CN112645908B - 一种制备马来酸酐的方法 - Google Patents
一种制备马来酸酐的方法 Download PDFInfo
- Publication number
- CN112645908B CN112645908B CN201910962494.4A CN201910962494A CN112645908B CN 112645908 B CN112645908 B CN 112645908B CN 201910962494 A CN201910962494 A CN 201910962494A CN 112645908 B CN112645908 B CN 112645908B
- Authority
- CN
- China
- Prior art keywords
- furfural
- metal oxide
- maleic anhydride
- reaction
- hydroxymethylfurfural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 20
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 29
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 24
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 78
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 33
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 33
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 239000011941 photocatalyst Substances 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 27
- 239000002028 Biomass Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 4
- 150000002240 furans Chemical class 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 51
- 238000005286 illumination Methods 0.000 description 27
- 239000010949 copper Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 R-TiO)2 Chemical compound 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
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
- C07D307/34—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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/745—Iron
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明涉及一种用金属氧化物或负载金属氧化物光催化生物质基呋喃衍生物糠醛和5‑羟甲基糠醛氧化到马来酸酐的方法。该方法用糠醛或5‑羟甲基糠醛作为反应底物，以氧气为氧化剂，用金属氧化物或负载金属氧化物为催化剂，在400～650nm可见光的照射下，实现其选择氧化到马来酸酐。其反应过程如下：将底物溶解于溶剂中，加入催化剂，对光反应器内气体进行氧气置换、密封，在400～650nm可见光照射下进行反应，反应温度不超过40℃，反应时间不低于0.5h，生成马来酸酐。该合成方法对于马来酸酐温和条件下的制备可能有重要的应用。
Description
技术领域
本发明涉及一种制备马来酸酐的制备方法，具体涉及到一种用金属氧化物和/或负载金属氧化物光催化糠醛和/或5-羟甲基糠醛氧化制备马来酸酐的方法。
背景技术
马来酸酐及其酸(马来酸，富马酸)是重要的化工中间体，广泛应用于生产不饱和聚酯树脂、γ-丁内酯、琥珀酸、1,4-丁二醇、醇酸树脂等，也应用于农药和医药。目前主要用含钒、磷、钼等的催化剂高温气相氧化苯或丁烷制备马来酸酐(Ullmann’s Encyclopediaof Industrial Chemistry,6th Edition，US5726327，US5646304，US6002019)。
随着石化资源的日益消耗及环境问题的突出，开发更绿色和可持续的反应路径和反应原料受到越来越广泛的关注。而生物质是自然界天然的储量巨大的可再生碳资源，从生物质制备化学品是一条可以减少对石油化学品依赖的可行路径。糠醛和5-羟甲基糠醛是重要的生物质化学品，可以从葡萄糖、果糖和木糖制得，也可以从可再生的农林废弃物比如粮食作物残渣、木材废料等不可食用部分制得(Energy Environ.Sci.2016,9,1144-1189；Green Chem.2018,20,3657-3682)。从糠醛或5-羟甲基糠醛制备马来酸酐已经有报道，可以用钒基催化剂和杂多酸来实现这一过程(Green Chem.2011,13,554-557；ChemSusChem2012,5,1984-1990；ChemSusChem 2012,5,1984-1990；ChemSusChem 2018,11,612-618)，这些过程多为均相或气相催化过程，并且存在反应温度过高、需要添加酸或用酸做溶剂等条件苛刻的问题，近年来也有课题组用多相催化剂，用氧气或双氧水为氧源在比较温和的条件下实现了从糠醛或5-羟甲基糠醛到马来酸酐的过程(Green Chem.,2016,18,643–647；Green Chem.,2017,19,914–918；Green Chem.,2017,19,98–101)，但是这些反应过程的优选溶剂多为酸。
近年来，光催化在有机合成方面得到了越来越广泛的关注，多种金属氧化物或负载金属氧化物在有机物的光催化氧化方面有比较好的活性(Green Chem.2018,20,4790-4833)。把光催化应用于有机合成能够在温和的条件下高效的进行。
发明内容
本发明涉及一种用金属氧化物或负载金属氧化物光催化生物质基呋喃衍生物糠醛或5-羟甲基糠醛氧化到马来酸酐的方法。该方法用糠醛或5-羟甲基糠醛作为反应底物，以氧气为氧化剂，用金属氧化物或负载金属氧化物为催化剂，在400～650nm可见光的照射下，实现糠醛的选择氧化到马来酸酐。本发明实现了温和条件下将可再生的生物质基化合物糠醛或5-羟甲基糠醛高效转化到马来酸酐，对于光催化有机物氧化和马来酸酐的制备可能有重要作用。
