EP3194332A1 - Dihydrogen production process - Google Patents
Dihydrogen production processInfo
- Publication number
- EP3194332A1 EP3194332A1 EP15762713.4A EP15762713A EP3194332A1 EP 3194332 A1 EP3194332 A1 EP 3194332A1 EP 15762713 A EP15762713 A EP 15762713A EP 3194332 A1 EP3194332 A1 EP 3194332A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bbn
- chosen
- tbd
- sncl
- formic acid
- 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- Withdrawn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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 140
- 235000019253 formic acid Nutrition 0.000 claims abstract description 71
- 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 abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 69
- 230000008569 process Effects 0.000 claims abstract description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 238000002485 combustion reaction Methods 0.000 claims abstract description 6
- 235000013305 food Nutrition 0.000 claims abstract description 6
- 238000005272 metallurgy Methods 0.000 claims abstract description 5
- 238000007670 refining Methods 0.000 claims abstract description 4
- -1 trityl cation Chemical class 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 57
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 22
- 150000007530 organic bases Chemical class 0.000 claims description 22
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000002841 Lewis acid Substances 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000007517 lewis acids Chemical class 0.000 claims description 15
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 claims description 14
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- PBBOKJIYEZCTEH-UHFFFAOYSA-N chloro(dicyclohexyl)borane Chemical compound C1CCCCC1B(Cl)C1CCCCC1 PBBOKJIYEZCTEH-UHFFFAOYSA-N 0.000 claims description 9
- AZYGEWXDKHFOKB-UHFFFAOYSA-N 2-chloro-1,3,2-benzodioxaborole Chemical compound C1=CC=C2OB(Cl)OC2=C1 AZYGEWXDKHFOKB-UHFFFAOYSA-N 0.000 claims description 8
- YAYIUFDUYUYPJC-UHFFFAOYSA-N 9-iodo-9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2I YAYIUFDUYUYPJC-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 125000006267 biphenyl group Chemical group 0.000 claims description 7
- 150000001639 boron compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- IQRBNRFCRAJXJF-UHFFFAOYSA-N 9-benzyl-9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2CC1=CC=CC=C1 IQRBNRFCRAJXJF-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 150000002291 germanium compounds Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000080 stannane Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 5
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 5
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims description 5
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 5
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 4
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 claims description 4
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000002484 inorganic compounds Chemical class 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 claims description 3
- BGLCFPWEIFATPF-UHFFFAOYSA-N cyclopropane Chemical compound C1C[CH+]1 BGLCFPWEIFATPF-UHFFFAOYSA-N 0.000 claims description 3
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- MXBZSBSKUMTJDH-UHFFFAOYSA-N 1,3-ditert-butylimidazol-1-ium Chemical compound CC(C)(C)N1C=C[N+](C(C)(C)C)=C1 MXBZSBSKUMTJDH-UHFFFAOYSA-N 0.000 claims description 2
- DFRWCJYSXGNOFD-UHFFFAOYSA-N 4,6,11-tri(propan-2-yl)-1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CN(C(C)C)P2N(C(C)C)CCN1CCN2C(C)C DFRWCJYSXGNOFD-UHFFFAOYSA-N 0.000 claims description 2
- WFHPXSHLCFHEIA-UHFFFAOYSA-N 4,6,11-tris(2-methylpropyl)-1,4,6,11-tetraza-5-phosphabicyclo[3.3.3]undecane Chemical compound C1CN(CC(C)C)P2N(CC(C)C)CCN1CCN2CC(C)C WFHPXSHLCFHEIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical class [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000005323 carbonate salts Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- NUDLYJBPZJQGBY-UHFFFAOYSA-N dihydroxy-methyl-diphenyl-lambda5-phosphane Chemical compound C=1C=CC=CC=1P(O)(O)(C)C1=CC=CC=C1 NUDLYJBPZJQGBY-UHFFFAOYSA-N 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- OAADXJFIBNEPLY-UHFFFAOYSA-N methoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OC)C1=CC=CC=C1 OAADXJFIBNEPLY-UHFFFAOYSA-N 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 claims description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- YYCADXIEDQKBBF-UHFFFAOYSA-N 1,3-ditert-butyl-4,5-dihydroimidazol-1-ium Chemical compound CC(C)(C)N1CC[N+](C(C)(C)C)=C1 YYCADXIEDQKBBF-UHFFFAOYSA-N 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical class [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 description 33
- 125000003545 alkoxy group Chemical group 0.000 description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 16
- 238000006356 dehydrogenation reaction Methods 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 125000002560 nitrile group Chemical group 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052768 actinide Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001723 carbon free-radicals Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 150000002169 ethanolamines Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical class C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SYSFTTYJTWPOOR-UHFFFAOYSA-N (2-diphenylphosphanyl-1-naphthalen-1-yl-3h-naphthalen-2-yl)-diphenylphosphane Chemical group C1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2)C1(P(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)C1=CC=CC=C1 SYSFTTYJTWPOOR-UHFFFAOYSA-N 0.000 description 1
- HBXRPXYBMZDIQL-UHFFFAOYSA-N 1$l^{2}-borolane Chemical compound [B]1CCCC1 HBXRPXYBMZDIQL-UHFFFAOYSA-N 0.000 description 1
- CENMEJUYOOMFFZ-UHFFFAOYSA-N 1,3,2-benzodioxaborole Chemical compound C1=CC=C2OBOC2=C1 CENMEJUYOOMFFZ-UHFFFAOYSA-N 0.000 description 1
- GONBKFIOUGPBTG-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-1-ium Chemical compound CC1=CC(C)=CC(C)=C1N1C=[N+](C=2C(=CC(C)=CC=2C)C)CC1 GONBKFIOUGPBTG-UHFFFAOYSA-N 0.000 description 1
- CSRGPERAJKNQMM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)imidazol-1-ium Chemical compound CC1=CC(C)=CC(C)=C1N1C=[N+](C=2C(=CC(C)=CC=2C)C)C=C1 CSRGPERAJKNQMM-UHFFFAOYSA-N 0.000 description 1
- SCEZRJLZOZKPBC-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]-4,5-dihydroimidazol-1-ium Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1C=[N+](C=2C(=CC=CC=2C(C)C)C(C)C)CC1 SCEZRJLZOZKPBC-UHFFFAOYSA-N 0.000 description 1
- FENRCIKTFREPGS-UHFFFAOYSA-N 1,3-ditert-butyl-2h-imidazol-1-ium-2-ide Chemical compound CC(C)(C)N1[C]N(C(C)(C)C)C=C1 FENRCIKTFREPGS-UHFFFAOYSA-N 0.000 description 1
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- FAJVCTREFNLKIW-UHFFFAOYSA-N 4,5-dichloro-1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-1-ium Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1C(Cl)=C(Cl)[N+](C=2C(=CC=CC=2C(C)C)C(C)C)=C1 FAJVCTREFNLKIW-UHFFFAOYSA-N 0.000 description 1
- IYDIZBOKVLHCQZ-UHFFFAOYSA-N 9-(9-borabicyclo[3.3.1]nonan-9-yl)-9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2B1C2CCCC1CCC2 IYDIZBOKVLHCQZ-UHFFFAOYSA-N 0.000 description 1
- NXHUKDCGEGEZCX-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonan-9-yl trifluoromethanesulfonate Chemical compound C1CCC2CCCC1B2OS(=O)(=O)C(F)(F)F NXHUKDCGEGEZCX-UHFFFAOYSA-N 0.000 description 1
- FYZDPIIMSZAKGP-UHFFFAOYSA-N 9-bromo-9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2Br FYZDPIIMSZAKGP-UHFFFAOYSA-N 0.000 description 1
- UPAXWIAOGNDSPP-UHFFFAOYSA-N 9-chloro-9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2Cl UPAXWIAOGNDSPP-UHFFFAOYSA-N 0.000 description 1
- FXQGHJNDNWMEMI-UHFFFAOYSA-N 9-fluoro-9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2F FXQGHJNDNWMEMI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000208152 Geranium Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910008433 SnCU Inorganic materials 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005334 azaindolyl group Chemical group N1N=C(C2=CC=CC=C12)* 0.000 description 1
- YGXMUPKIEHNBNQ-UHFFFAOYSA-J benzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.C1=CC=CC=C1.C1=CC=CC=C1 YGXMUPKIEHNBNQ-UHFFFAOYSA-J 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- BIOOXWXQBSHAMB-UHFFFAOYSA-N borinane Chemical compound B1CCCCC1 BIOOXWXQBSHAMB-UHFFFAOYSA-N 0.000 description 1
- XQIMLPCOVYNASM-UHFFFAOYSA-N borole Chemical compound B1C=CC=C1 XQIMLPCOVYNASM-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- ZDQWVKDDJDIVAL-UHFFFAOYSA-N catecholborane Chemical compound C1=CC=C2O[B]OC2=C1 ZDQWVKDDJDIVAL-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- XNYOSXARXANYPB-UHFFFAOYSA-N dicyclohexylborane Chemical compound C1CCCCC1BC1CCCCC1 XNYOSXARXANYPB-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 125000005469 ethylenyl group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000003965 isoxazolidinyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005470 propylenyl group Chemical group 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- KEFOZNJTQPJEOB-UHFFFAOYSA-N pyridine-2,3-diimine Chemical compound N=C1C=CC=NC1=N KEFOZNJTQPJEOB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide 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
- 239000011973 solid acid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000005458 thianyl group Chemical group 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- 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
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/063—Refinery processes
- C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/068—Ammonia synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a process for producing dihydrogen from formic acid.
- It also relates to the use of the dihydrogen produced by the process of the invention, in a fuel cell, in a combustion engine, in the production of ammonia and methanol, in petroleum refining, in the sectors of the metallurgy, electronics and food.
- the invention further relates to a method for producing energy, comprising a step of producing dihydrogen from formic acid by the process according to the invention.
- Hydrogen or H 2
- Hydrogen is an attractive fuel that is carbon-free and can be used to fuel fuel cells and serve as an alternative to fossil carbon fuels.
- Hydrogen can only play its role as an energy carrier if it can be stored efficiently, for a limited cost and under acceptable safety conditions.
- Dihydrogen is a gas characterized by a low density energy density (0.010 MJ / L), at atmospheric pressure (1 ⁇ 0.3 atm) and ambient temperature (20 ⁇ 5 ° C), compared in particular with diesel ( 38.6 MJ / L), the storage of H 2 in a dense liquid or solid form is then necessary to facilitate its transport and distribution. In this context, different storage routes are being studied. At atmospheric pressure (1 ⁇ 0.3 atm) and ambient temperature (20 ⁇ 5 ° C), a volume of 11 m 3 is required to store 1 kg dihydrogen.
- the metal hydrides for example MgH 2
- the storage of H 2 in the form of formic acid has many advantages because it makes it possible to reach a good density of dihydrogen (53 kgH 2 / m 3 ) at atmospheric pressure (1 ⁇ 0.3 atm) and ambient temperature (20 ⁇ 5 ° C).
- the formic acid is low in toxicity and non-corrosive in dilute medium, that is to say an aqueous medium containing at most 85% by volume of formic acid relative to the total volume of the medium.
- the dihydrogen thus stored is released by a dehydrogenation reaction of formic acid.
- the dehydrogenation reaction of formic acid requires the use of catalysts to accelerate the release of H 2 and CO 2 .
- the liberated dihydrogen can be used as fuel.
- the catalysts used in the dehydrogenation reactions of formic acid consist of complexes of metals such as ruthenium, platinum, rhodium or nickel, metals which are often expensive and / or toxic.
- metals such as ruthenium, platinum, rhodium or nickel
- metals which are often expensive and / or toxic.
- the technical challenge is to develop effective catalysts that overcome the problems of toxicity, availability and costs generally associated with H 2 and C0 2 .
- the dehydrogenation reaction of formic acid can also be carried out in a basic medium to improve the performance of the catalyst, for example by adding a stoichiometric amount of triethylamine (NEt 3 ) as shown in Scheme 2 or using an aqueous solution.
- NEt 3 triethylamine
- Catalysts known to promote the dehydrogenation reaction of formic acid are based on transition metal complexes or inorganic heterogeneous systems.
- a recent review (M. Grasemann, G. Laurenczy, Energ Environ Sci 2012, 5, pages 8171-8181) describes the state of the art and some examples of typical catalysts which are gathered below.
- Homogeneous phase catalyst systems known to promote the dehydrogenation reaction of formic acid are transition metal complexes.
- the first work in this area was carried out by Coffey which showed that the iridium complex IrH 2 Cl (PPh 3 ) 3 made it possible to obtain rotation frequencies or TOF (Turnover Frequency) of 1187 h -1 at a temperature of 100 to 117 ° C (RS Coffey, Chem, 1967, pages 923-924).
- TOF Teurnover Frequency
- the Aries group (A. Boddien, B. Loges, H. Junge, F. Gartner, JR Noyes, M. Aries, Adv Synth Synth 2009, 351, pages 2517-2520) has studied a large number of complexes. of ruthenium to catalyze the dehydrogenation of formic acid.
- Myers and Berben (TW Myers, LA Berben, Chem Sci, 2014, 5, pages 2771-2777) developed aluminum (III) complexes stabilized by bis-imino-pyridine ligands that have an initial maximal TOF. of 5200 h -1 for the dehydrogenation of formic acid, carried out at 65 ° C in THF, in the presence of triethylamine as additive.
- Heterogeneous catalysts have also been described in the literature to promote the catalytic dehydrogenation of formic acid. These are then metal systems, most often nanoparticles, used in the form of alloys or mono-metallic systems. This field of research has been the subject of recent reviews, available in the literature (S. Enthaler, J. von Langermann, T. Schmidt, Environ Energy Sci., 2010, 3, pages 1207-1217, M. Grasemann, G. Laurenczy, Energ Sci 2012, 5, pages 8171-8181).
- Group IIA alkaline earth metals from the Periodic Table of Elements (such as magnesium and calcium);
- Group IIIA metals namely, aluminum, gallium, indium and thallium.
- transition metals from Group IB to VIIIB of the Periodic Table of the Elements such as nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium, iridium;
- rare earths whose atomic number is between 57 and 71 (such as lanthanum, cerium, praseodymium, neodymium); or
- the present invention is specifically intended to meet these needs by providing a process for producing dihydrogen from formic acid, characterized in that the formic acid is contacted
- Lewis acids said Lewis acids being selected from organic or inorganic boron compounds, organic or inorganic silicon compounds, oxoniums, carbocations, organic or inorganic germanium compounds and organic or inorganic compounds tin; and eventually
- an organic base selected from nitrogenous organic bases, phosphorus organic bases, carbon bases, and oxygenated organic bases;
- the process of the invention makes it possible to produce dihydrogen with a variety of catalysts.
- the catalysts used in the process of the invention have the advantage of overcoming the toxicity problems generally observed for metal catalysts and cost problems associated with the use of precious metals.
- the catalyst used does not contain:
- Group IIIA metals selected from aluminum, gallium, indium and thallium.
- Group IB to VIIIB transition metals of the Periodic Table of Elements selected from nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium and, iridium;
- rare earths whose atomic number is between 57 and 71 chosen from lanthanum, cerium, praseodymium and neodymium); or
- the production of dihydrogen from formic acid by the process of the invention can also be accompanied by the concomitant production of C0 2 .
- the dihydrogen will be mixed with the carbon dioxide. This mixture can be used as it is or the dihydrogen and the carbon dioxide can be separated according to the methods known to those skilled in the art such as, for example, the separation H 2 / CO 2 by adsorption of CO 2 on ethanolamines or by separation. cryogenic.
- the CO2 thus formed can be used / recycled in the process of the invention as inerting gas or can be recovered in order to be converted into various chemical compounds, for example formic acid by the methods known to those skilled in the art, such as examples described by Morris, AJ, Meyer, GJ, Fujita, E.,
- catalyst within the meaning of the invention is meant any compound capable of modifying, in particular by increasing, the speed of the chemical reaction in which it participates, and which is regenerated at the end of the reaction.
- This definition encompasses both catalysts, that is, compounds that exert their catalytic activity without the need for any modification or conversion, and compounds (also called pre-catalysts) that are introduced into the medium. and converted therein to a catalyst.
- a cocatalyst is a compound which is not a catalyst but which, in combination with a catalyst, makes it possible to improve the catalytic activity of said catalyst.
- TON number of rotation
- TOF rotation frequency
- n o HCOOH
- HCOOH the amount of formic acid material, i.e., the number of moles of formic acid, at the start of the reaction
- end (HCOOH) corresponds to the amount of formic acid, that is to say the number of moles of formic acid, at the end of the reaction.
- TON and TOF the more efficient the catalyst.
- alkyl means a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms.
- linear or branched saturated alkyl there may be mentioned, for example, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl and dodecanyl radicals and their branched isomers.
- cyclic alkyl there may be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicylco [2,1,1] hexyl, bicyclo [2,2,1] heptyl.
- Unsaturated cyclic alkyls include, for example, cyclopentenyl and cyclohexenyl.
- alkenyl or “alkynyl” is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 1 to 12 carbon atoms comprising at least one double (alkenyl) or a triple bond (alkynyl) .
- alkenyl or “alkynyl” is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 1 to 12 carbon atoms comprising at least one double (alkenyl) or a triple bond (alkynyl) .
- alkenyl or “alkynyl” is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 1 to 12 carbon atoms comprising at least one double (alkenyl) or a triple bond (alkynyl) .
- alkenyl or “alkynyl” is meant a linear
- the alkyl, alkenyl and alkynyl group within the meaning of the invention, may be optionally substituted by one or more hydroxyl groups; one or more alkoxy groups; one or more siloxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO 2 ); one or more nitrile groups (-CN); one or more aryl groups, with the alkoxy and aryl groups as defined in the context of the present invention.
- aryl generally refers to a cyclic aromatic substituent having from 6 to 20 carbon atoms.
- the aryl group may be mono- or polycyclic.
- the aryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more "siloxy" groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more several nitro groups (-NO 2 ), one or more nitrile groups (-CN), one or more alkyl groups, with the alkoxy and alkyl groups as defined in the context of the present invention.
- heteroaryl generally denotes a mono- or polycyclic aromatic substituent comprising from 5 to 10 members, of which at least 2 are carbon atoms, and at least one heteroatom chosen from nitrogen, oxygen, boron and silicon. , phosphorus or sulfur.
- the heteroaryl group may be mono- or polycyclic.
- furyl benzofuranyl, pyrrolyl, indolyl, isoindolyl, azaindolyl, thiophenyl, benzothiophenyl, pyridyl, quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, pyrazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl and pyrimidilyl groups; , pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl.
- the heteroaryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (- ⁇ O 2 ). , one or more nitrile groups (-CN), one or more aryl groups, one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention.
- heterocycle generally refers to a saturated or initiated 5 to 10 membered mono- or polycyclic substituent containing from 1 to 4 heteroatoms selected independently of one another from nitrogen, oxygen, boron, silicon, phosphorus or sulfur.
- heteroatoms selected independently of one another from nitrogen, oxygen, boron, silicon, phosphorus or sulfur.
- the heterocycle may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more aryl groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more groups. nitro (-NO 2 ), one or more nitrile groups (-CN), one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention,
- alkoxy means an alkyl, alkenyl and alkynyl group, as defined above, bonded through an oxygen atom (-O-alkyl, O-alkenyl, O-alkynyl).
- amino group is meant a group of formula -NR 7 R 8 , in which: R 7 and R 8 represent, independently of one another, a hydrogen atom, an alkyl group, a group alkenyl, an alkynyl group, an aryl group, a heteroaryl group, a heterocycle, a silyl group, a siloxy group, with alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, silyl, siloxy, as defined in the context of the present invention; or ⁇ R 7 and R 8, taken together with the nitrogen atom to which they are bonded, form a heterocycle optionally substituted by one or more hydroxyl groups; one or more alkyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO- 2 ); one or more nitrile groups (-CN); one or more
- halogen atom is meant an atom chosen from fluorine, chlorine, bromine and iodine atoms.
- sioxy group is meant a silyl group, as defined below, linked by an oxygen atom (-O-Si (X) 3 ) with X as defined below.
- sil group is meant a group of formula [-Si (X) 3 ] in which each X, independently of one another, is selected from a hydrogen atom; one or more halogen atoms selected from fluorine, chlorine, bromine or iodine atoms; one or more alkyl groups; one or more alkoxy groups; one or more amino groups; one or more aryl groups; one or more siloxy groups; with the alkyl, alkoxy, aryl and siloxy groups as defined in the context of the present invention.
