System and method for large scale synthesis of metal cyanometallates

Patent metadata

Field	Value
Publication number	US-9567231-B2
Application number	US-201615230395-A
Country	US
Kind code	B2
Filing date	Aug 6, 2016
Priority date	Mar 28, 2012
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

A system and method are presented for the large scale synthesis of metal cyanometallates (MCMs). First and second precursor solutions are added to a main reactor, where the first precursor includes M1 metal cations. The second precursor solution includes A X′ M2(CN) Z′ , where M1 and M2 are from a first group of metals and A is from a second group of metals including alkali or alkaline earth metals. In response to stirring the first and second precursors, MCM particles are formed with the formula A X M1 N M2 M (CN) Z .d[H 2 O] ZEO .e[H 2 O] BND , in solution. In response to aging in the secondary reactor, the size of the MCM particles is increases. The aged MCM particles in solution are then transferred to a separation tank, where the aged MCM particles are filtered from the solution and collected. The solution reclaimed from the separation tank back is added back into the main reactor.

First claim

We claim:

1. A method for large scale synthesis of metal cyanometallates (MCMs), the method comprising:
adding a first precursor solution to a main reactor, where the first precursor includes M1 metal cations;
adding a second precursor solution of A X′ M2(CN) Z′ to the main reactor,
where M1 and M2 are from a first group of metals and A is from a second group of metals;
where X′ is in the range of 1 to 5;
where Z′ is in the range of 2 to 6;

in response to stirring the first and second precursors in the main reactor, forming MCM particles, with the formula A X M1 N M2 M (CN) Z .d[H 2 O] ZEO .e[H 2 O] BND , in solution:
where [H 2 O] ZEO is zeolitic water,
where [H 2 O] BND is lattice bound water,
where x is in the range of 0.5 to 2;
where m is in the range of 0.5 to 1.5;
where N is in the range of 0.5 to 1.5;
where z is in the range of 5 to 6;
where d is 0;
where e is in the range of greater than 0 and less than 8;

transferring the MCM particles in solution to a secondary reactor;
in response to aging in the secondary reactor, growing (increasing) the size of the MCM particles;
transferring the aged MCM particles in solution to a separation tank;
filtering the aged MCM particles from the solution;
collecting the filtered MCM particles; and,
adding solution reclaimed from the separation tank back into the main reactor.

2. The method of claim 1 wherein transferring the MCM particles in solution to the secondary reactor includes transferring the MCM particles in solution to a plurality of secondary reactors connected in parallel between the main reactor and the separation tank.

3. The method of claim 1 wherein collecting the filtered MCM particles includes collecting MCM particles having a size of 0.5 microns or larger.

4. The method of claim 1 further comprising:
adding a third precursor selected from the group consisting of salts, carbonaceous materials, organics, polymers, or combinations thereof, into a vessel selected from the group consisting of the main reactor, the secondary reactor, the separation tank, or combinations thereof; and,
coating MCM particle surfaces with the third precursor material.

5. The method of claim 1 wherein adding the first and second precursors to the main reactor includes adding the first and second precursors in a water solution; and,
the method further comprising:
heating the main reactor to a temperature in a range between 20 and 100 degrees C.

6. The method of claim 1 wherein adding the first and second precursors to the main reactor includes adding the first and second precursors in a high boiling point solution; and,
the method further comprising:
heating the main reactor to a temperature in a range of 20 to 120 degrees C.

7. The method of claim 1 wherein transferring the MCM particles in solution to the secondary reactor includes:
heating the secondary reactor to a temperature in a range of 20 to 200 degrees C.; and,
maintaining a pressure in a range of 1 to 3 atmospheres.

8. The method of claim 1 where A is selected from the group consisting of lithium, (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), magnesium (Mg), aluminum (Al), and zinc (Zn).

9. The method of claim 1 wherein M1 and M2 are independently selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zn, calcium (Ca), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), strontium (Sr), barium (Ba), and magnesium (Mg).

