US20100183497A1 - System and method for ammonia synthesis - Google Patents
System and method for ammonia synthesis Download PDFInfo
- Publication number
- US20100183497A1 US20100183497A1 US12/752,018 US75201810A US2010183497A1 US 20100183497 A1 US20100183497 A1 US 20100183497A1 US 75201810 A US75201810 A US 75201810A US 2010183497 A1 US2010183497 A1 US 2010183497A1
- Authority
- US
- United States
- Prior art keywords
- nano
- catalyst particles
- sized
- ammonia
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims description 23
- 238000003786 synthesis reaction Methods 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 98
- 239000002245 particle Substances 0.000 claims abstract description 75
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 28
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 15
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 26
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000640 Fe alloy Inorganic materials 0.000 abstract description 3
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 238000009620 Haber process Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 238000005067 remediation Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- -1 Al2O3 Chemical class 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- the disclosure relates generally to the synthesis of useful chemical byproducts and, more specifically, to the synthesis of ammonia using nano-size metal catalyst particles.
- Ammonia synthesis is an important industrial process. Ammonia is produced in huge quantities worldwide, for use in the fertilizer industry, as a precursor for nitric acid and nitrates for the explosives industry, and as a raw material for various industrial chemicals.
- the Haber-Bosch process is the most widespread ammonia manufacturing process used today.
- the Haber-Bosch process was invented in the early 1900s in Germany and is fundamental to modern chemical engineering.
- the Haber-Bosch process uses an iron catalyst to improve NH 3 yields. Being a transition metal with partially occupied d-bands, iron represents a surface suitable for adsorption and dissociation of N 2 molecules.
- An example of a commonly used iron catalyst is reduced magnetite ore (Fe 3 O 4 ) enriched (“promoted”) with oxides of, for example, aluminum, potassium, calcium, magnesium, or silicon.
- ammonia is synthesized using hydrogen (H 2 ) and nitrogen (N 2 ) gases according to the net reaction (N 2 +3H 2 ⁇ 2NH 3 ).
- H 2 hydrogen
- N 2 nitrogen
- the mechanism for iron-catalyzed ammonia synthesis is stated below in four dominant reaction steps, wherein “ads” denotes a species adsorbed on the iron catalyst and “g” denotes a gas phase species:
- the rate limiting step in the conversion of nitrogen and hydrogen into ammonia has been determined to be the adsorption and dissociation of the nitrogen on the catalyst surface. Thermodynamic equilibrium of the reaction is shifted towards ammonia product by high pressure and low temperature. However, in practice, both high pressures and temperatures are used due to a sluggish reaction rate. Due to overall low reaction efficiency when hydrogen and nitrogen are first passed over the catalyst bed, most ammonia production plants utilize multiple adiabatically heated catalyst beds with cooling between beds, typically with axial or radial flow. High pressure favors the adsorption process as well, but at a cost of increased operational and capital costs.
- the Kellogg Advanced Ammonia Process was developed using a ruthenium catalyst supported on carbon.
- the KAAP catalyst is reported to be 40% more active than the traditional iron catalysts.
- Use of this catalyst allowed the reactor pressure to be reduced, but the high cost of the precious metal ruthenium catalyst and the sensitivity of the catalyst to impurities in the hydrogen feed stock have prevented widespread use for ammonia synthesis.
- Other catalysts being studied include cobalt doped with ruthenium, but few encouraging results have been exhibited to date. Thus, after almost 90 years of ammonia synthesis, the Haber-Bosch process remains the most commonly used ammonia synthesis mechanism.
- iron-based catalysts have been used in industrial ammonia synthesis.
- This catalyst is prepared by melting magnetite (Fe 3 O 4 ) with a promoter compounds, for example potassium or calcium, and solidifying. The resulting porous material is then crushed into granules, generally in the size range of 1-10 millimeters.
- Active catalyst is then produced by reduction of iron oxides with hydrogen and nitrogen gas mixture, to give porous iron, and unreduced promoter oxides. Approximately 50% of this catalyst is void volume.
- Non-ferrous metal oxides may also be incorporated into the granules.
- U.S. Pat. No. 6,716,791 describes the addition of cobalt and titanium oxides in a 0.1-3.0% weight ratio as additional promoters to aluminum, potassium, calcium, and magnesium.
- U.S. Pat. No. 3,653,831 describes the addition of platinum to improve reaction efficiency, however given the expense of platinum this may not be feasible at large scales.
- Other promoters such as cerium described in U.S. Pat. No. 3,992,328 have also been shown to increase activity.
- Other improvements include alternative catalysts, such as those described in U.S. Pat. Nos. 4,163,775 and 4,179,407. These supported catalysts include ruthenium, rhodium, lanthanides and alloys.
- the invention described herein comprises the synthesis of ammonia by providing core-shell iron/iron oxide nanoparticles on ferrous catalysts to improve catalytic activity while maintaining durability.
- systems and methods for the synthesis of ammonia are disclosed that are capable of being used in both traditional and new ammonia reactor bed designs.
- the function of the nano-size catalyst particles is improved by dispersing or separating the particles using a support material, thereby reducing or eliminating sintering of adjacent particles.
- the result are systems and methods that can operate at much lower pressures than the Haber-Bosch process and that can maintain catalysis efficiency over time.
- methods of synthesizing ammonia comprising reacting a supply of nitrogen gas and hydrogen gas in the presence of nano-sized metal catalyst particles disposed on a support material that is configured to disperse the catalyst particles, wherein the reaction proceeds at a pressure less than about 500 atm., preferably less than about 200 atm., and more preferably less than about 100 atm.
- the reaction proceeds cost effectively at pressures less than about 10 atm.
- at least a portion of the nano-sized metal catalyst particles are selected from the group consisting of iron, cobalt, ruthenium, alloys thereof, and mixtures thereof.
- at least a portion of the nano-sized metal catalyst particles comprise a metal core and an oxide shell.
- the support material comprises a porous structure.
- the support material comprises a matrix, tubes, granules, a honeycomb, or the like.
- the support material comprises magnetite or other ferrous materials, silicon nitride, silicon carbide, silicon dioxide, aluminum oxide, and/or cordierite, as examples.
- the support material is configured to separate the catalyst nano-particles.
- the support material further comprises promoter molecules located adjacent the surface of the nano-sized metal catalyst particles.
- at least a portion of the promoter molecules comprise one or more of the elements selected from the group consisting of Groups 1, 2, 6, 9, 13, 14 and the lanthanide series on the periodic table, including but not limited to aluminum, potassium, calcium, magnesium, and/or silicon.
- oxides, including core-shell oxides, of promoter material are also contemplated for promoting ammonia synthesis.
- at least some portion of the promoter comprises nano-scale material to further enhance interaction between the promoter particle and the nano-catalyst.
- the promoter particle size is about 100 nanometers or smaller, although large nanoscale particles are also suitable for enhanced promotion.
- the nanosized metal catalyst particles are disposed in a bed, with or without the support material.
- an ammonia synthesis reactor is provided, with nano-sized metal catalyst particles disposed within the reactor, wherein the catalyst particles may be disposed on a support material that is configured to disperse the catalyst particles.
- the nano-sized metal catalyst particles are selected from the group consisting of iron, cobalt, ruthenium, alloys thereof, and mixtures thereof.
- at least a portion of the nano-sized metal catalyst particles comprise a metal core and an oxide shell.
- the support material comprises a porous structure.
- the support material comprises a matrix, tubes, granules, a honeycomb, or the like.
- the support material comprises magnetite or other ferrous materials, silicon nitride, silicon carbide, silicon dioxide, aluminum oxide, or cordierite, by way of example.
- the support material is configured to separate the catalyst particles.
- the reactor further comprises at least one inlet for providing hydrogen gas and nitrogen gas to the nano-sized metal catalyst particles and at least one outlet for removing ammonia gas generated in the presence of the nano-sized metal catalyst particles.
