WO2015026234A1 - Supported metal nanoparticle-based catalyst for the hydrogenation of a levulinic acid source - Google Patents
Supported metal nanoparticle-based catalyst for the hydrogenation of a levulinic acid source Download PDFInfo
- Publication number
- WO2015026234A1 WO2015026234A1 PCT/NL2014/050569 NL2014050569W WO2015026234A1 WO 2015026234 A1 WO2015026234 A1 WO 2015026234A1 NL 2014050569 W NL2014050569 W NL 2014050569W WO 2015026234 A1 WO2015026234 A1 WO 2015026234A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal
- support
- catalyst
- oxide
- ruthenium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 22
- 239000002082 metal nanoparticle Substances 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 102
- 239000002184 metal Substances 0.000 claims abstract description 101
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 53
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 51
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005470 impregnation Methods 0.000 claims abstract description 35
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 96
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 150000001450 anions Chemical class 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 12
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 12
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- -1 alkyl pentenoates Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 238000007142 ring opening reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 claims description 4
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004375 physisorption Methods 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- FYBCSLFQRDQHAI-UHFFFAOYSA-N 4-hydroxypentanamide Chemical compound CC(O)CCC(N)=O FYBCSLFQRDQHAI-UHFFFAOYSA-N 0.000 claims description 2
- KYLUHLJIAMFYKW-UHFFFAOYSA-N 5-methyl-3-methylideneoxolan-2-one Chemical compound CC1CC(=C)C(=O)O1 KYLUHLJIAMFYKW-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical group 0.000 claims description 2
- YVIVRJLWYJGJTJ-UHFFFAOYSA-N gamma-Valerolactam Chemical compound CC1CCC(=O)N1 YVIVRJLWYJGJTJ-UHFFFAOYSA-N 0.000 claims description 2
- MBAHGFJTIVZLFB-UHFFFAOYSA-N methyl pent-2-enoate Chemical class CCC=CC(=O)OC MBAHGFJTIVZLFB-UHFFFAOYSA-N 0.000 claims description 2
- YIYBQIKDCADOSF-UHFFFAOYSA-N pentenoic acid group Chemical class C(C=CCC)(=O)O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 description 19
- 239000002245 particle Substances 0.000 description 13
- 235000002639 sodium chloride Nutrition 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012696 Pd precursors Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002969 pentanoic acid esters Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FILVIKOEJGORQS-UHFFFAOYSA-N 1,5-dimethylpyrrolidin-2-one Chemical compound CC1CCC(=O)N1C FILVIKOEJGORQS-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241001125222 Centurio Species 0.000 description 1
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- BGLUXFNVVSVEET-UHFFFAOYSA-N beta-angelica lactone Chemical compound CC1OC(=O)C=C1 BGLUXFNVVSVEET-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B01J35/393—
-
- B01J35/613—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- B01J35/30—
Definitions
- the invention relates to a method for preparing a chemical compound from a levulinic acid source.
- LA Levulinic acid
- VDL gamma-valerolactone
- MTHF methyltetrahydrofuran
- PA pentanoic acid
- PD pentanediol
- PE pentanoic acid ester
- WO -A- 2006/067171 relates to a process for the hydrogenation of a lactone, a carboxylic acid ester or a carboxylic acid, for example LA, in the presence of a bifunctional heterogeneous catalyst comprising (i) a zeolite or another strongly acidic component and (ii) a hydrogenating metal component.
- a bifunctional heterogeneous catalyst comprising (i) a zeolite or another strongly acidic component and (ii) a hydrogenating metal component.
- a catalyst useful in catalysing a conversion of a levulinic acid source into another useful chemical compound, such as GVL in particular a catalyst that is advantageous in one or more of the following aspects: catalytic activity, catalytic selectivity towards a specific useful compound of interest, catalytic productivity, robustness under reaction conditions (resistance to leaching or sintering).
- a specific group of catalysts display a satisfactory activity, selectivity and/or productivity for a prolonged period of time in a method for converting a levulinic acid source into another useful compound, such as GVL. More in particular the inventors found that such catalysts are preparable by a specific method.
- the invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydride, levulinic acid salts, levulinic acid esters and levulinic acid amides, to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal catalyst on a support is obtainable by a metal-ion wet-impregnation method, preferably an anion-excess wet-impregnation method and wherein the metal comprises ruthenium.
- a levulinic acid source preferably a compound selected from the group of levulinic acid, levulinic acid anhydride, levulinic acid salts, levulinic acid esters and levulinic acid amides
- a metal catalyst on a support is obtainable by a metal-ion wet-impregnation method, preferably an anion-excess
- the invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium.
- a levulinic acid source preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides
- a metal catalyst on an oxide support wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and
- the invention relates to a metal catalyst on an oxide support, in particular a metal oxide support or a silica support, wherein the metal comprises ruthenium and wherein the catalyst is obtainable by an anion excess wet- impregnation method.
- the invention relates to a metal catalyst on an oxide support, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium. In particular good results have been achieved with a metal alloy of ruthenium and palladium on an titanium oxide support.
- the invention relates to a method for preparing a metal catalyst on an oxide support (for use in a method) according to the invention, comprising
- a impregnation solution comprising a precursor for the metal catalyst - i.e. metal ions, including ruthenium ions, plus counter- anions for the metal ions (in an amount sufficient to maintain the electrochemical balance of the precursor) and an additional source of anions, i.e. the excess anions (together with counter-cations in an amount to maintain the electrochemical balance of the additional source of anions);
- an oxide support in particular a metal oxide support or a silica support
- a catalyst prepared according to the method of the invention has properties that are different from known catalysts, also if the known catalyst is made of the same catalytic metal and the same type of support material.
- a catalyst according to the invention is particularly
- the catalyst has a productivity of at least 10 molcvL . gmetai " 1 . hr 1 , preferably of at least 15 molcvL . gmetai 1 . hr 1 , more preferably of at least 25 molcvL . gmetai 1 . hr 1 , and even more preferably of at least 35 molcvL . gmetai 1 . hr 1 .
- the productivity usually is less than 250 molcvL . gmetai 1 . hr 1 , preferably 150 molcvL . gmetai 1 . hr 1 or less, more preferably 75 molcvL .
- gmetai 1 . hr 1 or less even more preferably 55 molcvL . gmetai 1 . hr 1 or less, in particular 25 molcvL . gmetai " 1 . hr 1 or less, more in particular 20 molcvL . gmetai "1 . hr 1 or less .
- the productivity can be calculated by determining the moles of GVL produced (by means of GC analysis of samples taken from the reactor and quantification with an internal standard) as a function of time and divided by the grams of catalyst added to the reaction under the following conditions: reaction in liquid phase (dioxane), initially 10 wt.% LA (based on the weight of LA+dioxane), 1 wt.% (total) metal based on the weight of the metal catalyst including support, 473 K, 40 bar Lb.
- the invention is in particular advantageous in that it allows the essentially complete (e.g. > 99 wt.%) conversion of an LA source, in particular LA, to a desired product, in particular GVL, without noticeable degradation of LA source, in particular without noticeable decarboxylation of LA or further hydrogenation of GVL.
- Figure 1 shows a STEM - EDX mapping of a RuPd catalyst prepared according to the invention.
- Figure 2 shows the production of GVL during the hydrogenation of LA using monometallic 1% Ru/Ti02 (Ru, ⁇ ) made with a metal ion impregnation method with anion excess and a bimetallic 1% Ru-Pd/Ti02 (RuPd, A) made with a metal ion impregnation method with anion excess.
- Figure 3 shows a comparison of particle sizes for the fresh and spent Ru, Pd, Ru-Pd, catalysts made with anion excess using TEM.
- Figure 4 shows the recyclability of bimetallic RuPd/Ti02 catalyst. Recyclability tests were performed at different LA conversion levels and GVL selectivities.
- the metal catalyst on the support is abbreviated herein after as “the metal catalyst”.
- metal is generally used herein in a strict sense, namely to refer to the metallic form of one or more elements, unless specified or evident otherwise (e.g. when referring to metal ions or to a metal salt).
- metal catalyst is used for a catalyst that comprises at least one catalytically active metallic element (characteristically ruthenium).
- a specific form of a metal is an alloy.
