Electrocatalytic conversion of sulfuryl fluoride into useful chemicals

Abstract

The present disclosure provides an electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals in the presence of one or both of CH4 and CO2, which includes an electrocatalytic reactor (101), wherein the electrocatalytic reactor (101) is equipped with asymmetric electrodes, wherein the cathode is a Copper-Manganese (Cu-Mn) alloy, and the anode is metallic Copper (Cu), wherein these electrodes act as electrocatalyst, and acidified deionised water (H3O +) acts as electrolyte, and a catalyst initiator mixture is included in the acidified deionised water (H3O +) The electrocatalytic conversion occurs under an applied DC power of 25W (i.e., 5V and 5A), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form Ethene sulphonyl Fluoride (ESF), or in the presence of a chloride medium to Ethene sulphonyl chloride (ESC).

Description

[0001] TITLE

[0002] ELECTROCATALYTIC CONVERSION OF SULFURYL FLUORIDE INTO USEFUL CHEMICALS

[0003] CROSS REFERENCE TO RELATED APPLICATIONS

[0004] The present application is based upon and claims priority to India Complete patent application number 202441032990 filed on April 22, 2025, which in turn claims priority to India Provisional patent application number 202441032990 filed on April 25, 2024, the entire contents of which are herein incorporated by reference.

[0005] FIELD

[0006] The present disclosure relates to electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals, more particularly relates to an electrocatalytic reaction system for conversion of sulfuryl fluoride containing gases into useful chemicals.

[0007] BACKGROUND

[0008] Since methyl bromide is a strong ozone-depleting substance (ODS), it is largely replaced by Sulfuryl Fluoride (SO2F2) under the Montreal Protocol on Substances that Deplete the Ozone Layer and its subsequent amendments [United Nations Environment Programme, 2006].

[0009] Sulfuryl fluoride (SO2F2) is a man-made pesticide & insecticide that is also a powerful Green House Gas (GHG). SO2F2 accumulates in the atmosphere and contribute heavily to global warming. This behaviour of SO2F2 as GHG is attributed to its prolonged atmospheric lifetime. Several thousands of ppm of SO2F2 were applied over a day for fumigation purposes especially for pest control in various applications. As the exposure limit or threshold of SO2F2 is in the range of 5-10 ppm and being acutely toxic, reduction in SO2F2 levels to < 1 ppm becomes mandatorily necessary. All the excess SO2F2 goes to the environment and causes air pollution and health hazard to the living beings breathing it. The other sources of SO2F2 comes from the postharvest fumigation of dried fruits, tree nuts, grains, and flours [Environmental Protection Agency, 2004, 2005]. SO2F2 is also released in stack air (TRI Explorer, 2006, Environmental Protection Agency, http: / / www.epa.gov / triexplorer) as a byproduct from several manufacturing processes (M. Krieger, Dow AgroSciences, personal communication, 2008).

[0010] Again, semiconductor industries use SO2F2 as plasma cleaning gas resulted in emissions to the atmosphere [Hobbs and Hart, 2005]. SO2F2 is also used as a blanketing gas in the magnesium industry to replace sulfur hexafluoride (SFe) as SFe is an exceptionally larger global warming gas. SFe during electrical discharges in transformers also release trace amounts of SO2F2 [KoTeTi et al., 1997; Pradayrol et al., 1997],

[0011] It is also reported in several literature that more than 88% of SO2F2 emitted to the atmosphere (> 1.62 Gg per year), results from fumigant usage, and the atmospheric lifetime of SO2F2 is approximately 4.5 years. Even though the environmental hazard by SO2F2 is known, its environmental fate is not yet fully understood.

[0012] USA alone contributes significantly to the SO2F2 emissions, however, complete information on how SO2F2 emissions are distributed across the USA and the globe is not available. National Oceanic and Atmospheric Administration’s (NOAA) Global Greenhouse Gas Reference Network (GGGRN) and a geostatistical inverse model provides concrete evidence of California contributing heavily to SO2F2 emissions globally. California alone emits 60-85% of SO2F2 emissions approximately 0.26 (± 0.10) Gg per year. Globally, California contributes to 5.5- 12% of global SO2F2 emissions. In situ observations from the Advanced Global Atmospheric Gases Experiment (AGAGE) show a global increase of SO2F2 mole fraction from 0.3 ± 0.02 to 2.5 ± 0.08 ppt from 1978 to 2019, and a global increase in SO2F2 emissions from 0.5 ± 0.4 Gg yr1to 2.9 ± 0.4 Gg yr1from 1978 to 2019. SO2F2 degrades via photolysis and reaction with nascent oxygen in the stratosphere via UV absorption. The lifetime of SO2F2 in the four stratospheric boxes is very long (comparable with N2O) of the order of 700 years of photolysis and more than 4700 years of ozone reaction leading to slow and steady destruction of the stratosphere. The rate of degradation of SO2F2 in the troposphere is by reaction with OH or NO3 radicals or O3 and is very slow.

