Production of metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-10525440-B2
Application number	US-201916297413-A
Country	US
Kind code	B2
Filing date	Mar 8, 2019
Priority date	May 27, 2015
Publication date	Jan 7, 2020
Grant date	Jan 7, 2020

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. A process for producing metal organic frameworks, the process comprising:
mixing at least two different precursor solutions for forming the metal organic framework (MOF) through inline mixing to form a solution mixture, the precursor solutions comprising a first precursor solution comprising at least one multidentate linking ligand in solvent; and a second precursor solution comprising a metal cluster or metallic salt thereof in solvent,
introducing the solution mixture into an apparatus which comprises: a tubular flow reactor which comprises a tubular body having an inlet into which, in use, the solution mixture is fed and flows, said tubular body including at least one annular loop comprising a coil; and a flow restriction device comprising a back-pressure controller downstream of the tubular reactor for controlling the pressure within the tubular reactor, and
promoting a reaction within the tubular flow reactor to form the metal organic framework,
wherein the precursor solutions are mixed through inline mixing in a feed conduit fluidly connected to the inlet of the tubular body and the resulting solution mixture being fed into said inlet at room temperature, the two or more precursor solutions being mixed at or proximate said inlet,
and wherein the solution mixture flows through said tubular body mixing the precursor compounds therein to produce the metal organic frameworks.

2. The process according to claim 1 , wherein the apparatus further comprises an inline mixer located at or proximate the inlet to the tubular body, the inline mixer mixing the precursor solutions through inline mixing in said feed conduit fluidly connected to the inlet of the tubular body.

3. The process according to claim 1 , further including the step of:
applying a high frequency ultrasound of at least 20 kHz to a MOF containing solution sourced from the tubular flow reactor, thereby separating the MOF material from solution as an aggregated sediment which settles out of the MOF containing solution.

4. The process according to claim 3 , wherein the yield of MOF from the apparatus is greater than 60%.

5. The process according to claim 1 , wherein the tubular body comprises a heated tubular body in which the solution mixture is 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.

6. The process according to claim 5 , wherein the tubular body is located inside a heated housing and the housing is heated via heating inlet and outlet port connections through which heated fluid is fed and extracted to heat the tubular body.

7. The process according to claim 5 , wherein the tubular body heats the precursor compounds to a temperature of between 20 and 200° C.

8. The process according to claim 1 , wherein the apparatus further includes a separator 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 process according to claim 8 , wherein the housing comprises a container including at least one wall position to contact the MOF containing, and the transducer is high frequency ultrasound transducer is position within the reservoir or in engagement with the at least one wall.

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

11. The process according to claim 8 , wherein the applied high frequency ultrasound is at least one of:
between 400 kHz to 4 MHz or
greater than 1 MHz.

12. The process according to claim 8 , wherein the applied high frequency ultrasound is at least one of:
between 600 kHz and 2 MHz; or
between 1 MHz and 4 MHz.

13. The process according to claim 8 , wherein at least one contaminant includes occluded unreacted ligands within pores of the MOF.

14. The process according to claim 1 , wherein the metal organic framework comprises 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, and wherein the at least two different precursor solutions comprise a first precursor solution comprising at least one of the multidentate linking ligands; and a second precursor solution comprising a metal cluster or a metallic salt thereof.

15. The process according to claim 14 , wherein each metal cluster comprises two or more metal ions and each ligand of the plurality of multidentate ligand includes two or more carboxylates.

16. The process according to claim 14 , wherein at least one ligand of the plurality of multidentate ligand comprises an organic ligand which is at least bidentate and is selected from the group consisting of formic acid, acetic acid, oxalic acid, propanoic acid, butanedioic acid, (E)-butenedioic acid, benzene-1,4-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid, 2-bromo-1,4-benzenedicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, biphenyl-3,3′,5,5′-tetracarboxylic acid, biphenyl-3,4′,5-tricarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 1,3,5-tris(4-carboxyphenyl)benzene, (2E,4E)-hexa-2,4-dienedioic acid, 1,4-naphthalenedicarboxylic acid, pyrene-2,7-dicarboxylic acid, 4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid, aspartic acid, glutamic acid, adenine, 4,4′-bypiridine, pyrimidine, pyrazine, pyridine-4-carboxylic acid, pyridine-3-carboxylic acid, imidazole, 1H-benzimidazole, 2-methyl-1H-imidazole, and mixtures thereof.

17. The process according to claim 14 , wherein the metal ion is selected from the group consisting of Group 1 through 16 metals of the IUPAC Periodic Table of the Elements including actinides, and lanthanides, and combinations thereof.

18. The process according to claim 14 , wherein the multidentate linking ligand has 6 or more atoms that are incorporated in aromatic rings or non-aromatic rings.

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 Dean
• Monch Andreas Alexander

Classifications

• C07F19/005

  without metal-C linkages · CPC title

• C07F19/00

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

• C07F5/061

  with C-aluminium linkage · CPC title

• C07F5/003

  without C-Metal linkages · CPC title

• C07F1/005

  without C-Metal linkages · CPC title