Reactor assembly line in a process plant for electrocatalytic reduction of GHG emissions

Abstract

The present disclosure provides 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 VAPs, wherein the electrocatalytic reactor is equipped with symmetric or asymmetric electrodes (cathode and anode) that act as electrocatalyst, which are dipped in an electrolytic reaction solution that includes acidified deionised water (H3O+) and a catalyst initiator An external current of 1 to 5 A applied to the electrodes in a voltage range of 1 to 5 V for 3 to 5 hours, which initiates C-C coupling or C-O coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or react with in-situ produced H2 gas, leading to the formation of VAPs.

Description

[0001] TITLE

[0002] REACTOR ASSEMBLY LINE IN A PROCESS PLANT FOR ELECTROCATALYTIC REDUCTION OF GHG EMISSIONS

[0003] CROSS REFERENCE TO RELATED APPLICATIONS

[0004] The present application claims priority to India complete patent application number 202443047237 filed on June 19, 2024, which is a patent of addition based upon and claims priority to India complete patent application number 202341066700 filed on March 08, 2024, which is based upon and claims priority to India provisional patent application number 202341066700 filed on October 05, 2023, and, the entire contents of which is herein incorporated by reference.

[0005] FIELD

[0006] The present disclosure relates to conversion of green-house gas (GHG) emissions into value added products (VAPs), more particularly relates to reactor assembly line, and process steps in a process plant for electrocatalytic reduction of greenhouse gas (GHG) emissions into VAPs.

[0007] BACKGROUND

[0008] Gases that trap heat in the atmosphere are called greenhouse gases (GHG). During the daytime, the sun warms the earth’s surface by shining through the atmosphere, and at night, the earth's surface cools, releasing the heat back into the air. But some of the heat is trapped by the greenhouse gases in the atmosphere. That's what keeps the earth’s temperature at an average 14°C (57°F). The gases act like the glass walls of a greenhouse - hence the name, greenhouse gases. Without this greenhouse effect, temperatures would drop to as low as -18°C (-0.4°F); too cold to sustain life on earth. But human activities are changing earth's natural greenhouse effect with a dramatic increase in the release of greenhouse gases. Scientists agree greenhouse gases are the cause of global warming and climate change. Since the Industrial Revolution, humans have been releasing larger quantities of greenhouse gases into the atmosphere. In the past century that amount has increased dramatically, with the knock-on effect of global warming. Global temperatures have accelerated in the past 30 years and are now the highest since records began. Greenhouse gases include carbon dioxide, methane, ozone, nitrous oxide, chlorofluorocarbons, and water vapor.

[0009] The urgency of the climate crisis and the increase in natural gas production accelerate the need for an efficient way to convert GHG such as methane into liquid fuels and other commodity chemicals.

[0010] Methane is normally sourced from feedstocks from natural gas, coal bed, methane hydrate due to their less cost and abundance. As conversion of GHG emissions such as methane to ethylene or any other value-added products is a high temperature operated process i.e. about 700-850°C, a direct conversion of methane without forming syngas as intermediate makes the process more economical and environmentally benign. Therefore, design and development of process and technology for selective conversion of methane and GHG emissions to high-value- added chemicals under room temperature and ambient conditions becomes a challenging task. It had been demonstrated at R&D scale that metal complexes of Hg, Pt, Pd, Au, Ru, Rh, and V acts as catalyst for selective oxidation of GHG emissions comprising of methane, CO2, CO, H2, N2, H2S, SOx, NOx, etc in a strong acid medium, such as oleum, trifluoroacetic acid, hydrochloric acid, or hydrobromic acid at 80°C-500°C. Other methods involved molecule-sieve-based catalysts, such as ZSM-518-21 and MOR, to convert GHG emissions with methane to methanol at much lower temperatures like 50°C- 225°C. But all the said methods or catalysts converted methane and / or CO2 with low yield. Thus, the major bottleneck involves (i) the direct room- temperature conversion of GHG emissions without other energy input and (ii) replacement of precious-metal catalysts.

[0011] The electrochemical reactions of CO2 and N2 are of interest to many researchers for the synthesis of chemicals and for approaches to decrease global warming. Works has been done by the inventors of the present invention, and other researchers aiming at synthesizing specialty chemicals such as formates, acetates, urea, methanol, ethanol, isoamyl alcohol and n-butanol from CO2, or combination of CO2 and N2. Most of the steel plants emit flue gas with combination of 10-15% of CO2, 80-85% of N2 and small amounts of other gases like SOXand NOX. As these flue gases are let out into the atmosphere, they increase GHG emissions and also the chemically inert and important energy carrier N2 gas is left unused.

[0012] To reduce the GHG emissions and to utilize the excess N2 gas untapped so far in steel industries, it is essential to reduce CO2 or CO gases to fuels such as methanol, ethanol, butanol, isoamyl alcohol, acetates etc., whereas N2 can be reduced to the most important energy carrier Ammonia.

[0013] As N2 reduction to ammonia is normally carried out by Haber-Bosch process which is energy intensive process occurring at very high temperatures and pressure, where high temperature is required to achieve N=N bond breaking, and high pressure is required to increase the reaction rate.

[0014] Hence the present inventors aim for a technique, where ammonia is formed at ambient temperature and pressure, and hence less energy intensive, yet leads to a near 100% conversion efficiency and greater than 90% Faradaic efficiency.

[0015] IN202341047481 discloses a method of electrochemical conversion of carbon dioxide into value-added products, wherein the method utilises an electrochemical reactor having metallic Copper (Cu) or Cu-alloy symmetric electrodes (cathode and anode).