[0013] IN202341066700 (Granted Patent No. 558979) discloses an electrocatalytic reactor for conversion of Green House Gas (GHG) emissions into value-added products.

[0014] IN202443036111 (Granted Patent No. 561581) discloses an electrocatalytic reactor for conversion of Green House Gas (GHG) emissions that include CO2, CH4 and N2 into p-Xylene and other value-added products.

[0015] IN202443047237 discloses an electrocatalytic reactor with the arrangement of the reactor assembly line, and process steps in a process plant for electrocatalytic reduction of green-house gas (GHG) emissions into value-added products.

[0016] DE3145012C2 discloses a method for removing sulfuryl fluoride from exhaust gases by reacting the exhaust gas with alkali hydroxides and / or carbonates, in which the reaction is carried out in dilute aqueous alkali hydroxide and / or carbonate solution on an activated carbon contact.

[0017] EP4422777A1 discloses a method for scrubbing sulfuryl fluoride accomplished by placing a fluid comprising sulfuryl fluoride in contact with an aqueous solution of a base and a peroxide having at least one -O-OH group.

[0018] DE4441796A1 discloses a method of deriving a toxic gas-air mixture containing sulfuryl fluoride (SO2F2) as an active ingredient from a treatment room in which the SO2F2 was effective for pest control for a period of exposure, wherein the toxic gas-air mixture containing SO2F2 is diverted from the treatment area into an apparatus containing cone, alkali. The SO2F2 reacts with the alkali and the products are retained in the apparatus.

[0019] US7261868B2 discloses method for the decomposition of fluorine compounds comprising a step of contacting said fluorine compounds, in the presence of water vapor, oxygen and an inert gas as a dilutant gas, with a fluorine compounds decomposition catalyst, wherein the catalyst for decomposition of SO2F2 contains at least one selected from Pd, Pt, Cu, Mn, Fe, Co, Rh, Ir and Au in the form of a metal or an oxide.

[0020] The present inventors have identified a solution for the above-mentioned problems by converting SO2F2 in the presence of other GHG emission gases such as CO2, CH4 into ethene sulphonyl chloride / Fluoride through electrocatalytic reaction process. The process involves asymmetric C-C coupling leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CH2=CH-SO2F (Ethene sulphonyl Fluoride, ESF). ESF is otherwise called as “Molecular Plugins”, the Micheal reactivity of ESF is utilized extensively in synthesis of dyes, Photoresists, ion-exchange resins, lubrication oil, pharmaceuticals etc.

[0021] SUMMARY

[0022] The present disclosure provides an electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals in the presence of one or both of CPE and CO2, wherein the electrocatalytic reaction system (100) includes an electrocatalytic reactor (101), wherein the electrocatalytic reactor (101) is equipped with asymmetric electrodes (cathode and anode), wherein the cathode is a Copper-Manganese (Cu-Mn) alloy, and the anode is metallic Copper (Cu), wherein these electrodes act as electrocatalyst, and acidified deionised water (H3O+) acts as electrolyte, wherein a catalyst initiator mixture is included in the acidified deionised water (H3O+). The electrocatalytic conversion occurs under an applied power of 25W (i.e., 5V and 5A), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CPE=CH-SO2F (Ethene sulphonyl Fluoride, ESF), or in the presence of a chloride medium to CH2=CH-SO2CI (Ethene sulphonyl chloride, ESC). A method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals is also provided. In an aspect, the Cu-Mn alloy cathode includes less than or equal to 2.5% by weight of Mn.

[0023] The catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K).

[0024] In an aspect, the gas mixture purged from the gas tank (102) is green-house-gas (GHG) that includes SO2F2, and one or both of CO2 and CH4, and optionally other gases.

[0025] When the gas mixture includes SO2F2, CO2, and CH4, the ratio of SO2F2, CO2, and CH4 is 1:1:1; when the gas mixture includes SO2F2 and CO2, the ratio of SO2F2 and CO2, is 1:2; and when the gas mixture includes SO2F2 and CH4, the ratio of SO2F2 and CH4, is 1:2.

[0026] A concentrated acid is used in the acidified deionised water, wherein the concentrated acid is selected from HC1, H2SO4, HNO3, H3PO4.

[0027] In an aspect, the different fractions of the product formed are condensed from an evaporator tank (109), and separated based on their boiling points.

[0028] BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0029] Fig. 1 is an illustration of the Electrocatalytic reaction system of the present disclosure.

[0030] Fig. 2 illustrates UV-VIS spectroscopy of the gaseous product sample.

[0031] Fig. 3 illustrates the Fourier Transform Infrared Spectroscopy (FTIR) analysis of the gaseous product sample.

[0032] Fig. 4 illustrates Gas Chromatography-Mass Spectrometry analysis of the gaseous product sample.