- substantially(ly) or “essential(ly)” is generally used herein to indicate that it has the general character, appearance or function of that which is specified. When referring to a quantifiable feature, these terms are in particular used to indicate that it is for more than 50 %, in particular at least 75 %, more in particular at least 90 %, even more in particular at least 95 % of the maximum that feature.
- phrases "essentially consisting" of a substance (e.g. a metal) as used herein, in general means that other components than said substance are not detectible or present at a level that is generally considered an impurity.
- "essentially consisting of means for more that 98 wt.%, more in particular for more than 99 wt.%, more in particular for more than 99.5 wt.%.
- the term "catalytic activity" is defined (calculated) as the initial reaction rate per unit mass of catalyst. In practice this is determined by determining the (slope of concentration of LA-source vs time graph at short reaction times/time derivative of the LA-source concentration at short reaction times) divided by the grams of metal added to the reaction. A short reaction time depends on the reaction conditions and typically reflects the time wherein the first 10 mol.% or less of the initially present LA-source are converted.
- the phrase "catalytic selectivity towards a specific useful compound” is defined (calculated) as ratio of the molar amount of the reactant (LA-source) converted to said compound (e.g. GVL) relative to the total molar amount of converted reactant (LA-source).
- the term “catalytic productivity” is defined (calculated) as moles of desired product (e.g. GVL) per gram of metal per unit of time.
- Resistance to leaching can be determined by determining the concentration of metal in the liquid phase after set reaction time, e.g. an hour, a day or a week.
- the metal concentration can be determined by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectroscopy (ICP-OES).
- reaction conditions of the method for preparing the chemical compound from a levulinic acid source can be chosen dependent on the compound of interest, the levulinic acid source, the information disclosed herein, the cited prior art and references cited therein, common general knowledge and optionally a limited amount of testing.
- the LA source is selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides.
- Angelica lactone is a preferred LA lactone. In particular, good results have been achieved with levulinic acid.
- the reduction reaction for converting the LA source preferably is a hydrogenation reaction.
- Suitable reducing agents are preferably selected from the group of hydrogen, formic acid and formate salts, in particular a formate salt of formate and a monovalent cation, such as ammonium formate or sodium formate.
- GVL is formed in the hydrogenation reaction.
- reaction conditions for the hydrogenation reaction can be based on common general knowledge and the information provided in the present disclosure.
- GVL is usually prepared at a temperature in the range of
- 25-250 °C preferably at a temperature in the range of 120-230 °C, and more preferably at a temperature in the range of 180-220 °C.
- GVL is usually prepared at a hydrogen pressure of 1-100 bar, preferably of 20-70 bar, in particular of 40-50 bar.
- the molar ratio of formate to the LA-source is typically at least about 1.
- the formate can be applied in any excess, but usually the ratio of formate to the LA-source is 1000 or less, in particular 100 or less, and more in particular 10 or less.
- the amount of catalyst can be chosen based on common general knowledge, depending on the type of reactor system.
- the GVL prepared in accordance with the invention can be used in the preparation of another compound.
- the GVL is subjected to a an acid or base catalysed ring-opening reaction to produce a mixture of pentenoic acids.
- the GVL is subjected to an acid or base- catalysed ring-opening reaction in the presence of an alcohol to produce a mixture of alkyl pentenoates, preferably methyl pentenoates.
- the GVL is subjected to an acid or base- catalysed ring-opening in the presence of ammonia to produce a mixture of pentenenitriles.
- the double bond can be in the 2-, the 3- or the 4- position.
- the double bond may be cis or trans.
- These ring opening reactions can be advantageously performed in the gas phase or in the liquid phase. In the latter case the ring-opening reaction can advantageously be executed as a reactive distillation.
- the GVL is subjected to an acid or base- catalyzed reaction with an aldehyde to form an alpha-alkylidene-gamma- valerolactone.
- the aldehyde used is formaldehyde which when used in the reaction forms alpha-methylene-gamma-valerolactone.
- the GVL is subjected to a reaction with ammonia or an N-alkylamine to form 5-methyl-pyrrolidinone or N- alkyl- 5-methyl- pyrrolidinone.
- the N-alkylamine used is methylamine, which when used in the reaction forms N-methyl-5-methyl-pyrrolidinone.
- the GVL is hydrogenated to form 1,5- pentanediol.
- the GVL is hydrogenated to form 2- methyltetrahydrofuran.
- the GVL is hydrogenated to form pentanoic acid.
- the LA-source is converted into a salt of 4- hydroxypentanoic acid or 4-hydroxypentanamide.
- the invention relates to the use of gamma- valerolactone prepared in accordance with the invention in the production of a fuel; a monomer, in particular a monomer for the production of a poly amide; or a solvent.
- GVL can be converted into methyltetrahydrofuran which is suitable for use as a solvent or a fuel.
- the catalyst of the invention comprises ruthenium and optionally one or more other metals.
- the metal essentially consists of ruthenium.
- ruthenium Such a catalyst, in particular when obtained by an anion excess impregnation method, has been found to be advantageously suitable for converting an LA source to GVL due to its high catalytic activity and high selectivity towards GVL.
- the metal catalyst comprises ruthenium and at least one other metal, preferably palladium or platinum.
- Ruthenium and the other metal(s) preferably form an alloy.
- a preferred alloy essentially consists of ruthenium and at least one of palladium and platinum.
- the molar ratio of the total of the metals other than ruthenium (such as palladium or platinum) to ruthenium in this embodiment can be chosen within wide limits, usually in the range of 1:99 to 90: 10, in particular in the range of 5:95 to 80:20, and more in particular in the range of 20:80 to 70:30. If palladium is present, the ratio of palladium to ruthenium is preferably at least 10:90, in particular at least 30:70, and more in particular at least 40:60. In general, the higher the palladium content, the longer the catalyst maintains a satisfactory selectivity towards GVL.
- the total metal concentration usually is in the range of 0.1-10 wt.%, in particular in the range of 0.5- 5 wt.%.
- the metal catalyst usually contains at least 0.1 wt.% ruthenium, based on the total weight of metal(s) and support, preferably at least 0.3 wt.% ruthenium, in particular at least 0.5 wt.% ruthenium.
- the ruthenium content of the metal catalyst, based on the total weight of metal(s) and support usually is less than 10 wt.%, preferably 5 wt.% or less, in particular 2 wt.% or less.
- the support preferably is a non-acidic or weakly acidic oxide.
- a weakly acidic support is in particular a support having an isoelectric point at a
- IEP temperature of 25 °C
- the IEP of the support usually is 14 or less.
- the highly acidic metal oxide WO3 typically has an IEP of 0.2- 0.5.
- S1O2 has a lower acidity, its IEP typically being in the range of 1.7-3.5.
- the IEP typically is 4- 11, for Ti0 2 it typically is 3.9-8.2.
- the IEP of MgO is 12- 13. IEPs of many oxides are readily available in the art (Marek
- Silica (S1O2) is a preferred non-metal oxide support for a metal catalyst of the invention. It has advantageous processing properties, such as pelletizing properties.
- the supported metal catalyst is in the form of a pellet, and preferably comprises a metal catalyst on a silica support.
- Titanium oxide and zirconium oxide are preferred metal oxide support materials.
- the oxide may be synthetic or a natural mineral.
- the titanium oxide comprises anatase or rutile.
- good results have been achieved with a support comprising both anatase and rutile (70- 80 wt.% anatase and 30-20 wt.% rutile).
- a support is commercially available from Evonik (P25-Ti0 2 )
- Non-acidic support material is magnesium oxide.
- the size of the support material is not critical. Usually, when preparing the catalyst on support a particulate support is provided, such as a powder. In an advantageous embodiment for the preparation of the catalyst, the particles are microp articles (particles typically having a size ⁇ 1 mm, in particular in the range of 1-200 micrometer). After the catalyst has been prepared, it may be used as such or may be shaped in a desired form, e.g. pelletized.
- the metal catalyst on the support i.e. including support
- the BET surface is at least 40 m 2 /g.
- the BET surface is 800 m 2 /g or less, in particular 400 m 2 /g or less, more in particular 200 m 2 /g or less. In an embodiment, the BET surface is 75 m 2 /g or less, and in particular 60 m 2 /g or less.