10. A large scale metal cyanometallate (MCM) synthesizer, the synthesizer comprising:
a main reactor comprising:
an inlet configured to accept:
a first precursor solution including M1 metal cations;
a second precursor solution of A X′ M2(CN) Z′ , where M1 and M2 are from a first group of metals and A is from a second group of metals, where X′ is in the range of 1 to 5, and where Z′ is in the range of 2 to 6;
a reclaimed solution;

a stirring mechanism;
a heating mechanism;
an outlet to supply a solution of MCM particles having an average first size, with the formula A X M1 N M2 M (CN) Z .d[H 2 O] ZEO .e[H 2 O] BND :
where [H 2 O] ZEO is zeolitic water,
where [H 2 O] BND is lattice bound water,
where X is in the range of 0.5 to 2;
where M is in the range of 0.5 to 1.5;
where N is in the range of 0.5 to 1.5;
where Z is in the range of 5 to 6;
where d is 0;
where e is in the range of greater than 0 and less than 8;

a pressurized secondary reactor having an inlet to accept the solution of MCM particles, a heating mechanism, and an outlet to supply aged MCM particles in solution having an average second size greater than the average first size; and,
a separation tank having an inlet to accept the aged MCM particles in solution, a filter to separate the aged MCM particles from the solution, and an outlet to supply the filtered MCM particles and reclaimed solution.

11. The synthesizer of claim 10 further comprising:
a plurality of pressurized secondary reactors, each having an inlet connected to the main reactor output, and an output connected to the separation tank inlet.

12. The synthesizer of claim 10 wherein the separation tank first outlet supplies filtered MCM particles having a size of 0.5 microns or larger.

13. The synthesizer of claim 10 wherein the main reactor accepts a third precursor selected from the group consisting of salts, carbonaceous materials, organics, polymers, or combinations thereof; and,
wherein the main reactor outlet supplies MCM particle surfaces coated with the third precursor material.

14. The synthesizer of claim 10 wherein the first and second precursors solutions comprise water; and
wherein heating mechanism heats the main reactor to a temperature in a range between 20 and 100 degrees C.

15. The synthesizer of claim 10 wherein the first and second precursors solutions comprise a high boiling point solution; and
wherein heating mechanism heats the main reactor to a temperature in a range between 20 and 120 degrees C.

16. The synthesizer of claim 10 wherein the heating mechanism heats the secondary reactor to a temperature in a range of 20 to 200 degrees C., while maintaining a pressure in a range of 1 to 3 atmospheres.

17. The synthesizer of claim 10 wherein the separation tank inlet accepts a third precursor made from a material selected from the group consisting of salts, carbonaceous materials, organics, polymer materials, and combinations thereof, and,
wherein the separation tank outlet supplies filtered MCM particle surfaces coated with the third precursor material.

18. The synthesizer of claim 10 wherein the secondary reactor accepts a third precursor made from a material selected from the group consisting of salts, carbonaceous materials, organics, polymer materials, and combinations thereof, and,
wherein the secondary reactor outlet supplies aged MCM particle surfaces coated with the third precursor material.

19. The synthesizer of claim 10 where A is selected from the group consisting of lithium, (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), calcium (Ca), magnesium (Mg), aluminum (Al), and zinc (Zn).

20. The synthesizer of claim 10 wherein M1 and M2 are independently selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zn, calcium (Ca), niobium (Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), strontium (Sr), ba

Assignees

• Sharp Laboratories America Inc

Inventors

• Lu Yuhao
• Pan Wei
• Vail Sean
• Lee Jong-Jan

Classifications

• B01J2219/00051

  Controlling the temperature · CPC title

• C01P2006/40

  Electric properties · CPC title

• B01J19/2445

  placed in parallel · CPC title

• H01M10/054

  Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium · CPC title

• C01C3/11 Primary

  Complex cyanides · CPC title