- the reactor is configured to operate at a pressure less than about 500 atm., preferably less than about 200 atm., and more preferably less than about 100 atm.
- the reactor is a plug flow reactor, a packed bed reactor, an adiabatic reactor, or an isothermal reactor.
- the nano-sized metal catalyst particles are disposed in a packed bed within the reactor.
- the support material further comprises promoter molecules located adjacent the surface of the nano-sized metal catalyst particles. In certain embodiments, at least a portion of the promoter molecules are selected from the group consisting of aluminum, potassium, calcium, magnesium, and silicon.
- a NO x remediation system comprising a hydrogen gas supply and a nitrogen gas supply.
- the system further comprises a reactor in fluid communication with the hydrogen gas supply and the nitrogen gas supply comprising nano-sized metal catalyst particles, wherein the nano-sized metal catalyst particles are disposed on a support material that is configured to disperse the catalyst particles, and wherein the reactor is configured to generate ammonia gas at a pressure less than about 500 atm., preferably less than about 200 atm., and more preferably less than about 100 atm.
- the system further comprises an exhaust supply configured to provide a gas stream comprising NO x emissions and a selective catalytic reduction (SCR) system in fluid communication with the reactor and the exhaust supply, wherein the SCR system is configured to facilitate the reaction of the ammonia gas and the NO x emissions.
- SCR selective catalytic reduction
- FIG. 1 is a schematic of a reactor comprising a bed of nano-sized metal catalyst particles.
- FIG. 2 is an SEM of nano-sized ferrous catalyst particles with an oxide layer.
- an example system 10 comprising at least one reactor 12 .
- the reactor 12 comprises a plug flow reactor.
- One or more alternative reactors can be used instead of or in conjunction with a plug flow reactor, for example, packed bed, adiabatic, and/or iso-thermal reactors.
- one or more reactors can be connected in series.
- N 2 gas 3 and H 2 gas 5 are introduced into the at least one reactor 12 .
- the gases pass through a bed 14 of supported nano-sized metal catalyst particles disposed within the at least one reactor 12 .
- a stream of NH 3 gas 17 exits the at least one reactor 12 .
- the stream of NH 3 gas 17 can be collected in a reservoir of water (not shown) after suitable cooling, to take advantage of the extensive solubility of ammonia in water.
- the supported nano-sized metal catalyst particles are disposed on the walls of the at least one reactor 14 . In certain embodiments, the supported nano-sized metal catalyst particles are disposed within or on channels in the reactor 14 . In certain embodiments, the supported nano-sized metal catalyst particles are piled in a packed bed configuration within the reactor. Alternative configurations for arranging the supported particles within the at least one reactor 14 can also be used. As used herein, “bed” 14 is used to refer to any suitable arrangement of supported nano-sized metal catalyst particles within the at least one reactor 14 and is not intended to be limited to a packed bed configuration.
- the N 2 gas 3 and H 2 gas 5 are introduced into the at least one reactor 12 at a pressure below about 200 atm, preferably below about 100 atm, and more preferably between about 1 atm and 20 atm (e.g., between about 3 and 10 atm). Additional examples of pressures which have been demonstrated to be suitable for ammonia synthesis are about 4 atm and about 7 atm.
- the gases are heated to temperatures between about 200° C. and 600° C., and preferably between about 400° C. and 450° C.
- the gases 3 , 5 are heated before entering the bed 14 .
- the gases are heated inside the bed 14 .
- the molar ratio of N 2 gas 3 to H 2 gas 5 introduced into the reactor 12 is about 1:10, 1:5, 1:2, or 1:1.
- the molar ratio of N 2 gas 3 to H 2 gas 5 is about 1:3.
- the N 2 gas 3 can be removed from compressed air using an oxygen exclusion membrane. It is desirable to remove oxygen gas from the N 2 gas 3 feed because oxygen can reduce the efficiency of the reactions described above (e.g., by a side reaction to form water).
- the H 2 gas 5 can be obtained from reformed natural gas. In preferred embodiments, the H 2 gas 5 is provided by electrolysis of water.
- Nano-sized metal catalyst particles as used herein refer to metal nanoparticles, metal alloy nanoparticles, nanoparticles having a metal or metal alloy core and an oxide shell, or mixtures thereof.
- the particles are preferably generally spherical, as shown in FIG. 2 .
- the individual nanoparticles have a diameter less than about 50 nm, more preferably between about 15 and 25 nm, and most preferably between about 1 and 15 nm.
- These particles can be produced by vapor condensation in a vacuum chamber. A preferable vapor condensation process yielding highly uniform metal nanoparticles is described in U.S. Pat. No. 7,282,167 to Carpenter, which is hereby expressly incorporated by reference in its entirety.
- the nano-sized metal catalyst particles are disposed on a support material configured to disperse or separate the particles. It was surprisingly discovered that a reactor 12 comprising a packed bed of unsupported nano-sized metal catalyst particles nanoparticles tended to lose catalysis efficiency over time. At high temperatures, the nanoparticles sintered with adjacent nanoparticles, reducing the overall area available for reaction on the particles' surfaces. The reduction of surface area due to temperature-induced sintering resulted in a loss of catalytic activity over time.
- Suitable structures for the support material include, but are not limited to, silicon nitride, silicon carbide, silicon dioxide (silica), and aluminum oxide (alumina) matrices, granules, or tubes.
- An example of a suitable support material is silica or alumina granules about 30 microns in diameter or Si 3 N 4 microtubes.
- Another example of a suitable support material is a cordierite honeycomb.
- a porous material e.g., porous granules
- the support material can further comprise promoter molecules disposed on or near the surface of the support material that contact, and in certain embodiments, are fused to the outer surface of the catalyst particles.
- suitable promoter molecules include, but are not limited to, aluminum, potassium, calcium, magnesium, and silicon. Promoter molecules can advantageously increase the catalytic activity of nitrogen absorption and reaction with hydrogen during ammonia synthesis by facilitating electron transfer.
- the nano-sized metal catalyst particles comprise nano-sized ferrous (iron or iron alloy) catalyst particles.
- suitable metals can include cobalt, ruthenium, and alloys thereof.
- Mixtures of suitable metal catalyst particles can also be used in certain embodiments.
- certain embodiments can comprise a mixture of nano-sized iron and cobalt catalyst particles, a mixture of cobalt and ruthenium catalyst particles, a mixture of iron and ruthenium catalyst particles, or a mixture of iron, cobalt, and ruthenium catalyst particles.
- the nano-sized catalyst particles have a metal or metal oxide core and an oxide shell.
- the nano-sized ferrous catalyst particles comprise an iron or iron alloy core and an oxide shell.
- An oxide shell can advantageously provide means for stabilizing the metal or metal oxide core.
- the oxide shell has a shell thickness between about 0.5 and 25 nm, more preferably between about 0.5 and 10 nm, and most preferably between about 0.5 and 1.5 nm. Examples of nano-sized ferrous catalyst particles comprising an oxide coating thickness between about 0.5 and 1.5 nm are shown in FIG. 2 . These particles can be produced by vapor condensation in a vacuum chamber, and the oxide layer thickness can be controlled by introduction of air or oxygen into the chamber as the particles are formed.
- NO x remediation systems are provided. These systems can be integrated, for example, with internal combustion engines.
- a vehicle comprising an on-board NO x remediation system is provided.
- the NO x remediation systems disclosed herein advantageously reduce or eliminate NO x emissions from internal combustion engines by introducing ammonia or urea (which is produced by reaction of ammonia and carbon dioxide) into the exhaust stream.
- An example NO x remediation system comprises a reactor as described above. H 2 and N 2 gases are passed to the reactor, which comprises a bed of supported nano-sized metal catalyst particles. As described above, H 2 gas can be produced by an electrolyzer system. In certain embodiments in which a NO x remediation system is onboard a vehicle, the electrolyzer is powered by the vehicle's battery and/or engine alternator. N 2 gas can be obtained by processing compressed air (e.g., from the brake system) through an oxygen exclusion filter. A stream of NH 3 is produced by the reactor.
