CN118439915A - Method for converting biomass into triphenyl compound - Google Patents
Method for converting biomass into triphenyl compound Download PDFInfo
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- CN118439915A CN118439915A CN202310052194.9A CN202310052194A CN118439915A CN 118439915 A CN118439915 A CN 118439915A CN 202310052194 A CN202310052194 A CN 202310052194A CN 118439915 A CN118439915 A CN 118439915A
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- reaction
- biomass
- heteropolyacid
- catalyst
- triphenyl
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- 239000002028 Biomass Substances 0.000 title claims abstract description 35
- -1 triphenyl compound Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002240 furans Chemical class 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000008096 xylene Substances 0.000 claims abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 5
- 239000002841 Lewis acid Substances 0.000 claims abstract description 5
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003738 xylenes Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 24
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 24
- 238000005406 washing Methods 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- WTQFIWBPGZZVFN-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] WTQFIWBPGZZVFN-UHFFFAOYSA-N 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- WSVIUXVBNODWOP-UHFFFAOYSA-N cerium(3+) trinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Ce+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WSVIUXVBNODWOP-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 235000000346 sugar Nutrition 0.000 description 1
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for converting biomass into a triphenyl compound. The triphenyl compound includes at least one of benzene, toluene and xylene; the method comprises the following steps: in a multiphase reaction system containing an organic solvent, a catalyst and a biomass-based reaction substrate, taking nitrogen or carbon dioxide gas as a protective atmosphere, carrying out thermocatalytic or photocatalytic reaction on the biomass-based reaction substrate, and separating a product to obtain an organic phase containing a triphenyl compound; wherein the catalyst is heteropolyacid/metal organic framework catalytic material, has Lewis acid and Bronsted acid sites which are uniformly distributed, and the content of heteropolyacid is between 1 and 30 percent mmol. The raw materials involved in the synthetic route of the invention are furan derivatives and propenyl compounds, and the sources are wide; the preparation method of the catalyst has simple process and low cost; the catalytic reaction can be carried out under the condition of thermocatalysis or photocatalysis, and excellent synthesis yield of the 'triphenyl'.
Description
Technical Field
The invention belongs to the field of synthesis of biomass-based chemicals, and relates to a method for converting biomass into a triphenyl compound.
Background
Benzene is a basic chemical raw material, is often used as a solvent, can participate in various reactions, and is a raw material of plastics, rubber, fibers, dyes, pesticides and the like. "triphenyl" chemicals include benzene, toluene, and xylene. Para-xylene (PX) is one of the important products of aromatic hydrocarbons, and is mainly used as a basic organic chemical raw material to oxidize and synthesize para-dibenzoic acid (PTA) so as to produce polyethylene terephthalate (PET). The production and consumption of polyester in China account for 97% of the total consumption of paraxylene. Polyester is used as a necessity for modern life, the demand is continuously rising, but the self-supporting capacity of China is not matched with the larger demand, and the import proportion is still more than 50%. Toluene is a common bulk fine chemical, and its oxidation product benzoic acid is widely used as a preservative, a bacteriostatic agent, a resin plasticizer, a flavoring agent, and the like.
To date, the mature triphenyl production process is still through naphtha fractionation, or further reforming, aromatics extraction. In recent years, a plurality of patents disclose new ways for preparing triphenyl, including methane aromatization, aromatic hydrocarbon preparation from methanol and the like, but large-scale production is not seen due to economic and technical problems. The preparation of the triphenyl compound by the chemical processes has extremely strong dependence on fossil energy and does not meet the aim of sustainable development of energy. Therefore, the search and development of green energy for synthesizing triphenyl is the direction of increasing researchers.
Renewable biomass molecules are considered to be a potential chemical feedstock for the production of high value chemicals. Synthetic routes to furan derivatives derived from sugars as biomass-based reaction substrates are well appreciated, but current research has focused only on the synthetic routes to furan derivatives and ethylene, which is still a product of the petrochemical industry. It is also an important issue to find a biomass energy source that can replace ethylene, and propylene-based compounds derived from biomass are currently the best quality alternatives.
Most of catalysts used in the synthesis route of furan derivatives and ethylene are molecular sieve catalysts, wherein the highest yield is H-Beta molecular sieve, the yield of paraxylene after modification is up to 97%, but the reaction can be achieved only by applying 40bar pressure at 573K high temperature, and severe reaction conditions lead to serious carbon deposition behavior of the catalyst, thus causing limitation to further application.
