WO2009025835A1 - Synthèse d'ammoniac par plasma non thermique - Google Patents

Synthèse d'ammoniac par plasma non thermique Download PDF

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Publication number
WO2009025835A1
WO2009025835A1 PCT/US2008/009948 US2008009948W WO2009025835A1 WO 2009025835 A1 WO2009025835 A1 WO 2009025835A1 US 2008009948 W US2008009948 W US 2008009948W WO 2009025835 A1 WO2009025835 A1 WO 2009025835A1
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catalyst
ammonia
electrodes
packed bed
electrode
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PCT/US2008/009948
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English (en)
Inventor
Roger Ruan
Shaobo Deng
Zhiping Le
Paul Chen
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Regents Of The University Of Minnesota
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Publication of WO2009025835A1 publication Critical patent/WO2009025835A1/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
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J8/0207—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 the fluid flow within the bed being predominantly horizontal
    • B01J8/0214—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 the fluid flow within the bed being predominantly horizontal in a cylindrical annular shaped bed
    • 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
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0417—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the synthesis reactor, e.g. arrangement of catalyst beds and heat exchangers in the reactor
    • C01C1/0435—Horizontal reactors
    • 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
    • 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
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B01J2219/083—Details relating to the shape of the electrodes essentially linear cylindrical
    • 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
    • B01J2219/0837—Details relating to the material of the electrodes
    • B01J2219/0841—Metal
    • 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
    • B01J2219/0837—Details relating to the material of the electrodes
    • B01J2219/0843—Ceramic
    • 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
    • B01J2219/0845—Details relating to the type of discharge
    • B01J2219/0847—Glow 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
    • 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
    • B01J2219/0845—Details relating to the type of discharge
    • B01J2219/0849—Corona pulse 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
    • 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
    • B01J2219/0883—Gas-gas
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to thermal plasma reactors and to the use of non-thermal plasma to dissociate gas molecules to produce reactants, in particular, to use such reactants to produce ammonia.
  • Nitrogen fertilizer is a necessary macronutrient and is applied infrequently and normally prior to or concurrently with seeding.
  • Nitrogen based fertilizers include ammonia, ammonium nitrate and anhydrous urea, all being products based on the production of ammonia.
  • Ammonia is generated from a process commonly known as the Haber-Bosch Process.
  • the Haber-Bosch Process includes the reaction of nitrogen and hydrogen to produce ammonia.
  • the Haber-Bosch Process has been used since the early 1900s to produce ammonia which in turn has been used to produce anhydrous ammonia, ammonium nitrate and urea for use as fertilizer.
  • the Haber-Bosch Process utilizes nitrogen obtained from air by fractional distillation and hydrogen obtained from methane (natural gas) or naphtha. There is an estimate that the Haber-Bosch Process produces 100 million tons of nitrogen fertilizer per year and consumes 1% of the world's annual energy supply. Nitrogen fertilizer, however, is responsible for sustaining approximately 40% of the earth's population.
  • a method for producing ammonia comprises introducing N 2 and H 2 into a non-thermal plasma in the presence of a catalyst.
  • the catalyst is effective to promote the dissociation of N 2 and H 2 , which is used to form ammonia.
  • the apparatus includes a gas inlet and a gas outlet, first and second electrodes, and a reaction chamber between the first and second electrodes.
  • the reaction chamber includes a catalyst containing packed bed, which is fluidically coupled to the gas inlet and the gas outlet. At least one dielectric barrier electrically isolates at least one of the first or second electrodes from the reaction chamber.
  • Figure 2 is a diagrammatical view of another embodiment of the reactor.
  • Figure 3 is a diagrammatical view of another embodiment of the reactor.
  • Figure 4 is a diagrammatical view of yet another embodiment of the reactor.
  • Figure 5 is a diagrammatical view of yet another embodiment of the reactor.
  • Figure 6 is a diagrammatical view of still another embodiment of the reactor.
  • Figure 7 is a graphical view of ammonia yield in NTP.
