CN109485621A - A method of producing gamma valerolactone - Google Patents
A method of producing gamma valerolactone Download PDFInfo
- Publication number
- CN109485621A CN109485621A CN201811469298.5A CN201811469298A CN109485621A CN 109485621 A CN109485621 A CN 109485621A CN 201811469298 A CN201811469298 A CN 201811469298A CN 109485621 A CN109485621 A CN 109485621A
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- CN
- China
- Prior art keywords
- copper
- catalyst
- iron
- levulic acid
- reaction
- 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.)
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000003054 catalyst Substances 0.000 claims abstract description 119
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000010949 copper Substances 0.000 claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 54
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- 239000010457 zeolite Substances 0.000 claims abstract description 37
- 150000002148 esters Chemical class 0.000 claims abstract description 35
- -1 zeolite molecular sieve class Chemical class 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 36
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 229940058352 levulinate Drugs 0.000 claims description 13
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- WZUQMOGWPIRDHH-UHFFFAOYSA-N butyl 2-methyl-3-oxobutanoate Chemical compound CCCCOC(=O)C(C)C(C)=O WZUQMOGWPIRDHH-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 3
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 2
- VVHXYVGAMODMHK-UHFFFAOYSA-N copper nitric acid hydrate Chemical group [Cu].[N+](=O)(O)[O-].O VVHXYVGAMODMHK-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- HUTBITLDXCEAPZ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;iron Chemical compound [Fe].OC(=O)CC(O)(C(O)=O)CC(O)=O HUTBITLDXCEAPZ-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 125000004492 methyl ester group Chemical group 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910017827 Cu—Fe Inorganic materials 0.000 description 120
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 45
- 239000007789 gas Substances 0.000 description 21
- 238000004587 chromatography analysis Methods 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 12
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- CIMUUFUVEIMCEI-UHFFFAOYSA-J [Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O CIMUUFUVEIMCEI-UHFFFAOYSA-J 0.000 description 1
- GSGBONVNIUEIBM-UHFFFAOYSA-N [Zr+4].[O-2].[Zn+2].[Cu+2].[O-2].[O-2].[O-2] Chemical compound [Zr+4].[O-2].[Zn+2].[Cu+2].[O-2].[O-2].[O-2] GSGBONVNIUEIBM-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- OSFGNZOUZOPXBL-UHFFFAOYSA-N nitric acid;trihydrate Chemical compound O.O.O.O[N+]([O-])=O OSFGNZOUZOPXBL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention discloses a kind of catalyst for being produced the method for gamma valerolactone by levulic acid and its esters low temperature hydrogenation and its being used.The catalyst of levulic acid according to the present invention and its esters low temperature hydrogenation production gamma valerolactone, is a kind of copper and iron bimetallic catalyst of low carrying capacity being supported on zeolite molecular sieve class carrier.The method of production gamma valerolactone provided by the invention is using alkane as reaction dissolvent, and in the presence of above-mentioned catalyst, levulic acid and its esters react synthesis gamma valerolactone with hydrogen.In the present invention, up to 100%, the yield of gamma valerolactone is more than 99% for levulic acid and its conversion ratio of esters.The method of the present invention simple process, reaction condition is mild, and hydrogenolysis temperature is lower, and reaction time is short, and yield is higher, and the metal ladings of catalyst are lower, heat-resisting, simple separation, that is, reusable, and during the preparation process, copper forms effective active phase CuFeO with iron2, it is able to ascend the reactivity of carbonyl.
Description
Technical field
The present invention relates to a kind of synthetic methods by levulic acid and its esters low temperature hydrogenation preparation gamma valerolactone.Specifically
Ground, the present invention relates to a kind of synthetic methods using carried copper iron catalyst preparation gamma valerolactone.
Background technique
The biomass for being hopeful to replace increasingly exhausted fossil energy is that a kind of green for being prevalent in nature can be again
Production-goods source can be downgraded to the plateform molecules of the biomass derived of a variety of high values by chemical conversion process.As it
In a member, gamma valerolactone (GVL, molecular formula C5H8O2) with its strong respond, hypotoxicity the advantages that, be widely used in food
The fields such as essence, fuel additive, industrial solvent and medicine and the intermediate of chemicals synthesis.
In general, gamma valerolactone can be added hydrogen by the levulic acid and its esters of biomass derived to obtain in hydrogen atmosphere
, catalyst includes homogeneous catalysis system and heterogeneous catalysis system, and the homogeneous catalyst with single-activity site is in low temperature
Excellent Hydrogenation is typically exhibited in terms of hydrogenolysis, but is gradually replaced by heterogeneous system since recycling separation is difficult.
It is compared with numerous heterogeneous noble metals and cheap metal catalyst (such as Pt, Pd, Rh, Ni, Cu etc.), ruthenium and iridium catalysis
The effect that levulic acid and its esters add hydrogen to prepare GVL is best, reaction condition also relatively it is mild (Green Chem [J] .2012,
14,688).But the low abundance of noble metal and high cost run counter to the principle of economy and sustainable development, are urged using transition metal
Agent has caused more concerns as substitute.