[0016] IN202341066700 discloses an electrocatalytic reactor for conversion of Green House Gas (GHG) emissions into value-added products (VAPs), which is equipped with symmetric or asymmetric electrodes (cathode and anode) that act as electrocatalyst, which are dipped in an electrolytic reaction solution that includes acidified deionised water (H3O+) and a catalyst initiator. Application of current of 1 to 5 A to the electrodes in a voltage range of 1 to 5 V for 3 to 5 hours, initiates C-C coupling or C-0 coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or react with in-situ produced H2 gas, leading to the formation of VAPs. US9816035B2 discloses a process and system for producing a synthetic hydrocarbon having a desired H / C ratio is disclosed. Organic material is biochemically digested in a two stage biodigester for separately producing a hydrogen containing biogas substantially free of methane in a first stage and a methane containing biogas in a second stage. The methane containing biogas is reformed in a first reformer to generate hydrogen gas and carbon monoxide gas, which are then combined in a mixer with the hydrogen containing biogas into a syngas in amounts to achieve in the syngas an overall H / C ratio substantially equal to the desired H / C ratio. The syngas is reacted with a catalyst in a second reformer, a Fischer-Tropsch (FT) reactor, to produce the hydrocarbon. Using a two stage biodigester allows for the generation of separate hydrogen and methane streams, a more economical generation of the FT syngas and reduced fouling of the FT catalyst.

[0017] US9163180B2 discloses a process for the conversion of carbon-based material to fuel bases by a hybrid route combining direct ebullent bed liquefaction and indirect liquefaction by gasification followed by a Fischer-Tropsch synthesis, including a stage of production of hydrogen resulting from non-fossil resources and a reverse water gas reaction stage.

[0018] US20230287286A1 discloses processes for producing high biogenic concentration Fischer-Tropsch liquids derived from the organic fraction of municipal solid wastes (MSW) feedstock that contains a relatively high concentration of biogenic carbon (derived from plants) and a relatively low concentration of non-biogenic carbon (derived from fossil sources) wherein the biogenic content of the Fischer-Tropsch liquids is the same as the biogenic content of the feedstock.

[0019] WO2020176575A1 discloses method of electrochemical reduction of CO2 includes the use of a catalyst of Cu / CmO particles including C11 / CU2O interfaces, which is included in an electrochemical cell for the conversion of CO2 to value- added products. The electrochemical cell may include an anode, a cathode including the C11 / CU2O particles including Cu / Cu20 interfaces, and an aqueous medium containing CO2 or CC>3(’2). The CO2 or CC>3(’2)is reduced by contacting the CU / CU2O particles with the aqueous medium while supplying electricity to the cell.

[0020] Journal article, “Oxide Derived Copper for Electrochemical Reduction of CO2 to C2+Products”, Nanomaterials, 2022, 12(8):1380; doi:10.3390 / nanol2081380, discloses a study directed to electrochemical reduction of CO2 on copper electrode derived from cupric oxide (CuO), named oxide derived copper (ODCu), in the potential range of -1.0 V to -1.5 V versus RHE. The CuO nanoparticles were prepared by the hydrothermal method. The ODCu electrode was used for carbon dioxide reduction and the results revealed that this electrode is highly selective for C2+products with enhanced current density at significantly less overpotential.

[0021] Journal article “Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu-Pd catalysts with different mixing patterns”, J. Am. Chem. Soc. 2017, vol. 139, issue.l, pages: 47-50; doi:10.1021 / jacs.6bl0740, discloses bimetallic Cu-Pd catalysts for reduction of carbon dioxide to Ci or C2 chemicals.

[0022] CN 104321293 A discloses a process for the preparation of methanol having the process a carbon oxides per-pass conversion equal to or higher than 65%, and a selectivity to methanol formation equal to or higher than 75% by submitting carbon dioxide, carbon monoxide or a mixture of carbon monoxide and carbon dioxide to a hydrogenation reaction using a specific metal compound and specific reaction conditions of temperature, pressure, space velocity and a specific range of molar ratio of hydrogen to carbon dioxide, of hydrogen to carbon monoxide, or of hydrogen to the mixture of carbon monoxide and carbon dioxide. It further relates to a process for converting the methanol obtained into dimethyl ether or into a mixture of (C2-C8) alkene and (C1-C8) alkane.

[0023] Journal article “Chong Wang et al. Silver-modified copper foam electrodes for enhanced reduction of CO2 to C2+ products, Mater. Adv., 2022, 3, 4964-4972, DOI: 10.1039 / D2MA00188H” discloses an Ag-modified Cu / CuO-Ag catalyst with a porous structure via a galvanic replacement reaction method, which reduced CO2 to C2+ products with the faradic efficiency (FE) of 52.5% at 1.1 V (vs. RHE). DI states that the experimental results and density functional theory (DFT) calculations show that the addition of Ag in Cu is beneficial to increasing the coverage of *CO on the Cu surface, which can decrease the potential barrier energy of the C-C coupling reaction and favour the generation of C2+ products.

[0024] Journal article “Mun, Yeongdong et al. (2019). Cu-Pd Alloy Nanoparticles as Highly Selective Catalysts for Efficient Electrochemical Reduction of CO2 to CO. Applied Catalysis B: Environmental, (), S0926337319300219. doi: 10.1016 / j.apcatb.2019.01.021” discloses alloying of Cu with Cu-Pd in 1:1 ratio achieves CO2 to CO electrochemical reduction of 87% CO faradic efficiency (FE). D2 discloses that this increase in the FE of CO2 to CO conversion suppresses the formation of hydrocarbons from CO2.

[0025] Journal article “M. Watanabe, M. Shibata, A. Kato, M. Azuma, T. Sakata, J. Electrochem. Soc. 1991, 138, 3382-3389” discloses Cu based alloys such as Cu- Zn, Cu-Cd, Cu-Ag, Cu-Sn and Cu-Pb as electrocatalyst for CO2 electrochemical reduction into CH3OH, HCOOH, and CO in highly selective approach via low overpotentials on Cu-alloy catalysts.

