WO2018215202A1 - Catalyseur pour synthèse de l'ammoniac - Google Patents
Catalyseur pour synthèse de l'ammoniac Download PDFInfo
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- WO2018215202A1 WO2018215202A1 PCT/EP2018/061907 EP2018061907W WO2018215202A1 WO 2018215202 A1 WO2018215202 A1 WO 2018215202A1 EP 2018061907 W EP2018061907 W EP 2018061907W WO 2018215202 A1 WO2018215202 A1 WO 2018215202A1
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- WIPO (PCT)
- Prior art keywords
- catalyst
- catalysts
- ammonia
- hydrogen gas
- carbon
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 46
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 42
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 41
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 230000005611 electricity Effects 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 230000000694 effects Effects 0.000 description 16
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000009620 Haber process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000010494 dissociation reaction Methods 0.000 description 6
- 230000005593 dissociations Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000011874 heated mixture Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- AEHYRSFAEUPFTN-UHFFFAOYSA-N [Ru].[Ba] Chemical compound [Ru].[Ba] AEHYRSFAEUPFTN-UHFFFAOYSA-N 0.000 description 1
- NFOLKIRGUDNDAA-UHFFFAOYSA-N [Ru].[Ba].[Li] Chemical compound [Ru].[Ba].[Li] NFOLKIRGUDNDAA-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- 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 present invention relates to a catalyst for catalysing the synthesis of ammonia N3 ⁇ 4 from hydrogen gas H 2 and nitrogen gas N 2 . It also relates to methods and apparatus for synthesis of ammonia N3 ⁇ 4 from nitrogen N 2 and hydrogen H 2 .
- Fig. 1 represents an outline schematic of the well-known Haber-Bosch method for ammonia synthesis.
- a 3:1 ratio of hydrogen (H 2 ) 10 and nitrogen (N 2 ) 12 gases are supplied to a heat process 14.
- the heated mixture of H 2 and N 2 gases 16 is passed over a hot iron catalyst 18, which catalyses synthesis of a portion of the heated mixture of H 2 and N 2 gases into ammonia (NH 3 ) .
- NH 3 ammonia
- a ratio of 20% NH 3 to 80% unreacted N 2 and H 2 is achieved.
- the resultant ammonia- containing mixture 20 is cooled in a condenser 22, such that the synthesised ammonia 24 liquefies and is removed from the process .
- the process is usually operated continuously for maximum efficiency.
- the hot iron catalyst 18 requires to be maintained at high temperatures, around 400°C - 500°C, to favour the formation of ammonia and at high pressure, around 15-30 MPa, to achieve an acceptable rate of synthesis.
- Ruthenium (Ru) catalysts are also known for use in such processes. Maintenance of such a high-temperature, high pressure environment means that the process consumes a large amount of energy, typically derived from fossil fuels.
- fossil-fuelled hydrogen generation is employed, which is also a high- temperature process, and waste heat from hydrogen generation may be used to heat the catalyst and the H 2 and N 2 mixture.
- Current research examines ammonia generation and combustion as a manner for storage of renewable energy, and as a carbon- free fuel.
- renewable energy sources may provide intermittent power, for example from solar or wind power. For this reason, it has sometimes been considered inappropriate to run a Haber-Bosch process from renewable energy sources, as use of an intermittent energy source will compromise the efficiency and/or cost of a standard synthesis process.
- Ammonia production plants are currently powered by energy derived from fossil fuel.
- the inventors have unexpectedly found that exceptional promotion by Li renders Li-Ru catalysts suitable for ammonia synthesis at low pressure (0.1-5.0 MPa) but effective over a range of 0.1-40.0 MPa.
- the Li-promoted Ru catalysts of the invention have been found to outclass conventional commercial Fe counterparts by 350 fold; and also to outclass other conventional catalytic systems many fold.
- the role of Li in 2 activation over a catalytic Ru surface are elucidated below .
- Electric power generated from renewable energy sources such as wind or solar power at smaller units provide for local grid use but can also be used to produce hydrogen via electrolysis of water for ammonia synthesis without carbon emission 5 .
- Momentary unbalance of electrical generation and consumption into and from a grid system due to fluctuations in supply and load may be smoothed by synthesising H 3 as an operating reserve capacity.
- 3 ⁇ 4 manufactured by electrolysis at low pressure would require an efficient catalyst for high production rate of NH 3 in such smaller units.
