EP3740465A1 - Procede de production de monoxyde de carbone - Google Patents
Procede de production de monoxyde de carboneInfo
- Publication number
- EP3740465A1 EP3740465A1 EP19700315.5A EP19700315A EP3740465A1 EP 3740465 A1 EP3740465 A1 EP 3740465A1 EP 19700315 A EP19700315 A EP 19700315A EP 3740465 A1 EP3740465 A1 EP 3740465A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- formula
- carbon atoms
- formate
- crown
- 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.)
- Pending
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 124
- 230000008569 process Effects 0.000 claims abstract description 96
- -1 alkyl formate Chemical compound 0.000 claims abstract description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000006315 carbonylation Effects 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 4
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 55
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 235000019253 formic acid Nutrition 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 125000002619 bicyclic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 claims description 2
- HELCSRZMDRYPIJ-UHFFFAOYSA-N 1,4,7,10,13,16-hexathiacyclooctadecane Chemical compound C1CSCCSCCSCCSCCSCCS1 HELCSRZMDRYPIJ-UHFFFAOYSA-N 0.000 claims description 2
- RVJABZUDCPZPPM-UHFFFAOYSA-N 1,4,7,10,13,16-hexazacyclooctadecane Chemical compound C1CNCCNCCNCCNCCNCCN1 RVJABZUDCPZPPM-UHFFFAOYSA-N 0.000 claims description 2
- LIVCAIOLNUODDU-UHFFFAOYSA-N 1,5,9,13-tetrathiacyclohexadecane Chemical compound C1CSCCCSCCCSCCCSC1 LIVCAIOLNUODDU-UHFFFAOYSA-N 0.000 claims description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- DSFHXKRFDFROER-UHFFFAOYSA-N 2,5,8,11,14,17-hexaoxabicyclo[16.4.0]docosa-1(22),18,20-triene Chemical compound O1CCOCCOCCOCCOCCOC2=CC=CC=C21 DSFHXKRFDFROER-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 239000002739 cryptand Substances 0.000 claims description 2
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 claims description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 2
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 claims description 2
- RRBYUSWBLVXTQN-VZCHMASFSA-N tricyclene Natural products C([C@@H]12)C3C[C@H]1C2(C)C3(C)C RRBYUSWBLVXTQN-VZCHMASFSA-N 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 47
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 230000006324 decarbonylation Effects 0.000 description 12
- 238000006606 decarbonylation reaction Methods 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- SMTUJUHULKBTBS-UHFFFAOYSA-N benzyl(trimethyl)azanium;methanolate Chemical compound [O-]C.C[N+](C)(C)CC1=CC=CC=C1 SMTUJUHULKBTBS-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 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 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001723 carbon free-radicals Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000012552 review Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- IPGCWJJEORAUSJ-UHFFFAOYSA-N (2,3,4-trichlorophenyl) formate Chemical compound ClC1=CC=C(OC=O)C(Cl)=C1Cl IPGCWJJEORAUSJ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- 239000003795 chemical substances by application 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
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 230000010354 integration Effects 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 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 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 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
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 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
- 239000011787 zinc oxide Substances 0.000 description 2
- 240000000489 Agave utahensis Species 0.000 description 1
- BHELIUBJHYAEDK-OAIUPTLZSA-N Aspoxicillin Chemical compound C1([C@H](C(=O)N[C@@H]2C(N3[C@H](C(C)(C)S[C@@H]32)C(O)=O)=O)NC(=O)[C@H](N)CC(=O)NC)=CC=C(O)C=C1 BHELIUBJHYAEDK-OAIUPTLZSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000010744 Boudouard reaction Methods 0.000 description 1
- 102100037328 Chitotriosidase-1 Human genes 0.000 description 1
- 101000879661 Homo sapiens Chitotriosidase-1 Proteins 0.000 description 1
- KFNNIILCVOLYIR-UHFFFAOYSA-N Propyl formate Chemical compound CCCOC=O KFNNIILCVOLYIR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001944 continuous distillation Methods 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
