WO2020064466A1 - Catalyseur pour la synthèse d'acides alcanesulfoniques - Google Patents

Catalyseur pour la synthèse d'acides alcanesulfoniques Download PDF

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Publication number
WO2020064466A1
WO2020064466A1 PCT/EP2019/075036 EP2019075036W WO2020064466A1 WO 2020064466 A1 WO2020064466 A1 WO 2020064466A1 EP 2019075036 W EP2019075036 W EP 2019075036W WO 2020064466 A1 WO2020064466 A1 WO 2020064466A1
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WIPO (PCT)
Prior art keywords
organic
sulfur trioxide
peroxoacid
alkane
oxoacid
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PCT/EP2019/075036
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English (en)
Inventor
Timo Ott
Ingo Biertuempel
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Basf Se
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Publication of WO2020064466A1 publication Critical patent/WO2020064466A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide

Definitions

  • the present invention relates to novel uses of organic peroxoacids comprising functional groups as catalysts in the preparation of alkanesulfonic acids from alkanes and sulfur trioxide, methods for the production of alkanesulfonic acids employing said catalysts as well as reaction mixtures comprising said catalysts.
  • the invention particularly relates to the production of methanesulfonic acid from methane and sulfur trioxide employing organic peroxoacids comprising functional groups as catalysts.
  • Alkanesulfonic acids are organic acids that can reach a similar acid strength as that of inorganic mineral acids, for example, sulfuric acid.
  • inorganic mineral acids for example, sulfuric acid.
  • the sulfonic acids are non-oxidizing and do not give off vapors that are harmful to health, as can be observed with hydrochloric and nitric acids.
  • many sulfonic acids, for example, methanesulfonic acid are biologically degradable.
  • the applications of sulfonic acids are many, for example, in cleaning agents, surfactants, galvanic and electronic industry, as catalysts, and in organic synthesis, pharmaceutical chemistry, for example, as protective groups.
  • the salts of sulfonic acids are employed, for example, as surfactants, for example, sodium dodecylsulfonate, or in the electroplating industry, especially as tin, zinc, silver, lead and indium, but also other metal, alkylsulfonates.
  • organic salts are employed in pharmaceutical chemistry.
  • the very high solubility of alkyl sulfonates plays an important role, in particular. Further, no harmful gases are formed in electrolysis, and the use of toxic compounds, for example, cyanide, which is common in many cases, is dispensed with.
  • the structurally simplest representative of alkanesulfonic acids is methanesulfonic acid.
  • reaction conditions in conventional processes of alkanesulfonic acid production can result in undesirable side products, which even manifest themselves as disturbing inhibitors in the produc- tion of alkanesulfonic acids. This may lead to termination of the actual reaction for preparing the alkanesulfonic acid, but also to impurities, formation of side products and poor yields, based on sulfur trioxide and methane.
  • WO 2007/136425 A2 discloses the use of the compound di(methanesulfonyl) peroxide (DMSP), which must be prepared by a complex electrolysis and, in addition, is a crystallizable highly explo- sive solid, as an initiator in a reaction in which methanesulfonic acid is formed from sulfur trioxide and methane.
  • DMSP di(methanesulfonyl) peroxide
  • WO 2015/071365 A1 and WO 2015/071455 A1 both describe processes for the sulfonation of alkanes. The main steps are:
  • the initiator is particularly prepared by reacting an alkanesulfonic acid ALK-SO3H, i.e. the desired product, with hydrogen peroxide in order to form an initiator- precursor ALK-SO2-O-OH. Said initiator-precursor is then reacted with SO3 yielding initiator compounds such as ALK-SO2-O-O-SO3H.
  • ALK-SO2-O-O-SO3H alkanesulfonic acid
  • the object of the present invention is solved by the use of a compound comprising an organic peroxoacid or a salt thereof, wherein the organic peroxoacid comprises a peroxoacid group and at least one additional functional group, as a catalyst in the preparation of alkane sulfonic acids from alkanes and sulfur trioxide, especially in the preparation of methane sulfonic acid from methane and sulfur trioxide.