- Wind energy may be used to make electricity and then to perform the Haber-Bosch process to make NH 3 locally by electricity derived from wind energy.
- An outline schematic of an example "eHB" (electrolysis-Haber-Bosch) system is shown in Fig. 2.
- Wind energy from wind farms is transferred into electricity which supports the demand profiles such as the electricity grid.
- Surplus electricity for example generated when strong wind is encountered may be employed for the energy storage system (ESS) .
- ESS energy storage system
- Water is electrolyzed using surplus electricity into 3 ⁇ 4 .
- a mechanical vapour compression unit MVC
- the plant-formed 3 ⁇ 4, and 2 from air separation, are then condensed as a stock of supply gases for ammonia synthesis.
- Fig. 2 shows a schematic view of an eHB process integrating the ammonia synthesis energy storage system (ESS) and electricity produced by wind energy.
- Fig. 2 illustrates such a system driven by an intermittent electrical power input from a wind farm which is provided to satisfy a given electricity demand (demand profile) .
- Surplus power from the wind farm is used to operate an Energy Storage System (ESS) consisting of 3 ⁇ 4, 2 and N3 ⁇ 4 production modules.
- ESS Energy Storage System
- Excess electrical power is stored by electrolysing water to generate 3 ⁇ 4, by extracting 2 from air and synthesising NH 3 from these gases. Power deficits are overcome by converting NH 3 from NH 3 storage back to electricity. This ensures that (a) the demand profile is satisfied, and (b) a minimum level of operation of the ESS is maintained.
- ESS Energy Storage System
- the reaction conditions are usually set at a temperature regime of 400-500 °C, and pressures of 15-30 MPa under a maximal flow of reactant gases.
- catalyst selection can be less critical since slightly less active, or deactivated, catalysts such as Fe- based catalysts can reach the same conversion rates at smaller reactant flows.
- NH 3 generation in a small-scale eHB plant requires that catalysts show significant activity at a lower pressure to minimise the cost of investment and mitigate safety risks. It is thus of great significance to reduce the reaction pressure below the typical pressures employed in the Haber-Bosch process to reduce operational cost and energy requirements and achieve the eHB process.
- the eHB process requires that the catalyst works under a relatively low reaction pressure. Compared with the conventional commercial Fe, Ru is a better candidate for the eHB process as it is relatively active at low pressure 7 .
- Ru catalyst is not presently applied in the Haber-Bosch NH 3 synthesis industry, partly because the practicality of such catalyst may be limited by its vulnerability to be poisoned by carbon deposition from CH 4 decomposition, and the high cost of Ru catalysts.
- the 3 ⁇ 4 is generated from electrolysis of water, there is no risk that the 3 ⁇ 4 may contain CH 4 , so the poisoning risk is avoided. This makes Ru a potential candidate for low pressure synthesis .
- alkali metals with strong electron donation ability are generally employed to improve traditional Fe- or Ru- based catalysts
- a lithium-promoted ruthenium catalyst is provided. Such catalyst may provide higher activity for ammonia synthesis than the conventional standard iron catalyst.
- Use of a lithium-promoted ruthenium catalyst allows ammonia production rates to be achieved comparable with the conventional fossil-fuelled Haber-Bosch process, but at reduced temperature and/or pressure. The production rate may be ramped up and down according to availability of energy, without such a large loss in efficiency as would be observed by applying intermittent energy supply to the conventional Haber-Bosch process.
- Fig. 1 represents an outline schematic of the Haber-Bosch method for ammonia synthesis
- Fig. 2 an outline schematic of an electrolysis-Haber-Bosch (eHB) method for ammonia synthesis
- Figs. 3a - 3e represent physicochemical properties and catalytic performance of catalysts according to embodiments of the present invention
- Fig. 4 illustrates an effect of increasing lithium (Li) concentration in the preparation of a Ru catalyst for ammonia synthesis
- Fig. 5 illustrates a comparison of the catalytic activity of certain catalysts of the present invention against a conventional Fe and Ru catalysts at various pressures.
- the present invention provides a catalyst for ammonia synthesis.
- the catalyst of the present invention is a lithium (Li ) -promoted barium-ruthenium (Ba-Ru) catalyst on a carbon support.
- An activated carbon support is employed.
