WO2017050936A1 - Process - Google Patents
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- Publication number
- WO2017050936A1 WO2017050936A1 PCT/EP2016/072608 EP2016072608W WO2017050936A1 WO 2017050936 A1 WO2017050936 A1 WO 2017050936A1 EP 2016072608 W EP2016072608 W EP 2016072608W WO 2017050936 A1 WO2017050936 A1 WO 2017050936A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- less
- reaction mixture
- organic
- linker compound
- organic linker
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 67
- 230000008569 process Effects 0.000 title claims description 57
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 66
- -1 linker compound Chemical class 0.000 claims abstract description 45
- 239000011541 reaction mixture Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 26
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 20
- 238000005112 continuous flow technique Methods 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 150000007942 carboxylates Chemical group 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 2
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 125000005647 linker group Chemical group 0.000 description 38
- 235000002639 sodium chloride Nutrition 0.000 description 21
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000013207 UiO-66 Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000001905 inorganic group Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- DAWHTISAONTGQE-UHFFFAOYSA-N 3-(2-phenylphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1C(O)=O DAWHTISAONTGQE-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 2
- 101100489581 Caenorhabditis elegans par-5 gene Proteins 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- OTAJGWQCQIEFEV-UHFFFAOYSA-N pyrene-2,7-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=C2C=CC3=CC(C(=O)O)=CC4=CC=C1C2=C43 OTAJGWQCQIEFEV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000013341 scale-up Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- ZOQCTFVIEBUWIT-UHFFFAOYSA-N 1,2,3,3a-tetrahydropyrene-2,7-dicarboxylic acid Chemical compound C1=C2CC(C(=O)O)CC(C=C3)C2=C2C3=CC(C(O)=O)=CC2=C1 ZOQCTFVIEBUWIT-UHFFFAOYSA-N 0.000 description 1
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 1
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- PAAYYTAKLZCRDE-UHFFFAOYSA-N 2-butylterephthalic acid Chemical compound CCCCC1=CC(C(O)=O)=CC=C1C(O)=O PAAYYTAKLZCRDE-UHFFFAOYSA-N 0.000 description 1
- JRMAQQQTXDJDNC-UHFFFAOYSA-N 2-ethoxy-2-oxoacetic acid Chemical compound CCOC(=O)C(O)=O JRMAQQQTXDJDNC-UHFFFAOYSA-N 0.000 description 1
- 239000013273 3D metal–organic framework Substances 0.000 description 1
- YROTZTMCXKTYMW-UHFFFAOYSA-N 4-[4-(4-carboxyphenyl)buta-1,3-diynyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC#CC1=CC=C(C(O)=O)C=C1 YROTZTMCXKTYMW-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ORAAZVDXWSKZHK-UHFFFAOYSA-N Bis-(1-chloro-2-propyl) phosphate Chemical compound CC(CCl)OP(O)(=O)OC(C)CCl ORAAZVDXWSKZHK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 241000723346 Cinnamomum camphora Species 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XMAAINZKCZUYAX-UHFFFAOYSA-M [O-]C(C(C=C1)=CC=C1[Zn+])=O.C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1 Chemical compound [O-]C(C(C=C1)=CC=C1[Zn+])=O.C1=C(C=C(C=C2)N=C2C=C(C=C2)NC2=CC(C=C2)=NC2=C2)NC2=C1 XMAAINZKCZUYAX-UHFFFAOYSA-M 0.000 description 1
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- AXLLOYXRJRMBEW-UHFFFAOYSA-N adamantane;benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1.C1C(C2)CC3CC1CC2C3 AXLLOYXRJRMBEW-UHFFFAOYSA-N 0.000 description 1
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- VNXSDDLAAPKDBL-UHFFFAOYSA-N benzene;2-phenylbenzoic acid Chemical compound C1=CC=CC=C1.OC(=O)C1=CC=CC=C1C1=CC=CC=C1.OC(=O)C1=CC=CC=C1C1=CC=CC=C1.OC(=O)C1=CC=CC=C1C1=CC=CC=C1 VNXSDDLAAPKDBL-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
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- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 125000004051 hexyl group Chemical class [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical class C(CCCC)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- JARIJYUQOKFVAJ-UHFFFAOYSA-M sodium;4-carboxy-2-sulfobenzoate Chemical compound [Na+].OC(=O)C1=CC=C(C([O-])=O)C(S(O)(=O)=O)=C1 JARIJYUQOKFVAJ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Definitions
- the present invention relates to a continuous flow process for preparing metal organic frameworks (MOFs), in particular to a continuous flow process for preparing Zr-MOFs.