  • a compound comprising an organic peroxoacid or a salt thereof, wherein the organic peroxoacid comprises a peroxoacid group and at least one additional functional group, as a catalyst in the preparation of alkane sulfonic acids from alkanes and sulfur trioxide, especially in the preparation of methane sulfonic acid from methane and sulfur trioxide.
  • methane, ethane, propane, butane, isopropane, isobutane or a higher alkane can be reacted with sulfur trioxide to form the
  • organic peroxoacids comprising functional groups show a similar catalytic activity as peroxoacids derived from the desired alkane sulfonic acids.
  • peroxoacids derived from the desired alkane sulfonic acid which comprise no functional groups other than the persulfonic acid group itself, may be employed as catalysts in the preparation of alkane sulfonic acids from alkanes and sulfur trioxide and the desired product is not required as a precursor of the catalyst.
  • any organic peroxoacid comprising functional groups can be employed according to the invention. Such organic peroxoacids or their corresponding oxoacids or derivatives thereof are cheaply available from commercial dis tributors.
  • the peroxoacid is used as a catalyst in a condensed-phase homogeneous process.
  • the peroxoacid catalyst is solved in the same phase as the reactants, i.e., an alkane and sulfur trioxide.
  • the assumed catalytic cycle is exemplary described for the employment of me- thane as alkane.
  • the same catalytic cycle is assumed to apply to other alkanes.
  • the peroxoacid according to the invention can be described by the formula R-O-O-H. Without the intention of being bound by theory, it is assumed that the peroxoacid acts by activating sulfur trioxide towards the reaction with an alkane.
  • the peroxoacid reacts with sulfur trioxide upon which an activated form of sulfur trioxide is formed:
  • said activated form is able to react with methane in order to form methanesul- fonic acid upon which the peroxoacid is regenerated:
  • the peroxoacid comprises at least one organic peroxoacid of sulfur, phosphorus, silicon, boron, nitrogen or carbon. Any suitable peroxoacid of said elements can be used.
  • the peroxoacids are typically derived from the corresponding oxoacid of the respective element.
  • the peroxoacid group is selected from the group consisting of -SO2-O-O-X, -CO-O-O-X, -P0(0H)-0-0-X, PS(0H)-0-0-X, wherein X is H,
  • the organic peroxoacid comprises at least one additional functional group.
  • the additional functional group may particularly be selected from the group consisting of carbon double bonds, carbon triple bonds, aryl groups, heteroaryl groups and functional groups comprising heteroatoms, especially functional groups comprising O, S, N, P, Si, B, Se, Te, F, Cl, Br, I, Mg or Li atoms.
  • aryl groups such as F, Cl, Br, I, and siloxane groups.
  • the functional groups, particularly aryl groups may be further derivatized and may contain fur- ther functional groups.
  • Examples of functional groups according to the invention comprise par- ticularly phenyl groups, carbonyl groups, ether groups, thioether groups, thioketone groups and halide groups.
  • Suitable organic peroxoacids according to the invention are peroxybenzoic acid and trifluoroperacetic acid. Any of the aforementioned examples may be derivatized and/or sub- stituted with side chains, particularly with alkyl groups, aryl groups or halogen atoms.
  • the organic peroxoacid is part of or bound to an organic or inorganic polymer.
  • Any suitable polymer may be chosen.
  • the polymer backbone may constitute the addi- tional functional group, particularly in cases where the polymer backbone comprises heteroa- toms.
  • Particularly preferred polymers comprise polysiloxanes, polyolefins, vinyl polymers, poly- ether, polyester, polyamides and polyurethanes.
  • the peroxoacid group may be bound to the polymeric backbone or may be contained in a polymeric side chain.
  • Particularly preferred are polymers comprising -SO 2 -OOH groups.
  • the polymer may have any suitable structure. Particularly, homopolymers, copolymers, block copolymers, graft copolymers or comb copolymers may be employed.
  • the polymers may have a dendrimer structure.