- the catalyst is (i) a Lewis acid, chosen from:
- organic or inorganic boron compounds chosen from organoboranes, haloboranes, alkoxyboranes, borinium cations, borenium cations, boronium cations, organoborates, said organic or inorganic boron compounds being advantageously chosen from BF 3 , BF 3 (Et 2 O), BCI 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane, Me-TBD- ⁇ + ⁇ , Me-TBD-BBN + CF 3 SO 3 -, (TDB-BBN)
- the organic or inorganic silicon compounds chosen from organosilanes, halosilanes, alkoxysilanes and silylium cations of formula (R 1 R 2 R 3 ) Si + with R 1 , R 2 and R 3 , independently of one of the other, representative a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic silicon compounds being advantageously chosen from SiCl 4 , Me 3 SiCl, and 3 Si + and Me 3 Si + ;
- the organic or inorganic divalent or tetravalent germanium compounds chosen from organogermans, halogenogermans, alkoxygermans and germanium cations of formula (R 9 R 10 R 11 ) Ge + with R 9 , R 10 and R 11 independently of one of the other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic geranium compounds being preferably chosen from GeCl 2 , GeBr 2 , GeCl 4 , Ge (OEt 2 ) 4 , Me 3 GeCl, Me 2 ClGe + , and 3 Ge + and Me 3 Ge + ;
- the organic or inorganic compounds of tin of oxidation degree + IV or + II chosen from stannous chloride derivatives the cations of formula R 20 Sn + with R 20 representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, organostannanes, halostannanes, alkoxystannanes, stannic cations of formula (R 12 R 13 R 14 ) Sn + with R 12 , R 13 , R 14 , independently of each other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic tin compounds being advantageously chosen from SnCl 2 , SnCl 4 , nBu 2 SnCl 2 , Cy 3 SnCl, Bu 3 SnHt
- the anionic counterion of the above-mentioned silylium cations, oxoniums, carbocations, cations and germanium cations is, advantageously, a halide chosen from F-, Cl-, Br- and ⁇ , or a chosen anion. from BF 4 -, SbF 6 -, B (C 6 F 5 ) 4 - 5 B (C 6 H 5 ) 4 - CF 3 S0 3 - or TfO and PF 6 -
- the catalyst is (i) a Lewis acid, chosen from:
- organic or inorganic boron compounds chosen from organoboranes, haloboranes, alkoxyboranes, borinium cations, borenium cations, boronium cations, organoborates, said organic or inorganic boron compounds being advantageously chosen from BF 3 , BF 3 (Et 2 0), BCI 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3, B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane, Me-TBD- BBN + I -, Me-TBD-BBN + CF 3 S0 3 -, (TDB-BBN
- the organic or inorganic divalent or tetravalent germanium compounds chosen from organogermans, halogenogermans, alkoxygermans and germanium cations of formula (R 9 R 10 R 11 ) Ge + with R 9 , R 10 and R 11 independently of one of the other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic germanium compounds being preferably chosen from GeCl 2 , GeBr 2 , GeCl 4 , Ge (OEt 2 ) 4s Me 3 GeCl, Me 2 ClGe + , and 3 Ge + and Me 3 Ge + ; and - organic or inorganic compounds of the oxidation state of the tin or + IV + II selected from derivatives of stannous chloride, the cation of the formula R 20 Sn + with R representing a hydrogen atom, an alkyl group,
- the anionic counterion of the above-mentioned germanium and stannous and stannous cations is, advantageously, a halide selected from F-, Cl-, Br- and l-, or an anion chosen from BF 4 -, SbF 6 -, B (C 6 F 5 ) 4 -, B (C 6 H 5 y, CF 3 SO 3 - or TfO and PF 6 -,
- the process for producing dihydrogen from formic acid is characterized in that the formic acid is brought into contact with at least one catalyst
- said catalyst being a Lewis acid, selected from
- organic or inorganic boron compounds chosen from BF 3 , BF 3 (Et 2 0), BCI 3, diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9 -borabicyclo [3.3.1 Jnonane, Me-TBD-BBN + I, -, the
- anionic counterion of silylium cations, oxoniums, carbocations, stannic cations and germanium cations being a halide selected from F-, Cl-, Br- and I-, or an anion selected from BF 4 -, SbF 6 - B (C 6 F S ) 4 -, B (C 6 H 5 ) 4 -, CF 3 SO 3 - or TfO - and PF 6 -. ; with at least one compound selected from
- an organic base selected from nitrogenous organic bases, phosphorus organic bases, carbon bases, and oxygenated organic bases;
- the catalyst (TBD-BBN) 2 can result from the dimerization of TBD-BBN, TBD-BBN-CO 2 corresponds to an adduct between the TBD BBN and CO 2 and TBD-BBN-BBN correspond to an adduct between TBD-BBN and 9-BBN.
- Me-TBD-BBNX (TBD-BBN) 2 , TBD-BBN-CO 2 and TBD-BBN-BBN can be obtained, for example, according to the protocols described below in the examples.
- Me-TBD-BBN + CF 3 SO 3 as well as Me-TBD-BBN + X- in which X- is selected from fluorine, chlorine and bromine can also be prepared by replacing the 9-iodo-9-borabicyclo reagent.
- the Lewis acid catalyst is selected from
- R 2 BX or R is a linear, branched or cyclic, saturated, optionally substituted alkyl group comprising 1 to 12 carbon atoms, and X is chosen from Cl-, Bf-, 1-, an alkoxide radical; such as methoxide
- BF 3 BF 3 (Et 2 O), BC 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-3 chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane , Me-TBD-BBNX Me-TBD-BBN + CF 3 SO 3 -, (TDB-BBN) 2 , TBD-BBN-CO 2, TBD-BBN-BBN, [TBDH + , BBN ( OCHO) 2 -], [Et 3 NH + , Cy 2 B (OCHO) 2 -];
- the formic acid is brought into contact with (i) a Lewis acid as catalyst and (ii) an organic base as cocatalyst.
- the organic base (ii) can be chosen from: - nitrogenous organic bases which are advantageously secondary or tertiary amines chosen from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethyleamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine
- the phosphorus-containing organic bases which are advantageously alkyl or aryl phosphines, for example chosen from triphenylphosphine, 2,2-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP), triisopropylphosphine, 1,2-bis; (diphenylphosphino) ethane (dppe), tricyclohexylphosphine (PCy 3 ); alkyl and aryl phosphonates, for example, selected from diphenyl phosphate, triphenyl phosphate (TPP), tri (isopropylphenyl) phosphate (TIPP), cresyldiphenyl phosphate (CDP), tricresyl phosphate (TCP); the alkyl and aryl phosphates, e.g., selected from di-n-butyl phosphate (DBP), tris (2-ethylhexyl) phosphate 5
- N-heterocyclic carbenes examples are shown below;
- the organic base is a nitrogenous organic base selected from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine (DIPEA or DIEA).
- TBD triazabicyclodecene
- Me-TBD N-methyltriazabicyclodecene
- DBU 1,8-diazabicyclo [5.4.0] undec-7-ene
- DMAP 4-dimethylaminopyridine
- DABCO 1, 4-diazabicyclo [2.2.2] octane
- proline
- the formic acid is brought into contact with (i) a Lewis acid as catalyst and (iii) a halide salt as cocatalyst.
- the halide salt (iii) may be chosen from the chloride, bromide, iodide and fluoride salts, said halide salts being chosen, for example, from NaF, NaCl, NaBr, NaI, KCl, LiCl, [(n-Bu 4 ) N , F], [(n-Bu 4 ) N + , Cl,] [(n-Bu 4 ) N + , ⁇ r], [(n-Bu 4 ) N + , I ], [PPh 4 + , F], [PPh4 + , C1], [PPh4 + , Br] and [PPh4 + , I].
- the process for producing dihydrogen from formic acid is characterized in that the formic acid is brought into contact with:
- said catalyst being a Lewis acid, selected from
- a derivative of formula R 2 BX or R is a linear, branched or cyclic alkyl group, saturated, optionally substituted, comprising 1 to 12 carbon atoms and X is chosen from C1-, Br-, 1- halogenides, alkoxides; such as methoxide-OMe or ethoxide -OEt, OTf, NTf 2 or H.
- BBNI B-chlorocatecholborane
- B (C 6 F 5 ) 3 B-methoxy-9-borabicyclo [33.1] nonane
- B-methoxy-9-BBN B-benzyl-9-borabicyclo [ 3.3.1] nonane
- Me-TBD-BBN + 1-, Me-TBD-BBN + CF 3 So 3 (TDB-BBN) 2 , TBD-BBN-C0 2 , TBD-BBN-BBN , [TBDH + , BBN (OCHO) 2 ⁇ ], [EtsNFf, Cy 2 B (OCHO) 2 -];
- nitrogenous organic bases selected from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), the proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine (DIPEA or DIEA); and or
- the process for producing dihydrogen according to the invention can thus implement:
- a Lewis acid in admixture with at least one co-catalyst which may be (ii) an organic base or (iii) a halide salt, or
- the Lewis acid may be in admixture with (ii) an organic base and / or (iii) a halide salt, as defined above.
- a halide salt as defined above.
- chlorodicyclohexylborane / Me-TBD ⁇ -chlorocatecholborane / DBU
- chlorodicyclohexylborane / BV Me 9-iodo-9-borabicyclo [3.3. l] nonane / NEt 3 .
- the Lewis acid may be covalently associated with (ii) an organic base and / or (iii) a halide salt.
- a molecule in which (i) is covalently associated with (iii) TBD-BBN-BBN and TBD-BBN-C0 2 will be mentioned.
- the catalysts may, where appropriate, be immobilized on heterogeneous supports, for example, in order to ensure easy separation of said catalyst and / or its recycling.
- Said heterogeneous supports may be chosen from supports based on silica gel or on plastic polymers such as, for example, polystyrene; carbon supports selected from carbon nanotubes; silica carbide; alumina; or magnesium chloride (MgCl 2 ).
- the production of dihydrogen from formic acid by the process of the invention can be accompanied by the concomitant production of carbon dioxide.
- the mixture of dihydrogen and carbon dioxide can be used as it is or the dihydrogen and carbon dioxide can be separated according to the methods known to those skilled in the art such as, for example, H 2 / CO 2 separation by adsorption of CO2 on ethanolamines or cryogenic separation.
- the hydrogen produced can therefore be used directly in fuel cells or in an internal combustion engine.
- the carbon dioxide can be used:
- the process of the invention may optionally be carried out in the presence of at least one basic additive.
- Said additive may be an organic or inorganic base having a pKa greater than that of formic acid, that is to say a pKa greater than 3.7 to make it possible to generate formate ions HCOO- from the acid formic thus contributing to the acceleration of the reaction rate and thus the production of dihydrogen.
- said basic additive may also contribute to trapping in solution, in the form of carbonate or hydrogencarbonate ions, for example, all or part of the CO 2 produced, thus making it possible to obtain pure dihydrogen or a mixture of gases enriched in H 2 .
- Said basic additive may be chosen, for example, from
- organic amines chosen from triethylamine, piperidine and 4-dimethylaminopyridine (DMAP),
- the inorganic carbon bases chosen from the carbonates C0 3 2- salts, the hydrogencarbonate salts HCO 3 -, said carbonate salts C0 3 2- and hydrogen carbonate HCO 3 - being chosen from CaCO 3 and NaHCO 3 ,
- the oxygenated inorganic bases chosen from the hydroxide salts HO - said hydroxide salts being chosen from KOH and NaOH.
- the amount of basic additive used can be from 0 to , 1 to 1 molar equivalents, inclusive, relative to the number of moles of formic acid.
- the production of dihydrogen according to the process of the invention can occur under a pressure of CO 2 , H 2 , dinitrogen (N 2 ), argon or a mixture of at least two of these gases.
- the production of dihydrogen from formic acid by the process of the invention can occur under the pressure of the gases formed (H 2 or H 2 + CO 2 mixture), under the pressure of inert gases (N 2 and / or argon), or under reduced pressure by collecting the gases formed in a low pressure system, for example, in a burette.
- the process of the invention can then take place at a pressure of between 0.1 and 200 bar, preferably between 0.1 and 75 bar, preferably between 0.1 and 30 bar, more preferably between 0.1 and 10 bar. , terminals included.
- reaction of the formic acid with the catalyst (i) and optionally the compounds (ii) and / or (iii), and optionally in the presence of a basic additive as defined above can be carried out at a temperature of temperature between 15 and 150 ° C, preferably between 15 and 130 ° C, inclusive.
- the duration of the reaction depends on the conversion rate of formic acid.
- the reaction is advantageously maintained until the total conversion of the formic acid.
- the duration of the reaction may be from 5 minutes to 200 hours, preferably from 10 minutes to 48 hours, limits included.
- the process for producing dihydrogen from the formic acid according to the invention may also take place in a mixture of at least two solvent (s) chosen from:
- alcohols preferably ethanol or ethylene glycol
- ethers preferably diethyl ether, or THF
- hydrocarbons preferably benzene or toluene
- Nitrogen solvents preferably pyridine, or acetonitrile
- sulfoxides preferably dimethyl sulphoxide
- alkyl halides preferably chloroform, or methylene chloride
- a supercritical fluid preferably supercritical CO 2 .
- reagents used in the process of the invention in particular, formic acid, (pre) catalysts, cocatalysts, basic additives, are, in general, commercial compounds or can be prepared by processes already described in the literature and known to those skilled in the art.
- the amount of catalyst used in the process of the invention is from 0.0001 to 1 molar equivalent, preferably from 0.001 to 1 molar equivalent, more preferably from 0.001 to 0.5 molar equivalents, inclusive, in relation to the number of molars. mole of formic acid.
- the dihydrogen obtained by the process of the invention can be used in particular for the production of ammonia and methanol, and the refining of petroleum. It can also be used in the sectors of metallurgy and electronics, pharmacy as well as in the processing of food products.
- the hydrogen produced by the process of the invention can combine with oxygen in the air to produce electricity by releasing only water. Hydrogen therefore represents a strong potential for providing clean energy and ensuring security of supply.
- the invention also relates to the use of the dihydrogen produced by the process of the invention, in a fuel cell, in a combustion engine, in the production of ammonia and methanol, in the refining of petroleum, in Metallurgy, Electronics and Food.
- Another object of the invention relates to a method for producing energy, characterized in that it comprises a step of producing dihydrogen from formic acid by the process according to the invention.
- the catalytic dehydrogenation reaction of formic acid shown in scheme 5, can be carried out according to the following experimental protocol: 1. In an inert atmosphere of argon or nitrogen, in a glove box, the formic acid, the pre-catalyst (from 1 to 0.001 equivalents) and optionally the solvent and the basic additive are introduced into a tube of Schlenk which is then sealed by a tap J. Young. The order of introduction of the reagents does not matter.
- the Schlenk is then heated to a temperature between 25 and 140 ° C until the total conversion of formic acid (from 5 minutes to 150 hours of reaction).
- the emitted gases may be collected during the reaction by a burette system or connected to a device using the emitted gases, such as a PEMFC fuel cell.
- the gases can be stored in the enclosure of the closed reaction medium if it can withstand the gas pressure generated.
- the catalysts Me-TBD-BBN + 1-, (TDB-BBN) 2 , TBD-BBN-CO 2 , TBD-BBN-BBN, [TBDH + , BBN (OCHO) 2 -] and [Et 3 NH + , Cy 2 B (OCHO) 2 -] were prepared according to the following protocols:
- 9-BBN dimer 342 mg, 1.4 mmol, 0.5 equiv
- 5 mL of toluene 5 mL
- the suspension obtained is stirred until the solid is completely dissolved, and then formic acid (258 mg, 211 ⁇ l, 5.6 mmol, 2 equiv) is added using a syringe followed by TBD (390 mg, 2.8 mmol). , 1 equiv) at one time.
- TBD 390 mg, 2.8 mmol
- 1 equiv 1 equiv
- the reaction is then stirred for 2 h at room temperature and then pentane (5 mL) is added.
- Cy 2 BH dicyclohexylborane is synthesized from a procedure described in the literature and is used without special purification.
- the catalysts [TBDH + , BBN (OCHO) 2 -] and [Et 3 NH + , Cy 2 B (OCHO) 2 -] can be represented as follows:
- the separation can be achieved by methods known to those skilled in the art such as, for example, separation H2 / CO 2 by adsorption of CO 2 on ethanolamines or by cryogenic separation.
- the amount of each gas in the mixture can be determined, for example, by collecting the gases in a burette and analyzing the composition of the mixture by gas chromatography. These techniques are techniques commonly used in this field and well known to those skilled in the art. In the table above, the formic acid conversion efficiencies quoted correspond to the conversion efficiencies of formic acid to an equimolar mixture of H 2 and CO 2 .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a process for producing dihydrogen from formic acid. It also relates to the use of the dihydrogen produced by the process of the invention, in a fuel cell, in a combustion engine, in the production of ammonia and methanol, in oil refining, and in the metallurgy, electronics and food sectors. The invention also relates to an energy production process comprising a step of producing dihydrogen from formic acid by the process according to the invention.
Description
PROCEDE DE PRODUCTION DE DIHYDROGENE PROCESS FOR PRODUCING DIHYDROGEN
La présente invention concerne un procédé de production du dihydrogène à partir de l'acide formique. The present invention relates to a process for producing dihydrogen from formic acid.
Elle concerne également l'utilisation du dihydrogène produit par le procédé de l'invention, dans une pile à combustible, dans un moteur à combustion, dans la production d'ammoniac et de méthanol, dans le raffinage du pétrole, dans les secteurs de la métallurgie, de l'électronique et de l'alimentaire. It also relates to the use of the dihydrogen produced by the process of the invention, in a fuel cell, in a combustion engine, in the production of ammonia and methanol, in petroleum refining, in the sectors of the metallurgy, electronics and food.
L'invention concerne encore un procédé de production d'énergie, comprenant une étape de production de dihydrogène à partir de l'acide formique par le procédé selon l'invention. The invention further relates to a method for producing energy, comprising a step of producing dihydrogen from formic acid by the process according to the invention.
Le dihydrogène ou H2, est un carburant attrayant qui est sans carbone et qui peut être utilisé pour alimenter des piles à combustibles et servir ainsi d'alternative aux carburants carbonés fossiles. Hydrogen, or H 2 , is an attractive fuel that is carbon-free and can be used to fuel fuel cells and serve as an alternative to fossil carbon fuels.
Le dihydrogène ne peut jouer son rôle de vecteur d'énergie que si l'on peut le stocker efficacement, pour un coût limité et dans des conditions de sécurité acceptables. Hydrogen can only play its role as an energy carrier if it can be stored efficiently, for a limited cost and under acceptable safety conditions.
Le dihydrogène étant un gaz qui se caractérise par une densité d'énergie volumique faible (0,010 MJ/L), à pression atmosphérique (1 ± 0,3 atm) et température ambiante (20 ± 5°C), comparée notamment au diesel (38,6 MJ/L), le stockage de H2 sous une forme liquide ou solide dense est alors nécessaire pour faciliter son transport et sa distribution. Dans ce contexte, différentes voies de stockage sont en cours d'étude. A pression atmosphérique (1 ± 0,3 atm) et température ambiante (20 ± 5°C), il faut un volume de 11 m3 pour stocker 1 kg dihydrogène. Dihydrogen is a gas characterized by a low density energy density (0.010 MJ / L), at atmospheric pressure (1 ± 0.3 atm) and ambient temperature (20 ± 5 ° C), compared in particular with diesel ( 38.6 MJ / L), the storage of H 2 in a dense liquid or solid form is then necessary to facilitate its transport and distribution. In this context, different storage routes are being studied. At atmospheric pressure (1 ± 0.3 atm) and ambient temperature (20 ± 5 ° C), a volume of 11 m 3 is required to store 1 kg dihydrogen.
Les technologies de stockage actuelles compriment à haute pression (>700 bars) ou liquéfient le dihydrogène à -253 °C pour atteindre des densités respectives de 42 et 70 kgH2/m3. Le stockage sous la forme d'hydrures métalliques, tels que MgH2, permet d'atteindre des densités de 110 kgH2/m3. En somme, ces procédés sont énergivores et peuvent consommer jusqu'à un tiers de l'énergie contenue dans le gaz, tout en associant des risques supplémentaires (pressions élevées, hydrures métalliques réactifs vis-à-vis de l'eau, etc.). Par exemple, une pression de 700 bars et plus pose des problèmes de sécurité. La réactivité des hydrures métalliques vis-à-vis de l'eau pose des problèmes de stabilité du matériau de stockage. En effet, après hydrolyse, les hydrures métalliques comme par exemple MgH2, sont inutilisables pour stocker H2.
Le stockage de H2 sous la forme d'acide formique présente de nombreux avantages car il permet d'atteindre une bonne densité de dihydrogène (53 kgH2/m3) à la pression atmosphérique (1 ± 0,3 atm) et température ambiante (20 ± 5°C). Par ailleurs, l'acide formique est peu toxique et non corrosif en milieu dilué, c'est-à-dire un milieu aqueux contenant au plus 85% en volume d'acide formique par rapport au volume total du milieu. Le dihydrogène ainsi stocké est libéré par une réaction de déshydrogénation de l'acide formique. Comme montré dans le schéma 1, la réaction de déshydrogénation de l'acide formique nécessite l'emploi de catalyseurs permettant d'accélérer la libération de H2et de CO2. Le dihydrogène libéré peut être utilisé comme combustible. Current storage technologies compress at high pressure (> 700 bar) or liquefy the hydrogen at -253 ° C to reach respective densities of 42 and 70 kgH 2 / m 3 . Storage in the form of metal hydrides, such as MgH 2 , makes it possible to reach densities of 110 kgH 2 / m 3 . In short, these processes are energy-intensive and can consume up to one third of the energy contained in the gas, while associating additional risks (high pressures, reactive metal hydrides with respect to water, etc.). . For example, a pressure of 700 bars or more poses security problems. The reactivity of the metal hydrides with respect to water poses problems of stability of the storage material. In fact, after hydrolysis, the metal hydrides, for example MgH 2 , are unusable for storing H 2 . The storage of H 2 in the form of formic acid has many advantages because it makes it possible to reach a good density of dihydrogen (53 kgH 2 / m 3 ) at atmospheric pressure (1 ± 0.3 atm) and ambient temperature (20 ± 5 ° C). Moreover, the formic acid is low in toxicity and non-corrosive in dilute medium, that is to say an aqueous medium containing at most 85% by volume of formic acid relative to the total volume of the medium. The dihydrogen thus stored is released by a dehydrogenation reaction of formic acid. As shown in Scheme 1, the dehydrogenation reaction of formic acid requires the use of catalysts to accelerate the release of H 2 and CO 2 . The liberated dihydrogen can be used as fuel.
