WO2023193425A1 - Method for preparing 2-methyltetrahydrofuran by using waste biomass - Google Patents
Method for preparing 2-methyltetrahydrofuran by using waste biomass Download PDFInfo
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- WO2023193425A1 WO2023193425A1 PCT/CN2022/128901 CN2022128901W WO2023193425A1 WO 2023193425 A1 WO2023193425 A1 WO 2023193425A1 CN 2022128901 W CN2022128901 W CN 2022128901W WO 2023193425 A1 WO2023193425 A1 WO 2023193425A1
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- WIPO (PCT)
- Prior art keywords
- methyltetrahydrofuran
- catalyst
- preparation
- furfural
- biomass
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- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002028 Biomass Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 title claims abstract description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940038531 phenylhydrazine hydrochloride Drugs 0.000 claims abstract description 22
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910002482 Cu–Ni Inorganic materials 0.000 claims abstract description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229920002488 Hemicellulose Polymers 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 230000032683 aging Effects 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 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000012824 chemical production Methods 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 26
- 229960005215 dichloroacetic acid Drugs 0.000 description 15
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000003599 detergent Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229940040102 levulinic acid Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010653 organometallic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention relates to the technical field of chemical production, and specifically relates to a method for preparing 2-methyltetrahydrofuran by utilizing waste biomass.
- 2-Methyltetrahydrofuran is an important organic intermediate and excellent solvent. Because of its moderate boiling point, low solubility in water, easy separation from water, and similar Lewis basicity to tetrahydrofuran, it can be used in many applications. In organometallic reactions, it is currently being widely used in industrial production as a new type of solvent. Because 2-methyltetrahydrofuran can be miscible with gasoline in any proportion and has excellent oxidation and vapor pressure properties, it can also be used as a vehicle fuel additive to replace part of gasoline. In addition, 2-methyltetrahydrofuran is also a raw material in the pharmaceutical industry and can be used in the synthesis of anti-hemorrhoidal drugs such as primary aminoquinine phosphate.
- Biomass refers to various organisms formed through photosynthesis, including all animals, plants and microorganisms.
- Biomass energy is the energy form of solar energy stored in biomass in the form of chemical energy. It has always been one of the important energy sources for human survival. It is the fourth largest energy source after coal, oil and natural gas. In the entire energy occupies an important position in the system. Using biomass as raw material, a variety of platform-based compounds can be obtained after treatment, and then it is very easy to convert platform-based compounds into a variety of valuable chemicals.
- Furfural is produced from waste biomass and then hydrogenated using furfural as raw material. This method has mature technology, stable technology, wide sources of raw materials, and low cost. It also broadens the utilization pathways of furfural.
- Chinese patent CN110078687A discloses a preparation method of 2-methyltetrahydrofuran, which uses the biomass-based platform compound levulinic acid and its ester derivatives under the catalysis of a copper-nickel bimetallic catalyst to prepare 2-methyltetrahydrofuran through temperature-raising hydrogenation. .
- This invention reports for the first time that a copper-nickel bimetallic catalytic system using an alkane solvent can hydrogenate and reduce levulinic acid and its esters to 2-methyltetrahydrofuran in one step with high selectivity and high efficiency. However, this invention does not Conduct further research on reaction conditions.
- the object of the present invention is to provide a method for preparing 2-methyltetrahydrofuran using waste biomass.
- the method of the present invention can be prepared at a lower pressure than the existing technology and is easier to operate; another object of the present invention is to provide A catalyst with high activity for preparing 2-methyltetrahydrofuran. Under the action of this catalyst, dimethyltetrahydrofuran can be prepared under relatively low pressure; another object of the present invention is to provide a method for producing 2-methyltetrahydrofuran from waste.
- the method for preparing furfural in a substance has a high yield of furfural prepared by the method of the present invention, which is beneficial to increasing the yield in the subsequent preparation of 2-methyltetrahydrofuran.
- a catalyst for preparing 2-methyltetrahydrofuran including a bimetal catalyst, a hydrazine derivative, and sodium vanadate.
- the bimetallic catalyst includes a Cu-Ni catalyst.
- Cu-Ni catalyst can directly produce 2-methyltetrahydrofuran from furfural through one-step hydrogenation, which is simpler than the commonly used two-step hydrogenation method.
- the preparation of the catalyst includes the following steps:
- the hydrazine derivatives include phenylhydrazine hydrochloride.
- the weight ratio of metal catalyst, hydrazine derivatives and sodium vanadate is 2-5:1-2:1-2.
- the invention also discloses a method for preparing 2-methyltetrahydrofuran from waste biomass, which is characterized in that it includes the following steps:
- the preparation of 2-methyltetrahydrofuran includes using a catalyst to catalytically hydrogenate furfural to obtain 2-methyltetrahydrofuran.
- the biomass includes hemicellulose-containing biomass.
- the biomass includes corn stover and/or corn cobs.
- the steps of preparing furfural include:
- the crushed biomass is added to the acid solution to heat up the reaction, and the distillate is collected and distilled again to obtain furfural.
- the acid solution includes sulfuric acid solution and Lewis acid solution.
- the Lewis acid solution includes aluminum chloride solution or ferric chloride solution.
- the final concentration of the sulfuric acid solution in the acid solution is 0.5-1 mol/L.
- the final concentration of the Lewis acid solution in the acid solution is 0.05-0.1 mol/L.
- the weight ratio of acid solution to biomass is 2-3:1.
- reaction temperature is 160-180°C.
- reaction time is 1-1.5h.
- diphenyl phosphite and dichloroacetic acid are also added during the preparation of furfural.
- the furfural will undergo side reactions such as degradation or polymerization under high temperature and acidic conditions.
- side reactions such as degradation or polymerization under high temperature and acidic conditions.
- diphenyl phosphite and dichloroacetic acid can make the furfural more stable and reduce the occurrence of side reactions. Increase the yield of furfural.
- the weight ratio of diphenyl phosphite and dichloroacetic acid is 0.1-0.2:1-3.
- the weight ratio of biomass, diphenyl phosphite and dichloroacetic acid is 1:0.01-0.02:0.1-0.3.
- the steps for preparing 2-methyltetrahydrofuran include:
- the weight ratio of furfural and catalyst is 100-150:1-2.
- the temperature of the catalytic hydrogenation reaction is 180-190°C.
- the pressure of the catalytic hydrogenation reaction is 2-4MPa.
- the catalytic hydrogenation reaction time is 3-5 hours.
- the invention also discloses the use of the above catalyst in preparing 2-methyltetrahydrofuran.
- waste biomass is first used to prepare furfural, and then the furfural is catalytically hydrogenated to prepare 2-methyltetrahydrofuran.