- BET advantageously is in the range of 20-75 m 2 /g, in particular in the range of 40-60 m 2 /g.
- BET advantageously is in the range of 50- 150 m 2 /g, in particular in the range of 75- 125 m 2 /g.
- BET usually is in the range of 50-800 m 2 /g, in particular in the range of 50-400 m 2 /g.
- the metal on the support is present on the support surface in the form of nanop articles (particles with a size of typically less than 100 nm), and in particular in the form of metal clusters, deposited on the support.
- These metal clusters preferably have a particle size, as determined by TEM in the range of 0.5 to 10 nm.
- a metal catalyst obtainable in accordance with the invention is characterisable by a relatively high abundance of metal clusters present on the support, more preferably clusters having a size of about 0.5 to 5 nm and/or a relatively low polydispersity with respect to the particle size distribution of the metal nano- particles.
- Chloride is in particular considered favourable for realising a random alloy formation.
- the metal-alloy is characterisable by an essentially homogeneous distribution of ruthenium and the other metal(s), in particular a random alloy structure, rather than e.g. a core-shell alloy which one would expect to perform differently.
- a homogeneous distribution and random alloy structure is determinable by XAFS or STEM, as illustrated by Figure 1. It has further been found that a metal catalyst wherein the metal is a metal alloy, in particular an alloy of ruthenium and palladium, the particle size stability of the metal particles is improved, compared to particles of a single metal, such as only ruthenium or only palladium.
- an a impregnation solution comprising a precursor for the metal catalyst.
- the liquid phase is usually a highly polar solvent, such as an aqueous liquid.
- highly polar means” having about the same polarity as water or a higher polarity than water.
- the metal precursor such as the ruthenium precursor respectively the palladium precursor, usually is a metal salt dissolved in water or an aqueous liquid.
- metal salts are halogen salts (chloride, fluoride, iodide and bromide) and organic acid salts. Good results have been achieved with a chloride salt. Chloride has been found in particular to contribute to providing a catalyst with good catalytic properties.
- the impregnation solution is essentially free (less than 1 wt.%) of nitrates and/or sulphates.
- the total concentration of the metal ions is usually in the range of 1 mg metal ions/mL to 100 mg metal ions 1/mL, preferably in the range of 5 mg metal ions/mL to 10 mg metal ions /mL.
- the impregnation solution preferably comprises an additional source of anions, in addition to the anions from the salt serving as the source for the metal ions which serve as the precursor for the catalytic metal and may be selected from the group of acids and salts of anions with volatile bases, in particular from the group of HC1, organic acids, ammonium chloride and salts of ammonium and an organic acid.
- an impregnation solution is used is called an anion excess
- the concentration of the acid or salt of the anions and a volatile base preferably is 10- 100 mL of a 0.1-10 M solution, in particular 15-30 mL of a 0.1 to 5 M solution, per 0.5 to 5 gram support.
- the impregnation may be carried out in a manner known per se.
- the support is advantageously mixed with the impregnation solution by agitation, for instance by vigorous stirring, e.g. using a magnetic bar/stirrer set-up above 900 rpm, whereby the mixing of support and impregnation liquid is effected.
- the impregnation can be carried out at any temperature between the melting point and the boiling point of the liquid phase, and is advantageously carried out at ambient temperature, e.g. at about 25 °C.
- the temperature is preferably raised to about 50-90 °C. This will allow evaporation of the solvent at a desired evaporation rate.
- the drying may be carried out in a manner known per se. In particular good results have been achieved with a method wherein the slurry of support in the impregnation solution is dried in hot open air atmosphere typically at a
- the drying is preferably carried out whilst agitating the slurry, for instance by stirring or drying in a fluidized bed.
- the agitation is preferably vigorous enough to achieve intensive mixing of the contents of the slurry.
- the drying is usually continued until a visually dry product is obtained.
- the drying usually takes 24 hours or less, in particular 1-20 hours, more in particular 5-20 hours.
- the dried product is ground, prior to reduction.
- the dried impregnated oxide support is reduced without first having been subjected to a calcination step.
- the catalyst is a non-calcined catalyst.
- calcination is generally known as a heat treatment of a catalyst precursor in an oxidizing atmosphere (of variable composition) for variable amount of time and at a temperature sufficient to convert essentially all precursors into oxides, i.e. to remove essentially all anions except oxygen as well as any solvent molecules.
- Reducing is preferably carried out using hydrogen, for instance 1-10 vol.% hydrogen in an inert gas, such as nitrogen, argon and/or helium.
- the reduction is preferably carried out at a temperature in the range of 250 °C to 600 °C.
- the temperature is gradually raised until the desired maximum temperature is reached, in particular at a ramp-rate in the range of 1-5 °C/min.
- an advantageous balance is reached between removing the anions, such as chloride ions, increasing the metal-support interaction and preventing the metal particles from sintering.
- a slower rate of ramping typically increases the dispersion of the metal particles within the catalyst.
- the reduction is preferably carried out for a period of at least 1 h, in particular for a period of 2 h to 10 h.
- RuC (Acros Chemicals) was used as the ruthenium precursor and was dissolved in deionized water to form an aqueous precursor solution with a ruthenium concentration of 5.28 mg / mL.
- the requisite amount of the precursor solution (1.89 mL for preparing a 1 wt.% Ru catalyst on support) was charged in to a clean 50 mL round bottomed flask fitted with a magnetic stirrer, after which the requisite amount of
- the slurry was stirred vigorously at 298 K for about 30 min and then the oil bath temperature was raised to 333 K, stirred for 1 h and then finally heated to 358 K. The slurry was stirred at this temperature overnight until all the water had evaporated.
- the solid powder denoted as the "dried sample” was ground thoroughly with a mortar and pestle and approximately 350 mg of this material was then reduced in a furnace at 723 K (approx. 2 K / min ramp rate) under a flow of 5 vol.% Lb / N2 (total flow: 420 mL/min ) for 4 h, without having been subjected to a calcination step. Finally the furnace was cooled rapidly to room temperature and the catalyst sample was used without any further modification.
- the resultant catalyst contained a 1 wt.% metal (Ru) concentration on a 1 g production scale.
- Reactions were performed with 10 wt.% levulinic acid (6.0 g, 51.7 mmol) in dioxane (54 g) with 1 wt.% catalyst (0.6 g).
- the reactions were run in a 100 mL Parr batch autoclave at a temperature of 473 K using a hydrogen pressure of 40 bar and a stirring speed of 1600 rpm.
- the batch autoclave reactor was loaded with catalyst, substrate and solvent, purged three times with argon after which the reaction mixture was heated to reaction temperature and charged with Lb to 40 bar. 1 mL of solution was sampled at various intervals during the reaction.
- the autoclave was cooled to room temperature, the Lb was released and 2 wt.% anisole was added as an internal standard.
- the catalyst was separated by filtration and washed with acetone.
- reaction products were analyzed using a Shimadzu GC-2010A gas chromatograph equipped with a CP-WAX 57-CB column (25 m x 0.2 mm x 0.2 ⁇ ) and FID detector. Products were identified with a GC-MS from Shimadzu with a CP-WAX 57CB column (30 m x 0.2 mm x 0.2 ⁇ ). Results
- the activity and selectivity of supported monometal Ru catalyst was found to be strongly influenced by both its preparation method and by alloying it with a second metal, such as Pd.
- the Ru catalyst according to the invention gave full conversion after 40 min with 99.0 mol.% selectivity to GVL (0.1 mol.% MTHF and 0.1 mol.% PD as a byproduct); cf. 43.3 mol.% conversion after 40 min for the comparative Ru catalyst (WI), and 99.5 mol.% selectivity to GVL.
- the productivity of the Ru/Ti02 catalyst according to the invention was 16.4 molcvL . g metai 1 . hr 1 , thus outperforming the catalysts listed in a recent LA hydrogenation review paper (Wright, W.R.H. et al. ChemSusChem 5 (2012) 1657- 1667).
- This Ru/Ti02 catalyst according to the invention was very active and gave excellent selectivity at short reaction times of 40 min. At longer reaction times, however, consecutive reactions took place causing a drop in selectivity and mass balance after 2 h (selectivity: 93.0 mol.% GVL, 1.2 mol.% PD, 0.7 mol.% MTHF).