本发明采用的技术方案为：
将底物溶解于溶剂中，加入催化剂，对光反应器内气体进行氧气置换、密封，在400～650nm可见光照射下进行反应，反应温度不超过40℃，反应时间不低于0.5h，生成马来酸酐。
所述负载金属氧化物的负载金属质量分数为0.01wt％～10.0wt％
反应所用的催化剂为金属氧化物或负载金属氧化物，其中：
(1)金属氧化物可以为Nb2O5，TiO2(包括R-TiO2，A-TiO2，P25)，Cu2O，CuO，V2O5，WO3，V2O5，ZrO2，α-Fe2O3中的一种或两种以上。
(2)负载金属氧化物可以为：Cu2O/Nb2O5，CuO/Nb2O5，FeO/Nb2O5，Fe2O3/Nb2O5，Co3O4/Nb2O5，Cu2O/R-TiO2，Cu2O/A-TiO2，Cu2O/P25，Cu2O/V2O5，Cu2O/WO3，Cu2O/V2O5，Cu2O/ZrO2，Cu2O/α-Fe2O3中的一种或两种以上。
所述生物质基呋喃衍生物为糠醛或5-羟甲基糠醛，结构式如下：
反应底物的浓度为0.1mmol/mL，催化剂的用量为10mg，溶剂体积为1mL。
所述溶剂为乙腈或三氟甲苯。
该反应体系在常压下进行，反应温度为20～40℃。
反应所用的可见光源波长为400～650nm，所述光源为单一波长、混合波长或连续波长，其光源功率可以为2～100W。
所述反应时间大于0.5h。
本发明与传统制备马来酸酐的方法想比较，具有以下优势：
1.原料易得，可再生；
2.反应条件温和，能耗低；
3.催化剂活性高，转化率最高可以达到100％，选择性最高大于90％。
具体实施方式
为了对本发明进行进一步详细说明，下面给出几个具体实施案例，但本发明不限于这些实施例。
实施例1
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为99％，马来酸酐收率为96％。
实施例2
将0.1mmol糠醛、10mg Cu2O/R-TiO2分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为96％，马来酸酐收率为85％。
实施例3
将0.1mmol糠醛、10mg Cu2O/P25分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为95％，马来酸酐收率为90％。
实施例4
将0.1mmol糠醛、10mg Cu2O/WO3分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为89％，马来酸酐收率为80％。
实施例5
将0.1mmol糠醛、10mg Cu2O分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为94％。
实施例6
将0.1mmol糠醛、10mg FeO/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为89％，马来酸酐收率为75％。
实施例7
将0.1mmol糠醛、10mg CuO/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为80％，马来酸酐收率为65％。
实施例8
将0.1mmol糠醛、10mg Co3O4/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为60％，马来酸酐收率为45％。
实施例9
将0.1mmol糠醛、10mg Cu2O/α-Fe3O4分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为70％，马来酸酐收率为55％。
实施例10
将0.1mmol5-羟甲基糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为98％，马来酸酐收率为90％。
实施例11
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL三氟甲苯中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为98％，马来酸酐收率为90％。
实施例12
将0.1mmol糠醛、10mg Cu2O/P25分散于1mL三氟甲苯中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为93％。
实施例13
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，6W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为98％，马来酸酐收率为92％。
实施例14
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，18W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为90％。
实施例15
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,365nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为99％，马来酸酐收率为89％。
实施例16
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应6h，反应结束后用HPLC定量，糠醛的转化率为85％，马来酸酐收率为79％。
实施例17
将0.1mmol糠醛、10mg Cu2O/Nb2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应24h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为96％。
实施例18
将0.1mmol糠醛、10mg Cu2O/V2O5分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为89％，马来酸酐收率为80％。
实施例19
将0.1mmol糠醛、10mgα-Fe3O4分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为75％，马来酸酐收率为60％。
实施例20
将0.1mmol糠醛、10mg Cu2O/P25分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,365nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为80％。