- the NH 3 stream is combined with exhaust from the internal combustion engine and directed into a selective catalytic reduction (SCR) catalyst and filter.
- SCR selective catalytic reduction
- the SCR catalyst comprises supported zeolites and nano-sized metal catalyst particles such as nano-sized vanadium or vanadium alloy catalyst particles.
- the SCR catalyst operates at a temperature between about 200° C. and 800° C. and more preferably between about 400° C. and 600° C.
- an electronic controller that uses the engine RPM and manifold pressure along with data from a NO x sensor on the exhaust of the SCR catalyst to increase or decrease the amount of current to the electrolyzer controlling the hydrogen input to the low pressure ammonia generator. The larger the amount of ammonia generated, the greater the overall NO x reduction in the exhaust stream.
- Synthesis of NH 3 was performed over a bed of nano-sized ferrous catalyst particles, manufactured using the vapor condensation process described in U.S. Pat. No. 7,282,167 to Carpenter, and supported with silicon nitride tubes.
- the nano-sized ferrous catalyst particles comprised an oxide coating between about 0.5 and 1.5 nanometer thickness. The particles had average diameters from 15 to 25 nanometers.
- the supported nano-sized ferrous catalyst particles were piled in a packed bed configuration within a plug flow reactor system. Hydrogen and nitrogen gases were introduced into to plug flow reactor system as described above at pressures between about 10 atm and 20 atm and a temperature of about 450° C.
- Nano-sized ferrous catalyst particles manufactured using the vapor condensation process described in U.S. Pat. No. 7,282,167 to Carpenter, and supported on SG9801R promoted iron from BASE.
- the nano-sized ferrous catalyst particles comprised an oxide coating between about 0.5 and 1.5 nanometer thickness rendering them air safe for mixing.
- the particles had an average diameter from 15 to 30 nanometers.
- the nano-sized iron and iron support particles were blended for 2 minutes at 20G with an acoustic mixer to distribute the nano-sized particles onto the support iron particles.
- Supported nano-sized ferrous catalyst particles were piled in a packed bed configuration within a plug flow reactor system.
- the supported nano-sized iron particles were reduced in a stream of hydrogen gas at 300° C.
- Hydrogen and nitrogen gasses were introduced into the plug flow reactor system as described above at pressures between about 5 atm and 10 atm and a temperature of 350° C. to 450° C.
- Ammonia production was quantified by bubbling the mixture of gasses flowing from the reactor through a measured amount of dilute sulfuric acid containing a phenolphthalein indicator and recording the time required to reach a pink end point.
- the experiment established the production of ammonia from hydrogen and nitrogen at vastly reduced pressures, as compared to industrial processes for ammonia synthesis, by a factor of 15 to 30.
- the kinetic rate of the adsorption and disassociation of the nitrogen and hydrogen was increased by as much as three orders of magnitude compared to conventional iron catalysts.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Dispersion Chemistry (AREA)
Abstract
Description
- This application is a continuation-in-part of U.S. patent application Ser. No. 12/418,356, filed Apr. 3, 2009, which is a continuation-in-part of U.S. patent application Ser. No. 12/266,477, filed on Nov. 6, 2008, which claims priority from Provisional Application No. 60/985,855, filed on Nov. 6, 2007, the entire contents of each of which are hereby incorporated by this express reference.
- 1. Technical Field
- The disclosure relates generally to the synthesis of useful chemical byproducts and, more specifically, to the synthesis of ammonia using nano-size metal catalyst particles.
- 2. Related Art
- Ammonia synthesis is an important industrial process. Ammonia is produced in huge quantities worldwide, for use in the fertilizer industry, as a precursor for nitric acid and nitrates for the explosives industry, and as a raw material for various industrial chemicals.
- Despite an energy production cost of about 35 to 50 GJ per ton of ammonia, the Haber-Bosch process is the most widespread ammonia manufacturing process used today. The Haber-Bosch process was invented in the early 1900s in Germany and is fundamental to modern chemical engineering.
- The Haber-Bosch process uses an iron catalyst to improve NH3 yields. Being a transition metal with partially occupied d-bands, iron represents a surface suitable for adsorption and dissociation of N2 molecules. An example of a commonly used iron catalyst is reduced magnetite ore (Fe3O4) enriched (“promoted”) with oxides of, for example, aluminum, potassium, calcium, magnesium, or silicon.
- In the Haber-Bosch process, ammonia is synthesized using hydrogen (H2) and nitrogen (N2) gases according to the net reaction (N2+3H2→2NH3). The mechanism for iron-catalyzed ammonia synthesis is stated below in four dominant reaction steps, wherein “ads” denotes a species adsorbed on the iron catalyst and “g” denotes a gas phase species:
-
N2(ads)→2N(ads) (1) -
H2(ads)→2H(ads) (2) -
N(ads)+3H(ads)→NH3(ads) (3) -
NH3(ads)→NH3(g) (4) - The rate limiting step in the conversion of nitrogen and hydrogen into ammonia has been determined to be the adsorption and dissociation of the nitrogen on the catalyst surface. Thermodynamic equilibrium of the reaction is shifted towards ammonia product by high pressure and low temperature. However, in practice, both high pressures and temperatures are used due to a sluggish reaction rate. Due to overall low reaction efficiency when hydrogen and nitrogen are first passed over the catalyst bed, most ammonia production plants utilize multiple adiabatically heated catalyst beds with cooling between beds, typically with axial or radial flow. High pressure favors the adsorption process as well, but at a cost of increased operational and capital costs.
- At pressures above 750 atm, there is an almost 100% conversion of reactants to the ammonia product. Because there are difficulties associated with containing larger amounts of materials at this high pressure, lower pressures of about 150 to 250 atm are used industrially. By using a pressure of around 200 atm and a temperature of about 500° C., the yield of ammonia is about 10 to 20%, while costs and safety concerns in the plant and during operation of the plant are minimized. Nevertheless, due in part to high pressures used in the process, ammonia production requires reactors with heavily-reinforced walls, piping and fittings, as well as a series of powerful compressors, all with high capital cost. In addition, generation of those high pressures during plant operation requires a large expenditure in energy.
- In an effort to reduce the energy requirements of this process, the Kellogg Advanced Ammonia Process (KAAP) was developed using a ruthenium catalyst supported on carbon. The KAAP catalyst is reported to be 40% more active than the traditional iron catalysts. Use of this catalyst allowed the reactor pressure to be reduced, but the high cost of the precious metal ruthenium catalyst and the sensitivity of the catalyst to impurities in the hydrogen feed stock have prevented widespread use for ammonia synthesis. Other catalysts being studied include cobalt doped with ruthenium, but few encouraging results have been exhibited to date. Thus, after almost 90 years of ammonia synthesis, the Haber-Bosch process remains the most commonly used ammonia synthesis mechanism.
- For the last 100 years, iron-based catalysts have been used in industrial ammonia synthesis. This catalyst is prepared by melting magnetite (Fe3O4) with a promoter compounds, for example potassium or calcium, and solidifying. The resulting porous material is then crushed into granules, generally in the size range of 1-10 millimeters. Active catalyst is then produced by reduction of iron oxides with hydrogen and nitrogen gas mixture, to give porous iron, and unreduced promoter oxides. Approximately 50% of this catalyst is void volume.
- Improvements to Haber-Bosch catalysts focus on the addition of promoters for improved activity ammonia synthesis. U.S. Pat. Nos. 4,789,657 and 3,951,862 describe processes of preparing a magnetite-based ammonia synthesis catalyst via the melting of iron oxide with other compounds, such as Al2O3, K2O, CaO, MgO, and SiO2, and grinding into granules. U.S. Pat. No. 5,846,507 describes an iron composition having a non-stoichiometric oxide content and additional promoters, prepared by melting. Suggestions of reducing the processing pressures have been made, but have not been achieved economically.