[0026] US2022119966A1 discloses a method of electrochemical reduction of CO2 involving the use of a catalyst of CU / CU2O nanoparticles including CU / CU2O interfaces wherein the catalyst may be included in an electrochemical cell for the conversion of CO2 to value-added products. The electrochemical cell may include an anode, a cathode including the Cu / CmO nanoparticles including Cu / Cu2O interfaces.

[0027] GB202202262D0 discloses a catalyst for the electrochemical conversion of carbon dioxide or carbon monoxide to a C2+ product wherein the catalyst comprises copper and a metal (M) selected from the group consisting of: yttrium (Y), zinc (Zn), lanthanum (La) and gadolinium (Gd); wherein the molar ratio of Cu: M is from 100: 1 to 100: 10. SUMMARY

[0028] The present disclosure provides an electrocatalytic reactor with the arrangement of the reactor assembly line, and the process steps in a process plant for electrocatalytic reduction of green-house gas (GHG) emissions into VAPs as shown in Fig. 1.

[0029] The electrocatalytic reactor is equipped with symmetric or asymmetric electrodes (cathode and anode), wherein the cathode is selected from metallic Copper (Cu), Cu-alloy, or Cu-doped Ti mesh, and the anode is selected from metallic Copper (Cu), Cu alloy, Ti Mesh, Cu-doped Ti Mesh, Carbon felt, or Cu-doped carbon felt, wherein these electrodes act as electrocatalyst, and acidified deionised water (H3O+) as electrolyte for generation of H2 gas through bulk electrocatalysis, wherein a catalyst initiator is included in the acidified deionised water (H3O+).

[0030] The method of electrocatalytic reduction operation occurs at ambient temperature, and 1 atm pressure. The application of the current density is continued for 3 to 5 hours. An external current of 1 to 5 A was applied to the electrodes in a voltage range of 1 to 5 V, which initiates C-C coupling or C-0 coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, leading to the formation of the VAPs.

[0031] The concentrated acid is selected from HC1, H2SO4, HNO3, H3PO4. The initiator mixture includes a mixture of 60% by weight of carbonates or bicarbonates of Mg or Na or K or a combination of carbonates and bicarbonates of Mg, Na and K with 40% by weight of MgO.

[0032] When the carbon containing gases in the GHG include CO2, CO, CH4, the VAPs produced are unsaturated hydrocarbons, ethanol, acetic acid, acetone, acetaldehyde, glycols, ethylene oxide, propionaldehyde, ethyl vinyl acetate, chloro acetyl chloride so on and so forth. When the gases in the GHG also include H2, N2, H2S, SOx, NOx, the VAPs produced additionally are primary amines, amides, thiophene azo dyes.

[0033] N2 in the GHG is reduced to ammonia at ambient temperature and pressure, with greater than 90% Faradaic efficiency, and about 100% conversion efficiency.

[0034] BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0035] Fig. 1 illustrates the reactor assembly line in a process plant for electrocatalytic reduction of green-house gas (GHG) emissions into VAPs.

[0036] LIST OF REFERENCE NUMERALS USED IN SPECIFICATION AND

[0037] DRAWINGS

[0038] 01. Electrocatalytic reactor

[0039] 02. Effluent tank

[0040] 03. Filtration unit

[0041] 04. Distillation tank

[0042] 05. Evaporator tank

[0043] 06. Condenser

[0044] 07. Storage tank

[0045] 08. Acid dispenser

[0046] 09. Water dispenser

[0047] 10. Thermal fluid bed reactor (TFBR)

[0048] 11. Condenser

[0049] 12. Gas trapping unit

[0050] 13. Moisture trapping unit

[0051] 14. Compressor

[0052] 15. Gas storage tank

[0053] 16. Acid tank

[0054] 17. Gas monitoring unit

[0055] 18. Air dryer

[0056] 19. Pressure gauge

[0057] 20. Filter 21. Flow meter

[0058] 22. Gate valve

[0059] 23. Gas pump

[0060] 24. Liquid pump

[0061] 25. Acid pump

[0062] 26. Slurry pump

[0063] DETAILED DESCRIPTION

[0064] 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.

[0065] 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.

[0066] In addition, it should be appreciated that any figures are provided herewith, they are for explanation purposes to persons ordinarily skilled in the art and that the drawings of them are not necessarily drawn to scale.

[0067] 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.

[0068] The present disclosure provides 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 VAPs as shown in Fig. 1.

[0069] The method for electrocatalytic reduction of Green House Gases (GHG) that includes carbon containing gases such as CO2, CO, CH4, as well as non-carbon containing gases such as H2, N2, H2S, S, SOx, NOx into value-added products (VAPs) such as ethanol, ethylene, propylene, other hydrocarbons, ammonia, urea, amines, acetic acid, Butadiene, Propionaldehyde, ethyl acetate, ethyl acetate esters, metal ethanoates, azo-dyes, ethylene vinyl acetate, chloro acetyl chloride etc.

[0070] The electrocatalytic reactor and method of the present disclosure also is able to perform electrocatalytic cracking of CH4 and NH3 gas into C, H2 gas, and N2 gas at high temperature, wherein the obtained carbon can be converted to graphene, MWCNTs, SWCNTs, and carbon black through continuous CVD.

[0071] Based on the GHG emission feed, and the products desired, the process parameters of the electrocatalytic reduction operation can be suitably customised by varying the electrochemical parameters, and the proportion of the catalyst initiator.

[0072] When the GHG emission feed is pure CO2 or a mixture of CO2, CO, CH4, H2, the electrocatalytic reduction of CO2 by the electrocatalytic reactor of the present disclosure, predominantly produces ethanol under ambient reaction conditions (i.e. at room temperature), When the GHG emission feed contains a mixture of CO2, CO, CH4, H2 having CO2 in the range of 4% to 99.9%, the electrocatalytic reduction of the mixture by the electrocatalytic reactor of the present disclosure predominantly produces ethylene, propylene, other hydrocarbons under ambient reaction conditions, which may form other products such as higher carbon alkenes, alkynes under high temperature (>100°C) conditions.