- the invention further relates to an apparatus arranged to perform said process.
- MOFs or "metal organic frameworks” are compounds having a lattice structure having vertices or “cornerstones” which are metal-based inorganic groups, for example metal oxides, linked together by organic linkers.
- the linkers are usually at least bidentate ligands which coordinate to the metal-based inorganic groups via functional groups such as carboxylate and/or amine.
- the porous nature of MOFs renders them promising materials for many applications such as gas storage and catalyst materials.
- MOF-5 in which each ZrLiO cornerstone is coordinated by six bis-carboxylate organic linkers.
- Other MOFs in which the inorganic cornerstone is for example chromium, copper, vanadium, cadmium or iron are also known.
- DMF dimethylformamide
- reactions conditions which are suitable for the production of certain MOFs may not be transferable to others where different metals are used.
- conditions found to be optimal for the production of MOFs containing main group metals from the second or third groups of the periodic table e.g.
- magnesium or aluminium are often not appropriate for the preparation of analogous frameworks wherein a transition metal is used.
- the present invention is particularly directed towards Zr-MOFs.
- An aqueous-based process for producing a Zr-MOF is reported by Yang et al in Angew. Chem. Int. Ed. 2013, 52, 10316-10320. This process involves a two-step synthesis. The product is obtained as a gel which, to be isolated, must be washed and recrystallised. This adds to the costs and timescale of the process, making it unsuitable for use on a larger industrial scale.
- the process should ideally be one which is "green” and thus considered environmentally friendly. It would also be advantageous to have a process which can be carried out quickly and cheaply and which offers
- MOFs may be prepared in a straightforward continuous flow process utilising an aqueous solvent which avoids the need for high temperatures and pressures.
- a flow reactor leads to a procedure which is applicable to use on an industrial scale and offers an environmentally friendly and cheap route to these valuable materials.
- the invention provides a continuous flow process for preparing a metal organic framework (MOF), comprising the steps:
- the metal organic framework is a zirconium-based metal organic framework (Zr-MOF).
- the invention provides apparatus arranged to perform a process as hereinbefore defined comprising a flow reactor arranged to receive a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent, wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
- the present invention describes a continuous flow process for the
- the process involves preparing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent and supplying said reaction mixture to a flow reactor at a particular temperature and pressure. The process typically involves subsequently collecting and isolating the MOF.
- MOF metal organic framework
- MOF is intended to cover any metal organic framework.
- MOFs typically comprise at least one metal ion or cluster of metal ions and at least one organic linker compound.
- the metal ion or cluster of metal ions may be any suitable metal selected from Groups 1 to 16 of the Periodic Table, preferably a metal selected from the group consisting of transition metals, alkaline earth metals, lanthanides and mixtures thereof.
- the metal ion may have any valence appropriate for the specific metal.
- the metal ion is selected from the group consisting of copper, zirconium, scandium, nickel, magnesium, bismuth, gallium, cobalt, zinc, aluminium, iron, cadmium, cerium and yttrium. Most preferably, the metal ion is zirconium. Whilst it is possible for a mixture of metal ions to be used, it is preferable if the MOF contains only a single type of metal ion.
- the process of the invention is used to prepare zirconium-based metal organic frameworks (Zr-MOFs).
- Zr-MOF zirconium-based metal organic frameworks
- the Zr-MOFs of the invention have "cornerstones" which are zirconium inorganic groups.