- Non-ferrous metal oxides may also be incorporated into the granules. For example, U.S. Pat. No. 6,716,791 describes the addition of cobalt and titanium oxides in a 0.1-3.0% weight ratio as additional promoters to aluminum, potassium, calcium, and magnesium. U.S. Pat. No. 3,653,831 describes the addition of platinum to improve reaction efficiency, however given the expense of platinum this may not be feasible at large scales. Other promoters, such as cerium described in U.S. Pat. No. 3,992,328 have also been shown to increase activity. Other improvements include alternative catalysts, such as those described in U.S. Pat. Nos. 4,163,775 and 4,179,407. These supported catalysts include ruthenium, rhodium, lanthanides and alloys.
- Ideally, highly active ammonia catalysts can be used without significant changes to the many existing ammonia plants that exist today; the best candidates would be a “drop in” solution for existing manufacturers. Retrofit and reconstruction of these plants could be costly should there be a need to change design based on catalyst properties, such as space velocity. The best candidate catalyst would exhibit increased activity, have similar basic properties as compared to existing catalysts, and reduce operating costs. Non-ferrous catalysts in the above referenced prior art do not overcome all of these constraints because 1) catalyst cost increases more than catalyst efficiency, 2) the catalyst may not have the same properties that allow for seamless operation in existing ammonia production plants, or 3) the catalyst may have high activity but do not meet long term durability requirements.
- The invention described herein comprises the synthesis of ammonia by providing core-shell iron/iron oxide nanoparticles on ferrous catalysts to improve catalytic activity while maintaining durability. In various embodiments herein, systems and methods for the synthesis of ammonia are disclosed that are capable of being used in both traditional and new ammonia reactor bed designs. The function of the nano-size catalyst particles is improved by dispersing or separating the particles using a support material, thereby reducing or eliminating sintering of adjacent particles. The result are systems and methods that can operate at much lower pressures than the Haber-Bosch process and that can maintain catalysis efficiency over time.
- In at least one embodiment of the present invention, methods of synthesizing ammonia are provided comprising reacting a supply of nitrogen gas and hydrogen gas in the presence of nano-sized metal catalyst particles disposed on a support material that is configured to disperse the catalyst particles, wherein the reaction proceeds at a pressure less than about 500 atm., preferably less than about 200 atm., and more preferably less than about 100 atm.
- In certain embodiments and applications, the reaction proceeds cost effectively at pressures less than about 10 atm. In certain embodiments of the inventive methods, at least a portion of the nano-sized metal catalyst particles are selected from the group consisting of iron, cobalt, ruthenium, alloys thereof, and mixtures thereof. In certain embodiments, at least a portion of the nano-sized metal catalyst particles comprise a metal core and an oxide shell. In certain embodiments, the support material comprises a porous structure. In certain embodiments, the support material comprises a matrix, tubes, granules, a honeycomb, or the like. In certain embodiments, the support material comprises magnetite or other ferrous materials, silicon nitride, silicon carbide, silicon dioxide, aluminum oxide, and/or cordierite, as examples. In certain embodiments, the support material is configured to separate the catalyst nano-particles. In certain embodiments, the support material further comprises promoter molecules located adjacent the surface of the nano-sized metal catalyst particles. In certain embodiments, at least a portion of the promoter molecules comprise one or more of the elements selected from the group consisting of
Groups 1, 2, 6, 9, 13, 14 and the lanthanide series on the periodic table, including but not limited to aluminum, potassium, calcium, magnesium, and/or silicon. It should also be recognized that oxides, including core-shell oxides, of promoter material are also contemplated for promoting ammonia synthesis. In one embodiment, at least some portion of the promoter comprises nano-scale material to further enhance interaction between the promoter particle and the nano-catalyst. Preferably, the promoter particle size is about 100 nanometers or smaller, although large nanoscale particles are also suitable for enhanced promotion. In certain embodiments, the nanosized metal catalyst particles are disposed in a bed, with or without the support material. - In at least one embodiment of the present invention, an ammonia synthesis reactor is provided, with nano-sized metal catalyst particles disposed within the reactor, wherein the catalyst particles may be disposed on a support material that is configured to disperse the catalyst particles. In certain embodiments of the reactor, at least a portion of the nano-sized metal catalyst particles are selected from the group consisting of iron, cobalt, ruthenium, alloys thereof, and mixtures thereof. In certain embodiments, at least a portion of the nano-sized metal catalyst particles comprise a metal core and an oxide shell. In certain embodiments, the support material comprises a porous structure. In certain embodiments, the support material comprises a matrix, tubes, granules, a honeycomb, or the like. In certain embodiments, the support material comprises magnetite or other ferrous materials, silicon nitride, silicon carbide, silicon dioxide, aluminum oxide, or cordierite, by way of example. In certain embodiments, the support material is configured to separate the catalyst particles.
- The reactor further comprises at least one inlet for providing hydrogen gas and nitrogen gas to the nano-sized metal catalyst particles and at least one outlet for removing ammonia gas generated in the presence of the nano-sized metal catalyst particles. The reactor is configured to operate at a pressure less than about 500 atm., preferably less than about 200 atm., and more preferably less than about 100 atm. In certain embodiments, the reactor is a plug flow reactor, a packed bed reactor, an adiabatic reactor, or an isothermal reactor. In certain embodiments, the nano-sized metal catalyst particles are disposed in a packed bed within the reactor. In certain embodiments, the support material further comprises promoter molecules located adjacent the surface of the nano-sized metal catalyst particles. In certain embodiments, at least a portion of the promoter molecules are selected from the group consisting of aluminum, potassium, calcium, magnesium, and silicon.
- In at least one embodiment of the present invention, a NOx remediation system is provided that comprises a hydrogen gas supply and a nitrogen gas supply. The system further comprises a reactor in fluid communication with the hydrogen gas supply and the nitrogen gas supply comprising nano-sized metal catalyst particles, wherein the nano-sized metal catalyst particles are disposed on a support material that is configured to disperse the catalyst particles, and wherein the reactor is configured to generate ammonia gas at a pressure less than about 500 atm., preferably less than about 200 atm., and more preferably less than about 100 atm. The system further comprises an exhaust supply configured to provide a gas stream comprising NOx emissions and a selective catalytic reduction (SCR) system in fluid communication with the reactor and the exhaust supply, wherein the SCR system is configured to facilitate the reaction of the ammonia gas and the NOx emissions.
-
FIG. 1 is a schematic of a reactor comprising a bed of nano-sized metal catalyst particles. -
FIG. 2 is an SEM of nano-sized ferrous catalyst particles with an oxide layer. - The features mentioned above in the summary, along with other features of the inventions disclosed herein, are described below with reference to the drawings. The illustrated embodiments in the figures listed below are intended to illustrate, but not to limit, the inventions.