实施例21
将0.1mmol糠醛、10mg Cu2O/A-TiO2分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,365nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为85％。
实施例22
将0.1mmol 5-羟甲基糠醛、10mg Cu2O/P25分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为90％，马来酸酐收率为79％。
实施例23
将0.1mmol 5-羟甲基糠醛、10mg Cu2O/R-TiO2分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为89％，马来酸酐收率为75％。
实施例24
将0.1mmol 5-羟甲基糠醛、10mg Cu2O分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为95％，马来酸酐收率为86％。
实施例25
将0.1mmol 5-羟甲基糠醛、10mg CuO分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为60％，马来酸酐收率为45％。
实施例26
将0.1mmol 5-羟甲基糠醛、10mg Cu2O分散于1mL三氟甲苯中，加入磁子，用氧气充分置换后密封，室温下，9W,455nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为78％，马来酸酐收率为69％。
实施例27
将0.1mmol 5-羟甲基糠醛、10mg Cu2O分散于1mL乙腈中，加入磁子，用氧气充分置换后密封，室温下，9W,365nm光照下搅拌反应12h，反应结束后用HPLC定量，糠醛的转化率为100％，马来酸酐收率为79％。
Claims (8)
1.一种制备马来酸酐的方法，其特征在于：以金属氧化物或负载金属氧化物为光催化剂，以糠醛或5-羟甲基糠醛为反应底物，由光催化剂和反应底物组成光催化体系，加入溶剂，以氧气为氧化剂，在400~650 nm可见光的照射下，在温度不超过40 °C的条件下，实现糠醛或5-羟甲基糠醛高效转化到马来酸酐；反应用到的溶剂为乙腈或三氟甲苯，反应所用的催化剂为金属氧化物或负载金属氧化物，其中：
（1）金属氧化物为Cu2O，α-Fe2O3中的一种；（2）负载金属氧化物A/B为： CuO/ Nb2O5，FeO/Nb2O5， Cu2O/ R-TiO2，Cu2O/ A-TiO2，Cu2O/ P25，Cu2O/ V2O5，Cu2O/ WO3， Cu2O/α-Fe2O3中的一种；A/B中A为被负载金属氧化物；B为负载金属氧化物，其中负载金属质量分数为0.01wt%~10.0wt%；
负载金属氧化物催化剂用浸渍法制备：把负载金属氧化物分散于被负载金属前驱体溶液，搅拌12-20 h，60-100 °C下蒸干水，150-450 °C下在氩气和/或空气中处理1-4 h。
2.按照权利要求1所述的方法，其特征在于：
具体步骤为：将糠醛或5-羟甲基糠醛溶于溶剂中，加入金属氧化物和/或负载金属氧化物催化剂，随后将光反应器中气氛置换为氧气，在温度不超过40 °C的条件下，400~650 nm的可见光照射反应，生成氧化产物马来酸酐。
3.按照权利要求1所述的方法，其特征在于：反应底物的浓度为0.05-0.25 mmol/mL，催化剂的用量为5-10 mg，溶剂体积为1-2 mL。
4.按照权利要求1所述的方法，其特征在于：糠醛或5-羟甲基糠醛转化马来酸酐体系在常压下进行。
5.按照权利要求1所述的方法，其特征在于：糠醛或5-羟甲基糠醛转化马来酸酐体系的反应温度为20~40 °C。
6.按照权利要求1所述的方法，其特征在于：糠醛或5-羟甲基糠醛转化马来酸酐体系的反应温度为35 °C。
7.按照权利要求1所述的方法，其特征在于：反应所用的可见光源波长为455 nm，所述光源为单一波长、混合波长或连续波长，其光源功率为2~100 W。
8.按照权利要求1所述的方法，其特征在于：糠醛或5-羟甲基糠醛转化马来酸酐体系的反应时间大于0.5 h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910962494.4A CN112645908B (zh) | 2019-10-11 | 2019-10-11 | 一种制备马来酸酐的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910962494.4A CN112645908B (zh) | 2019-10-11 | 2019-10-11 | 一种制备马来酸酐的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112645908A CN112645908A (zh) | 2021-04-13 |
| CN112645908B true CN112645908B (zh) | 2022-05-06 |
Family
ID=75342855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910962494.4A Active CN112645908B (zh) | 2019-10-11 | 2019-10-11 | 一种制备马来酸酐的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112645908B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198469A (zh) * | 2021-05-07 | 2021-08-03 | 云南大学 | 一种铜钛异质结光催化剂及其制备方法和应用 |
| CN114395091A (zh) * | 2021-12-31 | 2022-04-26 | 南京瑞固聚合物有限公司 | 抗泥型聚羧酸减水剂及其合成工艺 |
| CN114751880B (zh) * | 2022-04-21 | 2024-01-30 | 重庆工商大学 | 一种马来酸酐的合成方法 |
| CN115403542A (zh) * | 2022-09-14 | 2022-11-29 | 广东工业大学 | 一种用呋喃单侧基单体合成马来酸酐的方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372685A (zh) * | 2010-08-20 | 2012-03-14 | 中国科学院大连化学物理研究所 | 一种催化氧化5-羟甲基糠醛制备马来酸酐的方法 |