  • the organic peroxoacid used as a catalyst according to the invention may be obtainable by a reaction of the corresponding oxoacid with a peroxide. More preferably, the peroxoacid may be obtainable by a reaction of the corresponding oxoacid with hydrogen peroxide or a salt thereof. Without the intention of being bound by theory, the reaction of an oxoacid with hydrogen perox- ide can for example be described by
  • the object of the invention is therefore solved by the use of a mix- ture comprising a peroxide and an organic oxoacid or a derivative thereof, wherein the oxoacid comprises at least one additional functional group, as catalyst in the preparation of alkanesul- fonic acids from alkanes and sulfur trioxide, especially in the preparation of methanesulfonic acid from methane and sulfur trioxide.
  • the mixture may comprise a solvent.
  • hydrogen peroxide or a salt thereof is employed as peroxide compound. Suitable salts of hydrogen peroxide particularly comprise alkaline metal peroxides or alkaline-earth metal perox- ides, such as sodium peroxide (Na 2 0 2 ).
  • the oxoacid used in the mixture according to the invention must be suitable to yield a stable peroxoacid upon the reaction with a peroxide.
  • the catalyst corn- pound is produced in situ in the reaction mixture.
  • the additional functional group may preferably be selected from the group consisting of carbon double bonds, carbon triple bonds, aryl groups, heteroaryl groups and functional groups corn- prising heteroatoms, especially functional groups comprising O, S, N, P, Si, B, Se, Te, F, Cl, Br, I, Mg or Li atoms. Particularly preferred are aryl groups, halogen atoms, such as F, Cl, Br, I, and siloxane groups.
  • the functional groups, particularly aryl groups may be further derivatized and may contain fur- ther functional groups. Examples of functional groups according to the invention comprise par- ticularly phenyl groups, carbonyl groups, ether groups, thioether groups, thioketone groups and halide groups.
  • the organic oxoacid is part of or bound to an organic or inorganic polymer.
  • Any suitable polymer may be chosen.
  • the polymer backbone may constitute the addi- tional functional group, particularly in cases where the polymer backbone comprises heteroa- toms.
  • Particularly preferred polymers comprise polysiloxanes, polyolefins, vinyl polymers, poly- ether, polyester, polyamides and polyurethanes.
  • the peroxoacid group may be bound to the polymeric backbone or may be contained in a polymeric side chain.
  • Particularly preferred are polymers comprising -SO2-OH groups.
  • the polymer may have any suitable structure. Particularly, homopolymers, copolymers, block copolymers, graft copolymers or comb copolymers may be employed.
  • the polymers may have a dendrimer structure.
  • the organic oxoacid is an oxoacid of sulfur, phosphorus, silicon, boron, nitrogen or carbon or a derivative thereof, especially an acid halide.
  • the object of the invention is solved by a process for the prepara- tion of alkanesulfonic acids from alkanes and sulfur trioxide comprising the steps of i) providing sulfur trioxide;
  • reaction product for example, by distillation or extraction.
  • step iv) an or- ganic peroxoacid, comprising at least one additional functional group, is added as catalyst.
  • Said peroxoacid corresponds to the abovementioned organic peroxoacids with additional functional groups, which may be used as catalysts.
  • Sulfur trioxide may be provided in the form of oleum, i.e., a solution of sulfur trioxide in sulfuric acid. Instead of oleum also pure sulfur trioxide can be employed. This avoids the preparation of sulfur trioxide solutions. The reaction conditions are here without added solvents. Further, non- reacted sulfur trioxide can evaporate, avoiding the necessity of quenching it. In a further embodiment, sulfur trioxide is used in a form of oleum with a trioxide content of 50 % (w/w) or less, or 65 % (w/w) or more.
  • the temperature during the reaction is preferably within a range from above 0 °C to 70 °C, es- pecially from 10 °C to 65 °C, preferably from 20 °C to 60 °C. Surprisingly the formation of side products was lower at lower temperatures. If the temperature is around 0 °C or 10 °C, the reac- tion takes place but needs a longer time so that for an economically process the temperature is preferably 20 °C or above, especially about 40 °C to 55 °C.
  • the pressure is set to be within a range from 1 to 200 bar, preferably from 50 to 150 bar, espe- cially from 80 to 120 bar.
  • the use of pure sulfur trioxide is preferred in the process for manufacturing alkane sulfonic acids according to the present invention.
  • a circulation of solvent is not necessary, alkanes comprising higher amounts of impurities compared to the prior art can be used.
