CN111099946A - Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin - Google Patents
Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin Download PDFInfo
- Publication number
- CN111099946A CN111099946A CN201911377945.4A CN201911377945A CN111099946A CN 111099946 A CN111099946 A CN 111099946A CN 201911377945 A CN201911377945 A CN 201911377945A CN 111099946 A CN111099946 A CN 111099946A
- Authority
- CN
- China
- Prior art keywords
- microwave
- lignin
- aromatic hydrocarbon
- nitrogen
- tubular reactor
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for preparing aromatic hydrocarbon compounds by microwave-assisted depolymerization of lignin, which comprises the steps of firstly, uniformly mixing the lignin with the particle size of 20-150 meshes and molybdenum disulfide with the particle size of 60-100 meshes, and placing the mixture in a microwave tubular reactor; then introducing nitrogen into the microwave tubular reactor to exhaust air in a reaction system, keeping the nitrogen continuously introduced, and then introducing methanol gas and hydrogen chloride gas, wherein the volume flow ratio of the introduced nitrogen to the methanol gas to the hydrogen chloride gas is (0.1-1) to (0.01-0.1); and finally, starting a microwave tubular reactor, wherein the microwave frequency is 2.45GHz, the microwave power is 800-1200W, heating to 750-850 ℃, keeping the temperature for 5-10 minutes, condensing the generated depolymerized steam, and condensing the condensed liquid to obtain the aromatic hydrocarbon compound. The invention utilizes the characteristic that the lignin is rich in aromatic rings to efficiently and directionally convert the lignin into aromatic hydrocarbon compounds.
Description
Technical Field
The invention belongs to the field of lignin energy utilization, and particularly relates to a method for preparing an aromatic hydrocarbon compound by lignin microwave-assisted depolymerization.
Background
The lignin is one of three main components in the wood biomass raw material, has high carbon content and is rich in aromatic ring structures, so that the lignin is an ideal raw material for preparing aromatic hydrocarbon compounds. At present, lignin is mainly derived from byproducts in pulping and papermaking and biomass refining processes (bioethanol), the production amount of the lignin is large, but the lignin is mainly used as low-value fuel for direct combustion at present, and the utilization added value is low. Lignin has shown great potential in the conversion to aromatic hydrocarbons. At present, the method for converting lignin into aromatic hydrocarbons is mainly a high-temperature high-pressure catalytic hydrogenation method, which is not only harsh in operation and reaction conditions, but also relatively serious in condensation process due to the fact that raw materials and products are in a system in the reaction process, so that the conversion rate of aromatic hydrocarbons is low and carbon deposition inactivation of a catalyst is easily caused. Therefore, there is a need for a new and effective method to promote efficient conversion of lignin.
Disclosure of Invention
The invention aims to provide a method for preparing aromatic hydrocarbon compounds by microwave-assisted depolymerization of lignin, which aims to solve the problems of low additional value, difficult effective utilization and the like in the utilization process of the traditional lignin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing aromatic hydrocarbon compounds by microwave-assisted depolymerization of lignin comprises the following steps:
the method comprises the following steps: uniformly mixing lignin with the particle size of 20-150 meshes and molybdenum disulfide with the particle size of 60-100 meshes, and placing the mixture in a microwave tubular reactor;
step two: introducing nitrogen into the microwave tubular reactor to exhaust air in a reaction system, keeping the nitrogen continuously introduced, and then introducing methanol gas and hydrogen chloride gas, wherein the volume flow ratio of the introduced nitrogen to the methanol gas to the hydrogen chloride gas is (0.1-1) to (0.01-0.1);
step three: and starting the microwave tubular reactor, wherein the microwave frequency is 2.45GHz, the microwave power is 800-1200W, heating to 750-850 ℃, keeping the temperature for 5-10 minutes, condensing the generated depolymerized steam, and condensing the liquid obtained by condensation to obtain the aromatic hydrocarbon compound.
Further, the lignin in the first step is one of alcoholysis lignin, sulfate lignin and lignosulfonate.
Further, the mass ratio of the lignin to the molybdenum disulfide in the step one is 1 (0.5-3).
Further, when nitrogen is introduced into the microwave tubular reactor in the second step to exhaust air in the reaction system, the nitrogen flow rate corresponding to each gram of lignin is 1-5 mL/min, and the nitrogen introduction time is 5-10 minutes.
Further, the condensation temperature in the third step is-40 ℃.