- the catalyst according to the invention showed very limited leaching (i.e. loss of 0.5 wt.% loss of the total amount of ruthenium originally present after 10 h in neat LA) and very limited sintering was observed.
- PdC salt (Sigma Aldrich) was dissolved in deionized water to form an aqueous precursor solution with a resultant palladium concentration of 3.02 mg / mL. This solution was slowly cooled and used as the palladium precursor solution. This solution was used together with the Ru precursor solution of Example 1 in amounts to provide a molar ratio of Ru:Pd of 1:1. The requisite amount of the precursor solution was charged in to a clean 50 mL round bottomed flask fitted with a magnetic stirrer, after which the requisite amount of concentrated HCl
- Example 1 A RuPd on Ti02 catalyst was obtained, comprising 1 wt.% of the Ru-Pd alloy (molar ratio Ru:Pd 1: 1).
- the Ru-Pd metal alloy catalyst was found to have a high activity (i.e. full conversion after 30 min, 99.6 mol.% selectivity to GVL, 0.1 mol.% PD, 0.3 mol.% MTHF; note that this is at only 0.49 wt.% Ru metal loading), and stayed completely selective also at longer reaction times (1 h, sel. 99.2 mol.% GVL, 0.2 mol.% PD, 0.4 mol.% MTHF, 0.1 mol.% PA)
- the productivity of the RuPd/Ti0 2 catalyst was 17.2 molcvL . gmetai 1 . hr 1 .
- This catalyst was also compared with a catalyst, prepared with the same method as described in Example 1, except that all Ru was replaced by Pd.
- This Pd/Ti02 catalyst shows negligible activity with respect to the conversion of levulinic acid. Characterization of the catalyst
- Figure 1 shows a STEM - EDX mapping of a RuPd catalyst prepared according to Example 2 (molar ratio of Ru:Pd of 1: 1). Details about the mapping can be found in "Aberration Corrected Analytical Electron Microscopy Studies Of Bimetallic Nanopar tides", A.A. Herzing, M.Watanabe, C.J.Kiely, J.Edwards,
- the images are STEM high angle annular dark field (HAADF) images of the metallic particles obtained using an aberration corrected JEM ARM-200F STEM operating at 200 kV.
- XEDS X-ray energy dispersive
- Figure-2 shows that the GVL yield (A), was stable for several hours even after reaching quantitative conversion when the bimetallic catalyst was used.
- the GVL yield started to drop after reaching a maximum of 99.0%. This is because of the further hydrogenation of the product GVL to 1,4-pentanediol (PD) and
- MTHF methyltetrahydrofuran
- Figure -3 shows the results from the TEM measurements of the metal particle sizes for the fresh (white bars) and spent (grey bars) monometallic (Ru or Pd) and bimetallic (Ru-Pd) catalysts, made with a method of the invention. From the figure it is evident that the metal particle sizes increased when the monometallic catalysts were used once. However, the particle sizes remained the same for the bimetallic catalysts even after 3 runs (grey, hatched bar). This shows that alloying Pd with Ru substantially helps in stabilizing the small particle for several cycles. This stability of the small particles, in the case of bimetallic catalysts, resulted in the catalytic activity of the recovered catalysts.
- Figure-4 shows the catalytic activity of the fresh and recovered bimetallic catalysts.
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Abstract
The invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal catalyst on a support is obtainable by an metal-ion impregnation method, which metal-ion impregnation method uses an anion-excess, and wherein the metal comprises ruthenium, in particular ruthenium and palladium.
Description
Title: Supported metal nanoparticle-based catalyst for the hydrogenation of a levulinic acid source
The invention relates to a method for preparing a chemical compound from a levulinic acid source.
Levulinic acid (LA) has been identified as a promising, renewable platform molecule, that can be converted by a catalytic reaction, such as a hydrogenation or deoxygenation reaction, to another valuable chemical, such as gamma-valerolactone (GVL), methyltetrahydrofuran (MTHF), pentanoic acid (PA), pentanediol (PD) or a pentanoic acid ester (PE). These products can be used as renewable fuels, additives, solvents and chemical building blocks.
Various catalysts have been evaluated for their use in the conversion of levulinic acid, including supported noble metal and base metal catalysts (Wright, W.R.H. et al. ChemSusChem 5 (2012) 1657- 1667).
WO -A- 2006/067171 relates to a process for the hydrogenation of a lactone, a carboxylic acid ester or a carboxylic acid, for example LA, in the presence of a bifunctional heterogeneous catalyst comprising (i) a zeolite or another strongly acidic component and (ii) a hydrogenating metal component. The Examples describe a method of preparing the catalyst using an incipient wetness
impregnation procedure, wherein zeolite or silica (as comparison) is impregnated with unspecified metal solutions, dried, and then calcined. In one of the examples ethyl levulinate is hydrogenated in the presence of various catalysts. The major reaction products in the experiments with the metal-zeolite catalysts (plus silica binder) are ethyl pentanoate and pentanoic acid. The experiments with the catalysts without the zeolite have GVL as major reaction product, but show considerably less catalytic activity.
Limited examples are available on beneficial effects of alloying in LA hydrogenation reactions. Wettstein, S.G. et al. showed that alloying Ru with Sn is beneficial for catalyst stability (Appl. Catal. B. 117 (2012) 321-329). Van den Brink, P.J. et al., on the other hand, described in WO-A-2006/067171 that a catalyst
comprising an alloy of Pt with Ru or Re on a ΤΪΟ2 and Zr02 support did not improve the performance, but rather seemed to reduce the initial activity and enhanced deactivation for instance for ruthenium on a titania support.
There remains a need for a catalyst useful in catalysing a conversion of a levulinic acid source into another useful chemical compound, such as GVL, in particular a catalyst that is advantageous in one or more of the following aspects: catalytic activity, catalytic selectivity towards a specific useful compound of interest, catalytic productivity, robustness under reaction conditions (resistance to leaching or sintering).
In particular the inventors have found that a specific group of catalysts display a satisfactory activity, selectivity and/or productivity for a prolonged period of time in a method for converting a levulinic acid source into another useful compound, such as GVL. More in particular the inventors found that such catalysts are preparable by a specific method.
Accordingly, the invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydride, levulinic acid salts, levulinic acid esters and levulinic acid amides, to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal catalyst on a support is obtainable by a metal-ion wet-impregnation method, preferably an anion-excess wet-impregnation method and wherein the metal comprises ruthenium.
Further, the invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium.
Further, the invention relates to a metal catalyst on an oxide support, in particular a metal oxide support or a silica support, wherein the metal comprises ruthenium and wherein the catalyst is obtainable by an anion excess wet- impregnation method.
Further, the invention relates to a metal catalyst on an oxide support, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium. In particular good results have been achieved with a metal alloy of ruthenium and palladium on an titanium oxide support.
Further, the invention relates to a method for preparing a metal catalyst on an oxide support (for use in a method) according to the invention, comprising
- providing a impregnation solution comprising a precursor for the metal catalyst - i.e. metal ions, including ruthenium ions, plus counter- anions for the metal ions (in an amount sufficient to maintain the electrochemical balance of the precursor) and an additional source of anions, i.e. the excess anions (together with counter-cations in an amount to maintain the electrochemical balance of the additional source of anions);
- providing an oxide support, in particular a metal oxide support or a silica support;
impregnating the oxide support with the impregnation solution;
- drying the oxide support impregnated with the impregnation solution; and,
- reducing said metal ions present in or on the impregnated oxide support, thereby forming the metal catalyst on the oxide support.
As illustrated in the Examples, a catalyst prepared according to the method of the invention has properties that are different from known catalysts, also if the known catalyst is made of the same catalytic metal and the same type of support material. A catalyst according to the invention is particularly
advantageous in that it has an improved catalytic activity, catalytic selectivity towards a specific useful compound of interest, especially GVL, catalytic
productivity or robustness (resistance to leaching or sintering).
