Ammonia membrane reactor comprising a composite membrane

Patent metadata

Field	Value
Publication number	US-2022347644-A1
Application number	US-202217859485-A
Country	US
Kind code	A1
Filing date	Jul 7, 2022
Priority date	Dec 19, 2018
Publication date	Nov 3, 2022
Grant date	—

Abstract

The present specification discloses a membrane reactor comprising a reaction region; a permeate region; and a composite membrane disposed at a boundary of the reaction region and the permeate region, wherein the reaction region comprises a bed filled with a catalyst for dehydrogenation reaction, wherein the composite membrane comprises a support layer including a metal with a body-centered-cubic (BCC) crystal structure, and a catalyst layer including a palladium (Pd) or a palladium alloy formed onto the support layer, wherein ammonia (NH3) is supplied to the reaction region, the ammonia is converted into hydrogen (H2) by the dehydrogenation reaction in the presence of the catalyst for dehydrogenation reaction, and the hydrogen permeates the composite membrane and is emitted from the membrane reactor through the permeate region.

First claim

1 . A membrane reactor comprising a reaction region; a permeate region; a reinforcement insert, and a composite membrane disposed at a boundary of the reaction region and the permeate region,
wherein the reaction region comprises a bed filled with a catalyst for dehydrogenation reaction, wherein the dehydrogenation catalyst includes ruthenium carried on a metal-doped porous support, wherein a dopant metal of the metal-doped porous support is one or more of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), or lanthanum (La); wherein the composite membrane comprises a support layer including a metal with a body-centered-cubic (BCC) crystal structure, and a catalyst layer including a palladium (Pd) or a palladium alloy formed onto the support layer, wherein the metal with the body-centered-cubic (BCC) crystal structure includes one or more of vanadium (V), niobium (Nb), or Tantalum (Ta), and a surface of the support layer is in contact with the reaction region and a surface of the catalyst layer is in contact with the permeate region, wherein ammonia (NH 3 ) is supplied to the reaction region, the ammonia is converted into hydrogen (H 2 ) by the dehydrogenation reaction in the presence of the catalyst, and the hydrogen permeates the composite membrane and is emitted from the membrane reactor through the permeate region, wherein the reinforcement insert is disposed at an end of the composite membrane to prevent material failure by embrittlement, and the membrane reactor overlaps a portion of the reinforcement insert, wherein the reinforcement insert is a sealing part that seals the composite membrane.

2 . (canceled)

3 . (canceled)

4 . The membrane reactor according to claim 1 , wherein the support layer includes an oxide with catalytic activity and the oxide includes one or more of V 2 O 5 , Ta 2 O 5 , or Nb 2 O 5 .

5 . The membrane reactor according to claim 1 , wherein the catalyst layer has a thickness of 0.1 to 5 m.

6 . The membrane reactor according to claim 1 , wherein the composite membrane has hydrogen permeability of 2×10 −8 mol m −1 s −1 Pa −0.5 to 3×10 −7 mol m −1 s −1 Pa −0.5 .

7 . (canceled)

8 . The membrane reactor according to claim 1 , wherein the porous support comprises one or more selected from the group consisting of Al 2 O 3 , SiO 2 , TiO 2 , CeO 2 , CuO, MgO, Nb 2 O 5 , WO 3 , ZrO 2 , FeO, La 2 O 3 , Activated Carbon, Graphene, and hexagonal Boron nitrides.

9 . The membrane reactor according to claim 1 , wherein the dehydrogenation catalyst is impregnated with ruthenium in the amount of 0.1-10.0 wt. %, with respect to a total weight of the metal-doped porous support.

10 . The membrane reactor according to claim 1 , wherein the porous support-based catalyst includes one or more selected from the group consisting of X zeolite, Y zeolite, ZSM-5 zeolite, beta zeolite, L zeolite, and A zeolite.

11 . The membrane reactor according to claim 1 , wherein the purity of hydrogen emitted from the membrane reactor is 99.999% or more.

12 . The membrane reactor according to claim 1 , wherein the operating temperature of the membrane reactor is 350 to 550° C.