In summary, the synthesis of triphenyl compounds using biomass-based reaction substrates is currently faced with the problems of: firstly, how to use renewable biomass molecules with wide sources as raw materials, and the reaction raw materials have proper reactivity, so that the whole route is economical and green sustainable; secondly, the high-performance catalyst is utilized to realize the synthesis of the triphenyl compound under a milder condition, so as to promote the industrialization process of converting biomass into triphenyl.
Disclosure of Invention
Aiming at the problems of the insufficient existing reaction path, harsh reaction conditions and the like of the preparation of the triphenyl compound by the biomass base, the invention provides a low-energy synthesis route for synthesizing the triphenyl for biomass, wherein the sources of raw materials involved in the synthesis route are furan derivatives and propenyl compounds, and the sources are wide; the preparation method of the catalyst has simple process and low cost; the catalytic reaction can be carried out under the condition of thermocatalysis or photocatalysis, and excellent synthesis yield of the 'triphenyl'.
In a first aspect, the present invention provides a method of converting biomass to a triphenyl compound that includes at least one of benzene, toluene, and xylene; the method comprises the following steps: in a multiphase reaction system containing an organic solvent, a catalyst and a biomass-based reaction substrate, taking nitrogen or carbon dioxide gas as a protective atmosphere, carrying out thermocatalytic or photocatalytic reaction on the biomass-based reaction substrate, and separating a product to obtain an organic phase containing a triphenyl compound; wherein the catalyst is heteropolyacid/metal organic framework catalytic material, has Lewis acid and Bronsted acid sites which are uniformly distributed, and the content of heteropolyacid is between 1 and 30 percent mmol.
Preferably, the biomass-based reaction substrate comprises a furan derivative and a propenyl compound, and the molar ratio of the furan derivative to the propenyl compound is 1-10: 1 to 100; preferably, the furan derivative comprises at least one of dimethylfuran, methylfuran and furan, and the propenyl compound comprises at least one of acrylonitrile, acrolein, acrylate and acrylic acid.
Preferably, the mass ratio of the catalyst to the biomass-based reaction substrate is 1-20: 1 to 300; preferably, the concentration of the biomass-based reaction substrate occupying organic solvent is 1 to 10: 1-50 g/mL.
Preferably, the organic solvent comprises one or more of acetone, n-heptane, cyclohexane, n-hexane and 1, 4-dioxane.
Preferably, the reaction temperature of the thermocatalytic reaction is 25-200 ℃ and the reaction time is 1-36 h.
Preferably, the wavelength of the light source for the photocatalytic reaction is between 360 and 450nm, and the reaction time is between 0.5 and 5 hours.
Preferably, the heteropolyacid/metal organic framework catalytic material loads the heteropolyacid in the form of clusters in the multistage Kong Long of the metal organic framework; preferably, the pore canal size of the heteropolyacid/metal organic framework catalytic material is of a mesoporous structure; more preferably, the mesoporous size is 2 to 10nm and the porosity is 30 to 60%.
Preferably, the preparation method of the heteropolyacid/metal organic framework catalytic material comprises the following steps: filling the mixed solution containing heteropoly acid, solvent and metal salt into an autoclave, heating for 12-72 hours at 100-180 ℃, and drying the obtained product to obtain the heteropoly acid/metal organic framework catalytic material; preferably, the metal salt is selected from at least one of bismuth nitrate, ferric nitrate, zinc nitrate, copper nitrate, cerium nitrate, zirconium nitrate and hydrates thereof; more preferably, the solvent is selected from at least one of water, methanol, ethanol, acetone, acetonitrile, dichloromethane, N-dimethylformamide.
Preferably, the heteropolyacid is at least one selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid.
In a second aspect, the present invention provides the use of a heteropolyacid/metal organic framework catalytic material in the conversion of biomass to a triphenyl compound, particularly xylene.
Drawings
FIG. 1 is a transmission electron microscope image of the heteropolyacid/metal-organic framework catalytic material obtained in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the heteropolyacid/metal-organic framework catalytic material obtained in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
The method for preparing the triphenyl compound (triphenyl aromatic hydrocarbon) by converting biomass based on the heteropolyacid/metal organic framework catalyst material according to the present invention is described below.
