Production of metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-2016346756-A1
Application number	US-201615172942-A
Country	US
Kind code	A1
Filing date	Jun 3, 2016
Priority date	May 27, 2015
Publication date	Dec 1, 2016
Grant date	—

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

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:
a tubular flow reactor which comprises a heated tubular body having an inlet into which, in use, precursor solutions are fed and flow, said precursor solutions comprising precursor compounds which form the metal organic framework, 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 inline mixer located at or proximate the inlet to the heated tubular body, the inline mixer mixing the precursor solutions through inline mixing in a feed conduit fluidly connected to the inlet of the tubular body, wherein the precursor compounds are provided as at least two different precursor solutions fed into the same inlet of the tubular reactor at room temperature, the at least two different precursor solutions comprising a first precursor solution comprising at least one of the multidentate linking ligand; and a second precursor solution comprising the metal cluster or a metallic salt thereof, and wherein the at least two different precursor solutions are mixed at or proximate that inlet of the tubular reactor and 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 . An apparatus according to claim 1 , wherein the average radius of each annular loop is between 10 and 1000 mm, preferably between 20 and 500 mm.

3 . An apparatus according to claim 1 , wherein the annular loops form a substantially tubular shaped coil radially centred about the central axis.

4 . An apparatus according to claim 1 , wherein the length of the coil is greater than 50 mm, preferably greater than 100 mm, more preferably between 20 and 2000 mm.

5 . An apparatus according to claim 1 , wherein the internal diameter of the tubular body is between 0.5 mm and 50 mm, preferably between 1 and 15 mm.

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

7 . An apparatus according to claim 1 , wherein the tubular body heats the precursor compounds to a temperature of between 20 and 200° C., preferably between 25 and 150° C., more preferably between 25 and 130° C.

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

11 . An apparatus according to claim 8 , wherein the applied high frequency ultrasound is between 400 kHz to 4 MHz, preferably between 600 kHz and 2 MHz, more preferably between 600 kHz and 1 MHz.

12 . An apparatus according to claim 8 , wherein at least one contaminant includes occluded unreacted ligands within pores of the MOF.

13 . An apparatus according to claim 1 , wherein the MOF 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 precursor compounds comprise at least one of the multidentate linking ligand; or the metal cluster or a metallic salt thereof.

14 . A system for producing a metal organic framework (MOF), 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.

15 . An apparatus according to claim 1 , wherein the precursor compounds are provided in at least two different precursor solutions containing different precursor compounds, the precursor solutions being mixed through inline mixing in a feed conduit fluidly connected to the inlet of the tubular body where the different precursor solutions are fed into the same inlet, the two or more precursor solutions being mixed at or proximate that inlet.

16 . An 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.

17 . An apparatus according to claim 16 , wherein the tubular reactor comprises a tube and shell reactor type.

18 . An apparatus according to claim 1 , wherein each metal cluster comprises two or more metal ions and each ligand of the plurality of multidentate ligand includes two or more carboxylates.

19 . An apparatus according to claim 1 , wherein at least one ligand of the plurality of charged multidentate linking ligands 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.

20 . An apparatus according to claim 1 , 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.

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

• C07F19/00

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

• C07F19/005

  without metal-C linkages · CPC title

• C07F5/003

  without C-Metal linkages · CPC title

• C07F5/061

  with C-aluminium linkage · CPC title