13 . The membrane reactor according to claim 1 , further comprising an inlet for a sweep gas, wherein the sweep gas is supplied to the permeate region of the membrane reactor.

14 . (canceled)

15 . The membrane reactor according to claim 13 , wherein the sweep gas is supplied at the flow rate of less than 50% of the volumetric flowrate of the hydrogen emitted from the membrane reactor through the permeate region.

16 . (canceled)

17 . A hydrogen fuel cell system comprising:
the membrane reactor according to claim 1 ; and a hydrogen fuel cell, wherein hydrogen emitted from the membrane reactor is directly supplied to the fuel cell.

18 . The membrane reactor according to claim 1 , wherein the membrane reactor encapsulates a portion of the reinforcement insert.

19 . The membrane reactor according to claim 10 , wherein the dehydrogenation catalyst is impregnated with the ruthenium in an amount of 1 wt. % to 7 wt. %, with respect to a total weight of the metal-doped porous support.

20 . The membrane reactor according to claim 1 , wherein the dopant metal of the metal-doped porous support comprises lanthanum, the lanthanum acting as a Lewis acid site to facilitate absorption of the ammonia to promote the dehydrogenation reaction, wherein the lanthanum increases the activity of the catalyst due to an increase in electron density caused by an electronic interaction between the ruthenium and the lanthanum.

21 . The membrane reactor according to claim 20 , wherein the lanthanum is doped at 1 to 20 mol % with respect to the porous support, and the dehydrogenation catalyst is a pellet-type catalyst.

22 . The membrane reactor according to claim 21 , wherein the pellet-type catalyst has (i) a surface area of 10-200 m 2 g −1 , (ii) a pore size of 0.1-1.0 cm 3 g −1 , and (iii) a pore diameter of 100-200 Å.

23 . A method of processing ammonia comprising:
flowing ammonia into a reactor comprising a reaction region; a permeate region; a reinforcement insert, and a composite membrane disposed at a boundary of the reaction region and the permeate region, wherein the reaction region comprises a bed filled with a catalyst for dehydrogenation reaction, wherein the dehydrogenation catalyst includes ruthenium carried on a metal-doped porous support, wherein a dopant metal of the metal-doped porous support is one or more of sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), or lanthanum (La); wherein the composite membrane comprises a support layer including a metal with a body-centered-cubic (BCC) crystal structure, and a catalyst layer including a palladium (Pd) or a palladium alloy formed onto the support layer, wherein the metal with the body-centered-cubic (BCC) crystal structure includes one or more of vanadium (V), niobium (Nb), or Tantalum (Ta), and a surface of the support layer is in contact with the reaction region and a surface of the catalyst layer is in contact with the permeate region, converting the ammonia into hydrogen (H 2 ) by the dehydrogenation reaction in the presence of the catalyst, and separating the hydrogen using the composite membrane with the hydrogen entering the permeate region, wherein the reinforcement insert is disposed at an end of the composite membrane to prevent material failure by embrittlement, and the membrane reactor overlaps a portion of the reinforcement insert, wherein the reinforcement insert is a sealing part that seals the composite membrane.

24 . The method of processing ammonia according to claim 23 , comprising supplying sweep gas to the permeate region of the membrane reactor.

25 . The method of processing ammonia according to claim 24 , wherein the sweep gas is supplied at the flow rate of less than 50% of the volumetric flow rate of the hydrogen emitted from the membrane reactor through the permeate region.

Assignees

• Korea Inst Sci & Tech

Inventors

• Jo Young Suk
• Yoon Chang Won
• Sohn Hyuntae
• Jeong Hyangsoo
• Jang Seong Cheol
• Kim Yeong Cheon
• Han Jonghee
• Nam Suk Woo

Classifications

• Y02P20/133

  Renewable energy sources, e.g. sunlight · CPC title

• B01J8/009 Primary

  Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane · CPC title

• B01J2208/00973

  Products · CPC title

• B01D53/228

  characterised by specific membranes · CPC title

• C01B3/047 Primary

  Decomposition of ammonia · CPC title