- Lithium (Li) is rarely considered for use to improve conventional Fe- or Ru- based catalysts for ammonia synthesis, because of the anticipated inferior electron donation capacity of Li compared to other alkali metals.
- the present invention however provides superior activity of Ru catalysts when promoted by Li.
- Li-enhanced Ru catalysts outclass those of all reported catalytic systems at low pressure (0.1-5.0 MPa) , yet provides catalytic activity comparable to conventional Fe based catalysts at much higher pressures and similar temperatures: up to 40.0 MPa and 700°C.
- the regenerative electron donation of Li-Ru and surface stabilization to lower the energy barrier for dissociation of nitrogen triple bonds are noted in this efficient catalyst.
- Table 1 shows a comparison of reactivity in the reduction of 2 to NH 3 over Ru, Fe, Co-based catalysts, along with others from the literature.
- Commercial Fe catalyst with multi promotors composed of Fe30 4 or Fe 2 ⁇ 03, AI 2 O 3 , K 2 0, CaO, MgO and S1O 2 is evaluated, which displays a good reaction rate of 95, 600 ymol g C at ⁇ 1 h ⁇ 1 under operating pressure of 15 MPa (entry 12) .
- the reaction rate dramatically attenuates to 3, 600 ymol g C at ⁇ 1 h ⁇ 1 when reducing the pressure to 1 MPa (entry 13) .
- Fe catalyst is thus not a good candidate for the ESS system since it is too sensitive to the reduced pressure.
- Ru with higher electron density of d-orbitals can donate electrons into the anti-bonding orbital of adsorbed N 2 , facilitating its dissociation and hence can work under a lower pressure as compared to Fe based catalysts.
- a caesium-enhanced ruthenium (Cs-Ru) - based catalyst (entries 4, 7) is one of the most active Ru catalysts claimed for N3 ⁇ 4 synthesis with an enhanced reaction rate. 15 ' 16
- Ru/Ci 2 A7:e ⁇ and Co-LiH catalysts may be used as NH 3 -synthesis catalysts due to effective electron back donation from metal to N 2 . 17,18
- the results shown in Table 1 clearly indicate that the Ba-Ru-Li catalyst of the present invention significantly outclasses these catalytic systems.
- the ammonia production rate of the Ba-Ru-Li catalyst of the present invention is 12.9 folds than that of commercial Fe and 5.6 folds than that of Ba-Ru/AC at 1 MPa (entries 9, 13 and 3) .
- the Ba-Ru-Li catalyst of the present invention is 5 folds more active than (entries 5, 6, 9 and 10) Ru/Pr 2 ⁇ 0 3 which regarded as effective under low pressure 19 .
- the superiority of Ba-Ru-Li catalyst of the present invention is more apparent when the activity is compared in term of moles N3 ⁇ 4 ammonia per mole of alkali metal used. Its activity is almost 348.3 fold than that of commercial Fe at 1 MPa and is much better than all systems reported in literature. Interestingly, the Ba-Ru-Li catalyst of the present invention shows a rate comparable to that of the commercial Fe catalysts at 15 MPa but under a significantly reduced pressure of 3 MPa. Even evaluated at 1 MPa, the Ba-Ru-Li catalyst of the present invention also gives a considerable activity (entry 10).
- Figs. 3a - 3e represent physicochemical properties and catalytic performance of catalysts according to embodiments of the present invention.
- Fig. 3a represents width angle x-ray diffusion patterns of reduced Ru-Li/AC (4.8 wt% Ru, 7.6 wt% Li) samples. Vertical lines indicate the reference signal of Ru cluster. No obvious peak shift of Ru and Ru-Li samples is observed.
- Fig. 3b represents a typical TEM image of reduced Ba-Ru-Li sample (4.8 wt% Ru, 7.6 wt% Li) showing the homogeneous distribution of Ru nanoparticles with average particle size of 2.9 nm.
- Fig. 3c represents a typical high resolution TEM image of reduced Ru nanoparticle in Ru-Li/AC sample. Highlighted points represent the stepped atoms in the nanoparticle as B5 sites (which consist of an arrangement of three Ru atoms in one layer and two further Ru atoms in an internal layer) .
- the inset image is the Fourier transition of the 2-nm nanoparticle showing the majority lattice face of hep (101) .
