CN115475657A - Application of multifunctional polymeric ionic liquid solid base in efficient catalysis of conversion of lignin into monocyclic aromatic compounds - Google Patents
Application of multifunctional polymeric ionic liquid solid base in efficient catalysis of conversion of lignin into monocyclic aromatic compounds Download PDFInfo
- Publication number
- CN115475657A CN115475657A CN202211168608.6A CN202211168608A CN115475657A CN 115475657 A CN115475657 A CN 115475657A CN 202211168608 A CN202211168608 A CN 202211168608A CN 115475657 A CN115475657 A CN 115475657A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- lignin
- ionic liquid
- reaction
- multifunctional
- 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.)
- Pending
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 44
- -1 monocyclic aromatic compounds Chemical class 0.000 title abstract description 23
- 239000007787 solid Substances 0.000 title description 6
- 238000006555 catalytic reaction Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 18
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- WCOYPFBMFKXWBM-UHFFFAOYSA-N 1-methyl-2-phenoxybenzene Chemical compound CC1=CC=CC=C1OC1=CC=CC=C1 WCOYPFBMFKXWBM-UHFFFAOYSA-N 0.000 claims description 9
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical group O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000856 hastalloy Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 claims 2
- 239000003341 Bronsted base Substances 0.000 claims 1
- 239000011830 basic ionic liquid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 150000007527 lewis bases Chemical class 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 abstract description 12
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 150000001336 alkenes Chemical group 0.000 description 7
- 238000000691 measurement method Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010506 ionic fission reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CDZAAIHWZYWBSS-UHFFFAOYSA-N 2-bromoethyl prop-2-enoate Chemical compound BrCCOC(=O)C=C CDZAAIHWZYWBSS-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- 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
- C07C37/004—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from plant material or from animal material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Botany (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of new material synthesis, and relates to a method for preparing a stable and efficient alkaline multifunctional polymeric ionic liquid catalyst and converting lignin into monocyclic aromatic compounds by directional cracking. The method comprises the steps of taking divinylbenzene as a crosslinking agent and linked magnetic nanoparticles and a double-alkaline ionic liquid as a catalyst, depolymerizing highly crosslinked C-O bridge bonds in lignin in 20 ml n-hexane at 300 ℃ and 5 MPa of original hydrogen pressure, and obtaining the monocyclic aromatic compound with the concentration of 21.99 wt%. The excellent yield of the monomer aromatic compound is probably due to the double-base synergy, excellent hydrophobic property and rich mesoporous structure of the catalyst, so that the stable catalytic activity of the multifunctional polymerization ionic liquid catalyst in the lignin depolymerization process is ensured. The rich pore structure of the catalyst can limit the substrate, thereby ensuring the stable and rapid depolymerization of the raw material. After the reaction is finished, the catalyst is quickly recovered by the adsorption of an external magnetic field and can be repeatedly used. After the lignin is used as a substrate and repeatedly circulated for five times, the reaction yield is not obviously reduced. The catalyst system has the excellent characteristics of simple operation at the display position, good reusability, high yield, simple catalyst recovery and the like, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of new material synthesis, particularly relates to the technical field of preparation of lignin-based monocyclic aromatic compounds, and particularly relates to a double-base synergistic hydrophobic mesoporous catalyst for preparing lignin-derived monocyclic aromatic compounds, and a preparation method and application thereof.
Background
Lignin, the most abundant renewable aromatic resource on earth, is considered as an important alternative to provide sustainable liquid fuels and valuable chemicals. It is well known that lignin is derived from various agricultural and forestry residues or pulp and paper manufacture, and is second only to cellulose, the second most naturally abundant biopolymer. The macromolecular biopolymers in lignin comprise predominantly small organic phenylpropane units, i.e.p-coumaryl, coniferyl and sinapyl units, which makes it a valuable resource for the production of aroma chemicals. During the last decades, lignin has been used as a waste as the most abundant natural resource and exported in the form of combustion heat, and these traditional ways of use have limited their further high value added utilization. Therefore, from the environmental and economic aspects, the development of practical techniques for the directed conversion of lignin to high value-added chemicals has received a high level of attention。
Generally, the directional cleavage of lignin on basic catalysts is one of the feasible methods for selective depolymerization of the highly cross-linked C-O bonds in the lignin structure, ultimately leading to abundant aromatics. It has been found that much effort has been made by the predecessors to convert lignin to various valuable aromatic compounds using alkaline catalysts. For example, a series of Ni-Au and Pd/C with NaOH can be used to depolymerize lignin to light aromatics, and the results show that their yields are positively correlated to the amount of homogeneous base NaOH added. Although the above-mentioned alkali catalysts show good performance in the directional depolymerization of lignin, the homogeneous alkali in the reaction causes serious pollution to the ecological environment because it is difficult to separate from the liquid phase mixture. In addition, heterogeneous base catalysts such as alkaline earth oxides, mixed metal oxides, zeolites, hydrotalcites, and supported hydroxides and oxides show great promise in industrial applications due to their excellent catalytic activity and easy recycling properties. However, due to the formation of H in the reaction 2 O, which easily leads to leaching and deactivation of the base sites, ultimately leading to impaired catalytic efficiency of the heterogeneous base catalyst. To alleviate these problems, it is a major task of current work to produce a solid base catalyst with easy recovery, water resistance, good stability and high catalytic efficiency.