Actuellement, les catalyseurs utilisés dans les réactions de déshydrogénation de l'acide formique sont constitués de complexes de métaux comme le ruthénium, le platine, le rhodium ou le nickel, métaux souvent coûteux et/ou toxiques. Dans le cadre de la déshydrogénation de l'acide formique en H2 et C02, le défi technique à relever est de mettre au point des catalyseurs efficaces qui s'affranchissent des problèmes de toxicité, de disponibilité et de coûts généralement associés à l'utilisation de catalyseurs métalliques connus, notamment des catalyseurs à base de métaux précieux. At present, the catalysts used in the dehydrogenation reactions of formic acid consist of complexes of metals such as ruthenium, platinum, rhodium or nickel, metals which are often expensive and / or toxic. In the context of the dehydrogenation of formic acid in H 2 and C0 2 , the technical challenge is to develop effective catalysts that overcome the problems of toxicity, availability and costs generally associated with H 2 and C0 2 . use of known metal catalysts, especially catalysts based on precious metals.
La réaction de déshydrogénation de l'acide formique peut également être conduite en milieu basique pour améliorer les performances du catalyseur, par exemple, en ajoutant une quantité sous stœchiométrique de triéthylamine (NEt3) comme montré dans le schéma 2 ou en utilisant une solution aqueuse de formiate de sodium comme illustré par le schéma 3 : The dehydrogenation reaction of formic acid can also be carried out in a basic medium to improve the performance of the catalyst, for example by adding a stoichiometric amount of triethylamine (NEt 3 ) as shown in Scheme 2 or using an aqueous solution. of sodium formate as illustrated by Scheme 3:
Schéma 3 Figure 3
Les bases organiques et additifs basiques classiquement utilisés pour promouvoir la déshydrogénation de l'acide formique sont décrits dans la revue de Bélier et al. (H. Junge, A. Boddien, F. Capitta, B. Loges, J. R. Noyés, S. Gladiaîi, M. Bélier, Tetrahedron lett. 2009, 50, pages 1603-1606). The organic bases and basic additives conventionally used to promote the dehydrogenation of formic acid are described in the review of Aries et al. (H. Junge, A. Boddien, F. Capitta, B. Loges, J. R. Noyes, S. Gladiaii, M. Aries, Tetrahedron Lett., 2009, 50, pp. 1603-1606).
Les catalyseurs connus pour promouvoir la réaction de déshydrogénation de l'acide formique sont basés sur des complexes de métaux de transition ou des systèmes hétérogènes inorganiques. Une revue récente (M. Grasemann, G. Laurenczy, Energ. Environ. Sci 2012, 5, pages 8171-8181) décrit l'état de l'art et quelques exemples de catalyseurs type qui sont rassemblés ci-dessous. Catalysts known to promote the dehydrogenation reaction of formic acid are based on transition metal complexes or inorganic heterogeneous systems. A recent review (M. Grasemann, G. Laurenczy, Energ Environ Sci 2012, 5, pages 8171-8181) describes the state of the art and some examples of typical catalysts which are gathered below.
Les systèmes catalytiques en phase homogène connus pour promouvoir la réaction de déshydrogénation de l'acide formique sont des complexes de métaux de transition. Les premiers travaux dans ce domaine ont été réalisés par Coffey qui a montré que le complexe d'iridium IrH2Cl(PPh3)3 permettait d'obtenir des fréquences de rotation ou TOF (Turnover Frequency en anglais) de 1187 h-1 à une température de 100 à 117°C (R. S. Coffey, Chem. Commun. 1967, pages 923-924). En utilisant le complexe [Ir(C5Me5)(4,4'-dmydroxy-2,2'-bipyridine)], Himeda (Y. Himeda, Green Chem 2009, 11, pages 2018-2022) a obtenu une fréquence de rotation ou TOF de 3100 h-1 à 60°C. Homogeneous phase catalyst systems known to promote the dehydrogenation reaction of formic acid are transition metal complexes. The first work in this area was carried out by Coffey which showed that the iridium complex IrH 2 Cl (PPh 3 ) 3 made it possible to obtain rotation frequencies or TOF (Turnover Frequency) of 1187 h -1 at a temperature of 100 to 117 ° C (RS Coffey, Chem, 1967, pages 923-924). Using the complex [Ir (C 5 Me 5 ) (4,4'-dmhydroxy-2,2'-bipyridine)], Himeda (Y. Himeda, Green Chem 2009, 11, pages 2018-2022) obtained a frequency rotation or TOF of 3100 h -1 at 60 ° C.
Le groupe de Bélier (A. Boddien, B. Loges, H. Junge, F. Gartner, J. R. Noyés, M. Bélier, Adv. Synth. Catal. 2009, 351, pages 2517-2520) a étudié un grand nombre de complexes moléculaires du ruthénium pour catalyser la déshydrogénation de l'acide formique. Parmi eux, un catalyseur généré in situ à partir de [RuCl2(benzene)]2 et de 6 équivalents de l,2-bis(diphénylphosphino)éthane, permet d'atteindre un nombre de rotation ou TON (Turnover number en anglais) de 260 000 après deux mois de réaction (TOF = 900 h-1) pour la déshydrogénation de l'acide formique à 40°C, avec la N,N~ diméthyl-n-hexylamine comme additif basique. The Aries group (A. Boddien, B. Loges, H. Junge, F. Gartner, JR Noyes, M. Aries, Adv Synth Synth 2009, 351, pages 2517-2520) has studied a large number of complexes. of ruthenium to catalyze the dehydrogenation of formic acid. Among them, a catalyst generated in situ from [RuCl 2 (benzene)] 2 and 6 equivalents of 1,2-bis (diphenylphosphino) ethane, makes it possible to achieve a number of rotation or TON (Turnover number in English) of 260,000 after two months of reaction (TOF = 900 h -1 ) for the dehydrogenation of formic acid at 40 ° C, with N, N-dimethyl-n-hexylamine as basic additive.
Bélier, Laurenczy et al (A. Boddien, D. Mellmann, F. Gartner, R. Jackstell, H. Junge, P. J. Dyson, G. Laurenczy, R. Ludwig, M. Bélier, Science, 2011, 333, pages 1733- 1736) ont ensuite étudié une série de catalyseurs basés sur des complexes du fer. Cette étude a permis de montrer que le complexe [Fe(BF4)2] 6H20 a une activité catalytique élevée dans la déshydrogénation de l'acide formique, conduisant à une fréquence de rotation ou TOF de 1942 h-1 après 3 heures à 40 °C.
En 2014, Myers et Berben (T. W. Myers, L. A. Berben, Chem Sci, 2014, 5, pages 2771-2777) ont développé des complexes d'aluminium(III) stabilisés par des ligands bis- imino-pyridine qui possèdent un TOF maximal initial de 5200 h-1 pour la déshydrogénation de l'acide formique, réalisée à 65°C dans le THF, en présence de triéthylamine comme additif. Aries, Laurenczy et al (A. Boddien, D. Mellmann, F. Gartner, R. Jackstell, H. Junge, PJ Dyson, G. Laurenczy, R. Ludwig, M. Aries, Science, 2011, 333, pages 1733- 1736) then studied a series of catalysts based on iron complexes. This study has shown that the complex [Fe (BF4) 2 ] 6H 2 0 has a high catalytic activity in the dehydrogenation of formic acid, leading to a rotation frequency or TOF of 1942 h -1 after 3 hours at 40 ° C. In 2014, Myers and Berben (TW Myers, LA Berben, Chem Sci, 2014, 5, pages 2771-2777) developed aluminum (III) complexes stabilized by bis-imino-pyridine ligands that have an initial maximal TOF. of 5200 h -1 for the dehydrogenation of formic acid, carried out at 65 ° C in THF, in the presence of triethylamine as additive.
Des catalyseurs hétérogènes ont également été décrits dans la littérature pour promouvoir la déshydrogénation catalytique de l'acide formique. Ce sont alors des systèmes métalliques, le plus souvent des nanoparticules, utilisés sous la forme d'alliages ou de systèmes mono-métalliques. Ce domaine de recherche a fait l'objet de revues récentes, disponibles dans la littérature (S. Enthaler, J. von Langermann, T. Schmidt, Energ. Environ. Sci. 2010, 3, pages 1207-1217 ; M. Grasemann, G. Laurenczy, Energ. Environ. Sci 2012, 5, pages 8171-8181). Heterogeneous catalysts have also been described in the literature to promote the catalytic dehydrogenation of formic acid. These are then metal systems, most often nanoparticles, used in the form of alloys or mono-metallic systems. This field of research has been the subject of recent reviews, available in the literature (S. Enthaler, J. von Langermann, T. Schmidt, Environ Energie Sci., 2010, 3, pages 1207-1217, M. Grasemann, G. Laurenczy, Energ Sci 2012, 5, pages 8171-8181).
Cet état de l'art révèle que l'ensemble des catalyseurs connus à l'heure actuelle pour promouvoir la production de dihydrogène à partir de l'acide formique repose sur des systèmes métalliques, le plus souvent basés sur des métaux nobles. This state of the art reveals that all of the catalysts known at present for promoting the production of dihydrogen from formic acid are based on metal systems, most often based on noble metals.
Il existe donc un réel besoin d'un catalyseur permettant la production de dihydrogène à partir de l'acide formique, qui soit efficace (capable d'augmenter la vitesse de la conversion de l'acide formique en H2 et Co2), peu coûteux et/ou peu toxique comparé aux catalyseurs connus. There is therefore a real need for a catalyst for the production of dihydrogen from formic acid, which is effective (capable of increasing the rate of conversion of formic acid to H 2 and Co 2 ), little expensive and / or low toxicity compared to known catalysts.
En particulier, il existe un réel besoin d'un catalyseur, tel que défini ci-dessus, qui ne contienne pas : In particular, there is a real need for a catalyst, as defined above, which does not contain:
- de métaux alcalinoterreux du Groupe IIA du Tableau Périodique des Eléments (comme le magnésium et le calcium) ; - Group IIA alkaline earth metals from the Periodic Table of Elements (such as magnesium and calcium);
- de métaux du groupe IIIA, à savoir, l'aluminium, le gallium, l'indium et le thallium. Group IIIA metals, namely, aluminum, gallium, indium and thallium.
- de métaux de transition du Groupe IB à VIIIB du Tableau Périodique des Eléments (comme le nickel, le fer, le cobalt, le zinc, le cuivre, le rhodium, le ruthénium, le platine, le palladium, l'iridium) ; transition metals from Group IB to VIIIB of the Periodic Table of the Elements (such as nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium, iridium);
- de terres rares dont le numéro atomique est compris entre 57 et 71 (comme le lanthane, le cérium, le praséodyme, le néodyme) ; ou rare earths whose atomic number is between 57 and 71 (such as lanthanum, cerium, praseodymium, neodymium); or
- d'actinides dont le numéro atomique est compris entre 89 et 103 (comme le thorium, l'uranium).
La présente invention a précisément pour but de répondre à ces besoins en fournissant un procédé de production de dihydrogène à partir de l'acide formique, caractérisé en ce que l'acide formique est mis en contact - actinides whose atomic number is between 89 and 103 (such as thorium, uranium). The present invention is specifically intended to meet these needs by providing a process for producing dihydrogen from formic acid, characterized in that the formic acid is contacted
avec au moins un catalyseur choisi parmi : with at least one catalyst chosen from:
(i) les acides de Lewis, lesdits acides de Lewis étant choisis parmi les composés organiques ou inorganiques de bore, les composés organiques ou inorganiques de silicium, les oxoniums, les carbocations, les composés organiques ou inorganiques du germanium et les composés organiques ou inorganiques d'étain ; et éventuellement (i) Lewis acids, said Lewis acids being selected from organic or inorganic boron compounds, organic or inorganic silicon compounds, oxoniums, carbocations, organic or inorganic germanium compounds and organic or inorganic compounds tin; and eventually
avec au moins un composé choisi parmi with at least one compound selected from
(ii) une base organique choisie parmi les bases organiques azotées, les bases organiques phosphorées, les bases carbonées, et les bases organiques oxygénées ; et/ou (ii) an organic base selected from nitrogenous organic bases, phosphorus organic bases, carbon bases, and oxygenated organic bases; and or
(iii) un sel d'halogénure. (iii) a halide salt.
Le procédé de l'invention permet de produire du dihydrogène avec un grand choix de catalyseurs. The process of the invention makes it possible to produce dihydrogen with a variety of catalysts.
Les catalyseurs utilisés dans le procédé de l'invention présentent l'avantage de permettre de s'affranchir des problèmes de toxicité généralement observés pour les catalyseurs métalliques ainsi que des problèmes de coûts associés à l'utilisation de métaux précieux. The catalysts used in the process of the invention have the advantage of overcoming the toxicity problems generally observed for metal catalysts and cost problems associated with the use of precious metals.
En effet, dans le procédé de P invention, le catalyseur mis en œuvre ne contient pas : Indeed, in the process of the invention, the catalyst used does not contain:
- de métaux alcalinoterreux du Groupe IIA du Tableau Périodique des Eléments choisis parmi le magnésium et le calcium ; - Group IIA alkaline earth metals from the Periodic Table of the Elements selected from magnesium and calcium;
- de métaux du groupe IIIA choisis parmi l'aluminium, le gallium, l'indium et le thallium. Group IIIA metals selected from aluminum, gallium, indium and thallium.
- de métaux de transition du Groupe IB à VIIIB du Tableau Périodique des Eléments choisis parmi le nickel, le fer, le cobalt, le zinc, le cuivre, le rhodium, le ruthénium, le platine, le palladium et l,iridium ; - of Group IB to VIIIB transition metals of the Periodic Table of Elements selected from nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium and, iridium;
- de terres rares dont le numéro atomique est compris entre 57 et 71 choisis parmi le lanthane, le cérîum, le praséodyme et le néodyme) ; ou rare earths whose atomic number is between 57 and 71 chosen from lanthanum, cerium, praseodymium and neodymium); or
- d'actinides dont le numéro atomique est compris entre 89 et 103 choisis parmi le thorium et l,uranium.
Par ailleurs, la production du dihydrogène à partir de l'acide formique par le procédé de l'invention peut également être accompagnée par la production concomitante du C02. Dans ce cas, le dihydrogène sera en mélange avec le dioxyde de carbone. Ce mélange peut être utilisé tel quel ou le dihydrogène et le dioxyde de carbone peuvent être séparés selon les méthodes connues de l'homme du métier comme par exemple, la séparation H2/CO2 par adsorption du CO2 sur des éthanolamines ou par séparation cryogénique. - actinides whose atomic number is between 89 and 103 chosen from thorium and, uranium. On the other hand, the production of dihydrogen from formic acid by the process of the invention can also be accompanied by the concomitant production of C0 2 . In this case, the dihydrogen will be mixed with the carbon dioxide. This mixture can be used as it is or the dihydrogen and the carbon dioxide can be separated according to the methods known to those skilled in the art such as, for example, the separation H 2 / CO 2 by adsorption of CO 2 on ethanolamines or by separation. cryogenic.
Le CO2 ainsi formé peut être utilisé/recyclé dans le procédé de l'invention comme gaz d'inertage ou être récupéré pour être transformé en différents composés chimiques comme par exemple l'acide formique par les méthodes connues de l'homme du métier comme par exemple celles décrites par Morris, A. J., Meyer, G. J., Fujita, E., The CO2 thus formed can be used / recycled in the process of the invention as inerting gas or can be recovered in order to be converted into various chemical compounds, for example formic acid by the methods known to those skilled in the art, such as examples described by Morris, AJ, Meyer, GJ, Fujita, E.,
Accounts Chem Res 2009, 42, 1983. Accounts Chem Res 2009, 42, 1983.
Par catalyseur, au sens de l'invention, on entend tout composé capable de modifier, notamment en augmentant, la vitesse de la réaction chimique à laquelle il participe, et qui est régénéré à la fin de la réaction. Cette définition englobe à la fois les catalyseurs, c'est-à-dire les composés qui exercent leur activité catalytique sans avoir besoin de subir une quelconque modification ou conversion, et les composés (appelés également pré-catalyseurs) qui sont introduits dans le milieu réactionnel et qui y sont convertis en un catalyseur. By catalyst, within the meaning of the invention is meant any compound capable of modifying, in particular by increasing, the speed of the chemical reaction in which it participates, and which is regenerated at the end of the reaction. This definition encompasses both catalysts, that is, compounds that exert their catalytic activity without the need for any modification or conversion, and compounds (also called pre-catalysts) that are introduced into the medium. and converted therein to a catalyst.
Au sens de l'invention, un co-catalyseur est un composé qui n'est pas un catalyseur mais, qui, en association avec un catalyseur, permet d'améliorer l'activité catalytique dudit catalyseur. For the purposes of the invention, a cocatalyst is a compound which is not a catalyst but which, in combination with a catalyst, makes it possible to improve the catalytic activity of said catalyst.
Dans le cadre de l'invention, le nombre de rotation (TON) et la fréquence de rotation (TOF) du catalyseur sont définis comme suit : In the context of the invention, the number of rotation (TON) and the rotation frequency (TOF) of the catalyst are defined as follows:
où no(HCOOH) correspond à la quantité de matière d'acide formique, c'est-à-dire le nombre de mole d'acide formique, en début de réaction et nfin(HCOOH) correspond à la quantité de matière d'acide formique, c'est-à-dire le nombre de mole d'acide formique, en fin de réaction. Plus les TON et les TOF sont élevés et plus le catalyseur est efficace.
On entend par « alkyle », au sens de la présente invention, un radical carboné linéaire, ramifié ou cyclique, saturé, éventuellement substitué, comprenant 1 à 12 atomes de carbone. A titre d' alkyle saturé, linéaire ou ramifié, on peut citer par exemple les radicaux méthyle, éthyle, propyle, butyle, pentyle, hexyle, octyle, nonyle, décyle, undécyle, dodécanyle et leurs isomères ramifiés. Comme alkyle cylique, on peut citer les radicaux cyclopropyle, cyclobutyle, cyclopentyle, cyclohexyle, bicylco[2,l,l] hexyle, bicyclo[2,2,l] heptyle. Comme alkyles cycliques insaturés, on peut citer par exemple le cyclopentényle, le cyclohexényle. where n o (HCOOH) corresponds to the amount of formic acid material, i.e., the number of moles of formic acid, at the start of the reaction and the end (HCOOH) corresponds to the amount of formic acid, that is to say the number of moles of formic acid, at the end of the reaction. The higher the TON and TOF, the more efficient the catalyst. For the purposes of the present invention, the term "alkyl" means a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms. As linear or branched saturated alkyl, there may be mentioned, for example, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl and dodecanyl radicals and their branched isomers. As cyclic alkyl, there may be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicylco [2,1,1] hexyl, bicyclo [2,2,1] heptyl. Unsaturated cyclic alkyls include, for example, cyclopentenyl and cyclohexenyl.
Par « alcényle » ou « alcynyle », on entend un radical carboné insaturé linéaire, ramifié ou cyclique, éventuellement substitué, ledit radical carboné insaturé comprenant 1 à 12 atomes de carbone comprenant au moins une double (alcényle) ou une triple liaison (alcynyle). A ce titre, on peut citer, par exemple, les radicaux éthylényle, propylényle, butényle, pentényle, hexényle, acétylényle, propynyle, butynyle, pentynyle, hexynyle et leurs isomères ramifiés. By "alkenyl" or "alkynyl" is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 1 to 12 carbon atoms comprising at least one double (alkenyl) or a triple bond (alkynyl) . As such, there may be mentioned, for example, ethylenyl, propylenyl, butenyl, pentenyl, hexenyl, acetylenyl, propynyl, butynyl, pentynyl, hexynyl and their branched isomers.
Le groupe alkyle, alcényle et alcynyle, au sens de l'invention, peuvent être éventuellement substitués par un ou plusieurs groupes hydroxyle ; un ou plusieurs groupes alkoxy ; un ou plusieurs groupes siloxy ; un ou plusieurs atomes d'halogène choisis parmi les atomes de fluor, chlore, brome et iode ; un ou plusieurs groupes nitro (-NO2) ; un ou plusieurs groupes nitrile (-CN) ; un ou plusieurs groupes aryle, avec les groupes alkoxy et aryle tels que définis dans le cadre de la présente invention. The alkyl, alkenyl and alkynyl group, within the meaning of the invention, may be optionally substituted by one or more hydroxyl groups; one or more alkoxy groups; one or more siloxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO 2 ); one or more nitrile groups (-CN); one or more aryl groups, with the alkoxy and aryl groups as defined in the context of the present invention.
