WO2023205841A1 - Appareil et procédé de production d'ammoniac - Google Patents

Appareil et procédé de production d'ammoniac Download PDF

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WO2023205841A1
WO2023205841A1 PCT/AU2023/050335 AU2023050335W WO2023205841A1 WO 2023205841 A1 WO2023205841 A1 WO 2023205841A1 AU 2023050335 W AU2023050335 W AU 2023050335W WO 2023205841 A1 WO2023205841 A1 WO 2023205841A1
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gas
liquid
plasma
electrode
reactor
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PCT/AU2023/050335
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English (en)
Inventor
Patrick Cullen
Renwu Zhou
Tianqi ZHANG
Rusen ZHOU
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The University Of Sydney
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Priority claimed from AU2022901095A external-priority patent/AU2022901095A0/en
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Publication of WO2023205841A1 publication Critical patent/WO2023205841A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0494—Preparation of ammonia by synthesis in the gas phase using plasma or electric discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00592—Controlling the pH
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/026—Particulate material comprising nanocatalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00177—Controlling or regulating processes controlling the pH
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • B01J2219/0811—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes employing three electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0815—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes involving stationary electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0884—Gas-liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical

Definitions

  • the present invention relates to an apparatus and method for producing ammonia.
  • Ammonia is one of the world’s most important industrial chemicals, that supports a quadrupling of the world’s food crops, thereby enabling agriculture to sustain an ever-expanding global population.
  • Ammonia has nine times the energy density of Li-ion batteries, and three times the energy density of compressed hydrogen, creating potential as a carbon-free energy carrier [1 ],
  • the Haber-Bosch (HB) process (N2+3H2 2NH3) dominants today’s ammonia synthesis, but it requires high temperatures and pressures, the feed of ultra- pure H2, and large and centralized plants to achieve its economic viability.
  • the reactant hydrogen is typically derived from the reforming of fossil hydrocarbons and results in an annual CO2 emission of 300 Mt, accounting for ⁇ 1.5% of all greenhouse gas emissions [2,3],
  • NTP non-thermal plasma
  • the energy introduced mainly heats the electrons, creating a thermal nonequilibrium, energy-efficient and highly reactive environment [7]
  • NTP can be powered by renewable electricity [6,7]
  • NTP has demonstrated encouraging yields of ammonia; however, the hydrogen species in these reports comes from high-purity H2, which is obtained from energy and carbon-intensive reforming processes [4,8], Substitution of H2O for H2 is, therefore, a key to making NTP-enabled ammonia synthesis sustainable.
  • the present invention seeks to provide an apparatus and method for producing ammonia, which will overcome or substantially ameliorate at least some of the deficiencies of the prior art, or to at least provide an alternative.
  • a plasma-bubble reactor comprising: a vessel configured to hold a liquid; and - a plasma generating means, in association with the vessel, configured to receive an input feed comprising dinitrogen (N2) gas and generate a plasma from the N2 gas to produce an activated N2 gas encapsulated within a plurality of bubbles formed in the liquid, wherein the activated N2 gas reacts with water (H2O) at a plasma-liquid interface formed between the bubbles and the surrounding liquid to produce ammonia (NH3).
  • N2 dinitrogen
  • the input feed is dinitrogen (N2) gas.
  • the plasma generating means comprises two or more electrodes, wherein at least one of the two or more electrodes is a high voltage (HV) electrode at least partially immersed within the liquid, and configured to generate an electric discharge through the liquid for activating the N2 gas encapsulated within the bubbles when a potential difference is applied across the electrodes.
  • HV high voltage
  • each of the two or more electrodes is at least partially immersed within the liquid.
  • the other of the two or more electrodes is a ground electrode electrically connected to an external wall of the vessel.
  • the HV electrode is partially enclosed within a column defining a gas passage extending partially along a length of the HV electrode, wherein the column is in fluid communication with the input feed and configured with one or more outlets at a lower portion thereof to allow the activated N2 gas encapsulated within the bubbles to exit therefrom into the liquid in the vessel.
  • the two or more electrodes are electrically connected to a DC or AC power supply.
  • the reactor comprises a catalyst for catalysing the reaction between the activated N2 gas and H2O.