Typically, the catalyst has a productivity of at least 10 molcvL . gmetai" 1 . hr1, preferably of at least 15 molcvL . gmetai 1 . hr1, more preferably of at least 25 molcvL . gmetai 1 . hr1 , and even more preferably of at least 35 molcvL . gmetai 1 . hr1. In practice the productivity usually is less than 250 molcvL . gmetai 1 . hr1, preferably 150 molcvL . gmetai 1 . hr1 or less, more preferably 75 molcvL . gmetai 1 . hr1 or less, even more preferably 55 molcvL . gmetai 1 . hr1 or less, in particular 25 molcvL . gmetai"
1 . hr1 or less, more in particular 20 molcvL . gmetai"1 . hr1 or less . The productivity can be calculated by determining the moles of GVL produced (by means of GC analysis of samples taken from the reactor and quantification with an internal standard) as a function of time and divided by the grams of catalyst added to the reaction under the following conditions: reaction in liquid phase (dioxane), initially 10 wt.% LA (based on the weight of LA+dioxane), 1 wt.% (total) metal based on the weight of the metal catalyst including support, 473 K, 40 bar Lb.
The invention is in particular advantageous in that it allows the essentially complete (e.g. > 99 wt.%) conversion of an LA source, in particular LA, to a desired product, in particular GVL, without noticeable degradation of LA source, in particular without noticeable decarboxylation of LA or further hydrogenation of GVL.
Figure 1 shows a STEM - EDX mapping of a RuPd catalyst prepared according to the invention.
Figure 2 shows the production of GVL during the hydrogenation of LA using monometallic 1% Ru/Ti02 (Ru, ·) made with a metal ion impregnation method with anion excess and a bimetallic 1% Ru-Pd/Ti02 (RuPd, A) made with a metal ion impregnation method with anion excess.
Figure 3 shows a comparison of particle sizes for the fresh and spent Ru, Pd, Ru-Pd, catalysts made with anion excess using TEM. (Blank bar = fresh catalyst; Grey bar = spent catalyst after 1 run; gray, striped bar = spent catalyst after 3 consecutive runs)
Figure 4 shows the recyclability of bimetallic RuPd/Ti02 catalyst. Recyclability tests were performed at different LA conversion levels and GVL selectivities.
The term "or" as used herein is defined as "and/or" unless specified otherwise.
The term "a" or "an" as used herein is defined as "at least one" unless specified otherwise.
The phrase "the metal catalyst on the support" is abbreviated herein after as "the metal catalyst".
The term "metal" is generally used herein in a strict sense, namely to refer to the metallic form of one or more elements, unless specified or evident
otherwise (e.g. when referring to metal ions or to a metal salt). Thus, the term "metal catalyst" is used for a catalyst that comprises at least one catalytically active metallic element (characteristically ruthenium). A specific form of a metal is an alloy.
When referring to a noun (e.g. a compound, an additive, etc.) in the singular, the plural is meant to be included.
For the purpose of clarity and a concise description features are described herein as part of the same or separate embodiments, however, it will be appreciated that the scope of the invention may include embodiments having combinations of all or some of the features described.
The term "substantial(ly)" or "essential(ly)" is generally used herein to indicate that it has the general character, appearance or function of that which is specified. When referring to a quantifiable feature, these terms are in particular used to indicate that it is for more than 50 %, in particular at least 75 %, more in particular at least 90 %, even more in particular at least 95 % of the maximum that feature.
The phrase "essentially consisting" of a substance (e.g. a metal) as used herein, in general means that other components than said substance are not detectible or present at a level that is generally considered an impurity. In particular, "essentially consisting of means for more that 98 wt.%, more in particular for more than 99 wt.%, more in particular for more than 99.5 wt.%.
As used herein, the term "catalytic activity" is defined (calculated) as the initial reaction rate per unit mass of catalyst. In practice this is determined by determining the (slope of concentration of LA-source vs time graph at short reaction times/time derivative of the LA-source concentration at short reaction times) divided by the grams of metal added to the reaction. A short reaction time depends on the reaction conditions and typically reflects the time wherein the first 10 mol.% or less of the initially present LA-source are converted.
As used herein, the phrase "catalytic selectivity towards a specific useful compound" is defined (calculated) as ratio of the molar amount of the reactant (LA-source) converted to said compound (e.g. GVL) relative to the total molar amount of converted reactant (LA-source).
As used herein the term "catalytic productivity" is defined (calculated) as moles of desired product (e.g. GVL) per gram of metal per unit of time.
The term "impregnation" is also referred herein as "wet-impregnation".
Resistance to leaching can be determined by determining the concentration of metal in the liquid phase after set reaction time, e.g. an hour, a day or a week. The metal concentration can be determined by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectroscopy (ICP-OES).
The reaction conditions of the method for preparing the chemical compound from a levulinic acid source can be chosen dependent on the compound of interest, the levulinic acid source, the information disclosed herein, the cited prior art and references cited therein, common general knowledge and optionally a limited amount of testing.
Usually, the LA source is selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides. Angelica lactone is a preferred LA lactone. In particular, good results have been achieved with levulinic acid.
The reduction reaction for converting the LA source preferably is a hydrogenation reaction. Suitable reducing agents are preferably selected from the group of hydrogen, formic acid and formate salts, in particular a formate salt of formate and a monovalent cation, such as ammonium formate or sodium formate. Preferably GVL is formed in the hydrogenation reaction.
The reaction conditions for the hydrogenation reaction can be based on common general knowledge and the information provided in the present disclosure.
In particular, GVL is usually prepared at a temperature in the range of
25-250 °C, preferably at a temperature in the range of 120-230 °C, and more preferably at a temperature in the range of 180-220 °C.
In particular, GVL is usually prepared at a hydrogen pressure of 1-100 bar, preferably of 20-70 bar, in particular of 40-50 bar.
In case formic acid ("hydrogen formate") or a formate salt is used, the molar ratio of formate to the LA-source is typically at least about 1. The formate can be applied in any excess, but usually the ratio of formate to the LA-source is 1000 or less, in particular 100 or less, and more in particular 10 or less.
The amount of catalyst can be chosen based on common general knowledge, depending on the type of reactor system.
The GVL prepared in accordance with the invention can be used in the preparation of another compound.
In a specific embodiment, the GVL is subjected to a an acid or base catalysed ring-opening reaction to produce a mixture of pentenoic acids.
In a specific embodiment, the GVL is subjected to an acid or base- catalysed ring-opening reaction in the presence of an alcohol to produce a mixture of alkyl pentenoates, preferably methyl pentenoates.
In a specific embodiment, the GVL is subjected to an acid or base- catalysed ring-opening in the presence of ammonia to produce a mixture of pentenenitriles. In these mixtures the double bond can be in the 2-, the 3- or the 4- position. Where applicable, the double bond may be cis or trans. These ring opening reactions can be advantageously performed in the gas phase or in the liquid phase. In the latter case the ring-opening reaction can advantageously be executed as a reactive distillation.
In a specific embodiment, the GVL is subjected to an acid or base- catalyzed reaction with an aldehyde to form an alpha-alkylidene-gamma- valerolactone. Preferably, the aldehyde used is formaldehyde which when used in the reaction forms alpha-methylene-gamma-valerolactone.
In a specific embodiment, the GVL is subjected to a reaction with ammonia or an N-alkylamine to form 5-methyl-pyrrolidinone or N- alkyl- 5-methyl- pyrrolidinone. Preferably, the N-alkylamine used is methylamine, which when used in the reaction forms N-methyl-5-methyl-pyrrolidinone.
In a specific embodiment, the GVL is hydrogenated to form 1,5- pentanediol.
In a specific embodiment, the GVL is hydrogenated to form 2- methyltetrahydrofuran.
In a specific embodiment, the GVL is hydrogenated to form pentanoic acid.
In a specific embodiment, the LA-source is converted into a salt of 4- hydroxypentanoic acid or 4-hydroxypentanamide.
In a preferred embodiment, the invention relates to the use of gamma- valerolactone prepared in accordance with the invention in the production of a fuel; a monomer, in particular a monomer for the production of a poly amide; or a solvent. For instance GVL can be converted into methyltetrahydrofuran which is suitable for use as a solvent or a fuel.
Typically the catalyst of the invention comprises ruthenium and optionally one or more other metals.
In a specific embodiment, the metal essentially consists of ruthenium. Such a catalyst, in particular when obtained by an anion excess impregnation method, has been found to be advantageously suitable for converting an LA source to GVL due to its high catalytic activity and high selectivity towards GVL.