Le terme « aryle » désigne de manière générale un substituant aromatique cyclique comportant de 6 à 20 atomes de carbone. Dans le cadre de l'invention le groupe aryle peut être mono- ou polycyclique. A titre indicatif, on peut citer les groupes phényle, benzyle et naphtyle. Le groupe aryle peut être éventuellement substitué par un ou plusieurs groupes hydroxyle, un ou plusieurs groupes alkoxy, un ou plusieurs groupes «siloxy», un ou plusieurs atomes d'halogène choisis parmi les atomes de fluor, chlore, brome et iode, un ou plusieurs groupes nitro (-NO2), un ou plusieurs groupes nitrile (-CN), un ou plusieurs groupes alkyle, avec les groupes alkoxy et alkyle tels que définis dans le cadre de la présente invention. The term "aryl" generally refers to a cyclic aromatic substituent having from 6 to 20 carbon atoms. In the context of the invention, the aryl group may be mono- or polycyclic. As an indication, mention may be made of phenyl, benzyl and naphthyl groups. The aryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more "siloxy" groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more several nitro groups (-NO 2 ), one or more nitrile groups (-CN), one or more alkyl groups, with the alkoxy and alkyl groups as defined in the context of the present invention.
Le terme « hétéroaryle » désigne de manière générale un substituant aromatique mono- ou polycyclique comportant de 5 à 10 membres dont au moins 2 atomes de carbone, et au moins un hétéroatome choisi parmi l'azote, l'oxygène, le bore, le silicium, le phosphore ou le soufre. Le groupe hétéroaryle peut être mono- ou poly- cyclique. A titre
indicatif, on peut citer les groupes furyle, benzofuranyle, pyrrolyle, indolyle, isoindolyle, azaindolyle, thiophényle, benzothiophényle, pyridyle, quinolinyle, isoquinolyle, imidazolyle, benzimidazolyle, pyrazolyle, oxazolyle, isoxazolyle, benzoxazolyle, thiazolyle, benzothiazolyle, isothiazolyle, pyridazinyle, pyrimidilyle, pyrazinyle, triazinyle, cinnolinyle, phtalazinyle, quinazolinyle. Le groupe hétéroaryle peut être éventuellement substitué par un ou plusieurs groupes hydroxyle, un ou plusieurs groupes alkoxy, un ou plusieurs atomes d'halogène choisis parmi les atomes de fluor, chlore, brome et iode, un ou plusieurs groupes nitro (-Ν02), un ou plusieurs groupes nitrile (-CN), un ou plusieurs groupes aryle, un ou plusieurs groupes alkyle, avec les groupes alkyle, alkoxy et aryle tels que définis dans le cadre de la présente invention. The term "heteroaryl" generally denotes a mono- or polycyclic aromatic substituent comprising from 5 to 10 members, of which at least 2 are carbon atoms, and at least one heteroatom chosen from nitrogen, oxygen, boron and silicon. , phosphorus or sulfur. The heteroaryl group may be mono- or polycyclic. As mention may be made of furyl, benzofuranyl, pyrrolyl, indolyl, isoindolyl, azaindolyl, thiophenyl, benzothiophenyl, pyridyl, quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, pyrazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, pyridazinyl and pyrimidilyl groups; , pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl. The heteroaryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (-ΝO 2 ). , one or more nitrile groups (-CN), one or more aryl groups, one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention.
Le terme « hétérocycle » désigne de manière générale un substituant mono- ou polycyclique, comportant de 5 à 10 membres, saturé ou instauré, contenant de 1 à 4 hétéroatomes choisis indépendamment l'un de l'autre, parmi l'azote, l'oxygène, le bore, le silicium, le phosphore ou le soufre. A titre indicatif, on peut citer le borolane, le borole, le borinane, le 9-borabicyclo[3.3.1]nonane (9-BBN), le 1,3,2-benzodioxaborole (catecholborane ou catBH), pinacholborane (pinBH), les substituants morpholinyle, pipéridinyle, pipérazinyle, pyrrolidinyle, imidazolidinyle, imidazolinyle, pyrazolidinyle, tétrahydrofuranyle, tétrahydropyranyle, thianyle, oxazolidinyle, isoxazolidinyle, thiazolidinyle, isothiazolidinyle. L'hétérocycle peut être éventuellement substitué par un ou plusieurs groupes hydroxyle, un ou plusieurs groupes alkoxy, un ou plusieurs groupes aryle, un ou plusieurs atomes d'halogène choisis parmi les atomes de fluor, chlore, brome et iode, un ou plusieurs groupes nitro (-NO2), un ou plusieurs groupes nitrile (-CN), un ou plusieurs groupes alkyle, avec les groupes alkyle, alkoxy et aryle tels que définis dans le cadre de la présente invention, The term "heterocycle" generally refers to a saturated or initiated 5 to 10 membered mono- or polycyclic substituent containing from 1 to 4 heteroatoms selected independently of one another from nitrogen, oxygen, boron, silicon, phosphorus or sulfur. As an indication, mention may be made of borolane, borole, borinane, 9-borabicyclo [3.3.1] nonane (9-BBN), 1,3,2-benzodioxaborole (catecholborane or catBH), pinacholborane (pinBH) morpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, tetrahydrofuranyl, tetrahydropyranyl, thianyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolidinyl substituents. The heterocycle may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more aryl groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more groups. nitro (-NO 2 ), one or more nitrile groups (-CN), one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention,
Le terme « alkoxy » signifie un groupe alkyle, alcényle et alcynyle, tels que définis ci-dessus, lié par un atome d'oxygène (-O-alkyle, O-alcényle, O-alcynyle). The term "alkoxy" means an alkyl, alkenyl and alkynyl group, as defined above, bonded through an oxygen atom (-O-alkyl, O-alkenyl, O-alkynyl).
Par groupe « amino », on entend un groupe de formule -NR7R8, dans laquelle : ■ R7 et R8 représentent, indépendamment l'un de l'autre, un atome d'hydrogène, un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe hétéroaryle, un hétérocycle, un groupe silyle, un groupe siloxy, avec les groupes alkyle, alcényle, alcynyle, aryle, hétéroaryle, hétérocycle, silyle, siloxy, tels que définis dans le cadre de la présente invention ; ou
■ R7 et R8, pris ensemble avec l'atome d'azote auquel ils sont liés, forment un hétérocycle éventuellement substitué par un ou plusieurs groupes hydroxyle ; un ou plusieurs groupes alkyle ; un ou plusieurs groupes alkoxy ; un ou plusieurs atomes d'halogène choisis parmi les atomes de fluor, chlore, brome et iode ; un ou plusieurs groupes nitro (-NO-2) ; un ou plusieurs groupes nitrile (-CN) ; un ou plusieurs groupes aryle ; avec les groupes alkyle, alkoxy et aryle tels que définis dans le cadre de la présente invention. By "amino" group is meant a group of formula -NR 7 R 8 , in which: R 7 and R 8 represent, independently of one another, a hydrogen atom, an alkyl group, a group alkenyl, an alkynyl group, an aryl group, a heteroaryl group, a heterocycle, a silyl group, a siloxy group, with alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycle, silyl, siloxy, as defined in the context of the present invention; or ■ R 7 and R 8, taken together with the nitrogen atom to which they are bonded, form a heterocycle optionally substituted by one or more hydroxyl groups; one or more alkyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO- 2 ); one or more nitrile groups (-CN); one or more aryl groups; with the alkyl, alkoxy and aryl groups as defined in the context of the present invention.
Par atome d'halogène, on entend un atome choisi parmi les atomes de fluor, chlore, brome et iode. By halogen atom is meant an atom chosen from fluorine, chlorine, bromine and iodine atoms.
Par groupe « siloxy », on entend un groupe silyle, tel que défini ci-dessous, lié par un atome d'oxygène (-O-Si(X)3) avec X tel que défini ci-dessous. By "siloxy" group is meant a silyl group, as defined below, linked by an oxygen atom (-O-Si (X) 3 ) with X as defined below.
Par groupe « silyle », on entend un groupe de formule [-Si(X)3] dans lequel chaque X, indépendamment l'un de l'autre, est choisi parmi un atome d'hydrogène ; un ou plusieurs atomes d'halogène choisis parmi les atomes de fluor, chlore, brome ou iode ; un ou plusieurs groupes alkyle ; un ou plusieurs groupes alkoxy ; un ou plusieurs groupes arnino ; un ou plusieurs groupes aryle ; un ou plusieurs groupes siloxy ; avec les groupes alkyle, alkoxy, aryle et siloxy tels que définis dans le cadre de la présente invention. By "silyl" group is meant a group of formula [-Si (X) 3 ] in which each X, independently of one another, is selected from a hydrogen atom; one or more halogen atoms selected from fluorine, chlorine, bromine or iodine atoms; one or more alkyl groups; one or more alkoxy groups; one or more amino groups; one or more aryl groups; one or more siloxy groups; with the alkyl, alkoxy, aryl and siloxy groups as defined in the context of the present invention.
Dans le procédé de l'invention, le catalyseur est (i) un acide de Lewis, choisi parmi : In the process of the invention, the catalyst is (i) a Lewis acid, chosen from:
- les composés organiques ou inorganiques de bore choisis parmi les organoboranes, les halogénoboranes, les alcoxyboranes, les cations boriniums, les cations boréniums, les cations boroniums, les organoborates, lesdits composés organiques ou inorganiques de bore étant avantageusement choisis parmi le BF3, le BF3(Et2O), le BCI3, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicyclo[3.3.1]nonane (BBNI), le B- chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9-borabicyclo[3.3.1]nonane (B- méthoxy-9-BBN), le B-benzyl-9-borabicyclo[3.3.1]nonane, le Me-TBD-ΒΒΝ+Γ, le Me-TBD-BBN+CF3SO3-, le (TDB-BBN)2, le TBD-BBN-CO2, le TBD-BBN-BBN, le [TBDH+, BBN(OCHO)2-], le [Et3NH+, Cy2B(OCHO)21 ; the organic or inorganic boron compounds chosen from organoboranes, haloboranes, alkoxyboranes, borinium cations, borenium cations, boronium cations, organoborates, said organic or inorganic boron compounds being advantageously chosen from BF 3 , BF 3 (Et 2 O), BCI 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane, Me-TBD- ΒΒΝ + Γ, Me-TBD-BBN + CF 3 SO 3 -, (TDB-BBN) 2 , TBD-BBN-CO 2 , TBD-BBN-BBN, [TBDH + , BBN (OCHO) 2 -], [Et 3 NH + , Cy 2 B (OCHO) 2 1;
- les composés organiques ou inorganiques de silicium choisis parmi les organosilanes, les halogénosilanes, les alcoxysilanes, les cations silylium de formule (R1R2R3)Si+ avec R1, R2, R3, indépendamment l'un de l'autre, représentant
un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, lesdits composés organiques ou inorganiques de silicium étant avantageusement choisis parmi SiCl4, Me3SiCl, Et3Si+ et Me3Si+ ; the organic or inorganic silicon compounds chosen from organosilanes, halosilanes, alkoxysilanes and silylium cations of formula (R 1 R 2 R 3 ) Si + with R 1 , R 2 and R 3 , independently of one of the other, representative a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic silicon compounds being advantageously chosen from SiCl 4 , Me 3 SiCl, and 3 Si + and Me 3 Si + ;
- les composés organiques ou inorganiques de germanium divalent ou tétravalent choisis parmi les organogermanes, les halogénogermanes, les alcoxygermanes, les cations germanium de formule (R9R10R11)Ge+ avec R9, R10, R11, indépendamment l'un de l'autre, représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, lesdits composés organiques ou inorganiques de géranium étant avantageusement choisis parmi GeCl2, GeBr2, GeCl4, Ge(OEt2)4, Me3GeCl, Me2ClGe+, Et3Ge+ et Me3Ge+ ; the organic or inorganic divalent or tetravalent germanium compounds chosen from organogermans, halogenogermans, alkoxygermans and germanium cations of formula (R 9 R 10 R 11 ) Ge + with R 9 , R 10 and R 11 independently of one of the other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic geranium compounds being preferably chosen from GeCl 2 , GeBr 2 , GeCl 4 , Ge (OEt 2 ) 4 , Me 3 GeCl, Me 2 ClGe + , and 3 Ge + and Me 3 Ge + ;
- les composés organiques ou inorganiques de l'étain de degré d'oxydation + IV ou + II choisis parmi les dérivés de chlorure stanneux, les cations de formule R20Sn+ avec R20 représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, les organostannanes, les halogénostannanes les alcoxystannanes, les cations stanniques de formule (R12R13R14)Sn+ avec R12, R13, R14, indépendamment l'un de l'autre, représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, lesdits composés organiques ou inorganiques d'étain étant avantageusement choisis parmi SnCl2, SnCL4, nBu2SnCl2, Cy3SnCl, Bu3SnHt tBu2SnCl2, «BuSnCl3, Me2SnCl, SnBu4, tetraisopropoxystannane, tetrakis(acétyloxy)stannane, Me3SnCl, Et3Sn+ et Me3Sn+ ; the organic or inorganic compounds of tin of oxidation degree + IV or + II chosen from stannous chloride derivatives, the cations of formula R 20 Sn + with R 20 representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, organostannanes, halostannanes, alkoxystannanes, stannic cations of formula (R 12 R 13 R 14 ) Sn + with R 12 , R 13 , R 14 , independently of each other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic tin compounds being advantageously chosen from SnCl 2 , SnCl 4 , nBu 2 SnCl 2 , Cy 3 SnCl, Bu 3 SnHt tBu 2 SnCl 2 , BuSnCl 3 , Me 2 SnCl, SnBu 4 , tetraisopropoxystannane , tetrakis (acetyloxy) stannane, Me 3 SnCl And 3 Sn + and Me 3 Sn + ;
- les oxoniums de formule (R15R16R17)O+ avec R15, R16, R17, indépendamment l'un de l'autre, représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués ; lesdits oxoniums étant avantageusement choisis parmi (CH3)3O+ et (CH3CH2)3O+;
- les carbocations de formule (R4R5R6)C+ avec R4, R5, R6, indépendamment l'un de l'autre, représentant un atome d'hydrogène, un groupe alkyle, un groupe alcényle un groupe aryle, un groupe alkoxy, un groupe amino, un groupe silyle, un groupe siloxy et un atome d'halogène, Iesdîts groupes alkyle, alcényle, amino, alkoxy et aryle étant éventuellement substitués ; lesdits carbocations étant avantageusement choisis parmi le cation trityle ((C6H5)C+), le tropylium (C7H7)+, le cation benzylique (C6HSCH2 +), le cation allylique (CH3-CH+-CH=CH2), le méthylium (CH3 +) et le cyclopropylium (C3H5 +). the oxoniums of formula (R 15 R 16 R 17 ) O + with R 15 , R 16 and R 17 , independently of one another, representing a hydrogen atom, an alkyl group, an alkoxy group, a amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted; said oxoniums being advantageously chosen from (CH 3 ) 3 O + and (CH 3 CH 2 ) 3 O + ; the carbocations of formula (R 4 R 5 R 6 ) C + with R 4 , R 5 and R 6 , independently of each other, representing a hydrogen atom, an alkyl group, an alkenyl group, a group aryl, an alkoxy group, an amino group, a silyl group, a siloxy group and a halogen atom, wherein the alkyl, alkenyl, amino, alkoxy and aryl groups are optionally substituted; said carbocations being advantageously chosen from trityl cation ((C 6 H 5 ) C + ), tropylium (C 7 H 7 ) + , benzyl cation (C 6 H S CH 2 + ), allylic cation (CH 3 - CH + -CH = CH 2 ), methylium (CH 3 + ) and cyclopropylium (C 3 H 5 + ).
Il est à noter que le contre ion anionique des cations silylium, des oxoniums, des carbocations, des cations stanniques et des cations germanium précités est, avantageusement, un halogénure choisi parmi F-, Cl-, Br- et Γ, ou un anion choisi parmi BF4-, SbF6-, B(C6F5)4-5 B(C6H5)4- CF3S03- ou TfO et PF6-It should be noted that the anionic counterion of the above-mentioned silylium cations, oxoniums, carbocations, cations and germanium cations is, advantageously, a halide chosen from F-, Cl-, Br- and Γ, or a chosen anion. from BF 4 -, SbF 6 -, B (C 6 F 5 ) 4 - 5 B (C 6 H 5 ) 4 - CF 3 S0 3 - or TfO and PF 6 -
De préférence, le catalyseur est (i) un acide de Lewis, choisis parmi : Preferably, the catalyst is (i) a Lewis acid, chosen from:
- les composés organiques ou inorganiques de bore choisis parmi les organoboranes, les halogénoboranes, les alcoxyboranes, les cations boriniums, les cations boréniums, les cations boroniums, les organoborates, lesdits composés organiques ou inorganiques de bore étant avantageusement choisis parmi le BF3, le BF3(Et20), le BC13, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicyclo[3.3.1]nonane (BBNI), le B- chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9-borabicyclo[3.3.1]nonane (B- méthoxy-9-BBN), le B-benzyl-9-borabicyclo[3.3.1]nonane, le Me-TBD-BBN+I -, le Me-TBD-BBN+CF3 S03-, le (TDB-BBN)2, le TBD-BBN-C02, le TBD-BBN- BBN, le [TBDFT, BBN(OCHO)2 _], et le [Et3NH+, Cy2B(OCHO)21 ; et the organic or inorganic boron compounds chosen from organoboranes, haloboranes, alkoxyboranes, borinium cations, borenium cations, boronium cations, organoborates, said organic or inorganic boron compounds being advantageously chosen from BF 3 , BF 3 (Et 2 0), BCI 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3, B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane, Me-TBD- BBN + I -, Me-TBD-BBN + CF 3 S0 3 -, (TDB-BBN) 2 , TBD-BBN-C0 2 , TBD-BBN-BBN, [TBDFT, BBN (OCHO) 2 _ ], and [Et 3 NH + , Cy 2 B (OCHO) 2 1; and
- les composés organiques ou inorganiques de germanium divalent ou tétravalent choisis parmi les organogermanes, les halogénogermanes, les alcoxygermanes, les cations germanium de formule (R9R10R11)Ge+ avec R9, R10, R11, indépendamment l'un de l'autre, représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, lesdits composés organiques ou inorganiques de germanium étant avantageusement choisis parmi GeCl2, GeBr2, GeCl4, Ge(OEt2)4s Me3GeCl, Me2ClGe+, Et3Ge+ et Me3Ge+ ; et
- les composés organiques ou inorganiques de l'étain de degré d'oxydation + IV ou + II choisis parmi les dérivés de chlorure stanneux, les cations de formule R20Sn+ avec R représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, les organostannanes, les halogénostannanes, les alcoxystannanes, les cations stanniques de formule (R12R13R14)Sn+ avec R12, R13, R14, indépendamment l'un de l'autre, représentant un atome d'hydrogène, un groupe alkyle, un groupe alkoxy, un groupe amino, un groupe aryle, lesdits groupes alkyle, amino, alkoxy et aryle étant éventuellement substitués, lesdits composés organiques ou inorganiques d'étain étant avantageusement choisis parmithe organic or inorganic divalent or tetravalent germanium compounds chosen from organogermans, halogenogermans, alkoxygermans and germanium cations of formula (R 9 R 10 R 11 ) Ge + with R 9 , R 10 and R 11 independently of one of the other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic germanium compounds being preferably chosen from GeCl 2 , GeBr 2 , GeCl 4 , Ge (OEt 2 ) 4s Me 3 GeCl, Me 2 ClGe + , and 3 Ge + and Me 3 Ge + ; and - organic or inorganic compounds of the oxidation state of the tin or + IV + II selected from derivatives of stannous chloride, the cation of the formula R 20 Sn + with R representing a hydrogen atom, an alkyl group, alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, organostannanes, halostannans, alkoxystannanes, stannic cations of formula (R 12 R 13 R 14 ) Sn + with R 12 , R 13 , R 14 , independently of each other, representing a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group, said alkyl, amino, alkoxy and aryl groups being optionally substituted, said organic or inorganic tin compounds being advantageously chosen from
SnCI2, SnCL,, «Bu2SnCl2, Cy3SnCl, Bu3SnH, tBu2SnCl2, nBuSnCl3, Me2SnCl, SnBu4, tetraisopropoxystannane, tetrakis(acétyloxy)stannane, Me3SnCl, Et3Sn+ et Me3Sn+ . SnCl 2, SnCl ,, "Bu 2 SnCl 2, Cy 3 SnCl, Bu 3 SnH, Bu 2 SnCl 2, nBuSnCl 3, Me 2 SnCl SnBu4, tetraisopropoxystannane, tetrakis (acetyloxy) stannane, Me 3 SnCl, and 3 Sn + and Me 3 Sn + .