[0073] When the GHG emission feed contains flue gas i.e. a mixture of N2, CO2, CO, CH4, H2 having CO2 in the range of 4% to 99.9%, the electrocatalytic reduction of the mixture by the electrocatalytic reactor of the present disclosure predominantly produces ammonia, Urea, hydrocarbons under ambient reaction conditions, which may form other products such as higher chain saturated and unsaturated hydrocarbons, long chain hydrocarbon based amines (primary, secondary and tertiary) etc under high temperature (>100°C) conditions.

[0074] N2 in the GHG is reduced to ammonia at ambient temperature and pressure, with greater than 90% Faradaic efficiency, and about 100% conversion efficiency.

[0075] In an aspect CH4 in the GHG is electrocatalytically reduced to ethylene through the following reaction pathway:

[0076] 2CH4^C2H6+ 4H++ 2e"

[0077] The pathway of the elementary steps for reduction of GHG emission feed when it contains a mixture CO2, CO, CH4, H2 having CO2 in the range of 4% to 99.9% involves the following: O2’-CU-CH2-CH2-CU-O2’ CH2=CH2+ 2CuO

[0078] The pathway of the elementary steps for reduction of GHG emission feed when it contains flue gas i.e. a mixture of N2, CO2, CO, CH4, H2 having CO2 in the range of 4% to 99.9% involves the following: inert gas

[0079] O2-CU-CH2-CH2-CU-O2-CH2=CH2+ 2CuO

[0080] The electrocatalytic reactor:

[0081] The electrocatalytic reactor of the present disclosure for conversion of Green House Gas (GHG) emissions that include carbon containing gases as well as noncarbon containing gases into value-added products (VAPs), wherein the electrocatalytic reactor is equipped with symmetric or asymmetric electrodes (cathode and anode), wherein the cathode is selected from metallic Copper (Cu), Cu-alloy, or Cu-doped Ti mesh, and the anode is selected from metallic Copper (Cu), Cu alloy, Ti Mesh, Cu-doped Ti Mesh, Carbon felt, or Cu-doped carbon felt, wherein these electrodes act as electrocatalyst, and acidified deionised water (H3O+) as electrolyte for generation of H2gas through bulk electrocatalysis, wherein a catalyst initiator is included in the acidified deionised water (H3O+).

[0082] Fig. 1 illustrates the reactor assembly line in the process plant for electrocatalytic reduction of green-house gas (GHG) emissions into VAPs.

[0083] As shown in Fig. 1, the reactor assembly line operates with the following functions.

[0084] 01. Electrocatalytic reactor - The Electrocatalytic reactor is equipped with two to eight electrodes, both symmetric and asymmetric as per the requirement of the electrocatalytic reaction. The reactor is double jacketed to handle the temperature fluctuations of the environment, so that the reaction is occurring at room temperature. The inner wall of the electrocatalytic reactor is lined with acrylate to make it electrically insulating and avoid taking part in the electrocatalytic conversion. The reactor is capable of handling pressure up to 50 bar. First embodiment: In a first embodiment, the electrocatalytic reactor is of 2000 litres capacity made of SS316 and is capable of handling 15 Tonnes of GHG in a day.

[0085] Second embodiment: In a second embodiment, the electrocatalytic reactor is of 4000 litres capacity made of SS316 and is capable of handling 30 Tonnes of GHG in a day.

[0086] 02. Effluent Tank - The effluent tank is flushed with the reaction solution from the electrocatalytic reactor.

[0087] In the first embodiment, the effluent tank is of 1500 litres capacity made of SS316.

[0088] In the second embodiment, the effluent tank is of 3000 litres capacity made of SS316.

[0089] 03. Filtration Unit - The reaction solution from the effluent tank, if possesses solid particles are present, it is filtered in the filtration unit to remove the solid precipitate. The filtrate obtained is passed into the next step.

[0090] In the first embodiment, the filtration unit is made of four 500 litres tanks connected in series.

[0091] In the second embodiment, the filtration unit is made of four 1000 litres tanks connected in series.

[0092] 04. Distillation tank - The distillation tank is a coil heated tank with temperature sensors and digital temperature monitoring controls. The maximum temperature achieved by this unit is 120°C with ± 1°C accuracy.

[0093] In the first embodiment, the distillation tank is a coil heated tank of 2000 litres.

[0094] In the second embodiment, the distillation tank is a coil heated tank of 4000 litres. 05. Evaporator tank - The evaporator tank is a coil heated tank to evaporate moisture from the solid slurry obtained as output of the filtration unit.

[0095] In the first embodiment, the evaporator tank is of 1500 litres capacity made of SS316.

[0096] In the second embodiment, the evaporator tank is of 3000 litres capacity made of SS316.

[0097] 06. Condenser unit - Condenser is used to condense the vapours distilling out of the distillation system.

[0098] 07. Storage tank - Storage tank is employed to store the liquid products obtained from the electrocatalytic conversion of GHG emissions.

[0099] In the first embodiment, the storage tank is of 1500 litres capacity made of SS316. In the second embodiment, the storage tank is of 3000 litres capacity made of SS316.

[0100] 08. Acid dispenser - Acid dispenser is a tank that automatically dispenses the concentrated acid such as HC1, H2SO4, HNO3, H3PO4 according to the requirement of the electrocatalytic reaction. The acid dispenser is connected with a timer and programmed to dispense a fixed amount of acid in a fixed periodic interval of the reaction.

[0101] In the first embodiment, the acid dispenser tank is of 100 litres capacity made of SS316, which is programmed to dispense 20 litres of acid every one hour of the reaction.

[0102] In the second embodiment, the acid dispenser tank is of 200 litres capacity made of SS316, which is programmed to dispense 40 litres of acid every one hour of the reaction. 09. Water dispenser - Water dispenser tank stores water and dispense automatically to the electrocatalytic reactor as and when it is required.