- the present invention uses a Cu-Ni bimetallic catalyst in combination with phenylhydrazine hydrochloride and sodium vanadate as a catalyst for the hydrogenation reaction. Using this catalyst can make the hydrogenation reaction occur at a lower temperature.
- the reaction is carried out under pressure and has low requirements on reaction equipment, which is conducive to large-scale preparation; in addition, the addition of phenylhydrazine hydrochloride and sodium vanadate effectively improves the activity of the catalyst, making the furfural conversion rate close to 100%; and, phenylhydrazine hydrochloride and vanadium
- the addition of sodium acid also reduces by-products in the process of preparing 2-methyltetrahydrofuran to a certain extent, increasing the selectivity of 2-methyltetrahydrofuran to more than 75%.
- the present invention also adds diphenyl phosphite and dichloroacetic acid, which effectively reduces the occurrence of side reactions after the preparation of furfural, thereby increasing the yield of furfural to more than 50%.
- Figure 1 shows the mass spectrum of 2-methyltetrahydrofuran.
- the mass of hemicellulose M the mass of neutral detergent fiber - acidic detergent fiber.
- the yield of furfural prepared in Example 1-3 is close to and higher than that of furfural prepared in Example 4-6, and the yield of furfural prepared in Example 4-6 is close to; It shows that the use of diphenyl phosphite and dichloroacetic acid in the process of preparing furfural can effectively increase the yield of furfural; but when only diphenyl phosphite or dichloroacetic acid is used, the yield of furfural is the same as that without adding diphenyl phosphite. The yield of furfural produced when using ester and dichloroacetic acid is close, indicating that only using diphenyl phosphite or dichloroacetic acid cannot significantly improve the yield of furfural.
- the chromatographic column is an HP-5MS chromatographic column, the detector is a hydrogen flame ion detector, and a nitrogen atmosphere; the chromatographic conditions are as follows: 60°C Keep the temperature constant for 2 minutes and 155°C for 4 minutes; column temperature 50-220°C, injection temperature 250°C, and injection volume 1 ⁇ L; after measurement, use the area normalization method to calculate the conversion rate of furfural and the selectivity of 2-methyltetrahydrofuran. The calculation results are shown in Table 2.
- the furfural conversion rate in Examples 10-12 is extremely low, indicating that the reaction cannot proceed normally. It can be judged that the reaction cannot occur normally under the condition of pressure drop without adding phenylhydrazine hydrochloride and sodium vanadate.
- the selectivity of 2-methyltetrahydrofuran prepared in Examples 1-6 is higher than that of 2-methyltetrahydrofuran prepared in Examples 1-9 and Comparative Example 1, It shows that fewer side reactions and by-products are produced in the process of preparing 2-methyltetrahydrofuran in Examples 1-6; it shows that during the preparation process, the addition of phenylhydrazine hydrochloride and sodium vanadate can also reduce the production of by-products, thereby increasing
- the selectivity of 2-methyltetrahydrofuran; the selectivity of tetrahydrofuran in Examples 10-12 is extremely low, indicating that the reaction cannot proceed normally. It can be judged that when phenylhydrazine hydro
Abstract
The present invention provides a method for preparing 2-methyltetrahydrofuran by using waste biomass and belongs to the technical field of chemical production. In preparation of 2-methyltetrahydrofuran in the present invention, a catalyst is used to perform catalytic hydrogenation on furfural to obtain 2-methyltetrahydrofuran. In a preparation process, a Cu-Ni bimetallic catalyst is used in cooperation with phenylhydrazine hydrochloride and sodium vanadate to serve as a hydrogenation reaction catalyst, and, by using the catalyst, a hydrogenation reaction can be carried out under a relatively low pressure and has a low requirement for a reaction apparatus, thus facilitating large-scale preparation. In addition, the activity of the catalyst is effectively improved by the addition of the phenylhydrazine hydrochloride and the sodium vanadate, making a furfural conversion ratio close to 100%.
Description
本发明涉及化工生产技术领域，具体涉及一种利用废弃生物质制备2-甲基四氢呋喃的方法。The invention relates to the technical field of chemical production, and specifically relates to a method for preparing 2-methyltetrahydrofuran by utilizing waste biomass.
2-甲基四氢呋喃是一种重要的有机中间体和优良的溶剂，由于它沸点适中，在水中的溶解度较小，与水分离容易，同时具有与四氢呋喃相似的路易斯碱性，故可以应用到很多有机金属反应中，目前正作为一种新型溶剂被广泛应用于工业生产中。因2-甲基四氢呋喃可与汽油以任意比例互溶，具有优异的氧化和蒸汽压等性质，故还可作为汽车燃料添加剂代替部分汽油。此外，2-甲基四氢呋喃还是制药工业的原料，可用于抗痔药磷酸伯氨奎等的合成。2-Methyltetrahydrofuran is an important organic intermediate and excellent solvent. Because of its moderate boiling point, low solubility in water, easy separation from water, and similar Lewis basicity to tetrahydrofuran, it can be used in many applications. In organometallic reactions, it is currently being widely used in industrial production as a new type of solvent. Because 2-methyltetrahydrofuran can be miscible with gasoline in any proportion and has excellent oxidation and vapor pressure properties, it can also be used as a vehicle fuel additive to replace part of gasoline. In addition, 2-methyltetrahydrofuran is also a raw material in the pharmaceutical industry and can be used in the synthesis of anti-hemorrhoidal drugs such as primary aminoquinine phosphate.
生物质是指通过光合作用而形成的各种有机体，包括所有的动植物和微生物。生物质能则是太阳能以化学能形式储存在生物质中的能量形式，它一直是人类赖以生存的重要能源之一，是仅次于煤炭、石油、天然气之后第四大能源，在整个能源系统中占有重要的地位。以生物质为原料，经过处理可以得到多种平台基化合物，再通过平台基化合物为原料十分容易转化得到多种有价值的化学品。Biomass refers to various organisms formed through photosynthesis, including all animals, plants and microorganisms. Biomass energy is the energy form of solar energy stored in biomass in the form of chemical energy. It has always been one of the important energy sources for human survival. It is the fourth largest energy source after coal, oil and natural gas. In the entire energy occupies an important position in the system. Using biomass as raw material, a variety of platform-based compounds can be obtained after treatment, and then it is very easy to convert platform-based compounds into a variety of valuable chemicals.
