Method and device for ammonia storage and delivery using in-situ re-saturation of a delivery unit

• US 9,400,064 B2
• Filed: 06/03/2013
• Issued: 07/26/2016
• Est. Priority Date: 05/23/2007
• Status: Active Grant

• Current Assignee: Amminex Emissions Technology A/S (Faurecia SA)
• Original Assignee: Amminex A/S
• Inventors: Johannessen, Tue
• Primary Examiner(s): DRODGE, JOSEPH W
• Application Number:
  US13/908,257
• Publication Number:
  US 20130263927A1
• Time in Patent Office: 1,149 Days
• Field of Search: 95/14, 951/28, 951/30, 961/08, 961/09, 961/21, 961/22, 961/26, 602/73, 602/74, 602/86, 602/95, 602/97, 602/99, 603/00, 603/01, 603/04, 603/11, 206/0.7, 222/1, 222/3, 137/1, 137/334, 137/572, 422/114, 422/168, 422/171, 422/173, 422/177, 422/182, 422/183, 423/212, 423/213.2, 423/213.5, 423/213.7, 423/239.1, 423/237, 423/351, 423/352, 423/383, 429/400, 429/428, 429/433, 429/434, 429/435, 429/443, 429/444, 429/512, 429/513, 429/515
• US Class Current: 1/1
• CPC Class Codes: B01D 2251/2062 Ammonia
• CPC Class Codes: B01D 2251/40 Alkaline earth metal or magnesium compounds
• CPC Class Codes: B01D 2251/402 of magnesium
• CPC Class Codes: B01D 2251/404 of calcium
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2255/2045 Calcium
• CPC Class Codes: B01D 2255/2047 Magnesium
• CPC Class Codes: B01D 2255/20738 Iron
• CPC Class Codes: B01D 2255/20753 Nickel
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/406 Ammonia
• CPC Class Codes: B01D 2258/01 Engine exhaust gases
• CPC Class Codes: B01D 53/58 Ammonia
• CPC Class Codes: B01D 53/8634 Ammonia
• CPC Class Codes: B01D 53/90 Injecting reactants
• CPC Class Codes: B01D 53/9431 Processes characterised by a specific device
• CPC Class Codes: C01C 1/006 making use of solid ammonia storage materials, e.g. complex ammine salts
• CPC Class Codes: F01N 2610/02 the substance being ammonia or urea
• CPC Class Codes: F01N 2610/06 the substance being in the gaseous form
• CPC Class Codes: F01N 2610/10 the substance being heated, e.g. by heating tank or supply line of the added substance
• CPC Class Codes: F01N 2610/105 : Control thereof
• CPC Class Codes: F01N 2610/12 : the substance being in solid form, e.g. pellets or powder
• CPC Class Codes: F01N 2610/14 : Arrangements for the supply of substances, e.g. conduits
• CPC Class Codes: F01N 2610/1406 : Storage means for substances, e.g. tanks or reservoirs
• CPC Class Codes: F01N 3/2066 : Selective catalytic reduction [SCR]
• CPC Class Codes: F01N 3/208 : Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
• CPC Class Codes: F16K 49/00 : Means in or on valves for heating or cooling heating or cooling of pipes or pipe systems F16L53/00; thermal insulation in connection with pipes or pipe systems F16L59/16
• CPC Class Codes: Y02T 10/12 : Improving ICE efficiencies
• CPC Class Codes: Y10T 137/0318 : Processes
• CPC Class Codes: Y10T 137/6416 : With heating or cooling of the system

Abstract

Disclosed is a method for storing and delivering ammonia, wherein a first ammonia adsorbing/absorbing material having a higher vapor pressure at a given temperature than a second ammonia adsorbing/absorbing material is used as an ammonia source for said second ammonia adsorbing/absorbing material when said second adsorbing/absorbing material is depleted of ammonia by consumption, and a device for performing the method.