[0033] Fig. 5 illustrates Mass spectrometry analysis of the gaseous product sample for the GC peak at 12.69 mins. LIST OF REFERENCE NUMERALS USED IN SPECIFICATION AND DRAWINGS

[0034] 100 - Electrocatalytic reaction system

[0035] 101 - Electrocatalytic reactor

[0036] 102 - Gas tank

[0037] 103 - Acid tank

[0038] 104 - Water dispenser

[0039] 105 - Catalyst initiator tank

[0040] 106 - Catalyst initiator dissolution tank

[0041] 107 - Reacted liquid Collection tank

[0042] 108 - Filtration unit

[0043] 109 - Evaporator tank

[0044] 110 - Three-stage Condenser

[0045] 111 - ESF / ESC collection tank

[0046] 112 - ESF / ESC storage tank

[0047] 113 - Moisture trapping unit

[0048] 114 - Unreacted Ethylene Storage tank

[0049] DETAILED DESCRIPTION

[0050] The subject matter of the present disclosure is described in detail with reference to the accompanying drawings. Unless otherwise specified, all the technical and scientific terms used herein have the same meaning as is generally understood by a person skilled in the art pertaining to the present disclosure. Headings are used solely for organizational purposes, and are not intended to limit the disclosure in any way.

[0051] The use of the singular includes the plural unless specifically stated otherwise. As used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well. The use of “or” means “and / or” unless stated otherwise. Unless otherwise indicated, all numbers used herein to express quantities, dimensions, and so forth used should be understood as being modified in all instances by the term "about." It is to be understood that wherein a numerical range is recited, it includes all values within that range, and all narrower ranges within that range, whether specifically recited or not. As used herein, "including," "containing" and like terms are understood to be synonymous with "comprising" and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, phases or method steps.

[0052] In addition, it should be appreciated that any figures provided herewith are for explanation purposes to persons ordinarily skilled in the art and that the drawings of them are not necessarily drawn to scale.

[0053] Any method / process steps and / or operations and / or instructions used in this disclosure, are for illustrative purposes in a particular order and / or grouping. Other orders and / or grouping of the process steps or its portions and / or operations or its portions and / or instructions or its portions are possible and, one or more of the process steps and / or operations and / or instructions can be combined and / or deleted.

[0054] The present disclosure provides an electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals in the presence of one or both of CH4 and CO2, wherein the electrocatalytic reaction system (100) includes an electrocatalytic reactor (101), wherein the electrocatalytic reactor (101) is equipped with asymmetric electrodes (cathode and anode), wherein the cathode is a Copper-Manganese (Cu-Mn) alloy, and the anode is metallic Copper (Cu), wherein these electrodes act as electrocatalyst, and acidified deionised water (H3O+) acts as electrolyte, wherein a catalyst initiator mixture is included in the acidified deionised water (H3O+). The electrocatalytic conversion occurs under an applied power of 25W (i.e., 5V and 5A), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CH2=CH-SO2F (Ethene sulphonyl Fluoride, ESF), or in the presence of a chloride medium to CH2=CH-SO2CI (Ethene sulphonyl chloride, ESC).

[0055] A concentrated acid is used in the acidified deionised water, wherein the concentrated acid is selected from HC1, H2SO4, HN03, H3PC>4. The catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgC03and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K).

[0056] In an aspect, the catalyst initiator mixture includes a mixture of 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 6.25% by weight each of Na2CO3, NaHCO3, K2CO3, and KHCO3.

[0057] In an aspect, the electrocatalytic reactor of the present disclosure converts sulfuryl fluoride (SO2F2) present in Green-house gas (GHG) emissions into useful chemicals, wherein the GHG emissions also includes CO2 or CH4, or both CO2 or CH4.

[0058] In an aspect, the Cu-Mn alloy cathode includes less than or equal to 2.5% by weight of Mn.

[0059] In an embodiment, a method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals is provided. The method includes the steps of: setting up an electrocatalytic reactor (101) having a reactor vessel equipped with asymmetric electrodes (cathode and anode), wherein the cathode is an alloy of Copper-Manganese (Cu-Mn), and the anode is metallic Copper (Cu); dispensing a measured quantity of deionised water from a water dispenser (104) into the reactor vessel at a rate of 3 to 5 litres per minute (LPM); dispensing a measured quantity of a catalyst initiator mixture from a Catalyst initiator tank (105) to deionised water present in a catalyst initiator dissolution tank (106), wherein the catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCO3and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K), wherein the measured quantity of the initiator mixture is 30 to 35% of the weight of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); agitating the catalyst initiator dissolution tank (106) to form a homogeneous initiator solution; dispensing the initiator solution from the catalyst initiator dissolution tank (106) into the reactor vessel of the electrocatalytic reactor (101); dispensing a measured quantity of concentrated acid from an acid tank (103) into the reactor vessel every hour until the completion of the reaction, wherein the measured quantity of the concentrated acid dispensed every hour is 2 to 4% of the weight of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); purging a measured quantity of gas mixture of sulfuryl fluoride (SO2F2), CO2, and CH4 from a gas tank (102) into the reactor vessel at a rate of 2001bs per hour (IbH), wherein the gas mixture includes SO2F2, and one or both of CO2, and CH4, wherein the measured quantity of the gas mixture dispensed is 4 to 5 times the volume of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); and applying a DC power of 25W (i.e., 5V and 5 A) to the cathode and the anode through an external power source to initiate the electrocatalytic conversion in the electrocatalytic reactor (101) at normal temperature and pressure (NTP), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CH2=CH- SO2F (Ethene sulphonyl Fluoride, ESF), or in the presence of a chloride medium, the ethylene formed from CO2 and CH4 reacts with SO2F2 to form CH2=CH-SO2CI (Ethene sulphonyl chloride, ESC), wherein the completion of the reaction occurs when the reacted liquid in the reactor vessel turns from turbidity to clear solution.

