Controlled production of ammonia

• US 20010042378A1
• Filed: 06/12/2001
• Published: 11/22/2001
• Est. Priority Date: 09/20/1995
• Status: Active Grant

• Current Assignee: Charles M. Byrd, Dennis M. Pfister
• Original Assignee: Charles M. Byrd, Dennis M. Pfister
• Inventors: Pfister, Dennis M., Byrd, Charles M.
• Granted Patent: US 6,430,943 B2
• Time in Patent Office: Days
• US Class Current: 62/112
• CPC Class Codes: C01B 6/065 Hydrides of arsenic or antimony
• CPC Class Codes: C01C 1/006 making use of solid ammonia storage materials, e.g. complex ammine salts
• CPC Class Codes: C09K 5/047 for absorption-type refrigeration systems
• CPC Class Codes: F25B 17/08 the absorbent or adsorbent being a solid, e.g. salt F25B17/12 takes precedence
• CPC Class Codes: F25B 2333/005 the generator or boiler uses electromagnetic energy in the form of microwaves for desorbing the sorbate from the sorbate/sorbent compound
• CPC Class Codes: F25B 35/04 using a solid as sorbent
• CPC Class Codes: F25B 49/046 Operating intermittently
• CPC Class Codes: F25D 23/12 Arrangements of compartments additional to cooling compartments; Combinations of refrigerators with other equipment, e.g. stove
• CPC Class Codes: H01L 23/427 Cooling by change of state, e.g. use of heat pipes by liquefied gas H01L23/445
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: H05B 6/701 using microwave applicators
• CPC Class Codes: H05B 6/80 Apparatus for specific applications stoves or ranges F24C7/02
• CPC Class Codes: H05B 6/802 for heating fluids methods of heating fluids in conventional microwave ovens H05B6/687
• CPC Class Codes: H05B 6/808 Microwave heating adapted for vending machines
• CPC Class Codes: H05K 7/20363 Refrigerating circuit comprising a sorber

Abstract

Improved methods for the controlled generation of ammonia from an ammoniated metal salt at substantially ambient temperature by applying microwave energy to the salt. The ammoniated salts have the formula MA_n·(NH₃), wherein M is at least one metal selected from the group consisting of alkali metals, alkaline earth metals, scandium, ytterbium, the lanthanides, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, tin, and aluminum; A is at least one ion selected from the group consisting Cl⁻, Br⁻, F⁻, I⁻, ClO₃⁻, ClO₄⁻, BF₄⁻, AlCl₄⁻, PF₆⁻, SbCl₆⁻, and SbF₆⁻; and SbF₆⁻ n is from 1 to 6; and X is from 1 to 8. The methods are useful in, inter alia, absorption type refrigeration systems where ammonia is used as a refrigerant and the salt is used as a sorbent bed.

Claims

1. A method for the generation of ammonia comprising:

(a) providing an ammoniated metal salt having the formula MA_n·

X(NH₃), wherein

M is at least one metal selected from the group consisting of alkali metals, alkaline earth metals, scandium, ytterbium, the lanthanides, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, tin, and aluminum,

A is at least one ion selected from the group consisting Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

,

n is from 1 to 6, and

X is from 1 to 8; and

(b) applying microwave energy to said salt at substantially ambient temperature for a time sufficient to produce said ammonia.

2. The method of

claim 1

wherein:

M is at least one of copper, silver, and gold;

A is at least one Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 1.

3. The method of

claim 1

wherein:

M is at least one of chromium, manganese, iron, cobalt, nickel, palladium, platinum, copper, zinc, cadmium, and mercury;

A is at least Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 2.

4. The method of

claim 1

wherein:

M is at least one of scandium, ytterbium, the lanthanides, chromium, molybdenum, tungsten, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, and iridium;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 3.

5. The method of

claim 1

wherein:

M is at least one of titanium, zirconium, hafnium, vanadium, niobium, molybdenum, tungsten, and osmium;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 4.

6. The method of

claim 1

wherein:

M is at least one of niobium, tantalum, tungsten, and molybdenum;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 5.

7. The method of

claim 1

wherein:

M is tungsten;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 6.

8. The method of

claim 1

wherein M is at least one of alkaline earth metals, chromium, manganese, iron, cobalt, nickel, cadmium, zinc, tantalum, rhenium, sodium, potassium, cesium, aluminum, and copper, and A is Cl−

or Br−

.

9. The method of

claim 1

wherein M is at least one of chromium, manganese, iron, cobalt, nickel, cadmium, zinc, tantalum or rhenium, and A is Cl⁻

or Br⁻

.

