EP4151774A1 - Verfahren zur herstellung von methansulfonsäure - Google Patents

Verfahren zur herstellung von methansulfonsäure Download PDF

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Publication number
EP4151774A1
EP4151774A1 EP21198115.4A EP21198115A EP4151774A1 EP 4151774 A1 EP4151774 A1 EP 4151774A1 EP 21198115 A EP21198115 A EP 21198115A EP 4151774 A1 EP4151774 A1 EP 4151774A1
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EP
European Patent Office
Prior art keywords
msa
methane
reaction
mbs
current density
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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Application number
EP21198115.4A
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English (en)
French (fr)
Inventor
Ferdi Schueth
Joel BRITSCHGI
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Studiengesellschaft Kohle gGmbH
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Studiengesellschaft Kohle gGmbH
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Priority to EP21198115.4A priority Critical patent/EP4151774A1/de
Publication of EP4151774A1 publication Critical patent/EP4151774A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/29—Coupling reactions

Definitions

  • the present invention relates to a process for the production of methane sulfonic acid from methane and sulfur trioxide in oleum.
  • MSA Due to its unique properties, MSA is already used in some processes and demand is expected to increase further in the near future.
  • the numerous advantages of MSA are: strongly acidic without being oxidizing, low vapor pressure and odorless, low toxicological risk, high solubility of its salts, high chemical stability and additionally it is biodegradable. All these characteristics make MSA attractive for use in e.g. the electronics industry for electroplating, for cleaning processes, for metal recycling, or in ionic liquids for a number of other processes.
  • methane derivatives are used and then converted in multi-step redox reactions. This is not only unfavorable due to the number of reaction steps but also because side products are generated.
  • a more attractive pathway is the direct sulfonation of methane, which is known for more than twenty years.
  • the sulfonation usually takes place in oleum and is initiated by a metal peroxo- or peroxosulfate species.
  • Methane sulfonic acid in contrast to methyl bisulfate (MBS), is considered a high value-added product and a green acid (for example, non-oxidant, low vapor pressure, bio-degradable, and so on) with uses in the pharma, electronic and cleaning industry.
  • Basickes et al. ( Basickes, Hogan, Sen, J. Am . Chem. Soc. 1996, 11, 13111- 13112 ) describe the radical-initiated functionalization of methane and ethane in fuming sulfuric acid. Temperatures of 90°C and above are necessary and the yield of MSA is low.
  • Mukhopadhyay and Bell report the direct sulfonation of methane at low pressure to methanesulfonic acid in the presence of potassium peroxydisphosphate as the initiator.
  • a temperature of 95°C is chosen and the conversion rate of SO 3 is below 30%.
  • WO 2004/041399 A2 and US 7,119,226 B2 both suggest a radical pathway and chain reaction for the production of methane sulfonic acid.
  • radical chain reactions usually result in undesirable side products, which even manifest themselves as disturbing inhibitors in the production of alkane sulfonic acids, which may lead to termination of the actual reaction for preparing the alkane sulfonic acid and further to impurities, formation of side products and poor yields based on sulfur trioxide and methane.
  • WO 2018/146153 describes a method for the production of alkane sulfonic acids, especially methane sulfonic acid, from alkane, especially methane, in which a carbocation is assumingly formed as intermediate.
  • alkane sulfonic acids especially methane sulfonic acid
  • the problem is solved by an electrochemical process for the production of methane sulfonic acid (MSA) from methane and sulfur trioxide, wherein methane and fuming sulfuric acid are electrolyzed with at least one electrode as anode, preferably at least one BDD electrode or a resistant electrode made from another anode material such as FTO or Pt/lr, ITO, ATO, lead, stainless steel, gold, and alloys thereof, in a pressurized reactor under a methane pressure in the range of at least 30 bar and at most 200 bar in a temperature range of 50°C to 120°C, preferably for a reaction time range which is adjusted depending on the current density and is preferably more than 2 hours, and the MSA is separated from obtained reaction mixture, for instance by distillation or other suitable separation methods such as column chromatography, fractional freezing, ion chromatography, membrane separation.
  • MSA methane sulfonic acid
  • the current density at the anode is usually kept between 0.5 mA/cm 2 to 20 mA/cm 2 during current flow and can be varied in the progress of the reaction or even paused for a determined amount of time during the reaction so that times of current flow and current-less times may be changed in intervalls.
  • the pressure in the pressurized reactor is preferably kept in the range of 50 to 120 bar.
  • the reaction can be carried out at temperatures, where unselective and uncontrolled radical chain reactions do not take place as observed in the prior art where high temperatures are required.
  • the inventive process can, for example, efficiently be carried out already at about 50°C or slightly higher.
  • substances promoting the decomposition of any initiators to radicals or stabilizing said radicals, as used in the prior art is not required in the inventive process as such initiators are not used in the inventive process.
  • no such substances are added in the invention.
  • Such substances include metal salts ⁇ e.g., Pt, Hg, Rh). They show detrimental side effects of triggering side reactions, which can be avoided by the present invention.
  • the temperature in the pressurized reactor is preferably kept in a temperature range of 50°C to 100°C, and the reaction time in the pressurized reactor is usually kept between 3 and 24 hours, depending on the strength of the current density.
  • the reaction mixture in the pressurized reaction vessel is preferably agitated, advantageously with a high-speed stirrer in order to safeguard an intimate contact between the anode, the fuming sulfuric acid and the methane.
  • the stirring speed should be in the range of 600 rpm to 1800 rpm.
  • any electrode fulfilling these properties such as FTO or Pt/lr, ITO, ATO, lead, stainless steel, gold, and alloys thereof, depending on the actual conditions might also be used
  • the electrolyte is fuming sulfuric acid having a concentration of 20 to 30 wt.%. SO 3 .
  • concentrations of concentrated sulfuric acid with SO 3 in a concentration up to 45 wt.%, or even higher up to 60 wt.% are also possible.
  • MSA concentration increases over time at all the current densities applied in shorter reaction times up to three hours. At reaction times longer than 3 hours, however, the current density will influence the yield significantly. At higher current density, the product as well as intermediate species can be decomposed faster which will lead to a decreased concentration compared to lower current densities. As the current density can also be adapted over the time this is actually an advantage as it gives room to find and tune an optimum setting between reaction kinetics and product or intermediate stability.
  • the reaction can also take place if electrolysis and pressurization of the reactor are done in separate steps. After one hour of electrolysis of Oleum the reactor can be pressurized with methane immediately or after stirring without current for a time between 0 and 60 min in between. With increasing pause-time as intermediate stirring the concentration of MSA decreases. This shows that an active species is formed during electrolysis which decomposes slowly.
  • the reactor was heated to 70 °C under stirring at 1200 rpm where a pressure of 90 bar was reached, then a current density of 3.125 mA/cm 2 was kept for 18000 seconds. Afterwards the autoclave was placed in an ice bath and cooled down to 25 °C before the pressure was released. The liquid sample was then analyzed by 1 H-NMR using sodium methyl sulfate as an internal standard for quantification. The concentration of MSA was 1.5 M, which is a yield of 24% based on SO 3 . Per every electron passed, 4.7 molecules of MSA were generated. The concentration of by-product methyl bisulfate was 1.4 mM, resulting in a selectivity towards MSA of 99.9%.
  • the reactor was heated to 70 °C under stirring at 1200 rpm where a pressure of 90 bar was reached, then a current density of 1.25 mA/cm 2 was kept for 16 hours. Afterwards the autoclave was placed in an ice bath and cooled down to 25 °C before the pressure was released. The liquid sample was then analyzed by 1 H-NMR using sodium methyl sulfate as an internal standard for quantification. The concentration of MSA was 1.9 M, which is a yield of 32% based on SO 3 . Per every electron passed, 4.9 molecules of MSA were generated. The concentration of by-product methyl bisulfate was 55 mM, resulting in a selectivity towards MSA of more than 97%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP21198115.4A 2021-09-21 2021-09-21 Verfahren zur herstellung von methansulfonsäure Withdrawn EP4151774A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP21198115.4A EP4151774A1 (de) 2021-09-21 2021-09-21 Verfahren zur herstellung von methansulfonsäure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP21198115.4A EP4151774A1 (de) 2021-09-21 2021-09-21 Verfahren zur herstellung von methansulfonsäure

