FR3129941A1 - Process for the production of tetrahydrothiophene - Google Patents
Process for the production of tetrahydrothiophene Download PDFInfo
- Publication number
- FR3129941A1 FR3129941A1 FR2112997A FR2112997A FR3129941A1 FR 3129941 A1 FR3129941 A1 FR 3129941A1 FR 2112997 A FR2112997 A FR 2112997A FR 2112997 A FR2112997 A FR 2112997A FR 3129941 A1 FR3129941 A1 FR 3129941A1
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- FR
- France
- Prior art keywords
- process according
- tetrahydrothiophene
- catalyst
- reaction
- weight
- 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.)
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Links
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims 2
- 239000012071 phase Substances 0.000 claims 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000010908 decantation Methods 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- -1 CO 2 Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Procédé de production de tétrahydrothiophène L’invention porte sur un procédé de production de tétrahydrothiophène comprenant une étape de réaction de 1,4-butanediol ou de tétrahydrofurane, en présence de sulfure d’hydrogène (H2S), et éventuellement de dioxyde de carbone en phase gaz, à une température comprise entre 200 et 320°C, en présence d’alumine en tant que catalyseur comportant une teneur en oxyde de sodium inférieure à 0,3% en poids par rapport au poids total du catalyseur.Process for the production of tetrahydrothiophene The invention relates to a process for the production of tetrahydrothiophene comprising a step of reacting 1,4-butanediol or tetrahydrofuran, in the presence of hydrogen sulphide (H2S), and optionally of carbon dioxide in phase gas, at a temperature between 200 and 320° C., in the presence of alumina as catalyst comprising a sodium oxide content of less than 0.3% by weight relative to the total weight of the catalyst.
Description
La présente invention concerne un procédé de production de tétrahydrothiophène conduisant à un rendement amélioré.The present invention relates to a process for producing tetrahydrothiophene resulting in improved yield.
Le tétrahydrothiophène est un composé présentant un grand intérêt industriel. Il est connu pour être utilisé comme additif dans les gaz consommables pour déceler d’éventuelles fuites en raison de son odeur très caractéristique. De ce fait, il est présent dans le gaz injecté sur le réseau d’alimentation domestique, dans les réseaux de transport de gaz, dans les appareils de stockage et dans les interconnexions avec les autres réseaux de transport de gaz.Tetrahydrothiophene is a compound of great industrial interest. It is known to be used as an additive in consumable gases to detect possible leaks due to its very characteristic smell. It is therefore present in the gas injected into the domestic supply network, in the gas transport networks, in the storage devices and in the interconnections with the other gas transport networks.
Il est connu de synthétiser le tétrahydrothiophène, ci-après noté THT, à partir de 1,4-butanediol, ci-après noté BDO ou bien de tétrahydrofurane, noté THF, et de sulfure d’hydrogène, ci-après noté H2S en présence de catalyseur hétérogène.It is known to synthesize tetrahydrothiophene, hereinafter denoted THT, from 1,4-butanediol, hereinafter denoted BDO or else from tetrahydrofuran, denoted THF, and hydrogen sulphide, hereinafter denoted H 2 S in the presence of heterogeneous catalyst.
Il est admis dans la littérature, que la première étapein situest la transformation du BDO en THF selon la réaction suivante :
1,4-BDO →THF + H2OIt is accepted in the literature that the first step in situ is the transformation of BDO into THF according to the following reaction:
1,4-BDO →THF + H 2 O
La deuxième étape est la transformation du THF, en présence de H2S, en THT selon la réaction suivante :
THF + H2S →THT + H2OThe second step is the transformation of THF, in the presence of H 2 S, into THT according to the following reaction:
THF + H 2 S →THT + H 2 O
Or, les réactions secondaires suivantes peuvent se produire en fonction des conditions opératoires :
THT →DiHydroThiophène + H2
THT →Thiophène + 2H2
THT + H2→Propylène + CH3SH
THT + H2→Butène + H2SHowever, the following side reactions may occur depending on the operating conditions:
THT →DiHydroThiophene + H 2
THT →Thiophene + 2H 2
THT + H 2 →Propylene + CH 3 SH
THT + H 2 →Butene + H 2 S
De plus, cette synthèse peut générer des produits de dégradation, tels que du CO2, de l’éthylène et des mercaptans en C1à C4.Moreover, this synthesis can generate degradation products, such as CO 2 , ethylene and C 1 to C 4 mercaptans.
Or, au regard des considérations écologiques actuelles, il existe aujourd'hui un réel besoin pour un procédé de synthèse de tétrahydrothiophène plus performant, c’est-à-dire dont le rendement est plus élevé et le taux de produits secondaires plus faibles.However, in view of current ecological considerations, there is now a real need for a more efficient tetrahydrothiophene synthesis process, i.e. one with a higher yield and a lower level of secondary products.
En effet, ces produits secondaires ou sous-produits de réaction sont difficilement recyclables. Ils sont généralement incinérés, et conduisent à de fortes émissions d’oxydes de soufre (SO2) dans l’atmosphère, potentiellement responsables de pluies acides. Or, à l’heure actuelle, ces rejets ne sont plus tolérés.Indeed, these secondary products or reaction by-products are difficult to recycle. They are generally incinerated, and lead to strong emissions of sulfur oxides (SO 2 ) into the atmosphere, potentially responsible for acid rain. However, at the present time, these rejections are no longer tolerated.