  • Figure 8 is a schematic diagram one catalyst mechanism.
  • Figure 9 is an energy index showing different ionization levels.
  • Figure 10 is a graphical view of ammonia yield versus voltage in a NTP reactor.
  • Figure 11 is a graphical view of ammonia yield versus reaction temperature in a NTP reactor.
  • Figure 12 is a graphical view showing ammonia yield versus selected levels of N 2 to H 2 in a NTP reactor.
  • Figure 13 is graphical view showing ammonia yield versus reaction time in a NTP reactor.
  • Figure 14 is a schematic view of one process of this invention.
  • Figure 15 is a schematic view of another embodiment utilizing the NTP reactor.
  • An aspect of the present disclosure relates to a method in which a non-thermal plasma (NTP) in a silent discharge (dielectric barrier discharge) reactor is used to assist catalyzed reactions.
  • NTP non-thermal plasma
  • Such reactions when utilizing only a catalyst in conventional thermal chemistry require large amounts of energy in terms of high temperatures and/or high pressures to achieve the desired reaction.
  • Synthetic gas made primarily of carbon monoxide and H 2 may be used to form various synthetic hydrocarbon products.
  • Syngas is made through gasification of a solid carbon based source such as coal or biomass.
  • Syngas as a feedstock is the Fischer-Tropsch process which is a catalyzed reaction wherein carbon monoxide and hydrogen are converted into various liquid hydrocarbons.
  • Typical catalysts used are based on iron, cobalt and ruthenium. Resulting products are synthetic waxes, synthetic fuels and olefins. It has been found that the use of NTP in a silent discharge reactor will assist in driving such a reaction at reduced temperatures and pressures.
  • One aspect of this disclosure is the production of ammonia from atmospheric hydrogen and nitrogen utilizing non-thermal plasma (NTP) in a silent discharge reactor. Atmospheric nitrogen and hydrogen are reacted under ambient conditions under atmospheric pressure in an NTP silent discharge reactor to produce ammonia. The ammonia is then further processed to produce nitrogen-based fertilizers such as anhydrous ammonia, ammonium nitrate or urea.
  • NTP non-thermal plasma
  • NTP electrically energized matter in a gaseous state which is not in thermodynamic equilibrium, with the energized matter being generated through electric discharge in a gaseous volume.
  • a simple NTP reactor may consist of two electrodes with a space (the discharge volume) and sometimes one or two insulating or dielectric layers in between and connected to a high voltage power supply.
  • dielectric discharge barrier DBD is meant a non-thermal discharge generated by the application of high voltages across small gaps wherein a non-conducting coating prevents the transition of the plasma discharge into an arc.
  • NTP The energy in NTP is thus directed preferentially to the electron-impact dissociation and ionization of the background gas to produce NTP species including electrically neutral gas molecules, charged particles in the form of positive ions, negative ions, free radicals, energetic electrons, and quanta of electromagnetic radiation (photons). These species have an energy level in the range of about 2 to 10 eV at temperature close to ambient condition.
  • the NTP reactor 100 includes a gas inlet 102, a gas outlet 104, and a packed catalyst bed 106 disposed between gas inlet 102 and gas outlet 104. The reaction occurs within the packed catalyst bed 106 as the gas flows through.
  • the NTP reactor 100 also includes dielectric barriers 112 and 114. In the reactor configuration of Figure 1, the dielectric barriers 112 and 114 are cylindrical in form with dielectric barrier 112 positioned within and spaced from dielectric barrier 114.
  • the packed bed 106 is positioned between the barriers 112 and 114. hi one example, the packed bed 106 is contained between quartz tubes 115, which act as the dielectric barriers 112 and 114.
  • the electrodes 108 and 110 are attached to the respective tubes 115 and are electrically coupled to a power source 116.
  • Power source 116 applies a voltage across electrodes 108 and 110.
  • each of the electrodes 108 and 110 is physically and electrically isolated from the gas in the flow path 112 by one of the dielectric barriers 112 and 114, respectfully.