- Typical zirconium inorganic groups include zirconium ions connected by bridging oxygen or hydroxide groups. These inorganic groups are further coordinated to at least one organic linker compound. In some cases, the inorganic groups may be further connected to non- bridging modulator species, complexing reagents or ligands (e.g.
- the zirconium oxide unit is usually based on an idealized octahedron of Zr-ions which are ⁇ 3-bridged by 0 2 ⁇ and/or OH " ions via the faces of the octahedron and further saturated by coordinating moieties containing O-atoms like carboxylate groups.
- the idealised Zr oxide cluster is considered to be a Zr 6 03 2 -cluster which comprises between 6 and 12 (preferentially as close as possible to 12) carboxylate groups.
- the cluster may be represented by the formula Zr 6 O x (OH)8_ x wherein x is in the range 0 to 8.
- the cluster may be represented by the formula
- Zr-MOFs are well known in the art and cover structures in which the zirconium cornerstone is linked to an at least bidentate organic linker compound to form a coordinated network.
- the structures may be one- two- or three-dimensional.
- the Zr-MOF usually comprises pores which are present in the voids between the coordinated network of zirconium ions and organic linker compounds.
- the pores are typically micropores, having a diameter of 2 nm or less, or mesopores, having a diameter of 2 to 50 nm.
- the Zr-MOF may comprise additional metal ions other than zirconium, such as hafnium, titanium, or cerium, however preferably zirconium is the only metal ion present. If additional metal ions are present these may be present in an amount of up 50 wt% relative to total amount of metal ions, preferably up to 25 wt%, more preferably up to 10 wt%, e.g. up to 5 wt%.
- the Zr-MOFs of the invention particularly preferably have cornerstones having at least 12 coordination sites for the organic linkers, e.g. 12-24, preferably at least 14, 16 or 18, most especially 24. In this way at least 6, more preferably at least 8, especially at least 12 bidentate ligand groups of the organic linkers can bind to each cornerstone.
- the surface area of the MOF is preferably at least 400 m 2 /g, more preferably at least 500 m 2 /g, especially at least 700 m 2 /g, such as at least 1020 m 2 /g, for example at least 1050 m 2 /g, e.g. at least 1200 m 2 /g.
- the surface area may be up to 10000 m 2 /g, especially up to 5000 m 2 /g. It will be understood that, where functionalised organic linker compounds are used, the presence of additional, and often bulky, groups may affect (i.e. reduce) the surface area of the MOF.
- the MOFs of the invention comprise at least one organic linker compound.
- the organic linker compound is typically at least bidentate, i.e. has at least two functional groups capable of coordinating to the metal ion.
- the organic linker compound may also be tridentate (i.e. containing three functional groups) or tetradentate (i.e. containing four functional groups).
- the MOF may have a metal ion to organic linker molecule ratio of from 1 :0.45 to 1 :0.55, especially l :0.49 to 1 :0.51, particularly 1 :0.5.
- Other preferred metal ion to organic linker molecule ratios are 0.5 : 1 , 1 : 1, 3: 1 and 1 :3, especially 1 : 1.
- the organic linker compounds of the MOFs of the invention may be any organic linker molecule or molecule combination capable of binding to at least two inorganic cornerstones and comprising an organic moiety.
- organic moiety we mean a carbon based group which comprises at least one C-H bond and which may optionally comprise one or more heteroatoms such as N, O, S, B, P, Si. Typically, the organic moiety will contain 1 to 50 carbon atoms.
- the organic linker compound may be any of the linkers conventionally used in MOF production. These are generally compounds with at least two cornerstone binding groups, e.g. carboxylates, optionally with extra functional groups which do not bind the cornerstones but may bind metal ions on other materials it is desired to load into the MOF. The introduction of such extra functionalities is known in the art and is described for example by Campbell in JACS 82:3126-3128 (1960).
- the organic linker compound may be in the form of the compound itself or a salt thereof, e.g. a disodium 1 ,4-benzenedicarboxylate salt or a monosodium 2- sulfoterephthalate salt.
- the organic linker compound is preferably water soluble.