- In various embodiments, systems and methods of ammonia production are provided. Referring first
FIG. 1 , anexample system 10 is shown comprising at least onereactor 12. In preferred embodiments, thereactor 12 comprises a plug flow reactor. One or more alternative reactors can be used instead of or in conjunction with a plug flow reactor, for example, packed bed, adiabatic, and/or iso-thermal reactors. As an example, one or more reactors can be connected in series. - N2 gas 3 and H2 gas 5 are introduced into the at least one
reactor 12. The gases pass through abed 14 of supported nano-sized metal catalyst particles disposed within the at least onereactor 12. A stream of NH3 gas 17 exits the at least onereactor 12. In certain embodiments, the stream of NH3 gas 17 can be collected in a reservoir of water (not shown) after suitable cooling, to take advantage of the extensive solubility of ammonia in water. - In certain embodiments, the supported nano-sized metal catalyst particles are disposed on the walls of the at least one
reactor 14. In certain embodiments, the supported nano-sized metal catalyst particles are disposed within or on channels in thereactor 14. In certain embodiments, the supported nano-sized metal catalyst particles are piled in a packed bed configuration within the reactor. Alternative configurations for arranging the supported particles within the at least onereactor 14 can also be used. As used herein, “bed” 14 is used to refer to any suitable arrangement of supported nano-sized metal catalyst particles within the at least onereactor 14 and is not intended to be limited to a packed bed configuration. - The N2 gas 3 and H2 gas 5 are introduced into the at least one
reactor 12 at a pressure below about 200 atm, preferably below about 100 atm, and more preferably between about 1 atm and 20 atm (e.g., between about 3 and 10 atm). Additional examples of pressures which have been demonstrated to be suitable for ammonia synthesis are about 4 atm and about 7 atm. In certain embodiments, the gases are heated to temperatures between about 200° C. and 600° C., and preferably between about 400° C. and 450° C. In certain embodiments, thegases bed 14. In certain embodiments, the gases are heated inside thebed 14. In certain embodiments, the molar ratio of N2 gas 3 to H2 gas 5 introduced into thereactor 12 is about 1:10, 1:5, 1:2, or 1:1. Preferably, the molar ratio of N2 gas 3 to H2 gas 5 is about 1:3. - In certain embodiments, the N2 gas 3 can be removed from compressed air using an oxygen exclusion membrane. It is desirable to remove oxygen gas from the N2 gas 3 feed because oxygen can reduce the efficiency of the reactions described above (e.g., by a side reaction to form water). In certain embodiments, the H2 gas 5 can be obtained from reformed natural gas. In preferred embodiments, the H2 gas 5 is provided by electrolysis of water.
- Nano-sized metal catalyst particles as used herein refer to metal nanoparticles, metal alloy nanoparticles, nanoparticles having a metal or metal alloy core and an oxide shell, or mixtures thereof. The particles are preferably generally spherical, as shown in
FIG. 2 . Preferably the individual nanoparticles have a diameter less than about 50 nm, more preferably between about 15 and 25 nm, and most preferably between about 1 and 15 nm. These particles can be produced by vapor condensation in a vacuum chamber. A preferable vapor condensation process yielding highly uniform metal nanoparticles is described in U.S. Pat. No. 7,282,167 to Carpenter, which is hereby expressly incorporated by reference in its entirety. - The nano-sized metal catalyst particles are disposed on a support material configured to disperse or separate the particles. It was surprisingly discovered that a
reactor 12 comprising a packed bed of unsupported nano-sized metal catalyst particles nanoparticles tended to lose catalysis efficiency over time. At high temperatures, the nanoparticles sintered with adjacent nanoparticles, reducing the overall area available for reaction on the particles' surfaces. The reduction of surface area due to temperature-induced sintering resulted in a loss of catalytic activity over time. - Experiments confirmed that sintering could be minimized and catalysis efficiency could be maintained by disposing the nano-sized metal catalyst particles on a support material, thereby dispersing or separating adjacent nanoparticles. Suitable structures for the support material include, but are not limited to, silicon nitride, silicon carbide, silicon dioxide (silica), and aluminum oxide (alumina) matrices, granules, or tubes. An example of a suitable support material is silica or alumina granules about 30 microns in diameter or Si3N4 microtubes. Another example of a suitable support material is a cordierite honeycomb. In certain embodiments, a porous material (e.g., porous granules) can be used.
- In certain embodiments, the support material can further comprise promoter molecules disposed on or near the surface of the support material that contact, and in certain embodiments, are fused to the outer surface of the catalyst particles. Examples of suitable promoter molecules include, but are not limited to, aluminum, potassium, calcium, magnesium, and silicon. Promoter molecules can advantageously increase the catalytic activity of nitrogen absorption and reaction with hydrogen during ammonia synthesis by facilitating electron transfer.
- In preferred embodiments, the nano-sized metal catalyst particles comprise nano-sized ferrous (iron or iron alloy) catalyst particles. Other suitable metals can include cobalt, ruthenium, and alloys thereof. Mixtures of suitable metal catalyst particles can also be used in certain embodiments. For example, certain embodiments can comprise a mixture of nano-sized iron and cobalt catalyst particles, a mixture of cobalt and ruthenium catalyst particles, a mixture of iron and ruthenium catalyst particles, or a mixture of iron, cobalt, and ruthenium catalyst particles.
- As described above, in certain embodiments, at least a portion of the nano-sized catalyst particles have a metal or metal oxide core and an oxide shell. In preferred embodiments, the nano-sized ferrous catalyst particles comprise an iron or iron alloy core and an oxide shell. An oxide shell can advantageously provide means for stabilizing the metal or metal oxide core. Preferably, the oxide shell has a shell thickness between about 0.5 and 25 nm, more preferably between about 0.5 and 10 nm, and most preferably between about 0.5 and 1.5 nm. Examples of nano-sized ferrous catalyst particles comprising an oxide coating thickness between about 0.5 and 1.5 nm are shown in
FIG. 2 . These particles can be produced by vapor condensation in a vacuum chamber, and the oxide layer thickness can be controlled by introduction of air or oxygen into the chamber as the particles are formed. - In certain embodiments, NOx remediation systems are provided. These systems can be integrated, for example, with internal combustion engines. In at least one embodiment, a vehicle comprising an on-board NOx remediation system is provided. The NOx remediation systems disclosed herein advantageously reduce or eliminate NOx emissions from internal combustion engines by introducing ammonia or urea (which is produced by reaction of ammonia and carbon dioxide) into the exhaust stream.
- An example NOx remediation system comprises a reactor as described above. H2 and N2 gases are passed to the reactor, which comprises a bed of supported nano-sized metal catalyst particles. As described above, H2 gas can be produced by an electrolyzer system. In certain embodiments in which a NOx remediation system is onboard a vehicle, the electrolyzer is powered by the vehicle's battery and/or engine alternator. N2 gas can be obtained by processing compressed air (e.g., from the brake system) through an oxygen exclusion filter. A stream of NH3 is produced by the reactor.
- The NH3 stream is combined with exhaust from the internal combustion engine and directed into a selective catalytic reduction (SCR) catalyst and filter. Preferably, the SCR catalyst comprises supported zeolites and nano-sized metal catalyst particles such as nano-sized vanadium or vanadium alloy catalyst particles. In certain embodiments, the SCR catalyst operates at a temperature between about 200° C. and 800° C. and more preferably between about 400° C. and 600° C.
- To determine how much NH3 is required for NOx reduction, in certain embodiments there is provided an electronic controller that uses the engine RPM and manifold pressure along with data from a NOx sensor on the exhaust of the SCR catalyst to increase or decrease the amount of current to the electrolyzer controlling the hydrogen input to the low pressure ammonia generator. The larger the amount of ammonia generated, the greater the overall NOx reduction in the exhaust stream.
- Synthesis of NH3 was performed over a bed of nano-sized ferrous catalyst particles, manufactured using the vapor condensation process described in U.S. Pat. No. 7,282,167 to Carpenter, and supported with silicon nitride tubes. The nano-sized ferrous catalyst particles comprised an oxide coating between about 0.5 and 1.5 nanometer thickness. The particles had average diameters from 15 to 25 nanometers.
- The supported nano-sized ferrous catalyst particles were piled in a packed bed configuration within a plug flow reactor system. Hydrogen and nitrogen gases were introduced into to plug flow reactor system as described above at pressures between about 10 atm and 20 atm and a temperature of about 450° C.
- Ammonia was detected and alkalinity tests conducted with pH paper yielded a pH of 11, typical of ammoniacal solutions in water. The experiment established the production of ammonia from hydrogen and nitrogen at vastly reduced pressures, as compared to industrial processes for ammonia synthesis, by a factor of 15 to 30. The kinetic rate of the adsorption and disassociation of the nitrogen and hydrogen was increased by as much as three orders of magnitude.
