AMMONIA DECOMPOSITION OVER MEDIUM ENTROPY METAL ALLOY CATALYSTS
A method of catalytic ammonia decomposition is provided. The method includes: flowing ammonia into a reactor charged with a medium entropy metal alloy (MEA) catalyst including a first principal metal, a second principal metal, and a third principal metal, where each of the principal metals is independently selected without repetition from the group consisting of Co, Cr, Fe, Mn, Ni, Al, Cu, Zn, Ti, Zr, Mo, V, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, Ce, Y, Yb, Sn, Ga, In, and Be; and catalytically decomposing the ammonia into hydrogen and nitrogen over the MEA catalyst in the reactor at a reaction temperature between 200° C. and 900° C.
1 . A method of catalytic ammonia decomposition, the method comprising:
flowing ammonia into a reactor charged with a medium entropy metal alloy (MEA) catalyst comprising
a first principal metal,
a second principal metal, and
a third principal metal, wherein each of the principal metals is independently selected without repetition from the group consisting of Co, Cr, Fe, Mn, Ni, Al, Cu, Zn, Ti, Zr, Mo, V, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, Ce, Y, Yb, Sn, Ga, In, and Be; and
catalytically decomposing the ammonia into hydrogen and nitrogen over the MEA catalyst in the reactor at a reaction temperature between 200° C. and 900° C.
2 . The method of claim 1 , further comprising:
prior to flowing the ammonia into the reactor, purging the reactor with an inert gas comprising nitrogen or a noble gas; and
after catalytically decomposing the ammonia, separating the hydrogen using a hydrogen separation membrane.
3 . The method of claim 1 , wherein a combination of the three principal metals is FeMnCo, FeMnNi, FeMnMo, FeMnCu, FeMoCo, FeMoNi, FeMoCu, MnCoNi, MnCoCu, MnCoMo, MnNiCu, MnNiMo, MoCoNi, FeCoCu, FeNiCu, MoCoCu, MoNiCu, or CoNiCu.
4 . The method of claim 1 , wherein the three principal metals of the MEA catalyst are equimolar to each other.
5 . The method of claim 1 , wherein the MEA catalyst further comprises a fourth principal metal, wherein the fourth principal metal is independently selected without repetition from the group consisting of Co, Cr, Fe, Mn, Ni, Al, Cu, Zn, Ti, Zr, Mo, V, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, Ce, Y, Yb, Sn, Ga, In, and Be.
6 . The method of claim 5 , wherein a combination of the four principal metals is FeMnCoNi, FeMnCoCu, FeMnCoMo, FeMnNiMo, FeMnNiCu, FeMnMoCu, FeCoNiMo, FeCoNiCu, FeCoCuMo, CoNiCuMn, CoNiCuMo, MnMoCoNi, MnMoCoCu, or MnMoNiCu.
7 . The method of claim 5 , wherein the four principal metals of the MEA catalyst are equimolar to each other.
8 . The method of claim 1 , wherein the MEA catalyst further comprises a promoter comprising molybdenum, calcium, cesium, rare earth metal, non-reducible metal oxide, or metal chloride at an atomic percentage (at %) of 0.5 at % to 10 at %.
9 . The method of claim 8 , wherein the promoter comprises:
a non-reducible metal oxide selected from the group consisting of Li 2 O, K 2 O, Na 2 O, Cs 2 O, BeO, MgO, CaO, SrO, BaO, P 2 O 5 , Al 2 O 3 , Al 2 O 4 , SiO 2 , TiO 2 , ZrO 2 , CeO 2 , Y 2 O 3 , La 2 O 3 , Er 2 O 3 and any combination thereof; or
a metal chloride selected from the group consisting of metal chlorides of Li, Na, Ca, K, Cs, Fr, Fe, Co, Mn, Mg, Al, Ni, Mo, Cu, Pd, Pt, Ce, Mg, La, Nd, Ge, Re, and any combination thereof.