- 230000009849 deactivation Effects 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QSBFECWPKSRWNM-UHFFFAOYSA-N dibenzo-15-crown-5 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 QSBFECWPKSRWNM-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 125000005469 ethylenyl group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- PKAUVIXBZJUYRV-UHFFFAOYSA-N methane;hydroiodide Chemical compound C.I PKAUVIXBZJUYRV-UHFFFAOYSA-N 0.000 description 1
- ABOLASSOZLXVLW-UHFFFAOYSA-N methanol;2-phenylethanamine Chemical class OC.NCCC1=CC=CC=C1 ABOLASSOZLXVLW-UHFFFAOYSA-N 0.000 description 1
- 239000013580 millipore water Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 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
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001577 simple distillation Methods 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
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- RUPAXCPQAAOIPB-UHFFFAOYSA-N tert-butyl formate Chemical compound CC(C)(C)OC=O RUPAXCPQAAOIPB-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 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
- 230000035899 viability Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UZVNCLCLJHPHIF-NOJKMYKQSA-J zinc;(1e)-2-(ethylcarbamoylamino)-n-methoxy-2-oxoethanimidoyl cyanide;manganese(2+);n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S.CCNC(=O)NC(=O)C(\C#N)=N\OC UZVNCLCLJHPHIF-NOJKMYKQSA-J 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/27—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for the production of carbon monoxide using a derivative of formic acid, in particular an alkyl formate.
- It also relates to a process chosen from among the methanol production process, the process for the production of acetic acid (Monsanto and Cativa processes), the process for the hydroformylation of olefins (oxo and aldox process, the production process of hydrocarbons (Fischer-Tropsch process), or the nickel carbonylation process (Mond process), comprising a step of producing carbon monoxide employing an alkyl formate of formula (I) by the process according to the invention.
- a process chosen from among the methanol production process, the process for the production of acetic acid (Monsanto and Cativa processes), the process for the hydroformylation of olefins (oxo and aldox process, the production process of hydrocarbons (Fischer-Tropsch process), or the nickel carbonylation process (Mond process) comprising a step of producing carbon monoxide employing an alkyl formate of formula (I) by the process according to the invention.
- Fossil fuels account for more than 85% of global energy production, while organic chemical consumables (plastics, fertilizers, textiles, etc.) come from 95% of the use of oil and natural gas.
- the challenge is to develop efficient catalysts for the recycling of C0 2 and biomass waste.
- CO would be an intermediate, a convenient source of carbon to meet this challenge, the latter having for example been used by Germany during the Second World War to produce liquid fuels by the Fisher-Tropsch process.
- Carbon monoxide can be produced by partial oxidation of gaseous hydrocarbons from natural gas or by the gasification of coal or coke.
- Shell process or Texaco process use high temperatures (1000-1500 ° C) as well as high pressures (60-80 bar) leading to the production of a gas mixture, requiring purifications for the production of a pure gas.
- multiple side reactions occur due to high temperatures (Gaurav Nahar, Valerie Dupont: Hydrogen production from simple alkanes and oxygenated hydrocarbons over ceria zirconia supported catalysts: Review. Renewable and Sustainable Energy Reviews. Band 32, 2014, S. 777-796, doi: 10.1106 / j.rser.2013.12.040).
- rWGSR reverse water gas shift reaction
- the equilibrium constant is only 0.5 at 750 ° C. requiring hard temperature conditions.
- the choice of the catalyst will then depend on this operating temperature. According to Pioneer Astronautics' experiments in Lakewood, Colorado, the best low temperature catalyst for this reaction is a mixture of copper and nickel supported on the silica. This catalyst is exclusively selective for CO (i.e., it produces only carbon monoxide) with 60% conversion of CO 2 to CO, at 350 ° C, 150 torr, and a ratio of 1 ⁇ 4 C0 2 / H 2 reactor feed (Whitlow, Jonathan E., Parish (2003), "Operation, Modeling and Analysis of the Reverse Water Gas Shift Process", 10.1063 / 1.1541409).