[0103] In the first embodiment, the water dispenser tank is of 2000 litres capacity made of SS316.

[0104] In the second embodiment, the water dispenser tank is of 4000 litres capacity made of SS316.

[0105] 10. Thermal Fluid Bed reactor (TFBR) - Thermal Fluid Bed reactor is filled with black pebbles as bed up to 75% of the volume. It is heated by heating coil up to temperature of 150°C. The distillate from distillation tank is passed into the thermal fluid bed reactor (TFBR) to convert into gaseous product. The gas sensors attached to the reactor senses unsaturated hydrocarbons like ethylene, butadiene and the acid is condensed and drained into acid storage tank.

[0106] In the first and second embodiments, the thermal fluid bed reactor (TFBR) is made of SS316.

[0107] 11. Condenser - A condenser to condense acid vapours into liquid.

[0108] 12. Gas trapping unit - A gas trapping unit is a tank with molecular sieves to trap the gaseous product such as ethylene, butadiene etc.

[0109] In the first and second embodiments, the gas trapping unit is made of SS316.

[0110] 13. Moisture trapping unit - Remaining moisture and acid escaping from the thermal fluid bed reactor (TFBR) is trapped in moisture trapping unit.

[0111] 14. Compressor - A compressor to compress gaseous product from gas trapping unit up to 15 bar. 15. Gas storage tank - The compressed gaseous product at 15 bar is stored in a gas storage tank, wherein the gas storage tank is capable of handling up to 25 bar pressure.

[0112] In the first embodiment, the gas storage tank is of 1500 litres capacity made of SS316.

[0113] In the second embodiment, the gas storage tank is of 3000 litres capacity made of SS316.

[0114] 16. Acid tank - From the moisture trapping unit, the acid and water condense and gets stored in an acid tank.

[0115] In the first embodiment, the acid tank is of 1000 litres capacity made of S S316. In the second embodiment, the acid tank is of 2000 litres capacity made of SS316.

[0116] 17. Gas Monitoring unit - It is an automated gas analyzing system (RGA unit) that can analyze the percentage composition of GHG in terms of CO2, CO, CH4, ethylene, S, H2S, SOx, NOx and all essential GHG gases. The RGA is SCADA based unit that would automatically prompt the composition of the GHG emissions, gaseous product, any escaping gases from the electrocatalytic reactor as and when required.

[0117] 18. Air Dryer - Utilized to dry the evaporated solid precipitates to attain dry particles for further processing.

[0118] 19. Pressure Gauge - Gauges to monitor the inlet GHG, output gases, any gas leak across the plant and the pressure of the gases. 20. Filter - Filters at appropriate places in the plant to remove particulate matters that are associated with the GHG emissions. Filters of appropriate mess size will be employed as per the PM size in the emissions.

[0119] 21. Flow Meter - To monitor the set flow of GHG, acid, water, gaseous products etc.

[0120] 22. Gate Value - Manual Gate values are also provided for emergency applications.

[0121] 23. Gas pump - Pump to handle GHG emissions at 50 bar, to pump the gaseous product at 15 bar to the storage tank etc.

[0122] 24. Liquid pump - Pump to handle liquid distillate into the storage tank.

[0123] 25. Acid pump - Pump to handle acid or acidic solutions.

[0124] 26. Slurry pump - Pump to handle slurry of solid precipitates from the filtration unit.

[0125] All the units are connected by SS316 pipelines and automated with SC AD A unit operation. The technical drawing of all the components and its dimensions are provided in the figures following this section.

[0126] The catalyst initiator:

[0127] The catalyst initiator for of the present disclosure is a mixture of 60% by weight of carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 40% by weight of MgO in distilled water to facilitate the reaction of the short-lived cation radical intermediates formed by C- C coupling or C-0 coupling reactions on the cathode surface leading to hydrolysis and VAPs formation with high specificity and selectivity. In preferred embodiments of the present disclosure, the catalyst initiator mixture can be the following combinations:

[0128] - 60% by weight of MgCCh with 40% by weight of MgO.

[0129] - 60% by weight of a mixture of MgCCh and one or more of Na^COi. K2CO3, NaHCCh, or KHCO3 with 40% by weight of MgO.

[0130] The method of electrocatalytic conversion of GHG into VAPs when GHG emission feed contains a mixture CO2. CO, CH4, H2 having CO2 in the range of 4% to 99.9%:

[0131] The method of electrocatalytic conversion of Green House Gas (GHG) emissions that include carbon containing gases as well as non-carbon containing gases into value-added products (VAPs) includes the steps of:

[0132] - adding deionised water to an electrocatalytic reactor vessel and dipping a cathode, and an anode in the deionised water;

[0133] - purging GHG into the deionised water in the reactor vessel from an external GHG source;

[0134] - applying current density to the cathode and anode through an external power source; wherein the power source set at voltage of up to 5V and current of up to 5A;

[0135] - adding a catalyst initiator to the deionised water in the reactor vessel forming an initiator solution; and

[0136] - adding a concentrated acid to the initiator solution in the reactor vessel with constant stirring to form an electrolytic reaction solution, which produces H2 gas in-situ from the electrolytic reaction solution on the cathode surface, wherein the applied current density initiates the C-C coupling or C-0 coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, forming organic acid anions and alkoxides, wherein, on the anode, when the anode contains proton formation, oxygen evolution occurs, wherein the evolved oxygen reacts with the cation radical resulting in the oxidization of the same to form the value-added products (VAPs) such as acetone, acetaldehyde, acetic acid, ethylene oxide, wherein, additionally, on the anode, when the anode contains Cu, dissolution of Cu occurs forming Cu2+ions, wherein, the organic acid anions and alkoxides react with the Cu2+ions forming metallorganic complexes; wherein, the metallorganic complexes are left for hydrolysis for about 24 hours at 35° to 45° C to form the value-added products (VAPs),