Copper-based catalysts have greater activity to hydrogen hydrogenation carbon-oxygen bond, but usually reaction temperature needs to reach 200 DEG C
When above, the outstanding Hydrogenation of copper-based catalysts competence exertion.And reduce load capacity of the input of energy consumption usually to increase copper
As cost, the excessively high particle that will lead to of the metal ladings of catalyst is easy aggregation and inactivates.The Cu coexisted0With Cu1+Between association
It is to guarantee the key factor of copper base catalyst performance with effect.And Cu1+The unstability in site can also aggravate catalyst inactivation.Cause
This exploitation is used for low temperature hydrogenolysis, and has low metal carrying capacity and stable Cu1+Copper-based catalysts be highly important.
Patent CN 101733123A develops acid-resistant catalyst for levulic acid hydrogenation synthesis gamma valerolactone, and
Point out that copper has preferable Hydrogenation as main active component.But catalyst needs the high temperature by 700-1500 DEG C or more
To obtain acid-fast ability, preparation process is cumbersome and risky for processing.Patent CN 107694573A is disclosed using copper zinc zirconium oxide
Catalyst ethyl levulinate adds the method for hydrogen preparation gamma valerolactone, and proposes that the copper of one-component can be by levulinic
Acid corrosion and inactivate.But the severe reaction conditions of this method, temperature are up to 200-260 DEG C.CN 104829559A develops copper
The method that chromium oxide catalyst is catalyzed methyl ester levulinate hydrogenation synthesis gamma valerolactone in situ in methyl alcohol, this method are being urged
Chromium ion can be generated by being difficult to avoid that in the preparation and treatment process of agent, and to environment, there are hidden danger with human health.CN
102617519A develops a kind of method that skeletal copper catalyst is used for levulic acid hydrogenation synthesis gamma valerolactone, although it is mentioned
The activity and selectivity of skeletal copper catalyst, but the party can be improved to use group VIII transition metal (including Fe) modification
The copper atom utilization rate of method is not high, and in fact the document using Fe to be added to three metals formed in albronze
Or catalyst more than three kinds of metals.
Compared with the prior art, the advantages of the present invention are as follows urge by the carried copper iron double metal of carrier of zeolite molecular sieve
Agent, the catalyst preparation is simple, environmentally friendly, low in cost, and atom utilization is high, excellent catalytic effect, to levulic acid
And its esters selective hydrogenation synthesis gamma valerolactone has general applicability.Reaction system mild condition of the present invention, energy consumption compared with
Low, production cost is low, has a good application prospect.
Summary of the invention
Synthesizing for gamma valerolactone is prepared by levulic acid and its esters low temperature hydrogenation the object of the present invention is to provide a kind of
Method and its catalyst used.
For this purpose, the present invention provides following aspects:
<1>a kind of method by levulic acid and its esters low temperature hydrogenation production gamma valerolactone of, which comprises
Or mixtures thereof alkane of liquid is in as reaction dissolvent, in the presence of carried copper iron catalyst, by acetyl using room temperature
Propionic acid and its esters are reacted with hydrogen generates gamma valerolactone.
<2>method according to<1>, wherein the levulic acid and its esters includes levulic acid, levulic acid
Or mixtures thereof ester.
<3>is according to mentioned-above method, wherein the levulinate is selected from methyl ester levulinate, levulic acid
Ethyl ester, Butyl acetylpropanoate, the levulic acid tert-butyl ester, levulic acid isopropyl ester, or mixtures thereof.
<4>is according to mentioned-above method, wherein the temperature of the reaction is 20-250 DEG C.
<5>is according to mentioned-above method, wherein copper and iron bimetallic is catalyst in the carried copper iron catalyst
Active constituent, wherein the content of copper is the 0.8-25.8wt% of entire catalyst, and the molar ratio of copper and iron is 0.3-10.
<6>is according to mentioned-above method, wherein it is x that the carried copper iron catalyst, which is carried on general structure,
(M2O)·x’(M’O)·y(Al2O3)·(SiO2)·z(H2O on zeolite molecular sieve carrier), wherein M is the first major element
Monovalent cation, M ' be the second major element bivalent cation, x, x ', y, z be any rational.
<7>is according to mentioned-above method, wherein the carried copper iron catalyst is prepared using co-impregnation, institute
Stating co-impregnation includes: that the soluble copper salt as copper source is dissolved in water or organic solvent with the soluble ferric iron salt as source of iron
Afterwards, it is added and is impregnated for the carrier of supported copper iron catalyst, then calcined impregnation product, such as calcine in air,
It is restored in hydrogen again.
<8>is according to mentioned-above method, wherein copper source be selected from nitric acid copper hydrate, copper sulfate hydrate,
At least one of chlorination copper hydrate, basic copper carbonate and copper acetate soluble copper salt, and the source of iron is selected from lemon
Sour iron, ferric perchlorate, ferrous sulfate hydrate, ferrous sulfate hydrate, oxamide molysite hydrate, ferric oxalate hydrate, nitric acid
At least one of iron hydrate, Iron trichloride hexahydrate and frerrous chloride soluble ferric iron salt.