The heteropolyacid/metal organic framework catalytic material is a metal organic framework catalytic material rich in lewis acids (L-acids) and bronsted acids (B-acids). Wherein, lewis acid mainly acts on cycloaddition reaction, and Bronsted acid acts on dehydration reaction which is continued after cycloaddition, so as to accelerate the generation of the triphenyl compound. The molar content of the heteropolyacid in the catalytic material is 1-30%.
The heteropolyacid/metal organic framework catalytic material has multi-stage mesopores. The method is characterized in that the heteropolyacid/metal organic framework catalytic material loads the heteropolyacid into a multistage hole cage of the metal organic framework in a cluster mode. Preferably, the pore size of the heteropolyacid/metal organic framework catalytic material is mesoporous. More preferably, the mesoporous size is from 2 to 10nm and the porosity is from 1 to 100%, preferably from 30 to 60%.
The preparation method of the heteropolyacid/metal organic framework catalytic material comprises the following steps:
The heteropoly acid (which may also be referred to as a polyacid precursor), the solvent, and the metal salt are mixed to obtain a mixed solution. The heteropolyacid is at least one selected from phosphotungstic acid, phosphomolybdic acid and silicotungstic acid. The metal salt may be a metal salt having Lewis acidity. As an example, the metal salt is selected from at least one of bismuth nitrate, ferric nitrate, zinc nitrate, copper nitrate, cerium nitrate, zirconium nitrate, and hydrates thereof. In some embodiments, the molar ratio of the heteropolyacid to the metal salt is between 0.005 and 0.5.
The manner of mixing the heteropolyacid, the solvent and the metal salt is not limited. The heteropolyacid, solvent, metal salt may be directly mixed. Two-step mixing may also be used. The two-step mixing may include: mixing heteropoly acid with a first solvent to obtain a first mixed solution; mixing metal salt with a second solvent to obtain a second mixed solution; the first mixed liquid and the second mixed liquid are then mixed. The concentration of the first mixed solution may be, for example, 10to 500g/L. In the mixed solution, the solvent (first solvent, second solvent) is independently selected from at least one of water, methanol, ethanol, acetone, acetonitrile, dichloromethane, and N, N-dimethylformamide.
And (3) loading the mixed solution into an autoclave, heating at 100-180 ℃ for reaction for 12-72 hours, and drying the generated product to obtain the catalyst. The autoclave may be a stainless steel autoclave with a polytetrafluoroethylene liner. The filling degree of the mixed solution can be 10-80%. By way of example, the volume of the polytetrafluoroethylene liner satisfies 50 to 100mL.
The catalytic material obtained as described above may be washed and dried in order to further improve the purity of the catalyst. For example, the catalyst is added to deionized water, washed by ultrasonic vibration, filtered by suction, and dried.
Of course, the above-described washed and dried catalyst may also be further processed. Dispersing the catalyst in a third solvent and mixing to obtain a third mixed solution. The mass-volume concentration of the catalyst and the third mixed solution may be, for example, 10 to 500g/L. And continuously adding the fourth mixed solution into the third mixed solution. And mixing cetyl trimethyl ammonium bromide, concentrated ammonia water and a fourth solvent to obtain a fourth mixed solution. The mass-volume concentration of the mixture of the catalyst and the fourth liquid may be, for example, 10 to 100 g.L -1. The third solvent and the fourth solvent are independently selected from at least one of water, methanol, ethanol, isopropanol, n-butanol and benzyl alcohol. The mass volume ratio of the cetyl trimethyl ammonium bromide to the concentrated ammonia water can be 0.1-100 mg: 0.1-10 mL. Separating the mixed liquid. The obtained solid is dispersed in an alcohol-water mixed solution for alcohol washing. The volume ratio of the alcohol to the water of the alcohol-water mixed solution is 1:1-10:1. And drying the recovered solid to obtain the catalyst material.
The heteropolyacid/metal organic framework catalytic material is prepared by a one-step method, so that a complicated catalyst preparation process is avoided. Moreover, all the used raw materials are commercial raw materials, and further optimization purification and resynthesis are not needed. In addition, the preparation method has mild reaction conditions and simple process, and has wide application prospects in the fields of acid catalytic energy conversion, photocatalytic carbon-carbon bond coupling conversion and the like.
The triphenyl compound can be prepared by a thermocatalytic method or a photocatalytic reaction.