使用废弃生物质制得糠醛后以糠醛为原料经加氢制得，此方法工艺成熟，技术稳定，原料来源广泛，成本较低，同时也拓宽了糠醛的利用途径。中国专利CN110078687A公开了一种2-甲基四氢呋喃的制备方法，使用生物质基平台化合物乙酰丙酸及其酯类衍生物在铜镍双金属催化剂的催化下，升温加氢制备2-甲基四氢呋喃。该发明第一次报道了使用烷烃类溶剂的铜镍双金属催化体系可以高选择性、高效率的将乙酰丙酸及其酯类化合物一步加氢还原至2-甲基四氢呋喃，但该发明未就反应条件做进一步研究。Furfural is produced from waste biomass and then hydrogenated using furfural as raw material. This method has mature technology, stable technology, wide sources of raw materials, and low cost. It also broadens the utilization pathways of furfural. Chinese patent CN110078687A discloses a preparation method of 2-methyltetrahydrofuran, which uses the biomass-based platform compound levulinic acid and its ester derivatives under the catalysis of a copper-nickel bimetallic catalyst to prepare 2-methyltetrahydrofuran through temperature-raising hydrogenation. . This invention reports for the first time that a copper-nickel bimetallic catalytic system using an alkane solvent can hydrogenate and reduce levulinic acid and its esters to 2-methyltetrahydrofuran in one step with high selectivity and high efficiency. However, this invention does not Conduct further research on reaction conditions.
发明内容Contents of the invention
本发明的目的在于提供一种利用废弃生物质制备2-甲基四氢呋喃的方法，本发明方法可在相对于现有技术较低的压力下进行制备，更易操作；本发明的另一个目的在于提供一种具有高活性的制备2-甲基四氢呋喃的催化剂，在这种催化剂的作用下，可以在相对较低的压力下制备二甲基四氢呋喃；本发明的再一个目的在于提供一种从废弃生物质中制备糠醛的方法，使用本发明方法制得的糠醛得率高，有利于后续制备2-甲基四氢呋喃时提高得率。The object of the present invention is to provide a method for preparing 2-methyltetrahydrofuran using waste biomass. The method of the present invention can be prepared at a lower pressure than the existing technology and is easier to operate; another object of the present invention is to provide A catalyst with high activity for preparing 2-methyltetrahydrofuran. Under the action of this catalyst, dimethyltetrahydrofuran can be prepared under relatively low pressure; another object of the present invention is to provide a method for producing 2-methyltetrahydrofuran from waste. The method for preparing furfural in a substance has a high yield of furfural prepared by the method of the present invention, which is beneficial to increasing the yield in the subsequent preparation of 2-methyltetrahydrofuran.
为达到上述发明目的，采用如下技术方案：In order to achieve the above-mentioned purpose of the invention, the following technical solutions are adopted:
一种制备2-甲基四氢呋喃的催化剂，包括双金属催化剂、肼类衍生物、钒酸钠。A catalyst for preparing 2-methyltetrahydrofuran, including a bimetal catalyst, a hydrazine derivative, and sodium vanadate.
优选地，双金属催化剂包括Cu-Ni催化剂。Preferably, the bimetallic catalyst includes a Cu-Ni catalyst.
使用Cu-Ni催化剂可以使糠醛由一步加氢直接制得2-甲基四氢呋喃，相比于常用的两步加氢法更加简便。The use of Cu-Ni catalyst can directly produce 2-methyltetrahydrofuran from furfural through one-step hydrogenation, which is simpler than the commonly used two-step hydrogenation method.
优选地，催化剂的制备包括如下步骤：Preferably, the preparation of the catalyst includes the following steps:
将硝酸铜、硝酸镍和硝酸钙加入酸性硅溶胶中，混匀后边搅拌边加入碳酸钠溶液；搅拌至无沉淀增加时静置陈化；陈化后洗涤、烘干研磨成粉即得双金属催化剂。Add copper nitrate, nickel nitrate and calcium nitrate to the acidic silica sol, mix and add sodium carbonate solution while stirring; stir until no precipitation increases and let it stand for aging; after aging, wash, dry and grind into powder to obtain bimetal catalyst.
优选地，肼类衍生物包括盐酸苯肼。Preferably, the hydrazine derivatives include phenylhydrazine hydrochloride.
现有技术中制备2-甲基四氢呋喃需要在高压下进行催化加氢，压力较低时反应难以进行；将双金属催化剂与盐酸苯肼和钒酸钠进行配合使用时，则可在较低的压力下催化活性和糠醛转化率。In the prior art, the preparation of 2-methyltetrahydrofuran requires catalytic hydrogenation under high pressure, and the reaction is difficult to proceed when the pressure is low; when a bimetallic catalyst is used in combination with phenylhydrazine hydrochloride and sodium vanadate, the reaction can be carried out at a lower pressure. Catalytic activity and furfural conversion under pressure.
优选地，金属催化剂、肼类衍生物、钒酸钠的重量比为2-5:1-2:1-2。Preferably, the weight ratio of metal catalyst, hydrazine derivatives and sodium vanadate is 2-5:1-2:1-2.
本发明还公开了一种利用废弃生物质制备2-甲基四氢呋喃的方法，其特征在于，包括如下步骤：The invention also discloses a method for preparing 2-methyltetrahydrofuran from waste biomass, which is characterized in that it includes the following steps:
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
其中，2-甲基四氢呋喃的制备包括使用催化剂对糠醛进行催化加氢制得2-甲基四氢呋喃。Among them, the preparation of 2-methyltetrahydrofuran includes using a catalyst to catalytically hydrogenate furfural to obtain 2-methyltetrahydrofuran.
优选地，生物质包括含半纤维素的生物质。Preferably, the biomass includes hemicellulose-containing biomass.
更优选地，生物质包括玉米秸秆和/或玉米芯。More preferably, the biomass includes corn stover and/or corn cobs.
优选地，糠醛的制备的步骤包括：Preferably, the steps of preparing furfural include:
将粉碎后的生物质加入酸液升温反应，收集馏出物后再次蒸馏即得糠醛。The crushed biomass is added to the acid solution to heat up the reaction, and the distillate is collected and distilled again to obtain furfural.
优选地，酸液包括硫酸溶液和路易斯酸溶液。Preferably, the acid solution includes sulfuric acid solution and Lewis acid solution.
更优选地，路易斯酸溶液包括氯化铝溶液或氯化铁溶液。More preferably, the Lewis acid solution includes aluminum chloride solution or ferric chloride solution.
更优选地，酸液中硫酸溶液的终浓度为0.5-1mol/L。More preferably, the final concentration of the sulfuric acid solution in the acid solution is 0.5-1 mol/L.
更优选地，酸液中路易斯酸溶液的终浓度为0.05-0.1mol/L。More preferably, the final concentration of the Lewis acid solution in the acid solution is 0.05-0.1 mol/L.
更优选地，酸液与生物质的重量比为2-3:1。More preferably, the weight ratio of acid solution to biomass is 2-3:1.
更优选地，反应温度为160-180℃。More preferably, the reaction temperature is 160-180°C.