In another specific embodiment the metal catalyst comprises ruthenium and at least one other metal, preferably palladium or platinum. Ruthenium and the other metal(s) preferably form an alloy. A preferred alloy essentially consists of ruthenium and at least one of palladium and platinum. An alloy of ruthenium and palladium, in particular an alloy essentially consisting of ruthenium and palladium, has been found to be particularly advantageous due to its high catalytic activity and high selectivity toward GVL for a prolonged time.
The molar ratio of the total of the metals other than ruthenium (such as palladium or platinum) to ruthenium in this embodiment can be chosen within wide limits, usually in the range of 1:99 to 90: 10, in particular in the range of 5:95 to 80:20, and more in particular in the range of 20:80 to 70:30. If palladium is present, the ratio of palladium to ruthenium is preferably at least 10:90, in particular at least 30:70, and more in particular at least 40:60. In general, the higher the palladium content, the longer the catalyst maintains a satisfactory selectivity towards GVL.
The total metal concentration usually is in the range of 0.1-10 wt.%, in particular in the range of 0.5- 5 wt.%.
The metal catalyst usually contains at least 0.1 wt.% ruthenium, based on the total weight of metal(s) and support, preferably at least 0.3 wt.% ruthenium, in particular at least 0.5 wt.% ruthenium. The ruthenium content of the metal catalyst, based on the total weight of metal(s) and support usually is less than 10 wt.%, preferably 5 wt.% or less, in particular 2 wt.% or less.
The support preferably is a non-acidic or weakly acidic oxide. A weakly acidic support is in particular a support having an isoelectric point at a
temperature of 25 °C (hereafter "IEP") of more than 1.5, in particular of more than 3.5, and more in particular 3.9 or more. The IEP of the support usually is 14 or less. For example, the highly acidic metal oxide WO3 typically has an IEP of 0.2- 0.5. S1O2 has a lower acidity, its IEP typically being in the range of 1.7-3.5. For Zr02, the IEP typically is 4- 11, for Ti02 it typically is 3.9-8.2. Typically, the IEP of MgO is 12- 13. IEPs of many oxides are readily available in the art (Marek
Kosmulski, "Chemical Properties of Material Surfaces", Marcel Dekker, 2001).
Silica (S1O2) is a preferred non-metal oxide support for a metal catalyst of the invention. It has advantageous processing properties, such as pelletizing properties. In a specific embodiment, the supported metal catalyst is in the form of a pellet, and preferably comprises a metal catalyst on a silica support.
In particular, good results have been achieved with a metal oxide support. Titanium oxide and zirconium oxide are preferred metal oxide support materials. The oxide may be synthetic or a natural mineral. In an advantageous embodiment, the titanium oxide comprises anatase or rutile. In particular, good results have been achieved with a support comprising both anatase and rutile (70- 80 wt.% anatase and 30-20 wt.% rutile). Such a support is commercially available from Evonik (P25-Ti02)
An example of a non-acidic support material is magnesium oxide.
The size of the support material is not critical. Usually, when preparing the catalyst on support a particulate support is provided, such as a powder. In an advantageous embodiment for the preparation of the catalyst, the particles are microp articles (particles typically having a size < 1 mm, in particular in the range of 1-200 micrometer). After the catalyst has been prepared, it may be used as such or may be shaped in a desired form, e.g. pelletized.
In an embodiment, the metal catalyst on the support (i.e. including support) has a BET surface, as determined by N2 physisorption of at least 25 m2/g, in particular of at least 30 m2/g. Preferably the BET surface is at least 40 m2/g.
Usually, the BET surface is 800 m2/g or less, in particular 400 m2/g or less, more in particular 200 m2/g or less. In an embodiment, the BET surface is 75 m2/g or less, and in particular 60 m2/g or less. In particular for a Ti02 support, BET
advantageously is in the range of 20-75 m2/g, in particular in the range of 40-60 m2/g. In particular for a Zr02 support, BET advantageously is in the range of 50- 150 m2/g, in particular in the range of 75- 125 m2/g. In particular for a silica support, BET usually is in the range of 50-800 m2/g, in particular in the range of 50-400 m2/g.
In an advantageous embodiment, the metal on the support is present on the support surface in the form of nanop articles (particles with a size of typically less than 100 nm), and in particular in the form of metal clusters, deposited on the support. These metal clusters preferably have a particle size, as determined by TEM in the range of 0.5 to 10 nm.
It is further contemplated that - in an advantageous embodiment - a metal catalyst obtainable in accordance with the invention is characterisable by a relatively high abundance of metal clusters present on the support, more preferably clusters having a size of about 0.5 to 5 nm and/or a relatively low polydispersity with respect to the particle size distribution of the metal nano- particles. Without being bound by theory, it is contemplated that the excess anions - in particular chloride ions - stabilise relatively small ruthenium or ruthenium- palladium alloy nanop articles or clusters. Chloride is in particular considered favourable for realising a random alloy formation.
With respect to the metal catalyst, wherein the metal is an alloy, it is further contemplated that - in an advantageous embodiment - the metal-alloy is characterisable by an essentially homogeneous distribution of ruthenium and the other metal(s), in particular a random alloy structure, rather than e.g. a core-shell alloy which one would expect to perform differently. A homogeneous distribution and random alloy structure is determinable by XAFS or STEM, as illustrated by Figure 1. It has further been found that a metal catalyst wherein the metal is a metal alloy, in particular an alloy of ruthenium and palladium, the particle size stability of the metal particles is improved, compared to particles of a single metal, such as only ruthenium or only palladium.
In a method for preparing the metal catalyst on an oxide an a impregnation solution is provided comprising a precursor for the metal catalyst. The liquid phase is usually a highly polar solvent, such as an aqueous liquid. As
used herein "highly polar means" having about the same polarity as water or a higher polarity than water.
The metal precursor, such as the ruthenium precursor respectively the palladium precursor, usually is a metal salt dissolved in water or an aqueous liquid. Examples of metal salts are halogen salts (chloride, fluoride, iodide and bromide) and organic acid salts. Good results have been achieved with a chloride salt. Chloride has been found in particular to contribute to providing a catalyst with good catalytic properties. Preferably the impregnation solution is essentially free (less than 1 wt.%) of nitrates and/or sulphates. The total concentration of the metal ions is usually in the range of 1 mg metal ions/mL to 100 mg metal ions 1/mL, preferably in the range of 5 mg metal ions/mL to 10 mg metal ions /mL.
For preparing a catalyst with an improved catalytic property with respect to the reduction of an LA source, the impregnation solution preferably comprises an additional source of anions, in addition to the anions from the salt serving as the source for the metal ions which serve as the precursor for the catalytic metal and may be selected from the group of acids and salts of anions with volatile bases, in particular from the group of HC1, organic acids, ammonium chloride and salts of ammonium and an organic acid. In particular good results have been achieved with a chloride, in particular hydrochloric acid. A method wherein such an impregnation solution is used is called an anion excess
impregnation method. The concentration of the acid or salt of the anions and a volatile base, preferably is 10- 100 mL of a 0.1-10 M solution, in particular 15-30 mL of a 0.1 to 5 M solution, per 0.5 to 5 gram support.
The impregnation may be carried out in a manner known per se.
The support is advantageously mixed with the impregnation solution by agitation, for instance by vigorous stirring, e.g. using a magnetic bar/stirrer set-up above 900 rpm, whereby the mixing of support and impregnation liquid is effected. The impregnation can be carried out at any temperature between the melting point and the boiling point of the liquid phase, and is advantageously carried out at ambient temperature, e.g. at about 25 °C. During or after mixing of the support with the impregnation solution, the temperature is preferably raised to about 50-90 °C. This will allow evaporation of the solvent at a desired evaporation rate.
The drying may be carried out in a manner known per se. In particular good results have been achieved with a method wherein the slurry of support in the impregnation solution is dried in hot open air atmosphere typically at a
temperature in the range of 50-95 °C. The drying is preferably carried out whilst agitating the slurry, for instance by stirring or drying in a fluidized bed. The agitation is preferably vigorous enough to achieve intensive mixing of the contents of the slurry. The drying is usually continued until a visually dry product is obtained. The drying usually takes 24 hours or less, in particular 1-20 hours, more in particular 5-20 hours.