The method for preparing the triphenyl compound through the thermocatalytic reaction comprises the following steps: adding furan derivative (such as at least one selected from dimethyl furan, methyl furan and furan), propenyl compound (such as at least one selected from acrylonitrile, acrolein, acrylic acid ester and acrylic acid) and the heteropolyacid/metal organic framework catalytic material into a reactor, dispersing uniformly, introducing non-oxidizing gas (nitrogen or CO 2 gas) for exhaust treatment, adding a heat source, and synthesizing the triphenyl compound under the condition of closed atmosphere. The exhaust time is 5-60 min. The reaction temperature of the thermocatalytic reaction is 25-200 ℃, and the reaction time is 1-72 h, preferably 1-36 h. The product was collected. The liquid after the reaction can be filtered and injected into a gas chromatograph to detect the liquid phase product.
The method for preparing a triphenyl compound by a photocatalytic reaction includes: adding furan derivatives (such as at least one selected from dimethylfuran, methylfuran and furan), propenyl compounds (such as at least one selected from acrylonitrile, acrolein, acrylic acid ester and acrylic acid) and the heteropolyacid/metal organic framework catalytic material into a reactor, dispersing uniformly, and introducing non-oxidizing gas (nitrogen or CO 2 gas) for exhaust treatment. The exhaust time is 5-60 min. The excitation light source of the photocatalytic reaction can have a wavelength of 360-450 nm. The reaction time can be 0.5 to 5 hours. The product was collected. The liquid after the reaction can be filtered and injected into a gas chromatograph to detect the liquid phase product.
In the above-mentioned thermocatalytic or photocatalytic reaction, the reaction pressure of the non-oxidizing gas (one of nitrogen gas and CO 2 gas) is 0.1 to 0.3MPa.
As an example, biomass-based paraxylene is produced by cycloaddition, dehydration, decarboxylation by thermocatalysis or photocatalysis using the catalyst, furan derivative (one selected from dimethylfuran, methylfuran, and furan), acryl compound (one selected from acrylonitrile, acrolein, acrylic acid ester, and acrylic acid), and optional solvent as reaction materials.
In summary, the invention provides a technology for preparing 'triphenyl' (benzene, toluene and xylene) by reacting furan derivatives with propenyl compounds through photocatalysis or thermocatalysis, which overcomes the problems of the insufficient existing reaction paths and harsh reaction conditions in the preparation of the triphenyl compounds by biomass base, and provides a synthesis route with low energy consumption for synthesizing 'triphenyl' for biomass. The method is synthesized by a one-pot method, has the advantages of high conversion rate, good selectivity of the triphenyl compound, good stability of the catalyst, low reaction temperature and small pressure, and realizes green conversion of synthesizing the triphenyl compound from biomass.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
1.0G of phosphomolybdic acid and 0.40g of copper nitrate nonahydrate were weighed out in 10mL of water and stirred at room temperature for 1 hour. Pouring the raw materials into a synthesis kettle with the volume of 50mL, standing at 180 ℃ and crystallizing for 12h, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
Fig. 1 is an SEM image of the catalyst. It can be seen that the catalyst particles exhibit an octahedral shape.
Figure 2 is an XRD pattern of the catalyst. It can be seen that the catalyst has good crystallinity.
2, 5-Dimethylfuran and acrylonitrile are taken as reaction substrates, and the two are put into a reaction bottle in a molar ratio of 1:3, wherein the input amount of the reaction substrates is 8g. Then 10mL of acetone was added as a solvent, and the prepared catalyst was dispersed in a reaction flask and was exhausted with carbon dioxide gas for 30min. The input of the catalyst is 1.0g, the reaction pressure is 0.1MPa, the reaction temperature is 120 ℃, and the reaction time is 5h. The reaction products were analyzed off-line by gas chromatography, the reaction products were mainly aromatic hydrocarbons, and para-xylene was the main product in the aromatic hydrocarbons, and the results are shown in table 1.
Triphenyl conversion (%) = (number of moles of furans in 1-product/number of moles of furans before reaction) ×100%
Triphenylselectivity (%) = (moles of triphenylamine in product/moles of reacted furans) ×100%
Triphenyl yield (%) = conversion (%) x selectivity
Example 2
1.0G of silicotungstic acid and 0.9g of copper nitrate nonahydrate were weighed out in 50mL of water and stirred at room temperature for 1h. Pouring the raw materials into a synthesis kettle with the volume of 100mL, standing at 160 ℃ and crystallizing for 24 hours, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
The preparation of triphenyl is essentially the same as in example 1, except that: 2, 5-dimethyl furanstat is replaced by methyl furan, acrylonitrile is replaced by acrolein which is used as raw material, the reaction heating is replaced by using a 450nm LED light source, and the reaction time is 2 hours. The reaction products were analyzed off-line by gas chromatography, the reaction products were mainly aromatic hydrocarbons, toluene was the main product in the aromatic hydrocarbons, and the results are shown in table 1.
