EP3066069A1 - Method for synthesising esters and catalyst for said synthesis - Google Patents
Method for synthesising esters and catalyst for said synthesisInfo
- Publication number
- EP3066069A1 EP3066069A1 EP14806021.3A EP14806021A EP3066069A1 EP 3066069 A1 EP3066069 A1 EP 3066069A1 EP 14806021 A EP14806021 A EP 14806021A EP 3066069 A1 EP3066069 A1 EP 3066069A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- alcohol
- catalyst
- synthesis
- ppm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 41
- 150000002148 esters Chemical class 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims description 42
- 230000015572 biosynthetic process Effects 0.000 title claims description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- -1 octanol- 1-ol Chemical compound 0.000 claims description 13
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 239000012429 reaction media Substances 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960000735 docosanol Drugs 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940043348 myristyl alcohol Drugs 0.000 claims description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960001109 policosanol Drugs 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229940012831 stearyl alcohol Drugs 0.000 claims description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 14
- 230000008878 coupling Effects 0.000 abstract description 13
- 238000010168 coupling process Methods 0.000 abstract description 13
- 150000001298 alcohols Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- 238000012417 linear regression Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- MUALQNISLTWHQC-UHFFFAOYSA-N bis(2-dicyclohexylphosphanylethyl)azanide ruthenium(2+) Chemical compound C1(CCCCC1)P(CCN(CCP(C1CCCCC1)C1CCCCC1)[Ru+])C1CCCCC1 MUALQNISLTWHQC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WCXCSMJYCFMAKS-UHFFFAOYSA-N bis(2-dipropylphosphanylethyl)azanide ruthenium(2+) Chemical compound C(CC)P(CCN(CCP(CCC)CCC)[Ru+])CCC WCXCSMJYCFMAKS-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- NDWFDLCIEWNKGN-UHFFFAOYSA-N butan-1-ol;butyl butanoate Chemical compound CCCCO.CCCCOC(=O)CCC NDWFDLCIEWNKGN-UHFFFAOYSA-N 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940078812 myristyl myristate Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- YEUGYZMSJJSMMP-UHFFFAOYSA-N ruthenium(2+);triphenylphosphane Chemical compound [Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YEUGYZMSJJSMMP-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- DZKXJUASMGQEMA-UHFFFAOYSA-N tetradecyl tetradecanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCC DZKXJUASMGQEMA-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LONVIDHKZOSXFR-UHFFFAOYSA-N C1(CCCCC1)P(CC[Ru]N)C1CCCCC1 Chemical compound C1(CCCCC1)P(CC[Ru]N)C1CCCCC1 LONVIDHKZOSXFR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UOZHTFJSZUJPOM-UHFFFAOYSA-N bis(2-diphenylphosphanylethyl)azanide ruthenium(1+) Chemical compound C1(=CC=CC=C1)P(CCN(CCP(C1=CC=CC=C1)C1=CC=CC=C1)[Ru])C1=CC=CC=C1 UOZHTFJSZUJPOM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GQFWSAKCCNATEV-UHFFFAOYSA-M carbon monoxide chlororuthenium 2-diphenylphosphanyl-N-(2-diphenylphosphanylethyl)ethanamine Chemical compound [O+]#[C-].[Ru]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCNCCP(C=1C=CC=CC=1)C1=CC=CC=C1 GQFWSAKCCNATEV-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002366 time-of-flight method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Definitions
- the invention relates to a process for synthesizing esters from starting materials, preferably biosourced, by dehydrogenating coupling in the presence of a catalyst.
- the starting materials can be biosourced alcohols such as fatty alcohols and / or polyols (for example glycerol) derived from oleaginous plants, or else be alcohols produced by fermentation of the biomass (for example ethanol and butanol). ).
- biosourced alcohols such as fatty alcohols and / or polyols (for example glycerol) derived from oleaginous plants, or else be alcohols produced by fermentation of the biomass (for example ethanol and butanol).
- esters and in particular ethyl acetate, are synthesized on an industrial scale using starting materials of fossil origin (ethylene in the case of ethyl acetate) via multi-process methods. steps.