If desired, the dried product is ground, prior to reduction.
Advantageously, the dried impregnated oxide support is reduced without first having been subjected to a calcination step. Thus, in a preferred embodiment the catalyst is a non-calcined catalyst. As is generally known,
'reducing' means that the metal ions that are the precursor for the metal catalysts are reduced from the ionic state to the metallic state (oxidation state = 0). In the art, calcination is generally known as a heat treatment of a catalyst precursor in an oxidizing atmosphere (of variable composition) for variable amount of time and at a temperature sufficient to convert essentially all precursors into oxides, i.e. to remove essentially all anions except oxygen as well as any solvent molecules.
Reducing is preferably carried out using hydrogen, for instance 1-10 vol.% hydrogen in an inert gas, such as nitrogen, argon and/or helium. The reduction is preferably carried out at a temperature in the range of 250 °C to 600 °C. Preferably, the temperature is gradually raised until the desired maximum temperature is reached, in particular at a ramp-rate in the range of 1-5 °C/min. In particular within this range, an advantageous balance is reached between removing the anions, such as chloride ions, increasing the metal-support interaction and preventing the metal particles from sintering. A slower rate of ramping typically increases the dispersion of the metal particles within the catalyst.
The reduction is preferably carried out for a period of at least 1 h, in particular for a period of 2 h to 10 h.
The resultant metal catalyst on the metal oxide support is then allowed to cool.
The invention is illustrated by the following examples. Example 1 Ru catalyst Preparation of the catalyst
RuC (Acros Chemicals) was used as the ruthenium precursor and was dissolved in deionized water to form an aqueous precursor solution with a ruthenium concentration of 5.28 mg / mL.
The requisite amount of the precursor solution (1.89 mL for preparing a 1 wt.% Ru catalyst on support) was charged in to a clean 50 mL round bottomed flask fitted with a magnetic stirrer, after which the requisite amount of
concentrated HC1 (37.5%) was added and the volume finally adjusted to 25 mL to obtain a final HC1 concentration of 0.5 M in deionized water. The round bottom flask was submerged in a temperature controlled oil bath and the mixture was then agitated at 298 K using a hot plate stirrer (1200 rpm). After 15 min of stirring, 0.99 gram of the support (P25-Ti02, obtained from Evonik) was added slowly with constant stirring at 298 K for about 30 min.
After the completion of the support addition, the slurry was stirred vigorously at 298 K for about 30 min and then the oil bath temperature was raised to 333 K, stirred for 1 h and then finally heated to 358 K. The slurry was stirred at this temperature overnight until all the water had evaporated. The solid powder, denoted as the "dried sample" was ground thoroughly with a mortar and pestle and approximately 350 mg of this material was then reduced in a furnace at 723 K (approx. 2 K / min ramp rate) under a flow of 5 vol.% Lb / N2 (total flow: 420 mL/min ) for 4 h, without having been subjected to a calcination step. Finally the furnace was cooled rapidly to room temperature and the catalyst sample was used without any further modification.
The resultant catalyst contained a 1 wt.% metal (Ru) concentration on a 1 g production scale.
Method of testing the catalyst
Reactions were performed with 10 wt.% levulinic acid (6.0 g, 51.7 mmol) in dioxane (54 g) with 1 wt.% catalyst (0.6 g). The reactions were run in a 100 mL
Parr batch autoclave at a temperature of 473 K using a hydrogen pressure of 40 bar and a stirring speed of 1600 rpm. Before starting the reaction, the batch autoclave reactor was loaded with catalyst, substrate and solvent, purged three times with argon after which the reaction mixture was heated to reaction temperature and charged with Lb to 40 bar. 1 mL of solution was sampled at various intervals during the reaction. After the reaction, the autoclave was cooled to room temperature, the Lb was released and 2 wt.% anisole was added as an internal standard. The catalyst was separated by filtration and washed with acetone.
The reaction products were analyzed using a Shimadzu GC-2010A gas chromatograph equipped with a CP-WAX 57-CB column (25 m x 0.2 mm x 0.2 μιη) and FID detector. Products were identified with a GC-MS from Shimadzu with a CP-WAX 57CB column (30 m x 0.2 mm x 0.2 μπι). Results
The activity and selectivity of supported monometal Ru catalyst was found to be strongly influenced by both its preparation method and by alloying it with a second metal, such as Pd.
The 1 wt.% Ru/Ti02 catalyst prepared via the impregnation method according to the invention, using anion excess (as described herein above in these examples) proved to be very active when compared to a comparable 1 wt.% Ru/Ti02 catalysts prepared by standard wet impregnation (WI), as described in 'Luo, W. et al. Journal of Catalysis 301 (2013) 175-186'.
The Ru catalyst according to the invention gave full conversion after 40 min with 99.0 mol.% selectivity to GVL (0.1 mol.% MTHF and 0.1 mol.% PD as a byproduct); cf. 43.3 mol.% conversion after 40 min for the comparative Ru catalyst (WI), and 99.5 mol.% selectivity to GVL.
The productivity of the Ru/Ti02 catalyst according to the invention was 16.4 molcvL . g metai 1 . hr1, thus outperforming the catalysts listed in a recent LA hydrogenation review paper (Wright, W.R.H. et al. ChemSusChem 5 (2012) 1657- 1667). This Ru/Ti02 catalyst according to the invention was very active and gave excellent selectivity at short reaction times of 40 min. At longer reaction times,
however, consecutive reactions took place causing a drop in selectivity and mass balance after 2 h (selectivity: 93.0 mol.% GVL, 1.2 mol.% PD, 0.7 mol.% MTHF).
The catalyst according to the invention showed very limited leaching (i.e. loss of 0.5 wt.% loss of the total amount of ruthenium originally present after 10 h in neat LA) and very limited sintering was observed.
Example 2
PdC salt (Sigma Aldrich) was dissolved in deionized water to form an aqueous precursor solution with a resultant palladium concentration of 3.02 mg / mL. This solution was slowly cooled and used as the palladium precursor solution. This solution was used together with the Ru precursor solution of Example 1 in amounts to provide a molar ratio of Ru:Pd of 1:1. The requisite amount of the precursor solution was charged in to a clean 50 mL round bottomed flask fitted with a magnetic stirrer, after which the requisite amount of concentrated HCl
(37.5%) was added and the volume finally adjusted to 25 mL to obtain a final HCl concentration of 0.5 M in deionized water. Method conditions were further the same as in Example 1. A RuPd on Ti02 catalyst was obtained, comprising 1 wt.% of the Ru-Pd alloy (molar ratio Ru:Pd 1: 1).
Results
The Ru-Pd metal alloy catalyst was found to have a high activity (i.e. full conversion after 30 min, 99.6 mol.% selectivity to GVL, 0.1 mol.% PD, 0.3 mol.% MTHF; note that this is at only 0.49 wt.% Ru metal loading), and stayed completely selective also at longer reaction times (1 h, sel. 99.2 mol.% GVL, 0.2 mol.% PD, 0.4 mol.% MTHF, 0.1 mol.% PA) The productivity of the RuPd/Ti02 catalyst was 17.2 molcvL . gmetai 1 . hr1.
This catalyst was also compared with a catalyst, prepared with the same method as described in Example 1, except that all Ru was replaced by Pd. This Pd/Ti02 catalyst shows negligible activity with respect to the conversion of levulinic acid.
Characterization of the catalyst
Figure 1 shows a STEM - EDX mapping of a RuPd catalyst prepared according to Example 2 (molar ratio of Ru:Pd of 1: 1). Details about the mapping can be found in "Aberration Corrected Analytical Electron Microscopy Studies Of Bimetallic Nanopar tides", A.A. Herzing, M.Watanabe, C.J.Kiely, J.Edwards,
M.Conte, Z.R.Tang and G.J.Hutchings, Faraday Discussions 138 (2008) 337-351 or "Nanostructural and Chemical Characterization of Supported Metal Oxide
Catalysts by Aberration Corrected Analytical Electron Microscopy", W. Zhou, I. E. Wachs, C. J. Kiely, Current Opinion in Solid State and Materials Science 16 (2012) 10-22. The images are STEM high angle annular dark field (HAADF) images of the metallic particles obtained using an aberration corrected JEM ARM-200F STEM operating at 200 kV. X-ray energy dispersive (XEDS) spectra were acquired from individual nanoparticles larger than 1 nm in size by rastering the beam over the entire particle, while using a JEOL Centurio 0.9sr silicon drift detector.