[0137] The method of electrocatalytic conversion of GHG into VAPs when GHG emission feed contains flue gas i.e. a mixture of N2, CO2, CO, CH4, H2 having CO2 in the range of 4% to 99.9% includes the steps of:

[0138] The method of electrocatalytic conversion of Green House Gas (GHG) emissions that include carbon containing gases as well as non-carbon containing gases into value-added products (VAPs) includes the steps of:

[0139] - adding deionised water to an electrocatalytic reactor vessel and dipping a cathode, and an anode in the deionised water;

[0140] - purging GHG into the deionised water in the reactor vessel from an external GHG source;

[0141] - applying current density to the cathode and anode through an external power source; wherein the power source set at voltage of up to 5V and current of up to 5A;

[0142] - adding a catalyst initiator to the deionised water in the reactor vessel forming an initiator solution; and

[0143] - adding a concentrated acid to the initiator solution in the reactor vessel with constant stirring to form an electrolytic reaction solution, which produces H2 gas in-situ from the electrolytic reaction solution on the cathode surface, wherein the applied current density initiates the C-C coupling or C-0 coupling or C-N coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, forming organic acid anions and alkoxides, wherein, on the anode, when the anode contains proton formation, oxygen evolution occurs, wherein the evolved oxygen reacts with the cation radical resulting in the oxidization of the same to form the value-added products (VAPs) such as acetone, acetaldehyde, acetic acid, ethylene oxide, wherein, additionally, on the anode, when the anode contains Cu, dissolution of Cu occurs forming Cu2+ions, wherein, the organic acid anions and alkoxides react with the Cu2+ions forming metallorganic complexes; wherein, the metallorganic complexes are left for hydrolysis for about 24 hours at 35° to 45° C to form the value-added products (VAPs), wherein, on the anode, when the anode contains Ti Mesh or Carbon felt i.e. in the absence of Cu, the VAPs formed include Ethylene Vinyl Acetate, Chloro Acetyl Chloride.

[0144] The application of the current density to the electrodes is continued for 3 to 5 hours.

[0145] The Cu-alloy for the electrodes can be selected from Cu / CuO, Cu / Ag, Cu / Ti, Cu / Pt, and Cu / Pd, wherein the alloying substance i.e., CuO, Ag, Ti, Pt, and Pd is present in an amount of less than or equal to 2.5% by weight.

[0146] In the Cu-doped Ti Mesh electrodes, the dopant Cu is present in an amount of less than or equal to 2% by weight. Similarly, in the Cu-doped carbon felt, the dopant Cu is present in an amount of less than or equal to 2% by weight.

[0147] The concentrated acid added to the initiator solution in the reactor vessel is selected from HC1, H2SO4, HNO3, H3PO4.

[0148] In an aspect, the purging of GHG into the deionised water in the reactor vessel from an external GHG source at a flow rate of 30-50 Litre / hour (LPH).

[0149] An external current of 1 to 5 A was applied to the electrodes in a voltage range of 1 to 5 V, which facilitates the formation of organic cation radical intermediates, which lead to the formation of the VAPs.

[0150] The overall method of operation of the reactor assembly line in the process plant for electrocatalytic reduction of green-house gas (GHG) emissions into VAPs is described below.

[0151] As disclosed before the different units in the reactor assembly line, the method of electrocatalytic conversion of Green House Gas (GHG) emissions that include carbon containing gases as well as non-carbon containing gases into value-added products (VAPs) through an electrocatalytic reactor assembly line, wherein the method comprising the following steps:

[0152] - supplying deionised water from the water dispenser (09) to the electrocatalytic reactor (01) and dipping one or more cathode, and one or more anode in the deionised water;

[0153] - purging GHG into the deionised water in the reactor (01) from an external GHG source;

[0154] - applying current density to the cathode and anode through an external power source; wherein the power source set at voltage of IV to 5V and current of 1 A to 5 A;

[0155] - adding a catalyst initiator to the deionised water in the reactor (01) forming an initiator solution; and

[0156] - supplying a concentrated acid from the acid dispenser (08) to the initiator solution in the reactor (01) with constant stirring to form an electrolytic reaction solution, which produces H2 gas in- situ from the electrolytic reaction solution on the cathode surface, wherein the applied current density initiates the C-C coupling or C-0 coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, forming organic acid anions and alkoxides, wherein, on the anode, the value-added products (VAPs) are formed turning the electrolytic reaction solution to a dispersion,

[0157] - transferring the dispersion to the filtration unit (03),

[0158] - transferring the filtrate from the filtration unit (03) to the distillation tank (04) for distillation, and the residue from the filtration unit (03) to the evaporator tank (05) for drying;

[0159] - transferring the distillate from the distillation tank (04) to the condenser (11), from where the condensate that includes the VAPs is transferred to the storage tank (07);

[0160] - transferring the condensate from the storage tank (07) to the thermal fluid bed reactor (TFBR) (10) for forming gaseous VAPs;

[0161] - transferring the gaseous VAPs to the moisture trapping unit (13) to render the formed VAPs free of any moisture present in them;

[0162] - transferring the moisture free VAPs to the gas trapping unit (12), to render the VAPs free of any residual gas or fluid within their structural space;

[0163] - transferring the residual gas free gaseous VAPs to the compressor (14), and from the compressor (14) to the gas storage tank (15).

[0164] Utility requirements for the First embodiment:

[0165] A. Power requirement: The power requirement for the different units of the electrocatalytic reactor assembly line is provided in Table 1.

[0166] Table 1: Power requirement

[0167] B. Water requirement: The water requirement at the different units of the electrocatalytic reactor assembly line is provided in Table 2.

[0168] Table 2: Water requirement

[0169] C. Initiator requirement: The amount of initiator required is about 2kg per batch.