- the global market for ethyl acetate was 2.5 million tonnes / year in 2008.
- ruthenium-based catalyst it is known to use a ruthenium-based catalyst to carry out the dehydrogenating coupling of ethanol using, for example, carbonylchlorohydrido [bis (2-diphenylphosphinoethyl) amino] ruthenium (II), of formula A (CAS: 1295649- 40-9), Trade Name: Ru-MACHO, or D (see below) (see M. Nielsen, H. Junge, A. Kammer and M. Aries, Angew Chem Int., Ed., 2012, 51, 5711-5713 and EP2599544A1) or irans-RuCl2 (PPh3) [PyCH2NH (CH2) 2PPh2], of formula B (see D. Spasyuk and D.
- Another catalyst used for this same reaction is the catalyst carbonylhydrido (tetrahydroborato) [bis (2-diphenylphosphinoethyl) amino] ruthenium (II), of formula C (CAS: 1295649-41 -0), Trade Name: Ru-MACHO-BH .
- This reaction is described in the patent application WO2012 / 144650 where this synthesis requires the presence of a hydrogen acceptor such as a ketone, for example, 3-pentanone.
- 3-pentanone acts as a hydrogen acceptor. So a quantity at least The stoichiometric 3-pentanone is used in the examples and the reactions described are therefore not accompanied by the evolution of gaseous hydrogen.
- ruthenium-based catalyst for carrying out the dehydrogenating coupling of butanol using, for example, trans-RuH 2 (CO) [HN (C 2 H 4 P / ' Pr 2) 2], of formula D, (M. Bertoli, A. Choualeb, AJ Lough, Moore B., D. Spasyuk and D. Gusev, Organometallics, 2011, 30, 3479-3482) or [RuH (PNN) (CO)], of formula E (cf. J. Zhang, G. Leitus, Y. Ben-David and D. Milstein, J. Am Chem Soc, 2005, 727, 10840-10841) in the presence of solvent and in the absence of base and acceptor. 'hydrogen.
- these catalysts require long reaction times and high catalytic loads to obtain yields of up to 90% in summer.
- the invention relates to a process for the synthesis of an ester from an alcohol which comprises the use of a catalyst of formula 1 below, in the absence of ketones, aldehydes, alkenes alkynes, soda, EtONa, MeONa or BuOK.
- a catalyst of formula 1 below, in the absence of ketones, aldehydes, alkenes alkynes, soda, EtONa, MeONa or BuOK.
- R identical or different, being an alkyl or aryl group, and more particularly a phenyl, isopropyl or cyclohexyl group and:
- Z is either a hydrogen atom or an HBH3 group, preferably Z is an HBH3 group;
- R is a phenyl group
- Z is either a hydrogen atom or an HBH3 group
- R when R is a cyclohexyl group, Z is either a hydrogen atom or an HBH3 group;
- Y is a CO carbonyl group.
- Y may be a phosphine PR'3, where R 'is a C1-C12 alkyl or C6-C12 aryl group, more particularly a methyl, ethyl, / -propyl or phenyl group.
- said synthesis is carried out in the absence of a hydrogen acceptor compound and in the absence of base. This synthesis is therefore carried out without external addition of these compounds.
- the invention relates to a method comprising the following step (s):
- hydrogen acceptor refers to organic compounds that are capable of reacting with molecular hydrogen, H2, to form a novel compound under the reaction conditions of ester synthesis.
- H2 molecular hydrogen
- it may be compounds such as ketones, aldehydes, alkenes and alkynes.
- the method according to the invention also makes it possible to obtain gaseous molecular hydrogen. It separates from the reaction medium by simple phase separation and can be evacuated and / or collected directly.
- base refers to a compound capable of capturing one or more protons.
- base particularly refers to bases such as sodium hydroxide or alkoxylated alkali metal salts, in particular EtONa, MeONa or BuOK.
- the reaction is carried out in the absence of toluene or xylene and in particular in the absence of solvent.