- Fig. 3d represents carbon monoxide (CO) chemical sorption on the reduced Ba-Ru/AC and Ba-Ru-Li/AC samples. Note that the Ba-Ru-Li/AC sample shows a reduced amount of CO chemical sorption, indicating that the surface of Ru nanoparticles is at least partially covered by Li species.
- CO carbon monoxide
- Fig. 3e represents catalytic results of Ba-Ru/AC promoted by a series of compositional Li. As shown, a volcano relationship between activity and Li loading is exhibited, indicating an optimization in lithiation before excessive coverage is evident.
- the reaction conditions used for the test in question were: 5 MPa; 743 K; 62, 400 ml g cat ⁇ 1 h ⁇ 1 .
- the Ru nanoparticles in Ba-Ru-Li/AC are homogeneously distributed on the carbon support with average particle size of 2 nm.
- Fig. 3c clearly shows that the Ru nanoparticle having a size of 2 nm in the Ba-Ru-Li/AC is covered with high density of stepped sites for B5 type, which benefits for the catalytic reduction of N 2 .
- the present inventors have found that Li + may preferentially take residence on the surface of Ru nanoparticles rather than penetrating into interstitial of Ru lattices. From the width angle x-ray diffusion patterns in Fig. 3a, the diffraction peaks of metallic Ru show no obvious shift upon the addition of Li + into the system, indicating no expansion of Ru lattice. This can also be directly observed from the high resolution TEM image of Fig. 3c.
- the number of exposed Ru metallic sites may be determined by carbon monoxide (CO) chemical sorption.
- the values are 78.1 ymol.g -1 and 19.5 ymol.g -1 for Ba-Ru/AC and Ba-Ru-Li/Ac, respectively, suggesting the partial coverage or decoration of Li + on the Ru (Fig. 3d) .
- the present inventors anticipate that surface Ru atoms promoted by Li + instead of Li° to provide active sites for 2 activation to N3 ⁇ 4 . Indeed, a volcano relationship is obtained when NH 3 production rate is plotted against Li + loading with an optimum value reaching at around 15 wt% (Fig. 3e) . Excessive loading of Li + could reduce the number of exposed Ru active sites despite the beneficial promotion effect. Unlike the case of Li + promotion to Ru, Li + does not seem to offer much significant promotion to Fe for the ammonia synthesis (Table 1, entries 14 and 15) . Alkali promotors or supports Na , K and Cs to Ru nanoparticles have been proposed to boost catalytic activity m converting 2 to N3 ⁇ 4 m 3 ⁇ 4 .
- Electrons are thought to transfer from the alkali metals to the Ru nanoparticles and thus promoting the electron density of Ru into the pi star anti-bonding orbital of 2 to facilitate the dissociation of the N ⁇ N nitrogen-nitrogen triple bonds N ⁇ N.
- the promotion ranking should follow: Cs + > K + > Na + > Li + .
- the present inventors have found that Li + with the highest electronegativity displays higher electronic promotion than all other alkali ions especially in low pressure.
- the combination of the Haber-Bosch process at low pressure and the wind energy (referred to here as eHB) supports a great opportunity for the current energy-urgent society.
- the present invention may enable efficient NH 3 synthesis in small unit plants at relatively low pressure by use of simple Ba- Ru-Li/AC catalysts.
- a catalyst is prepared by impregnating Ru particles into a carbon support.
- the carbon support may have previously been prepared by heating a carbon support to 950°C in a gas mixture comprising 5% 3 ⁇ 4 in argon, to perform a chemical reduction and to provide an activated carbon with a high surface area.
- Li metal is then incorporated into the Ru nanoparticles.
- the incorporation of lithium metal may be achieved by preparation with lithium acetate dehydrate.
- the catalyst is promoted by introducing barium. Promotion by barium may be achieved by use of barium nitrate solution. Promotion to a catalyst is achieved by adding a small quantity of chemical - barium, in this example - to greatly enhance its catalytic performance.
- barium carbonate is formed as a structural promotor such that its presence on a catalyst particle as high melting compound can prevent the aggregation of small metal particles.
- the lithium role is thought to be as an electronic promotor which enhances electron richness of Ru for the activation of N 2 . Barium and lithium are accordingly thought to work as two independent promotors to Ru metal .
- the lithium-barium-ruthenium (Ba-Ru-Li) catalysts so prepared have been shown to exhibit a higher activity than conventional Fe or Ru based catalysts.