Le contre ion anionique des cations germanium et stanniques et stanneux, précités est, avantageusement, un halogénure choisi parmi F-, Cl-, Br- et l-, ou un anion choisi parmi BF4-, SbF6-, B(C6F5)4-, B(C6H5y, CF3SO3- ou TfO et PF6-, The anionic counterion of the above-mentioned germanium and stannous and stannous cations is, advantageously, a halide selected from F-, Cl-, Br- and l-, or an anion chosen from BF 4 -, SbF 6 -, B (C 6 F 5 ) 4 -, B (C 6 H 5 y, CF 3 SO 3 - or TfO and PF 6 -,
Selon un mode de réalisation particulier, le procédé de production de dihydrogène à partir de l'acide formique, est caractérisé en ce que l'acide formique est mis en contact : avec au moins un catalyseur According to a particular embodiment, the process for producing dihydrogen from formic acid is characterized in that the formic acid is brought into contact with at least one catalyst
(i) ledit catalyseur étant un acide de Lewis, choisi parmi (i) said catalyst being a Lewis acid, selected from
- les composés organiques ou inorganiques de bore choisis parmi le BF3, le BF3(Et20), le BCI3, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicycIo[3.3.1]nonane (BBNI), le B- chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9-borabicyclo[3.3.1]nonane (B- méthoxy-9-BBN), le B-benzyl-9-borabicyclo[3.3.1 Jnonane, le Me-TBD-BBN+I,-, leorganic or inorganic boron compounds chosen from BF 3 , BF 3 (Et 2 0), BCI 3, diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9 -borabicyclo [3.3.1 Jnonane, Me-TBD-BBN + I, -, the
Me-TBD-BBN+CF3SO3-, le (TDB-BBN^, le TBD-BBN-C02, le TBD-BBN-BBN, le [TBDH+, BBN(OCHO)2-], le [Et3NH+, Cy2B(OCHO)2] ; Me-TBD-BBN + CF 3 SO 3 -, (TDB-BBN ^, TBD-BBN-C0 2 , TBD-BBN-BBN, [TBDH + , BBN (OCHO) 2 -], [And 3 NH + , Cy 2 B (OCHO) 2 ];
- les composés organiques ou inorganiques de silicium choisis SiCL4, Me3SiCl, Et3Si+ et Me3Si+ ; les composés organiques ou inorganiques de germanium divalent ou tétravalent choisis parmi GeCl2, GeBr2, GeCU, Ge(OEt2)4, Me3GeCl, Me2ClGe+, Et3Ge+ et Me3Ge+ ;
- les composés organiques ou inorganiques d'étain choisis parmi SnCI2, SnC1 4, 4Bu2SnCl2, Cy3SnCl, Bu3SnH, tBu2SnCI2, nBuSnCl3, Me2SnCl, SnBu4, tetraisopropoxystannane, tetrakis(acétyloxy)stannane, Me3SnCl. Et3Sn+ et Me3Sn+ ; - les oxoniums choisis parmi (CH3)3O+ et (CH3CH2)3O+; the selected organic or inorganic silicon compounds SiCl 4 , Me 3 SiCl, and 3 Si + and Me 3 Si + ; organic or inorganic divalent or tetravalent germanium compounds selected from GeCl 2 , GeBr 2 , GeCU, Ge (OEt 2 ) 4 , Me 3 GeCl, Me 2 ClGe + , and 3 Ge + and Me 3 Ge + ; - organic or inorganic tin compounds selected from SnCl 2, SnC1 4, 4BU 2 SnCl 2, Cy 3 SnCl, Bu 3 SnH, tBu 2 SnCl 2, nBuSnCl 3, Me 2 SnCl, SnBu 4 tetraisopropoxystannane, tetrakis (acetyloxy ) stannane, Me 3 SnCl. And 3 Sn + and Me 3 Sn + ; oxoniums chosen from (CH 3 ) 3 O + and (CH 3 CH 2 ) 3 O + ;
- les carbocations choisis parmi le cation trityle ((C6H5)3C+), le tropylium (C7H7)+, le cation benzylique (C6H5CH2 +), le cation allylique (CH3-CH+-CH=CH2), le méthylium (CH3 +) et le cyclopropylium (C3H5 +) ; the carbocations chosen from the trityl cation ((C 6 H 5 ) 3 C + ), the tropylium (C 7 H 7 ) + , the benzyl cation (C 6 H 5 CH 2 + ), the allylic cation (CH 3 -CH + -CH = CH 2 ), methylium (CH 3 + ) and cyclopropylium (C 3 H 5 + );
avec le contre ion anionique des cations silylium, des oxoniums, des carbocations, des cations stanniques et des cations germanium étant un halogénure choisi parmi F-, Cl-, Br- et I-, ou un anion choisi parmi BF4-, SbF6- B(C6FS)4-, B(C6H5)4-, CF3SO3- ou TfO-et PF6-. ; avec au moins un composé choisi parmi with the anionic counterion of silylium cations, oxoniums, carbocations, stannic cations and germanium cations being a halide selected from F-, Cl-, Br- and I-, or an anion selected from BF 4 -, SbF 6 - B (C 6 F S ) 4 -, B (C 6 H 5 ) 4 -, CF 3 SO 3 - or TfO - and PF 6 -. ; with at least one compound selected from
(ii) une base organique choisie parmi les bases organiques azotées, les bases organiques phosphorées, les bases carbonées, et les bases organiques oxygénées ; et/ou (ii) an organic base selected from nitrogenous organic bases, phosphorus organic bases, carbon bases, and oxygenated organic bases; and or
(iii) un sel d' halogénure. (iii) a halide salt.
Parmi les catalyseurs organiques de bore, comme indiqué dans le schéma 4 ci- dessous, le catalyseur (TBD-BBN)2 peut résulter de la dimérisation de TBD-BBN, le TBD-BBN-CO2 correspond à un adduit entre le TBD-BBN et le CO2 et le TBD-BBN- BBN correspond à un adduit entre le TBD-BBN et le 9-BBN. Among the organic boron catalysts, as shown in Scheme 4 below, the catalyst (TBD-BBN) 2 can result from the dimerization of TBD-BBN, TBD-BBN-CO 2 corresponds to an adduct between the TBD BBN and CO 2 and TBD-BBN-BBN correspond to an adduct between TBD-BBN and 9-BBN.
Schéma 4 Figure 4
Le Me-TBD-BBNX le (TBD-BBN)2, le TBD-BBN-CO2 et le TBD-BBN-BBN peuvent être obtenus, par exemple, selon les protocoles décrits ci-dessous dans les exemples. Me-TBD-BBN+CF3SO3 ainsi que Me-TBD-BBN+ X- dans lequel X- est choisis parmi le fluor, le chlore et le brome peuvent également être préparés en remplaçant le réactif 9-iodo-9-borabicyclo[3.3.1]nonane par le 9-borabicyclo[3.3.1]nonyl trifluoromethanesulfonate, 9-fluoro-9-borabicyclo[3.3.1]nonane, le 9-chloro-9- borabicyclo[3.3.1]nonane ou le 9-bromo-9-borabicyclo[3.3.1]nonane dans le protocole de synthèse de Me-TBD-BBN+ 1- décrit ci-après. Me-TBD-BBNX (TBD-BBN) 2 , TBD-BBN-CO 2 and TBD-BBN-BBN can be obtained, for example, according to the protocols described below in the examples. Me-TBD-BBN + CF 3 SO 3 as well as Me-TBD-BBN + X- in which X- is selected from fluorine, chlorine and bromine can also be prepared by replacing the 9-iodo-9-borabicyclo reagent. [3.3.1] Nonane by 9-borabicyclo [3.3.1] nonyl trifluoromethanesulfonate, 9-fluoro-9-borabicyclo [3.3.1] nonane, 9-chloro-9-borabicyclo [3.3.1] nonane or 9 -bromo-9-borabicyclo [3.3.1] nonane in the synthesis protocol of Me-TBD-BBN + 1- described hereinafter.
Les carbocations cités ci-dessus sont commerciaux ou peuvent être facilement synthétisés par l'homme du métier par différents procédés de synthèse, par exemple : le procédé de bassin de cation (cation pool), le procédé redox interne, le procédé utilisant un groupement partant, les procédés utilisant des acides de Lewis ou de Bronsted. Ces procédés sont décrits dans les références suivantes : R. R. Naredla et D. A. Klumpp, Chem. Rev. 2013, 113, pages 6905-6948 ; M. Saunders. et H. A. Jimenez-Vazquez, Chem. Rev. 1991, 91, pages 375-397. The carbocations mentioned above are commercial or can easily be synthesized by those skilled in the art by various synthetic methods, for example: the cation pool process, the internal redox process, the method using a leaving group methods using Lewis or Bronsted acids. These methods are described in the following references: R. R. Naredla and D. A. Klumpp, Chem. Rev. 2013, 113, pp. 6905-6948; Mr. Saunders. and H. A. Jimenez-Vazquez, Chem. Rev. 1991, 91, pages 375-397.
De préférence, (i) le catalyseur un acide de Lewis est choisi parmi Preferably, (i) the Lewis acid catalyst is selected from
- un dérivé de formule R2BX ou R est un groupe alkyle linéaire, ramifié ou cyclique, saturé, éventuellement substitué, comprenant 1 à 12 atomes de carbone, et X est choisi parmi Cl-, Bf-, 1-, un radical alcoxyde tel que méthoxydea derivative of formula R 2 BX or R is a linear, branched or cyclic, saturated, optionally substituted alkyl group comprising 1 to 12 carbon atoms, and X is chosen from Cl-, Bf-, 1-, an alkoxide radical; such as methoxide
-OMe ou éthoxyde -OEt, OTf, NTf2 et H. -OMe or ethoxide -OEt, OTf, NTf 2 and H.
- le BF3, le BF3(Et2O), le BC3, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicycIo[3.3.1]nonane (BBNI), le B-chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9- borabicyclo[3.3.1]nonane (B-méthoxy-9-BBN), le B-benzyl-9- borabicyclo[3.3.1]nonane, le Me-TBD-BBNX le Me-TBD-BBN+ CF3 SO3-, le (TDB-BBN)2, le TBD-BBN-CO2, le TBD-BBN-BBN, le [TBDH+, BBN(OCHO)2-], le [Et3NH+, Cy2B(OCHO)2-]; BF 3 , BF 3 (Et 2 O), BC 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), B-3 chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane , Me-TBD-BBNX Me-TBD-BBN + CF 3 SO 3 -, (TDB-BBN) 2 , TBD-BBN-CO 2, TBD-BBN-BBN, [TBDH + , BBN ( OCHO) 2 -], [Et 3 NH + , Cy 2 B (OCHO) 2 -];
SnC12, SnC14, nBu2SnCl2, Cy3SnC1, Bu3SnH, tBu2SnC12, nBuSnC13, Me2SnC1, SnBm, tetraisopropoxystannane, tetrakis(acétyIoxy)stannane, Me3SnC1, Et3Sn+ et Me3Sn+ ;
avec le contre ion anionique des cations stanniques et stanneux étant un anion non coordinant choisi parmi BF4-, SbF6-, B(C6F5)4-, B(C6H5)4-, CF3SO3- ou TfD-et PF6-. ou un halogénure choisi parmi F-, Cl-, Br- et l-. SnC1 2 SnC1 4, nBu 2 SnCl 2, Cy 3 SnC1, Bu 3 SnH, tBu 2 SnC1 2 nBuSnC1 3, Me 2 SnC1, SnBm, tetraisopropoxystannane, tetrakis (acétyIoxy) stannane, Me 3 SnC1, and 3 Sn + and Me 3 Sn + ; with the anionic counterion of the stannous and stannous cations being a non-coordinating anion selected from BF 4 -, SbF 6 -, B (C 6 F 5 ) 4 -, B (C 6 H 5 ) 4 -, CF 3 SO 3 - or TfD-and PF 6 -. or a halide selected from F-, Cl-, Br- and l-.
Il est à noter que dans le procédé de l'invention aucun liquide ionique n'est mis en œuvre, en particulier en tant que catalyseur. It should be noted that in the process of the invention no ionic liquid is used, in particular as a catalyst.
Selon une variante du procédé de l'invention, l'acide formique est mis en contact avec (i) un acide de Lewis comme catalyseur et (ii) une base organique comme co- catalyseur. According to a variant of the process of the invention, the formic acid is brought into contact with (i) a Lewis acid as catalyst and (ii) an organic base as cocatalyst.
La base organique (ii) peut être choisie parmi : - les bases organiques azotées qui sont avantageusement des aminés secondaires ou tertiaires choisies parmi le triazabicyclodécène (TBD) ; le N- méthyltriazabicyclodécène (Me-TBD), le l,8-diazabicyclo[5.4.0]undéc-7-ène (DBU), la triméthylamine, la triéthyleamine, la pipéridine, la 4- diméthylarninopyridine (DMAP), le l,4-diazabicyclo[2.2.2]octane (DABCO), la proline, le phénylalanine, un sel de thiazolium, la N-diisopropyléthylamine The organic base (ii) can be chosen from: - nitrogenous organic bases which are advantageously secondary or tertiary amines chosen from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethyleamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine
(DIPEA ou DIEA) ; (DIPEA or DIEA);
- les bases organiques phosphorées qui sont avantageusement des alkyles ou aryles phosphines, par exemple, choisies parmi le triphénylphosphine, le 2,2 - bis(diphénylphosphino)-l,l'-binaphthyle (BINAP), le triisopropylphosphine, 1,2- bis(diphénylphosphino)éthane (dppe), la tricyclohexylphosphine (PCy3) ; les alkyle et aryle phosphonates, par exemple, choisies parmi le diphénylphosphate, le triphénylphosphate (TPP), le tri(isopropyIphényl)phosphate (TIPP), le crésyldiphenyl phosphate (CDP), le tricrésylphosphate (TCP) ; les alkyle et aryle phosphates, par exemple, choisis parmi le di-n-butylphosphate (DBP), le tris-(2- éthylhexyl)-phosphate5 le triéthyl phosphate ; les alkyle et aryle phosphinites et phosphonites, par exemple, choisis parmi les méthyldiphénylphosphinite et méthyldiphénylphosphonite, les aza-phosphines, par exemple, choisies parmi le 2,8,9-triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane (BVMe) et le 2,8,9-triisobutyl-2,5,8,9-tetraaza-l-phosphabicyclo[3.3.3]undecane (BViBu) ; les bases carbonées pour lesquelles la protonation a lieu sur un atome de carbone, choisies avantageusement parmi les carbènes N-hétérocycliques issus d'un sel
d'imidazolium, ledits carbènes étant, par exemple, choisis parmi les sels les sels de 1.3-bis(2,6-diisopropylpheéyl)-lH-iniidazol-3-ium (également appelé IPr), 1,3- bis(2,6-diisopropylphényl)-4,5-dihydro-lH-imidazol-3-ium (également appelé s- IPr), l,3-bis(2,4,6-triméthylphényl)-lH-imidazol-3-ium (également appelé IMes), 1,3-bis(2,4,6-triméthylphényl)-4,5-dihydro- lH-imidazol-3-ium (également s- IMes), 4,5-dichloro-l ,3-bis(2,6-diisopropyIphényl)-lH-imidazol-3-ium (également appelé CI2-IPr), l,3-di-tert-butyl-lH-imidazol-3-ium (également appelé ItBu), 1,3- di-tert-butyl-4,5-dib.ydro-lH-imidazol-3-ium (également appelé s-ItBu), lesdits sels étant sous la forme de sels de chlorure, par exemple ; et les bases oxygénées choisies parmi, par exemple, le peroxyde d'hydrogène ; le peroxyde de benzoyle ; l'oxyde de pyridine (PyO), l'oxyde de N- méthylmorpholine et le l-λ1-oxidanyl-2,2,6,6-tétraméthylpipéridine. the phosphorus-containing organic bases which are advantageously alkyl or aryl phosphines, for example chosen from triphenylphosphine, 2,2-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP), triisopropylphosphine, 1,2-bis; (diphenylphosphino) ethane (dppe), tricyclohexylphosphine (PCy 3 ); alkyl and aryl phosphonates, for example, selected from diphenyl phosphate, triphenyl phosphate (TPP), tri (isopropylphenyl) phosphate (TIPP), cresyldiphenyl phosphate (CDP), tricresyl phosphate (TCP); the alkyl and aryl phosphates, e.g., selected from di-n-butyl phosphate (DBP), tris (2-ethylhexyl) phosphate 5 triethyl phosphate; alkyl and aryl phosphinites and phosphonites, for example, selected from methyldiphenylphosphinite and methyldiphenylphosphonite, aza-phosphines, for example, selected from 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (BV Me ) and 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (BV iBu ); the carbon bases for which the protonation takes place on a carbon atom, chosen advantageously from the N-heterocyclic carbenes derived from a salt imidazolium, ledits carbenes being, for example, selected from salts salts of 1,3-bis (2,6-diisopropylpheyl) -1H-iniidazol-3-ium (also called IPr), 1,3-bis (2, 6-diisopropylphenyl) -4,5-dihydro-1H-imidazol-3-ium (also called s-IPr), 1,3-bis (2,4,6-trimethylphenyl) -1H-imidazol-3-ium (also called IMes), 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydro-1H-imidazol-3-ium (also s-IMes), 4,5-dichloro-1,3-bis (2,6-diisopropylphenyl) -1H-imidazol-3-ium (also called CI 2 -IPr), 1,3-di-tert-butyl-1H-imidazol-3-ium (also called ItBu), 1.3 di-tert-butyl-4,5-dib.hydro-1H-imidazol-3-ium (also called s-ItBu), said salts being in the form of chloride salts, for example; and oxygen bases selected from, for example, hydrogen peroxide; benzoyl peroxide; pyridine oxide (PyO), N-methylmorpholine oxide and 1-λ 1 -oxidanyl-2,2,6,6-tetramethylpiperidine.
Des exemples de carbènes N-hétérocycliques sont représentés ci-dessous ; Examples of N-heterocyclic carbenes are shown below;
Quelques-unes des abréviations utilisées sont :
Some of the abbreviations used are:
De préférence, la base organique est une base organique azotée choisies parmi le triazabicyclodécène (TBD) ; le N-méthyltriazabicyclodécène (Me-TBD), le 1,8- diazabicyclo[5.4.0]undéc-7-ène (DBU), la triméthylamine, la triéthylamine, la pipéridine, la 4-diméthylaminopyridine (DMAP), le l,4-diazabicyclo[2.2.2]octane (DABCO), la proline, le phénylalanine, un sel de thiazolium, la N~diisopropyléthylamine (DIPEA ou DIEA). Selon une autre variante du procédé de l'invention, l'acide formique est mis en contact avec (i) un acide de Lewis comme catalyseur et (iii) un sel d'halogénure comme co-catalyseur.
Le sel d'halogénure (iii) peut être choisi parmi les sels de chlorure, de bromure, de l'iodure et de fluorure, lesdits sels d'halogénure étant choisis, par exemple, parmi NaF, NaC1, NaBr, Nal, KC1, LiC1, [(n-Bu4)N, F], [(n-Bu4)N+,CI,] [(n-Bu4)N+ ,Βr], [(n- Bu4)N+,I], [PPh4 +,F], [PPh4+,C1], [PPh4+,Br] et [PPh4+,I]. Selon un mode de réalisation particulier de l'invention, le procédé de production de dihydrogène à partir de l'acide formique, est caractérisé en ce que l'acide formique est mis en contact : Preferably, the organic base is a nitrogenous organic base selected from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine (DIPEA or DIEA). According to another variant of the process of the invention, the formic acid is brought into contact with (i) a Lewis acid as catalyst and (iii) a halide salt as cocatalyst. The halide salt (iii) may be chosen from the chloride, bromide, iodide and fluoride salts, said halide salts being chosen, for example, from NaF, NaCl, NaBr, NaI, KCl, LiCl, [(n-Bu 4 ) N , F], [(n-Bu 4 ) N + , Cl,] [(n-Bu 4 ) N + , Βr], [(n-Bu 4 ) N + , I ], [PPh 4 + , F], [PPh4 + , C1], [PPh4 + , Br] and [PPh4 + , I]. According to a particular embodiment of the invention, the process for producing dihydrogen from formic acid is characterized in that the formic acid is brought into contact with:
avec au moins un catalyseur with at least one catalyst
(i) ledit catalyseur étant un acide de Lewis, choisi parmi (i) said catalyst being a Lewis acid, selected from
- un dérivé de formule R2BX ou R est un groupe alkyle linéaire, ramifié ou cyclique, saturé, éventuellement substitué, comprenant 1 à 12 atomes de carbone et X est choisi parmi les halogènures Cl-, Br-, 1-, les alcoxydes tels que le méthoxyde - OMe ou l'éthoxyde -OEt, OTf, NTf2ou encore H. a derivative of formula R 2 BX or R is a linear, branched or cyclic alkyl group, saturated, optionally substituted, comprising 1 to 12 carbon atoms and X is chosen from C1-, Br-, 1- halogenides, alkoxides; such as methoxide-OMe or ethoxide -OEt, OTf, NTf 2 or H.