The ionic liquid is widely applied in the lignin stabilization process due to the obvious characteristics of low volatility, stable thermodynamic property, adjustable solubility, designability and the like. Therefore, the ionic liquid has the outstanding characteristic of good solubility to lignin, thereby improving the subsequent depolymerization efficiency. Currently, various ionic liquids are generally used only as solvents for dissolving matrices. It is worth emphasizing that the various tunable anions and cations in ionic liquids allow to achieve the goal of designing functional groups. Furthermore, there is little literature on ionic liquids to cleave lignin. So far, ionic liquids with both bronzes and lewis basic sites have not been fully studied in the direction of lignin catalyzed depolymerization. The separation of the ionic liquid containing the Broenss and Lewis double-basic sites in the reaction mixture is solved, and the convenience of the ionic liquid in application in various fields is improved to a great extent. Furthermore, polyionic liquids incorporate functional ionic liquids into the polymer backbone, which combines the advantages of high molecular weight polymers and ionic liquids. Another great advantage of polyionic liquids is that their chemical modification can bind the desired functional groups by engineering specific cationic and anionic moieties in the polymer backbone according to the task requirements. Given these design inspiration, it would be a very valuable proposition to design and manufacture ideal polymeric ionic liquids with hydrophobic properties by precisely controlling the hydrophobic functionality. In addition, the accurate construction of the multifunctional ionic liquid with the basic sites and the hydrophobicity can solve the problems existing in the non-immobilized ionic liquid. Therefore, there is a need for more efficient strategies for preparing multifunctional polymeric ionic liquids having basic active sites and hydrophobic functional groups.
It is well known that basic multifunctional polymeric ionic liquids are attracting increasing attention of researchers due to their tunable functionality. The catalytic activity of the multifunctional basic polymeric ionic liquids containing basic centers increases with increasing basic strength and hydrophobic properties. Thus, there are two main strategies to enhance the catalytic activity of multifunctional basic polymeric ionic liquids with basic sites. One is to make multifunctional basic polymeric ionic liquid with multiple strong basic sites, and the other is to use anhydrous microenvironment to enhance the water resistance and deactivation resistance of the basic sites. In other words, the high catalytic activity of the multifunctional polymeric ionic liquid containing basic sites may not only provide multiple basic active sites, but also exhibit unique hydrophobic properties, which subsequently provide a more favorable microenvironment for lignin catalytic cleavage. In addition, the desired multifunctional basic polymeric ionic liquids also have an abundant mesoporous structure, thereby providing higher substrate concentrations at the catalytic sites. However, the directional synthesis of a multifunctional basic polymerization ionic liquid catalyst having multiple strong basic sites, well-defined mesoporous channels and hydrophobic properties at the same time remains a great challenge in the current research.