更优选地，反应时间为1-1.5h。More preferably, the reaction time is 1-1.5h.
更优选地，制备糠醛的过程中还添加亚磷酸二苯酯和二氯乙酸。More preferably, diphenyl phosphite and dichloroacetic acid are also added during the preparation of furfural.
制备糠醛的过程中，制得的糠醛会在高温和酸性条件下发生降解或是聚合等副反应，亚磷酸二苯酯和二氯乙酸的添加可以使得到的糠醛更加稳定减少副反应的发生，使糠醛的产率提高。In the process of preparing furfural, the furfural will undergo side reactions such as degradation or polymerization under high temperature and acidic conditions. The addition of diphenyl phosphite and dichloroacetic acid can make the furfural more stable and reduce the occurrence of side reactions. Increase the yield of furfural.
更进一步优选地，亚磷酸二苯酯和二氯乙酸的重量比为0.1-0.2:1-3。More preferably, the weight ratio of diphenyl phosphite and dichloroacetic acid is 0.1-0.2:1-3.
更进一步优选地，生物质、亚磷酸二苯酯和二氯乙酸的重量比为1:0.01-0.02:0.1-0.3。More preferably, the weight ratio of biomass, diphenyl phosphite and dichloroacetic acid is 1:0.01-0.02:0.1-0.3.
优选地，2-甲基四氢呋喃的制备的步骤包括：Preferably, the steps for preparing 2-methyltetrahydrofuran include:
将糠醛和催化剂升温进行催化加氢反应即得2-甲基四氢呋喃。Raise the temperature of furfural and catalyst to perform catalytic hydrogenation reaction to obtain 2-methyltetrahydrofuran.
更优选地，糠醛和催化剂的重量比为100-150:1-2。More preferably, the weight ratio of furfural and catalyst is 100-150:1-2.
更优选地，催化加氢反应的温度为180-190℃。More preferably, the temperature of the catalytic hydrogenation reaction is 180-190°C.
更优选地，催化加氢反应的压力为2-4MPa。More preferably, the pressure of the catalytic hydrogenation reaction is 2-4MPa.
更优选地，催化加氢反应的时间为3-5h。More preferably, the catalytic hydrogenation reaction time is 3-5 hours.
本发明还公开了上述催化剂在制备2-甲基四氢呋喃中的用途。The invention also discloses the use of the above catalyst in preparing 2-methyltetrahydrofuran.
与现有技术相比，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:
本发明先使用废弃生物质制备得到糠醛之后，再将制得的糠醛催化加氢制备2-甲基四氢呋喃。在制备2-甲基四氢呋喃的过程中，本发明使用Cu-Ni双金属催化剂与盐酸苯肼和钒酸钠配合使用作为加氢反应的催化剂，使用这种催化剂可以使加氢反应在较低的压力下进行反应，对反应设备要求低，有利于大规 模制备；此外，盐酸苯肼和钒酸钠的加有效提高了催化剂的活性，使糠醛转化率接近100％；并且，盐酸苯肼和钒酸钠的加入还一定程度上减少了制备2-甲基四氢呋喃过程中的副产物，使得2-甲基四氢呋喃的选择性增加，达到75％以上。本发明在使用废弃生物质制备糠醛的过程中，还添加了亚磷酸二苯酯和二氯乙酸，有效减少了糠醛制备后副反应的发生，从而提高了糠醛的产率，达到50％以上。In the present invention, waste biomass is first used to prepare furfural, and then the furfural is catalytically hydrogenated to prepare 2-methyltetrahydrofuran. In the process of preparing 2-methyltetrahydrofuran, the present invention uses a Cu-Ni bimetallic catalyst in combination with phenylhydrazine hydrochloride and sodium vanadate as a catalyst for the hydrogenation reaction. Using this catalyst can make the hydrogenation reaction occur at a lower temperature. The reaction is carried out under pressure and has low requirements on reaction equipment, which is conducive to large-scale preparation; in addition, the addition of phenylhydrazine hydrochloride and sodium vanadate effectively improves the activity of the catalyst, making the furfural conversion rate close to 100%; and, phenylhydrazine hydrochloride and vanadium The addition of sodium acid also reduces by-products in the process of preparing 2-methyltetrahydrofuran to a certain extent, increasing the selectivity of 2-methyltetrahydrofuran to more than 75%. In the process of using waste biomass to prepare furfural, the present invention also adds diphenyl phosphite and dichloroacetic acid, which effectively reduces the occurrence of side reactions after the preparation of furfural, thereby increasing the yield of furfural to more than 50%.
图1为2-甲基四氢呋喃的质谱图。Figure 1 shows the mass spectrum of 2-methyltetrahydrofuran.
这里将详细地对示例性实施例进行说明，以下示例性实施例中所描述的实施方式并不代表与本公开相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本公开的一些方面相一致的方法的例子。Exemplary embodiments will be described in detail herein, and the implementations described in the following example embodiments do not represent all implementations consistent with the present disclosure. Rather, they are merely examples of approaches consistent with aspects of the disclosure as detailed in the appended claims.
下述实施例中的实验方法，如无特殊说明，均为常规方法，或按照制造厂商所建议的条件。下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The experimental methods in the following examples, unless otherwise specified, are all conventional methods or in accordance with the conditions recommended by the manufacturer. Materials, reagents, etc. used in the following examples can all be obtained from commercial sources unless otherwise specified.
实施例1Example 1
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
将300g粉碎后颗粒直径在5mm左右的玉米秸秆与800g酸液混合，其中，酸液中硫酸浓度为0.5mol/L，氯化铝浓度为0.05mol/L；混合后加入4.5g亚磷酸二苯酯和45g二氯乙酸，升温至170℃反应1h，期间冷凝回收馏出物，将馏出物蒸发浓缩后再次蒸馏，收集160-170℃馏分即得糠醛；Mix 300g of crushed corn straw with a particle diameter of about 5mm and 800g of acid solution. The concentration of sulfuric acid in the acid solution is 0.5mol/L and the concentration of aluminum chloride is 0.05mol/L; after mixing, add 4.5g of diphenyl phosphite. The ester and 45g of dichloroacetic acid are heated to 170°C and reacted for 1 hour. During this period, the distillate is condensed and recovered. The distillate is evaporated and concentrated and then distilled again. The 160-170°C fraction is collected to obtain furfural;
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
将3g硝酸铜、3g硝酸镍和1g硝酸钙加入80mL酸性硅溶胶中，混匀后边搅拌边加入20mL 1mol/L的碳酸钠溶液；搅拌至无沉淀增加时静置陈化1.5h；陈化后洗涤、烘干研磨成粉即得双金属催化剂；取3g双金属催化剂加入1g盐酸苯肼和1g钒酸钠混匀即得催化剂；Add 3g copper nitrate, 3g nickel nitrate and 1g calcium nitrate into 80mL acidic silica sol, mix and add 20mL 1mol/L sodium carbonate solution while stirring; stir until no precipitation increases and let stand for 1.5h; after aging Wash, dry and grind into powder to obtain the bimetallic catalyst; take 3g of the bimetallic catalyst, add 1g of phenylhydrazine hydrochloride and 1g of sodium vanadate, and mix well to obtain the catalyst;
将100g糠醛和1.5g催化剂混合后置于密封反应器，通入氮气置换空 气后再通入氢气置换氮气，并加压至2MPa；升温至187℃反应4h后过滤即得2-甲基四氢呋喃。Mix 100g of furfural and 1.5g of catalyst and place it in a sealed reactor. Pass in nitrogen to replace the air, then pass in hydrogen to replace the nitrogen, and pressurize to 2MPa; heat to 187°C and react for 4 hours, then filter to obtain 2-methyltetrahydrofuran.