Publications (1)

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EP4151774A1 true EP4151774A1 (de) 2023-03-22

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EP21198115.4A Withdrawn EP4151774A1 (de) 2021-09-21 2021-09-21 Verfahren zur herstellung von methansulfonsäure

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Citations (8)

* 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
WO2004041399A2 (en) 2002-11-05 2004-05-21 Richards Alan K Anhydrous conversion of methane and other light alkanes into methanol and other derivatives, using radical pathways and chain reactions with minimal waste products
US20050070614A1 (en) 2003-06-21 2005-03-31 Richards Alan K. Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds
US7119226B2 (en) 2004-04-20 2006-10-10 The Penn State Research Foundation Process for the conversion of methane
US10047020B2 (en) 2013-11-27 2018-08-14 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
WO2018146153A1 (en) 2017-02-07 2018-08-16 Grillo-Werke Ag Method for the production of alkane sulfonic acids
US20190186026A1 (en) * 2016-08-11 2019-06-20 Massachusetts Institute Of Technology Electrochemical oxidation of aliphatic and aromatic compounds
WO2019212835A2 (en) * 2018-03-10 2019-11-07 Richards Alan K Compounds, processes, and machinery for converting methane gas into methane-sulfonic acid

Patent Citations (8)

* 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
WO2004041399A2 (en) 2002-11-05 2004-05-21 Richards Alan K Anhydrous conversion of methane and other light alkanes into methanol and other derivatives, using radical pathways and chain reactions with minimal waste products
US20050070614A1 (en) 2003-06-21 2005-03-31 Richards Alan K. Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds
US7119226B2 (en) 2004-04-20 2006-10-10 The Penn State Research Foundation Process for the conversion of methane
US10047020B2 (en) 2013-11-27 2018-08-14 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
US20190186026A1 (en) * 2016-08-11 2019-06-20 Massachusetts Institute Of Technology Electrochemical oxidation of aliphatic and aromatic compounds
WO2018146153A1 (en) 2017-02-07 2018-08-16 Grillo-Werke Ag Method for the production of alkane sulfonic acids
WO2019212835A2 (en) * 2018-03-10 2019-11-07 Richards Alan K Compounds, processes, and machinery for converting methane gas into methane-sulfonic acid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BASICKESHOGANSEN, J. AM . CHEM. SOC., vol. 11, 1996, pages 13111 - 13112
LOBREEBELL, IND. ENG. CHEM . RES., vol. 40, 2001, pages 736 - 742
MUKHOPADHYAYBELL, ORGANIC PROCESS RESEARCH & DEVELOPMENT, vol. 7, 2003, pages 161 - 163

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