  • Dielectric barriers 112 and 114 therefore prevent current from flowing through the packed bed 106 and thereby allow electrodes 108 and 110 to generate an electric field across packed bed 106.
  • Barriers 112 and 114 also physically isolate the gas and packed bed 106 from the electrodes 108 and 110 to help prevent corrosion of the electrodes and contamination of the gas.
  • NTP reactor 100 includes only a single dielectric barrier 112 or 114 between electrodes 108 and 110.
  • the electrode having no dielectric barrier can be in contact with the packed catalyst bed and/or the gas in the reaction chamber formed between the electrodes.
  • the "exposed" electrode can include a material that can serve as an additional reaction catalyst.
  • the electrode can include silver, copper, aluminum oxide, and/or iron, etc., which, depending on the gas being treated can function as a catalyst.
  • the reactor 150 is similar in flow path configuration to the reactor 100 of Figure 1.
  • the reactor 150 includes inner cylindrical dielectric barrier/electrode 158 and outer cylindrical dielectric barrier/electrode 160 with the inner dielectric barrier/electrode 158 (such as an electrode attached to a quartz tube) positioned within and spaced from the outer cylindrical dielectric barrier/electrode 160 (such as another electrode attached to a larger quartz tube).
  • the dielectric barrier/electrode in Figure 2 and in subsequent descriptions of other reactors are referred to as one unit for convenience's sake, but are the same or similar component wise as the dielectric barrier and electrode described with reference to Figure 1, for example.
  • Catalyst is positioned in the space between the barrier/electrodes 158 and 160 to form a packed bed 156. Again, the dielectric barriers electrically and physically isolate the respective electrodes from the gas being treated and the packed catalyst bed.
  • An inlet 152 provides an access point for the gas to flow into the packed bed, exiting the packed bed through outlet 154. Current is supplied to the electrodes of the barrier/electrode elements 158 and 160 from power source 162.
  • the reactor 170 includes a cylindrical inner electrode 172 positioned within and spaced from an outer dielectric barrier/electrode 174.
  • the inner electrode 172 includes a stainless steel tube with no dielectric barrier insulating the electrode from packed bed 178.
  • inner electrode 172 can include a dielectric barrier in alternative embodiments.
  • the inner dielectric electrode 172 is held in a spaced-apart position from the outer dielectric barrier/electrode 174 by spacers 175.
  • the inner electrode 172 extends centrally through spacers 175 and the outer dielectric barrier/electrode 174 encompasses the outer periphery of the spacers 175 thereby forming a space for a catalyst packed bed 178 to be positioned between the inner electrode 172 and the outer dielectric barrier/electrode 174 and to provide a means to hold the dielectric barrier/electrodes 172 and 174 in a spaced apart relationship.
  • the inner electrode 172 is hollow and includes an inlet 176 for gas to enter. Gas flows through the dielectric barrier/electrode 172 up to a gas-permeable section 180.
  • gas permeable section 180 can include a section of tube 172 through which a plurality of holes are formed.
  • gas permeable section 180 the gas enters the catalyst packed bed 178 for the production of ammonia.
  • Ammonia produced in the catalyst packed bed re-enters electrode tube 172 through the same gas permeable section 180 and exits the dielectric barrier/electrode tube 172 through outlet 182.
  • Current is supplied to the dielectric barrier/electrodes 172 and 174 from source 184 to produce the electric field through the packed bed 178.
  • gas permeable section 180 can include any suitable gas permeable material such as a membrane or filter.
  • gas permeable section 180 includes a porous ceramic material. Another embodiment of the NTP reactor is generally indicated at
  • the reactor 190 includes an outer cylindrical dielectric barrier/electrode 192 and an inner dielectric barrier/electrode 194 extending centrally through the outer cylindrical dielectric barrier/electrode 192.
  • inner electrode 194 can include a solid wire or hollow cylinder, for example, with or without a dielectric barrier isolating the electrode from catalyst containing packed bed 196.