- water soluble we mean that it preferably has a solubility in water which is high enough to enable the formation of a homogenous solution in water.
- the solubility of the organic linker compound in water may be at least 1 g/L at room temperature (i.e. 18 to 30 °C) and pressure (i.e. 0.5 to 3 bar) (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
- the organic linker compound typically comprises at least two functional groups capable of binding to the inorganic cornerstone.
- binding we mean linking to the inorganic cornerstone by donation of electrons (e.g. an electron pair) from the linker to the cornerstone.
- the linker comprises two, three or four functional groups capable of such binding.
- the organic linker comprises at least two functional groups selected from the group of carboxylate (COOH), amine (NH 2 ), nitro (N0 2 ), anhydride and hydroxyl (OH) or a mixture thereof.
- the linker comprises two, three or four carboxylate or anhydride groups, most preferably carboxylate groups.
- the organic linker compound comprising said at least two functional groups may be based on a saturated or unsaturated aliphatic compound or an aromatic compound. Alternatively, the organic linker compound may contain both aromatic and aliphatic moieties.
- the aliphatic organic linker compound may comprise a linear or branched Ci_ 2 o alkyl group or a C 3 _i 2 cycloalkyl group.
- alkyl is intended to cover linear or branched alkyl groups such as all isomers of propyl, butyl, pentyl and hexyl. In all embodiments, the alkyl group is preferably linear. Particularly preferred cycloalkyl groups include cyclopentyl and cyclohexyl.
- the organic linker compound comprises an aromatic moiety.
- the aromatic moiety can have one or more aromatic rings, for example two, three, four or five rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in condensed form.
- the aromatic moiety particularly preferably has one, two or three rings, with one or two rings being particularly preferred, most preferably one ring.
- Each ring of said moiety can independently comprise at least one heteroatom such as N, O, S, B, P, Si, preferably N, O and/or S.
- the aromatic moiety preferably comprises one or two aromatic C6 rings, with the two rings being present either separately or in condensed form.
- Particularly preferred aromatic moieties are benzene, naphthalene, biphenyl, bipyridyl and pyridyl, especially benzene.
- Suitable organic linker compounds include oxalic acid, ethyloxalic acid, fumaric acid, 1,3,5-benzene tribenzoic acid (BTB), benzene tribiphenylcarboxylic acid (BBC), 5, 15 -bis (4-carboxyphenyl) zinc (II) porphyrin (BCPP), 1,4-benzene dicarboxylic acid (BDC), 2-amino-l,4-benzene dicarboxylic acid (R3-BDC or H2N BDC), 1,2,4,5-benzene tetracarboxylic acid, 2-nitro- 1,4- benzene dicarboxylic acid ⁇ , ⁇ -azo-diphenyl 4,4'-dicarboxylic acid, eye lo butyl- 1,4- benzene dicarboxylic acid (R6-BDC), 1,2,4-benzene tricarboxylic acid, 2,6- naphthalene dicarboxylic acid (NDC), ⁇
- Anhydrides may also be used, particularly those which are converted to dicarboxylic acids under the aqueous conditions used in the invention.
- the organic linker compound is selected from the group consisting of 1 ,4-benzene dicarboxylic acid (BDC), 2- amino- 1,4-benzene dicarboxylic acid, 1,2,4-benzene tricarboxylic acid, 1,2,4,5- benzene tetracarboxylic acid and 2-nitro- 1,4-benzene dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid (H2CDC), N,N'-piperazinebis(methylenephosphonic acid) or mixtures thereof.
- BDC 1 ,4-benzene dicarboxylic acid
- 2- amino- 1,4-benzene dicarboxylic acid 1,2,4-benzene tricarboxylic acid
- 1,2,4,5- benzene tetracarboxylic acid 2-nitro- 1,4-benzene dicarboxylic acid
- 1,4- cyclohexane dicarboxylic acid H2CDC
- a mixture of two or more of the above-mentioned linkers may be used. It is preferable, however, if only one type of linker is used.