Example 3
1.0G of phosphomolybdic acid and 0.40g of copper nitrate nonahydrate were weighed out in 10mL of water and stirred at room temperature for 1 hour. Pouring the raw materials into a synthesis kettle with the volume of 50mL, standing at 130 ℃ and crystallizing for 72h, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
The preparation of triphenyl is essentially the same as in example 1, except that: 2, 5-dimethylfuran was replaced with furan and acrylonitrile with acrylic acid. The reaction products were mainly aromatic hydrocarbons, benzene being the main product in the aromatic hydrocarbons, and the results are shown in table 1.
Example 4
0.25G of silicotungstic acid and 0.9g of copper nitrate nonahydrate were weighed out in 50mL of water and stirred at room temperature for 1h. Pouring the raw materials into a synthesis kettle with the volume of 100mL, standing at 160 ℃ and crystallizing for 24 hours, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
The preparation of triphenyl is essentially the same as in example 2, except that: methyl furan was replaced with furan and reaction heating was replaced with a 365nm LED light source. The reaction products were mainly aromatic hydrocarbons, benzene being the main product in the aromatic hydrocarbons, and the results are shown in table 1.
Example 5
1.0G of phosphomolybdic acid and 0.50g of copper nitrate were weighed out in 10mL of water and stirred at room temperature for 1 hour. Pouring the raw materials into a synthesis kettle with the volume of 50mL, standing at 180 ℃ and crystallizing for 12h, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
The preparation of triphenyl is essentially the same as in example 1, except that: acrylonitrile is replaced with acrylic acid. The reaction products were mainly aromatic hydrocarbons, of which paraxylene was the main product in aromatic hydrocarbons, and the results are shown in table 1.
Example 6
1.0G of silicotungstic acid and 0.5g of cerium nitrate nonahydrate were weighed out and dissolved in 50mL of water, and stirred at room temperature for 1h. Pouring the raw materials into a synthesis kettle with the volume of 100mL, standing at 160 ℃ and crystallizing for 24 hours, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
The preparation of triphenyl is essentially the same as in example 2, except that: acrolein is replaced with acrylic acid. The reaction products were mainly aromatic hydrocarbons, toluene was the main product in the aromatic hydrocarbons, and the results are shown in table 1.
Example 7
The catalyst was prepared as in example 1.
Substantially the same as in example 1, except that: the catalyst loading was 0.05g. The reaction products were mainly aromatic hydrocarbons, of which paraxylene was the main product in aromatic hydrocarbons, and the results are shown in table 1.
Example 8
The catalyst was prepared as in example 1.
Substantially the same as in example 1, the only difference is that: the catalyst loading was 0.10g and acrylonitrile was replaced with acrolein. The reaction products were mainly aromatic hydrocarbons, of which paraxylene was the main product in aromatic hydrocarbons, and the results are shown in table 1.
Example 9
The catalyst was prepared as in example 2.
Substantially the same as in example 2, the only difference is that: 2, 5-dimethylfuran was replaced with methylfuran. The reaction products were mainly aromatic hydrocarbons, toluene was the main product in the aromatic hydrocarbons, and the results are shown in table 1.
Example 10
The catalyst was prepared as in example 1.
Substantially the same as in example 1, the only difference is that: the reaction temperature was 180℃and the reaction time was 24 hours. The reaction products were mainly aromatic hydrocarbons, of which paraxylene was the main product in aromatic hydrocarbons, and the results are shown in table 1.
Example 11
The catalyst was prepared as in example 1.
Substantially the same as in example 1, the only difference is that: the reaction heating was replaced by using a 410nm LED light source. The reaction products were mainly aromatic hydrocarbons, of which paraxylene was the main product in aromatic hydrocarbons, and the results are shown in table 1.