- the SM process utilizes ZnO-Al catalysts at 600 ° C or ZnO-Cr catalysts for temperatures above 600 ° C (Park, S.W., Joo, O.S., Jung, K.D. Kim, H., & Han, S.H., 2000, Korean Journal of Chemical Engineering, 17 (6), 719-722, https://doi.org/l0.l007/BF02699l23).
- the electrochemical reduction of CO 2 consists in reacting CO 2 with several electrons and protons to produce synthetic hydrocarbons and oxygenated compounds.
- Two technologies can be cited: High temperature electrolysis: co-electrolysis of C0 2 and water. Water and C0 2 are co-electrolyzed at high temperature (700-800 ° C) to produce syngas (CO + H 2 ) which catalytically results in hydrocarbons or alcohols. This system uses both electrical energy and heat to reduce the C0 2 molecule.
- Electrolysis at room temperature (20 to 25 ° C) in electro-catalytic cells the electrons are supplied by electrical energy, usually from solar panels or other renewable energies, and hydrogen ions by a chemical element (HCl, for example) or hydrogen gas directly.
- electrical energy usually from solar panels or other renewable energies
- hydrogen ions by a chemical element (HCl, for example) or hydrogen gas directly.
- a major industrial source of CO is the "producer gas" in English, which results from the combustion of coal at high temperatures. 31 can be obtained, for example, in an oven, in which the air passes through a bed of coal. The initially produced C0 2 equilibrates with the remaining hot carbon to give CO. The reaction of CO 2 with carbon to give CO is described as the Boudouard reaction.
- CO is the predominant product.
- Another industrial source of CO is the "activation of carbon” or “steam activation of carbon” process, which is an endothermic reaction between water vapor and carbon at about 1000 ° C:
- the reduction process can be favored by heating, exploiting the positive entropy of the reaction.
- the Ellingham diagram shows that CO formation is favored over C0 2 at high temperature.
- Carbon monoxide can be produced by dehydration of formic acid with concentrated sulfuric acid.
- the reaction is stoichiometric and employs a strong concentrated acid (Emest R. Schierz J. Am Chem., Soc., 1923, 45 (2), pp 447-455, DOI: 10, 1021 / ja01655a021). * A homogeneous mixture of powdered zinc and calcium carbonate heated to
- Methane iodide and silver nitrate can react in water to form
- Fleischer describes a recyclable CO equivalent from a well-chosen amine using a formylation reaction in the presence of C0 2 .
- CO is liberated at room temperature in DMF in the presence of a base in stoichiometric amount, generally carbonate (Gehrtz P, Hirschbeck V, Fleischer I, Chem., 2015, vol: 51 (63), pp. : 12574-12577).
- Carbon monoxide can be produced by the decarbonylation of alkyl formates by a metal catalyst (copper, ruthenium, rhodium, osmium), such as Doyle's methods in 1981, Alper in 1987, Leismann in 1989, and Mortreux in 1992. In these processes the temperatures are above 100 ° C (Doyle G, Exxon Research and Engeneering Co., 1981, pp: 1-4); Zahalka H, Alper H, Tetrahedron Letters, 1987, vol: 28 (20), pp: 2215-2216). Disadvantages: Use of metals for decarbonylation as well as temperature of the order of 100 ° C.
- a metal catalyst copper, ruthenium, rhodium, osmium
- Carbon monoxide can be produced by the decarbonylation of alkyl formates by an organic catalyst. This is described in a 1984 patent with guanidines with reaction temperatures between 140 ° C and 150 ° C in the absence of solvent (EP0115387B1, 1984 pp: 1-4).
- Carbon monoxide can still be produced with amines and phosphines as a catalyst at 190 ° C without solvent, as published by Abbayes in 1993 (Vega F, Clement J, Abbey H, Tetrahedron Letters, 1993, vol .: 34 (50), pp: 8117-8118).