<9>is according to mentioned-above method, wherein the temperature of the calcining is 100-800 DEG C, the temperature of the reduction is
100-800℃。
<10>reacts initial hydrogen pressure wherein the temperature of the reaction is 20-250 DEG C according to mentioned-above method
For 0.01-8MPa, reaction time 20min-24h.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
Method provided by the invention by levulic acid and its esters low temperature hydrogenation production gamma valerolactone, use are heterogeneous
Catalyst system, the carried copper iron double metal catalyst, using zeolite molecular sieve as carrier, have lower metal ladings and
Stable Cu1+Active site is able to ascend the reactivity of carbonyl.It is provided by the invention by levulic acid and its esters low temperature hydrogenation
Produce gamma valerolactone method, realize low metal carrying capacity catalyst low temperature hydrogenation reaction, have simple process, high activity,
The features such as highly selective, reaction condition is mild, and reaction time is short, is resistant to functional group can be incited somebody to action by simple separation means
Catalyst recycling.It was proved that method of the invention can achieve levulic acid and its esters 100% convert, gal
The yield of horse valerolactone is up to 99.5%.
Specific embodiment
Specifically, the method for the present invention by levulic acid and its esters low temperature hydrogenation production gamma valerolactone,
Be using alkane as reaction dissolvent, in the presence of the copper and iron bimetallic catalyst being supported on zeolite molecular sieve carrier, acetyl
Propionic acid and its esters are reacted with hydrogen generates gamma valerolactone.
Term " carried copper iron catalyst " as used in the present invention, which refers to, loads to carrier for copper and iron double metal
Upper catalyst obtained, is totally different from the skeletal copper catalyst that CN 102617519A is referred to.Skeletal copper catalyst be by
The alloy of cupric is after alkali process, the copper-based catalysts of the porous matrix structure of formation, and active component content is high and easy
It is lost, preparation method is complicated and has pollution, and main active constituent is copper-bearing alloy.And the support type copper and iron catalysis of the application
Agent increases the dispersion degree and utilization rate of active component, enhances the stability of active component using zeolite molecular sieve as carrier,
Main active constituent is copper simple substance and delafossite phase.
Term " levulic acid and its esters " as used in the present invention refer to levulic acid, levulinate or its
The mixture for the type and ratio of anticipating.But consider from production cost, it is preferable to use levulic acid, methyl ester levulinate, levulinic
Acetoacetic ester, levulic acid propyl ester etc. are used as reaction raw materials, and if using mixture as in the case where raw material, levulic acid
Molar ratio between levulinate is preferably 0.01-1, more preferably 0.01-0.1.
Term " levulinate " as used in the present invention refers to the ester that levulic acid and Condensation of Alcohols are formed, including
But be not limited to methyl ester levulinate, ethyl levulinate, Butyl acetylpropanoate, the levulic acid tert-butyl ester, levulic acid isopropyl ester,
Or mixtures thereof, etc..Wherein the alcohols includes methanol, ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol, butanediol, diethyl two
Alcohol, etc..
Being suitble to the alkane used in reaction system of the present invention as reaction dissolvent is the branch that room temperature is in liquid
The mixture of chain or linear paraffin or its any kind and ratio.Its specific example include: ethane, propane, butane, normal butane,
Hexane, n-hexane, heptane, normal octane, etc..Term " room temperature " has the common meaning in chemical field, refers to about 25 DEG C of left sides
Right temperature.
In the present invention, it can be as the alkane of solvent and the ratio of levulic acid and its esters as reaction raw materials
Arbitrary proportion.But from productivity effect consider, it is preferable to use mass ratio be 25-200, more preferably 50-100.
In being suitable for the carried copper iron catalyst used in the present invention, copper and iron bimetallic is the activity of catalyst
Ingredient, wherein the content of copper is the 0.8-25.8wt%, preferably 1.2-11.56wt%, more preferably 2.5- of entire catalyst
8.0wt%, and the molar ratio of copper and iron is 0.3-10, preferably 0.5-2, more preferable 0.8-1.5.
In an embodiment of preparation method of the present invention, specific steps include: by levulic acid and its esters, copper and iron
Molecular sieve catalyst and alkane solvent mixing are added in closed container, and after excluding air, it is suitable to be filled with into said mixture
Hydrogen carries out hydrogenation reaction after temperature is arranged.After reaction, by catalyst with react after mixed solution separate and recover, be used in combination
Organic solvent is rinsed, that is, catalyst can be recycled and be re-used for preparation gamma valerolactone；It is molten after being reacted in the present invention
Liquid determines the yield of gamma valerolactone by gas chromatogram fixative；The detection method is preferably internal standard method, and internal standard compound is excellent
It is selected as methyl phenyl ethers anisole.
In a preferred embodiment in accordance with this invention, using n-hexane as reaction dissolvent, with levulic acid and its esters
As reaction raw materials, solvent and raw material can be arbitrary proportion.
In a preferred embodiment in accordance with this invention, levulic acid and its esters refer to levulic acid and levulic acid
Ester, the levulinate refer to the ester that levulic acid and Condensation of Alcohols are formed, including but not limited to methyl ester levulinate, second
Acyl ethyl propionate, Butyl acetylpropanoate, the levulic acid tert-butyl ester, the mixture of levulic acid isopropyl ester etc. or its arbitrary proportion.