  • the plasma is generated by applying a potential difference across the two or more electrodes, wherein at least one of the two or more electrodes is a high voltage (HV) electrode at least partially immersed within the liquid, and configured to generate an electric discharge through the liquid for activating the N2 gas encapsulated within the bubbles, - wherein the HV electrode is partially enclosed within a column defining a gas passage extending partially along a length of the HV electrode, and
  • HV high voltage
  • the catalyst is dispersed within the liquid.
  • the catalyst is a metal or a metal oxide.
  • the catalyst comprises a metal oxide and/or a metal.
  • the catalyst comprises a catalytic metal selected from the group comprising palladium, nickel, platinum, rhodium, silver, ruthenium, cobalt, iron, molybdenum, tungsten and vanadium, in combination with a material which is an electron donor or a precursor of an electron donor.
  • the material is a metal or a metal oxide.
  • the metal oxide is magnesium oxide (MgO).
  • the catalyst comprises ruthenium (Ru)Zmagnesium oxide (MgO).
  • the ratio of ruthenium (Ru) to magnesium oxide (MgO) is about 5%.
  • the catalyst comprises silver nanoparticles.
  • the reactor further comprises an oxygen scavenger species dispersed within the liquid to suppress the formation of NOx.
  • the oxygen scavenger species is selected from the group consisting of methanol, ethanol, isopropyl alcohol and mannitol.
  • the oxygen scavenger species is present within the liquid in a range that falls between about 0.5% and about 2%.
  • a method for producing ammonia comprising the steps of: generating plasma from an input feed comprising dinitrogen (N2) gas to produce an activated N2 gas encapsulated within a plurality of bubbles formed in liquid; and reacting the activated N2 gas with water (H2O) at a plasma-liquid interface formed between the bubbles and the surrounding liquid to produce ammonia (NH 3 ).
  • the plasma is generated by applying a potential difference across two or more electrodes, wherein at least one of the two or more electrodes is a high voltage (HV) electrode at least partially immersed within the liquid, and configured to generate an electric discharge through the liquid for activating the N2 gas encapsulated within the bubbles.
  • HV high voltage
  • the electric discharge is a pulsed discharge.
  • the potential difference falls within a range of between about 1 kV and about 100kV.
  • the liquid is an aqueous medium.
  • the aqueous medium comprises an electrolyte.
  • the aqueous medium has a pH that falls within a range of between 5 and 6.
  • the aqueous medium has a pH of 5.6.
  • the reaction is carried out in a vessel substantially under atmospheric pressure and room temperature.
  • the reaction is carried out in a vessel substantially under atmospheric pressure and elevated temperature.
  • the elevated temperature falls within a range of 25°C and 50°C.
  • the input feed comprises a mixture of the dinitrogen (N2) gas and a second gas.
  • the second gas is oxygen (O2) gas.
  • the input feed comprises atmospheric air, comprising the dinitrogen (N2) gas.
  • the input feed comprises a mixture of the dinitrogen (N2) gas and water (H2O) in the form of water-saturated N2 gas.
  • the water (H2O) contained in the water-saturated N2 gas is at a concentration of 2.5%.
  • the method further comprises the step of:
  • the plasma is generated by applying a potential difference across two electrodes, wherein at least one of the two or more electrodes is a high voltage (HV) electrode at least partially immersed within the liquid, and configured to generate an electric discharge through the liquid for activating the N2 gas encapsulated within the bubbles,
  • HV high voltage
  • HV electrode is partially enclosed within a column defining a gas passage extending partially along a length of the HV electrode
  • the catalyst is dispersed within the liquid.