10. The method of

claim 1

wherein MA_n is one of NaAlCl₄, KAlCl₄, K₂ZnCl₄, K₂FeCl₅, or CsCuCl₃.

11. The method of

claim 1

wherein M is an alkali metal or an alkaline earth metal, A is Cl⁻

or Br⁻

, and n is 1 or 2.

12. A method of

claim 1

where said ammoniated metal salt is a chloride or bromide of strontium.

32. The method of

claim 1

wherein said ammoniated metal salt of step (A) further comprises ammonium.

33. The method of

claim 1

where said ammoniated metal salt of step (A) is partially ammoniated.

13. A method for cooling comprising,

(a) adsorbing ammonia onto a metal salt to provide a corresponding ammoniated metal salt;

(b) desorbing ammonia from said ammoniated metal salt by applying microwave energy thereto; and

(c) circulating said desorbed ammonia through a refrigeration sorption system to produce said cooling.

14. The method of

claim 13

wherein Step (a) comprises, (i) subjecting said metal salt to microwave energy to remove water and then (ii) exposing said metal salt to ammonia.

15. The method of

claim 13

wherein said application of microwave energy is at substantially ambient temperature and for a time sufficient to desorb said ammonia.

16. The method of

claim 13

wherein said ammoniated metal salt has the formula MA_n·

X(NH₃), wherein;

M is at least one metal selected from the group consisting of alkali metals, alkaline earth metals, scandium, ytterbium, the lanthanides, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, tin, and aluminum;

A is at least one ion selected from the group consisting of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

;

n is from 1 to 6; and

X is from 1 to 8.

17. The method of

claim 16

wherein:

M is at least one of copper, silver, and gold;

A is at least one Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 1.

18. The method of

claim 16

wherein:

M is at least one of chromium, manganese, iron, cobalt, nickel, palladium, platinum, copper, zinc, cadmium, and mercury;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 2.

19. The method of

claim 16

wherein:

M is at least one of scandium, ytterbium, the lanthanides, chromium, molybdenum, tungsten, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, and iridium;

A is at least one Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 3.

20. The method of

claim 16

wherein:

M is at least one of titanium, zirconium, hafnium, vanadium, niobium, molybdenum, tungsten, and osmium;

A is at least one ion of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 4.

21. The method of

claim 16

wherein:

M is at least one of niobium, tantalum, tungsten, and molybdenum;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 5.

22. The method of

claim 16

wherein:

M is tungsten;

A is at least one of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄⁻

, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

; and

n is 6.

23. The method of

claim 16

wherein M is at least one of alkaline earth metals, chromium, manganese, iron, cobalt, nickel, cadmium, zinc, tantalum, rhenium, sodium, potassium, cesium, aluminum, and copper, and A is Cl⁻

or Br⁻

.

24. The method of

claim 16

wherein M is at least one of chromium, manganese, iron, cobalt, nickel, cadmium, zinc, tantalum or rhenium, and A is Cl⁻

or Br⁻

.

25. The method of

claim 16

wherein MA_n is one of NaAlCl₄, KalCl₄, K₂ZnCl₄, K₂FeCl₅, or CsCuCl₃.

26. The method of

claim 16

wherein M is a alkali metal or an alkaline earth metal, A is Cl⁻

or Br⁻

, and n is 1 or 2.

27. A method of

claim 16

where said ammoniated metal salt is a chloride or bromide of strontium.

28. A method for cooling comprising,

(a) adsorbing ammonia onto a zeolite to provide a corresponding ammoniated zeolite;

(b) desorbing ammonia from said ammoniated zeolite by applying microwave energy thereto at substantially ambient temperature for a time sufficient to produce said ammonia; and

(c) circulating said desorbed ammonia through a refrigeration sorption system to produce said cooling.

29. A method for the generation of phosphine or arsine comprising,

(a) providing a ligated metal salt having the formula MAn·

X(EH₃);

wherein

M is at least one metal selected from the group consisting of alkali metals, alkaline earth metals, scandium, ytterbium, the lanthanides, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, tin, and aluminum;

A is at least one ion selected from the group consisting of Cl⁻

, Br⁻

, F⁻

, I⁻

, ClO₃⁻

, ClO₄⁻

, BF₄⁻

, AlCl₄, PF₆⁻

, SbCl₆⁻

, and SbF₆⁻

;

n is from 1 to 6;

X is from 1 to 8; and

E is P or As; and

(b) applying microwave energy to said salt at substantially ambient temperature for a time sufficient to produce said phosphine or arsine.

30. The method of

claim 29

wherein E is P.

31. The method of

claim 29

wherein E is As.