Comparative example 1
0G of silicotungstic acid and 0.40g of copper nitrate nonahydrate are weighed and dissolved in 10mL of water, and stirred for 1h at room temperature. Pouring the raw materials into a synthesis kettle with the volume of 50mL, standing at 180 ℃ and crystallizing for 12h, and then cooling, alcohol washing and water washing alternately for 3 times, and drying to obtain the catalyst.
The synthesis of paraxylene was carried out according to the reaction conditions of example 1, and the results are shown in Table 1.
TABLE 1
| Catalyst | Substrate conversion (%) | Product selectivity (%) | Product yield (%) |
| Example 1 | 79.2 | 51.0 | 40.4 |
| Example 2 | 75.3 | 48.4 | 36.5 |
| Example 3 | 40.2 | 54.8 | 20.2 |
| Example 4 | 49.9 | 39.6 | 19.8 |
| Example 5 | 57.8 | 47.5 | 27.5 |
| Example 6 | 65.3 | 43.6 | 28.5 |
| Example 7 | 66.8 | 17.3 | 11.6 |
| Example 8 | 73.1 | 32.1 | 23.5 |
| Example 9 | 80.1 | 50.0 | 40.0 |
| Example 10 | 43.2 | 80.0 | 34.6 |
| Example 11 | 99.9 | 98.1 | 98.0 |
| Comparative example 1 | 30.4 | 49.4 | 15.1 |
Claims (10)
1. A method of converting biomass into a triphenyl compound, wherein the triphenyl compound comprises at least one of benzene, toluene, and xylene; the method comprises the following steps: in a multiphase reaction system containing an organic solvent, a catalyst and a biomass-based reaction substrate, taking nitrogen or carbon dioxide gas as a protective atmosphere, carrying out thermocatalytic or photocatalytic reaction on the biomass-based reaction substrate, and separating a product to obtain an organic phase containing a triphenyl compound; wherein the catalyst is heteropolyacid/metal organic framework catalytic material, has Lewis acid and Bronsted acid sites which are uniformly distributed, and the content of heteropolyacid is between 1 and 30 percent mmol.
2. The method of claim 1, wherein the biomass-based reaction substrate comprises a furan derivative and a propenyl compound, and the molar ratio of the furan derivative to the propenyl compound is 1 to 10:1 to 100; preferably, the furan derivative comprises at least one of dimethylfuran, methylfuran and furan, and the propenyl compound comprises at least one of acrylonitrile, acrolein, acrylate and acrylic acid.
3. The method according to claim 1 or 2, characterized in that the mass ratio of catalyst to biomass-based reaction substrate is 1-20: 1 to 300; preferably, the concentration of the biomass-based reaction substrate occupying organic solvent is 1 to 10: 1-50 g/mL.
4. A method according to any one of claims 1 to 3, wherein the organic solvent comprises one or more of acetone, n-heptane, cyclohexane, n-hexane and 1, 4-dioxane.
5. The process according to any one of claims 1 to 4, wherein the reaction temperature of the thermocatalytic reaction is 25 to 200 ℃ and the reaction time is 1 to 36 hours.
6. The method according to any one of claims 1 to 5, wherein the light source wavelength of the photocatalytic reaction is between 360 and 450nm and the reaction time is between 0.5 and 5 hours.
7. The method according to any one of claims 1 to 6, wherein the heteropolyacid/metal organic framework catalytic material loads the heteropolyacid in the form of clusters in the multistage Kong Long of the metal organic framework; preferably, the pore canal size of the heteropolyacid/metal organic framework catalytic material is of a mesoporous structure; more preferably, the mesoporous size is 2 to 10nm and the porosity is 30 to 60%.
8. The method according to any one of claims 1 to 7, characterized in that the preparation method of the heteropolyacid/metal organic framework catalytic material comprises: filling the mixed solution containing heteropoly acid, solvent and metal salt into an autoclave, heating for 12-72 hours at 100-180 ℃, and drying the obtained product to obtain the heteropoly acid/metal organic framework catalytic material; preferably, the metal salt is selected from at least one of bismuth nitrate, ferric nitrate, zinc nitrate, copper nitrate, cerium nitrate, zirconium nitrate and hydrates thereof; more preferably, the solvent is selected from at least one of water, methanol, ethanol, acetone, acetonitrile, dichloromethane, N-dimethylformamide.
9. The method according to any one of claims 1 to 8, wherein the heteropolyacid is selected from at least one of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid.
10. The use of heteropoly acid/metal organic framework catalytic materials in the conversion of biomass to triphenyl compounds, especially xylenes.
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