Ammonia membrane reactor comprising a composite membrane

Patent metadata

Field	Value
Publication number	US-11465114-B2
Application number	US-201916719991-A
Country	US
Kind code	B2
Filing date	Dec 19, 2019
Priority date	Dec 19, 2018
Publication date	Oct 11, 2022
Grant date	Oct 11, 2022

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

What is claimed is:

1. 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 a dehydrogenation reaction,
wherein the catalyst for the dehydrogenation reaction includes ruthenium carried on a rubidium-doped porous support,
wherein the composite membrane comprises a support layer including a metal comprising a body-centered-cubic crystal structure, and a catalyst layer including a palladium or a palladium alloy disposed on the support layer,
wherein the metal with the body-centered-cubic crystal structure includes one or more of vanadium (V), niobium (Nb), or tantalum (Ta),
wherein 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 ) in the presence of the catalyst, and the hydrogen permeates the composite membrane and enters the permeate region.

2. The membrane reactor according to claim 1 , wherein the support layer includes a metal oxide and the metal oxide includes one or more of V 2 O 5 , Ta 2 O 5 , or Nb 2 O 5 .

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

4. 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 .

5. The membrane reactor according to claim 1 , wherein the porous support of the dehydrogenation catalyst of ruthenium 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 born nitrides.

6. The membrane reactor according to claim 5 , wherein the dehydrogenation catalyst is impregnated with the ruthenium in an amount of 0.1-10.0 wt. %, with respect to a total weight of the rubidium-doped porous support.

7. The membrane reactor according to claim 5 , wherein the dehydrogenation catalyst is impregnated with the ruthenium in an amount of 1 wt % to 7 wt. %, with respect to the total weight of the metal-doped porous support.

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

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

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

11. The membrane reactor according to claim 1 , wherein the membrane reactor further comprises a reinforcement insert, wherein the reinforcement insert is a sealing part disposed at an end of the composite membrane.

12. The membrane reactor according to claim 1 , wherein the rubidium is doped at 10 wt % to 30 wt % with respect to the porous support, and the dehydrogenation catalyst is a pellet-type catalyst.

13. The membrane reactor according to claim 12 , 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.

14. The membrane reactor according to claim 1 , wherein the dehydrogenation catalyst is a zeolite-based catalyst of Formula 1
Ru/X-Zeolite
wherein X is rubidium.

15. 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.

16. The membrane reactor according to claim 15 , wherein the sweep gas comprises one or more of N 2 , steam, argon, He, H 2 , or ethanol.

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

18. 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.

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

• B01J8/0278 Primary

  Feeding reactive fluids (for solid material B01J8/0015) · CPC title

• B01J2208/00973

  Products · CPC title

• B01J23/44

  Palladium · CPC title

• H01M8/0606

  with means for production of gaseous reactants · CPC title