In embodiments of the invention, the hydrogenation reaction temperature be 20-250 DEG C, preferably 100-180 DEG C, most
Preferably 140-150 DEG C.Initial Hydrogen Vapor Pressure is 0.01-8MPa.Preferably 1-4MPa, most preferably 2.5-3MPa.It is described
Reaction time be 20min-24h, preferably 2-5 hours, most preferably 3-4 hours.The input amount of catalyst is 10-200mg,
Preferably 50-60mg.
In the invention it has unexpectedly been found that still being able to obtain such as 20-100 DEG C at a temperature of extremely low hydrogenation reaction
100% conversion ratio.
In preferred embodiments, the levulic acid and its esters and the quality of copper and iron bimetallic catalyst compare model
It encloses and does not limit, but preferably 1: (0.42-0.97).One preparating example of copper and iron bimetallic catalyst of the invention is as follows.
The specific preparation step of the copper and iron bimetallic catalyst includes: to weigh the copper source and source of iron of suitable proportion, dissolution
Into proper amount of acetone, be added dropwise a small amount of (about 0.1-1ml) can dissolve or promote to dissolve the acid (such as nitric acid) of source of iron and copper source with
After forming uniform solution, the zeolite molecular sieve for being added at one time suitable proportion is stirred and impregnates, and obtains impregnation product.?
In such preparation process, copper forms effective active phase CuFeO with iron2, thus participating in being able to ascend carbonyl when catalysis is reacted
The reactivity of base.
The present invention does not have particular/special requirement to the ratio of copper source, source of iron and carrier, and the ratio makes copper and iron in catalyst
Content meet the content of copper and iron active component described in above scheme.The present invention is to the temperature of dipping without special limit
System, but consider from production cost, preferably 28-32 DEG C；The present invention is not particularly limited the additional amount of acetone and nitric acid.At this
In invention, the dip time is preferably 6-24h, most preferably 12-14h.The specific example of copper source includes copper nitrate
The soluble copper salts, preferably nitrate trihydrate such as hydrate, copper sulfate hydrate, chlorination copper hydrate, basic copper carbonate, copper acetate
Copper.And the specific example of the source of iron includes ironic citrate, ferric perchlorate, ferrous sulfate hydrate, ferrous sulfate hydrate, grass
The soluble ferric iron salts such as acid amide molysite hydrate, ferric oxalate hydrate, ferric nitrate hydrate, Iron trichloride hexahydrate, frerrous chloride,
Preferably nine water ferric nitrates.
Impregnation product is calcined, the presoma of copper and iron bimetallic catalyst is obtained.The calcining is usually in air
It carries out.Then with the copper and iron bimetallic catalyst for arriving zeolite molecular sieve load after hydrogen reducing catalyst precarsor.The present invention
To calcining and the initial temperature, heating rate, air-flow velocity and the equipment that restore without specifically limited.
In preferred embodiments, in the carried copper iron catalyst, copper and iron bimetallic be catalyst activity at
Point, wherein the content of copper is the 0.8-25.8wt%, preferably 1.2-11.56wt%, more preferably 2.5- of entire catalyst
8.0wt%, and the molar ratio of copper and iron is 0.3-10, preferably 0.5-2, more preferable 0.8-1.5.
In preferred embodiments, the calcination temperature of the bimetallic catalyst is 100-800 DEG C, preferably 350-
550℃；The temperature of the reduction is 100-800 DEG C, preferably 250-400 DEG C.
In preferred embodiments, the catalyst is carried on the zeolite molecular sieve carrier for having the following structure general formula
It is upper: x (M2O)·x’(M’O)·y(Al2O3)·(SiO2)·z(H2O), wherein M is the first major element monovalent cation, M '
For the second major element bivalent cation, x, x ', y, z be any rational.Zeolite molecular sieve with above structure general formula carries
Body can be commercially available, be also possible to homemade.For example, it is preferable to be SBA-15 (Catalyst Factory, Nankai Univ), MCM-41
(Catalyst Factory, Nankai Univ), MCM-22 (Catalyst Factory, Nankai Univ), SAPO-34 (Catalyst Factory, Nankai Univ), ZSM-35
(Catalyst Factory, Nankai Univ), HY (Catalyst Factory, Nankai Univ), USY (Catalyst Factory, Nankai Univ), (Nankai University urges MOR
Agent factory), ZSM-5 (Catalyst Factory, Nankai Univ), H β (Catalyst Factory, Nankai Univ) or any combination thereof.
Embodiment
Implementation process of the present invention is described further combined with specific embodiments below.Agents useful for same is commercially
It obtains.As described below is only the preferable embodiment of the present invention, but scope of protection of the present invention is not limited thereto.
Carried copper iron double metal catalyst as used in the following examples, can be prepared as follows:
0.1904g nitrate trihydrate copper and nine water ferric nitrate mixed dissolution of 0.404g are weighed in equipped with 30ml acetone and stirring magnetic
In the drying flask of son, after 0.5ml nitric acid is added dropwise to form clear solution, it is added at one time 1.5g SBA-15, impregnates 14
After hour, it is evaporated acetone, 6 hours are calcined in the air atmosphere at 350 DEG C, before obtaining copper and iron SBA-15 catalyst
Drive body.It is again 20ml/min in hydrogen flow rate by presoma, nitrogen flow rate is 300 DEG C of reductase 12s in the tube furnace of 30ml/min
Hour, heating rate is 10 DEG C/min, and it is that (copper is 3.5wt% with iron molar ratio that copper carrying capacity can be obtained, which is 2.8wt% iron carrying capacity,
1: 1.5) SBA-15 catalyst.
