Production of metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-10272412-B2
Application number	US-201615172942-A
Country	US
Kind code	B2
Filing date	Jun 3, 2016
Priority date	May 27, 2015
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

An apparatus for producing metal organic frameworks, comprising: a tubular flow reactor comprising a tubular body into which, in use, precursor compounds which form the metal organic framework are fed and flow, said tubular body including at least one annular loop.

First claim

The invention claimed is:

1. An apparatus for producing metal organic frameworks which comprise a plurality of metal clusters, each metal cluster including one or more metal ions; and a plurality of charged multidentate linking ligands connecting adjacent metal clusters, the apparatus comprising:
at least two precursor reservoirs that contain at least two different precursor solutions, wherein one precursor reservoir contains a precursor solution comprising at least one multidentate linking ligand, and another precursor reservoir contains a different precursor solution comprising at least one metal cluster or metallic salt thereof;
a tubular flow reactor which comprises a heated tubular body having an inlet into which, in use, the at least two different precursor solutions are fed and flow, and an outlet through which, in use, formed metal organic frameworks flow out of the tubular body, said tubular body including at least one annular loop comprising a coil;
a flow restriction device comprising a back-pressure controller downstream of the tubular reactor for controlling the pressure within the tubular reactor; and
an static inline mixer located at least one of (a) at or proximate the inlet to the heated tubular body within a feed conduit fluidly connected to the inlet of the tubular body and fluidly connected to the at least two precursor reservoirs; (b) within the tubular reactor, the inline mixer; or (c) the combination thereof, in use, mixes the at least two different precursor solutions from the precursor reservoirs through inline mixing,
wherein the precursor compounds are fed into the same inlet of the tubular reactor at room temperature,
and wherein the at least two different precursor solutions are heated during flow through the said tubular body, said flow through said tubular body mixing the precursor compounds therein to produce the metal organic frameworks.

2. The apparatus according to claim 1 , wherein the average radius of each annular loop is between 10 and 1000 mm.

3. The apparatus according to claim 1 , wherein the coil comprises a substantially tubular shaped coil radially centered about a central axis.

4. The apparatus according to claim 3 , wherein the length of the coil is greater than 50 mm.

5. The apparatus according to claim 1 , wherein the internal diameter of the tubular body is at least 1 mm.

6. The apparatus according to claim 1 , wherein the tubular body is located inside a heated housing.

7. The apparatus according to claim 1 , wherein the tubular body heats the precursor compounds to a temperature of between 20 and 200° C.

8. The apparatus according to claim 1 , further including an apparatus for separating a metal organic framework (MOF) from a solution, comprising:
a housing having a reservoir capable of receiving a MOF containing solution; and
a high frequency ultrasound transducer operatively connected to the reservoir and capable of applying megasonic frequencies of at least 400 kHz to the MOF containing solution.

9. The apparatus according to claim 8 , wherein the housing comprises a container including at least one wall positioned to contact the MOF containing solution, and the high frequency ultrasound transducer is positioned within the reservoir or in engagement with the at least one wall.

10. The apparatus according to claim 8 , wherein the housing comprises at least one reflector surface designed to reflect the applied megasonic frequencies within the reservoir.

11. The apparatus according to claim 8 , wherein the applied megasonic frequency is between 400 kHz and to 4 MHz.

12. A metal organic framework (MOF) production system, comprising:
an apparatus for forming a metal organic framework from precursor materials according to claim 1 ; and
an apparatus for washing and/or purifying the metal organic framework, comprising: a housing having a reservoir capable of receiving a MOF containing solution from the reactor; and a high frequency ultrasound transducer operatively connected to the reservoir and capable of applying megasonic frequencies of at least 20 kHz to the MOF containing solution.

13. The apparatus according to claim 8 , wherein the housing is heated via heating inlet and outlet port connections through which heated fluid is fed and extracted to heat the tubular body.

14. The apparatus according to claim 13 , wherein the tubular reactor comprises a tube and shell reactor type.

15. The apparatus according to claim 1 , further comprising a flow mixing junction fluidly connected to each of the at least two precursor reservoirs and the feed conduit, the flow mixing junction configured to merge the at least two different precursor solutions into the feed conduit, the at least two different precursor solutions flowing through the feed conduit as a mixed stream of precursor solutions to be fed into the inlet of the tubular reactor, wherein the precursor solutions in the feed conduit and fed into the tubular reactor consist of at least one multidentate linking ligand, at least one metal cluster or metallic salt thereof and at least one solvent.

16. An apparatus for producing metal organic frameworks which comprise a plurality of metal clusters, each metal cluster including one or more metal ions; and a plurality of charged multidentate linking ligands connecting adjacent metal clusters, the apparatus comprising:
at least two precursor reservoirs that contain at least two different precursor solutions, wherein one precursor reservoir contains a precursor solution comprising at least one multidentate linking ligand, and another precursor reservoir contains a different precursor solution comprising at least one metal cluster or metallic salt thereof;
a tubular flow reactor which comprises a heated tubular body having an inlet into which, in use, the at least two different precursor solutions are fed and flow, and an outlet through which, in use, formed metal organic frameworks flow out of the tubular body, said tubular body including at least one annular loop comprising a coil, the internal diameter of the tubular body being at least 1 mm;
a flow mixing junction fluidly connected to each of the at least two precursor reservoirs and a single feed conduit which is fluidly connected to the inlet of the tubular reactor, the flow mixing junction configured to merge the at least two different precursor solutions into the feed conduit, the at least two different precursor solutions flowing through the feed conduit as a mixed stream of precursor solutions to be fed into the inlet of the tubular reactor,
an inline mixer located at least one of (a) at or proximate the inlet to the heated tubular body within the feed conduit; (b) within the tubular reactor, the inline mixer; or (c) the combination thereof, in use, mixes the at least two different precursor solutions from the precursor reservoirs through inline mixing; and
a flow restriction device comprising a back-pressure controller downstream of the tubular reactor for controlling the pressure within the tubular reactor,
wherein the precursor compounds are fed into the same inlet of the tubular reactor at room temperature,
and wherein the at least two different precursor solutions are heated during flow through the said tubular body, said flow through said tubular body mixing the precursor compounds therein to produce the metal organic frameworks.

17. The apparatus according to claim 16 , wherein the inline mixer comprises a static inline mixer.

Assignees

• Commw Scient Ind Res Org

Inventors

• Rubio Martinez Marta
• Hill Matthew Roland
• Batten Michael
• Lim Kok Seng
• Polyzos Anastasios
• Barton Timothy Raymond
• Hadley Trevor Deon
• Monch Andreas Alexander

Classifications

• C07F1/005

  without C-Metal linkages · CPC title

• C07F19/005

  without metal-C linkages · CPC title

• B01J19/24

  Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) · CPC title

• C07F19/00

  Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 · CPC title

• C07F5/003

  without C-Metal linkages · CPC title