- solvent denotes a substance, liquid at its temperature of use, which has the property of dissolving, diluting or extracting the alcohols and / or, optionally, the catalyst, without chemically modifying them under the reaction conditions of the synthesis. esters.
- a solvent does not itself change under the conditions of the reaction in which it participates. . It can be compounds such as water, inorganic solvents, and organic solvents of hydrocarbon, oxygenated, and halogenated type.
- solvent in the absence of which the reaction is carried out can obviously also be a hydrogen acceptor and / or a base.
- solvent refers especially to ketones, such as 3-pentanone, acetone or cyclohexanone. It also denotes aromatic or aliphatic hydrocarbon compounds, optionally halogenated, ethers and alcohols.
- the expression "in the absence of” is used in its normal meaning which implies the absence in the initial reaction mixture of a sufficient quantity of the compound to play an effective role in the reaction as well as the absence of external addition. of this compound during the reaction.
- the presence in the reaction medium of a small amount (for example in the form of a trace) of a hydrogen acceptor, a base or a solvent will not influence the reaction substantially.
- the absence of solvent implies the absence of an amount sufficient to dissolve / dilute / extract the starting product (s) (ie the alcohol (s)) and the catalyst.
- this amount is generally greater than the numbers of moles of reagents, that is to say that the solvent is generally present in the reaction medium in a molar concentration greater than or equal to 50%.
- the expression "absence of” implies a molar concentration of said compound less than 10%, and more particularly less than 5%, or even its total absence, that is to say less than 0.001%.
- the catalyst charge used in the process according to the invention is less than 10000 ppm, more particularly less than 1000 ppm, even more particularly less than 500 ppm.
- This charge may be for example about 50 ⁇ 10 ppm.
- the catalyst charge used in the process according to the invention is chosen from a range of from 10000 ppm to 1 ppm, more particularly from 1000 ppm to 10 ppm and even more particularly from 500 ppm to 50 ppm.
- This charge may be for example about 225 ⁇ 10 ppm.
- the above proportions are given in relation to the molar amount of the starting materials.
- the temperature of the reaction medium is chosen from a temperature range of from 200 ° C. to 15 ° C., more particularly from 150 ° C. to 40 ° C. and even more particularly from 130 ° C. to 80 ° C. This temperature may be about 130 ⁇ 1 ° C.
- the reaction is carried out at a pressure ranging from 20 bar to 1 bar.
- a pressure ranging from 20 bar to 1 bar.
- no particular pressure is applied and the reaction is carried out at atmospheric pressure and / or in an open system.
- the alcohol reacted with the catalyst of formula 1 is a primary alcohol.
- the alcohol reacted with the catalyst of formula 1 is a primary alcohol, branched or unbranched, C1 to C30, in particular C2 to C6 or C8 to C22 and more particularly C16 to C18.
- it may be selected from the group consisting of ethanol, butanol, octanol-1-ol, 2-ethyl-1-hexanol, nonan-1-ol, decan-1-ol, and the like.
- the alcohol reacted with the catalyst of formula 1 is an alcohol where n is ⁇ 6, preferably the carbon number of this fatty alcohol is an even number and n>12;
- the starting compound (alcohol) may be present alone or in admixture with other reactants (i.e. other alcohols).
- the starting compound can be used in purified form or in crude form, in particular unrefined, this in particular when the compound is obtained from vegetable oils (eg oleaginous).
- a crude alcohol is generally a composition, for example a distillate, comprising not more than 90%, preferably not more than 80%, for example not more than 70% by volume of alcohol with respect to the total volume of the composition.
- the starting material may be a composition comprising less than 95%, preferably less than 85%, for example less than 75% by volume of alcohol relative to the total volume of the composition.
- the process is carried out in the absence of any additive (other than the catalyst) which may have an effect on the coupling reaction of alcohol and / or the production of molecular hydrogen.
- the process does not comprise a step of drying and / or degassing of the alcohols.
- the catalyst and particularly the catalysts where Z is HBH3 such as Ru-MACHO-BH, Formula C)) remains active in the presence of air and traces of water.
- the catalyst is preferably a catalyst of formula 1 in which the four R radicals are identical.