实施例2Example 2
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
将300g粉碎后颗粒直径在5mm左右的玉米芯与800g酸液混合，其中，酸液中硫酸浓度为1mol/L，氯化铁浓度为0.08mol/L；混合后加入3g亚磷酸二苯酯和30g二氯乙酸，升温至180℃反应1h，期间冷凝回收馏出物，将馏出物蒸发浓缩后再次蒸馏，收集160-170℃馏分即得糠醛；Mix 300g of crushed corncobs with a particle diameter of about 5mm and 800g of acid solution. The concentration of sulfuric acid in the acid solution is 1mol/L and the concentration of ferric chloride is 0.08mol/L. After mixing, add 3g of diphenyl phosphite and 30g dichloroacetic acid is heated to 180°C and reacted for 1 hour. During this period, the distillate is condensed and recovered. The distillate is evaporated and concentrated and then distilled again. The 160-170°C fraction is collected to obtain furfural;
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
将3g硝酸铜、3g硝酸镍和1g硝酸钙加入80mL酸性硅溶胶中，混匀后边搅拌边加入20mL 1mol/L的碳酸钠溶液；搅拌至无沉淀增加时静置陈化1.5h；陈化后洗涤、烘干研磨成粉即得双金属催化剂；取2g双金属催化剂加入1.2g盐酸苯肼和1.5g钒酸钠混匀即得催化剂；Add 3g copper nitrate, 3g nickel nitrate and 1g calcium nitrate into 80mL acidic silica sol, mix and add 20mL 1mol/L sodium carbonate solution while stirring; stir until no precipitation increases and let stand for 1.5h; after aging Wash, dry and grind into powder to obtain the bimetallic catalyst; take 2g of the bimetallic catalyst, add 1.2g of phenylhydrazine hydrochloride and 1.5g of sodium vanadate, and mix well to obtain the catalyst;
将120g糠醛和1.5g催化剂混合后置于密封反应器，通入氮气置换空气后再通入氢气置换氮气，并加压至3MPa；升温至190℃反应5h后过滤即得2-甲基四氢呋喃。Mix 120g of furfural and 1.5g of catalyst and place it in a sealed reactor. Pass in nitrogen to replace the air, then pass in hydrogen to replace the nitrogen, and pressurize to 3MPa; raise the temperature to 190°C and react for 5 hours, then filter to obtain 2-methyltetrahydrofuran.
实施例3Example 3
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
将100g粉碎后颗粒直径在5mm左右的玉米秸秆、200g粉碎后颗粒直径在5mm左右的玉米芯与800g酸液混合，其中，酸液中硫酸浓度为0.7mol/L，氯化铝浓度为0.06mol/L；混合后加入6g亚磷酸二苯酯和60g二氯乙酸，升温至180℃反应1.2h，期间冷凝回收馏出物，将馏出物蒸发浓缩后再次蒸馏，收集160-170℃馏分即得糠醛；Mix 100g of corn stalks with a particle diameter of about 5mm after crushing, 200g of corn cobs with a particle diameter of about 5mm after crushing, and 800g of acid solution. The concentration of sulfuric acid in the acid solution is 0.7mol/L and the concentration of aluminum chloride is 0.06mol. /L; after mixing, add 6g diphenyl phosphite and 60g dichloroacetic acid, raise the temperature to 180°C and react for 1.2 hours. During this period, the distillate is condensed and recovered. The distillate is evaporated and concentrated and then distilled again. The 160-170°C fraction is collected. Get furfural;
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
将3g硝酸铜、3g硝酸镍和1g硝酸钙加入80mL酸性硅溶胶中，混匀后边搅拌边加入20mL 1mol/L的碳酸钠溶液；搅拌至无沉淀增加时静置陈化1.5h；陈化后洗涤、烘干研磨成粉即得双金属催化剂；取5g双金属催化剂加入 2g盐酸苯肼和2g钒酸钠混匀即得催化剂；Add 3g copper nitrate, 3g nickel nitrate and 1g calcium nitrate into 80mL acidic silica sol, mix and add 20mL 1mol/L sodium carbonate solution while stirring; stir until no precipitation increases and let stand for 1.5h; after aging Wash, dry and grind into powder to obtain the bimetallic catalyst; take 5g of the bimetallic catalyst, add 2g of phenylhydrazine hydrochloride and 2g of sodium vanadate, and mix well to obtain the catalyst;
将150g糠醛和2g催化剂混合后置于密封反应器，通入氮气置换空气后再通入氢气置换氮气，并加压至4MPa；升温至180℃反应3.5h后过滤即得2-甲基四氢呋喃。Mix 150g of furfural and 2g of catalyst and place it in a sealed reactor. Pass in nitrogen to replace the air, then pass in hydrogen to replace the nitrogen, and pressurize to 4MPa; raise the temperature to 180°C and react for 3.5 hours, then filter to obtain 2-methyltetrahydrofuran.
实施例4Example 4
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
制备过程中不添加二氯乙酸，其余操作同实施例1。No dichloroacetic acid is added during the preparation process, and the remaining operations are the same as in Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
同实施例1。Same as Example 1.
实施例5Example 5
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
制备过程中不添加亚磷酸二苯酯，其余操作同实施例1。No diphenyl phosphite was added during the preparation process, and the remaining operations were the same as in Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
同实施例1。Same as Example 1.
实施例6Example 6
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
制备过程中不添加亚磷酸二苯酯和二氯乙酸，其余操作同实施例1。No diphenyl phosphite and dichloroacetic acid were added during the preparation process, and the remaining operations were the same as in Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
同实施例1。Same as Example 1.