- Mortreux proposed to use the alkyl formate system, sodium alkoxide in the presence of palladium in DCM in order to use formate as a carbonylation agent for alkyl halides. It uses 1.4 equivalents of alcoholate and heats up to at least 40 ° C in the presence of palladium (Carpentier J, Castanet Y, Brocard J, Mortreux A, Small F, Tetrahedron Letters, 1991, vol: 32 (36), pp : 4705-4708).
- Wu uses an aromatic triformate (TFBen) synthesized from formic acid that is used in situ in the presence of a complex of palladium and triethylamine at 100 ° C to carbonylate a halogenide.
- TFBen aromatic triformate
- Methyl formate is industrially produced by the carbonylation of methanol by carbon monoxide in the presence of a strong base, such as sodium methanoate (US 4216339):
- This method gives a selectivity of 96% with respect to methyl formate.
- the catalyst of this process is sensitive to water, which may be present in carbon monoxide, which is commonly derived from synthesis gas. Carbon monoxide must be dry.
- CO carbon monoxide
- Group IIA alkaline earth metals from the Periodic Table of Elements (such as magnesium and calcium); Group III A 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 the production of carbon monoxide (CO) in which an alkyl formate of formula (I)
- R is alkyl having 1 to 12 carbon atoms
- a catalyst selected from: alcoholates having a pKa> 15 in water, or a pKa > 27 in acetonitrile or DMSO; or
- the contacting takes place in a mixture of at least two polar and aprotic solvents at a temperature below 35 ° C., preferably at a temperature of less than or equal to at 30 ° C.
- alkyl formate of formula (I) makes it possible to serve as a liquid storage medium, rich in CO and a sustainable source of carbon monoxide (CO).
- Finding effective catalysts for the conversion of alkyl formate to CO that are inexpensive and / or low in toxicity and which allow gentle transformation has been found to be a technical challenge not obvious.
- the process of the invention can be an interesting alternative to conventional processes for obtaining CO, for example the partial oxidation of hydrocarbons, the reaction of the gas with reverse water (or "reverse water gas shift reaction", or rWGSR), coal combustion, stoichiometric reaction of formic acid with sulfuric acid or the various chemical reactions involving binding reaction conditions.
- rWGSR reverse water gas shift reaction
- coal combustion stoichiometric reaction of formic acid with sulfuric acid or the various chemical reactions involving binding reaction conditions.
- the process of the invention uses a catalytic regime (catalytic charge of 0.1 to 10%) and a percentage of CO in the molecule of 46.7% when using methyl formate (37.8% for the formate d ethyl, 31.8% for n-propyl formate, 27.5% for tert-butyl formate) far superior to other substitutes for CO other than methyl formate.
- methyl formate 37.8% for the formate d ethyl, 31.8% for n-propyl formate, 27.5% for tert-butyl formate
- the process of the invention releases gaseous CO that can be easily used in various processes using gaseous CO.
- the process of the invention makes it possible to produce carbon monoxide with a catalyst belonging to the family of strong bases (pKa> 15 in water, or pKa> 27 in acetonitrile or DMSO) and easily accessible.
- a catalyst belonging to the family of strong bases pKa> 15 in water, or pKa> 27 in acetonitrile or DMSO
- the use of catalysts based on noble or expensive metals or with expensive ligands is no longer necessary.
- toxic catalyst such as, for example, a source of fluoride is avoided.
- the catalysts used in the process of the invention have the advantage of overcoming the toxicity problems generally observed for metal catalysts as well as 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.
- transition metals of Group IB to VIIIB of the Periodic Table of the 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 - Actinides whose atomic number is between 89 and 103 selected from thorium and G uranium.
- catalyst within the meaning of the invention is meant a 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 referred to as "pre-catalysts") that are introduced into the process. reaction medium and which are converted into a catalyst.
- alkyl means a linear, branched or cyclic, saturated, optionally substituted carbon radical comprising 1 to 12 carbon atoms.
- the alkyl may include, for example, 1 to 8 carbon atoms, or 1 to 6 carbon atoms.
- saturated alkyl linear or branched, there may be mentioned for example the methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecanyl and their branched isomers.
- cyclic alkyl there may be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicylco [2,1,1] hexyl, bicyclo [2,2,1] heptyl radicals.
- alkenyl or “alkynyl” is meant a linear, branched or cyclic unsaturated carbon radical, optionally substituted, said unsaturated carbon radical comprising 2 to 12 carbon atoms comprising at least one double (alkenyl) or a triple bond (alkynyl) .
- Alkenyl or alkynyl may include, for example, 2 to 8 carbon atoms, or 2 to 6 carbon atoms.
- Unsaturated cyclic alkenyls include, for example, cyclopentenyl, cyclohexenyl.
- 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 halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO 2 ); one or more radical (ux) polystyrene; 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 may comprise, for example, from 6 to 10 carbon atoms.
- 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 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 alkyl groups, one or more radicals (ux) polystyrene; with the alkoxy and alkyl groups as defined in the context 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).
- halogen atom is meant an atom chosen from fluorine, chlorine, bromine and iodine atoms.
- additive means a compound capable of improving the solubility and reactivity of the reagents for the transformation of formates.
- the alkyl formate is of formula (I)
- R is alkyl of 1 to 12 carbon atoms, said alkyl may be optionally substituted with a substituent as defined above.
- R is an alkyl comprising 1 to 8 carbon atoms, said alkyl possibly being substituted by a substituent as defined above.
- R is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl.
- R is methyl, ethyl, propyl and -butyl.
- the process of the invention involves a catalyst in the family of strong bases, i.e. a catalyst which may be an alcoholate having a pKa ⁇ 15 in water; or a pKa> 27 in acetonitrile or DMSO or a nitrogen base having pKa> 15 in water; or a pKa> 27 in acetonitrile or DMSO.
- a catalyst in the family of strong bases, i.e. a catalyst which may be an alcoholate having a pKa ⁇ 15 in water; or a pKa> 27 in acetonitrile or DMSO or a nitrogen base having pKa> 15 in water; or a pKa> 27 in acetonitrile or DMSO.
- the catalyst is an alcoholate of formula (II)
- R ' is an alkyl comprising 1 to 6 carbon atoms, an alkenyl comprising 2 to 6 carbon atoms, an alkynyl comprising 2 to 6 carbon atoms or an aryl comprising 6 to 10 carbon atoms;
- M is an alkali metal selected from Li, Na, K, Cs or Rb; or
- M is a quaternary ammonium of formula (III)
- R 1, R 2 , R 3 , R 4 and R 5 represent, independently of one another, a hydrogen atom, an alkyl comprising 1 to 6 carbon atoms, an aryl comprising 6 to 10 carbon atoms; said alkyl and aryl being optionally substituted.
- R ' is an alkyl comprising 1 to 6 carbon atoms.
- the alkyl may be selected from methyl, ethyl, propyl, butyl, pentyl or hexyl.
- said alkali metal is preferably Li, Na, K or Rb.
- the alkoxide is selected from C33 ⁇ 4-OLi, CHa-ONa, CH 3 -OK, CH 3 -ORb, CH 3 CH 2 -OK, or / Bu-OK.
- R 1, R 2 , R 3 , R 4 and R 5 represent, independently of one another, a hydrogen atom, an alkyl comprising 1 to 6 carbon atoms, an aryl comprising 6 to 10 carbon atoms, said aryl being optionally substituted in particular by one or more radical (ux) polystyrene.
- the catalysts of formula (II), in which M is a quaternary ammonium of formula (III), may optionally be supported.
- the active phase is then grafted onto a support, for example a polymer support.
- M is a quaternary ammonium of formula (III)
- said quaternary ammonium is preferably (C 6 H 5 CH 2 ) (CH 3 ) 3 N + , or polystyrene- (C 6 H 4 CH 2 ) (CH 3 ) 3 N +, the latter being the supported form of benzyletriméthylammonium.
- M is a quaternary ammonium alcoholate is selected from CH 3 -0 (C l3 ⁇ 4CH 2 ) (CH) N + , or CH 3 -O polystyrene-
- benzyltrimethylammonium methanolates can be prepared according to the procedure described in Org. Synth. 1958, 38, 5 DOI: 10 .l5227 / orgsyn.038.0005 according to the reaction of FIG.
- the supported version of benzyltrimethylammonium methanolates in particular CH 3 -0 polystyrene- (C 6 H 5 CH 2 ) (CH 3 ) 3 N + may also be prepared according to the procedure described in Org. Synth. 1958, 38, 5 DOI: 10.15227 / orgsyn.038.0005.
- the commercial product in which the polymer is already grafted with ammonium is advantageously used.
- the catalyst is a nitrogenous base having a pKa> 15 in water; or a pKa> 27 in acetonitrile or DMSO.
- the catalyst is preferably an alkaline bicyclic guanidinate selected from bicyclic guanidinates of sodium or potassium, especially the sodium or potassium salt of the anion of 1,3,4,6 7,8-hexahydro-2H-pyrimido [1,2-ajpyrimidine (or Hhpp); or an alkali metal amide substituted with alkyls comprising 1 to 6 carbon atoms, especially the lithium, sodium or potassium salt of dimethylamide, diethylamide, or diisopropylamide.
- the method of the invention may, in addition, implement at least one additive.
- the additive whose role is to improve the solubility and reactivity of the reactants for the transformation of formates, can be chosen, for example, from among
- crown ethers chosen from 12-crown-4, 15-crown-5, 18-crown-6, dibenzo- 18-crown-6, benzo-18-crown-6, benzo-15- crown-5, or dibenzo- 15-crown-5;
- aza-rings selected from 1, 4,7, 10-tetraazacyclodoecane (cyclene), 1, 4,7, 10, 13, 16-hexaazacyclooctadecane (hexacyclene), or diaza-18-crown-6;
- crown thioethers selected from 1,5,9,13-tetrathiacyclohexadecane (16-Ane-S 4 ), or 1,4,7,10,13,16-hexathiacyclooctadecane (18-Ane-S 6 ); or
- CO carbon monoxide
- the solvent is preferably selected from
- ethers chosen from diethyl ether or tetrahydrofuran (THF);
- N N-dimethylformamide
- pyridine N-methyl-2-pyrrolidone
- NMP 1-methyl-2-pyrrolidone
- ketones chosen from acetone or butan-2-one; or
- sulfoxides such as dimethylsulfoxide (DMSO).
- the temperature of the production of carbon monoxide (CO) according to the process of the invention in which an alkyl formate of formula (I) is used is less than or equal to 30 ° C.
- the temperature is between 10 and 30, more preferably between 15 and 30 ° C inclusive.
- the conversion of the alkyl formate of formula (I) to CO generates a gas pressure resulting from the formation of carbon monoxide.
- the reaction can then take place under pressure of carbon monoxide (closed system), or under atmospheric pressure (1 bar or 10 5 Pa) of inert gases (N 2 and / or argon), for example, in a burette ( open system).
- inert gases N 2 and / or argon
- the production of carbon monoxide (CO) employing an alkyl formate preferably occurs in an inert atmosphere under a pressure of dinitrogen (N 2 ), argon or a mixture of these gases.
- the duration of the reaction depends on the conversion rate of the alkyl formate of formula (I).
- the reaction is advantageously maintained until the total conversion of the alkyl formate to CO.
- the duration of the reaction may be from 1 minutes to 200 hours, preferably from 5 minutes to 48 hours, more preferably from 15 minutes to 4 hours, limits included.
- the amount of catalyst used in the process of the invention is from 0.1 to 10 mol%, preferably from 2 to 5 mol%, inclusive, with respect to the alkyl formate of formula (I).
- the amount of additive is from 0.1 to 10 mol%, preferably from 2 to 5 mol%, inclusive, with respect to the alkyl formate of formula
- the alkyl formate of formula (I) can be obtained by the esterification of formic acid with an alcohol of formula ROH in which R is alkyl comprising 1 to 12 carbon atoms, in order to obtain the corresponding formate, for example by simple distillation. Distillation is possible and effective as long as there are no azeotropes between reagents, products and solvent and the following inequalities on boiling temperatures are satisfied:
- Teb (formate) Teb (formic acid) ⁇
- Formic acid in turn, can be obtained by the conventional industrial process, by hydrogenation or by electro-reduction at 2e of C0 2 (step (i)).
- the formation of formic acid can advantageously be carried out by reducing the C0 2 to 2e, preferably carried out according to the most selective and effective methods known to date.
- the catalytic hydrogenation of C0 2 can be carried out according to the protocol of Laurenczy et al (S. Moret, PJ Dyson, G. Laurenczy, Nat., 2014, 5, 1-7), making it possible to recover up to 1.9 M formic acid in DMSO.
- electro-reduction at 2e of C0 2 it can be conducted, for example, according to the conditions of Shibata et al. (N.
- step (i) may then be used in the next step (ii) which is the preparation of the alkyl formate of formula (I).
- Step (ii) consists in reacting:
- the formic acid obtained in the first step either directly in the same reaction medium or after having treated the catalyst by eliminating it or separating it from the reaction medium or, by deactivating it in the reaction medium;
- reaction medium is surmounted by a distillation apparatus (preferably with a Vigreux column) and heated to a temperature allowing the selective distillation of the target formate (for example between 62 ° C and 80 ° C for methyl formate):
- step (iii) The alkyl formate of formula (I) from step (ii) is then brought into contact with a catalyst as defined above, in a solvent chosen from those mentioned above, at a temperature of less than or equal to 40 ° C. (step (iii)).
- Figure 1 shows steps (i) to (iii) leading to the production of carbonyl by the method of the invention.
- Formic acid and alkyl formate are liquid under normal conditions of temperature and pressure (18 to 25 ° C and pressure lbar or 10 5 Pa), which makes it easy to transport with costs and therefore risks lower than the transport of gas such as hydrogen. This is particularly interesting when the production of formic acid and the decarbonylation of alkyl formate are carried out in two distinct places.
- Formic acid is non-toxic in dilute solution (concentration below 85% by mass in water) and is in fact a benign reagent.
- alkyl formates eg methyl or ethyl formate
- Most alkyl formates are non-toxic and therefore can be considered as benign reagents.
- the production of CO is catalyzed with a catalyst comprising an abundant alkali metal on the earth, unlike the catalysts of the state of the art which use metals having a low abundance, a high cost. and problematic toxicity.
- the catalysts used are commercial, or readily prepared by those skilled in the art from commercial and inexpensive reagents.
- metals such as those of the state of the art are used, the ligands used to stabilize them are expensive and their preparation usually requires multiple synthetic steps.
- step (i) there is compatibility between the steps (i) and (ii) described above when the catalytic hydrogenation is chosen as a CO 2 reduction process, and these two reactions can thus be carried out subsequently when the solvent used in step (i) is compatible with step (ii).
- the medium used is aqueous which is also compatible with step (ii).
- distillation is an effective method of purifying alkyl formate.
- alkyl formate there is no azeotrope especially between methyl formate, water and methanol.
- Distillation gives the anhydrous methyl formate (possibly with 0 to 15 mol% MeOH as impurity).
- the impurity can be characterized by analysis quantitative 1H NMR.
- the process of the invention can be used in all industrial processes and at the laboratory scale requiring pure carbon monoxide.
- Another subject of the invention relates to a process chosen from
- Nickel carbonylation process comprising a step of producing carbon monoxide employing an alkyl formate of formula (I) by the process according to the invention.
- Another subject of the invention relates to a "CO pump” or “liquid CO storage” process comprising a step of producing carbon monoxide using an alkyl formate of formula (I) according to the process of the invention.
- the invention as shown in FIG. 2. More particularly, the "CO pump” or “liquid CO storage” process is characterized in that it comprises
- step (A) the formation of G alkylformate of formula (I) by carbonylation of an alcohol of formula ROH, with R representing an alkyl comprising 1 to 12 carbon atoms, preferably a methyl, can be carried out following the industrial process described in US 4216339.
- FIG 1 shows steps (i) to (iii) which result in the production of carbonyl by the process of the invention.
- FIG. 2 represents the process of "CO pump” or “liquid CO storage” comprising a step of producing carbon monoxide employing an alkyl formate of formula (I) according to the process of the invention.
- FIG. 3 represents the reaction allowing the preparation of benzyltrimethylammonium methanolates CH 3 -O (CH CH 2 ) (CH 3 ) N + according to the procedure described in Org. Synth. 1958, 38, 5 DOI: 10. l5227 / orgsyn.038.0005.
- FIG. 4 represents the reaction allowing the preparation of the supported version of benzyltrimethylammonium methanolates, especially CH 3 -0 polystyrene- (C 6 H 4 CH 2 ) (CH 3 ) 3 N + according to the procedure described in Org. Synth. 1958, 38, 5 DOI: l0.l5227 / orgsyn.038.0005.
- carbon monoxide has been characterized by:
- reagents, catalysts, additives, solvents used are either commercial or prepared according to the reference indicated:
- Methyl formate Acros organics 500 mL 97% CAS: 107-31-3
- MeONa Sigma Aldrich 100G 95% CAS: 124-41-4
- MeORb Preparation according to the method described by S. I. Drakin, R.K. Kurmalieva, M. K. Karapet'yants, Teoreticheskaya i Eksperi mental 'naya Khimiya, 1966, Vol 2, pp. 40-44 Khpp: Preparation according to: M. P. Coles, P. B. Hitchcock, Aust. J. Chem., 2013, 66, 1124-1130.
- Nahpp Preparation according to: A. A. Mohamed, A. Mayer, P. E. Abdou, D. Irwin, L.
- Khpp Preparation according to: Mr. P. Coles, P. B. Hitchcock, Aust. J. Chem., 2013, 66, 1124-1130.
- the flask is then heated to a temperature selected according to the formate to allow continuous clean distillation of the formate.
- the calculated yield is the ratio of the number of moles of methyl formate recovered relative to the number of moles of formic acid introduced introduced corrected by the purity observed by 1 H NMR analysis.
- the catalyst, the alkyl formate, the solvent, and optionally an additive are introduced into a Schlenk tube which is then sealed by J. Young tap.
- the order of introduction of the reagents requires that either the catalyst or the formate be put in last.
- the Schlenk tube is then stirred at a temperature between 15 and 30 ° C.
- KHpp 1, 3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine, potassium salt.
- the conversion percentage is calculated by NMR analysis : H of the reaction crude, indirectly by integration of the alcohol G signal formed at the same time as the CO, relative to the alkyl formate introduced.
- the catalyst, the solvent, optionally an additive are introduced into a reaction flask provided with an isobaric dropping funnel.
- the order of introduction of the reagents does not matter.
- the flask is then stirred at room temperature (about 19 ° C) recovering carbon monoxide through a third neck.
- the catalyst, the alkyl formate, the solvent, and optionally an additive are introduced into a Schlenk tube which is then sealed by a J. Young tap.
- the order of introduction of the reagents requires that either the catalyst or the formate be put in last.
- the Schlenk tube is then stirred at a temperature between 15 and 30 ° C.
- the conversion percentage is calculated by NMR analysis of the reaction crude, indirectly by integration of the alcohol G signal formed at the same time as the CO, relative to the alkyl formate introduced.
- PS polystyrene radical
Abstract
Description
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GB1511961A (en) | 1976-03-12 | 1978-05-24 | Ucb Sa | Process for the production of methyl formate |
GB8301464D0 (en) * | 1983-01-19 | 1983-02-23 | Bp Chem Int Ltd | Decarbonylation process |
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