- Synthesis of ammonia was performed over a bed of nano-sized ferrous catalyst particles, manufactured using the vapor condensation process described in U.S. Pat. No. 7,282,167 to Carpenter, and supported on SG9801R promoted iron from BASE. The nano-sized ferrous catalyst particles comprised an oxide coating between about 0.5 and 1.5 nanometer thickness rendering them air safe for mixing. The particles had an average diameter from 15 to 30 nanometers. The nano-sized iron and iron support particles were blended for 2 minutes at 20G with an acoustic mixer to distribute the nano-sized particles onto the support iron particles.
- Supported nano-sized ferrous catalyst particles were piled in a packed bed configuration within a plug flow reactor system. The supported nano-sized iron particles were reduced in a stream of hydrogen gas at 300° C. Hydrogen and nitrogen gasses were introduced into the plug flow reactor system as described above at pressures between about 5 atm and 10 atm and a temperature of 350° C. to 450° C.
- Ammonia production was quantified by bubbling the mixture of gasses flowing from the reactor through a measured amount of dilute sulfuric acid containing a phenolphthalein indicator and recording the time required to reach a pink end point. The experiment established the production of ammonia from hydrogen and nitrogen at vastly reduced pressures, as compared to industrial processes for ammonia synthesis, by a factor of 15 to 30. The kinetic rate of the adsorption and disassociation of the nitrogen and hydrogen was increased by as much as three orders of magnitude compared to conventional iron catalysts.
- The foregoing description is that of preferred embodiments having certain features, aspects, and advantages. Various changes and modifications also may be made to the above-described embodiments without departing from the spirit and scope of the inventions. For example, it is contemplated that nano-sized materials made from processes other than the ones described in U.S. Pat. No. 7,282,167 to Carpenter would still achieve some or all of the advantages described above or inherent herein, including cost effective ammonia synthesis. It is also contemplated that pressures well below prior art conventional processing of 200 atmospheres can be achieved using the inventive process herein.
Claims (6)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/752,018 US20100183497A1 (en) | 2007-11-06 | 2010-03-31 | System and method for ammonia synthesis |
US13/050,823 US20110165055A1 (en) | 2007-11-06 | 2011-03-17 | System and method for ammonia synthesis |
US13/326,135 US20120082612A1 (en) | 2007-11-06 | 2011-12-14 | System and method for ammonia synthesis |
US13/585,640 US20120308467A1 (en) | 2007-11-06 | 2012-08-14 | System and method for ammonia synthesis |
US14/085,500 US9272920B2 (en) | 2007-11-06 | 2013-11-20 | System and method for ammonia synthesis |
US15/055,401 US20160175816A1 (en) | 2007-11-06 | 2016-02-26 | System and method for ammonia synthesis |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US98585507P | 2007-11-06 | 2007-11-06 | |
US12/266,477 US20090117014A1 (en) | 2007-11-06 | 2008-11-06 | System and method for ammonia synthesis |
US12/418,356 US20090202417A1 (en) | 2007-11-06 | 2009-04-03 | System and method for ammonia synthesis |
US12/752,018 US20100183497A1 (en) | 2007-11-06 | 2010-03-31 | System and method for ammonia synthesis |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/418,356 Continuation-In-Part US20090202417A1 (en) | 2007-11-06 | 2009-04-03 | System and method for ammonia synthesis |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/050,823 Continuation US20110165055A1 (en) | 2007-11-06 | 2011-03-17 | System and method for ammonia synthesis |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100183497A1 true US20100183497A1 (en) | 2010-07-22 |
Family
ID=42337108
Family Applications (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/752,018 Abandoned US20100183497A1 (en) | 2007-11-06 | 2010-03-31 | System and method for ammonia synthesis |
US13/050,823 Abandoned US20110165055A1 (en) | 2007-11-06 | 2011-03-17 | System and method for ammonia synthesis |
US13/326,135 Abandoned US20120082612A1 (en) | 2007-11-06 | 2011-12-14 | System and method for ammonia synthesis |
US13/585,640 Abandoned US20120308467A1 (en) | 2007-11-06 | 2012-08-14 | System and method for ammonia synthesis |
US14/085,500 Active 2028-11-07 US9272920B2 (en) | 2007-11-06 | 2013-11-20 | System and method for ammonia synthesis |
US15/055,401 Abandoned US20160175816A1 (en) | 2007-11-06 | 2016-02-26 | System and method for ammonia synthesis |
Family Applications After (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/050,823 Abandoned US20110165055A1 (en) | 2007-11-06 | 2011-03-17 | System and method for ammonia synthesis |
US13/326,135 Abandoned US20120082612A1 (en) | 2007-11-06 | 2011-12-14 | System and method for ammonia synthesis |
US13/585,640 Abandoned US20120308467A1 (en) | 2007-11-06 | 2012-08-14 | System and method for ammonia synthesis |
US14/085,500 Active 2028-11-07 US9272920B2 (en) | 2007-11-06 | 2013-11-20 | System and method for ammonia synthesis |
US15/055,401 Abandoned US20160175816A1 (en) | 2007-11-06 | 2016-02-26 | System and method for ammonia synthesis |
Country Status (1)
Country | Link |
---|---|
US (6) | US20100183497A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090117014A1 (en) * | 2007-11-06 | 2009-05-07 | Quantumsphere, Inc. | System and method for ammonia synthesis |
US20090202417A1 (en) * | 2007-11-06 | 2009-08-13 | Quantumsphere, Inc. | System and method for ammonia synthesis |
CN103717647A (en) * | 2011-08-05 | 2014-04-09 | 国立大学法人京都大学 | Metal nanoparticle-PCP complex and manufacturing method therefor |
CN105413755A (en) * | 2015-11-12 | 2016-03-23 | 河南中宏清洁能源股份有限公司 | Nanometer material modified nanometer synthetic ammonia catalyst |
US20180238219A1 (en) * | 2017-02-17 | 2018-08-23 | Ford Global Technologies, Llc | Methods and systems for an exhaust gas aftertreatment device |
CN113332983A (en) * | 2021-04-29 | 2021-09-03 | 杭州师范大学 | Porous rod-shaped Fe21.34O32Preparation method of/C nanorod composite material |
WO2023114890A1 (en) * | 2021-12-17 | 2023-06-22 | Remo Energy, Inc. | Systems and methods for producing renewable ammonia |
WO2024019244A1 (en) * | 2022-07-22 | 2024-01-25 | 울산과학기술원 | Nh3 preparation apparatus and nh3 synthesis method |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2150971B1 (en) | 2007-05-11 | 2018-11-28 | Umicore AG & Co. KG | Method and apparatus for making uniform and ultrasmall nanoparticles |
US8575059B1 (en) | 2007-10-15 | 2013-11-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
US9149797B2 (en) | 2009-12-15 | 2015-10-06 | SDCmaterials, Inc. | Catalyst production method and system |
US9126191B2 (en) | 2009-12-15 | 2015-09-08 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
US8557727B2 (en) | 2009-12-15 | 2013-10-15 | SDCmaterials, Inc. | Method of forming a catalyst with inhibited mobility of nano-active material |
US9119309B1 (en) | 2009-12-15 | 2015-08-25 | SDCmaterials, Inc. | In situ oxide removal, dispersal and drying |
US8803025B2 (en) | 2009-12-15 | 2014-08-12 | SDCmaterials, Inc. | Non-plugging D.C. plasma gun |
US8652992B2 (en) | 2009-12-15 | 2014-02-18 | SDCmaterials, Inc. | Pinning and affixing nano-active material |