- catalytic activity of the Ru content of the catalyst is promoted by the incorporation of Li into the catalyst support. Further improvement in catalytic activity may be achieved through use of a Ba promoter and/or a support of high surface area, for example of activated carbon (AC) .
- a Ba promoter and/or a support of high surface area for example of activated carbon (AC) .
- Fig. 4 illustrates an effect of increasing lithium (Li) concentration in the preparation of a Ru catalyst for ammonia synthesis .
- Fig. 5 illustrates a comparison of the catalytic activity of certain catalysts of the present invention against a conventional Fe and Ru catalysts at various pressures.
- the assumed reaction conditions are 470°C and weight-hourly- space-velocity (WHSV) of 835 h "1 .
- catalytic activity is observed at a temperatures in the range of 300 - 700°C and a pressure in the range of 3-40 MPa.
- Catalytic activity comparable to that of conventional iron catalysts may be obtained at much higher pressures and similar temperatures, for example in the range 30-50 MPa.
- Table 2 shows a comparative table of catalytic activity of example catalysts of the invention, and conventional catalysts, for illustration purposes only.
- Various ammonia catalysts have been developed; however, the catalyst of the present invention shows catalytic activity comparable to certain conventional catalysts but at significantly lower pressures than Fe-catalysts , for example.
- the reaction conditions considered include a reaction temperature of 400- 470°C.
- the embodiments described above comprise a carbon support which is activated by reduction by heating in hydrogen
- other embodiments employ a carbon support of carbon nanotubes.
- the carbon nanotubes may be activated in a similar manner.
- the carbon nanotubes may be found to provide a greater surface area per unit volume, and per unit mass, than other carbon supports.
- Yet other embodiments employ a carbon support of graphene.
- the graphene may be activated in a similar manner.
- the graphene may be found to provide a greater surface area per unit volume, and per unit mass, than other carbon supports.
- embodiments of the present invention employing carbon supports of carbon nanotubes or of graphene are as the embodiments described above with a carbon support.
- Embodiments of the invention provide apparatus for synthesising ammonia from nitrogen gas and hydrogen gas, comprising an electrical generator for generating electricity from a renewable energy source; an electrolyser for electrolysing water using electricity generated by the generator from the renewable energy source to generate the hydrogen gas, an air separator for separating air to provide the nitrogen gas, a catalyst as described above, and a heater and a compressor for heating and pressurizing the hydrogen gas and the nitrogen gas and passing the hydrogen gas and nitrogen gas over the catalyst.
- the present invention provides lithium-promoted ruthenium catalyst compositions and equipment for ammonia synthesis. Conventionally, only two types of commercial catalysts were available for ammonia synthesis.
- the Cs-Ru/MgO catalyst is a lower temperature, lower pressure, higher efficiency one, and the most popular, cheaper, catalysts are based on iron promoted with one of K 2 0, CaO, Si0 2 , Al 2 03,etc.
- the present invention relates to a new series of catalysts: Li-Ru type catalysts. Support for such catalysts can be provided in the form of activated carbons, MgO or AI 2 O 3 .
- Jacobsen, C. J. H. et al Structure sensitivity of supported ruthenium catalysts for ammonia synthesis. J. Mol. Catal. A: Chem. 163, 19-26 (2000).
- Kitano, M. et al . Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis. Nature Commun. 6 (2015) . Grigoriev, S. A., Porembsky, V. I. & Fateev, V. N. Pure hydrogen production by PEM electrolysis for hydrogen energy[J]. Int. J. Hydro. Energy 31, 171-175 (2006).
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Abstract
L'invention concerne un catalyseur permettant de catalyser la synthèse de l'ammoniac à partir d'hydrogène gazeux et d'azote gazeux, comprenant du ruthénium, du lithium métallique étant incorporé au catalyseur en tant que promoteur de l'activité catalytique du ruthénium.
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Cited By (3)
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CN111185164A (zh) * | 2020-03-06 | 2020-05-22 | 福州大学 | 一种以乙酸钌为前驱体的氨合成催化剂及其制备方法 |
CN111871412A (zh) * | 2020-07-30 | 2020-11-03 | 天津大学 | 一种Pt-CNTs/硅藻土其制备方法及用途 |
CN113318750A (zh) * | 2021-06-22 | 2021-08-31 | 吉林大学 | 流动相热催化氮气和氢气合成氨气的锂掺杂二维铁钼催化剂及其制备方法 |
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