实施例7Example 7
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
同实施例1。Same as Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
制备催化剂时不添加钒酸钠，制备2-甲基四氢呋喃时加压至8MPa，其余操作同实施例1。No sodium vanadate is added when preparing the catalyst. When preparing 2-methyltetrahydrofuran, the pressure is increased to 8MPa. The remaining operations are the same as in Example 1.
实施例8Example 8
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
同实施例1。Same as Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
制备催化剂时不添加盐酸苯肼，制备2-甲基四氢呋喃时加压至8MPa，其余操作同实施例1。When preparing the catalyst, no phenylhydrazine hydrochloride is added. When preparing 2-methyltetrahydrofuran, the pressure is increased to 8MPa. The remaining operations are the same as in Example 1.
实施例9Example 9
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
同实施例1。Same as Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
制备催化剂时不添加盐酸苯肼和钒酸钠，制备2-甲基四氢呋喃时加压至8MPa，其余操作同实施例1。When preparing the catalyst, phenylhydrazine hydrochloride and sodium vanadate are not added. When preparing 2-methyltetrahydrofuran, the pressure is increased to 8MPa. The remaining operations are the same as in Example 1.
实施例10Example 10
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
同实施例1。Same as Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
制备催化剂时不添加钒酸钠，其余操作同实施例1。No sodium vanadate is added when preparing the catalyst, and the remaining operations are the same as in Example 1.
实施例11Example 11
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
同实施例1。Same as Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
制备催化剂时不添加盐酸苯肼，其余操作同实施例1。No phenylhydrazine hydrochloride was added when preparing the catalyst, and the remaining operations were the same as in Example 1.
实施例12Example 12
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
同实施例1。Same as Example 1.
制备催化剂时不添加盐酸苯肼和钒酸钠，其余操作同实施例1。When preparing the catalyst, phenylhydrazine hydrochloride and sodium vanadate are not added, and the remaining operations are the same as in Example 1.
对比例1Comparative example 1
2-甲基四氢呋喃的制备Preparation of 2-methyltetrahydrofuran
(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;
制备过程中不添加亚磷酸二苯酯和二氯乙酸，其余操作同实施例1。No diphenyl phosphite and dichloroacetic acid were added during the preparation process, and the remaining operations were the same as in Example 1.
(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;
制备催化剂时不添加盐酸苯肼和钒酸钠，制备2-甲基四氢呋喃时加压至8MPa，其余操作同实施例1。When preparing the catalyst, phenylhydrazine hydrochloride and sodium vanadate are not added. When preparing 2-methyltetrahydrofuran, the pressure is increased to 8MPa. The remaining operations are the same as in Example 1.
试验例1Test example 1
糠醛产率测定Furfural yield determination
取实施例1-6中制得的糠醛进行产率的测定，具体步骤如下：The furfural prepared in Examples 1-6 was used to measure the yield. The specific steps are as follows:
取实施例1-6中的制备原料(玉米秸秆和/或玉米芯)测定其半纤维素的质量，记为M，取实施例1-6中制得的糠醛进行称重，记为m，计算糠醛产率；Take the preparation raw materials (corn straw and/or corncob) in Examples 1-6 and measure the quality of the hemicellulose, which is recorded as M. Take the furfural prepared in Examples 1-6 and weigh it, which is recorded as m. Calculate furfural yield;
产率(％)＝m/M×100％；Yield (%)=m/M×100%;
半纤维素含量测定步骤如下：The steps for determining hemicellulose content are as follows:
测定原料重量，记为m1；使用乙二胺四乙酸二钠与四硼酸钠配制成中性洗涤剂溶液；将原料与中性洗涤溶液加热回流；之后对进行抽滤，取滤渣使用清水和丙酮冲洗后干燥，对干燥滤渣进行称重，记为m2；中性洗涤纤维质量＝m1-m2；Determine the weight of the raw materials and record it as m1; use disodium ethylenediaminetetraacetate and sodium tetraborate to prepare a neutral detergent solution; heat the raw materials and neutral detergent solution to reflux; then perform suction filtration, and use clean water and acetone to collect the filter residue. After rinsing, dry the dried filter residue and weigh it, recorded as m2; neutral detergent fiber mass = m1-m2;
使用十六烷基三甲基溴化铵与硫酸配制成酸性洗涤剂，按照上述中性洗涤纤维质量的测定方法进行测定；Use cetyltrimethylammonium bromide and sulfuric acid to prepare an acidic detergent, and measure it according to the above-mentioned method for measuring the quality of neutral detergent fibers;
半纤维素的质量M＝中性洗涤纤维质量-酸性洗涤纤维。The mass of hemicellulose M = the mass of neutral detergent fiber - acidic detergent fiber.
产率测定结果如表1所示。The yield measurement results are shown in Table 1.
表1糠醛产率Table 1 Furfural yield
| | 糠醛产率(％)Furfural yield (%) |
| 实施例1Example 1 | 50.3450.34 |
| 实施例2Example 2 | 50.2250.22 |
| 实施例3Example 3 | 50.1550.15 |
| 实施例4Example 4 | 42.2042.20 |
| 实施例5Example 5 | 42.3542.35 |
| 实施例6Example 6 | 42.1742.17 |
由表1可知，实施例1-3中制得的糠醛产率接近且高于实施例4-6 中制得的糠醛的产率，并且实施例4-6制得的糠醛的产率接近；说明在制备糠醛的过程中使用亚磷酸二苯酯和二氯乙酸，能够有效增加糠醛的产率；但仅使用亚磷酸二苯酯或二氯乙酸时糠醛的产率与不添加亚磷酸二苯酯和二氯乙酸时制得的糠醛的产率接近，说明仅使用亚磷酸二苯酯或二氯乙酸不能使糠醛的产率有明显提高。As can be seen from Table 1, the yield of furfural prepared in Example 1-3 is close to and higher than that of furfural prepared in Example 4-6, and the yield of furfural prepared in Example 4-6 is close to; It shows that the use of diphenyl phosphite and dichloroacetic acid in the process of preparing furfural can effectively increase the yield of furfural; but when only diphenyl phosphite or dichloroacetic acid is used, the yield of furfural is the same as that without adding diphenyl phosphite. The yield of furfural produced when using ester and dichloroacetic acid is close, indicating that only using diphenyl phosphite or dichloroacetic acid cannot significantly improve the yield of furfural.
试验例2Test example 2
2-甲基四氢呋喃质谱表征Mass spectrometry characterization of 2-methyltetrahydrofuran
使用质谱仪对实施例1中制得的2-甲基四氢呋喃的分子量进行测定，测定结果如图1所示。The molecular weight of 2-methyltetrahydrofuran prepared in Example 1 was measured using a mass spectrometer, and the measurement results are shown in Figure 1.