The preparation method of other carrier loaded catalyst is similar with above-mentioned steps.
It is as used in the present invention be equipped with flame ionization detector and RTX-65 gas chromatographic column (30m ×
0.32mm × 0.25 μm) GC-2010plus (Shimadzu) gas chromatograph.
Embodiment 1. is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 140 DEG C, 3MPa hydrogen
Acyl ethyl propionate adds hydrogen to prepare gamma valerolactone
It weighs 0.5mmol ethyl levulinate respectively and 50mg is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve
It is placed in the dry autoclave with stirring magneton, adds 10ml n-hexane.Hydrogen is repeatedly filled with again after sealing
It deflates, to exclude the air in kettle.After being then charged with hydrogen to 3MPa, 140 DEG C are heated to, reacts 3 hours.Reaction kettle is cold
But to after room temperature, the compounding substances after reaction are collected with ethyl acetate, and 0.5mmol methyl phenyl ethers anisole internal standard compound is added, then used
Gas chromatography mass spectrometry and gas-chromatography carry out qualitative and quantitative.The results are shown in Table 1 for gas chromatographic analysis:
Mixture after above-mentioned reaction is centrifuged, the copper and iron being supported on zeolite molecular sieve isolated is double
Metallic catalyst is recycled, and is then flushed three times the catalyst that recycling obtains with ethyl acetate and n-hexane respectively, is obtained
Quadric catalysis agent.
1. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 140 DEG C, 3MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 99.5 |
| Cu-Fe/MCM-41 | 100 | 95.6 |
| Cu-Fe/HY | 100 | 97.7 |
| Cu-Fe/MCM-22 | 100 | 96.5 |
| Cu-Fe/SAPO-34 | 100 | 98.3 |
| Cu-Fe/ZSM-5 | 100 | 95.8 |
| Cu-Fe/ZSM-35 | 100 | 94.9 |
| Cu-Fe/USY | 100 | 99.0 |
| Cu-Fe/MOR | 100 | 98.4 |
| Cu-Fe/Hβ | 100 | 96.2 |
Embodiment 2
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is that temperature will be reacted
140 DEG C of degree is adjusted to 250 DEG C.The results are shown in Table 2 for gas chromatographic analysis:
2. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 250 DEG C, 3MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 99.0 |
| Cu-Fe/MCM-41 | 100 | 99.2 |
| Cu-Fe/HY | 100 | 99.1 |
| Cu-Fe/MCM-22 | 100 | 99.5 |
| Cu-Fe/SAPO-34 | 100 | 99.3 |
| Cu-Fe/ZSM-5 | 100 | 98.8 |
| Cu-Fe/ZSM-35 | 100 | 98.9 |
| Cu-Fe/USY | 100 | 99.5 |
| Cu-Fe/MOR | 100 | 99.4 |
| Cu-Fe/Hβ | 100 | 99.2 |
Embodiment 3
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is that temperature will be reacted
140 DEG C of degree is adjusted to 20 DEG C.The results are shown in Table 3 for gas chromatographic analysis:
3. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 20 DEG C, 3MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 82.4 |
| Cu-Fe/MCM-41 | 100 | 71.6 |
| Cu-Fe/HY | 100 | 73.2 |
| Cu-Fe/MCM-22 | 100 | 71.7 |
| Cu-Fe/SAPO-34 | 100 | 74.1 |
| Cu-Fe/ZSM-5 | 100 | 68.8 |
| Cu-Fe/ZSM-35 | 100 | 69.0 |
| Cu-Fe/USY | 100 | 77.3 |
| Cu-Fe/MOR | 100 | 76.5 |
| Cu-Fe/Hβ | 100 | 59.9 |
Embodiment 4
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is hydrogen in kettle
Atmospheric pressure 3MPa is adjusted to 0.01MPa.The results are shown in Table 4 for gas chromatographic analysis:
4. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and urges in 140 DEG C, 0.01MPa hydrogen
Change ethyl levulinate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 98.5 |
| Cu-Fe/MCM-41 | 99.3 | 94.2 |
| Cu-Fe/HY | 99.2 | 93.6 |
| Cu-Fe/MCM-22 | 100 | 95.3 |
| Cu-Fe/SAPO-34 | 100 | 92.6 |
| Cu-Fe/ZSM-5 | 99.4 | 94.1 |
| Cu-Fe/ZSM-35 | 99.4 | 94.5 |
| Cu-Fe/USY | 100 | 96.9 |
| Cu-Fe/MOR | 100 | 95.7 |
| Cu-Fe/Hβ | 99.1 | 93.4 |
Embodiment 5
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is hydrogen in kettle
Atmospheric pressure 3MPa is adjusted to 8MPa.The results are shown in Table 5 for gas chromatographic analysis:
5. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 140 DEG C, 8MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 99.5 |