- the catalyst is preferably a catalyst of formula 1, in which Z is ⁇ 3 and / or Y is a CO radical and R is phenyl radicals.
- the catalyst used is a catalyst of formula 1 in which the Z group is H and the Y group is a phosphine PR'3 where R 'is a C 1 -C 12 alkyl or C 6 aryl group. -C12, in particular a methyl, ethyl, isopropyl or phenyl group.
- the catalyst is the catalyst of Formula
- the invention also relates to the catalysts described in this application as such as well as to their manufacturing processes.
- a complex of formula 1c, 1b, 6a and 6c, and a complex of the same formula wherein the carbonyl substituent is substituted by a phosphine is an object of the invention.
- Their uses in catalytic synthesis processes as well as such processes are also objects of the invention.
- Catalytic synthesis processes may be hydrogenation, amine amination, amide synthesis or Guerbet reactions.
- the invention also relates to an ester obtained directly by the method described above. Brief description of the drawings
- FIG. 1 represents the evolution of the yield of ethyl acetate (FIG. 1 a) and of the TON (FIG. 1b) as a function of time for the dehydrogenating coupling of ethanol for different catalyst loads C according to example 1 at.
- FIG. 3 represents the evolution of the yield of the synthesis according to the invention of Example 1 c in ester (butyl butyrate) (FIGURE 3a) and TON (FIGURE 3b) as a function of time.
- FIG. 4 represents the evolution of the yield of the synthesis according to the invention of Example 1 d in ester (butyl butyrate) (FIGURE 4a) and TON (FIGURE 4b) as a function of time.
- FIGURE 5 shows the evolution of the yield of the synthesis according to the invention of Example 1 e in ester (butyl butyrate) (FIGURE 5a) and TON (FIGURE 5b) as a function of time.
- FIG. 6 represents the evolution of the TON and yield of myristyl myristate as a function of time for the dehydrogenating coupling of tetradecanol according to the invention described in Example 2.
- Example 1 a Synthesis of ethyl acetate from ethanol according to one embodiment of the invention using a catalyst of formula C:
- the samples are analyzed by gas chromatography equipped with a flame ionization detector (GC-FID, Agilent Technologies 7890A, GC System, Zebron ZB-Bioethanol column) for the determination of conversion and selectivity of the reaction and than material balance.
- GC-FID flame ionization detector
- MS mass spectrometer detector
- Coupling of ethanol to ethyl acetate in the presence of catalyst C proceeds to high speed, with the product ethyl acetate and traces of acetaldehyde ( ⁇ 1%).
- the coupling of ethanol to ethyl acetate was studied for two different catalyst loads C, 50 and 500 ppm (Table II, Figure 1).
- the dehydrogenating coupling of ethanol can be carried out with a low catalyst load, e.g. 50 ppm. Under these conditions, TOFo of the order of 500 h -1 are obtained and a TON greater than 6000 after 26 h of reaction is subsequently observed.
- 3-pentanone acts as a hydrogen acceptor.
- at least one stoichiometric amount of hydrogen acceptor (of solvent) is used in the examples of the literature and the reaction is therefore not accompanied by the release of two molecules of hydrogen per molecule of ester produced as in process of the invention wherein the hydrogen gas is released from the reaction medium.
- Example 1 c Synthesis of butyl butyrate according to one embodiment of the invention and according to equation 2 (above) using a catalyst of formula 6c:
- the catalyst 6c is active for the dehydrogenation esterification of butanol the absence of base and hydrogen acceptor.
- Example 1 d Synthesis of butyl butyrate according to one embodiment of the invention and according to equation 2 (above) using a catalyst of formula 1 b:
- Example 1a The samples are analyzed in the same manner as for Example 1a and the results compared with those of the pure products. The results obtained are compiled in Table VI and shown in Figures 4a and 4b.
- the catalyst 1b is active for the dehydrogenation esterification of butanol n the absence of solvent, base and hydrogen acceptor.
- Example 1e Synthesis of butyl butyrate according to one embodiment of the invention and according to equation 2 (above) using a catalyst of formula 1c:
- the catalyst 1c is active for the dehydrogenation esterification of butanol in the absence of solvent, base and hydrogen acceptor.
