwave frequency 2.45 GHz, microwave power 1200 W, heating The temperature was 650°C and the reaction time was 5 minutes. The thermal cracking vapor generated by microwave depolymerization is cooled at a condensation temperature of 5°C to obtain a solvent-based thermal cracking liquid. The solvent-based thermal cracking liquid is subjected to vacuum distillation, the vacuum distillation temperature is 35 ° C, and the relative vacuum degree is -0.095Mpa. When no distillate is distilled, the vacuum distillation is completed, and the component that is not distilled at this time is monophenol. class compounds. After weighing, the monophenolic compound was 6.8 g, and the yield reached 68%; the molecular weight determination range was concentrated in 95-131Da, indicating that the product was mainly monophenolic compound.
实施例3Example 3
以木质素磺酸盐原料为例介绍本发明的实施过程如下：Taking the lignosulfonate raw material as an example, the implementation process of the present invention is introduced as follows:
将10g木质素磺酸盐(粒径0.1～0.3mm，含水率5％)与8g的β-碳化硅颗粒(粒径0.45～0.6mm)混合均匀，进行微波解聚反应。微波解聚反应中连续通入200mL/min氮气、2mL/min氢气和50mL/min甲酸甲酯的混合气，开始进行微波解聚反应，微波解聚反应条件为微波频率2.45GHz、微波功率1000W、加热温度550℃、反应时间6分钟。微波解聚生成的热裂解蒸气在3℃冷凝温度下进行冷却，获得溶剂型热裂解液体。将溶剂型热裂解液体进行减压蒸馏，减压蒸馏温度30℃，相对真空度-0.090Mpa，当无蒸馏液馏出时，减压蒸馏结束，此时未蒸馏出的组分即为单酚类化合物。经称重，单酚类化合物为7.3g，产率达到73％；分子量测定范围集中在110～184Da，说明产物主要为单酚类化合物。10 g of lignosulfonate (particle size 0.1-0.3 mm, moisture content 5%) and 8 g of β-silicon carbide particles (particle size 0.45-0.6 mm) were mixed uniformly to carry out microwave depolymerization reaction. In the microwave depolymerization reaction, a mixture of 200 mL/min nitrogen, 2 mL/min hydrogen and 50 mL/min methyl formate was continuously fed to start the microwave depolymerization reaction. The microwave depolymerization reaction conditions were microwave frequency 2.45 GHz, microwave power 1000 W, The heating temperature was 550°C, and the reaction time was 6 minutes. The thermal cracking vapor generated by microwave depolymerization is cooled at a condensation temperature of 3 °C to obtain a solvent-based thermal cracking liquid. The solvent-based thermal cracking liquid is subjected to vacuum distillation, the vacuum distillation temperature is 30 ° C, and the relative vacuum degree is -0.090Mpa. When no distillate is distilled, the vacuum distillation is completed, and the component that is not distilled at this time is monophenol. class compounds. After weighing, the monophenolic compound was 7.3 g, and the yield reached 73%; the molecular weight measurement range was concentrated in 110-184Da, indicating that the product was mainly monophenolic compound.
上述实施例中的木质素也可以为硫酸盐木质素、脱碱木质素或水解木质素；有机蒸气也可以为乙醇、丙酮、乙二醛、甲酸或乙醚。The lignin in the above embodiments can also be sulfated lignin, dealkalized lignin or hydrolyzed lignin; the organic vapor can also be ethanol, acetone, glyoxal, formic acid or diethyl ether.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710602146.7A CN107337585B (en) | 2017-07-21 | 2017-07-21 | A method for preparing monophenolic compounds by microwave depolymerization of lignin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710602146.7A CN107337585B (en) | 2017-07-21 | 2017-07-21 | A method for preparing monophenolic compounds by microwave depolymerization of lignin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107337585A CN107337585A (en) | 2017-11-10 |
| CN107337585B true CN107337585B (en) | 2020-06-05 |
Family
ID=60216388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710602146.7A Active CN107337585B (en) | 2017-07-21 | 2017-07-21 | A method for preparing monophenolic compounds by microwave depolymerization of lignin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107337585B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987866B (en) * | 2018-01-15 | 2023-06-30 | 陕西科技大学 | Device and method for efficiently depolymerizing solid waste by microwaves and co-producing bio-oil and biochar |
| CN110407888B (en) * | 2019-08-09 | 2020-11-06 | 陕西科技大学 | Method for promoting depolymerization of sulfate lignin by using waste cigarette filter tip |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838453A (en) * | 2012-08-28 | 2012-12-26 | 华北电力大学 | Method to prepare phenolic organic mixture preparation by means of catalytic pyrolysis of biomass through coke |
| CN102939322A (en) * | 2010-03-18 | 2013-02-20 | 原子能与替代能源署 | Method for the depolymerisation of lignocellulosic biomass |
| CN103073395A (en) * | 2012-12-11 | 2013-05-01 | 浙江大学 | Technology for preparing micro-molecular phenolic compound through microwave reinforced continuous degradation of lignin in hydrogen donor |
| CN103910903A (en) * | 2013-01-08 | 2014-07-09 | 天津大学 | Application of molybdenum-based catalyst to prepare organic chemicals from lignin |