  • Impurities usually are enriched in the solvent leading to a reduced yield of alkane sulfonic acids.
  • solvents and thus a circulation of them impurities originating from the al- kanes are not negatively influencing the production of alkane sulfonic acids when pure sulfur trioxide is employed.
  • Sulfur trioxide especially pure sulfur trioxide is reacted with an alkane in a reactor.
  • alkanes with a low boiling point the use of a high-pressure reactor is necessary.
  • pentane and higher alkanes a common laboratory reactor is sufficient.
  • gaseous alkanes for example, methane
  • a pressure of 1 to 200 bar gas pressure is set.
  • the peroxoacid catalyst according to the present invention is added.
  • the catalyst may be provided in pure form or solved in a suitable solvent.
  • the initial molar ratio between the catalyst and SO 3 is in the range of 1 :50 to 1 : 10000, more preferably 1 :100 to 1 :500, particularly 1 :150.
  • the catalyst may be provided in a solvent, particularly in sulfuric acid.
  • the reaction mixture contains essentially of the respective al- kane sulfonic acid, especially methane sulfonic acid, as well as sulfuric acid.
  • This mixture of alkane sulfonic acid, especially methane sulfonic acid (MSA), and H2SO4 might afterwards be used as the respective mixture.
  • MSA methane sulfonic acid
  • H2SO4 hydrogen-sulfonic acid
  • the combination of an alkane sulfonic acid, especially methane sulfonic acid, and sulfuric acid provides a strong acid in which even gold might be dissolved enabling different fields of technical applicability.
  • the alkane sulfonic acid especially MSA
  • the method of the invention comprises the optional step of the purifying the reaction product, which might be done by distillation or extraction.
  • alkane sulfonic acids, and specially methane sulfonic acids might be used in different technical fields, i.e. as cleaning agent (cleaning comprising the area of cleaning and caring, home care as well as industrial and institutional cleaning of hard and soft surfaces, i.e.
  • MSA might also be used in galvanization process of plastics, the broad area of batteries, such as lead battery recy- cling and recycling in general, such as metal recycling, as well as borane generation are further possible areas of application.
  • the object of the invention is solved by a process for the prepara- tion of alkane sulfonic acids from alkanes and sulfur trioxide comprising the steps of i) providing sulfur trioxide;
  • reaction product for example, by distillation or extraction.
  • the process according to this embodiment of the invention differs from the aforementioned em- bodiment of the inventive process in that the catalyst is employed by introducing an oxoacid with an additional functional group and a peroxide rather than an organic peroxoacid.
  • the peroxoacid is thus formed in situ in the autoclave or laboratory reactor in which the reaction of sulfur trioxide and the alkane takes place.
  • any suitable oxoacid which can be used in a catalyst mixture in the preparation of alkane sul- fonic acids as defined above can be employed. Accordingly, the oxoacid needs to be capable of forming a stable peroxoacid.
  • hydrogen peroxide or a salt thereof such as sodium peroxide (Na 2 0 2 )
  • sodium peroxide Na 2 0 2
  • Any peroxide as described above may be used.
  • Both the oxoacid and the peroxide are added to the reactor. They can be added in a mixture, optionally with a solvent. Suitable solvents comprise sulfuric acid or a liquid alkane sulfonic acid, e.g. methane sulfonic acid.
  • the oxoacid and the peroxide may also be added separately but simultaneously. If both compounds are added separately, each may optionally be solved in a solvent, for example sulfuric acid. In yet another alternative, both compounds may be added sequentially, wherein each compound may be added as the first or the second compound.
  • the oxoacid and the peroxide are added in a molar ratio of 1 :5 to 5:1 , more prefera- bly in a molar ratio of 1 :2 to 2:1 , most preferably in a molar ratio of 1 :1.
  • the initial molar ratio between the oxoacid and the SO3 is preferably in the range of 1 :50 to 1 :10000, more preferably in the range of 1 :100 to 1 :500.
  • the object of the invention is solved by a mixture comprising an alkane, sulfur trioxide, an organic peroxoacid, comprising at least one additional functional group, and optionally a solvent.