- MOF is a Zr-MOF
- it is preferably of UiO-66 type.
- UiO-66 type Zr-MOFs cover structures in which the zirconium inorganic groups are
- the organic linker compound is 1 ,4-benzene dicarboxylic acid or a derivative thereof.
- 1 ,4-benzene dicarboxylic acid used in UiO-66 type Zr-MOFs include 2-amino-l,4-benzene dicarboxylic acid, 2-nitro-l,4-benzene dicarboxylic acid, 1,2,4-benzene tricarboxylic acid and 1,2,4,5-benzene
- the resulting MOF may be referred to as UiO-66(Zr).
- the linker is 2-amino-l,4-benzene dicarboxylic acid
- the resulting MOF may be referred to as UiO-66(Zr)-NH 2 .
- the linker is 1,2,4-benzene tricarboxylic acid
- the resulting MOF may be referred to as UiO- 66(Zr)-COOH.
- the linker is 1,2,4,5-benzene tetracarboxylic acid
- the resulting MOF may be referred to as UiO-66(Zr)-2COOH.
- a mixture of linkers may be used to introduce one or more functional groups within the pore space, e.g. by using aminobenzoic acid to provide free amine groups or by using a shorter linker such as oxalic acid.
- This introduction of functionalised linkers is facilitated by having a MOF with inorganic cornerstones with a high number of coordination sites. Where the number of these coordination sites exceed the number required to form the stable 3D MOF structure, functionalisation of the organic linkers may be effected, e.g. to carry catalytic sites, without seriously weakening the MOF structure.
- Functionalised MOF we mean a MOF wherein one or more of the backbone atoms of the organic linkers carries a pendant functional group or itself forms a functional group.
- Functional groups are typically groups capable of reacting with compounds entering the MOF or acting as catalytic sites for reaction of compounds entering the MOF. Suitable functional groups will be apparent to a person skilled in the art and in preferred embodiments of the invention include amino, nitro, thiol, oxyacid, halo (e.g. chloro, bromo, fluoro) and cyano groups or heterocyclic groups (e.g. pyridine), each optionally linked by a linker group, such as carbonyl.
- the functional group may also be a phosphorus-or sulfur-containing acid.
- a particularly preferred functional group is halo, most preferably a fluoro group.
- the functionalised MOF has a surface area of at least 400 m 2 /g, more preferably at least 500 m 2 /g, especially at least 700 m 2 /g, such as at least 1020 m 2 /g.
- the process of the invention is a continuous flow process for preparing a metal organic framework (MOF), comprising the steps:
- continuous flow process we mean one in which a chemical reaction is run in a continuously flowing stream rather than in a batch. Thus, it may be contrasted with a “batch process”.
- slurry we mean a suspension of solid particles in a liquid, i.e. a heterogenous mixture of at least one solid and at least one liquid.
- a “slurry” may be contrasted with a “solution”, which is a homogenous mixture.
- the organic linker compound may be any organic linker as hereinbefore defined. It will be understood that the organic linker described in the context of the MOF produced by the processes of the invention is the same organic linker which is used as a starting material in step (i) of the process of the invention, albeit that once bound to the metal ion or metal ion cluster the organic linker will be deprotonated. Thus all preferable embodiments defined above relating to the organic linker in the context of the MOF apply equally to this compound as a starting material.
- the metal ions may be provided in any conventional way, and thus any conventional source of metal ions may be used. However, the metal ions will typically be provided in the form of at least one metal salt, which may or may not be in its hydrated form. Whilst the use of a mixture of two or more different salts is encompassed by the invention, it is preferable if one salt is used.
- the salt is usually water soluble, i.e. preferably having a solubility of at least 1 g/L at room temperature (i.e. 18 to 30 °C) and pressure (i.e. 0.5 to 3 bar) (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
- RTP pressure
- Preferable metal ions are discussed above in the context of the MOF and all embodiments discussed therein apply equally here.
- Suitable counter-ions will be familiar to the skilled worker and may include halides (e.g. chlorides), acetates, nitrates, oxides, acrylates, carboxylates, sulfates, hydroxides, oxynitrates and oxychlorides.