[0060] It is to be noted that, with the teachings of the present disclosure, at least one of CO2 or CH4 is required for adequate amount of ethylene formation. Hence, when the gas mixture includes SO2F2, CO2, and CH4, the ratio of SO2F2, CO2, and CH4 is 1:1:1; when the gas mixture includes SO2F2 and CO2, the ratio of SO2F2 and CO2, is 1:2; and when the gas mixture includes SO2F2 and CH4, the ratio of SO2F2 and CH4, is 1:2. In an aspect, the chloride medium that converts the SO2F2 to CH2=CH-SO2C1 (Ethene sulphonyl chloride, ESC), is HC1.

[0061] In an aspect, the gas mixture purged from the gas tank (102) is Green-House-Gas (GHG) that includes SO2F2, and one or both of CO2 and CH4, and optionally other gases.

[0062] It is to be noted that, the total volume of deionised water, acid, and the catalyst initiator mixture should be such that the reactor vessel is filled up to 75% of its capacity, or as evident to a person skilled in the art to accomplish maximum utilisation of the available electrode surfaces, and without causing any overflow or any short circuit.

[0063] Reaction Mechanism involved in the electrocatalytic synthesis of ESF

[0064] The reaction pathway for the electroreduction of CH4 to ethylene on Cu-Mn alloy cathode surface:

[0065] Overall reaction:

[0066] The pathway of the elementary steps involves the following steps: where M is Cu-Mn alloy, where Mn is less than or equal to 2.5% by weight.

[0067] Methane activation occurs on a vacant electrocatalyst lattice site via the heterolytic cleavage of a C-H bond, having an activation free energy of 0.73 eV with respect to gas phase methane at 1 bar. This results in a CH3-intermediate bound to the Cu site, with the proton having been transferred to a p3-oxygen. The reaction pathway for the electroreduction of CO2 to ethylene on Cu-Mn alloy cathode surface:

[0068] Overall reaction:

[0069] 2CO2(g) + 12H++ 12e- CH2=CH2(g) + 4H2O

[0070] Intermediate reactions:

[0071] CO2(g) + 6H2O(1) + 8e- CH4(g) + 8OH"

[0072] 2CH4C2H6+ 4H++ 2e"

[0073] Further, SO2F2injection into the reaction mixture at atmospheric pressure, results in the formation of Ethene sulphonyl fluoride (ESF) or Ethene sulphonyl chloride (ESC).

[0074] With the presence of chloride medium such as HC1, ESF gets converted to ESC

[0075] The parameters that may influence the reaction rate and its selectivity are:

[0076] - onset potential,

[0077] - current density,

[0078] - over potential,

[0079] - the FE%,

[0080] - Tafel slope,

[0081] - the EE%, and

[0082] - stability of electrocatalyst.

[0083] Fig. 1 is an illustration of the Electrocatalytic reaction system of the present disclosure.

[0084] The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals comprises the following.

[0085] - an electrocatalytic reactor (101); - a gas tank (102);

[0086] - an acid tank (103);

[0087] - a water dispenser (104);

[0088] - a catalyst initiator tank (105);

[0089] - a catalyst initiator dissolution tank (106);

[0090] - a reacted liquid collection tank (107);

[0091] - a filtration unit (108);

[0092] - an evaporator tank (109);

[0093] - a three-stage condenser (110);

[0094] - an ESF / ESC collection tank (111);

[0095] - an ESF / ESC storage tank (112);