| WO2016003583A1 (en) * | 2014-07-01 | 2016-01-07 | Biomass Energy Enhancements Llc | Microwave produced pyrolysis oil from beneficiated organic-carbon-containing feedstock |
| CN106517190A (en) * | 2016-10-27 | 2017-03-22 | 陕西科技大学 | Co-production method of monophenol compound and activated carbon by lignin catalytic pyrolysis |
| CN106635110A (en) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues |
-
2017
- 2017-07-21 CN CN201710602146.7A patent/CN107337585B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102939322A (en) * | 2010-03-18 | 2013-02-20 | 原子能与替代能源署 | Method for the depolymerisation of lignocellulosic biomass |
| CN102838453A (en) * | 2012-08-28 | 2012-12-26 | 华北电力大学 | Method to prepare phenolic organic mixture preparation by means of catalytic pyrolysis of biomass through coke |
| CN103073395A (en) * | 2012-12-11 | 2013-05-01 | 浙江大学 | Technology for preparing micro-molecular phenolic compound through microwave reinforced continuous degradation of lignin in hydrogen donor |
| CN103910903A (en) * | 2013-01-08 | 2014-07-09 | 天津大学 | Application of molybdenum-based catalyst to prepare organic chemicals from lignin |
| WO2016003583A1 (en) * | 2014-07-01 | 2016-01-07 | Biomass Energy Enhancements Llc | Microwave produced pyrolysis oil from beneficiated organic-carbon-containing feedstock |
| CN106517190A (en) * | 2016-10-27 | 2017-03-22 | 陕西科技大学 | Co-production method of monophenol compound and activated carbon by lignin catalytic pyrolysis |
| CN106635110A (en) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues |
Non-Patent Citations (1)
| Title |
|---|
| 木质素液化产物中生物油的盐析萃取分离工艺;欧阳新平等;《华南理工大学学报(自然科学版)》;20161115(第11期);第7-11页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107337585A (en) | 2017-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108865196B (en) | Preparation method of biochar | |
| CN102807885B (en) | Method for preparing high-quality bio-oil based on microwave activation and pyrolysis gas recycling | |
| CN102963866B (en) | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis | |
| Li et al. | Microwave‐assisted hydrothermal liquefaction of lignin for the preparation of phenolic formaldehyde adhesive | |
| CN102580650A (en) | Continuous reaction device and method for microwave biomass pyrolysis | |
| CN104357071B (en) | A method for directional production of biomass charcoal, biomass oil and biomass gas by using microwave catalytic pyrolysis of biomass | |
| CN114790397B (en) | A method for preparing electrode materials by polymerizing and modifying biomass pyrolysis oil | |
| CN107337585B (en) | A method for preparing monophenolic compounds by microwave depolymerization of lignin | |
| CN102351564A (en) | Method for preparing wood ceramics by sintering coal tar pitch and biomass materials | |
| WO2018227842A1 (en) | Catalyst used for producing aromatic-rich biofuel, and method for preparing same | |
| CN102108301A (en) | Method for producing high-yield tar by pyrolyzing coal | |
| CN109232976B (en) | Nitrogen-phosphorus synergistic flame retardant containing cardanol base, and preparation method and application thereof | |
| CN102190298A (en) | Method for preparing active carbon from carbon byproduct in fast pyrolysis of forest remainder | |
| CN103484158B (en) | Method for preparing chemicals containing phenols and aromatic hydrocarbons from bio-oil pyrolysis lignin through catalysis | |
| CN114620724B (en) | Method for preparing formed active carbon by modifying bamboo pyrolysis gasification byproducts | |
| CN102807216A (en) | Method for preparing activated carbon with high specific surface area utilizing wood tar | |
| CN109675550B (en) | Molybdenum-boron/sepiolite catalyst and preparation method and application thereof | |
| CN105001902B (en) | A kind of guaiacol catalytic deoxidation Hydrogenation is for the method for hydrocarbon | |
| CN110205159A (en) | A kind of tar fused salt reforms beam system for the method and product of high quality oils | |
| CN113831927A (en) | Method for improving yield of low-metamorphic coal pyrolysis tar by utilizing biomass | |
| CN111099946B (en) | Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin | |
| CN112625764B (en) | Method for producing biofuel by efficiently converting lignin | |
| CN116000066A (en) | Method for treating woody plant garbage by microwave coupling alkali | |
| Wang | The study on physicochemical characteristics of wood treated by ultrasound-assisted extraction | |
| CN115521345B (en) | Method for depolymerizing industrial alkali lignin by inorganic molten salt hydrate system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240425 Address after: Room 1130, Building 1, No. 368, the Pearl River South Road, Mudu Town, Wuzhong District, Suzhou City, Jiangsu Province, 215101 Patentee after: Suzhou qinfengju Technology Co.,Ltd. Country or region after: China Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right |