- metal salts include zirconium sulfate, zirconium hydroxide, zirconium chloride (ZrC ) and zirconyl chloride ( ⁇ 0 ⁇ 2 ⁇ 2 0, wherein n is an integer from 1 to 10, preferably 8).
- the metal ions are zirconium metal ions.
- These zirconium metal ions may be provided in the form of a zirconium salt selected from the group consisting of hydroxide, sulfate or mixtures thereof.
- the salt is zirconium hydroxide (e.g. Zr(OH) 4 ) or zirconium sulfate (e.g. Zr(S0 4 ) 2 or Zr(S0 4 ) 2 .4H 2 0), especially zirconium sulfate.
- the zirconium ions will typically be in the +4 oxidation state, i.e. Zr 4+ ions.
- zirconium salts such as sulfate and hydroxide has cost advantages because these starting materials are relatively cheap to obtain. Moreover, these preferable salts are safer to handle than certain other common salts and do not lead to the production of highly corrosive hydrochloric acid as a side-product.
- a slurry reaction mixture of the metal salt and the at least one organic linker compound is prepared in aqueous solvent, i.e. a solvent comprising water.
- aqueous solvent i.e. a solvent comprising water.
- the pH of the aqueous solvent is preferably acidic, i.e. having a pH less than 7, more preferably pH 0-5, such as pH 0-3.
- the aqueous solvent consists of water.
- the aqueous solvent may comprise a mixture of water and acetic acid.
- the water and acetic acid may be present in a volume ratio of between 1 :5 and 5: 1, more preferably 1 :2 to 2: 1 , most preferably 1 : 1.
- the slurry reaction mixture does not comprise an organic solvent.
- reaction mixture prepared in step (i) of the processes of the invention is typically prepared by mixing the various components together in the aqueous solvent. Mixing may be carried out by any known method in the art, e.g.
- the mixture may be prepared by mixing a first component comprising an aqueous solvent and the metal salt and a second component comprising an aqueous solvent and the at least one organic linker compound.
- the mixing may occur in a mixing vessel such as a beaker.
- step (i) is carried out at or around atmospheric pressure, i.e. 0.5 to 3 bar, especially 1 bar.
- step (ii) of the process the reaction mixture prepared in step (i) is supplied to a flow reactor at a temperature of less than 150 °C and a pressure of less than 20 bar.
- Flow reactors are well known in the art. They carry material as a flowing stream. Reactants are continuously fed into the reactor and emerge as continuous stream of product.
- the flow reactor of the present invention may be any suitable type of flow reactor known in the art, but is typically tube-like and is made from a material which will not react with the reagents of the continuous flow process. Examples of suitable materials include stainless steel, glass and polymers.
- the flow reactor is at a temperature of less than 150 °C.
- the temperature is less than 120 °C, more preferably less than 110 °C, such as less than 100 °C.
- the temperature may be at least 35 °C, preferably at least 40 °C, more preferably at least 50 °C.
- An example temperature is 85 °C.
- the pressure of the flow reactor in step (ii) of the process is preferably less than 15 bar, more preferably less than 10 bar, even more preferably less than 5 bar, such as 0.5 to 3 bar, especially 1 to 2 bar.
- the method of heating may be by any known method in the art, such as heating in a conventional oven, a microwave oven or heating in an oil bath.
- step (ii) the reaction mixture is typically supplied to the flow reactor by way of at least one pump, which pumps the mixture through the flow reactor.
- a single pump is used. Where more than one pump is present, they are preferably connected in series.
- a suitable pump speed may be chosen to achieve a desired flow rate through the reactor and thus the residence time (i.e. reaction time) in the flow reactor.
- the residence time is also dependent upon the volume of the flow reactor. The skilled man would be able to select appropriate values based on the desired reaction time.
- the volume of the flow reactor may be in the range 100 ml to 5 litres, preferably 250 ml to 3 litres, more preferably 500 ml to 2 litres, such as 1.5 litres.
- Typical pumping speeds would be in the range 4 ml/min to 300 ml/min, preferably 8 ml/min to 150 ml/min, more preferably 10 ml/min to 50 ml/min, such as 20 ml/min.
- the residence time (i.e. reaction time/heating time) may be from 10 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 45 minutes to 2 hours, such as 75 minutes.
- a pump speed of 20 ml/min may be used, giving a reaction time of 75 minutes.
- the mild reactions conditions used in the process of the invention offer numerous advantages over those of previous methods wherein organic solvents were used as the reaction medium.
- the processes may be carried out in the absence of high pressures, temperatures or reaction times. This offers improvements in terms of costs, safety and suitability for industrial scale-up.
- slurry reaction mixture means that a wider range of starting materials may be employed compared with processes which require homogenous solutions. The process is thus potentially compatible with a large variety of MOFs. There is also a cost and time advantage, since slurries may be cheaper and easier to prepare than solutions.
- the molar ratio of total metal ions to total organic linker compound(s) present in the reaction mixture prepared in step (i) is typically 1 : 1, however in some embodiments an excess of the organic linker compound may be used.
- the molar ratio of total metal ions to total organic linker compound(s) in the reaction mixture is in the range 1 : 1 to 1 :5, such as 1 :4.
- step (ii) of the process additional comprise step (iii) in which steps (i) and (ii) are optionally repeated.
- steps (i) and (ii) may be repeated once or more than once, depending on factors such as the scale of the reaction or the nature of the apparatus employed.
- Step (iii) may be used when the reaction is performed on an industrial scale, for example, when large tanks or hoppers are refilled with the slurry reaction mixture to enable a continuous flow of said mixture to the flow reactor.
- the processes of the invention usually comprise a further step (iv) of isolating the MOF.
- the MOF is usually formed as a crystalline product which can be isolated quickly and simply by methods such as filtration, or centrifugation.
- This offers an improvement over some methods of the prior art which produce an amorphous or gel-like product which must be further recrystallized before it can be isolated.
- the processes of the present invention thus preferably eliminate the need for these additional steps.
- the isolation step (iv) is typically carried out by filtration, but isolation may also be performed by processes such as centrifugation, solid-liquid separations or extraction.
- the MOF is preferably obtained as a fine crystalline powder having crystal size of 0.1 to 100 ⁇ , such as 10 to 50 ⁇ .
- the processes of the invention may comprise additional steps, such as drying and/or cooling.
- additional steps such as drying and/or cooling.
- Cooling usually involves bringing the temperature of the reaction mixture back to room temperature, i.e. 18-30 °C.
- the invention relates to a metal organic framework
- the present invention also relates to an apparatus arranged to perform the processes as hereinbefore defined.
- the apparatus comprises a flow reactor arranged to receive a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent, wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
- the flow reactor comprises tubing in fluid communication with at least one pump, which pumps the reaction mixture through the reactor.
- the pump may be placed at one end of the tubing or part way along the length of the tubing. Preferably a single pump is used. If more than one pump is present, they are preferably connected in series.
- the apparatus comprises at least one pump connected via a first tube to a reaction vessel containing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent, and a second tube to a flow reactor.
- the invention relates to an apparatus arranged to perform the process as hereinbefore defined, wherein said apparatus comprises:
- reaction vessel containing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent;
- a first tube in fluid communication with the reaction vessel and at least one pump so as to allow the reaction mixture to flow from the reaction vessel to the at least one pump;
- the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
- the flow reactor is heated using an oven or microwave reactor.
- the pump may be a magnetic membrane pump.
- An example of this embodiment of the apparatus of the invention is shown in Figure 1.
- the apparatus of the invention may further comprise other components such as a sonicator, which can be used to enhance mixing.
- the apparatus of the invention does not comprise a back pressure regulator. This is because the apparatus is most preferably operated at atmospheric pressure, e.g. 1 to 3 bar.