[0096] - a moisture trapping unit (113); and

[0097] - an unreacted ethylene storage tank (114), wherein, the electrocatalytic reactor (101) includes a reactor vessel equipped with asymmetric electrodes (cathode and anode), wherein the cathode is an alloy of Copper-Manganese (Cu-Mn), and the anode is metallic Copper (Cu); wherein, the water dispenser (104) dispenses a measured quantity of deionised water into the reactor vessel at a rate of 3 to 5 litres per minute (LPM); wherein, the Catalyst initiator tank (105) dispenses a measured quantity of a catalyst initiator mixture to deionised water present in the catalyst initiator dissolution tank (106), wherein the catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K), wherein the measured quantity of the initiator mixture is 30 to 35% of the weight of deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); wherein, the catalyst initiator dissolution tank (106) is agitated to form a homogeneous initiator solution; wherein, the catalyst initiator dissolution tank (106) dispenses the initiator solution into the reactor vessel of the electrocatalytic reactor (101); wherein, the acid tank (103) dispenses a measured quantity of concentrated acid into the reactor vessel every hour until the completion of the reaction, wherein the measured quantity of the concentrated acid dispensed every hour is 2 to 4% of the weight of deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); wherein the gas tank (102) includes a gas mixture of SO2F2, and one or both of CO2 and CH4, wherein the gas tank dispenses a measured quantity of the gas mixture into the reactor vessel at a rate of 2001bs per hour (IbH), wherein the measured quantity of the gas mixture dispensed is 4 to 5 times the volume of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); wherein, when a power of 25W (i.e., 5V and 5A) is applied to the cathode and the anode through an external DC power source, it initiates the electrocatalytic conversion in the electrocatalytic reactor (101) at normal temperature and pressure (NTP), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CH2=CH-SO2F (Ethene sulphonyl Fluoride, ESF), or in the presence of a chloride medium, the ethylene formed from CO2 and CH4 reacts with SO2F2 to form CH2=CH-SO2CI (Ethene sulphonyl chloride, ESC), wherein the completion of the reaction occurs when the reacted liquid in the reactor vessel changes from turbidity to clear solution. wherein, a measured quantity of the reacted liquid is released from the electrocatalytic reactor (101) into a reacted liquid collection tank (107), which passes through the filtration unit (108) to remove any unreacted solids, the filtrate is transferred to an evaporator tank (109), and then to a three-stage condenser (110), where different fractions are condensed and separated based on their boiling points. Boiling points of ESF and ESC are as below.

[0098] - ESF: boiling point: 119 °C, and

[0099] - ESC (boiling point: 164.2 °C).

[0100] The products ESF / ESC are collected in the ESF / ESC collection tank (111), pressurized at 6-8 bar and finally stored in the ESF / ESC storage tank (112).

[0101] The moisture trapping unit (113) present in the electrocatalytic reaction system (100) separates and collects water (vapour) from the process. The collected water is sent to the water recycling unit (not shown), where it is purified and returned to the water dispenser (104) for reuse, ensuring a closed-loop water system.

[0102] Any ethylene that did not react with the SO2F2 (unreacted ethylene) is collected in the unreacted ethylene storage tank (114).

[0103] In an aspect, the electrocatalytic reaction system (100) is equipped with a Human Machine Interface (HMI) to visually monitoring and regulating various events / parameters that occur in the electrocatalytic reaction system (100). The events / parameters that are monitored and regulated include Pressure Transmitter, Level transmitter, Level sensor, Solenoid operated valves (SOVs), pumps, Temperature, Reaction time, timer settings for the SOVs and the pumps.

[0104] In an aspect, a computer is integrated to the electrocatalytic reaction system (100) that displays the information on the HMI, wherein the monitoring and regulation of various events are accessible on the HMI, wherein the HMI can be a computer display screen. In an aspect, the computer display screen is a touch screen. In an aspect the computer is a hand-held device that includes a touchscreen.

[0105] The HMI empowers a technician to select and switch ON or switch OFF the operation of the liquid line or the gas line. The HMI also allows a technician to set the operation of the electrocatalytic reaction system (100) in Auto-mode, Manual-mode, or Maintenance-mode.

[0106] Examples:

[0107] The present disclosure will now be explained in further detail by the following examples. These examples are illustrative of certain embodiments of the disclosure without limiting the scope of the present disclosure.

[0108] Example 1

[0109] A 5 tonnes per day (TPD) throughput of the GHG emissions to VAPs unit was designed for the electrocatalytic conversion of sulfuryl fluoride to useful chemicals.

[0110] The electrocatalytic reactor (101) was designed and operated with the following specifications:

[0111] - Electrocatalytic reactor vessel (made of stainless steel) capacity: 60 litres.

[0112] - Cathode: Cu-Mn alloy (2.5% by weight Mn) plate having dimension of 40 cm*10 cm*0.8cm (length*breadth*thickness).

[0113] - Anode: Cu plate having dimension of 40 cm*10cm*0.8cm

[0114] (length*breadth*thickness).

[0115] - Catalyst initiator mixture: Mixture of 75% MgCCh lite (60% MgCOs and 40% MgO) with 6.25% by weight each of Na^COi. NaHCOs. K2CO3, and KHCO3 in distilled water.

[0116] - 60 litres of deionised water was dispensed from the water dispenser (104) into the reactor vessel of the electrocatalytic reactor (101) at a rate of 3 litres per minute (LPM);

[0117] - 20 kgs of the catalyst initiator mixture was dispensed from the Catalyst initiator tank (105) to 10 litres of deionised water present in the catalyst initiator dissolution tank (106), and the catalyst initiator dissolution tank (106) was agitated to form a homogeneous initiator solution, and the homogeneous initiator solution was dispensed into the reactor vessel; - 2 litres of cone. HC1 was dispensed from the acid tank (103) into the reactor vessel every hour for 3 hours (0, 1st, and 2ndhour), i.e., until the completion of the reaction;

[0118] - 600 lbs of the gas mixture of sulfuryl fluoride (SO2F2), CO2, and CH4 (in a ratio of 1:1:1) was dispensed from the gas tank (102) into the reactor vessel at a rate of 2001bs per hour (IbH) for three hours, and

[0119] - a DC power of 25W (i.e., 5V and 5 A) was applied to the cathode and the anode through an external power source, and the electrocatalytic reaction was allowed to take place in the electrocatalytic reactor (101) at normal temperature and pressure (NTP), wherein the completion of the reaction was observed when the reacted liquid in the reactor vessel changes from turbidity to clear solution.