Considering the rich functionality of multifunctional polymeric ionic liquids and the enormous potential for depolymerization processes of lignin. We can design and prepare a material with both bransted-lewis double base sites, well-defined mesoporous channels and hydrophobicity, and then use it as a catalyst for lignin depolymerization. In this context, we have attempted to prepare the desired multifunctional polymeric ionic liquid by polymerizing a bronsted base-lewis base functionalized ionic liquid, i.e. 1- (2- (acryloyloxy) ethyl) -4-aza-1-azabicyclo [ 2.2.2 ] octane, and a hydrophobic crosslinker, divinylbenzene. However, no mesoporous structure was detected in the copolymers obtained with different cross-linkers/double basic active monomers (i.e. DVB/[ AD ] [ OH ]), and the specific surface area of the obtained catalyst did not reach the ideal target. And then when the vinyl modified magnetic ferroferric oxide nano particles are added into a cross-linking agent/double-alkaline active monomer copolymerization mixture with different molar ratios, the required functional polymerization ionic liquid catalyst containing the Bronsted-Lewis double-alkaline sites, rich mesoporous channels and hydrophobicity is successfully constructed. More exciting, the obtained multifunctional polymerization ionic liquid catalyst can efficiently produce the lignin-based monocyclic aromatic compound. In addition, it must be emphasized that the catalytic performance of the multifunctional polymerization ionic liquid catalyst synthesized by us in the production of lignin-based monocyclic aromatic compounds is not comparable to that of other solid bases.
Disclosure of Invention
In order to overcome the problems in the related technology, the invention provides a double-alkali synergistic hydrophobic multifunctional catalyst with rich mesopores for preparing a lignin-derived monocyclic aromatic compound, and a preparation method and application thereof.
The catalyst provided by the invention is a high-efficiency and environment-friendly multifunctional polymerization ionic liquid catalyst with double basic sites, hydrophobic characteristics and a definite mesoporous structure, and the preparation method comprises the following steps:
1)Fe 3 O 4 the preparation method of the magnetic nanoparticles comprises the following steps: first, feCl is added 3 •6H 2 O (11.7 g) and FeCl 2 ·4H 2 O (4.3 g) in N 2 Dissolved in deionized water (200 mL) under vigorous mechanical stirring at 85 ℃ for 1 hour under an atmosphere. By using NH 3 ·H 2 O (25 wt%) willThe pH was changed to 9. When the color of the bulk solution became black, the resulting Fe was filtered with a magnet 3 O 4 Nanoparticles and washed several times with deionized water. Finally, the desired Fe 3 O 4 The magnetic nanoparticles were dried in a vacuum oven at 90 ℃ for 6 h.
2) Terminal alkene modified Fe 3 O 4 The preparation method of the magnetic nanoparticles comprises the following steps: carrying out ultrasonic treatment on the Fe subjected to terminal alkene modification 3 O 4 The nanoparticles (5.0 g) were highly dispersed in ethanol (50 ml). Then, 5ml of NH 3 ·H 2 O (25 wt%) and 10 mL TEVS were added quickly to the solution system. Subsequently, the reaction was stirred at 50 ℃ for 48 hours, then collected by an external permanent magnet and washed three times with ethanol. Finally, the solid is dried in a vacuum oven at 45 ℃ for 12 hours to obtain brown magnetic nanoparticles, namely the terminated alkene modified Fe 3 O 4 And (3) nanoparticles.
3) Preparation of 1- (2- (acryloyloxy) ethyl) -1,4-diazabicyclo [ 2.2.2]octane-1-Bromide ([ AD ]][Br]): DABCO (5.9 g), 2-bromoethyl acrylate (9.4 g) and methanol (20 mL) were added to the flask, followed by N 2 The reaction was carried out under heating at 55 ℃ for 24 hours under an atmosphere. The mixed solution was then concentrated under reduced pressure to give a crude product. Ethyl acetate was then added, the product was precipitated under ultrasonic conditions, and the same operation was repeated 3 times to obtain the desired [ AD ]][Br]. Subsequently, amberlyst A-26 (OH) macroreticular ion exchange resin was highly dispersed in deionized water (50 ml) under vigorous mechanical agitation, and the mixed solution was then transferred to a glass chromatography column. Next, the thus-prepared [ AD having Lewis basic site][Br]Continuously added to the column and the resulting solution was collected. In addition, [ AD ] was titrated by standard silver nitrate solution and nitric acid][Br]In (Br) – ]Complete exchange to [ OH – ]. Finally, the sample was completely freed from water by vacuum at 60 ℃ for 12 hours to obtain the desired ionic liquid [ AD ] having both Bronsted and Lewis basic sites][OH]。
4) Multifunctional polymeric ionic liquid P (3 DVB- [ AD)][OH]) The preparation method of the catalyst comprises the following steps: first of all, the first step is to,under the condition of ultrasonic wave, fe modified by terminal alkene 3 O 4 Magnetic nanoparticles (200 mg) and methanol (20 mL) were added to a round bottom flask. Then, different molar ratios of DVB/[ AD ] were added to the flask][OH]And azobisisobutyronitrile (50 mg) as an initiator for polymerization, and adding a stirring rod at 80 deg.C o C heating reflux reaction for 24 hours. Then, the obtained product is washed with methanol three times and then dried in a vacuum oven at 65 ℃ for 6 hours to obtain the required magnetic multifunctional polymeric ionic liquid, namely P (xDVB- [ AD)][OH]) (x=0.5,1,2,3,4,5)。
5) The preparation method of the lignin derived monocyclic aromatic compound comprises the following steps: n-hexane and hydrophobic dibasic catalyst P (3 DVB- [ AD) with mesoporous pore canals][OH]) Mixing with lignin in autoclave, initial hydrogen pressure of 5 MPa, reaction temperature of 300 o And C, reacting for 8h to obtain the lignin derived monocyclic aromatic compound.