由图1可看出，2-甲基四氢呋喃的分子量为86.1，说明制备成功。As can be seen from Figure 1, the molecular weight of 2-methyltetrahydrofuran is 86.1, indicating that the preparation was successful.
试验例3Test example 3
2-甲基四氢呋喃色谱分析Chromatographic analysis of 2-methyltetrahydrofuran
取实施例1-9以及对比例1中制得的2-甲基四氢呋喃进行色谱分析，色谱柱为HP-5MS色谱柱，检测器为氢火焰离子检测器，氮气气氛；色谱条件如下：60℃恒温2min，155℃恒温4min；柱温50-220℃，进样温度250℃，进样量1μL；测定后使用面积归一法计算糠醛的转化率以及2-甲基四氢呋喃的选择性。计算结果如表2所示。Take the 2-methyltetrahydrofuran prepared in Examples 1-9 and Comparative Example 1 for chromatographic analysis. The chromatographic column is an HP-5MS chromatographic column, the detector is a hydrogen flame ion detector, and a nitrogen atmosphere; the chromatographic conditions are as follows: 60°C Keep the temperature constant for 2 minutes and 155°C for 4 minutes; column temperature 50-220°C, injection temperature 250°C, and injection volume 1 μL; after measurement, use the area normalization method to calculate the conversion rate of furfural and the selectivity of 2-methyltetrahydrofuran. The calculation results are shown in Table 2.
表22-甲基四氢呋喃色谱分析结果Table 22-Methyltetrahydrofuran chromatographic analysis results
| | 糠醛转化率(％)Furfural conversion rate (%) | 2-甲基四氢呋喃选择性(％)2-Methyltetrahydrofuran selectivity (%) |
| 实施例1Example 1 | 99.9299.92 | 76.276.2 |
| 实施例2Example 2 | 99.9599.95 | 75.875.8 |
| 实施例3Example 3 | 99.9199.91 | 75.575.5 |
| 实施例4Example 4 | 99.9399.93 | 75.775.7 |
| 实施例5Example 5 | 99.9699.96 | 75.275.2 |
| 实施例6Example 6 | 99.9599.95 | 75.975.9 |
| 实施例7Example 7 | 93.5593.55 | 68.768.7 |
| 实施例8Example 8 | 94.1794.17 | 68.468.4 |
| 实施例9Example 9 | 94.2194.21 | 68.268.2 |
| 实施例10Example 10 | 8.328.32 | 6.16.1 |
| 实施例11Example 11 | 8.528.52 | 6.66.6 |
| 实施例12Example 12 | 8.438.43 | 6.76.7 |
| 对比例1Comparative example 1 | 92.7792.77 | 68.868.8 |
由表2可知，对比糠醛转化率，实施例1-6中的糠醛转化率均接近100％，说明催化剂的催化活性高，并且高于实施例7-9以及对比例1中的催化剂活性；说明双金属催化剂与盐酸苯肼、钒酸钠共同使用时，催化活性得到明显提高，即使是在2-4MPa的条件下，仍能够发挥较高催化活性；而仅使用双金属催化剂(对比例1)时，即使是在8MPa的条件下，催化剂的催化活性依旧低于含盐酸苯肼、钒酸钠的催化剂；并且，双金属催化剂仅与盐酸苯肼或钒酸钠共同使用时，并不能明显增加活性；实施例10-12中糠醛转化率极低，说明反应无法正常进行，可以判断不添加盐酸苯肼和钒酸钠时，在压力交底情况下不能正常发生反应。对比2-甲基四氢呋喃选择性，实施例1-6中制得的2-甲基四氢呋喃的选择性较实施例1-9以及对比例1中制得的2-甲基四氢呋喃的选择性高，说明实施例1-6中制备2-甲基四氢呋喃的过程中产生的副反应和副产物较少；说明制备过程中，盐酸苯肼和钒酸钠的加入还能够减少副产物的生产，从而增加2-甲基四氢呋喃的选择性；实施例10-12中四氢呋喃选择性极低，说明反应无法正常进行，可以判断不添加盐酸苯肼和钒酸钠时，在压力交底情况下不能正常发生反应。As can be seen from Table 2, comparing the furfural conversion rates, the furfural conversion rates in Examples 1-6 are all close to 100%, indicating that the catalytic activity of the catalyst is high and higher than the catalyst activity in Examples 7-9 and Comparative Example 1; Explanation When the bimetallic catalyst is used together with phenylhydrazine hydrochloride and sodium vanadate, the catalytic activity is significantly improved, and it can still exert high catalytic activity even under the conditions of 2-4MPa; while only the bimetallic catalyst is used (Comparative Example 1) Even under the condition of 8MPa, the catalytic activity of the catalyst is still lower than that of the catalyst containing phenylhydrazine hydrochloride and sodium vanadate; and the bimetallic catalyst cannot be significantly increased when used only with phenylhydrazine hydrochloride or sodium vanadate. Activity; The furfural conversion rate in Examples 10-12 is extremely low, indicating that the reaction cannot proceed normally. It can be judged that the reaction cannot occur normally under the condition of pressure drop without adding phenylhydrazine hydrochloride and sodium vanadate. Comparing the selectivity of 2-methyltetrahydrofuran, the selectivity of 2-methyltetrahydrofuran prepared in Examples 1-6 is higher than that of 2-methyltetrahydrofuran prepared in Examples 1-9 and Comparative Example 1, It shows that fewer side reactions and by-products are produced in the process of preparing 2-methyltetrahydrofuran in Examples 1-6; it shows that during the preparation process, the addition of phenylhydrazine hydrochloride and sodium vanadate can also reduce the production of by-products, thereby increasing The selectivity of 2-methyltetrahydrofuran; the selectivity of tetrahydrofuran in Examples 10-12 is extremely low, indicating that the reaction cannot proceed normally. It can be judged that when phenylhydrazine hydrochloride and sodium vanadate are not added, the reaction cannot occur normally under pressure drop conditions.
本发明的操作步骤中的常规操作为本领域技术人员所熟知，在此不进行赘述。The conventional operations in the operating steps of the present invention are well known to those skilled in the art and will not be described in detail here.
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。The above-described embodiments describe the technical solutions of the present invention in detail. It should be understood that the above-mentioned are only specific embodiments of the present invention and are not intended to limit the present invention. Any work done within the scope of the principles of the present invention Any modifications, additions or similar substitutions shall be included in the protection scope of the present invention.