| CN104119305A (zh) * | 2013-04-27 | 2014-10-29 | 中国科学院大连化学物理研究所 | 一种催化氧化5-羟甲基糠醛制备马来酸酐的方法 |
| CN106279080A (zh) * | 2016-08-03 | 2017-01-04 | 天津工业大学 | 一种5‑羟甲基糠醛光催化制备2,5‑呋喃二甲酸的方法 |
-
2019
- 2019-10-11 CN CN201910962494.4A patent/CN112645908B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372685A (zh) * | 2010-08-20 | 2012-03-14 | 中国科学院大连化学物理研究所 | 一种催化氧化5-羟甲基糠醛制备马来酸酐的方法 |
| CN104119305A (zh) * | 2013-04-27 | 2014-10-29 | 中国科学院大连化学物理研究所 | 一种催化氧化5-羟甲基糠醛制备马来酸酐的方法 |
| CN106279080A (zh) * | 2016-08-03 | 2017-01-04 | 天津工业大学 | 一种5‑羟甲基糠醛光催化制备2,5‑呋喃二甲酸的方法 |
Non-Patent Citations (1)
| Title |
|---|
| Selective Conversion of Furfural to Maleic Anhydride and Furan with VOx/Al2O3 Catalysts;Noelia Alonso-Fagfflndez et al.,;《ChemSusChem》;20120730;第5卷;第1984-1990页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112645908A (zh) | 2021-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112645908B (zh) | 一种制备马来酸酐的方法 | |
| Li et al. | Highly efficient formic acid-mediated oxidation of renewable furfural to maleic acid with H 2 O 2 | |
| CN110102350B (zh) | 用于氧化合成2,5-呋喃二甲酸的催化剂及其制备方法和应用 | |
| Li et al. | Highly selective catalytic conversion of furfural to γ-butyrolactone | |
| CN111377890B (zh) | 由5-羟甲基糠醛生产2，5-呋喃二甲酸的方法 | |
| Ning et al. | The efficient oxidation of biomass-derived 5-hydroxymethyl furfural to produce 2, 5-diformylfuran over supported cobalt catalysts | |
| CN113387911A (zh) | 光催化5-羟甲基糠醛脱氢制备2,5-呋喃二甲醛的方法 | |
| CN111072601A (zh) | 一种5-羟甲基糠醛制备2，5-呋喃二甲醛的方法 | |
| CN113402485A (zh) | 复合熔盐水合物中纤维素转化制备5-羟甲基糠醛的方法 | |
| CN111087371A (zh) | 一种2,5-呋喃二甲醛的光催化合成方法 | |
| Sun et al. | Recent advances in the photocatalytic oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran | |
| CN112961123B (zh) | 一种催化糠醛和正丙醇氧化缩合制备3-(2-呋喃基)-2-甲基-2-丙烯醛的方法 | |
| CN105254599A (zh) | 一种以糠醛为原料制备γ-丁内酯的方法 | |
| Adebajo et al. | Recent advances in catalytic/biocatalytic conversion of greenhouse methane and carbon dioxide to methanol and other oxygenates | |
| CN113845500B (zh) | 一种催化氧化5-羟甲基糠醛制备5-甲酰基-2-呋喃甲酸的方法 | |
| Rodríguez-Padrón et al. | Biomass valorization: Catalytic approaches using benign-by-design nanomaterials | |
| CN110372508B (zh) | 一种丙酮酸乙酯的绿色制备方法 | |
| Jia et al. | Efficient aerobic oxidation of 5‐hydroxymethyl‐2‐furfural into 2, 5‐diformylfuran by Cu2V2O7‐Al2O3 spherical beads | |
| Li | Current approaches of the functional and synergetic catalytic systems for converting renewable carbohydrates into 2, 5-diformylfuran | |
| CN108970604B (zh) | 一种钼钒铌基复合氧化物及其合成方法与应用 | |
| CN114478445B (zh) | 一种生物质基呋喃化合物光催化氧化重整的方法 | |
| Zhang et al. | Production of 2, 5-Diformylfuran from biomass-derived glucose via one-pot two-step process | |
| Zhang et al. | Aerobic selective oxidation of biomass-derived 5-hydroxymethylfurfural to 2, 5-diformylfuran with active manganese dioxide catalyst | |
| CN109107605B (zh) | 一种具有高效光催化氧化性的十聚钨酸铵盐及其应用 | |
| CN111393397B (zh) | 一种2,5-呋喃二甲酸的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |