WO2020148510A1 - Procédé de prépraration d'un composé de formule rsh par hydrosulfuration - Google Patents
Procédé de prépraration d'un composé de formule rsh par hydrosulfuration Download PDFInfo
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- WO2020148510A1 WO2020148510A1 PCT/FR2020/050060 FR2020050060W WO2020148510A1 WO 2020148510 A1 WO2020148510 A1 WO 2020148510A1 FR 2020050060 W FR2020050060 W FR 2020050060W WO 2020148510 A1 WO2020148510 A1 WO 2020148510A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- mixed
- rare earth
- reaction
- sulphides
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- -1 rare earth sulfides Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 3
- 239000011949 solid catalyst Substances 0.000 claims abstract description 3
- 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 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 52
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 22
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 150000003568 thioethers Chemical class 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910017583 La2O Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
Definitions
- TITLE PROCESS FOR PREPARING A COMPOUND OF FORMULA RSH BY HYDROSULFURATION
- the invention relates to a process for the catalytic gas phase hydrosulfurization of a corresponding thiol alcohol. It is more particularly described for the manufacture of methanethiol from methanol and from hydrogen sulphide, without its scope being restricted therein.
- the invention provides a method which satisfies these requirements.
- This process makes it possible to prepare a compound of formula RSH where R represents an alkyl group, by gas phase catalytic reaction of hydrogen sulphide with a compound of formula ROH, in the presence of a solid catalyst, this catalyst comprising or consisting of a or pure or mixed rare earth (s) oxides, pure or mixed rare earth (s) sulphide (s) or pure rare earth (s) oxy-sulphide (s) or mixed, provided that when the rare earth is lanthanum, said catalyst is a mixed oxide of lanthanum and at least one metal selected from rare earths and when the rare earth is cerium, said catalyst is supported.
- a solid catalyst comprising or consisting of a or pure or mixed rare earth (s) oxides, pure or mixed rare earth (s) sulphide (s) or pure rare earth (s) oxy-sulphide (s) or mixed, provided that when the rare earth is lanthanum, said catalyst is a mixed oxide of lanthanum and at least one metal selected from rare earths and when
- the selectivity was improved significantly compared to the catalysts described in the prior art, in particular by a decrease which can reach an order of magnitude of at least 40% in non-products.
- recoverable products such as carbon monoxide, carbon dioxide, methane, hydrogen and dimethyl ether.
- the main product is methanethiol, and dimethylsulfide constitutes the majority secondary product.
- the latter can be skillfully recycled to be converted to methanethiol, thus increasing the overall yield of the methanethiol process.
- the reaction can be carried out over a wider and generally lower temperature range than those of known processes. More generally, this process has the advantage of being flexible and depending on the operating conditions such as the temperature, the selectivity can be oriented towards one product or another.
- rare earths we mean the 15 lanthanides (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium), as well as scandium and yttrium.
- lanthanides lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium
- the catalyst may be present in the form of an oxide (or oxyhydroxide), sulphide and any intermediate form containing S and O which is called oxysulphide.
- alkyl denotes a linear or branched monovalent hydrocarbon radical having from 1 to 20 carbon atoms, advantageously from 1 to 6 carbon atoms, such as methyl or ethyl , propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, n-hexyl or a cyclic monovalent hydrocarbon radical having from 3 to 20 carbon atoms, advantageously from 3 to 6 carbon atoms, such as cyclopropyl, cyclohexyl, but not limited to these radicals.
- the catalyst is chosen from rare earth oxides, hydroxides or even rare earth oxyhydroxides and at least one other metal which is not a rare earth.
- the catalyst can also be chosen from mixed oxides (hydroxides or oxyhydroxides) of rare earths and of at least one other metal which is not a rare earth.
- mixed oxides is understood to mean an oxide based on several rare earths.
- the catalyst can also be chosen from mixed sulphides of several rare earths, mixed sulphides of one or more rare earths and at least one other metal which is not a rare earth, oxy-sulphides of several rare earths.
- mixed oxidesulfides of one or more rare earths and at least one other metal which is not a rare earth and mixtures of said mixed oxides, mixed sulfides and mixed oxidesulfides.
- Said metal which is not a rare earth is preferably zirconium.
- the catalyst may also comprise, in addition to the aforementioned oxides, sulphides and / or oxysulphides, one or more oxides of different rare earth metals.
- the catalyst is supported, advantageously on alumina, pretreated or not, which makes it possible to circumvent the problems of blockages which can potentially be observed in the presence of materials based on rare earths in powder form.
- the process of the invention is particularly advantageous for the preparation of methanethiol by catalytic hydrosulfurization of methanol, but it may be suitable for obtaining any RSH compound, where R is an alkyl as defined above.
- the catalyst comprises or consists of mixed oxides of lanthanum, cerium, neodymium and zirconium; in this combination, the proportions of zirconium oxide and cerium are in the majority relative to those of the oxides of lanthanum and of neodymium.
- a support has also been developed which makes it possible to increase the performance of the catalysts used.
- This support can be an alumina modified with potassium, with a potassium content of between 0.1% and 20% (m / m), preferably between 0.5% and 10%, and more preferably between 0.5% and 5%.
- the use of ceria supported on an alumina thus modified is reported, in a range of supported cerium oxide contents of between 0.1% and 50% (m / m), preferably between 0.5% and 30% (m / m).
- the ratio of hydrogen sulphide to the ROH compound preferably ranges from 0.5 to 20, preferably from 1 to 15, and more preferably from 1 to 10.
- reaction temperatures it was previously indicated that one of the interests of the invention was to be able to widen the range of reaction temperatures.
- it can be carried out at a temperature of 200 ° C to 450 ° C, preferably from 250 ° C to 420 ° C, and more preferably from 275 ° C to 400 ° C, advantageously under a pressure of between 2 and 20 bar , preferably from 5 to 15 bar, and even more preferably from 7 to 14 bar and for a contact time of the ROH compound with the catalyst ranging from 0.1 seconds to 60 seconds.
- reaction is highly selective for methanethiol
- dimethylsulfide can also be formed.
- a reaction of catalytic conversion of said dimethylsulfide into methanethiol can then be carried out in addition, according to techniques well known to those skilled in the art, in order to further improve the yield of the process in methanethiol.
- Example 1 Manufacture of methanethiol from methanol, in the presence of a catalyst based on mixed oxides, according to the invention
- the catalyst was prepared by synthetic routes of mild chemistry. For example, it can be obtained according to the method described in patent FR2907445A1 or patent FR2859470A1.
- the specific surface of this catalyst is 75 m 2 .g _1 .
- the composition by weight of oxides is 2.0% La2O 3 , 21.3% CeO2, 5.1% Nd2O 3 and 71.6% ZrO 2 .
- a catalytic bed of 2 ml of catalyst diluted in carborundum with a particle size of between 0.400 and 0.500 nm is placed in a reactor with an internal diameter of 1.26 cm.
- the reactor inlet gases consist of a mixture of methanol and hydrogen sulfide.
- the process of the invention exhibits both a higher conversion of methanol and a higher selectivity to methanethiol, while producing very small quantities of light gases in favor of a greater selectivity to dimethylsulfide.
- Example 2 Manufacture of methanethiol from methanol, in the presence of a catalyst based on mixed oxides, according to the invention
- Cat2 catalyst is prepared using the same technique as Cat1 catalyst above.
- the specific surface of this catalyst is 59 m 2 .g _1 .
- the composition by weight of oxides is 1.75% of La2O 3 , 30.3% of Ced, 5.35% of Nd2O 3 and 62.6% of Zr0 2 .
- the performances of the catalysts were compared over a wide range of methanol conversions by varying the mass of catalyst introduced and the flow rate of the various reactants.
- Example 3 Manufacture of methanethiol from methanol. in the presence of a catalyst based on cerium oxide, supported on modified alumina, according to the invention
- the supported CatS3 catalyst is synthesized by successive impregnations and calcinations (450 ° C in air) of 100 g of commercial alumina with a specific surface area of 171 m 2 .g 1 with a solution of potassium hydroxide (38 g / L), then with a solution of cerium (III) nitrate (1151 g / L).
- the potassium content is 1.5% by mass, that of cerium oxide 3.5% by mass.
- the specific surface of the catalyst is 167 m 2 .g 1
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- Materials Engineering (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202080009410.6A CN113316567A (zh) | 2019-01-18 | 2020-01-16 | 通过硫氢化制备式rsh的化合物的方法 |
JP2021540242A JP2022517590A (ja) | 2019-01-18 | 2020-01-16 | 水硫化により式rshの物質を調製する方法 |
US17/423,267 US20220127222A1 (en) | 2019-01-18 | 2020-01-16 | Process for preparing a compound of formula rsh by hydrosulfurization |
EP20707306.5A EP3911627A1 (fr) | 2019-01-18 | 2020-01-16 | Procédé de prépraration d'un composé de formule rsh par hydrosulfuration |
SG11202106892YA SG11202106892YA (en) | 2019-01-18 | 2020-01-16 | Process for preparing a compound of formula rsh by hydrosulfurization |
KR1020217019582A KR20210116447A (ko) | 2019-01-18 | 2020-01-16 | 수소첨가황화에 의한 화학식 rsh의 화합물의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1900463A FR3091869B1 (fr) | 2019-01-18 | 2019-01-18 | Procede de preparation d’un compose de formule rsh par hydrosulfuration |
FR19/00463 | 2019-01-18 |
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WO2020148510A1 true WO2020148510A1 (fr) | 2020-07-23 |
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PCT/FR2020/050060 WO2020148510A1 (fr) | 2019-01-18 | 2020-01-16 | Procédé de prépraration d'un composé de formule rsh par hydrosulfuration |
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US (1) | US20220127222A1 (fr) |
JP (1) | JP2022517590A (fr) |
KR (1) | KR20210116447A (fr) |
CN (1) | CN113316567A (fr) |
FR (1) | FR3091869B1 (fr) |
SG (1) | SG11202106892YA (fr) |
WO (1) | WO2020148510A1 (fr) |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2859470A1 (fr) | 2003-09-04 | 2005-03-11 | Rhodia Elect & Catalysis | Composition a base d'oxyde de cerium et d'oxyde de zirconium a reductibilite et surface elevees, procede de preparation et utilisation comme catalyseur |
FR2907445A1 (fr) | 2006-10-20 | 2008-04-25 | Rhodia Recherches & Tech | Composition a acidite elevee a base d'oxyde de zirconium, d'oxyde de titane et d'oxyde de tungstene,procede de preparation et utilisation dans le traitement des gaz d'echappement |
WO2013092129A1 (fr) | 2011-12-19 | 2013-06-27 | Evonik Degussa Gmbh | Catalyseur destiné à la synthèse d'alkylmercaptans et procédé pour sa préparation |
Family Cites Families (4)
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US4313006A (en) * | 1980-09-03 | 1982-01-26 | Pennwalt Corporation | Process for converting dialkyl sulfides to alkyl mercaptans |
FR2773559B1 (fr) * | 1998-01-06 | 2001-05-25 | Occidental Chem Co | Production de mercaptans en utilisant des catalyseurs acides heterogenes |
DE102009027837A1 (de) * | 2009-07-20 | 2011-01-27 | Evonik Degussa Gmbh | Verfahren zur kontinuierlichen Herstellung von Methylmercaptan aus kohlenstoffhaltigen Verbindungen, Schwefel und Wasserstoff |
JP5752921B2 (ja) * | 2009-11-18 | 2015-07-22 | Jx日鉱日石エネルギー株式会社 | チオール化合物の製造方法 |
-
2019
- 2019-01-18 FR FR1900463A patent/FR3091869B1/fr active Active
-
2020
- 2020-01-16 CN CN202080009410.6A patent/CN113316567A/zh active Pending
- 2020-01-16 KR KR1020217019582A patent/KR20210116447A/ko not_active Application Discontinuation
- 2020-01-16 US US17/423,267 patent/US20220127222A1/en active Pending
- 2020-01-16 SG SG11202106892YA patent/SG11202106892YA/en unknown
- 2020-01-16 JP JP2021540242A patent/JP2022517590A/ja active Pending
- 2020-01-16 WO PCT/FR2020/050060 patent/WO2020148510A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2859470A1 (fr) | 2003-09-04 | 2005-03-11 | Rhodia Elect & Catalysis | Composition a base d'oxyde de cerium et d'oxyde de zirconium a reductibilite et surface elevees, procede de preparation et utilisation comme catalyseur |
FR2907445A1 (fr) | 2006-10-20 | 2008-04-25 | Rhodia Recherches & Tech | Composition a acidite elevee a base d'oxyde de zirconium, d'oxyde de titane et d'oxyde de tungstene,procede de preparation et utilisation dans le traitement des gaz d'echappement |
WO2013092129A1 (fr) | 2011-12-19 | 2013-06-27 | Evonik Degussa Gmbh | Catalyseur destiné à la synthèse d'alkylmercaptans et procédé pour sa préparation |
Non-Patent Citations (4)
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CATALYSIS LETTERS, vol. 128, 2009, pages 449 - 458 |
CRAIG P PLAISANCE ET AL: "Zeolite and Metal Oxide Catalysts for the Production of Dimethyl Sulfide and Methanethiol", CATALYSIS LETTERS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 128, no. 3-4, 26 November 2008 (2008-11-26), pages 449 - 458, XP019672020, ISSN: 1572-879X * |
M. ZIOLEK ET AL: "Influence of hydrogen sulfide adsorption on the catalytic properties of metal oxides", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL., vol. 97, no. 1, 21 March 1995 (1995-03-21), NL, pages 49 - 55, XP055627164, ISSN: 1381-1169, DOI: 10.1016/1381-1169(94)00068-9 * |
ZIOLEK ET AL., JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 97, 1997, pages 49 - 55 |
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Publication number | Publication date |
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US20220127222A1 (en) | 2022-04-28 |
TW202045474A (zh) | 2020-12-16 |
JP2022517590A (ja) | 2022-03-09 |
SG11202106892YA (en) | 2021-08-30 |
CN113316567A (zh) | 2021-08-27 |
KR20210116447A (ko) | 2021-09-27 |
FR3091869A1 (fr) | 2020-07-24 |
FR3091869B1 (fr) | 2021-01-22 |
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