  • the inventive mixture is capable of producing an alkane sulfonic acid. Particularly, if the mixture is set at a pressure of 1 to 100 bar and held at a temperature of 0 to 100 °C, an alkane sulfonic can be produced in an efficient way.
  • the organic peroxoacid acts as a catalyst.
  • the alkane is methane.
  • Such a preferred mixture is capable of form- ing methane sulfonic acid.
  • the object of the invention is solved by a mixture comprising an alkane, sulfur trioxide, an organic oxoacid, comprising at least one additional functional group, a peroxide, especially hydrogen peroxide or a salt thereof, and optionally a solvent, wherein the oxoacid is capable of forming an organic peroxoacid as defined above.
  • the inventive mixture is capable of producing an alkane sulfonic acid. Particularly, if the mixture is set at a pressure of 1 to 100 bar and held at a temperature of 0 to 100 °C, an alkane sulfonic can be produced in an efficient way.
  • the organic oxoacid and the peroxide react to in situ form an organic stable peroxoacid, which is capable of acting as catalyst.
  • the alkane is methane.
  • Such a preferred mixture is capable of form- ing methane sulfonic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne de nouvelles utilisations d'acides peroxoacides organiques comprenant des groupes fonctionnels en tant que catalyseurs dans la préparation d'acides alcanesulfoniques à partir d'alcanes et de trioxyde de soufre, des procédés de production d'acides alcanesulfoniques utilisant lesdits catalyseurs ainsi que des mélanges réactionnels comprenant lesdits catalyseurs. L'invention concerne en particulier la production d'acide méthane sulfonique à partir de méthane et de trioxyde de soufre utilisant des peroxoacides organiques comprenant des groupes fonctionnels en tant que catalyseurs.
PCT/EP2019/075036 2018-09-25 2019-09-18 Catalyseur pour la synthèse d'acides alcanesulfoniques WO2020064466A1 (fr)

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EP18196493 2018-09-25
EP18196493.3 2018-09-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022122556A1 (fr) * 2020-12-10 2022-06-16 Basf Se Procédé de décomposition contrôlée de composés peroxo
US11479522B2 (en) 2019-03-21 2022-10-25 Basf Se Method for the purification of alkanes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2493038A (en) 1946-05-31 1950-01-03 Houdry Process Corp Reaction of methane with sulfur trioxide
US20050070614A1 (en) 2003-06-21 2005-03-31 Richards Alan K. Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds
WO2007136425A2 (fr) 2006-05-19 2007-11-29 Richards, Alan, K. Élaboration de diméthyl éther ou d'oléfines à partir de méthane, en utilisant du di(méthyl-sulfonyl) peroxyde comme amorceur radicalaire
WO2015071455A1 (fr) 2013-11-18 2015-05-21 Grillo-Werke Ag Nouvel initiateur pour la préparation d'acides alcanesulfoniques à partir d'alcanes et d'oléum
WO2015071365A1 (fr) 2013-11-13 2015-05-21 Grillo Chemie Gmbh Procédé de préparation d'acides alcane-sulfoniques à partir de trioxyde de soufre et d'un alcane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2493038A (en) 1946-05-31 1950-01-03 Houdry Process Corp Reaction of methane with sulfur trioxide
US20050070614A1 (en) 2003-06-21 2005-03-31 Richards Alan K. Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds
WO2007136425A2 (fr) 2006-05-19 2007-11-29 Richards, Alan, K. Élaboration de diméthyl éther ou d'oléfines à partir de méthane, en utilisant du di(méthyl-sulfonyl) peroxyde comme amorceur radicalaire
WO2015071365A1 (fr) 2013-11-13 2015-05-21 Grillo Chemie Gmbh Procédé de préparation d'acides alcane-sulfoniques à partir de trioxyde de soufre et d'un alcane
WO2015071455A1 (fr) 2013-11-18 2015-05-21 Grillo-Werke Ag Nouvel initiateur pour la préparation d'acides alcanesulfoniques à partir d'alcanes et d'oléum

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11479522B2 (en) 2019-03-21 2022-10-25 Basf Se Method for the purification of alkanes
WO2022122556A1 (fr) * 2020-12-10 2022-06-16 Basf Se Procédé de décomposition contrôlée de composés peroxo

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