| Cu-Fe/MCM-41 | 100 | 99.3 |
| Cu-Fe/HY | 100 | 99.5 |
| Cu-Fe/MCM-22 | 100 | 99.5 |
| Cu-Fe/SAPO-34 | 100 | 99.2 |
| Cu-Fe/ZSM-5 | 100 | 99.5 |
| Cu-Fe/ZSM-35 | 100 | 99.1 |
| Cu-Fe/USY | 100 | 99.5 |
| Cu-Fe/MOR | 100 | 99.4 |
| Cu-Fe/Hβ | 100 | 99.4 |
Embodiment 6
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is catalyst
Input amount be adjusted to 100mg from 50mg.The results are shown in Table 6 for gas chromatographic analysis:
6. 100mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed in 140 DEG C, 3MPa hydrogen
Ethyl levulinate hydrogenation reaction result
Embodiment 7
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is catalyst
Input amount be adjusted to 30mg from 50mg.The results are shown in Table 7 for gas chromatographic analysis:
7. 30mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 140 DEG C, 3MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 99.1 |
| Cu-Fe/MCM-41 | 100 | 98.4 |
| Cu-Fe/HY | 100 | 98.7 |
| Cu-Fe/MCM-22 | 100 | 99.3 |
| Cu-Fe/SAPO-34 | 100 | 98.5 |
| Cu-Fe/ZSM-5 | 100 | 97.9 |
| Cu-Fe/ZSM-35 | 100 | 98.8 |
| Cu-Fe/USY | 100 | 98.6 |
| Cu-Fe/MOR | 100 | 98.9 |
| Cu-Fe/Hβ | 100 | 99.2 |
Embodiment 8
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；When difference is to react
Between 3 hour adjustments be 20min.The results are shown in Table 8 for gas chromatographic analysis:
8. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 140 DEG C, 3MPa hydrogen
Acyl ethyl propionate adds the reaction result of hydrogen 20min
Embodiment 9
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；When difference is to react
Between 3 hour adjustments be 24 hours.The results are shown in Table 9 for gas chromatographic analysis:
9. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 140 DEG C, 3MPa hydrogen
Acyl ethyl propionate adds 24 hours reaction results of hydrogen
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 99.0 |
| Cu-Fe/MCM-41 | 100 | 99.2 |
| Cu-Fe/HY | 100 | 99.1 |
| Cu-Fe/MCM-22 | 100 | 99.5 |
| Cu-Fe/SAPO-34 | 100 | 99.3 |
| Cu-Fe/ZSM-5 | 100 | 99.5 |
| Cu-Fe/ZSM-35 | 100 | 98.9 |
| Cu-Fe/USY | 100 | 99.5 |
| Cu-Fe/MOR | 100 | 99.4 |
| Cu-Fe/Hβ | 100 | 99.2 |
Embodiment 10
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is embodiment 1
The zeolite molecular sieve carried copper iron double metal catalyst of investment is adjusted to the quadric catalysis agent recycled in embodiment 1.Gas
The results are shown in Table 10 for analysis of hplc:
10. 50mg quadric catalysis agent of table is catalyzed ethyl levulinate in 140 DEG C, 3MPa hydrogen and adds hydrogen reaction in 3 hours
As a result
Embodiment 11
The present embodiment carries out hydrogenation reaction according to the scheme of embodiment 1；Difference is ethyl levulinate being adjusted to second
Acyl propionic acid.Gas chromatographic analysis result is as shown in table 11:
11. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed in 140 DEG C, 3MPa hydrogen
Levulic acid adds 3 hours reaction results of hydrogen
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 98.7 |
| Cu-Fe/MCM-41 | 100 | 93.4 |
| Cu-Fe/HY | 100 | 95.8 |
| Cu-Fe/MCM-22 | 100 | 95.6 |
| Cu-Fe/SAPO-34 | 100 | 97.1 |
| Cu-Fe/ZSM-5 | 100 | 96.9 |
| Cu-Fe/ZSM-35 | 100 | 93.7 |
| Cu-Fe/USY | 100 | 98.2 |
| Cu-Fe/MOR | 100 | 97.3 |
| Cu-Fe/Hβ | 100 | 95.5 |
Embodiment 12
The present embodiment carries out hydrogenation reaction according to the scheme of embodiment 1；Difference is ethyl levulinate being adjusted to second
Acyl methyl propionate.Gas chromatographic analysis result is as shown in table 12:
12. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed in 140 DEG C, 3MPa hydrogen
Methyl ester levulinate adds 3 hours reaction results of hydrogen
Embodiment 13
The present embodiment carries out hydrogenation reaction according to the scheme of embodiment 1；Difference is ethyl levulinate being adjusted to second
Acyl butyl propionate.Gas chromatographic analysis result is as shown in table 13:
13. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed in 140 DEG C, 3MPa hydrogen