  • the method further comprises the step of:
  • FIG. 1 shows (a) a schematic representation of a plasma-catalytic bubble (PCB) reactor and (b) an actual prototype of the PCB reactor (without catalyst) in operation;
  • PCB plasma-catalytic bubble
  • FIG. 2 shows schematic representations of three (3) different configurations of the plasma-catalytic bubble (PCB) reactor of FIG. 1 , including (a) plasma bubble column (PBC) generating both dielectric barrier discharge (DBD) and spark, (b) a PBC with catalysts packed in column, and (c) a PBC with catalysts in water;
  • FIG. 3 shows a plot of the normalized relative intensity (a.u.) from discharge optical emission spectra (OES) obtained from a comparison of the N2 + and NH species and ammonia (NH3) production rate (N2 flow rate of 1 L/min with 2.5% of H2O vapour) obtained using the plasma-bubble reactor 110 shown in FIG. 2(b), when the column 135 is packed with (a) plasma only (i.e., zero catalyst), (b) MgO, or (c) Ru/MgO;
  • OFES discharge optical emission spectra
  • NH3 ammonia
  • FIG. 4 shows a plot showing the amount (mg/hour) of ammonia (NH3) produced using the PBC reactor of Fig. 2(a) when performed at (a) pH 5.60, T 298 K, (b) pH 2.40, T 298 K, (c) pH 2.40, T 318 K, and (d) pH 2.40, T 318 K, in the presence of an oxygen (O2) scavenger; and
  • FIG. 5 shows schematic representations of a plasma bubble column reactor according to another preferred embodiment of the present invention, comprising (a) 2 columns, and (b) 3 columns.
  • the present invention is predicated on the finding of a one-step, plasma- driven process for producing ammonia (NH3) gas via clean and renewable sources.
  • NTP non-thermal plasma
  • the two key steps in this process mainly include plasma pre-activation and interactions between H2O and the plasma-activated N2 gas.
  • Various species including electrons, ions, radicals, molecular fragments
  • electrons, ions, radicals, molecular fragments with different energy levels are present in the plasma ionised gas.
  • NTP Different from thermal plasma (equilibrium plasma) with high bulk gas temperature (typically higher than 5 x 10 3 K), NTP operates in a more ambient temperature condition, but it gives enough energies to activate stable molecules and drive the reaction across the energy gap, with excellent selectivity of products and high energy efficiency.
  • This process is thus in stark contrast to the conventional Haber-Bosch (HB) process, which is energy-intensive and is highly eco-destructive and is not compatible with renewable-energy.
  • HB Haber-Bosch
  • current production plants need to be large, which then means a significant infrastructure is required to transport fertilizer to rural farms and locations.
  • the presently disclosed apparatus is capable of generating NH3 with a rate enhanced by ⁇ 100 times and an energy yield reduced by -4 times, when compared to the only other one-step nonthermal plasma (NTP) production of NHsfrom N2 and H2O, which is still challenged by slow production rate and high energy efficiency, with the best performing system which reports an ammonia production of 0.44 mg/h and energy yield of 40.82 kWh/mol (-2400 kWh/kg-NHs).
  • NTP nonthermal plasma
  • FIG. 1 (a) shows a plasma bubble reactor 5a comprising a catalyst packed within a reaction column of the reactor 5a, in which the reactor 5a is configured to activate dinitrogen (N2) gas using non-thermal plasma (NTP), generated by a High Voltage (HV) electrode immersed in a liquid medium comprising water (H2O), wherein the plasma-activated N2 reacts with H2O to produce ammonia (NH3) gas.
  • N2 non-thermal plasma
  • HV High Voltage
  • H2O High Voltage
  • the plasma bubble reactor 5a generates tuneable discharge regions (glow or DBD, and spark) and can be paired with catalysts either in the reaction column or directly in the bulk liquid (both termed plasma-catalytic bubbles, PCBs), further enabling thermodynamically unfavourable reactions to proceed under ambient conditions.
  • FIG. 1 (b) shows a prototype of a different plasma bubble reactor 5b in operation.
  • the plasma bubble reactor 5b is configured without a catalyst packed into the reaction column.
  • the plasma conditions and, where appropriate, coupling with a catalyst it is possible to produce NH3 gas as a chemical output.
  • FIG. 2 shows schematic representations of three (3) different configurations of a plasma-bubble reactor according to embodiments of the present invention, including (a) a reactor 10 equipped with a single plasma bubble column (PBC), (b) a reactor 110 equipped with a single plasma bubble column (PBC) comprising a catalyst supported within the column, and (c) a reactor 210 equipped with a single plasma bubble column (PBC) with a catalyst dispersed within the liquid medium.