In one embodiment according to the present invention, the molar ratio of the crosslinking agent and the reactive monomer is 0.5.
In an embodiment according to the invention, the P (3 DVB- [ AD)][OH]) Catalyst with specific surface area of 90.22 m 2. g -1 Average pore diameter of 4.11 nm and pore volume of 0.199 cm 3. g -1 。
In one embodiment according to the invention, the multifunctional polymeric ionic liquid does not add terminal alkene to modify Fe 3 O 4 The specific surface area of the catalyst synthesized under the condition is only 32.20 m 2. g -1 Average pore diameter of 7.01 nm and pore volume of 0.113 cm 3. g -1 。
In one embodiment according to the present invention, the lignin-derived monocyclic aromatic compounds have a total of 22 species, wherein the highest monomer component content is phenol (4.62 wt%).
In one embodiment according to the present invention, the total conversion of lignin is 41.24%, and the selectivity of the lignin-derived monocyclic aromatic compound is 21.99% (phenol 4.62%, 2-ethylphenol 3.16%).
By combining all the technical schemes, the invention has the advantages and positive effects that:
1) The multifunctional polyion liquid is innovatively prepared for the first time.
2) The multifunctional poly (ionic liquid) solid base catalyst shows the highest yield of the lignin-derived monocyclic aromatic compounds.
3) Taking phenoxytoluene as an example, we propose a possible reaction mechanism of the multifunctional polymerization ionic liquid catalyst. P (3 DVB- [ AD)][OH]) Lewis basic sites of the moderately basic nitrogen atom for hydrogen molecule activation followed by [ OH – ]The bronsted basic site of (b) is used for heterolytic cleavage of active hydrogen bonds to form a fixed H + And a movable H – . Since the carbon atom attached to the oxygen atom of phenoxytoluene carries a partial positive charge, it tends to accept mobile H from heterolytic cleavage of hydrogen-hydrogen bonds - Movable H - Transfer to the substitution site of phenoxytoluene results in the cleavage of the phenoxy bridge, producing benzene and benzyl cations. Benzyl cation immortal by abstraction of H + To produce benzyl alcohol. Or is movable H - Transfer to phenoxytoluene then results in the cleavage of the benzylic carbon oxygen bridge, producing toluene and a phenoxyanion. Phenoloxy anions with immovable H + The combination produces phenol. Furthermore, the directional catalytic conversion of lignin to monocyclic aromatic compounds is also performed by a similar catalytic mechanism.
4) Alkene-modified Fe 3 O 4 The nanoparticles act as a framework enhancer to enhance P (3 DVB- [ AD)][OH]) The catalyst has clear mesoporous channels: the clear mesoporous channel enhances H 2 The amount of adsorption of (a), increases the concentration of the substrate.
5) The P (3 DVB- [ AD ] [ OH ]) catalyst utilized after the catalytic reaction is finished is easily separated from the reaction mixture through a magnetic recovery device, so that the catalyst is convenient to use next time.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and together with the description, serve to explain the principles of the disclosure.
FIG. 1 is a graph of the basic characterization of the P (3 DVB- [ AD ] [ OH ]) catalyst in example 4 (a) of the present invention.
FIG. 2 is a graph of the cycle performance of the P (3 DVB- [ AD ] [ OH ]) catalyst of example 10 (a) provided by an example of the present invention: the recycled catalyst is applied to a lignin catalytic depolymerization diagram.
FIG. 3 is a graph showing a comparison of the lignin depolymerization residue from the P (3 DVB- [ AD ] [ OH ]) catalyst and the fresh lignin structure in example S6, which is provided by the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, which are only for illustrating the technical solutions of the present invention and are not to be construed as limiting the present invention.