[0120] - 75 litres of the reacted liquid is released from the electrocatalytic reactor (101) into the reacted liquid collection tank (107), which passed through the filtration unit (108) to remove any unreacted solids, the filtrate is transferred to the evaporator tank (109), and then to the three-stage condenser (110).

[0121] - The gaseous products after condensation were collected in the ESF / ESC collection tank (111), pressurized at 6-8 bar and finally stored in the ESF / ESC storage tank (112).

[0122] Evaluation of the gaseous product from the ESF / ESC storage tank (112);

[0123] A sample of the gaseous product from the ESF / ESC storage tank (112) was taken for evaluation.

[0124] UV-Vis spectroscopy of the gaseous product

[0125] The gaseous sample is subjected to UV-Vis analysis in the wavelength range of 180 to 1000 nm.

[0126] Fig. 2 illustrates UV-Vis spectroscopy of the gaseous product sample.

[0127] As shown in Fig. 2, the UV-Vis spectra showed a broad peak of good absorbance and intensity in the range of 186.5 nm to 280 nm. This broad peak depicts the presence of C=C group attached to S=O group. The broad nature of the peak up to 280 nm represents the presence of S=O and S-F / S-Cl linkages in the products formed in gaseous phase. Thus, UV-Vis demonstrates the formation of ESF / ESC as products.

[0128] FTIR analysis of the gaseous product sample

[0129] Fig. 3 illustrates the Fourier Transform Infrared Spectroscopy (FTIR) analysis of the gaseous product sample.

[0130] As shown in Fig. 3, the FTIR spectrum of the gaseous sample showed eight prominent peaks.

[0131] - broad moderate intensity peaks at 3362.33 cm'1with 75.78% transmittance confirming the presence of alcoholic OH group in the sample. This peak is a broad peak due to the H-bonding with the water vapour escaped with the ESF / ESC gas.

[0132] - the sharp less intense peak at 2380.44cm1with 92.91% transmittance indicates the presence of -CH2 group due to methylene or ethylene substitution in the products formed,

[0133] - moderate intense sharp peak at 2273.98 cm'1with transmittance of 75% depicts accounts for the presence of -C=S group,

[0134] - the cluster of peaks from 1600 to 800 cm'1indicates the presence of ethene sulphonyl Fluoride

[0135] (Ref. https :

[0136] Thus, the FTIR data confirms the presence of ethene sulphonyl Fluoride (ESF) as the product.

[0137] Gas Chromatography-Mass Spectrometry analysis of the gaseous product sample

[0138] Fig. 4 illustrates Gas Chromatography-Mass Spectrometry analysis of the gaseous product sample.

[0139] As shown in Fig. 4, the gas chromatography (GC) of the gaseous sample showed six peaks at retention times of 7.55, 9.37, 12.12, 12.69, 13.97, 15.57 mins. The 100% intensity peak is at 12.69 mins indicated fluorinated and chlorinated compounds in the gaseous product sample.

[0140] The product sample was further analysed through Mass spectrometry for the GC peak at 12.69 mins.

[0141] Fig. 5 illustrates Mass spectrometry analysis of the gaseous product sample for the GC peak at 12.69 mins.

[0142] From the NIST web book, the peaks for ESF are 59 in number and out of 59 peaks the most intense peaks are at m / z of 29, 27, 28 in the order top highest, next highest and third highest peaks. The next highest set of peaks around m / z of 56, 57, 58 and 59 accounts for the SO2F group.

[0143] Thus, formation of Ethene sulphonyl fluoride is evident from GC-MS. In addition a peak of m / z at 111, 112 indicates the molecular mass of C2H5SO2F (cf.

[0144] Advantages:

[0145] The electrocatalytic reaction for conversion of sulfuryl fluoride into useful chemicals of the present disclosure has the following non-limiting advantages.

[0146] - Reduction of sulfuryl fluoride, which is a toxic gas.

[0147] - Conversion of polluting gases into useful chemicals such as ESC.

[0148] - In addition to SO2F2 reduction, other GHG like CO2 and CH4 are also converted into ESC / ESF

[0149] - conversion of SO2F2 into useful chemical such as ESF / ESC which can be used as a reagent in Micheal addition by organic chemical industries

[0150] - ESC / ESF being a need of several industrial sectors (such as pesticides, chemical intermediates, paint & coating, pharmaceutical industries), getting ESC / ESF at a cheaper price will provide a cost-advantage to the industries, and in turn the final consumers of these industry sectors. - The present invention can cater to the high demand of ESC / ESF at a much cheaper price, where the current market price of 95% pure ESF (a precursor to ESC) is approximately Rs. 7500 per gram (Ref. Sigma Aldrich).