  • the catalyst packed bed 196 is disposed within the outer dielectric barrier/electrode 192.
  • Power source 198 provides current to the dielectric barrier/electrodes 192 and 194 to establish an electrical field in the catalyst packed bed 196.
  • gas enters the catalyst packed bed through inlet 200 located at one end of the dielectric barrier/electrode 192 and exits the catalyst packed bed through outlet 202 positioned at an opposite end of the packed bed 196.
  • Clamping flanges 204 and 206 retain the dielectric barrier/electrodes 192 and 194 in position as described.
  • the reactor 210 includes an outer cylindrical dielectric barrier/electrode 212 and an inner hollow cylindrical dielectric barrier/electrode 214 positioned centrally within the dielectric barrier/electrode 212.
  • the inner dielectric barrier/electrode 214 is held in position by end caps 218 and 220.
  • the end cap 218 includes a gas inlet 222 which provides a flow path into the hollow inner dielectric barrier/electrode 214 and end cap 220 includes a gas outlet 224 and provides a flow path for gas to exit the hollow inner dielectric barrier/electrode 214.
  • a catalyst packed bed 226 is positioned between the outer and inner dielectric barrier/electrodes 212 and 214. Gas enters and exits the catalyst packed bed 226 through a gas permeable section 228 in the inner hollow barrier/electrode 214. Current to produce the electric field through the catalyst packed bed is supplied by power source 230.
  • the reactor 240 is made of two outer dielectric barrier/electrode plates which will be referred to for convenience's sake as upper outer plate 242 and lower outer plate 244. It should be understood that the plates may take any type of spatial orientation instead of the horizontal orientation shown in the photo and drawing and still function in the same manner.
  • the plates 242 and 244 may be oriented vertically or in any other angular position between horizontal and vertical.
  • the plates 242 and 244 are spaced from each by spacer 246 which extends continuously around the periphery of the plates 242 and 244 and has an inner section of lesser thickness 243.
  • the plates 242 and 244 each include a dielectric component and an electrode component.
  • the dielectric component physically and electrically isolate the electrode component from the reaction chamber between the electrodes.
  • a catalyst packed bed is positioned between the upper and lower plates 242 and 244 separated by section 243 into two distinct packed bed regions 247 and 249.
  • the upper plate 242 includes a gas inlet 248 and a gas outlet 250 that are positioned on opposite sides of the packed bed to define a gas flow path through the packed bed region 247.
  • the lower plate 244 includes a gas inlet 252 and gas outlet 254 that are positioned on opposite sides of the packed bed region 249 to define a gas flow path through the packed bed region 249.
  • reactors may have multiple cylindrical packed catalyst beds or have multiple plate arrangements to increase the number of catalyst packed beds.
  • the multiple packed catalyst beds can be connected in series with one another and/or in parallel with one another, for example, for increasing treatment time or flow capacity, for example.
  • Dielectric barriers in all the reactor arrangements contemplated herein may be made of a number of materials known for their dielectric properties.
  • the dielectric barriers can include any material having a suitable relative dielectric constant, hi one embodiment, preferred dielectric constants range from 3-300. The higher the relative dielectric constant the better the performance.
  • the dielectric barriers can include plastic, Teflon® (registered trademark of E. I. du Pont de Nemours and Company), glass (such as quartz), ceramic, epoxy resin, and aluminum oxide.
  • An example of a ceramic includes Strontium Titanate (SrTiO 3 ). Other electrical insulating materials can also be used.
  • Electrodes are made of conductive materials such as copper and may take various shapes generally following the shape of the dielectric material, for example.
  • the attachment (and/or relative positioning) of the electrode to the dielectric material will depend on the dielectric material used and such attachments (and/or positioning) are well known in the art. What is important is that at least one, of the electrodes 108 and 110 is physically and electrically isolated from the H 2 and N 2 gas in the catalyst packed bed by a dielectric barrier in order to prevent an electrical conduction path through the gas and/or catalyst bed.
  • the electrodes can have a variety of configurations in alternative embodiments.