US8669202B2 (en) | 2011-02-23 | 2014-03-11 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PtPd catalysts |
MX2014001718A (en) * | 2011-08-19 | 2014-03-26 | Sdcmaterials Inc | Coated substrates for use in catalysis and catalytic converters and methods of coating substrates with washcoat compositions. |
US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
US9586179B2 (en) | 2013-07-25 | 2017-03-07 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters and methods of making and using same |
US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
CA2926133A1 (en) | 2013-10-22 | 2015-04-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
EP3119500A4 (en) | 2014-03-21 | 2017-12-13 | SDC Materials, Inc. | Compositions for passive nox adsorption (pna) systems |
WO2015164730A1 (en) * | 2014-04-25 | 2015-10-29 | The George Washington University | Process for the production of ammonia from air and water |
WO2016010969A1 (en) | 2014-07-14 | 2016-01-21 | Empire Technology Development Llc | Methods and systems for isolating nitrogen from a gaseous mixture |
US20170210632A1 (en) * | 2014-07-14 | 2017-07-27 | Empire Technology Development Llc | Methods and systems for producing ammonia |
DK3423407T3 (en) * | 2016-03-01 | 2022-09-12 | Starfire Energy | ELECTRICALLY ENHANCED HABER-BOSCH (EEHB) ANHYDROUS AMMONIA SYNTHESIS |
CN106799232B (en) * | 2016-12-15 | 2019-08-06 | 浙江工业大学 | A kind of iron based ammonia synthesis catalyst and its preparation method and application of the Nanoscale Iron modification of solid state chemical reaction preparation |
CN116637616A (en) | 2017-05-15 | 2023-08-25 | 星火能源 | Method for preparing catalyst carrier material |
US10787367B2 (en) | 2017-05-26 | 2020-09-29 | Starfire Energy | Removal of gaseous NH3 from an NH3 reactor product stream |
WO2019193594A1 (en) * | 2018-04-02 | 2019-10-10 | Ariel Scientific Innovations Ltd. | Electrocatalysts, the preparation thereof, and using the same for ammonia synthesis |
WO2020047109A1 (en) | 2018-08-28 | 2020-03-05 | Vivakor, Inc. | System and method for using a flash evaporator to separate bitumen and hydrocarbon condensate |
WO2020055385A1 (en) * | 2018-09-11 | 2020-03-19 | West Virginia University | Methods and compositions for microwave catalytic ammonia synthesis |
US10974969B2 (en) * | 2018-09-11 | 2021-04-13 | West Virginia University | Methods and compositions for microwave catalytic ammonia synthesis |
US20210238048A1 (en) * | 2018-10-30 | 2021-08-05 | West Virginia University | Methods and compositions for direct, simultaneous conversion of nitrogen and natural gas to value-added compounds |
EP3917668A4 (en) | 2019-01-31 | 2022-11-23 | Starfire Energy | Metal-decorated barium calcium aluminum oxide catalyst for nh3 synthesis and cracking and methods of forming the same |
WO2021041201A2 (en) * | 2019-08-23 | 2021-03-04 | Basf Corp. | Catalyst compositions and methods of preparation and use thereof |
KR102321424B1 (en) * | 2020-06-30 | 2021-11-03 | 울산과학기술원 | Mechanochemical ammonia synthesis method |
US20220388855A1 (en) * | 2021-06-07 | 2022-12-08 | FuelPositive Corporation | Modular, transportable clean hydrogen-ammonia maker |
Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3653831A (en) * | 1968-10-04 | 1972-04-04 | Chevron Res | Ammonia synthesis catalyst |
US3951862A (en) * | 1974-10-30 | 1976-04-20 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst |
US3992328A (en) * | 1974-10-30 | 1976-11-16 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process |
US4163775A (en) * | 1976-11-03 | 1979-08-07 | The British Petroleum Company Limited | Process for the synthesis of ammonia using catalysts supported on graphite containing carbon |
US4179407A (en) * | 1976-02-20 | 1979-12-18 | Ricoh Co., Ltd. | Catalyst bed for use in decomposition of ammonia gas |
US4235749A (en) * | 1979-09-17 | 1980-11-25 | Indianapolis Center For Advanced Research | Ammonia synthesis catalysts and process of making and using them |
US4623532A (en) * | 1977-05-20 | 1986-11-18 | University Of South Carolina | Catalysts for synthesis of ammonia |
US4698325A (en) * | 1985-04-22 | 1987-10-06 | Imperial Chemical Industries Plc | Catalysts for ammonia synthesis |
US4789657A (en) * | 1984-06-19 | 1988-12-06 | Fertimont S.P.A. | Process for preparing iron-based catalysts for the synthesis of ammonia and catalysts so obtained |
US4822586A (en) * | 1987-01-30 | 1989-04-18 | Shannahan Cornelius E | Ammonia synthesis method |
US5032364A (en) * | 1984-04-25 | 1991-07-16 | Imperial Chemical Industries, Plc | Ammonia synthesis plant |
US5846507A (en) * | 1994-05-26 | 1998-12-08 | Zhejiang University Of Technology | Fe1-x O-based catalyst for ammonia synthesis |
US6531704B2 (en) * | 1998-09-14 | 2003-03-11 | Nanoproducts Corporation | Nanotechnology for engineering the performance of substances |
US6716791B1 (en) * | 1998-03-13 | 2004-04-06 | Norsk Hydro Asa | Catalyst for the synthesis of ammonia from hydrogen and nitrogen |
US6716525B1 (en) * | 1998-11-06 | 2004-04-06 | Tapesh Yadav | Nano-dispersed catalysts particles |
US20050103990A1 (en) * | 2001-11-23 | 2005-05-19 | Cuong Pham-Huu | Composites based on carbon nanotubes or nanofibers deposited on an activated support for use in catalysis |
US20060039847A1 (en) * | 2004-08-23 | 2006-02-23 | Eaton Corporation | Low pressure ammonia synthesis utilizing adsorptive enhancement |
US20060099131A1 (en) * | 2004-11-03 | 2006-05-11 | Kellogg Brown And Root, Inc. | Maximum reaction rate converter system for exothermic reactions |
US7078130B2 (en) * | 2002-10-17 | 2006-07-18 | University Of Windsor | Metallic mesoporous transition metal oxide molecular sieves, room temperature activation of dinitrogen and ammonia production |
US7282167B2 (en) * | 2003-12-15 | 2007-10-16 | Quantumsphere, Inc. | Method and apparatus for forming nano-particles |
US20080161428A1 (en) * | 2004-07-02 | 2008-07-03 | Strait Richard B | Pseudoisothermal ammonia process |
US20090117014A1 (en) * | 2007-11-06 | 2009-05-07 | Quantumsphere, Inc. | System and method for ammonia synthesis |
US20090202417A1 (en) * | 2007-11-06 | 2009-08-13 | Quantumsphere, Inc. | System and method for ammonia synthesis |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2114461A (en) * | 1982-02-11 | 1983-08-24 | Johnson Matthey Plc | Ferreous catalyst system for ammonia synthesis |
US7029514B1 (en) * | 2003-03-17 | 2006-04-18 | University Of Rochester | Core-shell magnetic nanoparticles and nanocomposite materials formed therefrom |
-
2010
- 2010-03-31 US US12/752,018 patent/US20100183497A1/en not_active Abandoned
-
2011
- 2011-03-17 US US13/050,823 patent/US20110165055A1/en not_active Abandoned
- 2011-12-14 US US13/326,135 patent/US20120082612A1/en not_active Abandoned
-
2012
- 2012-08-14 US US13/585,640 patent/US20120308467A1/en not_active Abandoned
-
2013
- 2013-11-20 US US14/085,500 patent/US9272920B2/en active Active
-
2016
- 2016-02-26 US US15/055,401 patent/US20160175816A1/en not_active Abandoned
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3653831A (en) * | 1968-10-04 | 1972-04-04 | Chevron Res | Ammonia synthesis catalyst |
US3951862A (en) * | 1974-10-30 | 1976-04-20 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst |
US3992328A (en) * | 1974-10-30 | 1976-11-16 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process |