[0151] Applications:

[0152] The electrocatalytic reaction for conversion of sulfuryl fluoride into useful chemicals of the present disclosure has the following non-limiting industrial applications.

[0153] - Reduction of sulfuryl fluoride from GHG to useful chemicals.

[0154] - Reduction of sulfuryl fluoride from fumigation centres to useful chemicals.

[0155] - Conversion of SO2F2 into useful chemical such as ESF / ESC which can be used as a reagent in Micheal addition by organic chemical industries.

[0156] - ESC is consumed by industry sectors such as pesticides, chemical intermediates, paint and coating, pharmaceutical industries

[0157] - The end-user sectors include agriculture, health care, automotive and electronics industries.

[0158] Although the present disclosure is described in terms of one or more embodiments, it is to be understood that they have been presented by way of example, and are not limiting. Thus, the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

Claims

CLAIMS1. An electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals comprising:- an electrocatalytic reactor (101);- a gas tank (102);- an acid tank (103);- a water dispenser (104);- a catalyst initiator tank (105);- a catalyst initiator dissolution tank (106);- a reacted liquid collection tank (107);- a filtration unit (108);- an evaporator tank (109);- a three-stage condenser (110);- an ESF / ESC collection tank (111);- an ESF / ESC storage tank (112);- a moisture trapping unit (113); and- an unreacted ethylene storage tank (114), wherein, the electrocatalytic reactor (101) includes a reactor vessel equipped with asymmetric electrodes (cathode and anode), wherein the cathode is an alloy of Copper-Manganese (Cu-Mn), and the anode is metallic Copper (Cu); wherein, the water dispenser (104) dispenses a measured quantity of deionised water into the reactor vessel at a rate of 3 to 5 litres per minute (LPM); wherein, the Catalyst initiator tank (105) dispenses a measured quantity of a catalyst initiator mixture to deionised water present in the catalyst initiator dissolution tank (106), wherein the catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K), wherein the measured quantity of the initiator mixture is 30 to 35% of theweight of deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); wherein, the catalyst initiator dissolution tank (106) is agitated to form a homogeneous initiator solution; wherein, the catalyst initiator dissolution tank (106) dispenses the initiator solution into the reactor vessel of the electrocatalytic reactor (101); wherein, the acid tank (103) dispenses a measured quantity of concentrated acid into the reactor vessel every hour until the completion of the reaction, wherein the measured quantity of the concentrated acid dispensed every hour is 2 to 4% of the weight of deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); wherein the gas tank (102) includes a gas mixture of SO2F2, and one or both of CO2 and CH4, wherein the gas tank dispenses a measured quantity of the gas mixture into the reactor vessel at a rate of 2001bs per hour (IbH), wherein the measured quantity of the gas mixture dispensed is 4 to 5 times the volume of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); wherein, when a DC power of 25W (i.e., 5V and 5 A) is applied to the cathode and the anode through an external power source, it initiates the electrocatalytic conversion in the electrocatalytic reactor (101) at normal temperature and pressure (NTP), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CH2=CH-SO2F (Ethene sulphonyl Fluoride, ESF), or in the presence of a chloride medium, the ethylene formed from CO2 and CH4 reacts with SO2F2 to form CH2=CH-SO2CI (Ethene sulphonyl chloride, ESC), wherein the completion of the reaction occurs when the reacted liquid in the reactor vessel changes from turbidity to clear solution,wherein, a measured quantity of the reacted liquid is released from the electrocatalytic reactor (101) into a reacted liquid collection tank (107), which passes through the filtration unit (108) to remove any unreacted solids, the filtrate is transferred to an evaporator tank (109), and then to a three-stage condenser(110), where different fractions are condensed and separated based on their boiling points, wherein, the products ESF or ESC are collected in the ESF / ESC collection tank(111), pressurized at 6-8 bar, and finally stored in the ESF / ESC storage tank(112).

2. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein the Cu-Mn alloy cathode includes less than or equal to 2.5% of Mn.

3. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein the catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCO3and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K).

4. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein the catalyst initiator mixture includes a mixture of 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 6.25% by weight each of Na2CO3, NaHCO3, K2CO3, and KHCO3.

5. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein concentrated acid is used in the acidified deionised water, wherein the concentrated acid is selected from HC1, H2SO4, HN03, H3PO4.

6. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein the chloride medium that converts the SO2F2 to CH2=CH-SO2C1 (Ethene sulphonyl chloride, ESC), is HC1.

7. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein, the gas mixture purged from the gas tank (102) is green-house-gas (GHG) that includes SO2F2, and one or both of CO2 and CH4, and other gases.

8. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein, the ESF and ESC are differentially evaporated and subsequently condensed, wherein the boiling point of ESF is 119 °C, and the boiling point of ESC is 164.2 °C.

9. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein, the moisture trapping unit (113) present in the electrocatalytic reaction system (100) separates and collects water (vapour) from the process, wherein, the collected water is sent to the water recycling unit (not shown), where it is purified and returned to the water dispenser (104) for reuse, ensuring a closed-loop water system.

10. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein, any ethylene that did not react with the SO2F2 (unreacted ethylene) is collected in the unreacted ethylene storage tank (114).

11. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein the system is equipped with a Human Machine Interface (HMI) to visually monitoring and regulating various events / parameters that occur in the electrocatalytic reaction system (100), wherein, the events / parameters that are monitored and regulatedinclude Pressure Transmitter, Level transmitter, Level sensor, Solenoid operated valves (SOVs), pumps, Temperature, Reaction time, timer settings for the SOVs and the pumps.

12. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein the computer is integrated to the electrocatalytic reaction system (100) that displays the information on the HMI, wherein the monitoring and regulation of various events are accessible on the HMI, wherein the HMI can be a computer display screen, or a touch screen, wherein the HMI empowers a technician to select and switch ON or switch OFF the operation of the liquid line or the gas line, wherein the HMI also allows a technician to set the operation of the electrocatalytic reaction system (100) in Auto-mode, Manual-mode, or Maintenance-mode.

13. The electrocatalytic reaction system (100) for conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 1, wherein when the gas mixture includes SO2F2, CO2, and CH4, the ratio of SO2F2, CO2, and CH4 is 1:1:1; when the gas mixture includes SO2F2 and CO2, the ratio of SO2F2 and CO2, is 1:2; and when the gas mixture includes SO2F2 and CH4, the ratio of SO2F2 and CH4, is 1:2.

14. A method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals utilising an electrocatalytic reactor system (100), wherein the method includes the steps of: setting up an electrocatalytic reactor (101) having a reactor vessel equipped with asymmetric electrodes (cathode and anode), wherein the cathode is an alloy of Copper-Manganese (Cu-Mn), and the anode is metallic Copper (Cu); dispensing a measured quantity of deionised water from a water dispenser (104) into the reactor vessel at a rate of 3 to 5 litres per minute (LPM); dispensing a measured quantity of a catalyst initiator mixture from a Catalyst initiator tank (105) to deionised water present in a catalystinitiator dissolution tank (106), wherein the catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K), wherein the measured quantity of the initiator mixture is 30 to 35% of the weight of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); agitating the catalyst initiator dissolution tank (106) to form a homogeneous initiator solution; dispensing the initiator solution from the catalyst initiator dissolution tank (106) into the reactor vessel of the electrocatalytic reactor (101); dispensing a measured quantity of concentrated acid from an acid tank (103) into the reactor vessel every hour until the completion of the reaction, wherein the measured quantity of the concentrated acid dispensed every hour is 2 to 4% of the weight of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); purging a measured quantity of gas mixture of sulfuryl fluoride (SO2F2), CO2, and CH4 from a gas tank (102) into the reactor vessel at a rate of 2001bs per hour (IbH), wherein the gas mixture includes SO2F2, and one or both of CO2, and CH4, wherein the measured quantity of the gas mixture dispensed is 4 to 5 times the volume of the deionised water dispensed into the reactor vessel of the electrocatalytic reactor (101); and applying a DC power of 25W (i.e., 5V and 5 A) to the cathode and the anode through an external power source to initiate the electrocatalytic conversion in the electrocatalytic reactor (101) at normal temperature and pressure (NTP), wherein the applied power initiates C-C coupling reactions on the cathode surface leading to ethylene formation from CO2 and CH4 and further reaction of ethylene with SO2F2 to form CH2=CH- SO2F (Ethene sulphonyl Fluoride, ESF), or in the presence of a chloride medium, the ethylene formed from CO2 and CH4 reacts with SO2F2 to form CH2=CH-SO2CI (Ethene sulphonyl chloride, ESC), wherein the completion of the reaction occurs when the reacted liquid in the reactor vessel changes from turbidity to clear solution.

15. The method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 14, wherein when the gas mixture includes SO2F2, CO2, and CH4, the ratio of SO2F2, CO2, and CH4 is 1:1:1; when the gas mixture includes SO2F2 and CO2, the ratio of SO2F2 and CO2, is 1:2; and when the gas mixture includes SO2F2 and CH4, the ratio of SO2F2 and CH4, is 1:2.

16. The method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 14, wherein the Cu-Mn alloy cathode includes less than or equal to 2.5% of Mn.

17. The method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 14, wherein the catalyst initiator mixture includes 75% by weight of Magnesium carbonate lite (60% MgCCh and 40% MgO), and 25% by weight of a mixture of carbonates and bicarbonates of Sodium (Na) and Potassium (K).

18. The method of electrocatalytic conversion of sulfuryl fluoride (SO2F2) into useful chemicals as claimed in claim 14, wherein, the gas mixture purged from the gas tank (102) is green-house-gas (GHG) that includes SO2F2, and one or both of CO2 and CH4, and other gases.

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