Further, the method also comprises the fourth step of: and closing the microwave tubular reactor, stopping introducing the methanol gas and the hydrogen chloride gas, keeping introducing the nitrogen gas, stopping introducing the nitrogen gas when the temperature in the microwave tubular reactor is reduced to be below 150 ℃, and finishing the reaction.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention efficiently converts lignin into high-value aromatic hydrocarbon compounds through a microwave tubular reactor, uses hydrogen free radicals generated by methanol gas under the action of microwaves as a hydrogen source of a reaction system to break ether bonds and carbon-carbon bonds in the lignin, simultaneously uses strong aggressivity of hydrogen chloride gas at high temperature to attack phenolic compounds generated by lignin broken bonds and convert the phenolic compounds into chlorobenzene compounds, the chlorobenzene compounds are dechlorinated under the action of the hydrogen free radicals generated by the methanol to generate the aromatic hydrocarbon compounds, and the removed chlorine and the hydrogen free radicals are recombined to generate hydrogen chloride. Therefore, methanol is mainly used as a hydrogen source in the whole system, and hydrogen chloride is used as a gas catalyst, and the methanol and the hydrogen chloride cooperate with each other to ensure that the lignin is efficiently converted into the aromatic hydrocarbon compounds.
2. According to the invention, molybdenum disulfide plays a role of a microwave absorption medium to assist the lignin to rapidly heat up in the initial stage, and molybdenum disulfide also plays a role of catalysis to adsorb methanol and hydrogen chloride gas in the reaction process, so that higher contact area and efficiency are provided for the reaction of lignin, methanol and hydrogen chloride gas.
Detailed Description
Embodiments of the invention are described in further detail below:
a method for preparing aromatic hydrocarbon compounds by microwave-assisted depolymerization of lignin comprises the following steps:
the method comprises the following steps: uniformly mixing lignin with the particle size of 20-150 meshes and molybdenum disulfide with the particle size of 60-100 meshes, and placing the mixture in a microwave tubular reactor, wherein the lignin is one of alcoholysis lignin, sulfate lignin and lignosulfonate, and the mass ratio of the lignin to the molybdenum disulfide is 1 (0.5-3).
Step two: introducing nitrogen into the microwave tubular reactor to exhaust air in a reaction system, wherein the nitrogen flow corresponding to each gram of lignin is 1-5 mL/min, and the nitrogen introduction time is 5-10 minutes; keeping the nitrogen gas continuously introduced, and then introducing methanol gas and hydrogen chloride gas, wherein the volume flow ratio of the introduced nitrogen gas to the methanol gas to the hydrogen chloride gas is 1 (0.1-1) to (0.01-0.1).
Step three: starting a microwave tubular reactor, heating to 750-850 ℃ with the microwave frequency of 2.45GHz and the microwave power of 800-1200W, preserving the heat for 5-10 minutes, condensing the generated depolymerized steam at-40 ℃, and collecting the aromatic hydrocarbon compound as liquid.
Step four: and closing the microwave tubular reactor, stopping introducing the methanol gas and the hydrogen chloride gas, keeping introducing the nitrogen gas, stopping introducing the nitrogen gas when the temperature in the microwave tubular reactor is reduced to be below 150 ℃, and finishing the reaction.
The present invention is described in further detail below with reference to examples:
example 1
100g of alcoholysis lignin with the particle size of 20-80 meshes and 50g of molybdenum disulfide with the particle size of 60-80 meshes are uniformly mixed and placed in a microwave tubular reactor. After introducing 100mL/min of nitrogen gas for 5 minutes, 10mL/min of methanol gas and 1mL/min of hydrogen chloride gas were introduced simultaneously. Starting a microwave tubular reactor, heating to 750 ℃ with the microwave frequency of 2.45GHz and the microwave power of 800W, preserving the heat for 10 minutes, condensing the generated depolymerized steam at-40 ℃, and collecting the aromatic hydrocarbon compound as liquid. And closing the microwave tubular reactor, stopping introducing the methanol gas and the hydrogen chloride gas, keeping introducing the nitrogen gas, and stopping introducing the nitrogen gas when the temperature in the microwave tubular reactor is reduced to be below 150 ℃. The yield of the aromatic hydrocarbon compound collected was 24.3%, wherein the benzene, toluene and xylene contents were 76.5%.