- le BF3, le BF3(Et20), le BC13, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicyclo[3.3.î]nonaneBF 3 , BF 3 (Et 2 0), BCl 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane
(BBNI), le B-chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9- borabicyclo[33.1]nonane (B-méthoxy-9-BBN), le B-benzyl-9- borabicyclo[3.3.1]nonane, le Me-TBD-BBN+ 1-, le Me-TBD-BBN+CF3So3, le (TDB-BBN)2, le TBD-BBN-C02, le TBD-BBN-BBN, le [TBDH+, BBN(OCHO)2 ~], le [EtsNFf, Cy2B(OCHO)2-] ; (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [33.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [ 3.3.1] nonane, Me-TBD-BBN + 1-, Me-TBD-BBN + CF 3 So 3 , (TDB-BBN) 2 , TBD-BBN-C0 2 , TBD-BBN-BBN , [TBDH + , BBN (OCHO) 2 ~ ], [EtsNFf, Cy 2 B (OCHO) 2 -];
- SnCl2, SnCU, «Bu2SnCl2, Cy3SnCl, Bu3SnH, tBu2SnC12, nBuSnC13, Me2SnC1, SnBu4, tetraisopropoxystarmane, tetrakis(acétyloxy)stannane, Me3SnC1, Et3Sn+ et Me3Sn+ ; avec le contre ion anionique des cations stanniques et stanneux étant un anion non coordinant choisi parmi BF4, SbF6-, B(C6F5)4-, B(C6H5)4-, CF3S03- ou TfO,et PF6 ,.ou un halogénure choisi parmi F-, C1-, Br- et Γ. SnCl 2 , SnCu, Bu 2 SnCl 2 , Cy 3 SnCl 3 , Bu 3 SnH, tBu 2 SnCl 2 , nBuSnCl 3 , Me 2 SnCl, SnBu 4 , tetraisopropoxystarmane, tetrakis (acetyloxy) stannane, Me 3 SnCl, and Sn 3 + and Me 3 Sn + ; with the anionic counterion of the stannous and stannous cations being a non-coordinating anion selected from BF 4 , SbF 6 -, B (C 6 F 5 ) 4 -, B (C 6 H 5 ) 4 -, CF 3 SO 3 - or TfO , and PF 6 , or a halide selected from F-, Cl-, Br- and Γ.
avec au moins un composé choisi parmi with at least one compound selected from
(ii) les bases organiques azotées choisies parmi le triazabicyclodécène (TBD) ; le N- méthyltriazabicyclodécène (Me-TBD), le l,8-diazabicyclo[5.4.0]undéc-7-ène (DBU), la triméthylamine, la triéthylamine, la pipéridine, la 4- diméthylaminopyridine (DMAP), le l,4-diazabicyclo[2.2.2]octane (DABCO), la
proline, le phénylalanine, un sel de thiazolium, la N-diisopropyléthylamine (DIPEA ou DIEA) ; et/ou (ii) nitrogenous organic bases selected from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), the proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine (DIPEA or DIEA); and or
Le procédé de production de dihydrogène selon l'invention, peut ainsi mettre en œuvre : The process for producing dihydrogen according to the invention can thus implement:
- au moins (i) un acide de Lewis comme catalyseur (s), at least (i) a Lewis acid catalyst (s),
- au moins (i) un acide de Lewis en mélange avec au moins un co-catalyseur qui peut être (ii) une base organique ou (iii) un sel d'halogénure, ou encore at least (i) a Lewis acid in admixture with at least one co-catalyst which may be (ii) an organic base or (iii) a halide salt, or
- au moins (i) un acide de Lewis en mélange avec un mélange de co-catalayseurs (ii) et (iii). at least (i) a Lewis acid mixed with a mixture of co-catalyst (ii) and (iii).
Dans le procédé de l'invention, (i) l'acide de Lewis peut être en mélange avec (ii) une base organique et/ou (iii) un sel d'halogénure, tels que définis ci-dessus. A titre d'exemples de mélange de (i) et de (ii), on peut citer les mélanges chlorodicyclohexylborane/Me-TBD, B-chlorocatecholborane/DBU, chlorodicyclohexyIborane/BVMe ou 9-iodo-9-borabicyclo[3.3. l]nonane/NEt3. In the process of the invention, (i) the Lewis acid may be in admixture with (ii) an organic base and / or (iii) a halide salt, as defined above. By way of examples of mixtures of (i) and (ii), mention may be made of chlorodicyclohexylborane / Me-TBD, β-chlorocatecholborane / DBU, chlorodicyclohexylborane / BV Me or 9-iodo-9-borabicyclo [3.3. l] nonane / NEt 3 .
Dans le procédé de l'invention, (i) l'acide de Lewis peut s'associer par liaison covalente avec (ii) une base organique et/ou (iii) un sel d'halogénure. A titre d'exemple de molécule dans laquelle (i) s'associe par liaison covalente à (iii), on citera TBD-BBN-BBN et TBD-BBN-C02. In the process of the invention, (i) the Lewis acid may be covalently associated with (ii) an organic base and / or (iii) a halide salt. By way of example of a molecule in which (i) is covalently associated with (iii), TBD-BBN-BBN and TBD-BBN-C0 2 will be mentioned.
Les catalyseurs peuvent, le cas échéant, être immobilisés sur des supports hétérogènes, par exemple, afin d'assurer une séparation facile dudit catalyseur et/ou son recyclage. Lesdits supports hétérogènes peuvent être choisis parmi les supports à base de gel de silice ou de polymères plastiques comme, par exemple, le polystyrène ; les supports carbonés choisis parmi les nanotubes de carbone ; le carbure de silice ; l'alumine ; ou le chlorure de magnésium (MgCl2). The catalysts may, where appropriate, be immobilized on heterogeneous supports, for example, in order to ensure easy separation of said catalyst and / or its recycling. Said heterogeneous supports may be chosen from supports based on silica gel or on plastic polymers such as, for example, polystyrene; carbon supports selected from carbon nanotubes; silica carbide; alumina; or magnesium chloride (MgCl 2 ).
Comme déjà indiqué, la production de dihydrogène à partir de l'acide formique par le procédé de l'invention peut être accompagnée par la production concomitante de dioxyde de carbone. Dans ce cas, le mélange de dihydrogène et de dioxyde de carbone peut être utilisé tel quel ou le dihydrogène et le dioxyde de carbone peuvent être séparés
selon les méthodes connues de l'homme du métier comme par exemple, la séparation H2/CO2 par adsorption du CO2 sur des éthanolamines ou la séparation cryogénique. As already indicated, the production of dihydrogen from formic acid by the process of the invention can be accompanied by the concomitant production of carbon dioxide. In this case, the mixture of dihydrogen and carbon dioxide can be used as it is or the dihydrogen and carbon dioxide can be separated according to the methods known to those skilled in the art such as, for example, H 2 / CO 2 separation by adsorption of CO2 on ethanolamines or cryogenic separation.
Le dihydrogène produit peut donc être utilisé directement dans des piles à combustible ou dans un moteur à combustion interne. Dans le cas où le dihydrogène et le dioxyde de carbone sont séparés, le dioxyde de carbone peut être utilisé : The hydrogen produced can therefore be used directly in fuel cells or in an internal combustion engine. In the case where the dihydrogen and the carbon dioxide are separated, the carbon dioxide can be used:
- dans le procédé comme gaz d'inertage, peut être transformé en acide formique, en formamide, en méthanal, en méthanol et en méthane par des procédés connus, in the process as an inert gas, can be converted into formic acid, formamide, methanal, methanol and methane by known methods,
- dans l'industrie alimentaire en créant, par exemple, une atmosphère protectrice qui permet de contrôler la prolifération des microorganismes (larves d'insectes, bactéries, champignons, etc.) présents dans les denrées alimentaires, comme les céréales ou le pain de mie, en les privant d'oxygène, ou encore - in the food industry by creating, for example, a protective atmosphere that controls the proliferation of microorganisms (insect larvae, bacteria, fungi, etc.) present in foodstuffs, such as cereals or bread , by depriving them of oxygen, or
- pour produire des composés chimiques comme, par exemple, des combustibles, des polymères plastiques, des médicaments, des détergents, des molécules à hauts tonnages, traditionnellement obtenus par des méthodes pétrochimiques. to produce chemical compounds such as, for example, fuels, plastic polymers, drugs, detergents, high tonnage molecules, traditionally obtained by petrochemical methods.
Outre le catalyseur (i) et éventuellement les composés (ii) et/ou (iii), le procédé de l'invention, peut être éventuellement mis en œuvre en présence d'au moins un additif basique. Ledit additif peut être une base organique ou inorganique ayant un pKa supérieur à celui de l'acide formique, c'est-à-dire un pKa supérieur à 3,7 pour permettre de générer des ions formiates HCOO- à partir de l'acide formique contribuant ainsi à l'accélération de la vitesse de réaction et donc la production de dihydrogène. Par ailleurs, ledit additif basique peut également contribuer à piéger en solution, sous forme d'ions carbonate ou hydrogénocarbonate par exemple, tout ou partie du C02 produit, permettant ainsi d'obtenir du dihydrogène pur ou un mélange de gaz enrichi en H2. Ledit additif basique peut être choisi, par exemple, parmi In addition to the catalyst (i) and optionally the compounds (ii) and / or (iii), the process of the invention may optionally be carried out in the presence of at least one basic additive. Said additive may be an organic or inorganic base having a pKa greater than that of formic acid, that is to say a pKa greater than 3.7 to make it possible to generate formate ions HCOO- from the acid formic thus contributing to the acceleration of the reaction rate and thus the production of dihydrogen. Moreover, said basic additive may also contribute to trapping in solution, in the form of carbonate or hydrogencarbonate ions, for example, all or part of the CO 2 produced, thus making it possible to obtain pure dihydrogen or a mixture of gases enriched in H 2 . Said basic additive may be chosen, for example, from
- les aminés organiques choisies parmi la triéthylamine, la pipéridine et la 4- diméthylaminopyridine (DMAP), organic amines chosen from triethylamine, piperidine and 4-dimethylaminopyridine (DMAP),
- l'ammoniac et l'ammonique, - ammonia and ammonia,
- les bases inorganiques carbonées choisies parmi les sels de carbonates C03 2-, les sels d'hydrogénocarbonate HC03-, lesdits sels de carbonates C03 2- et d'hydrogénocarbonate HCO3- étant choisies parmi CaC03 et NaHC03, the inorganic carbon bases chosen from the carbonates C0 3 2- salts, the hydrogencarbonate salts HCO 3 -, said carbonate salts C0 3 2- and hydrogen carbonate HCO 3 - being chosen from CaCO 3 and NaHCO 3 ,
- les bases inorganiques oxygénées choisis parmi les sels d'hydroxyde HO- lesdits sels d'hydroxyde étant choisis parmi KOH et NaOH.
Lorsque l'acide formique est mis en contact avec au moins un catalyseur (i) et éventuellement les composés (ii) et/ou (iii), en présence d'un additif basique, la quantité d'additif basique utilisé peut être de 0,1 à 1 équivalent molaire, bornes incluses, par rapport au nombre de moles de l'acide formique. the oxygenated inorganic bases chosen from the hydroxide salts HO - said hydroxide salts being chosen from KOH and NaOH. When the formic acid is brought into contact with at least one catalyst (i) and optionally compounds (ii) and / or (iii), in the presence of a basic additive, the amount of basic additive used can be from 0 to , 1 to 1 molar equivalents, inclusive, relative to the number of moles of formic acid.
La production de dihydrogène selon le procédé de l'invention peut se produire sous une pression de C02, de H2, de diazote (N2), d'argon ou d'un mélange d'au moins deux de ces gaz. The production of dihydrogen according to the process of the invention can occur under a pressure of CO 2 , H 2 , dinitrogen (N 2 ), argon or a mixture of at least two of these gases.
Ainsi, la production de dihydrogène à partir de l'acide formique par le procédé de l'invention peut se produire sous la pression des gaz formés (H2 ou mélange H2 + C02), sous la pression de gaz inertes (N2 et/ou d'argon), ou sous une pression réduite en collectant les gaz formés dans un système à basse pression, par exemple, dans une burette. Thus, the production of dihydrogen from formic acid by the process of the invention can occur under the pressure of the gases formed (H 2 or H 2 + CO 2 mixture), under the pressure of inert gases (N 2 and / or argon), or under reduced pressure by collecting the gases formed in a low pressure system, for example, in a burette.
Le procédé de l'invention peut alors avoir lieu sous une pression comprise entre 0,1 et 200 bars, de préférence entre 0,1 et 75 bars, préférablernent entre 0,1 et 30 bars, plus préférentiellement entre 0,1 et 10 bars, bornes incluses. The process of the invention can then take place at a pressure of between 0.1 and 200 bar, preferably between 0.1 and 75 bar, preferably between 0.1 and 30 bar, more preferably between 0.1 and 10 bar. , terminals included.
La réaction de l'acide formique avec le catalyseur (i) et éventuellement les composés (ii) et/ou (iii), et le cas échéant en présence d'un additif basique tel que défini ci-dessus, peut être effectuée à une température comprise entre 15 et 150°C, de préférence entre 15 et 130°C, bornes incluses. The reaction of the formic acid with the catalyst (i) and optionally the compounds (ii) and / or (iii), and optionally in the presence of a basic additive as defined above, can be carried out at a temperature of temperature between 15 and 150 ° C, preferably between 15 and 130 ° C, inclusive.
La durée de la réaction dépend du taux de conversion de l'acide formique. La réaction est avantageusement maintenue jusqu'à la conversion totale de l'acide formique. La durée de la réaction peut être de 5 minutes à 200 heures, de préférence de 10 minutes à 48 heures, bornes incluses. The duration of the reaction depends on the conversion rate of formic acid. The reaction is advantageously maintained until the total conversion of the formic acid. The duration of the reaction may be from 5 minutes to 200 hours, preferably from 10 minutes to 48 hours, limits included.
Le procédé de production de dihydrogène à partir de l'acide formique selon l'invention peut encore avoir lieu dans un ou un mélange d'au moins deux solvant(s) choisi(s) parmi : The process for producing dihydrogen from the formic acid according to the invention may also take place in a mixture of at least two solvent (s) chosen from:
- l'eau ; - the water ;
- les alcools, de préférence Péthanol ou l'éthylène glycol ; alcohols, preferably ethanol or ethylene glycol;
- les éthers, de préférence, l'éther diéthylique, ou le THF ; ethers, preferably diethyl ether, or THF;
- les hydrocarbures, de préférence, le benzène, ou le toluène ; hydrocarbons, preferably benzene or toluene;
- les solvants azotés, de préférence, la pyridine, ou I'acétonitrile ; - Nitrogen solvents, preferably pyridine, or acetonitrile;
- les sulfoxydes, de préférence, le diméthylesulfoxyde ; sulfoxides, preferably dimethyl sulphoxide;
- les halogénures d'alkyle, de préférence, le chloroforme, ou le chlorure de méthylène ;
- un fluide supercritique, de préférence le C02 supercritique. alkyl halides, preferably chloroform, or methylene chloride; a supercritical fluid, preferably supercritical CO 2 .
Les différents réactifs utilisés dans le procédé de l'invention notamment, l'acide formique, les (pré-) catalyseurs, les co-catalyseurs, les additifs basiques, sont, en général, des composés commerciaux ou peuvent être préparés par les procédés déjà décrits dans la littérature et connus de l'homme du métier. The various reagents used in the process of the invention in particular, formic acid, (pre) catalysts, cocatalysts, basic additives, are, in general, commercial compounds or can be prepared by processes already described in the literature and known to those skilled in the art.
La quantité de catalyseur utilisé dans le procédé de l'invention est de 0,0001 à 1 équivalent molaire, de préférence de 0,001 à 1 équivalent molaire, plus préférentiellement de 0,001 à 0,5 équivalent molaire, bornes incluses, par rapport au nombre de mole d'acide formique. The amount of catalyst used in the process of the invention is from 0.0001 to 1 molar equivalent, preferably from 0.001 to 1 molar equivalent, more preferably from 0.001 to 0.5 molar equivalents, inclusive, in relation to the number of molars. mole of formic acid.
Les conditions opératoires indiquées ci-dessus, s'appliquent à tous les modes de réalisation du procédé de l'invention. The operating conditions indicated above apply to all the embodiments of the process of the invention.
Le dihydrogène obtenu par le procédé de l'invention peut être utilisé notamment pour la production d'ammoniac et de méthanol, et le raffinage du pétrole. Il peut également être employé dans les secteurs de la métallurgie et de l'électronique, de la pharmacie ainsi que dans le traitement de produits alimentaires. The dihydrogen obtained by the process of the invention can be used in particular for the production of ammonia and methanol, and the refining of petroleum. It can also be used in the sectors of metallurgy and electronics, pharmacy as well as in the processing of food products.
Utilisé dans une pile à combustible ou un moteur à combustion interne, le dihydrogène produit par le procédé de l'invention peut se combiner à l'oxygène de l'air pour produire de l'électricité en ne rejetant que de l'eau. Le dihydrogène représente donc un fort potentiel pour fournir de l'énergie propre et garantir la sécurité des approvisionnements. Used in a fuel cell or an internal combustion engine, the hydrogen produced by the process of the invention can combine with oxygen in the air to produce electricity by releasing only water. Hydrogen therefore represents a strong potential for providing clean energy and ensuring security of supply.
L'invention a également pour objet l'utilisation du dihydrogène produit par le procédé de l'invention, dans une pile à combustible, dans un moteur à combustion, dans la production d'ammoniac et de méthanol, dans le raffinage du pétrole, dans les secteurs de la métallurgie, de l'électronique et de l'alimentaire. The invention also relates to the use of the dihydrogen produced by the process of the invention, in a fuel cell, in a combustion engine, in the production of ammonia and methanol, in the refining of petroleum, in Metallurgy, Electronics and Food.
Un autre objet de l'invention concerne un procédé de production de l'énergie, caractérisé en ce qu'il comprend une étape de production de dihydrogène à partir de l'acide formique par le procédé selon l'invention. Another object of the invention relates to a method for producing energy, characterized in that it comprises a step of producing dihydrogen from formic acid by the process according to the invention.
D'autres avantages et caractéristiques de la présente invention apparaîtront à la lecture des exemples ci-dessous donnés à titre illustratif et non limitatif. EXEMPLES Other advantages and features of the present invention will appear on reading the examples below given for illustrative and non-limiting. EXAMPLES
La réaction catalytique de déshydrogénation de l'acide formique, présentée dans le schéma 5, peut être effectuée selon le protocole expérimental suivant :
1. Sous atmosphère inerte d'argon ou de dîazote, en boîte à gants, l'acide formique, le pré-catalyseur (de 1 à 0,001 équivalent) et, éventuellement, le solvant et l'additif basique sont introduits dans un tube de Schlenk qui est ensuite scellé par un robinet J. Young. L'ordre d'introduction des réactifs n'a pas d'importance. The catalytic dehydrogenation reaction of formic acid, shown in scheme 5, can be carried out according to the following experimental protocol: 1. In an inert atmosphere of argon or nitrogen, in a glove box, the formic acid, the pre-catalyst (from 1 to 0.001 equivalents) and optionally the solvent and the basic additive are introduced into a tube of Schlenk which is then sealed by a tap J. Young. The order of introduction of the reagents does not matter.
2. Le Schlenk est ensuite chauffé à une température comprise entre 25 et 140 °C jusqu'à la conversion totale de l'acide formique (de 5 minutes à 150 heures de réaction). 2. The Schlenk is then heated to a temperature between 25 and 140 ° C until the total conversion of formic acid (from 5 minutes to 150 hours of reaction).
3. Les gaz émis peuvent être collectés au cours de la réaction par un système de burettes ou bien connecté à un dispositif utilisant les gaz émis, telle qu'une pile à combustible PEMFC. Alternativement, les gaz peuvent être stockés dans l'enceinte du milieu réactionnel fermé si celle-ci peut supporter la pression de gaz générée. 3. The emitted gases may be collected during the reaction by a burette system or connected to a device using the emitted gases, such as a PEMFC fuel cell. Alternatively, the gases can be stored in the enclosure of the closed reaction medium if it can withstand the gas pressure generated.
Différents catalyseurs, additifs, solvants et températures ont été testés pour la réaction. Different catalysts, additives, solvents and temperatures were tested for the reaction.
Les catalyseurs Me-TBD-BBN+ l-, (TDB-BBN)2, TBD-BBN-C02, TBD-BBN- BBN, [TBDH+, BBN(OCHO)2-] et [Et3NH+, Cy2B(OCHO)2-] ont été préparés selon les protocoles suivants : The catalysts Me-TBD-BBN + 1-, (TDB-BBN) 2 , TBD-BBN-CO 2 , TBD-BBN-BBN, [TBDH + , BBN (OCHO) 2 -] and [Et 3 NH + , Cy 2 B (OCHO) 2 -] were prepared according to the following protocols:
. Synthèse de (TBD-BBN-)2 . Synthesis of (TBD-BBN-) 2
Un ballon de 20 mL équipé d'un barreau aimanté et fermé par un bouchon J. Young est chargé avec de la TBD (163,1 mg, 1,17 mmol, 1 éq), du dimère (9-BBN)2 (143,0 mg, 0,59 mmol, 0,5 éq) et du tétrahydrofurane (3,5 mL). Le ballon est fermé et la solution est agitée une heure à 70°C. Le mélange réactionnel est refroidi à température ambiante puis le solide est filtré sur fritté et lavé avec du diéthyléther. Un solide blanc est récupéré et séché sous pression réduite pour obtenir le produit (TBD-BBN)2 avec un rendement de 75% (194,9 mg). A 20 mL flask equipped with a magnetic bar and closed with a J. Young cap is loaded with TBD (163.1 mg, 1.17 mmol, 1 eq), dimer (9-BBN) 2 (143 0 mg, 0.59 mmol, 0.5 eq) and tetrahydrofuran (3.5 mL). The flask is closed and the solution is stirred for one hour at 70 ° C. The reaction mixture is cooled to room temperature and then the solid is sintered and washed with diethyl ether. A white solid is recovered and dried under reduced pressure to obtain the product (TBD-BBN) 2 with a yield of 75% (194.9 mg).
- Synthèse de TBD-BBN-CQ2 - Synthesis of TBD-BBN-CQ 2
Un ballon de 20 mL équipé d'un barreau aimanté et fermé par un bouchon J. Young est chargé avec de la (TBD-BBN)2 (71,0 mg, 0,14 mmol) et du tétrahydrofurane (4
mL). Le mélange réactionnel est mis sous atmosphère de C02 (1 bar). Le ballon est fermé et la solution est agitée 75 minutes à 100°C. Le solide blanc dans le mélange réactionnel se solubilise progressivement au cours du chauffage. Le mélange réactionnel est refroidi à température ambiante (environ 20°C) puis le solvant est évaporé sous pression réduite afin de récupérer TBD-BBN-C02 sous la forme d'un solide blanc avec un rendement quantitatif (84,0 mg). A 20 mL flask equipped with a magnetic bar and closed with a J. Young cap is loaded with (TBD-BBN) 2 (71.0 mg, 0.14 mmol) and tetrahydrofuran (4 mL). The reaction mixture is placed under a CO 2 atmosphere (1 bar). The flask is closed and the solution is stirred for 75 minutes at 100 ° C. The white solid in the reaction mixture gradually solubilizes during heating. The reaction mixture was cooled to room temperature (about 20 ° C) and then the solvent was evaporated under reduced pressure to recover TBD-BBN-CO 2 as a white solid in quantitative yield (84.0 mg).