  • the electrodes can be formed of thin planar sheets of conductive metal such as a copper foil or of a semiconductor. Other conductive or semi-conductive structures can also be used such a mesh, wire or strip.
  • the combination of electrodes can have a variety of different types, such as plate-to-plate, mesh-to-mesh, plate-to-wire, wire-to-wire, plate-to-mesh, and wire-to-mesh, for example.
  • the plates can be planar or cylindrical, for example.
  • the electrodes can be arranged coaxially with one another, wherein the outer electrode is tubular and the inner electrode is either tubular or a wire.
  • Power to the electrodes is supplied by any suitable high voltage power supply.
  • one of the electrodes serves as a ground electrode and the other serves as a high voltage electrode.
  • the power supply can include a pulsed direct-current (DC) or an alternating-current (AC) power supply that is capable of producing a voltage across the electrodes so as to form an electric discharge path across the catalyst packed bed. Since the electrodes have opposite polarity, an electric field is generated across the catalyst packed bed.
  • the power supply can have any suitable frequency and voltage output for achieving the desired effects. These values can be a function of desired electric field across the packed catalyst bed and the size of the gap, for example.
  • the power supply is configured to supply an output having a voltage in the range of HOV to 10OkV, such as 1000 V to 3OkV, and a frequency of 50Hz to 100 kHz. In other examples, the power supply is configured to supply an output voltage outside these ranges. In one specific embodiment, the power supply is configured to supply a standard utility line voltage of 110V at 60 Hz. Other types of power supplies can also be used, and their output voltages can have any suitable waveform, such as sinusoidal, square, or triangular.
  • plasma reactors can be used in alternative embodiments of the methods described herein.
  • the methods can be implemented with reactors such as, but not limited to, thermal plasma reactors, glow discharge reactors, pulsed electric field reactors, corona discharge reactors, etc.
  • Ruthenium has been found to be one suitable catalyst useful for this process when supported on an oxide particle (support) such as Magnesium Oxide (MgO).
  • Figure 7 illustrates ammonia yield under different comparative conditions in a bar graph format.
  • a Cs-promoted Ru catalyst on an MgO support without the use of a NTP at atmospheric pressure is well known to show no ammonia synthesis.
  • the first bar of Figure 7 shows the results of the use of an NTP reactor to promote ammonia synthesis without the use of a catalyst.
  • the yield of some ammonia suggests that the NTP provides energy to dissociate N 2 and H 2 allowing addition-reactions to form NH 3 .
  • FIG. 11 shows that ammonia yield peaks at about 24O 0 C utilizing a Cs- Ru/MgO-Ti ⁇ 2 catalyst with a volume ratio of N 2 volume to H 2 of approximately 1 :3.
  • the total flow rate through the NTP reactor was 60 ml/minute with a 5,000 v voltage and at a frequency of 10,000 Hz.
  • the effect of temperature utilizing this invention is less significant than the effect of temperature on conventional catalysis.
  • a more important observation is the non-equilibrium nature of the NTP assisted catalytic reaction. Using conventional thermal chemistry, the maximum yield of ammonia at 300 0 C is approximately 2.2% at equilibrium. Utilizing the chemistry of this invention, approximately 5.24% yield of ammonia at 300 0 C is achieved.
  • the optimal N 2 to H 2 ratio is in the range of approximately 1:3 to 1:5 as illustrated in Figure 12, in which a Cs-Ru/MgO- TiO 2 catalyst was used.
  • Figure 13 shows that the ammonia yield increased with increasing reaction time (residence time) until it reached its maximum of around approximately 12%.
  • the reaction system maintained the same activity for approximately 4 hours.
  • a 7,000 v voltage was used at a frequency of 11,000 Hz.
  • the example is intended for illustrative purposes only since numerous modifications and variations can be made to what is described in the example and still be within the scope of this invention.
  • ammonia was synthesized from H 2 and N 2 using non-thermal plasma with catalysts under atmosphere in a silent discharge type reactor.