Example 2
50g of kraft lignin with the particle size of 100-150 meshes and 150g of molybdenum disulfide with the particle size of 80-100 meshes are uniformly mixed and placed in a microwave tubular reactor. After introducing 250mL/min of nitrogen gas for 10 minutes, 250mL/min of methanol gas and 25mL/min of hydrogen chloride gas were introduced simultaneously. Starting a microwave tubular reactor, heating to 850 ℃ with the microwave frequency of 2.45GHz and the microwave power of 1200W, keeping the temperature for 5 minutes, condensing the generated depolymerized steam at-40 ℃, and collecting the aromatic hydrocarbon compound as liquid. And closing the microwave tubular reactor, stopping introducing the methanol gas and the hydrogen chloride gas, keeping introducing the nitrogen gas, and stopping introducing the nitrogen gas when the temperature in the microwave tubular reactor is reduced to be below 150 ℃. The yield of the aromatic hydrocarbon compound collected was 26.6%, wherein the benzene, toluene and xylene contents were 84.3%.
Example 3
Uniformly mixing 20g of lignosulfonate with the particle size of 50-100 meshes and 20g of molybdenum disulfide with the particle size of 60-100 meshes, and placing the mixture in a microwave tubular reactor. After introducing 60mL/min of nitrogen gas for 7 minutes, 30mL/min of methanol gas and 3mL/min of hydrogen chloride gas were introduced simultaneously. Starting a microwave tubular reactor, heating to 800 ℃ with the microwave frequency of 2.45GHz and the microwave power of 1000W, keeping the temperature for 8 minutes, condensing the generated depolymerized steam at-40 ℃, and collecting the aromatic hydrocarbon compound as liquid. And closing the microwave tubular reactor, stopping introducing the methanol gas and the hydrogen chloride gas, keeping introducing the nitrogen gas, and stopping introducing the nitrogen gas when the temperature in the microwave tubular reactor is reduced to be below 150 ℃. The yield of the aromatic hydrocarbon compound collected was 25.8%, wherein the benzene, toluene and xylene contents were 79.1%.
Claims (6)
1. A method for preparing aromatic hydrocarbon compounds by lignin microwave-assisted depolymerization is characterized by comprising the following steps:
the method comprises the following steps: uniformly mixing lignin with the particle size of 20-150 meshes and molybdenum disulfide with the particle size of 60-100 meshes, and placing the mixture in a microwave tubular reactor;
step two: introducing nitrogen into the microwave tubular reactor to exhaust air in a reaction system, keeping the nitrogen continuously introduced, and then introducing methanol gas and hydrogen chloride gas, wherein the volume flow ratio of the introduced nitrogen to the methanol gas to the hydrogen chloride gas is (0.1-1) to (0.01-0.1);
step three: and starting the microwave tubular reactor, wherein the microwave frequency is 2.45GHz, the microwave power is 800-1200W, heating to 750-850 ℃, keeping the temperature for 5-10 minutes, condensing the generated depolymerized steam, and condensing the liquid obtained by condensation to obtain the aromatic hydrocarbon compound.
2. The method for preparing aromatic hydrocarbon compounds by microwave-assisted depolymerization of lignin according to claim 1, wherein said lignin in the first step is one of alcoholysis lignin, kraft lignin and lignosulfonate.
3. The method for preparing the aromatic hydrocarbon compound through microwave-assisted depolymerization of lignin according to claim 1, wherein the mass ratio of the lignin to the molybdenum disulfide in the first step is 1 (0.5-3).
4. The method for preparing the aromatic hydrocarbon compound through microwave-assisted depolymerization of lignin according to claim 1, wherein when nitrogen is introduced into the microwave tubular reactor in the second step to exhaust air in the reaction system, the nitrogen flow rate corresponding to each gram of lignin is 1-5 mL/min, and the nitrogen introduction time is 5-10 minutes.
5. The method for preparing aromatic hydrocarbon compounds by microwave-assisted depolymerization of lignin according to claim 1, wherein the condensation temperature in step three is-40 ℃.