US4179407A (en) * | 1976-02-20 | 1979-12-18 | Ricoh Co., Ltd. | Catalyst bed for use in decomposition of ammonia gas |
US4163775A (en) * | 1976-11-03 | 1979-08-07 | The British Petroleum Company Limited | Process for the synthesis of ammonia using catalysts supported on graphite containing carbon |
US4623532A (en) * | 1977-05-20 | 1986-11-18 | University Of South Carolina | Catalysts for synthesis of ammonia |
US4235749A (en) * | 1979-09-17 | 1980-11-25 | Indianapolis Center For Advanced Research | Ammonia synthesis catalysts and process of making and using them |
US5032364A (en) * | 1984-04-25 | 1991-07-16 | Imperial Chemical Industries, Plc | Ammonia synthesis plant |
US4789657A (en) * | 1984-06-19 | 1988-12-06 | Fertimont S.P.A. | Process for preparing iron-based catalysts for the synthesis of ammonia and catalysts so obtained |
US4698325A (en) * | 1985-04-22 | 1987-10-06 | Imperial Chemical Industries Plc | Catalysts for ammonia synthesis |
US4822586A (en) * | 1987-01-30 | 1989-04-18 | Shannahan Cornelius E | Ammonia synthesis method |
US5846507A (en) * | 1994-05-26 | 1998-12-08 | Zhejiang University Of Technology | Fe1-x O-based catalyst for ammonia synthesis |
US6716791B1 (en) * | 1998-03-13 | 2004-04-06 | Norsk Hydro Asa | Catalyst for the synthesis of ammonia from hydrogen and nitrogen |
US6531704B2 (en) * | 1998-09-14 | 2003-03-11 | Nanoproducts Corporation | Nanotechnology for engineering the performance of substances |
US6716525B1 (en) * | 1998-11-06 | 2004-04-06 | Tapesh Yadav | Nano-dispersed catalysts particles |
US20050103990A1 (en) * | 2001-11-23 | 2005-05-19 | Cuong Pham-Huu | Composites based on carbon nanotubes or nanofibers deposited on an activated support for use in catalysis |
US7078130B2 (en) * | 2002-10-17 | 2006-07-18 | University Of Windsor | Metallic mesoporous transition metal oxide molecular sieves, room temperature activation of dinitrogen and ammonia production |
US7282167B2 (en) * | 2003-12-15 | 2007-10-16 | Quantumsphere, Inc. | Method and apparatus for forming nano-particles |
US20080161428A1 (en) * | 2004-07-02 | 2008-07-03 | Strait Richard B | Pseudoisothermal ammonia process |
US20060039847A1 (en) * | 2004-08-23 | 2006-02-23 | Eaton Corporation | Low pressure ammonia synthesis utilizing adsorptive enhancement |
US20060099131A1 (en) * | 2004-11-03 | 2006-05-11 | Kellogg Brown And Root, Inc. | Maximum reaction rate converter system for exothermic reactions |
US20090117014A1 (en) * | 2007-11-06 | 2009-05-07 | Quantumsphere, Inc. | System and method for ammonia synthesis |
US20090202417A1 (en) * | 2007-11-06 | 2009-08-13 | Quantumsphere, Inc. | System and method for ammonia synthesis |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090117014A1 (en) * | 2007-11-06 | 2009-05-07 | Quantumsphere, Inc. | System and method for ammonia synthesis |
US20090202417A1 (en) * | 2007-11-06 | 2009-08-13 | Quantumsphere, Inc. | System and method for ammonia synthesis |
CN103717647A (en) * | 2011-08-05 | 2014-04-09 | 国立大学法人京都大学 | Metal nanoparticle-PCP complex and manufacturing method therefor |
EP2740754A4 (en) * | 2011-08-05 | 2015-10-14 | Univ Kyoto | Metal nanoparticle-pcp complex and manufacturing method therefor |
US9586196B2 (en) | 2011-08-05 | 2017-03-07 | Kyoto University | Metal nanoparticle-PCP complex and manufacturing method therefor |
CN105413755A (en) * | 2015-11-12 | 2016-03-23 | 河南中宏清洁能源股份有限公司 | Nanometer material modified nanometer synthetic ammonia catalyst |
US20180238219A1 (en) * | 2017-02-17 | 2018-08-23 | Ford Global Technologies, Llc | Methods and systems for an exhaust gas aftertreatment device |
US11022015B2 (en) * | 2017-02-17 | 2021-06-01 | Ford Global Technologies, Llc | Methods and systems for an exhaust gas aftertreatment device |
CN113332983A (en) * | 2021-04-29 | 2021-09-03 | 杭州师范大学 | Porous rod-shaped Fe21.34O32Preparation method of/C nanorod composite material |
WO2023114890A1 (en) * | 2021-12-17 | 2023-06-22 | Remo Energy, Inc. | Systems and methods for producing renewable ammonia |
WO2024019244A1 (en) * | 2022-07-22 | 2024-01-25 | 울산과학기술원 | Nh3 preparation apparatus and nh3 synthesis method |
Also Published As
Publication number | Publication date |
---|---|
US20110165055A1 (en) | 2011-07-07 |
US9272920B2 (en) | 2016-03-01 |
US20120082612A1 (en) | 2012-04-05 |
US20140072499A1 (en) | 2014-03-13 |
US20160175816A1 (en) | 2016-06-23 |
US20120308467A1 (en) | 2012-12-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9272920B2 (en) | System and method for ammonia synthesis | |
US20120087854A1 (en) | System and method for ammonia synthesis | |
US20120082611A1 (en) | System and method for ammonia synthesis | |
Zhai et al. | Boosting soot combustion efficiency of Co3O4 nanocrystals via tailoring crystal facets | |
JP6025979B2 (en) | Methods and systems for forming ammonia and solid carbon products | |
US9783416B2 (en) | Methods of producing hydrogen and solid carbon | |
RU2126376C1 (en) | Process of partial catalytic oxidation of natural gas, process of synthesis of methanol and process of fischer- tropsch syntheses | |
ES2312832T3 (en) | METHOD OF CONVERSION OF HYDROCARBONS. | |
US9475699B2 (en) | Methods for treating an offgas containing carbon oxides | |
Dasireddy et al. | Selective catalytic reduction of NOx by CO over bimetallic transition metals supported by multi-walled carbon nanotubes (MWCNT) | |
US11390523B2 (en) | Method and plant for producing nitric acid | |
CN105209382A (en) | Method for oxidising ammonia and system suitable therefor | |
TW312631B (en) | ||
US20240024858A1 (en) | Ammonia decomposition catalyst | |
MX2008013754A (en) | Process for the removal of hydrogen cyanide and formic acid from synthesis gas. | |
JP2008074700A (en) | Catalyst form and method for producing synthesis gas | |
JP2003500323A (en) | Nitrous oxide purification method | |
Bu et al. | Efficient synthesis of imine from alcohols and amines over different crystal structure MnOX catalysts | |
JP4334577B2 (en) | Recycling method of absorbent material | |
Javaid et al. | Continuous dehydrogenation of aqueous formic acid under sub-critical conditions by use of hollow tubular reactor coated with thin palladium oxide layer | |
KR20220094149A (en) | Direct decomposition device and direct decomposition method for hydrocarbon | |
KR20080060739A (en) | Metallic structured catalyst and its manufacturing method and manufacturing method for liquid fuel production in fischer-tropsch synthesis using thereof | |
JP3717455B2 (en) | Hydrocarbon production process and catalyst by Fischer-Tropsch process | |
CN116196856A (en) | Device and method for producing cyclohexanone by oxidizing cyclohexene by using adipic acid production waste gas | |
Ekiert et al. | The possibility of implementation of spent iron catalyst for ammonia synthesis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: QUANTUMSPHERE, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CARPENTER, R. DOUGLAS;MALONEY, KEVIN;REEL/FRAME:024175/0536 Effective date: 20100310 |
|
AS | Assignment |
Owner name: BRICOLEUR PARTNERS, L.P., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:QUANTUMSPHERE, INC.;REEL/FRAME:025328/0917 Effective date: 20100924 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: QUANTUMSPHERE, INC., CALIFORNIA Free format text: RELEASE OF SECURITY INTEREST;ASSIGNOR:BRICOLEUR PARTNERS, L.P.;REEL/FRAME:033347/0072 Effective date: 20121015 |