[0170] D. Acid requirement: The amount of acid required is about 200 litres per batch. Five batches of operation @ 625 LPH of flow rate of GHG emissions is required to achieve 15TPD throughput of GHG. Risks and ways for mitigation:

[0171] The different risks scenario that may arise (especially in pilot scale plant execution) are as follows

[0172] - Interruption in the flow of GHG: The interruptions in the flow of GHG emissions from the source if monitored for all its components and composition via RGA unit which can analyze gas including CO2, CO, CH4, S, H2S, SOx, NOx, ethylene, H2, O2 and H2O. A shut down of DC power source to the electrocatalytic reactor will be triggered to avoid unnecessary functionality of the electrocatalytic reactor.

[0173] - Any short circuitry in the electrocatalytic reactor: The Programmable Logic Controller (PLC) system monitoring the reaction and parameters would alert the short circuitry in the electrocatalytic reactor which may occur due to electrodes / electrocatalysts touching the walls of the reactor or each other, or discontinuity in the electrodes / electrocatalysts, wiring and current collectors. In the case of short circuit in the electrocatalytic reactor, the reaction would be automatically shut down and the GHG emissions flow into the electrocatalytic reactor would be stopped.

[0174] - Power shut down in the plant and DC power source shut down: In case of power shut down, DC power source shuts down and the electrocatalytic reaction stops. Hence, it is recommended to go for uninterrupted Renewable driven power supply to the DC power source or DG based power supply. In such emergency situations, the PLC system would automatically cut off GHG supply and further electrocatalytic reaction in the reactor to avoid any unnecessary by-products.

[0175] Gas leakage from thermal fluid bed reactor (TFBR), electrocatalytic reactor and storage vessels: If the gas monitoring RGA unit, senses abnormal readings for the ethylene or other gaseous emissions from the fluid bed reactor, electrocatalytic reactor, automatic shutdown of the plant occurs to avoid accumulation gas in the vessels and reactors.

[0176] - Storage tank to evacuation process disruption: If the cables or process of evacuation of gaseous, liquid, or solid end-product is stopped or slowed down due to any unavoidable technical or emergency reasons, the production of the VAPs by electrocatalytic reactor would be stopped temporarily by triggering the shutdown of GHG input and DC power input to the electrocatalytic reactor. This would temporarily shut down the operation of the GHG emissions to VAPs plant and thus avoids the plant producing more products before evacuation of the already stored product tanks.

[0177] - Manual Gate valves are made available at every process junction to shut down the plant in case of emergency and extreme situations of automation failure.

[0178] - Automated Acid dispenser with timer based on the pH of the reaction solution. The pH shall be maintained between 5.5 to 8.5.

[0179] - Automated water dispenser for reaction, washing and cleaning purposes before and after the reaction.

[0180] - In case of formation of by-products, separation and storage of the same is also automated. The by-products are also VAPs and do not create any hazard or pollution to the environment. The design of the plant complies with Reuse, Repurpose, Renew, Recycle, Refuse (5R) and zero waste concept.

[0181] Advantages:

[0182] The reactor assembly line in the process plant for electrocatalytic reduction of green-house gas (GHG) emissions of the present disclosure has the following nonlimiting advantages. - The air-polluting GHG emission converted into useful raw material for industries.

[0183] - The source of the gases such as CO2, CO, N2are free of cost or negligible cost.

[0184] - VAPs produced is a building block for petrochemical industries and monomer for polymer industries, thus the demand is high.

[0185] - Carbon credits due to CH4 and / or CO2, SOx & NOx, S utilization - towards carbon neutral.

[0186] - Initiator and Grignard reagents enhance the specificity of the conversion.

[0187] - Presence of SOx and NOx does not interfere with the process.

[0188] - HER is taken as a beneficial reaction to produce in-house H2generation for reduction of N2and CO2 / CO.

[0189] - Excellent Faradaic efficiency (FE) of the process, leading to good yield of ethanol, thus highly economical.

[0190] - The FE% of the process is greater than 55% in dry CO2and > 75% in liq.CO2; > 85% for N2to form ammonia.

[0191] - Cost of ammonia and ethanol produced is approximately $0.32 / liter; if the N2 composition is high in flue gas, cost of ammonia produced is as low as $0.20 / liter (at par or less than the current market price).

[0192] - With 85% efficiency, per tonne of flue gas, 128.85 kg of ethanol, 722.50 kg of ammonia is expected thus the breakeven of the investment is faster.

[0193] - Ethanol produced is a vital fuel to automobile industries, essential precursor to medicinal and food industry, the demand is high.

[0194] - Ammonia produced is an important energy carrier and is of high demand in mobility, energy, food and medicine industries.

[0195] - Cost-effective ammonia production when compared to conventional Haber-Bosch process.

[0196] - Produced ammonia can be stored as ammonium hydroxide and hence avoids investment and safety associated with handling and storage issues.

[0197] - Less chemical intensive process, easy design and operation. - The electrodes as electrocatalyst employed is an earth abundant material and hence highly cost effective.

[0198] - Recycling of the electrode and electrocatalyst is highly feasible and facile making the process highly closed loop.

[0199] - Flow type electrocatalytic reactor design leads to high selectivity and yield of production of VAPs.

[0200] - Cost of ethylene produced is very low compared to the current market price, approximately $800 per ton.

[0201] - To process tonnes of GHG per day, continuous flow electrocatalytic reactor can be designed with ease and hence scaling up and mass production is highly feasible.

[0202] - Completely renewables driven - zero waste concept with 5R compliance.

[0203] Applications:

[0204] The reactor assembly line in the process plant for electrocatalytic reduction of green-house gas (GHG) emissions of the present disclosure has the following nonlimiting industrial applications.

[0205] - Production of VAPs from GHG.