10 . A method of catalytic ammonia decomposition, the method comprising:
providing a medium entropy metal alloy (MEA) catalyst in a fixed-bed tubular reactor, the MEA catalyst comprising
a first principal metal,
a second principal metal, and
a third principal metal, wherein each of the principal metals is independently selected without repetition from the group consisting of Co, Cr, Fe, Mn, Ni, Al, Cu, Zn, Ti, Zr, Mo, V, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, Ce, Y, Yb, Sn, Ga, In, and Be;
purging the fixed-bed tubular reactor with an inert gas;
heating the fixed-bed tubular reactor to a reaction temperature between 200° C. and 900° C.; and
flowing an ammonia gas into the fixed-bed tubular reactor to catalytically decompose ammonia into hydrogen and nitrogen over the MEA catalyst in the fixed-bed tubular reactor.
11 . The method of claim 10 , further comprising, prior to heating the fixed-bed tubular reactor to the reaction temperature, performing a catalyst reduction step.
12 . The method of claim 11 , wherein the catalyst reduction step comprises:
heating the fixed-bed tubular reactor to a catalyst reduction temperature between 500° C. and 700° C.; and
flowing a hydrogen gas into the fixed-bed tubular reactor at the catalyst reduction temperature.
13 . The method of claim 12 , wherein
the purging is performed at a rate of 20 mL/min to 200 mL/min;
the heating of the fixed-bed tubular reactor to the catalyst reduction temperature is performed at a rate of 10° C./min to 15° C./min;
the hydrogen gas is flowed at a rate of 20 mL/min to 200 mL/min; and
the ammonia gas is flowed at a rate of 5 mL/min to 200 mL/min.
14 . The method of claim 10 , wherein the reaction temperature is between 400° C. and 600° C.
15 . The method of claim 10 , wherein the MEA catalyst further comprises a fourth principal metal, wherein the fourth principal metal is independently selected without repetition from the group consisting of Co, Cr, Fe, Mn, Ni, Al, Cu, Zn, Ti, Zr, Mo, V, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, Ce, Y, Yb, Sn, Ga, In, and Be.
16 . The method of claim 10 , wherein the MEA catalyst further comprises a promoter at an atomic percentage (at %) of 0.5 at % to 10 at %, wherein the promoter comprises molybdenum, calcium, cesium, rare earth metal, a non-reducible metal oxide selected from the group consisting of Li 2 O, K 2 O, Na 2 O, Cs 2 O, BeO, MgO, CaO, SrO, BaO, P 2 O 5 , Al 2 O 3 , Al 2 O 4 , SiO 2 , TiO 2 , ZrO 2 , CeO 2 , Y 2 O 3 , La 2 O 3 , Er 2 O 3 , and any combination thereof, or a metal chloride selected from the group consisting of metal chlorides of Li, Na, Ca, K, Cs, Fr, Fe, Co, Mn, Mg, Al, Ni, Mo, Cu, Pd, Pt, Ce, Mg, La, Nd, Ge, Re, and any combination thereof.
17 . A method of developing an ammonia decomposition catalyst, the method comprising:
synthesizing, according to a series of recipes, a series of medium entropy metal alloy (MEA) catalysts, each MEA catalyst comprising
a first principal metal,
a second principal metal, and
a third principal metal, wherein each of the principal metals is independently selected without repetition from the group consisting of Co, Cr, Fe, Mn, Ni, Al, Cu, Zn, Ti, Zr, Mo, V, Ru, Rh, Pd, Ag, W, Re, Ir, Pt, Au, Ce, Y, Yb, Sn, Ga, In, and Be, and wherein each recipe contains information about a molar ratio of the three principal metals of the MEA catalyst;
performing a series of catalytic reaction tests using the series of MEA catalysts, each catalytic reaction test comprising
decomposing ammonia over one of the series of MEA catalysts in a fixed-bed tubular reactor at a reaction temperature of 600° C. or lower, and
calculating a hydrogen yield; and
determining an optimized recipe from the series of recipes based on a series of the hydrogen yield.
18 . The method of claim 17 , wherein the first principal metal is Fe and the second principal metal is Mn, Co, or Ni.
19 . The method of claim 17 , wherein the recipe provides an instruction to add a promoter to the MEA catalyst, and wherein the promoter comprises molybdenum, calcium, cesium, rare earth metal, non-reducible metal oxide, or metal chloride at an atomic percentage (at %) of 0.5 at % to 10 at %.
20 . The method of claim 17 , wherein the recipe comprises:
placing the first principal metal, the second principal metal, and the third principal metal, and zirconia media in a ball mill;
rotating the ball mill to produce a power mixture; and
separating the MEA catalyst from the zirconia media.