  • the results prove that the process of this invention can produce higher concentration ammonia as a synergistic effect of plasma and catalysts.
  • the measurement OfNH 3 concentrations The NH 3 concentrations of the vent gases of ammonia synthesis were estimated by bubbling the gases in a known volume of 0.1 N H 2 SO 4 solution till the methyl orange indicator changed color from red to yellow.
  • the concentration of ammonia was calculated according to the following formula:
  • Wm 3 X*22.4(L)
  • W MIX V ⁇ + VW (Y - Z + X)*22.4 (L)
  • V H2 V N2 the beginning flow velocity of H 2 and N 2 t: the spending time of methyl orange indicator changed color from red to yellow
  • the catalysts used in this example were oxide supported ruthenium with promoters, such as Ru-CsO/MgO.
  • the preparation of catalysts was as follows: A selected amount of Ru compounds was weighed and dissolved in water. The Ru compound was impregnated with MgO under room temperature for 6 hours. The result was dried with an infrared lamp and desiccated under 120 0 C for 2 hours. The dried compound was washed with diluted ammonia, and then washed again with water until a neutral pH was reached. The result was a dry, supported Ru catalyst.
  • Ammonia was produced using the apparatus shown in the flow chart of Figure 14. Schematic diagram of the experimental apparatus: (1) nitrogen;
  • VN 2 :VH 2 1 :3, voltage 5000V, frequency 8000Hz.
  • VN 2 :VH 2 1 :3, N 2 and H 2 total flow rate 60ml/min, voltage 5000V.
  • Catalyst Ru-Cs/MgO; voltage 9000V, frequency 9000Hz; N 2 and H 2 total flow rate 60ml/min.
  • the concentration of ammonia is 2.2 V/V %.
  • the maximum concentration of ammonia was 126000 (12.6 V/V %) under H 2 45 mL/min, N 2 15mL/min, Voltage 7000V and frequency 11000 Hz with Ru catalyst.
  • the production of ammonia utilizing the NTP reactor in another embodiment is part of a system for the production of ammonia, which can be produced from local wind-hydrogen as depicted in the figure below.
  • the wind-hydrogen can be generated on wind farms, or alternatively the hydrogen may be obtained from biomass degradation.
  • the production of ammonia from such renewable hydrogen sources can reduce air emissions, thermal pollution, water consumption and dependence on petrochemical sources of hydrogen.
  • Acceptable feed stock hydrogen may be obtained through electrolysis of water.
  • Hydrogen obtained from electrolysis can be fed directly to the NTP reactor.
  • hydrogen may be obtained from biomass conversion from the methane gas being produced. Creation of hydrogen gas from methane is a well known process.

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Abstract

L'invention concerne un procédé de fabrication de l'ammoniac comprenant l'introduction de N2 et de H2 dans un plasma non thermique en présence d'un catalyseur. Le catalyseur est efficace pour favoriser la dissociation du N2 et du H2 qui est utilisée pour former de l'ammoniac.