Claims

1. A device for providing ammonia to a consumption unit comprising at least two metal ammine complex salt ammonia storage materials capable of ab- or adsorbing and desorbing ammonia;

a first storage container with a first ammonia storage material of said at least two metal ammine complex salt ammonia storage materials;

a second storage container smaller than said first storage container with a second ammonia storage material of said at least two metal ammine complex salt ammonia storage materials;

said first and second ammonia storage materials being the same materials;

first heating means for heating the first ammonia storage material to release ammonia from the first storage container;

second heating means for heating the second ammonia storage material to release ammonia from the second storage container;

first means for delivering gaseous ammonia to the consumption unit;

second means for connecting the first storage container and delivering gaseous ammonia to the second storage container, said second means comprising a valve; and

a controller configured to control the valve and the heating of the first and second ammonia storage materials such that the valve is closed during heating the second ammonia storage material in said second container by said second heating means so as to prevent ammonia to be absorbed by the first ammonia storage material in said first storage container, wherein ammonia is delivered to the consumption unit by said heating of the second ammonia storage material by said second heating means, and the valve is opened so as to establish a fluid communication between said first and said second storage containers, when the second ammonia storage material is depleted of ammonia by consumption and the heating of the second ammonia storage material by said second heating means is stopped and the heating of said first ammonia storage material by said first heating means is initiated, whereby the first ammonia storage material due to its desorption of ammonia through the heating thereof by said first heating means serves as an ammonia source for re-saturating the second ammonia storage material.

2. The device according to claim 1, wherein the metal ammine complex salt is of the general formula:

M_a(NH₃)_nX_z, wherein M is one or more cations selected from the group consisting of alkali metals, alkaline earth metals, and transition metals, X is one or more anions selected from fluoride, chloride, bromide, iodide, nitrate, thiocyanate, sulphate, molybdate, and phosphate ions, a is the number of cations per salt molecule, z is the number of anions per salt molecule, and n is the coordination number of 2 to 12.

3. The device according to claim 1, wherein the first storage container is insulated.

4. The device according to claim 1, wherein any one or both of the first and the second ammonia storage materials is compacted to a unit with a density of above 75% of a theoretical density of the saturated solid ammonia storage material.

5. The device according to claim 1, wherein the consumption unit is a catalyst for a selective catalytic reduction of NO_x in an oxygen-containing exhaust gas from a combustion process or engine.

6. The device according to claim 1, wherein the consumption unit is a fuel cell consuming ammonia either

(a) directly, or

(b) via a catalytic ammonia cracking reactor for cracking ammonia into hydrogen and nitrogen.

7. The device according to claim 1, wherein the consumption unit is a NO_x removing system with control means for controlling one or both of said first and second delivery means.

8. A method of delivering ammonia to a consumption unit, wherein a second ammonia storage material of at least two metal ammine complex salt ammonia storage materials capable of ab- or adsorbing and desorbing ammonia in a second storage container having second heating means is heated by said second heating means, while a valve included in a line between the second storage container and a first storage container larger than said second storage container is closed during the heating of said second ammonia storage material by said second heating means so as to prevent ammonia to be absorbed by a first ammonia storage material of said at least two metal ammine complex salt ammonia storage materials capable of ab- or adsorbing and desorbing ammonia in said first storage container, and the valve is opened and the heating of said second ammonia storage material by said second heating means is stopped, when the second ammonia storage material is depleted of ammonia by consumption, and the heating of the said first ammonia storage material in said first storage container by said first heating means is initiated so as to establish a fluid communication between said first and said second storage containers, whereby the first ammonia storage material due to its desorption of ammonia through heating thereof by said first heating means serves as an ammonia source for re-saturating the second ammonia storage material;

wherein said first and second ammonia storage materials are the same materials.

9. The method according to claim 8, wherein said fluid communication is reinterrupted and reassumed.

10. The method according to claim 9, wherein the fluid communication is reinterrupted while the second ammonia storage material is again heated for desorption of ammonia, and the fluid communication is reassumed when the heating of the second ammonia storage material is stopped again.

11. The method according to claim 8, wherein the metal ammine complex salt is of the general formula:

M_a(NH₃)_nX_z, wherein M is one or more cations selected from the group consisting of alkali metals, alkaline earth metals, and transition metals, X is one or more anions selected from fluoride, chloride, bromide, iodide, nitrate, thiocyanate, sulphate, molybdate, and phosphate ions, a is the number of cations per salt molecule, z is the number of anions per salt molecule, and n is the coordination number of 2 to 12.

12. The method according to claim 8, wherein any one or both of the first and the second ammonia storage materials is compacted to a unit with a density of above 75% of a theoretical density of the saturated solid ammonia storage material.

13. The method according to claim 8, wherein desorbed ammonia is delivered to a catalyst for a selective catalytic reduction of NO_x in an oxygen-containing exhaust gas from a combustion process or engine.

14. The method according to claim 8, wherein the desorbed ammonia is delivered to a fuel cell, either

(a) directly, or

(b) via a catalytic ammonia cracking reactor for cracking ammonia into hydrogen and nitrogen.