- NMR 31 P ⁇ 1 H ⁇ (CD2CI2, 121, 5 MHz): ⁇ . 74.7 ppm. 1 H NMR and 31 P in agreement with the spectral data of the literature. See: Bertoli, M .; Choualeb, A .; Lough, AJ; Moore B .; Spasyuk, D .; Gusev DG Organometallics, 2011, 30, 3479.
- the white residue obtained is extracted with dichloromethane (3 ⁇ 5 ml) and filtered on sintered glass. The filtrate is then concentrated under reduced pressure (room temperature, 1 ⁇ 10 -3 mbar) to give the desired product as a white powder (30 mg, yield: 62%).
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1360981A FR3013046B1 (en) | 2013-11-08 | 2013-11-08 | METHOD FOR SYNTHESIZING ESTERS AND CATALYST OF SAID SYNTHESIS |
PCT/FR2014/052839 WO2015067899A1 (en) | 2013-11-08 | 2014-11-06 | Method for synthesising esters and catalyst for said synthesis |
Publications (1)
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EP3066069A1 true EP3066069A1 (en) | 2016-09-14 |
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EP14806021.3A Withdrawn EP3066069A1 (en) | 2013-11-08 | 2014-11-06 | Method for synthesising esters and catalyst for said synthesis |
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US (1) | US20160288111A1 (en) |
EP (1) | EP3066069A1 (en) |
JP (1) | JP2016537420A (en) |
BR (1) | BR112016010239A2 (en) |
CA (1) | CA2929462A1 (en) |
FR (1) | FR3013046B1 (en) |
WO (1) | WO2015067899A1 (en) |
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CA3000609C (en) * | 2015-09-30 | 2022-08-23 | Takasago International Corporation | Method for producing ruthenium complex |
JP6913635B2 (en) * | 2016-01-29 | 2021-08-04 | 高砂香料工業株式会社 | N, N-bis (2-dialkylphosphinoethyl) amine-borane complex and its production method, and method for producing a ruthenium complex using N, N-bis (2-dialkylphosphinoethyl) amine as a ligand. |
EP3737501A1 (en) * | 2018-01-10 | 2020-11-18 | Basf Se | Use of a ruthenium catalyst comprising a tetradentate ligand for hydrogenation of esters and/or formation of esters and a ruthenium complex comprising said tetradentate ligand |
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CN103492351B (en) * | 2011-04-22 | 2015-10-07 | 高砂香料工业株式会社 | By the ruthenium complex compound with tridentate ligand is used as the method that dehydrogenation oxidation Catalyst Production has the compound of carbonyl |
EP2599544A1 (en) * | 2011-12-01 | 2013-06-05 | Leibniz-Institut für Katalyse e.V. an der Universität Rostock | A process for producing alkyl esters by dehydrogenation of a primary alcohol using a homogenous catalyst system |
-
2013
- 2013-11-08 FR FR1360981A patent/FR3013046B1/en active Active
-
2014
- 2014-11-06 WO PCT/FR2014/052839 patent/WO2015067899A1/en active Application Filing
- 2014-11-06 JP JP2016552702A patent/JP2016537420A/en active Pending
- 2014-11-06 BR BR112016010239A patent/BR112016010239A2/en not_active IP Right Cessation
- 2014-11-06 CA CA2929462A patent/CA2929462A1/en not_active Abandoned
- 2014-11-06 EP EP14806021.3A patent/EP3066069A1/en not_active Withdrawn
- 2014-11-06 US US15/035,444 patent/US20160288111A1/en not_active Abandoned
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US20160288111A1 (en) | 2016-10-06 |
JP2016537420A (en) | 2016-12-01 |
BR112016010239A2 (en) | 2017-10-03 |
WO2015067899A1 (en) | 2015-05-14 |
CA2929462A1 (en) | 2015-05-14 |
FR3013046A1 (en) | 2015-05-15 |
FR3013046B1 (en) | 2015-11-06 |
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