PCT/US2008/009948 2007-08-21 2008-08-21 Synthèse d'ammoniac par plasma non thermique WO2009025835A1 (fr)

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WO2012025767A3 (fr) * 2010-08-27 2012-05-03 University Of Newcastle Upon Tyne Production d'ammoniac par des procédés intensifiés intégrés
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JP2015066468A (ja) * 2013-09-26 2015-04-13 住友化学株式会社 アンモニア合成触媒及びアンモニアの製造方法
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WO2019183646A1 (fr) * 2018-03-23 2019-09-26 Case Western Reserve University Synthèse d'ammoniac à l'aide d'électrons produits par plasma
CN110372006A (zh) * 2019-08-06 2019-10-25 湖南大学 介质阻挡放电低温等离子体协同催化剂制氨的方法及装置
CN111362278A (zh) * 2020-02-21 2020-07-03 中国科学院电工研究所 一种制备合成氨的装置及方法
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CN116351418A (zh) * 2023-04-13 2023-06-30 西安华大骄阳绿色科技有限公司 一种用于非热等离子体制氨的催化剂及其制备方法和应用

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US20130039834A1 (en) * 2010-02-26 2013-02-14 Spawnt Private S.À.R.L. Method for producing ammonia
US8871063B2 (en) 2010-06-30 2014-10-28 Casale Sa Process for selective removal of a product from a gaseous system
RU2597921C2 (ru) * 2010-06-30 2016-09-20 Касале Са Способ и реактор для селективного удаления продукта из газообразной системы
CN102958594A (zh) * 2010-06-30 2013-03-06 阿莫尼·卡萨尔公司 一种从气态体系中选择性去除产物的方法
WO2012000771A1 (fr) * 2010-06-30 2012-01-05 Ammonia Casale Sa Procédé et réacteur permettant de retirer sélectivement un produit d'un système gazeux
AU2011273749B2 (en) * 2010-06-30 2015-07-02 Casale Sa A process and a reactor for selective removal of a product from a gaseous system
US9416019B2 (en) 2010-08-27 2016-08-16 University Of Newcastle Upon Tyne Ammonia production by integrated intensified processes
AU2011294911B2 (en) * 2010-08-27 2016-02-11 University Of Newcastle Upon Tyne Ammonia production by integrated intensified processes
CN103249667A (zh) * 2010-08-27 2013-08-14 纽卡斯尔大学 利用整合强化方法的氨生产
WO2012025767A3 (fr) * 2010-08-27 2012-05-03 University Of Newcastle Upon Tyne Production d'ammoniac par des procédés intensifiés intégrés
US8978751B2 (en) 2011-03-09 2015-03-17 National Oilwell Varco, L.P. Method and apparatus for sealing a wellbore
EP2835351A4 (fr) * 2012-04-05 2015-12-09 Estrada Marcelo Acosta Équipement et procédé pour la production de gaz
EP2949625B1 (fr) * 2013-01-22 2022-09-07 Nippon Shokubai Co., Ltd. Procédé de synthèse d'ammoniac
WO2014115582A1 (fr) 2013-01-22 2014-07-31 株式会社日本触媒 Procédé de synthèse d'ammoniac et catalyseur pour la synthèse d'ammoniac
US10131545B2 (en) 2013-01-22 2018-11-20 Nippon Shokubai Co., Ltd. Ammonia synthesis method and catalyst for ammonia synthesis
JP2015066468A (ja) * 2013-09-26 2015-04-13 住友化学株式会社 アンモニア合成触媒及びアンモニアの製造方法
WO2019183646A1 (fr) * 2018-03-23 2019-09-26 Case Western Reserve University Synthèse d'ammoniac à l'aide d'électrons produits par plasma
US11679988B2 (en) 2018-03-23 2023-06-20 Case Western Reserve University Ammonia synthesis using plasma-produced electrons
WO2020176471A1 (fr) * 2019-02-25 2020-09-03 Aquaneers, Inc. Nanomatériau plasmonique catalytique
CN110372006A (zh) * 2019-08-06 2019-10-25 湖南大学 介质阻挡放电低温等离子体协同催化剂制氨的方法及装置
CN110372006B (zh) * 2019-08-06 2022-10-21 湖南大学 介质阻挡放电低温等离子体协同催化剂制氨的方法及装置
CN111362278A (zh) * 2020-02-21 2020-07-03 中国科学院电工研究所 一种制备合成氨的装置及方法
WO2021218048A1 (fr) * 2020-04-27 2021-11-04 中国华能集团清洁能源技术研究院有限公司 Système et procédé de stockage d'énergie pour coproduire de l'hydrogène et de l'urée
CN116121779A (zh) * 2023-04-04 2023-05-16 北京化工大学 一种等离子体辅助电催化合成氨装置及其合成方法
CN116351418A (zh) * 2023-04-13 2023-06-30 西安华大骄阳绿色科技有限公司 一种用于非热等离子体制氨的催化剂及其制备方法和应用

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