Un objectif de la présente invention est de fournir un procédé de préparation de tétrahydrothiophène plus performant.An object of the present invention is to provide a more efficient process for the preparation of tetrahydrothiophene.
Les présents inventeurs ont découvert de façon surprenante que le choix d’un catalyseur particulier associé à une gamme de température particulière permettait d’augmenter significativement le rendement de la réaction.The present inventors have surprisingly discovered that the choice of a particular catalyst associated with a particular temperature range makes it possible to significantly increase the yield of the reaction.
En d’autres termes, le choix du catalyseur permet de baisser significativement la température de la réaction permettant une économie énergétique. Par ailleurs, le choix de ce catalyseur permet d’augmenter le rendement de la réaction.In other words, the choice of the catalyst makes it possible to significantly lower the temperature of the reaction allowing an energy saving. Moreover, the choice of this catalyst makes it possible to increase the yield of the reaction.
Le procédé de production de tétrahydrothiophène selon l’invention est donc plus économique, présente des meilleures performances, tout en étant plus respectueux de l’environnement.
Brève description de l’invention The process for the production of tetrahydrothiophene according to the invention is therefore more economical, has better performance, while being more respectful of the environment.
Brief description of the invention
Ainsi, la présente invention a pour objet un procédé de production de tétrahydrothiophène comprenant une étape de réaction de 1,4-butanediol ou de tétrahydrofurane, en présence de sulfure d’hydrogène (H2S), et éventuellement de dioxyde de carbone en phase gaz, à une température comprise entre 200 et 320°C, en présence d’alumine en tant que catalyseur comportant une teneur en oxyde de sodium inférieure à 0,3% en poids par rapport au poids total du catalyseur.Thus, the subject of the present invention is a process for the production of tetrahydrothiophene comprising a step of reacting 1,4-butanediol or tetrahydrofuran, in the presence of hydrogen sulphide (H 2 S), and optionally of carbon dioxide in phase gas, at a temperature of between 200 and 320° C., in the presence of alumina as catalyst comprising a sodium oxide content of less than 0.3% by weight relative to the total weight of the catalyst.
Claims (9)
b) condensation du flux issu à l’étape définie à l’une quelconque des revendications précédentes pour obtenir un flux riche en tétrahydrothiophène et des évents gazeux contenant les incondensables éventuellement formés à l’issue de l’étape définie à l’une quelconque des revendications précédentes ;
c) au moins une étape de purification, de préférence par décantation, du flux riche en tétrahydrothiophène issu de l’étape b) avec séparation de la phase aqueuse, de la phase organique et des évents gazeux ;
d) éventuellement au moins une distillation de la phase organique pour isoler le tétrahydrothiophène des évents gazeux ;
e) récupération du tétrahydrothiophène isolé à l’étape c) et éventuellement à l’étape d),
les étapes b) et c) pouvant être successives ou simultanées.Process according to any one of the preceding claims, characterized in that it comprises the following successive steps:
b) condensation of the stream resulting from the step defined in any one of the preceding claims to obtain a stream rich in tetrahydrothiophene and gaseous vents containing the incondensables possibly formed at the end of the step defined in any one of the previous claims;
c) at least one stage of purification, preferably by decantation, of the stream rich in tetrahydrothiophene resulting from stage b) with separation of the aqueous phase, of the organic phase and of the gaseous vents;
d) optionally at least one distillation of the organic phase to isolate the tetrahydrothiophene from the gas vents;
e) recovery of the tetrahydrothiophene isolated in step c) and optionally in step d),
steps b) and c) possibly being successive or simultaneous.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2112997A FR3129941A1 (en) | 2021-12-06 | 2021-12-06 | Process for the production of tetrahydrothiophene |
| PCT/FR2022/052248 WO2023105153A1 (en) | 2021-12-06 | 2022-12-05 | Method for producing tetrahydrothiophene |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2112997 | 2021-12-06 | ||
| FR2112997A FR3129941A1 (en) | 2021-12-06 | 2021-12-06 | Process for the production of tetrahydrothiophene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| FR3129941A1 true FR3129941A1 (en) | 2023-06-09 |
Family
ID=80122434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR2112997A Pending FR3129941A1 (en) | 2021-12-06 | 2021-12-06 | Process for the production of tetrahydrothiophene |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR3129941A1 (en) |
| WO (1) | WO2023105153A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3819651A (en) * | 1969-07-18 | 1974-06-25 | Glanzstoff Ag | Process for the production of tetrahydrothiophene |
-
2021
- 2021-12-06 FR FR2112997A patent/FR3129941A1/en active Pending
-
2022
- 2022-12-05 WO PCT/FR2022/052248 patent/WO2023105153A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3819651A (en) * | 1969-07-18 | 1974-06-25 | Glanzstoff Ag | Process for the production of tetrahydrothiophene |
Non-Patent Citations (1)
| Title |
|---|
| MASHKINA A.V. ET AL: "Catalytic synthesis of thiolane from tetrahydrofuran and H2S", APPLIED CATALYSIS A: GENERAL, vol. 116, no. 1-2, 1 September 1994 (1994-09-01), AMSTERDAM, NL, pages 95 - 108, XP055934351, ISSN: 0926-860X, DOI: 10.1016/0926-860X(94)80282-3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023105153A1 (en) | 2023-06-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PLFP | Fee payment |
Year of fee payment: 2 |
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| PLSC | Publication of the preliminary search report |
Effective date: 20230609 |
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| PLFP | Fee payment |
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