6. The method for preparing the aromatic hydrocarbon compound by the microwave-assisted depolymerization of the lignin according to claim 1, further comprising the fourth step of: and closing the microwave tubular reactor, stopping introducing the methanol gas and the hydrogen chloride gas, keeping introducing the nitrogen gas, stopping introducing the nitrogen gas when the temperature in the microwave tubular reactor is reduced to be below 150 ℃, and finishing the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911377945.4A CN111099946B (en) | 2019-12-27 | 2019-12-27 | Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911377945.4A CN111099946B (en) | 2019-12-27 | 2019-12-27 | Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111099946A true CN111099946A (en) | 2020-05-05 |
| CN111099946B CN111099946B (en) | 2022-03-29 |
Family
ID=70425229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911377945.4A Active CN111099946B (en) | 2019-12-27 | 2019-12-27 | Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111099946B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795596A (en) * | 2021-01-29 | 2021-05-14 | 生帆 | Method for preparing hydrocarbon compound by using biomass material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046570A (en) * | 2016-07-19 | 2016-10-26 | 合肥毅创钣金科技有限公司 | Enzymatic hydrolysis lignin and silicon dioxide composite reinforced weather-resistant sealing rubber strip for switch cabinet |
-
2019
- 2019-12-27 CN CN201911377945.4A patent/CN111099946B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046570A (en) * | 2016-07-19 | 2016-10-26 | 合肥毅创钣金科技有限公司 | Enzymatic hydrolysis lignin and silicon dioxide composite reinforced weather-resistant sealing rubber strip for switch cabinet |
Non-Patent Citations (1)
| Title |
|---|
| WANG, WENLIANG等: "Catalytic pyrolysis of larch sawdust for phenol-rich bio-oil using different catalysts", 《RENEWABLE ENERGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112795596A (en) * | 2021-01-29 | 2021-05-14 | 生帆 | Method for preparing hydrocarbon compound by using biomass material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111099946B (en) | 2022-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109226188B (en) | Method for treating kitchen waste by hydrothermal carbonization coupled anaerobic digestion | |
| CN107987866B (en) | Device and method for efficiently depolymerizing solid waste by microwaves and co-producing bio-oil and biochar | |
| CN110272509B (en) | High-efficiency pretreatment separation hemicellulose of fibrous biomass and comprehensive utilization method thereof | |
| CN102963866B (en) | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis | |
| Kim et al. | CO2-cofed catalytic pyrolysis of tea waste over Ni/SiO2 for the enhanced formation of syngas | |
| Guo et al. | Applications of microwave energy in gas production and tar removal during biomass gasification | |
| Wang et al. | Breaking the lignin conversion bottleneck for multiple products: Co-production of aryl monomers and carbon nanospheres using one-step catalyst-free depolymerization | |
| CN111099946B (en) | Method for preparing aromatic hydrocarbon compound by microwave-assisted depolymerization of lignin | |
| CN104357071A (en) | Method for directionally producing biomass charcoal, biomass oil and biomass gas through microwave catalytic pyrolysis of biomass | |
| Tong et al. | Two-stage liquefaction of sewage sludge in methanol-water mixed solvents with low-medium temperature | |
| CN111996019A (en) | Paint-containing waste cracking process for harmless and recycling treatment | |
| CN111690429A (en) | Supercritical hydrothermal viscosity reduction method for oil sand asphalt | |
| US11939528B2 (en) | Method for preparing biochar and hydrogen by utilizing anaerobic fermentation byproducts | |
| CN101445736A (en) | Method of using biomass to prepare gas used for synthesizing alcohol ether in biomass preparation and device therefor | |
| CN110655057B (en) | Method for preparing biochar and hydrogen by using anaerobic fermentation byproducts | |
| CN106221719A (en) | A kind of method utilizing biomass microwave pyrolysis preparation bio oil | |
| Li et al. | Parametric study of the catalytic fast pyrolysis of rice husk over hierarchical micro-mesoporous composite catalyst in a microwave-heated fluidized bed | |
| CN107337585B (en) | Method for preparing monophenol compounds by microwave depolymerization of lignin | |
| CN109111935B (en) | Oil shale circulating fluidized bed dry distillation method and system based on methane-rich mixed gas | |
| CN110980702B (en) | Method for preparing graphene quantum dots by using waste tires through microwave assistance | |
| CN101845315A (en) | Method for directly liquefying hydrogen-donating coal in situ at low pressure | |
| CN112441885B (en) | Method for preparing 4-vinylphenol by using lignin at high yield | |
| CN112979423B (en) | Method for preparing guaiacol and phenol by microwave-assisted depolymerization of lignin | |
| Tan et al. | Challenges and Perspectives of the Conversion of Lignin Waste to High-Value Chemicals by Pyrolysis | |
| CN112625764B (en) | Method for producing biofuel by efficiently converting lignin |
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 |