[0206] Although the present disclosure is described in terms 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 abovedescribed exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

Claims

CLAIMS1. An electrocatalytic reactor assembly line for conversion of Green House Gas (GHG) emissions that include carbon containing gases as well as non-carbon containing gases into value-added products (VAPs) comprising: an electrocatalytic reactor (01), an effluent tank (02), a filtration unit (03), a distillation tank (04), an evaporator tank (05), a condenser (06), a storage tank (07), an acid dispenser (08), a water dispenser (09), a thermal fluid bed reactor (TFBR) (10), a condenser (11), a gas trapping unit (12), a moisture trapping unit (13), a compressor (14), a gas storage tank (15), an acid tank (16), a gas monitoring unit (17), an air dryer (18), a pressure gauge (19), a filter (20), a flow meter (21), a gate valve (22), a gas pump (23), a liquid pump (24), an acid pump (25), a slurry pump (26), wherein the electrocatalytic reactor comprises symmetric or asymmetric electrodes (cathode and anode), wherein the cathode is selected from metallic Copper (Cu), Cu-alloy, or Cu-doped Ti mesh; and the anode is selected from metallic Copper (Cu), Cu alloy, Ti Mesh, Cu-doped Ti Mesh, Carbon felt, or Cu-doped carbon felt, wherein the electrodes act as electrocatalyst, and acidified deionised water (H3O+) as electrolyte for generation of H2 gas through bulk electrocatalysis, wherein a catalyst initiator is included in the acidified deionised water (H3O+), wherein an external current of 1 to 5 A is applied to the electrodes in a voltage range of 1 to 5 V, which initiates C-C coupling or C-0 coupling or C-N coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, leading to the formation of the VAPs.

2. The electrocatalytic reactor as claimed in claim 1, wherein the concentrated acid added to the initiator solution in the reactor vessel is selected from HC1, H2SO4, HNO3, H3PO4.

3. The electrocatalytic reactor as claimed in claim 1, wherein the catalyst initiator mixture includes a mixture of 60% by weight of carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 40% by weight of MgO.

4. The electrocatalytic reactor as claimed in claim 1, wherein the catalyst initiator is a mixture of MgCCh and one or more of Na^COi, K2CO3, NaHCCh, or KHCO3 with 40% by weight of MgO.

5. A method of electrocatalytic conversion of Green House Gas (GHG) emissions that include carbon containing gases as well as non-carbon containing gases into value-added products (VAPs) through an electrocatalytic reactor assembly line, wherein the electrocatalytic reactor assembly line includes an electrocatalytic reactor (01), an effluent tank (02), a filtration unit (03), a distillation tank (04), an evaporator tank (05), a condenser (06), a storage tank (07), an acid dispenser (08), a water dispenser (09), a thermal fluid bed reactor (TFBR) (10), a condenser (11), a gas trapping unit (12), a moisture trapping unit (13), a compressor (14), a gas storage tank (15), an acid tank (16), a gas monitoring unit (17), an air dryer (18), a pressure gauge (19), a filter (20), a flow meter (21), a gate valve (22), a gas pump (23), a liquid pump (24), an acid pump (25), a slurry pump (26), the method comprising the steps of:- supplying deionised water from the water dispenser (09) to the electrocatalytic reactor (01) and dipping one or more cathode, and one or more anode in the deionised water;- purging GHG into the deionised water in the reactor (01) from an external GHG source;- applying current density to the cathode and anode through an external power source; wherein the power source set at voltage of IV to 5V and current of 1 A to 5 A;- adding a catalyst initiator to the deionised water in the reactor (01) forming an initiator solution; and- supplying a concentrated acid from the acid dispenser (08) to the initiator solution in the reactor (01) with constant stirring to form an electrolytic reaction solution, which produces H2 gas in-situ from the electrolytic reaction solution on the cathode surface, wherein the applied current density initiates the C-C coupling or C-0 coupling or C-N coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates reactwith the in-situ produced H2 gas, or both, forming organic acid anions and alkoxides, wherein, on the anode, the value-added products (VAPs) are formed turning the electrolytic reaction solution to a dispersion,- transferring the dispersion to the filtration unit (03),- transferring the filtrate from the filtration unit (03) to the distillation tank (04) for distillation, and the residue from the filtration unit (03) to the evaporator tank (05) for drying;- transferring the distillate from the distillation tank (04) to the condenser (11), from where the condensate that includes the VAPs is transferred to the storage tank (07);- transferring the condensate from the storage tank (07) to the thermal fluid bed reactor (TFBR) (10) for forming gaseous VAPs;- transferring the gaseous VAPs to the moisture trapping unit (13) to render the formed VAPs free of any moisture present in them;- transferring the moisture free VAPs to the gas trapping unit (12), to render the VAPs be free of any residual gas or fluid within their structural space;- transferring the residual gas free gaseous VAPs to the compressor (14), and from the compressor (14) to the gas storage tank (15).

6. The method as claimed in claim 5, wherein the concentrated acid added to the initiator solution in the reactor vessel is selected from HC1, H2SO4, HNO3, H3PO4.

7. The method as claimed in claim 5, wherein the initiator mixture includes a mixture of 60% by weight of carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 40% by weight of MgO.

8. The electrocatalytic reactor as claimed in claim 5, wherein the catalyst initiator is a mixture of MgCCh and one or more of Na2CC>3, K2CO3, NaHCOs. or KHCO3 with 40% by weight of MgO.

9. The method as claimed in claim 5, wherein when the carbon containing gases in the GHG include CO2, CO, CH4, the VAPs produced include ethanol, aceticacid, propanol (primary and secondary), butanol, isoamyl alcohol, acetone, acetic acid, esters, ethers, ethylene, butadiene, propionaldehyde, ethylene glycol, ethylene oxide.

10. The method as claimed in claim 5, wherein when the non-carbon containing gases in the GHG include H2, N2, H2S, S, SOx, NOx, the VAPs produced include ammonia, amines, thiophene azo dyes, ethylene vinyl acetate, chloro acetyl chloride.

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