- Synthèse de TBD-BBN-BBN - Synthesis of TBD-BBN-BBN
Un ballon de 20 mL équipé d'un barreau aimanté et fermé par un bouchon J. Young est chargé avec de la (TBD-BBN)2 (100,0 mg, 0,19 mmol, 1 éq), du dimère (9- BBN)2 (51,0 mg, 0,21 mmol, 1,1 éq) et du tétrahydrofurane (5 mL). Le ballon est fermé et la solution est agitée 150 minutes à 100°C. Le solide blanc dans le mélange réactionnel se solubilise progressivement au cours du chauffage. Le mélange réactionnel est refroidi à température ambiante puis le solvant est partiellement évaporer du mélange réactionnel jusqu'à environ 0,5 mL. Au cours de l'évaporation du solvant, un solide blanc apparaît. Le solide est filtré sur frité et lavé avec du diéthyléther froid (-40°C). Le solide est récupéré et séché sous pression réduite pour obtenir le produit TBD-BBN-BBN avec un rendement de 76% (110,5 mg). A 20 mL flask equipped with a magnetic bar and closed with a J. Young plug is loaded with (TBD-BBN) 2 (100.0 mg, 0.19 mmol, 1 eq), dimer (9- BBN) 2 (51.0 mg, 0.21 mmol, 1.1 eq) and tetrahydrofuran (5 mL). The flask is closed and the solution is stirred for 150 minutes at 100 ° C. The white solid in the reaction mixture gradually solubilizes during heating. The reaction mixture is cooled to room temperature and then the solvent is partially evaporated from the reaction mixture to about 0.5 mL. During evaporation of the solvent, a white solid appears. The solid is filtered on fried and washed with cold diethyl ether (-40 ° C). The solid is recovered and dried under reduced pressure to obtain the TBD-BBN-BBN product with a yield of 76% (110.5 mg).
- Synthèse de Me-TBD-BBN+ l- - Synthesis of Me-TBD-BBN + l-
Un ballon de 20 mL équipé d'un barreau aimanté et fermé par un bouchon J. Young est chargé avec de la Me-TBD (53,1 mg, 0,35 mmol, 1 éq) et du tétrahydrofurane (3,5 mL). La solution est agitée et une solution de 9-iodo-9-borabicyclo[3.3.1]nonane 1 M dans l'hexane (350 μL, 0,35 mmol, 1 éq) est ajoutée au mélange réactionnel. Un précipité blanc se forme immédiatement après ajout de la solution de 9-iodo-9- borabicyclo[3.3.1]nonane. Le ballon est fermé et la solution est agitée 30 minutes à température ambiante (environ 20°C). Le solide est filtré sur fritté et lavé avec du diéthyléther. Le solide est récupéré et séché sous pression réduite pour obtenir le produit Me-TBD-BBN+ I-avec un rendement de 81% (112,0 mg). A 20 mL flask equipped with a magnetic bar and closed with a J. Young plug is loaded with Me-TBD (53.1 mg, 0.35 mmol, 1 eq) and tetrahydrofuran (3.5 mL). . The solution is stirred and a solution of 1M 9-iodo-9-borabicyclo [3.3.1] nonane in hexane (350 μL, 0.35 mmol, 1 eq) is added to the reaction mixture. A white precipitate forms immediately after addition of the 9-iodo-9-borabicyclo [3.3.1] nonane solution. The flask is closed and the solution is stirred for 30 minutes at room temperature (about 20 ° C). The solid is sintered and washed with diethyl ether. The solid is recovered and dried under reduced pressure to obtain Me-TBD-BBN + I-product with a yield of 81% (112.0 mg).
1H NMR (200 MHz, CD2CI2): δ 4.13 (m, 1H), 3.95 (m, 1H), 3.75 (m, 2H), 3.48 (m, 4H), 3.10 (s, 3H), 2,49-1,18 (m, 18H) ppm. 1 H NMR (200 MHz, CD 2 Cl 2 ): δ 4.13 (m, 1H), 3.95 (m, 1H), 3.75 (m, 2H), 3.48 (m, 4H), 3.10 (s, 3H), 2 , 49-1.18 (m, 18H) ppm.
13C NMR (50 MHz, CD2CI2): δ 158.7, 48.7, 48.4, 43.4, 41.2, 36.1, 35.5, 31.5, 30.9, 25.9, 24.9, 20.9, 20.4 ppm. 1 3 C NMR (50 MHz, CD 2 CI 2 ): δ 158.7, 48.7, 48.4, 43.4, 41.2, 36.1, 35.5, 31.5, 30.9, 25.9, 24.9, 20.9, 20.4 ppm.
11B NMR (64 MHz, CD2C12): δ 57,2 ppm.
Analyse élémentaire: cale, pour C16H29BIN3 (M 401,14 g.mol-1) : C : 47.91, H : 7.29, N : 10.48. Found : C : 48.26, H 6.96; N 11.63. 11 B NMR (64 MHz, CD 2 C1 2 ): δ 57.2 ppm. Elemental analysis: Calcd, for C 16 H 29 BIN 3 (M 401.14 gmol -1 ): C: 47.91, H: 7.29, N: 10.48. Found: C: 48.26, H, 6.96; N 11.63.
Vue ORTEP de Me-TBD-BBN+ l-obtenu par diffraction des rayons X. ORTEP view of Me-TBD-BBN + 1-obtained by X-ray diffraction.
Synthèse de [TBDH+, BBN(OCHO)2-1. Synthesis of [TBDH + , BBN (OCHO) 2 -1.
Dans un ballon de 25 mL, muni d'un barreau aimanté et d'un robinet J-Young, est ajouté du dimère 9-BBN (342 mg, 1.4 mmol, 0.5 équiv.) et 5 mL de toluène. La suspension obtenue est agitée jusqu'à complète dissolution du solide puis l'acide formique (258 mg, 211 μί, 5.6 mmol, 2 équiv) est ajouté à l'aide d'une seringue suivi par la TBD (390 mg, 2.8 mmol, 1 équiv) en une seule fois. Un fort dégagement d'hydrogène gaz est observé. La réaction est alors agitée pendant 2 h à température ambiante puis du pentane (5 mL) est ajouté. Un solide blanc précipite, celui-ci est alors récupéré par filtration et lavé au pentane (3 x 2 mL). Le solide blanc ainsi récupéré est séché sous pression réduite pour obtenir [TBDH+, BBN(OCHO)2-] (930 mg) avec un rendement de 93 %. Ce dernier peut être recristallisé à partir d'une solution saturée de toluène. In a 25 mL flask fitted with a magnetic stir bar and a J-Young tap, 9-BBN dimer (342 mg, 1.4 mmol, 0.5 equiv) and 5 mL of toluene are added. The suspension obtained is stirred until the solid is completely dissolved, and then formic acid (258 mg, 211 μl, 5.6 mmol, 2 equiv) is added using a syringe followed by TBD (390 mg, 2.8 mmol). , 1 equiv) at one time. A strong release of hydrogen gas is observed. The reaction is then stirred for 2 h at room temperature and then pentane (5 mL) is added. A white solid precipitates, this is then recovered by filtration and washed with pentane (3 x 2 mL). The white solid thus recovered is dried under reduced pressure to obtain [TBDH + , BBN (OCHO) 2 -] (930 mg) in a yield of 93%. The latter can be recrystallized from a saturated solution of toluene.
1H NMR (200 MHz, CD3CN) δ 8.40 (s, 2H), 6.94 (bs, 2H), 3.23 (dd, J = 11.3, 5.3 Hz, 8H), 2.06 - 1.21 (m, 16H), 0.72 (bs, 2H). 1 H NMR (200 MHz, CD 3 CN) δ 8.40 (s, 2H), 6.94 (bs, 2H), 3.23 (dd, J = 11.3, 5.3 Hz, 8H), 2.06 - 1.21 (m, 16H), 0.72 (bs, 2H).
13C NMR (50 MHz, CD3CN) δ 167.23, 152.07, 47.43, 38.74, 32.07, 25.62, 21.16. 13 C NMR (50 MHz, CD 3 CN) δ 167.23, 152.07, 47.43, 38.74, 32.07, 25.62, 21.16.
11B NMR (64 MHz, CD3CN) δ 8.87. 1 1 B NMR (64 MHz, CD 3 CN) δ 8.87.
Analyse élémentaire: cale (%) pour C17H3oBN304 (351.25 g.mol-1): C 58.13, H 8.61, N 11.96; trouvé: C 58.12, H 8.58 N 12.16.
Elemental analysis: Calcium (%) for C 17 H 30 BN 3 O 4 (351.25 gmol -1 ): C 58.13, H 8.61, N 11.96; found: C 58.12, H 8.58 N 12.16.
Vue ORTEP de [TBDH+, BBN(OCHO)2- ] obtenu par diffraction des rayons X. Synthèse de [Et3NH+, Cy2B(OCHO)2-] ORTEP view of [TBDH + , BBN (OCHO) 2 -] obtained by X-ray diffraction. Synthesis of [Et 3 NH + , Cy 2 B (OCHO) 2 -]
Le dicyclohexylborane Cy2BH est synthétisé à partir d'une procédure décrite dans la littérature et est utilisé sans purification particulière. Cy 2 BH dicyclohexylborane is synthesized from a procedure described in the literature and is used without special purification.
Dans un ballon de 25 mL, muni d'un barreau aimanté et d'un robinet J-Young, est ajouté Cy2BH (481 mg, 2,7 mmol, 1 équiv.) et 5 mL de toluène. La suspension obtenue est agitée jusqu'à complète dissolution du solide puis l'acide formique (204 uL, 5.4 mmol, 2 équiv) est ajouté à l'aide d'une seringue suivi par la NEt3 (377 μL, 2.7 mmol, 1 equiv) en une seule fois. Un fort dégagement d'hydrogène gaz est observé. La réaction est alors agitée pendant 2 h à température ambiante puis le solvant est évaporé à sec pour laisser une huile très visqueuse. Après de multiples ajouts de pentane et trituration de l'huile dans de l'hexane, l'huile cristallise et un solide blanc est obtenu, celui-ci est alors récupéré par filtration et lavé au pentane (3 x 2 mL) et à Féther (3 x 2mL). Le solide blanc ainsi récupéré est séché sous pression réduite pour obtenir [Et3NH+, Cy2B(OCHO)2-] (901 mg) avec un rendement de 90 %. In a 25 mL flask equipped with a magnetic stir bar and a J-Young tap, Cy 2 BH (481 mg, 2.7 mmol, 1 equiv) and 5 mL of toluene are added. The suspension obtained is stirred until complete dissolution of the solid and formic acid (204 μL, 5.4 mmol, 2 equiv) is added using a syringe followed by NEt 3 (377 μL, 2.7 mmol, 1 equiv) at one time. A strong release of hydrogen gas is observed. The reaction is then stirred for 2 hours at room temperature and then the solvent is evaporated to dryness to leave a very viscous oil. After multiple additions of pentane and trituration of the oil in hexane, the oil crystallizes and a white solid is obtained, this is then recovered by filtration and washed with pentane (3 x 2 mL) and with ether. (3 x 2mL). The white solid thus recovered is dried under reduced pressure to obtain [Et 3 NH + , Cy 2 B (OCHO) 2 -] (901 mg) with a yield of 90%.
1H NMR (200 MHz, CD3CN) δ 8.77 (s, 1H, NH), 8.29 (s, 2H, HC(O)O), 3.13 (t, J= 7.2 Hz, 6H), 1.65 (d, J= 4.3 Hz, 4H), 1.50 (d, J= 12.8 Hz, 4H), 1.24 (t, J= 7.3 Hz, 9H), 1.12 (d, J= 7.6 Hz, 4H), 1.01 - 0.73 (m, 4H), 0.48 (tt, J= 12.0 Hz, 2H, CH-B) ppm. 1 H NMR (200 MHz, CD 3 CN) δ 8.77 (s, 1H, NH), 8.29 (s, 2H, HC (O) O), 3.13 (t, J = 7.2 Hz, 6H), 1.65 (d, J = 4.3 Hz, 4H), 1.50 (d, J = 12.8 Hz, 4H), 1.24 (t, J = 7.3 Hz, 9H), 1.12 (d, J = 7.6 Hz, 4H), 1.01 - 0.73 (m, 4H), 0.48 (tt, J = 12.0 Hz, 2H, CH-B) ppm.
13C NMR (50 MHz, CD3CN) δ 166.43, 47.39, 29.38, 28.50, 9.06. ppm. 1 3 C NMR (50 MHz, CD 3 CN) δ 166.43, 47.39, 29.38, 28.50, 9.06. ppm.
11B NMR (64 MHz, CD3CN) б 11.17 ppm. 1 1 B NMR (64 MHz, CD 3 CN) б 11.17 ppm.
Analyse élémentaire: cale. (%) pour C20H40BNO4 (369.30 g.mol-1): C 65.04, H 10.92, N 3.79; trouvé : C 63.05, H 11.03, N 3.41.
Un ensemble de résultats est présenté ci-dessous dans le Tableau 1, donnant des exemples de production de dihydrogène à partir de l'acide formique. Dans tous les essais réalisés, du CO2 est également obtenu. La quantité d'acide formique utilisée dans tous les essais est de 0,2 mmole. Différents catalyseurs ont aussi été testés. Elemental analysis: hold. (%) For C 2 0H 0BNO4 4 (369.30 g mol -1): C 65.04, H 10.92, N 3.79; found: C 63.05, H 11.03, N 3.41. A set of results is presented below in Table 1, giving examples of hydrogen production from formic acid. In all the tests carried out, CO 2 is also obtained. The amount of formic acid used in all the tests is 0.2 mmol. Different catalysts have also been tested.
Les catalyseurs [TBDH+, BBN(OCHO)2-] et [Et3NH+, Cy2B(OCHO)2-] peuvent être représentés comme suit : The catalysts [TBDH + , BBN (OCHO) 2 -] and [Et 3 NH + , Cy 2 B (OCHO) 2 -] can be represented as follows:
Comme déjà indiqué l'acide formique peut être converti en H2, ou en un mélange de H2 et de CO2 dont la séparation peut être réalisée par les méthodes connues de l'homme du métier comme par exemple, la séparation H2/CO2 par adsorption du CO2 sur des éthanolamines ou par séparation cryogénique. As already indicated formic acid can be converted to H 2 , or a mixture of H 2 and CO 2 , the separation can be achieved by methods known to those skilled in the art such as, for example, separation H2 / CO 2 by adsorption of CO 2 on ethanolamines or by cryogenic separation.
Lorsque le procédé de l'invention conduit à l'obtention d'un mélange de dihydrogène et de dioxyde de carbone, la quantité de chaque gaz dans le mélange peut être déterminée, par exemple, en collectant les gaz dans une burette et en analysant la composition du mélange par chromatographie gazeuse. Ces techniques sont des techniques couramment utilisées dans ce domaine et bien connues de l'homme du métier. Dans le tableau ci-dessus, les rendements de conversion de l'acide formique indiqués correspondent aux rendements de conversion de l'acide formique en un mélange équimolaire de H2 et de CO2. When the process of the invention leads to obtaining a mixture of dihydrogen and carbon dioxide, the amount of each gas in the mixture can be determined, for example, by collecting the gases in a burette and analyzing the composition of the mixture by gas chromatography. These techniques are techniques commonly used in this field and well known to those skilled in the art. In the table above, the formic acid conversion efficiencies quoted correspond to the conversion efficiencies of formic acid to an equimolar mixture of H 2 and CO 2 .
A 130 °C, le TOF maximal observé est de 4.44 h-1 et le TON maximal mesuré est de 100 (avec [Et3NH+,Cy2B(OCHO)2_]- comme catalyseur). Ces résultats démontrent, pour la première fois, que des catalyseurs ne mettant pas en jeu de métaux alcalino-terreux du Groupe IIA, de métaux du Groupe IIIA, de métaux de transition du Groupe IB à VIIIB, de terres rares ou d'actinides peuvent être utilisés pour promouvoir la production de dihydrogène à partir de l'acide formique.
At 130 ° C, the maximum observed TOF is 4.44 h -1 and the maximum TON measured is 100 (with [Et 3 NH +, Cy 2 B (OCHO) 2 _] - as the catalyst). These results demonstrate, for the first time, that catalysts that do not involve Group IIA alkaline earth metals, Group IIIA metals, Group IB to VIIIB transition metals, rare earths or actinides can be used to promote the production of dihydrogen from formic acid.
Claims
1. Procédé de production de dihydrogène à partir de l'acide formique, caractérisé en ce que l'acide formique est mis en contact : A process for producing dihydrogen from formic acid, characterized in that the formic acid is brought into contact with:
avec au moins un catalyseur with at least one catalyst
(i) ledit catalyseur étant un acide de Lewis, choisi parmi (i) said catalyst being a Lewis acid, selected from
- les composés organiques ou inorganiques de bore choisis parmi le BF3, le BF3(Et20), le BCI3, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicyclo[3.3.1]nonane (BBNI), le B- chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9-borabicyclo[3.3.1]nonane (B- méthoxy-9-BBN), le B-benzyl-9-borabicyclo[3.3.1]nonane, le Me-TBD-BBN+1,- leorganic or inorganic boron compounds chosen from BF 3 , BF 3 (Et 2 0), BCI 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1 nonane (BBNI), B-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl- 9-borabicyclo [3.3.1] nonane, Me-TBD-BBN + 1, - the
Me-TBD-BBN+CF3S03-, le (TDB-BBN)2, le TBD-BBN-C02, le TBD-BBN-BBN, le [TBDFH+, BBN(OCHO)2], le [Et3NFH+, Cy2B(OCHO)2-] ; Me-TBD-BBN + CF 3 S0 3 -, (TDB-BBN) 2 , TBD-BBN-C0 2 , TBD-BBN-BBN, [TBDFH + , BBN (OCHO) 2 ], [And 3 NFH + , Cy 2 B (OCHO) 2 -];
- les composés organiques ou inorganiques de silicium choisis S1CI4, Me3SiCl, Et3Si+ et Me3Si+ ; - les composés organiques ou inorganiques de germanium divalent ou tétravalent choisis parmi GeCl2, GeBr2, GeCl4, Ge(OEt2)4, Me3GeCl, Me2ClGe+, Et3Ge+ et Me3Ge+ ; the selected organic or inorganic silicon compounds S1CI 4 , Me 3 SiCl, and 3 Si + and Me 3 Si + ; organic or inorganic divalent or tetravalent germanium compounds chosen from GeCl 2 , GeBr 2 , GeCl 4 , Ge (OEt 2 ) 4, Me 3 GeCl, Me 2 ClGe + , and 3 Ge + and Me 3 Ge + ;
- les composés organiques ou inorganiques d'étain de degré d'oxydation + IV ou + II choisis parmi SnCl2, SnCl4, nBu2SnCl2, Cy3SnCl, Bu3SnH, tBu2SnCl2, «BuSnCl3j Me2SnCl, SnBu4, tetraisopropoxystannane, tetrakis(acétyloxy)stannane,- oxidation of organic or inorganic compounds of tin or + IV + II selected from SnCl 2, SnCl 4, nBu 2 SnCl 2, Cy 3 SnCl, Bu 3 SnH, tBu 2 SnCl 2, "BuSnCl 3j Me 2 SnCl, SnBu 4 , tetraisopropoxystannane, tetrakis (acetyloxy) stannane,
Me3SnCl, Et3Sn+ et Me3Sn+ ; Me 3 SnCl, and 3 Sn + and Me 3 Sn + ;
- les oxoniums choisis parmi (CH3)30+ et (CH3CH2)30+; oxoniums chosen from (CH 3 ) 3 0 + and (CH 3 CH 2 ) 3 0 + ;
- les carbocations choisis parmi le cation trityle ((C6H5)3C+), le tropylium (C7H7)+, le cation benzylique (C6H5CH2 +), le cation allylique (CH3-CH+-CH=CH2), le méthylium (CH3 +) et le cyclopropylium (C3H5 +) ; avec le contre ion anionique des cations silylium, des oxoniums, des carbocations, des cations stanniques et des cations germanium étant un halogénure choisi parmi F-, Cl-, Br- et I-, ou un anion choisi parmi BF4-, SbF6- B(C6F5)4-, B(C6H5)4-, CF3S03- ou TfO-et PF6-. ; avec au moins un composé choisi parmi
(ii) une base organique choisie parmi les bases organiques azotées, les bases organiques phosphorées, les bases carbonées, et les bases organiques oxygénées ; et/ou the carbocations chosen from the trityl cation ((C 6 H 5 ) 3 C + ), the tropylium (C 7 H 7 ) + , the benzyl cation (C 6 H 5 CH 2 + ), the allylic cation (CH 3 - CH + -CH = CH 2 ), methylium (CH 3 + ) and cyclopropylium (C 3 H 5 + ); with the anionic counterion of silylium cations, oxoniums, carbocations, stannic cations and germanium cations being a halide selected from F-, Cl-, Br- and I-, or an anion selected from BF 4 -, SbF 6 - B (C 6 F 5 ) 4-, B (C 6 H 5 ) 4 -, CF 3 S0 3 - or TfO-and PF 6 -. ; with at least one compound selected from (ii) an organic base selected from nitrogenous organic bases, phosphorus organic bases, carbon bases, and oxygenated organic bases; and or
(iii) un sel d'halogénure. (iii) a halide salt.