  • PBC single plasma bubble column
  • PBC single plasma bubble column
  • the catalyst is provided for the purpose of catalysing the reaction between the activated N2 gas and H2O.
  • the plasma-bubble reactor 10 comprises a vessel 15 that comprises a base 15a and a wall 15b upstanding from the base 15a to define a cavity 20 configured to hold a liquid medium 25 substantially within the cavity 20, and an opening 15c at an upper portion of the vessel 15.
  • the plasma-bubble reactor 10 further comprises a plasma generating means in the form of two electrodes 30, 40 that are located within the cavity 20 of the vessel 15, via the opening 15c, and partially immersed in the liquid medium 25.
  • the two electrodes 30, 40 are electrically connected to an AC power supply 50. Although it will be appreciated by persons of ordinary skill in the relevant art that in an alternative embodiment, the two electrodes 30, 40 may be electrically connected to a DC power supply (not shown).
  • the first electrode 30 is a High Voltage (HV) electrode (or cathode), while the second electrode 40 is a ground or counter electrode (or anode) electrically connected to the external wall 15b of the vessel 15.
  • HV High Voltage
  • the second electrode 40 is a ground or counter electrode (or anode) electrically connected to the external wall 15b of the vessel 15.
  • the HV electrode 30 is partially enclosed within a quartz column 35 defining a gas passage extending partially along a length of the HV electrode 30.
  • the column 35 comprises a gas inlet (not shown) at an upper portion thereof that is configured to fluidly receive an input feed comprising dinitrogen (N2) gas from a N2 gas supply (not shown), and one or more gas outlets 35a, 35b at a lower portion thereof, wherein the lower portion of the column 35 is fully immersed within the liquid medium 25.
  • N2 dinitrogen
  • the gas outlets 35a, 35b allow the activated N2 gas encapsulated within the bubbles to exit from the lower portion of the column 35 into the liquid medium 25.
  • an oxygen scavenger species may be dispersed within the liquid medium 25 to suppress the formation of NOx during the plasma driven process.
  • Suitable oxygen scavengers may be selected from the group consisting of methanol, ethanol, isopropyl alcohol and mannitol.
  • the oxygen scavenger species, ethanol is present within the liquid medium 25 in a range that falls between about 0.5% and about 2%.
  • the column 135 of the HV electrode 130 further comprises a catalyst supported therein for catalysing the reaction between the plasma-activated N2gas and H2O.
  • Catalysts can assist nitrogen activation and conversion by decreasing the required energy for N2 dissociative adsorption. It is established that catalysts packed within a plasma discharge can increase dinitrogen (N2) gas conversion and ammonia (NH3) production either through enhancing the plasma discharge and/or augmenting the activated dinitrogen (N2) gas and hydrogen (H) species over the catalytic surface
  • the catalyst comprises a catalytic metal selected from the group comprising palladium, nickel, platinum, rhodium, silver, ruthenium, cobalt, iron, molybdenum, tungsten and vanadium, in combination with a material which is an electron donor or a precursor of an electron donor.
  • the material in this case is either a metal or a metal oxide.
  • the catalyst comprises ruthenium (Ru) metal in combination with magnesium oxide (MgO) as a carrier.
  • ruthenium (Ru) metal in combination with magnesium oxide (MgO) as a carrier.
  • MgO magnesium oxide
  • the inventors have observed good results when the ratio of ruthenium (Ru) to magnesium oxide (MgO) is about 5%.
  • the catalyst may simply comprise of a catalytic metal oxide.
  • the catalytic metal oxide may comprise magnesium oxide (MgO).
  • the catalyst may comprise a plurality of silver nanoparticles.
  • the catalytically active material for catalysing the reaction between the plasma-activated N2 gas and H2O is simply dispersed within the liquid medium 25 within the vessel 15.
  • a potential difference is applied across the two electrodes 30, 40 causing the HV electrode 30 to generate an electric discharge within the column 35.
  • the electric discharge generates a plasma from the N2 gas that has been fed into the column 35 via the input feed to produce an activated N2 gas.
  • the activated N2 gas exits the column 35 via the gas outlets 35a, 35b and forms a plurality of bubbles in the liquid medium 25, which for the purpose of this embodiment is an aqueous liquid medium comprising an electrolyte.