Butyl acetylpropanoate adds 3 hours reaction results of hydrogen
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 99.0 |
| Cu-Fe/MCM-41 | 100 | 95.1 |
| Cu-Fe/HY | 100 | 97.3 |
| Cu-Fe/MCM-22 | 100 | 96.2 |
| Cu-Fe/SAPO-34 | 100 | 97.9 |
| Cu-Fe/ZSM-5 | 100 | 95.6 |
| Cu-Fe/ZSM-35 | 100 | 94.8 |
| Cu-Fe/USY | 100 | 98.7 |
| Cu-Fe/MOR | 100 | 96.5 |
| Cu-Fe/Hβ | 100 | 98.4 |
Embodiment 14
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is that temperature will be reacted
140 DEG C of degree is adjusted to 40 DEG C.Gas chromatographic analysis result is as shown in table 14:
14. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 40 DEG C, 3MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
Embodiment 15
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is that temperature will be reacted
140 DEG C of degree is adjusted to 80 DEG C.Gas chromatographic analysis result is as shown in Table 15:
15. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed second in 80 DEG C, 3MPa hydrogen
Acyl ethyl propionate hydrogenation reaction result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 100 | 95.5 |
| Cu-Fe/MCM-41 | 100 | 91.4 |
| Cu-Fe/HY | 100 | 93.8 |
| Cu-Fe/MCM-22 | 100 | 92.1 |
| Cu-Fe/SAPO-34 | 100 | 94.7 |
| Cu-Fe/ZSM-5 | 100 | 91.9 |
| Cu-Fe/ZSM-35 | 100 | 91.2 |
| Cu-Fe/USY | 100 | 95.3 |
| Cu-Fe/MOR | 100 | 94.6 |
| Cu-Fe/Hβ | 100 | 92.0 |
Embodiment 16
The present embodiment carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is that temperature will be reacted
140 DEG C of degree is adjusted to 100 DEG C.Gas chromatographic analysis result is as shown in table 16:
16. 50mg of table is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve and is catalyzed in 100 DEG C, 3MPa hydrogen
Ethyl levulinate hydrogenation reaction result
Comparative example 1
This comparative example carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is solvent just
Hexane is adjusted to ethyl alcohol.Gas chromatographic analysis result is as shown in table 17:
Table 17. is supported on the copper and iron bimetallic catalyst on zeolite molecular sieve in 140 DEG C, 3MPa hydrogen, alcohol solvent
Catalysis ethyl levulinate adds 3 hours reaction results of hydrogen
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 39.6 | 37.9 |
| Cu-Fe/MCM-41 | 27.4 | 25.2 |
| Cu-Fe/HY | 33.1 | 30.4 |
| Cu-Fe/MCM-22 | 26.8 | 22.5 |
| Cu-Fe/SAPO-34 | 29.5 | 26.1 |
| Cu-Fe/ZSM-5 | 32.7 | 30.3 |
| Cu-Fe/ZSM-35 | 36.2 | 30.7 |
| Cu-Fe/USY | 29.6 | 25.6 |
| Cu-Fe/MOR | 34.3 | 29.8 |
| Cu-Fe/Hβ | 31.9 | 28.8 |
Comparative example 2
This comparative example carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is solvent just
Hexane is adjusted to tetrahydrofuran.Gas chromatographic analysis result is as shown in table 18:
Table 18. be supported on the copper and iron bimetallic catalyst on zeolite molecular sieve 140 DEG C, 3MPa hydrogen, tetrahydrofuran it is molten
It is catalyzed ethyl levulinate in agent and adds 3 hours reaction results of hydrogen
Comparative example 3
This comparative example carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is solvent just
Hexane is adjusted to water.Gas chromatographic analysis result is as shown in table 19:
The copper and iron bimetallic catalyst that table 19. is supported on zeolite molecular sieve is urged in 140 DEG C, 3MPa hydrogen, aqueous solvent
Change ethyl levulinate and adds 3 hours reaction results of hydrogen
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| Cu-Fe/SBA-15 | 70.4 | 69.2 |
| Cu-Fe/MCM-41 | 64.6 | 61.3 |
| Cu-Fe/HY | 59.8 | 55.1 |
| Cu-Fe/MCM-22 | 60.5 | 56.8 |
| Cu-Fe/SAPO-34 | 62.1 | 59.4 |
| Cu-Fe/ZSM-5 | 66.7 | 63.7 |
| Cu-Fe/ZSM-35 | 69.2 | 68.5 |
| Cu-Fe/USY | 63.3 | 60.0 |
| Cu-Fe/MOR | 68.2 | 65.6 |
| Cu-Fe/Hβ | 65.9 | 64.9 |
The result of comparative example 1-3 illustrates that the selected specific alkane solvent of the present invention can obtain especially excellent
Reaction result, that is, levulic acid and its conversion ratio of esters can be made to reach 100%, and the yield of gamma valerolactone is big
More than 95%, highest can achieve 99.5% for part.