2. Procédé selon la revendication 2, caractérisé en ce que (i) l'acide de Lewis est choisi parmi 2. Method according to claim 2, characterized in that (i) the Lewis acid is chosen from
- un dérivé de formule R2BX ou R est un groupe alkyle linéaire, ramifié ou cyclique, saturé, éventuellement substitué, comprenant 1 à 12 atomes de carbone et X est choisi parmi les halogènures C1-, Br-, I-, les alcoxydes tels que le méthoxyde - OMe ou l'éthoxyde -OEt, -OTf, -NTf2 ou encore H a derivative of formula R 2 BX or R is a linear, branched or cyclic alkyl group, saturated, optionally substituted, comprising 1 to 12 carbon atoms and X is chosen from halogenides C1-, Br-, I-, alkoxides; such as methoxide-OMe or ethoxide -OEt, -OTf, -NTf 2 or H
- le BF3, le BF3(Et2O), le BC13, le diphényle hydroborane, le dicyclohexyle hydroborane, le chlorodicyclohexylborane, le 9-iodo-9-borabicyclo[3.3.1]nonane (BBNI), le B-chlorocatecholborane, le B(C6F5)3, le B-méthoxy-9- borabicyclo[3.3.1]nonane (B-méthoxy-9-BBN), le B-benzyI-9- borabicyclo[3.3.1]nonane, le Me-TBD-BBN+I-, le Me-TBD-BBN+CF3SO3-, le (TDB-BBN)2, le TBD-BBN-C02, le TBD-BBN-BBN, le [TBDH+, BBN(OCHO)2-], le [Et3NH+, Cy2B(OCHO)2-] ; BF 3 , BF 3 (Et 2 O), BCI 3 , diphenyl hydroborane, dicyclohexyl hydroborane, chlorodicyclohexylborane, 9-iodo-9-borabicyclo [3.3.1] nonane (BBNI), β-chlorocatecholborane, B (C 6 F 5 ) 3 , B-methoxy-9-borabicyclo [3.3.1] nonane (B-methoxy-9-BBN), B-benzyl-9-borabicyclo [3.3.1] nonane, Me-TBD-BBN + I-, Me-TBD-BBN + CF 3 SO 3 -, (TDB-BBN) 2 , TBD-BBN-CO 2 , TBD-BBN-BBN, [TBDH + , BBN (OCHO) 2 -], [Et 3 NH + , Cy 2 B (OCHO) 2 -];
- SnCl2, SnCI4, nBu2SnCl2, Cy3SnCl, Bu3SnH, tBu2SnCl2, nBuSnCl3, Me2SnCl, SnBu-4, tetraisopropoxystannane, tetrakis(acétyloxy)staimane, Me3SnCl, Et3Sn+ et Me3Sn+ ; SnCl 2 , SnCl 4 , nBu 2 SnCl 2 , Cy 3 SnCl, Bu 3 SnH, tBu 2 SnCl 2 , nBuSnCl 3 , Me 2 SnCl, SnBu 4 , tetraisopropoxystannane, tetrakis (acetyloxy) staimane, Me 3 SnCl, and 3 Sn + and Me 3 Sn + ;
avec le contre ion anionique des cations stanniques et stanneux étant un anion non coordinant choisi parmi BF4-, SbF6-, BiC6Fs)4, B(C6H5)4-, CF3SO3- ou TfO-et PF6-.ou un halogénure choisi parmi F', Cl-, Br- et I.- with the anionic counterion of stannous and stannous cations being a non-coordinating anion selected from BF 4 -, SbF 6 -, BiC 6 Fs) 4 , B (C 6 H 5 ) 4 -, CF 3 SO 3 - or TfO - and PF 6 - or a halide selected from F ' , Cl-, Br- and I-
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que (ii) la base organique est choisie parmi : 3. Method according to one of claims 1 or 2, characterized in that (ii) the organic base is chosen from:
- les bases organiques azotées qui sont des aminés secondaires ou tertiaires choisies parmi le triazabicyclodécène (TBD) ; le N-méthyltriazabicyclodécène (Me-TBD), le l,8-diazabicyclo[5.4.0]undéc-7-ène (DBU), la triméthylamine, la triéthylamine, la pipéridine, la 4-diméthylaminopyridine (DMAP), le 1,4-
diazabicyclo[2.2.2]octane (DABCO), la proline, le phénylalanine, un sel de thiazolium, la N-diisopropyléthylarnine (DIPEA ou DIEA) ; organic nitrogenous bases which are secondary or tertiary amines chosen from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4- diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine (DIPEA or DIEA);
- les bases organiques phosphorées qui sont des alkyles ou aryles phosphines choisies parmi le triphénylphosphine, le 2J2,-bis(diphénylphosphino)-l,l'- binaphthyle (BINAP), le triisopropylphosphine, l,2-bis(diphénylphosphino)éthane (dppe), la tricyclohexylphosphine (PCy3) ; les alkyle et aryle phosphonates choisies parmi le diphénylphosphate, le triphénylphosphate (TPP), le tri(isopropylphényl)phosphate (TIPP), le crésyldiphenyl phosphate (CDP), le tricrésylphosphate (TCP) ; les alkyle et aryle phosphates choisis parmi le di-n- butylphosphate (DBP), le tris-(2-éthylhexyl)-phosphate, le triéthyl phosphate ; les alkyle et aryle phosphinites et phosphonites choisis parmi les méthyldiphénylphosphinite et méthyldiphénylphosphonite, les aza-phosphines choisies parmi le 2,8,9-triisopropyl-2,5,8,9-tetraaza-l- phosphabicyclo[3.3.3]undecane (BVMe) et le 2,8,9-triisobutyl-2,5,8,9-tetraaza-l- phosphabicyclo[3.3.3]undecane (BViBu) ; the phosphorus organic bases which are alkyl or aryl phosphines chosen from triphenylphosphine, 2 J 2 , -bis (diphenylphosphino) -1, 1'-binaphthyl (BINAP), triisopropylphosphine, 1,2-bis (diphenylphosphino) ethane; (dppe), tricyclohexylphosphine (PCy3); alkyl and aryl phosphonates selected from diphenyl phosphate, triphenyl phosphate (TPP), tri (isopropylphenyl) phosphate (TIPP), cresyldiphenyl phosphate (CDP), tricresyl phosphate (TCP); alkyl and aryl phosphates selected from di-n-butyl phosphate (DBP), tris- (2-ethylhexyl) phosphate, triethyl phosphate; alkyl and aryl phosphinites and phosphonites chosen from methyldiphenylphosphinite and methyldiphenylphosphonite, the aza-phosphines chosen from 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (BV Me ) and 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (BV iBu );
- les bases carbonées choisies parmi les carbènes N-hétérocycliques issus d'un sel d'imidazolium, ledits carbènes étant choisis parmi les sels de l,3-bis(2,6- diisopropylpheéyl)-lH-imidazol-3-ium3 l,3-bis(2,6-diisopropyIphényl)-4,5- dihydro-lH-imidazol-3-ium, l,3-bis(23436-triméthylphényl)-lH-imidazoI-3-ium, 133-bis(2,4,6-triméthylphényI)-455-dihydro- 1 H-imidazol-3-ium, 4,5-dichloro- 1 ,3- bis(2,6-diisopTopylphényl)-lH-imidazol-3-ium, l,3-di-tert-butyl-lH-imidazol-3- ium, l,3-di-tert-butyl-4,5-dihydro-lH-imidazol-3-ium, lesdits sels étant sous la forme de sels de chlorure ; - carbonaceous bases chosen from the N-heterocyclic carbene from a salt of imidazolium carbenes ledits being selected from salts of l, 3-bis (2,6 diisopropylpheéyl) imidazol-3-ium 3 l , 3-bis (2,6-diisopropyIphényl) -4,5-dihydro-lH-imidazol-3-ium, l, 3-bis (2 3 4 3 6-trimethylphenyl) -LH-imidazol-3-ium, 1 3 3-bis (2,4,6-triméthylphényI) -4 May 5-dihydro-1H-imidazol-3-ium, 4,5-dichloro-1, 3- bis (2,6-diisopTopylphényl) -lH- imidazol-3-ium, 1,3-di-tert-butyl-1H-imidazol-3-ium, 1,3-di-tert-butyl-4,5-dihydro-1H-imidazol-3-ium, said salts being in the form of chloride salts;
- les bases oxygénées choisies parmi le peroxyde d'hydrogène ; le peroxyde de benzoyle ; l'oxyde de pyridine (PyO), l'oxyde de N-méthylmorpholine et le 1-λ1- oxidanyl-2,2,6>6-tétraméthylpipéridine. oxygen bases chosen from hydrogen peroxide; benzoyl peroxide; pyridine oxide (Pyo) oxide, N-methylmorpholine and 1-λ 1 - oxidanyl-2,2,6> 6-tetramethylpiperidine.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que (ii) la base organique est une base organique azotée choisie parmi le triazabicyclodécène (TBD) ; le N-méthyltriazabicyclodécène (Me-TBD), le l,8-diazabicyclo[5.4.0]undéc-7- ène (DBU), la triméthylamine, la triéthylamine, la pipéridine, la 4-diméthylaminopyridine (DMAP), le l,4-diazabicyclo[2.2.2]octane (DABCO), la proline, le phénylalanine, un sel de thiazolium, la N-diisopropyléthylamine (DIPEA ou DIEA).
4. Method according to any one of claims 1 to 3, characterized in that (ii) the organic base is a nitrogenous organic base selected from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1, 4-diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethylamine (DIPEA or DIEA).
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que (iii) le sel d'halogénure est choisi parmi les sels de chlorure, de bromure, de l'iodure et de fluorure lesdits sels d'halogénure étant choisis parmi NaF, NaC1, NaBr, Nal. KC1, LiCl,
5. Process according to any one of Claims 1 to 4, characterized in that (iii) the halide salt is chosen from the salts of chloride, bromide, iodide and fluoride, said halide salts being selected from NaF, NaCl, NaBr, NaI. KCl, LiCl,
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'acide formique est mis en contact avec (i) un acide de Lewis tel que défini à l'une des revendications 1 ou 2 et (ii) une base organique tel que défini à l'une des revendications 3 ou 4 et (iii) un sel d'halogénure tel que défini à la revendication 5. 6. Method according to any one of claims 1 to 5, characterized in that the formic acid is brought into contact with (i) a Lewis acid as defined in one of claims 1 or 2 and (ii) an organic base as defined in one of claims 3 or 4 and (iii) a halide salt as defined in claim 5.
7. Procédé selon l'une quelconque des revendications 1 à 6, mettant en œuvre, en outre, au moins un additif basique choisi parmi 7. Process according to any one of Claims 1 to 6, furthermore implementing at least one basic additive chosen from
- les aminés organiques choisies parmi la triéthylamine, la pipéridine et la 4- diméthylaminopyridine, organic amines chosen from triethylamine, piperidine and 4-dimethylaminopyridine,
- l'ammoniac et l'ammonique, - ammonia and ammonia,
- les bases inorganiques carbonées choisies parmi les sels de carbonates CO32- et les sels d'hydrogénocarbonate HCO3 -, lesdits sels de carbonates CO32- et d'hydrogénocarbonate HCO3- étant choisis parmi Ca-CO3 et NaHCO3, - carbonaceous inorganic bases selected from carbonates salts CO3 2- and salts hydrogencarbonate HCO 3 -, said carbonate salts CO3 2- and hydrogencarbonate HCO 3 - is selected from Ca-CO 3 and NaHCO 3,
-les bases inorganiques oxygénées choisis parmi les sels d'hydroxyde HO-, lesdits sels d'hydroxyde étant choisis parmi KOH et NaOH. the oxygenated inorganic bases chosen from the hydroxide salts HO -, said hydroxide salts being chosen from KOH and NaOH.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la quantité d'additif basique utilisé est de 0,1 à 1 équivalent molaire, bornes incluses, par rapport au nombre de moles de l'acide formique. 8. Process according to any one of claims 1 to 7, characterized in that the amount of basic additive used is from 0.1 to 1 molar equivalent, inclusive limits, relative to the number of moles of formic acid.
9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la production de dihydrogène se produit sous une pression de CO2, de H2, de diazote (N2), d'argon ou d'un mélange d'au moins deux de ces gaz. 9. Process according to any one of claims 1 to 8, characterized in that the production of dihydrogen occurs under a pressure of CO 2 , H 2 , dinitrogen (N 2 ), argon or a mixture at least two of these gases.
10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la production de dihydrogène a Heu sous une pression comprise entre 0,1 et 75 bars, de
préférence entre 0,1 et 30 bars, plus préférentiellement entre 0,1 et 10 bars, bornes incluses. 10. Process according to any one of Claims 1 to 9, characterized in that the production of dihydrogen is carried out under a pressure of between 0.1 and 75 bar, preferably between 0.1 and 30 bar, more preferably between 0.1 and 10 bar, inclusive.
11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la température de la réaction de l'acide formique avec le catalyseur, est comprise entre 15 et11. Process according to any one of claims 1 to 10, characterized in that the temperature of the reaction of formic acid with the catalyst is between 15 and
150°C, de préférence entre 15 et 130°C, bornes incluses. 150 ° C, preferably between 15 and 130 ° C, inclusive.
12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la durée de la réaction de l'acide formique avec le catalyseur éventuellement en présence d'un additif basique est de 5 minutes à 200 heures, de préférence de 10 minutes à 48 heures, bornes incluses. 12. Process according to any one of Claims 1 to 11, characterized in that the duration of the reaction of the formic acid with the catalyst optionally in the presence of a basic additive is from 5 minutes to 200 hours, preferably from 10 minutes to 48 hours, terminals included.
13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que la réaction est effectuée dans un ou un mélange d'au moins deux solvant(s) choisi(s) parmi : - l'eau ; 13. Method according to any one of claims 1 to 12, characterized in that the reaction is carried out in a mixture or at least two solvent (s) chosen (s) from: - water;
- les alcools, de préférence l'éthanol ou l'éthylène glycol ; alcohols, preferably ethanol or ethylene glycol;
- les éthers, de préférence, l'éther diéthylique, ou le THF ; ethers, preferably diethyl ether, or THF;
- les hydrocarbures, de préférence, le benzène, ou le toluène ; hydrocarbons, preferably benzene or toluene;
- les solvants azotés, de préférence, la pyridine, ou l'acétonitrile ; the nitrogenous solvents, preferably pyridine, or acetonitrile;
- les sulfoxydes, de préférence, le diméthylesulfoxyde ; sulfoxides, preferably dimethyl sulphoxide;
- les halogénures d'alkyle, de préférence, le chloroforme, ou le chlorure de méthylène ; alkyl halides, preferably chloroform, or methylene chloride;
- un fluide supercritique, de préférence le C02 supercritique. a supercritical fluid, preferably supercritical CO 2 .
14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la quantité de catalyseur est de 0,0001 à 1 équivalent molaire, de préférence de 0,001 à 1 équivalent molaire, plus préférentiellement de 0,001 à 0,5 équivalent molaire, bornes incluses, par rapport au nombre de mole d'acide formique. 14. Process according to any one of Claims 1 to 13, characterized in that the amount of catalyst is from 0.0001 to 1 molar equivalent, preferably from 0.001 to 1 molar equivalent, more preferably from 0.001 to 0.5 equivalent. molar, limits included, relative to the number of moles of formic acid.
15. Utilisation du dihydrogène produit par le procédé selon l'une quelconque des revendications 1 à 14, dans une pile à combustible, dans un moteur à combustion, dans la production d'ammoniac et de méthanol, dans le raffinage du pétrole, dans les secteurs de la métallurgie, de l'électronique et de l'alimentaire.
15. Use of the dihydrogen produced by the process according to any one of claims 1 to 14, in a fuel cell, in a combustion engine, in the production of ammonia and methanol, in the refining of petroleum, in the metallurgy, electronics and food sectors.
16. Procédé de production de l'énergie, caractérisé en ce qu'il comprend une étape de production de dihydrogène à partir de l'acide formique par le procédé selon l'une quelconque des revendications 1 à 14.
16. A method for producing energy, characterized in that it comprises a step of producing dihydrogen from formic acid by the method according to any one of claims 1 to 14.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1456949A FR3023839A1 (en) | 2014-07-18 | 2014-07-18 | PROCESS FOR PRODUCING DIHYDROGEN |
PCT/IB2015/055392 WO2016009384A1 (en) | 2014-07-18 | 2015-07-16 | Dihydrogen production process |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3194332A1 true EP3194332A1 (en) | 2017-07-26 |
Family
ID=51659880
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15762713.4A Withdrawn EP3194332A1 (en) | 2014-07-18 | 2015-07-16 | Dihydrogen production process |
Country Status (4)
Country | Link |
---|---|
US (1) | US20170144884A1 (en) |
EP (1) | EP3194332A1 (en) |
FR (1) | FR3023839A1 (en) |
WO (1) | WO2016009384A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11441089B2 (en) * | 2020-05-22 | 2022-09-13 | ExxonMobil Technology and Engineering Company | High napthenic content distillate fuel compositions |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130283675A1 (en) * | 2011-01-28 | 2013-10-31 | Education On Behalf Of University Of Oregon | Boron-nitrogen heterocycles |
US20130004800A1 (en) * | 2011-06-30 | 2013-01-03 | Formic Acid-Hydrogen Energy Development Corporation | Hydrogen generation system and method for generating hydrogen for mobile and power generator |
-
2014
- 2014-07-18 FR FR1456949A patent/FR3023839A1/en not_active Withdrawn
-
2015
- 2015-07-16 WO PCT/IB2015/055392 patent/WO2016009384A1/en active Application Filing
- 2015-07-16 EP EP15762713.4A patent/EP3194332A1/en not_active Withdrawn
- 2015-07-16 US US15/323,581 patent/US20170144884A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20170144884A1 (en) | 2017-05-25 |
FR3023839A1 (en) | 2016-01-22 |
WO2016009384A1 (en) | 2016-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Eisenberger et al. | Borocation catalysis | |
DeLaet et al. | Carbon dioxide chemistry and electrochemistry of a binuclear cradle complex of nickel (0), Ni2 (. mu.-CNMe)(CNMe) 2 (PPh2CH2PPh2) 2 | |
Leoni et al. | Coordinated water/anion hydrogen bonds and Pd-H bond acidity in cationic palladium (II) aquo hydrides and the x-ray crystal and molecular structures of trans-[(Cy3P) 2Pd (H)(H2O)] BF4 (Cy= cyclohexyl) | |
Brun et al. | Chiral N-phosphino sulfinamide ligands in rhodium (I)-catalyzed [2+ 2+ 2] cycloaddition reactions | |
US20160087295A1 (en) | Catalyst and Process for the Production of Hydrogen from Ammonia Boranes | |
Kameo et al. | Si–C bond cleavage by hydride complexes of rhodium and iridium: comparison of Si–C (sp 2) and Si–C (sp 3) activation | |
EP2488477A1 (en) | Process for producing methanol | |
Rosini et al. | First examples of homogeneous hydrogenolysis of thiophene to 1-butanethiolate and ethylthioketene ligands: synthesis and reactivity of (. eta. 4-C4H5S) ReH2 (PPh3) 2 | |
EP3429999A1 (en) | Method for preparing alkylamines | |
EP3374363B1 (en) | Method for preparing methoxyboranes and for producing methanol | |
WO2016009384A1 (en) | Dihydrogen production process | |
Wilklow-Marnell et al. | A POCO type pincer complex of iridium: Synthesis, characterization, and catalysis | |
Henrion et al. | Ruthenium complexes bearing amino-bis (phosphinite) or amino-bis (aminophosphine) ligands: Application in catalytic ester hydrogenation | |
CN114716466A (en) | Method for preparing chiral alpha-amino boric acid/boric acid ester through nickel-catalyzed asymmetric hydroamidation | |
EP3374364B1 (en) | Use of boron formates for reducing unsaturated organic functions | |
WO2016063227A1 (en) | Synthesis of esters by functionalisation of co2 | |
EP2981539B1 (en) | Method for preparing oxyborane compounds | |
WO2014057466A1 (en) | Method for preparing formamidines | |
US20190144369A1 (en) | Conversion of corn oil to upgraded biodiesel and poly(lactic acid) | |
JP6538580B2 (en) | Hydrogen oxidation catalyst | |
Kim et al. | Parent-amido (NH2) palladium (II) complexes: Synthesis, reactions, and catalytic hydroamination | |
Johnpeter et al. | Ru 2 (CO) 4 {OOC (CH 2) n CH 3} 2 L 2 sawhorse-type complexes containing μ 2-η 2-carboxylato ligands derived from saturated fatty acids | |
DiBenedetto | Transition Metals in Catalysis: Harnessing Metals to Form Carbon-Carbon and Carbon-Boron Bonds | |
Sinopalnikova | Arene ruthenium iminophosphonamide complexes: synthesis, reactivity and application in transfer hydrogenation of ketones | |
Gao et al. | X-type silyl ligands for transition-metal catalysis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20170111 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20200201 |