Example 1
The preparation method of the P (3 DVB- [ AD ] [ OH ]) catalyst comprises the following steps:
firstly, under the condition of ultrasonic wave, modifying terminal alkene into Fe 3 O 4 Nanoparticles (200 mg) and methanol (20 mL) were added to a round bottom flask. Then, different molar ratios of DVB/[ AD ] were added to the flask][OH]And initiator AIBN (50 mg) and then heated at reflux for 24 hours. Then, the obtained product was washed three times with methanol and then dried in a vacuum oven at 65 ℃ for 6 hours to obtain the desired multifunctional polymeric ionic liquid, i.e., P (xDVB- [ AD)][OH]) (x =0.5,1,2,3,4,5). Furthermore, during the preparation of the desired multifunctional polymeric ionic liquid, the starting materials, i.e., DVB, [ AD [ ]][OH]And terminal alkene modified Fe 3 O 4 The amounts added are specified in the experimental section. In addition, except for the addition of terminal-ene modified Fe 3 O 4 Outside the nanoparticles, by reaction with P (xDVB- [ AD)][OH]) Same procedure in the absence of terminal ene modified Fe 3 O 4 Preparation of P (xDVB- [ AD)][OH]) a 。
Example 2
The catalyst (0.10 g), phenoxytoluene (1.0 mmol) and n-hexane (20 ml) were poured into a 100ml stirred autoclave. With N in sequence 2 And H 2 After replacing the air in the autoclave, the autoclave was purged with a 5 MPa atmosphereThe Initial Hydrogen Pressure (IHP) is pressurized. The reaction was then heated to 300 deg.f oC And kept for 8h. After the reaction, the mixture was analyzed with an Agilent 7890/5975 gas chromatography-mass spectrometer (GC-MS) and the data was processed with Agilent MSD chemical workstation software. In addition, compounds were retrieved for all components by mass spectrometric identification and NIST-11 library. Quantitative analysis was performed using GC-MS and corresponding substrate as external standard.
Example 3
Except that the reaction temperature was 200 deg.C o C, the other reaction conditions and the measurement method were the same as in example 2, and the conversion of phenyloxymethylene hydrocracking was 43.8%. Wherein the selectivity of phenol in the product is 22.45 percent, the selectivity of toluene is 32.20 percent, and the selectivity of benzene is 9.66 percent.
Example 4
Except that the reaction temperature was 225 o C, the other reaction conditions and the measurement method were the same as in example 2, and the conversion of phenyloxymethylene hydrocracking was 65.92%. Wherein the selectivity of phenol in the product is 25.1%, the selectivity of toluene is 39.76%, and the selectivity of benzene is 9.66%.
Example 5
Except that the reaction temperature was 250 deg.C o C, other reaction conditions and measurement method are the same as example 2, and the conversion of phenoxytoluene hydrocracking is 75.92%. Wherein the selectivity of phenol in the product is 29.4%, the selectivity of toluene is 41.97%, and the selectivity of benzene is 12.59%.
Example 6
Except that the reaction temperature was 275 deg.C o C, the other reaction conditions and the measurement method are the same as those of example 2, and the conversion rate of the phenyloxymethylene hydrocracking is 84.80%. Wherein the selectivity of phenol in the product was 29.62%, the selectivity of toluene was 43.82%, and the selectivity of benzene was 14.16%.
Example 7
Except that the reaction temperature was 300 deg.C o C, the other reaction conditions and the measurement method were the same as in example 2, and the conversion of phenyloxymethylene hydrocracking was 98.70%. Wherein the selectivity of phenol in the product is 33.50%, the selectivity of toluene is 46.07%, and the selectivity of benzene is 12.20%.
Example 8
Except that the mass of the P (3, [ DVB ] - [ AD ] [ OH ]) catalyst was 0.07 g, the reaction conditions and the measurement method were the same as in example 2, and the conversion of phenoxytoluene hydrocracking was 87.40%. Wherein the selectivity of phenol in the product was 31.60%, the selectivity of toluene was 43.60%, and the selectivity of benzene was 13.60%.
Example 9
The reaction conditions and the measurement method were the same as in example 2 except that the reaction time was 6 hours, and the conversion of phenoxytoluene hydrocracking was 83.50%. Wherein the selectivity of phenol in the product is 30.10 percent, the selectivity of toluene is 43.30 percent, and the selectivity of benzene is 13.20 percent.
Example 10
Adding alkali lignin (100 mg) and multifunctional polymeric ionic liquid P (3 [ DVB ] 5363) into a Hastelloy autoclave (100 mL)]-[AD][OH]) Catalyst (100 mg) and n-hexane (20 mL). At an initial hydrogen pressure of 5 MPa and a reaction temperature of 300 o C. The reaction was carried out at a stirring speed of 200 rpm and a reaction time of 8h. Immediately after the reaction time was over, the autoclave was rapidly cooled in an ice-water bath. The liquid products were qualitatively analyzed by GC-MS and identified by comparison with peak retention time and mass spectra of authentic compounds. Wherein the total conversion rate of the lignin is 41.24%, and the yield of the lignin-derived aromatic hydrocarbon monomer is 21.99 wt%. The lignin-derived monocyclic aromatic species had a total of 22 species, with the highest relative yields of aromatic monomers in the product being toluene (4.62 wt.%) and 2-ethylphenol (3.16 wt.%), respectively.
It should be noted that the above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements within the spirit and principles of the invention may occur to those skilled in the art. The scope of the invention is to be determined by the appended claims.
Claims (10)
1. A method for preparing lignin-derived monomeric aromatic compounds under hydrogen-rich conditions, comprising polymerizing a multifunctional ionic liquid P (3 DVB- [ AD)][OH]) To catalyzeAgent, n-hexane as solvent, at 300 deg.C o C and 5 MPa under the initial hydrogen pressure reaction condition, reacting 8h in a Hastelloy autoclave to prepare the monomer aromatic compound.
2. A method for hydrocracking phenoxyl toluene under a hydrogen-rich condition is characterized by comprising the step of carrying out phenoxyl toluene hydrocracking reaction under corresponding conditions by using multifunctional polymeric ionic liquid P (3 DVB- [ AD ] [ OH ]) as a catalyst and n-hexane as a solvent to obtain corresponding phenol and toluene.
3. The method of claim 1, wherein the lignin-derived monomeric aromatic compound is 22 in total, with the highest content being toluene (4.64 wt%).
4. The method of claim 1, wherein the total lignin conversion is 41.24% and the selectivity to lignin-derived monomeric aromatic compounds is 21.99%.
5. The method of claim 1, wherein the catalyst has strong magnetic recoverability and is mainly prepared by performing a polymerization reaction on basic ionic liquid and terminal alkene-modified ferroferric oxide in the presence of an initiator.
6. The process according to claim 1, characterized in that the catalyst P (3 DVB- [ AD)][OH]) Having a Bronsted base (OH) - Site) and lewis base (N site), the participation of divinylbenzene not only can play a role of a cross-linking agent, but also can enhance the hydrophobicity of the catalyst, can enhance the water-resistant property of the catalyst under reaction conditions so as to maintain the stability of the catalyst, wherein the abundant specific surface area and mesoporous pores can improve the concentration of a substrate and increase the yield of the monomer aromatic compound.
7. The method of claim 1, wherein after the reaction is completed, the catalyst is separated from the product by an external magnetic field, and the supernatant is poured out as the product.
8. The method of claim 7, wherein after the reaction, the catalyst P (3 DVB- [ AD ] [ OH ]) is dried under vacuum at 65 ℃ for 6h and reused, and no significant decrease in reaction effect is observed, as shown in FIG. 2.