  • the aqueous medium has a pH that falls within a range of between 5 and 6.
  • the aqueous medium has a pH of 5.6.
  • the electric discharge is a pulsed discharge, that is repeatedly applied at a frequency that falls with a range of about 50 Hz and about 10 MHz.
  • the potential difference that is to be applied across the two electrodes 30, 40 typically falls within a range of between about 1 kV and about 100 kV.
  • the activated N2 gas encapsulated within the bubbles produces a plurality of excited molecules selected from the group consisting of N2*, N2 + , N, H and NH X (as well as NOx when supplying humid N2). These excited molecules then react with the water (H2O) in the aqueous liquid medium 25 at a plasma-liquid interface formed between the bubbles and the surrounding liquid medium 25 to produce ammonia (NH3) gas.
  • the reaction is carried out substantially under atmospheric pressure and at room temperature, although it will be appreciated by persons of ordinary skill in the relevant art that altering one or both of these parameters can be used as a means by which to increase or decrease the rate of conversion of N2 gas to ammonia (NH3) gas.
  • NH3 ammonia
  • the method may be performed under alternative conditions, whereby the reaction is carried out in the vessel 15 substantially under atmospheric pressure and an elevated temperature that falls within a range of 25°C and 50°C.
  • the inventors believe that the reaction at the plasma-liquid interface involves energetic electrons, as well as plasma-generated and activated gaseous species in thus-forming bubbles, that undergo further collisions, charge transfer, quenching and other reactions during the plasma propagation stage until reaching the plasma-liquid interface. In essence, the inventors believe that the closer these active species are to the plasma-liquid interface, the closer they are to the higher H2O content, which enables the formation of more H, sustained by water dissociation.
  • the column 135 of the HV electrode 130 is packed with a catalyst (labelled “X”) supported within the column 135 by a mesh plate and glass wool (not shown).
  • X a catalyst supported within the column 135 by a mesh plate and glass wool (not shown).
  • the inventors have found that packing the DBD discharge zones within the column 135 with catalytic pellets causes the discharge behaviour to shift from volumetric micro discharges to a combination of surface discharge on the catalyst surface and weak micro-discharges in the space between the catalysts, leading to an enhancement of reactive specie generation and conversion efficiency.
  • FIG. 3 shows a plot of the normalized relative intensity (a.u.) from discharge optical emission spectra (OES) obtained from a comparison of the N2 + and NH species and ammonia (NH3) concentration in the water (N2 flow rate of 1 L/min with 2.5% of H2O vapour) obtained using the plasma-bubble reactor 110 shown in FIG. 2(b), when the column 135 is packed with (a) plasma only (i.e. zero catalyst), (b) MgO, or (c) Ru/MgO.
  • OFES discharge optical emission spectra
  • the OES of the DBD indicate a higher intensity (or formation) of the reactive N2* and key intermediate NH species when the column 135 is packed with (b) MgO and (c) Ru/MgO under the same discharge conditions.
  • catalysts can also be simply dispersed within the liquid medium 25 in the vessel.
  • the catalyst is dispersed within the liquid medium 25.
  • No extra stirring systems are required since the gas inlets 235a, 235b and forming bubbles are able to disperse these catalysts.
  • the catalysts do not interface with the discharges (no visible changes in the optical emission spectra (OES) and other discharge properties, data not shown), however, their presence in the gasliquid interface may extend plasma effects.
  • OES optical emission spectra
  • FIG. 4 shows a plot showing the amount (mg/hour) of ammonia (NH3) produced using the PBC reactor of FIG. 2(a) when performed at different pH values and temperatures (K), with or without the presence of an oxygen (O2) scavenger.
  • ROS reactive oxygen species
  • FIG. 5 shows schematic representations of a plasma bubble column (PBC) reactor system according to another preferred embodiment of the present invention, whereby the system takes the form of (a) a PBC reactor 310 that is configured with 2 columns, and (b) a PBC reactor 410 that is configured with 3 columns.
  • a quartz column 345 comprising a low voltage (LV) electrode 340 partially enclosed there within is employed instead.