Example 3
The performance of the RuPd catalyst of Example 2 and the Ru catalyst of Example 1 (both prepared with an metal ion impregnation method with anion excess of the invention) were compared.
Selectivity
Figure-2 shows that the GVL yield (A), was stable for several hours even after reaching quantitative conversion when the bimetallic catalyst was used. However, in the case of monometallic metallic 1 wt%Ru/Ti02 catalyst (·), the GVL yield started to drop after reaching a maximum of 99.0%. This is because of the further hydrogenation of the product GVL to 1,4-pentanediol (PD) and
methyltetrahydrofuran (MTHF).
This clearly demonstrates the advantages of catalysts preparable by the impregnation method with anion excess, and in particular of the bimetallic RuPd catalyst for suppressing the un-wanted consecutive reactions and thereby increasing the yield of the most wanted product (GVL).
Particle Size, Stability and Reusability
Figure -3 shows the results from the TEM measurements of the metal particle sizes for the fresh (white bars) and spent (grey bars) monometallic (Ru or Pd) and bimetallic (Ru-Pd) catalysts, made with a method of the invention. From the figure it is evident that the metal particle sizes increased when the monometallic catalysts were used once. However, the particle sizes remained the same for the bimetallic catalysts even after 3 runs (grey, hatched bar). This shows that alloying Pd with Ru substantially helps in stabilizing the small particle for several cycles. This stability of the small particles, in the case of bimetallic catalysts, resulted in the catalytic activity of the recovered catalysts. Figure-4 shows the catalytic activity of the fresh and recovered bimetallic catalysts. The activity and selectivity (thus the yield of GVL) was stable for at least 3 catalytic runs. Thus, it is concluded that alloying Pd with Ru substantially influences the selectivity, stability and reusability of the catalyst for the hydrogenation of LA to GVL.
Claims
1. Method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal catalyst on a support is obtainable by an metal- ion impregnation method, which metal-ion impregnation method uses an anion- excess, and wherein the metal comprises ruthenium.
2. Method according to claim 1, wherein the metal essentially consists of ruthenium.
3. Method according to claim 1, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium.
4. Method according to any of the preceding claims, wherein the support is a non-acidic or weakly acidic metal oxide, preferably a titanium oxide or a zirconium oxide, in particular a titanium oxide comprising at least one titanium oxide selected from the group of anatase and rutile.
5. Method according to any of the claims 1-3, wherein the support is a silica.
6. Method according to any of the preceding claims, wherein the reduction reaction catalysed by the catalyst is a hydrogenation reaction, preferably a hydrogenation reaction wherein a reducing agent is selected from the group of hydrogen, formic acid and formate salts is used.
7. Method according to claim 6, wherein gamma- valerolactone, a salt of 4- hydroxypentanoic acid or 4-hydroxypentanamide is formed in the hydrogenation reaction.
8. Method according to claim 7, wherein gamma-valerolactone is converted into a fuel component; a monomer, in particular a monomer for the production of a polyamide; or a solvent.
9. Method according to claim 7 or 8, wherein gamma-valerolactone is in a specific embodiment, subjected to a further reaction step selected from:
- an acid or base catalysed ring-opening reaction to produce a mixture of pentenoic acids;
- an acid or base-catalysed ring-opening reaction in the presence of an alcohol to produce a mixture of alkyl pentenoates, preferably methyl pentenoates;
- an acid or base-catalysed ring-opening reaction in the presence of ammonia to produce a mixture of pentenenitriles;
- an acid or base-catalyzed reaction with an aldehyde to form an alpha- alkylidene-gamma-valerolactone , wherein preferably the aldehyde is formaldehyde, which when used in the reaction forms alpha-methylene- gamma-valerolactone;
- a reaction with ammonia or an N-alkylamine to form 5-methyl- pyrrolidinone or N- alkyl- 5-methyl-pyrrolidinone, wherein preferably the N- alkylamine is methylamine, which when used in the reaction forms N- me thyl - 5 - methyl-p yr roli dinone ;
- a hydrogenation reaction to form 1,5-pentanediol;
- a hydrogenation reaction to form 2-methyltetrahydrofuran; and,
- a hydrogenation reaction to form pentanoic acid.
10. Method according to any of the preceding claims, wherein the catalyst is non-calcined.
11. Method according to any of the preceding claims, wherein the metal catalyst on the support has a productivity in the hydrogenation of levulinic acid to gamma-valerolactone of at least 10 molcvL . gmetai"1 . hr1, preferably of at least 15 molcvL . gmetai 1 . hr1, and, in particular wherein the productivity is 15-75 molcvL . gmetai" 1 . hr"1.
12. Metal catalyst on an oxide support, wherein the metal comprises ruthenium and wherein the metal catalyst is obtainable by an anion excess impregnation method, the catalyst preferably having a productivity in the hydrogenation of levulinic acid to gamma-valerolactone of at least 10 molcvL . gmetai" 1 . hr 1, preferably of at least 15 molcvL . gmetai 1 . hr 1,; and in particular is 15-75 molcVL . gmetai"1 . hr"1.
13. Metal catalyst on an oxide support according to claim 12, wherein the support is a non-acidic or weakly acidic metal oxide.
14. Metal catalyst on an oxide support according to claim 12 or 13, wherein the support is titanium oxide.
15. Metal catalyst on an oxide support according to claim 14, wherein the support is a titanium oxide comprising at least one titanium oxide selected from the group of anatase and rutile.
16. Metal catalyst on an oxide support according to claim 12 or 13, wherein the support is a zirconium oxide,
17. Metal catalyst on an oxide support according to claim 12 or 13, wherein the support is a silica.
18. Metal catalyst on an oxide support according to any of the claim 12-17, wherein the metal essentially consists of ruthenium or wherein the metal is an alloy of ruthenium and at least one metal selected from the group of platinum and palladium.
19. Metal catalyst on an oxide support according to claim 18, wherein the metal is a metal alloy of ruthenium and palladium.
20. Metal catalyst on an oxide support according to any of the claims 12- 19, having a BET surface, as determined by N2 physisorption, in the range of
25-800 m2/g, in particular of 30-400 m2/g, more in particular of 40-200 m2/g.
21. Metal catalyst on an oxide support according to claim 20, having a BET surface, as determined by N2 physisorption, in the range of 40-60 m2/g.
22. Method for preparing a metal catalyst on an oxide support, comprising
- providing a impregnation solution comprising a precursor for the metal catalyst - i.e. metal ions, including ruthenium ions, plus counter -anions for the metal ions (in an amount sufficient to maintain the electrochemical balance of the precursor) and an additional source of anions, i.e. the excess anions (together with counter-cations in an amount to maintain the electrochemical balance of the additional source of anions);
- providing an oxide support, in particular a metal oxide support;
- impregnating the oxide support with the impregnation solution;
- drying the oxide support impregnated with the impregnation solution; and,
- reducing said metal ions present in or on the impregnated oxide support, thereby forming the metal catalyst on the oxide support.
23. Method according to claim 22, wherein the catalyst has a productivity in the hydrogenation of levulinic acid to gamma- valerolactone of at least 10 molcvL . gmetai 1 . hr1, preferably of at least 15 molcvL . gmetai" 1 . hr1, and in particular is 15- 75 molcVL . gmetai" 1 . hr"1.
24. Method according to claim 22 or 23, wherein the support and/or the metal are as defined in any of the claims 13-21.
25. Method according to claim 22 or 23, wherein the support is titanium oxide, wherein the metal essentially consists of ruthenium.
26. Method according to claim 22 or 23, wherein the support is titanium oxide, and the metal is an alloy of ruthenium and at least one metal selected from the group of platinum and palladium.
27. Method according to claim 26, wherein the metal is a metal alloy of ruthenium and palladium.
28. Method according to any of the claims 22-27, wherein said metal ions on the dried impregnated oxide support are reduced without the impregnated oxide support having been subjected to calcination.
29. Method according to any of the claims 22-28, wherein the precursor is a chloride salt and/or wherein the additional source of anions is provided as hydrochloric acid.
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