9. The method of claim 2, wherein the phenoxytoluene is added in an amount of 1 mmol.
10. The method of claim 2, wherein the catalyzed lignin residue shows a significant difference in structure from fresh lignin, demonstrating that the catalyst causes a change in lignin structure during depolymerization, as shown in fig. 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211168608.6A CN115475657A (en) | 2022-09-24 | 2022-09-24 | Application of multifunctional polymeric ionic liquid solid base in efficient catalysis of conversion of lignin into monocyclic aromatic compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211168608.6A CN115475657A (en) | 2022-09-24 | 2022-09-24 | Application of multifunctional polymeric ionic liquid solid base in efficient catalysis of conversion of lignin into monocyclic aromatic compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115475657A true CN115475657A (en) | 2022-12-16 |
Family
ID=84393419
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211168608.6A Pending CN115475657A (en) | 2022-09-24 | 2022-09-24 | Application of multifunctional polymeric ionic liquid solid base in efficient catalysis of conversion of lignin into monocyclic aromatic compounds |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115475657A (en) |
Citations (4)
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 |
CN109988115A (en) * | 2019-03-28 | 2019-07-09 | 枣庄学院 | A kind of double basic functionalized ionic liquids and preparation method thereof with surface-active |
CN111822047A (en) * | 2020-07-17 | 2020-10-27 | 曲阜师范大学 | Method for synthesizing indole derivatives by magnetic mesoporous polymeric ionic liquid supported catalysis |
CN113897247A (en) * | 2021-10-13 | 2022-01-07 | 曲阜师范大学 | Preparation of biodiesel by photo-magnetic dual-response emulsion method |
-
2022
- 2022-09-24 CN CN202211168608.6A patent/CN115475657A/en active Pending
Patent Citations (5)
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 |
CN109988115A (en) * | 2019-03-28 | 2019-07-09 | 枣庄学院 | A kind of double basic functionalized ionic liquids and preparation method thereof with surface-active |
WO2020192280A1 (en) * | 2019-03-28 | 2020-10-01 | 枣庄学院 | Double basic-functionalized ionic liquid with surface activity and preparation method therefor |
CN111822047A (en) * | 2020-07-17 | 2020-10-27 | 曲阜师范大学 | Method for synthesizing indole derivatives by magnetic mesoporous polymeric ionic liquid supported catalysis |
CN113897247A (en) * | 2021-10-13 | 2022-01-07 | 曲阜师范大学 | Preparation of biodiesel by photo-magnetic dual-response emulsion method |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gao et al. | Efficient mesoporous carbon-based solid catalyst for the esterification of oleic acid | |
CN112341394B (en) | Method for preparing cyclic carbonate ester by catalysis of hydrogen bond donor functionalized polymeric ionic liquid | |
CN112778533B (en) | Porphyrin-based porous organic polymer, preparation method thereof and synthesis method of cyclic carbonate | |
CN109453814B (en) | Multi-level pore polymer supported rhodium catalyst containing sulfonic group and phosphine ligand, preparation and application thereof | |
CN112044450A (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
US20230182122A1 (en) | Use of magnetic mesoporous poly(ionic liquid) interfacial catalyst in hydrogenation reaction and preparation of biodiesel | |
CN112521353A (en) | Method for preparing 2, 5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
CN109704902B (en) | Ionic liquid catalytic deoxidation method in lignin derivative hydrodeoxygenation process | |
CN115475657A (en) | Application of multifunctional polymeric ionic liquid solid base in efficient catalysis of conversion of lignin into monocyclic aromatic compounds | |
CN112705247B (en) | Solid acid catalyst and preparation method and application thereof | |
CN100374448C (en) | Diene silicoxyane linking disbenzocyclobutylene monomer and process for preparing prepolymer | |
CN113842952B (en) | Preparation method of high-activity alginate aerosol catalyst | |
CN114260024B (en) | Polyionic liquid catalyst, preparation method, monocyclic aromatic compound and application | |
CN114797969A (en) | Preparation method of novel multifunctional polyion liquid catalyst and lignin-based aromatic compound prepared by catalysis of novel multifunctional polyion liquid catalyst | |
JP5692704B2 (en) | Method for producing amide compound and catalyst thereof | |
CN113559930B (en) | Preparation method and application of solid catalyst taking sodium lignin sulfonate as carrier | |
CN115920962A (en) | Simple synthesis of novel triple-effect polyion liquid for efficiently producing lignite-derived aromatic hydrocarbons | |
Marrocchi et al. | Glycerol valorization: development of selective protocols for acetals production through tailor-made macroreticular acid resins | |
CN108047172B (en) | Method for preparing 2-methyl-5, gamma-dioxotetrahydrofuran-2-pentanoic acid by catalyzing levulinic acid | |
Chen et al. | Preparation of Aminated Lignin through Etherification and Amination | |
CN114656319B (en) | Preparation method of high-purity dicyclopentadiene | |
CN114702384B (en) | Method for preparing p-hydroxy cinnamic acid ester by catalyzing alcoholysis of lignin through enzymolysis lignin-based hierarchical porous carbon loaded molybdenum oxide | |
CN110560159B (en) | Catalyst for preparing tertiary carbonic acid glycidyl ester and preparation method thereof | |
CN112604622B (en) | Method for degrading unsaturated polyester resin by microwave | |
Zhang et al. | First evaluation of multifunctional poly (ionic liquid) s as novel strong bases in directional efficient valorization of 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 |