Comparative example 4
This comparative example carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1；Difference is copper and iron is double
Metallic catalyst is adjusted to corresponding zeolite molecular sieve carrier.Gas chromatographic analysis result is as shown in table 20:
20. zeolite molecular sieve carrier of table is catalyzed ethyl levulinate in 140 DEG C, 3MPa hydrogen and adds hydrogen reaction in 3 hours
As a result
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| SBA-15 | 8.6 | 4.2 |
| MCM-41 | 7.4 | 4.4 |
| HY | 3.1 | 0.4 |
| MCM-22 | 6.8 | 2.1 |
| SAPO-34 | 9.0 | 3.5 |
| ZSM-5 | 2.7 | 0.3 |
| ZSM-35 | 6.2 | 2.7 |
| USY | 9.6 | 4.6 |
| MOR | 4.3 | 1.8 |
| Hβ | 9.9 | 0.9 |
The result of comparative example 4 illustrates that zeolite molecular sieve carrier itself will not play the effect of catalysis.
Comparative example 5
This comparative example carries out the hydrogenation reaction of ethyl levulinate according to the scheme of embodiment 1, and difference is 50mg copper
Iron double metal catalyst is adjusted to the simple mixtures of 21.5mg copper powder and 28.5mg iron powder (copper is 1: 1.5 with iron molar ratio).
Gas chromatographic analysis result is as shown in table 21:
The mixture of table 21.21.5mg copper powder and 28.5mg iron powder is catalyzed ethyl levulinate in 140 DEG C, 3MPa hydrogen
Add 3 hours reaction results of hydrogen
| Catalyst type | Ethyl levulinate conversion ratio/% | Gamma valerolactone yield/% |
| 21.5mg copper powder and 28.5mg iron powder | 72.1 | 43.6 |
Experimental result shows that ethyl levulinate conversion ratio substantially reduces.This demonstrate that it is of the invention by levulic acid and
Its esters low temperature hydrogenation produces in the method for gamma valerolactone, plays the not instead of copper of catalytic action and the simple mixtures of iron,
Possessed effective active phase CuFeO in carried copper iron catalyst2, it is able to ascend the reactivity of carbonyl, so that turning
Rate is 100%.
The above detailed description of the present invention is only used for helping to understand that methods and techniques of the invention, the present invention are not limited to
In above embodiments.Those skilled in the art should be appreciated that without departing from the present invention, make to the present invention
Any change and modification be all defined within the scope of the invention as claimed.
Industrial feasibility
The present invention provides a kind of methods by levulic acid and its esters low temperature hydrogenation production gamma valerolactone.The present invention
Reaction system mild condition, energy consumption is lower, and production cost is low, has good prospects for commercial application.
Meanwhile it is as used in the present invention using zeolite molecular sieve as the carried copper iron double metal catalyst of carrier,
Preparation is simple, environmentally friendly, low in cost, and atom utilization is high, excellent catalytic effect, to levulic acid and its esters selectivity
Hydrogenation synthesis gamma valerolactone has general applicability, has potential industrial value.
Claims (10)
1. a kind of method by levulic acid and its esters low temperature hydrogenation production gamma valerolactone, which comprises with room temperature
Or mixtures thereof alkane in liquid is used as reaction dissolvent, in the presence of carried copper iron catalyst, by levulic acid and
Its esters is reacted with hydrogen generates gamma valerolactone.
2. according to the method described in claim 1, wherein the levulic acid and its esters includes levulic acid, levulic acid
Or mixtures thereof ester.
3. according to the method described in claim 2, wherein the levulinate is selected from methyl ester levulinate, levulic acid second
Ester, Butyl acetylpropanoate, the levulic acid tert-butyl ester, levulic acid isopropyl ester, or mixtures thereof.
4. according to the method described in claim 1, wherein the temperature of the reaction is 20-250 DEG C.
5. according to the method described in claim 1, copper and iron bimetallic is catalyst wherein in the carried copper iron catalyst
Active constituent, wherein the content of copper is the 0.8-25.8wt% of entire catalyst, and the molar ratio of copper and iron is 0.3-10.
6. according to the method described in claim 1, it is x (M that wherein the carried copper iron catalyst, which is carried on general structure,2O)·
x’(M’O)·y(Al2O3)·(SiO2)·z(H2O on zeolite molecular sieve carrier), wherein M is the first major element monovalence sun
Ion, M ' be the second major element bivalent cation, x, x ', y, z be any rational.
7. according to the method described in claim 1, wherein the carried copper iron catalyst is described using co-impregnation preparation
Co-impregnation includes: that the soluble copper salt as copper source is dissolved in water or organic solvent with the soluble ferric iron salt as source of iron
Afterwards, it is added and is impregnated for the carrier of supported copper iron catalyst, then calcine impregnation product, then it is gone back in hydrogen
It is former.
8. according to the method described in claim 7, wherein, copper source is selected from nitric acid copper hydrate, copper sulfate hydrate, chlorine
Change at least one of copper hydrate, basic copper carbonate and copper acetate soluble copper salt, and the source of iron is selected from citric acid
Iron, ferric perchlorate, ferrous sulfate hydrate, ferrous sulfate hydrate, oxamide molysite hydrate, ferric oxalate hydrate, ferric nitrate
At least one of hydrate, Iron trichloride hexahydrate and frerrous chloride soluble ferric iron salt.
9. the temperature of the reduction is according to the method described in claim 7, wherein the temperature of the calcining is 100-800 DEG C
100-800℃。
10. reaction initial hydrogen pressure is 0.01- according to the method described in claim 1, wherein reaction temperature is 20-250 DEG C
8MPa, reaction time 20min-24h.
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