Claims (8)
- 一种制备2-甲基四氢呋喃的催化剂，包括Cu-Ni催化剂、盐酸苯肼、钒酸钠；其中，Cu-Ni催化剂的制备步骤包括：将硝酸铜、硝酸镍和硝酸钙加入酸性硅溶胶中，混匀后边搅拌边加入碳酸钠溶液；搅拌至无沉淀增加时静置陈化；陈化后洗涤、烘干研磨成粉即得Cu-Ni催化剂。A catalyst for preparing 2-methyltetrahydrofuran, including a Cu-Ni catalyst, phenylhydrazine hydrochloride, and sodium vanadate; wherein, the preparation steps of the Cu-Ni catalyst include: adding copper nitrate, nickel nitrate, and calcium nitrate into acidic silica sol , mix evenly and then add sodium carbonate solution while stirring; stir until no precipitation increases and let it stand for aging; after aging, wash, dry and grind into powder to obtain the Cu-Ni catalyst.
- 一种利用废弃生物质制备2-甲基四氢呋喃的方法，其特征在于，包括如下步骤：A method for preparing 2-methyltetrahydrofuran from waste biomass, which is characterized in that it includes the following steps:(1)利用生物质制备糠醛；(1) Utilize biomass to prepare furfural;(2)2-甲基四氢呋喃的制备；(2) Preparation of 2-methyltetrahydrofuran;其中，2-甲基四氢呋喃的制备包括使用权利要求1所述的催化剂对糠醛进行催化加氢制得2-甲基四氢呋喃。Wherein, the preparation of 2-methyltetrahydrofuran includes using the catalyst of claim 1 to catalytically hydrogenate furfural to obtain 2-methyltetrahydrofuran.
- 如权利要求2所述的制备方法，其特征在于，所述生物质包括含半纤维素的生物质。The preparation method of claim 2, wherein the biomass includes hemicellulose-containing biomass.
- 如权利要求2所述的制备方法，其特征在于，所述利用生物质制备糠醛的步骤包括：The preparation method according to claim 2, wherein the step of preparing furfural from biomass includes:将粉碎后的生物质加入酸液升温进行反应，收集馏出物后再次蒸馏即得糠醛。The crushed biomass is added to the acid solution to heat up the reaction, and the distillate is collected and distilled again to obtain furfural.
- 如权利要求4所述的制备方法，其特征在于，所述酸液包括硫酸溶液和路易斯酸溶液。The preparation method according to claim 4, wherein the acid solution includes a sulfuric acid solution and a Lewis acid solution.
- 如权利要求5所述的制备方法，其特征在于，所述路易斯酸溶液选自氯化铝溶液或氯化铁溶液。The preparation method according to claim 5, characterized in that the Lewis acid solution is selected from aluminum chloride solution or ferric chloride solution.
- 如权利要求2所述的制备方法，其特征在于，所述2-甲基四氢呋喃的制备的步骤包括The preparation method according to claim 2, wherein the step of preparing 2-methyltetrahydrofuran includes将糠醛和催化剂升温进行催化加氢反应即得2-甲基四氢呋喃。Raise the temperature of furfural and catalyst to perform catalytic hydrogenation reaction to obtain 2-methyltetrahydrofuran.
- 权利要求1所述催化剂在制备2-甲基四氢呋喃中的用途。The use of the catalyst according to claim 1 in the preparation of 2-methyltetrahydrofuran.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030018205A1 (en) * | 2000-10-26 | 2003-01-23 | Irshad Ahmed | Processes for the preparatiion of 2-methylfuran and 2-methyltetrahydrofuran |
| US20100048922A1 (en) * | 2007-07-02 | 2010-02-25 | Basf Se | Process for one-stage preparation of 2-methyltetrahydrofuran from furfural over two catalysts in a structured bed |
| CN102558106A (en) * | 2011-12-15 | 2012-07-11 | 北京金骄生物质化工有限公司 | Method for preparing 2-methyltetrahydrofuran from waste biomass |
| CN102875500A (en) * | 2012-10-25 | 2013-01-16 | 凯莱英医药集团（天津）股份有限公司 | Continuous production method of 2-MeTHF (2-methyltetrahydrofuran) |
| CN108014798A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Hydrogenation for 2- methyltetrahydrofurans catalyst and its application method |
| CN113354602A (en) * | 2021-06-11 | 2021-09-07 | 江苏清泉化学股份有限公司 | Method for preparing 2-methyltetrahydrofuran by furfural hydrogenation in one step |
| CN114644605A (en) * | 2022-04-08 | 2022-06-21 | 安徽泽升科技有限公司 | Method for preparing 2-methyltetrahydrofuran by using waste biomass |
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| CN109943863B (en) * | 2019-04-11 | 2020-01-14 | 浙江工业大学 | Method for preparing 2, 5-dihydroxymethyl tetrahydrofuran by electrocatalysis of biomass compounds with vanadium-based catalyst |
| CN110078687B (en) * | 2019-06-05 | 2020-09-08 | 南京林业大学 | Preparation method of 2-methyltetrahydrofuran |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030018205A1 (en) * | 2000-10-26 | 2003-01-23 | Irshad Ahmed | Processes for the preparatiion of 2-methylfuran and 2-methyltetrahydrofuran |
| US20100048922A1 (en) * | 2007-07-02 | 2010-02-25 | Basf Se | Process for one-stage preparation of 2-methyltetrahydrofuran from furfural over two catalysts in a structured bed |
| CN102558106A (en) * | 2011-12-15 | 2012-07-11 | 北京金骄生物质化工有限公司 | Method for preparing 2-methyltetrahydrofuran from waste biomass |
| CN102875500A (en) * | 2012-10-25 | 2013-01-16 | 凯莱英医药集团（天津）股份有限公司 | Continuous production method of 2-MeTHF (2-methyltetrahydrofuran) |
| CN108014798A (en) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | Hydrogenation for 2- methyltetrahydrofurans catalyst and its application method |
| CN113354602A (en) * | 2021-06-11 | 2021-09-07 | 江苏清泉化学股份有限公司 | Method for preparing 2-methyltetrahydrofuran by furfural hydrogenation in one step |
| CN114644605A (en) * | 2022-04-08 | 2022-06-21 | 安徽泽升科技有限公司 | Method for preparing 2-methyltetrahydrofuran by using waste biomass |
Non-Patent Citations (1)
| Title |
|---|
| LI, SUIQIN: "Performance Study of Vanadium Nitride-Based Catalysts for the Paired Electrosynthesis of 5-Hydroxymethylfurfural", ENGINEERING SCIENCE & TECHNOLOGY I, CHINA MASTER’S THESES FULL-TEXT DATABASE (ELECTRONIC JOURNALS), no. 02, 15 February 2021 (2021-02-15), ISSN: 1674-0246 * |
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| CN114644605B (en) | 2022-10-14 |
| ZA202212205B (en) | 2023-04-26 |
| CN114644605A (en) | 2022-06-21 |
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