  • the column 345 in FIG. 5(a) also defines a gas passage extending along its length.
  • the HV column 335 and the LV column 345 each comprise a corresponding gas inlet 338, 348 at an upper portion thereof that is configured to fluidly receive an input feed comprising dinitrogen (N2) gas from a N2 gas supply (not shown).
  • the HV electrode 330 and the LV electrode 340 are each configured to generate an electric discharge through the liquid medium 25 for activating the N2 gas encapsulated within the bubbles formed when a potential difference is applied across the two electrodes 330, 340.
  • the LV column 345 also comprises one or more gas outlets 345a, 345b at a lower portion thereof, wherein the lower portion of each of the HV column 335 and the LV column 345 is fully immersed within the liquid medium 25 within the vessel 315 of the PBC reactor 310.
  • the gas outlets 345a, 345b allow the activated N2 gas encapsulated within the bubbles to exit from the lower portion of the corresponding HV column 335 and LV column 345 into the liquid medium 25.
  • a third quartz column 455 can be introduced into the vessel 415 of the PBC reactor 410.
  • the third column 455 also comprises a high voltage (HV) electrode 450 that can be connected to the same power source (not shown) as the other HV column 435 and the LV column 445.
  • the two HV electrodes 430, 450 and the LV electrode 440 are all configured to generate an electric discharge through the liquid medium 25 for activating the N2 gas encapsulated within the bubbles formed when a potential difference is applied across the three electrodes 430, 440, 450.
  • Table 1 provides experimental results obtained for different PBC reactor systems 10, 310, 410, equipped with either 1 , 2 or 3 columns (discharge power 25 W, D.l. water only (0.2 L), discharge duration 10 min, catalyst-free) at T 293 K (20 °C).
  • the 3-column PBC reactor system 410 shown in FIG. 5(b) generated ammonia (NH3) at a rate of 20.4 mg/h with an energy yield of 20.83 kWh/mol.
  • an oxygen species scavenger about 1 %
  • the addition of an oxygen species scavenger about 1 %) to the vessel 415 of the 3-column PBC reactor system 410 further doubled the ammonia (NH3) production, with the selectivity being increased by ⁇ 190%, and the energy yield being enhanced to ⁇ 10 kWh/mol.
  • Table 1 NH3, NO X (NO & NC>3 ⁇ ) generation results in different PBC reactor systems equipped with either 1, 2 or 3 columns (discharge power 25 W, D.l. water only (0.2 L), discharge duration 10 min, catalyst-free).
  • the present invention provides a number of advantages, including, but not limited to:
  • the reactor design could be used for other gas conversion processes such as CO2 and methane.
  • the reactor design overcomes heating build-up issues due to the use of the bubble interface as part of the reactor and the convection currents of the surrounding bulk water.
  • N2 pure dinitrogen
  • the input feed may comprise atmospheric air comprising the dinitrogen (N2) gas as the inlet gas.
  • the input feed may comprise a mixture of dinitrogen (N2) gas and oxygen (O2) gas as the inlet gas.
  • N2 dinitrogen
  • O2 oxygen
  • the input feed may comprise a mixture of the dinitrogen (N2) gas and water (H2O) in the form of water-saturated N2 gas.
  • the water (H2O) contained in the water- saturated N2 gas is present at a concentration of 2.5%.

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Abstract

Un réacteur à bulles de plasma et un procédé de production d'ammoniac (NH3) à l'aide dudit réacteur sont divulgués. Le réacteur comprend un récipient conçu pour contenir un liquide, et un moyen de génération de plasma, en association au récipient, conçu pour recevoir une alimentation d'entrée comprenant du diazote (N2) gazeux et pour générer un plasma à partir du gaz N2 afin de produire un gaz N2 activé encapsulé à l'intérieur d'une pluralité de bulles formées dans le liquide, le gaz N2 activé réagissant avec de l'eau (H2O) au niveau d'une interface plasma-liquide formée entre les bulles et le liquide environnant afin de produire de l'ammoniac (NH3).
PCT/AU2023/050335 2022-04-26 2023-04-26 Appareil et procédé de production d'ammoniac WO2023205841A1 (fr)

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