- MOF produced or formable by the processes of the present invention may be employed in any known application for such materials. Applications therefore include, but are not restricted to, electrode materials, drug reservoirs, catalyst materials, adsorbents and cooling media.
- FIG. 1 Example apparatus of the invention
- Figure 2 Powder X-ray diffraction pattern measured with a wavelength of 1.5406 A of UiO-66-COOH prepared as described in the first example.
- Figure 3 Powder X-ray diffraction pattern measured with a wavelength of 1.5406 A of UiO-66-COOH prepared as described in the second example.
- Figure 5 Powder pattern from [Al(OH)(FUM)] synthesised in a flow reactor.
- a pressure transmitting medium In order to pump a defined amount of slurry through the flow reactor, a pressure transmitting medium is necessary. Here, water was utilized and prior to the reaction the reactor was filled with water and preheated to the temperature given. After pumping the slurry into the reactor, additional water was again used to push the slurry to the end of the reactor. In a fully continuous mode the pressure transmitting medium would be the slurry itself.
- Trimellitic Anhydride (15.4 g) was thoroughly ground.
- the fine powder and Zr(S04)2 » 4H20 (7.1 g) were mixed with 100 mL water using a magnetic stirrer.
- the resulting slurry was transferred into the reactor using a magnetic membrane pump into the reactor which was preheated to 85 °C. Adjusting the pumping frequency (12 per minute) and the idle stroke (50 %) to suitable values, a residence time of 75 minutes in the reactor was achieved (Volume 1850 mL).
- the product was first collected in a beaker and separated by filtration while still hot. Afterwards the raw material was mixed with water (50 mL par 5 g) and heated for 15 minutes to 85 °C in order to remove residual linker molecules.
- the slurry was again filtrated while still hot and dried under ambient conditions. 6.1 g of a white powder were obtained.
- the PXRD pattern is shown in Figure 3.
- the sorption isotherm measured with nitrogen at 77 K after activation at 120 °C in vacuum (0.1 mbar) is shown in Figure 4.
- the apparent specific surface area evaluated with the BET method is 760 m 2 /g.
- Fumaric acid (H 2 FUM, 2.9 g), NaOH (3 g) and A1(S0 4 ) 2 - 18 H 2 0 (8.33 g) were mixed with 50 mL water using a magnetic stirrer.
- the resulting solution was transferred into the reactor using a magnetic membrane pump into the reactor which was preheated to 80 °C. Adjusting the pumping frequency (65 per minute) and the idle stroke (50 %) to suitable values, a residence time of 15 minutes in the reactor was achieved (Volume 1850 mL).
- the product was first collected in a beaker and separated by filtration while still hot.
- the PXRD pattern is shown in Figure 5.
- the sorption isotherm measured with nitrogen at 77 K after activation at 120 °C in vacuum (0.1 mbar) is shown in Figure 6.
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Abstract
The invention relates to a continuous flow process for preparing a metal organic framework (MOF), comprising the steps (i) preparing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent; (ii)supplying said reaction mixture to a flow reactor at a temperature of less than 150 °C and a pressure of less than 20 bar; and (iii) optionally repeating steps (i) and (ii).
Description
Process
Field of the Invention The present invention relates to a continuous flow process for preparing metal organic frameworks (MOFs), in particular to a continuous flow process for preparing Zr-MOFs. The invention further relates to an apparatus arranged to perform said process. Background
MOFs or "metal organic frameworks" are compounds having a lattice structure having vertices or "cornerstones" which are metal-based inorganic groups, for example metal oxides, linked together by organic linkers. The linkers are usually at least bidentate ligands which coordinate to the metal-based inorganic groups via functional groups such as carboxylate and/or amine. The porous nature of MOFs renders them promising materials for many applications such as gas storage and catalyst materials.
Perhaps the best known MOF is MOF-5 in which each ZrLiO cornerstone is coordinated by six bis-carboxylate organic linkers. Other MOFs in which the inorganic cornerstone is for example chromium, copper, vanadium, cadmium or iron are also known.
Numerous processes are known in the prior art for the production of MOFs. The most commonly used techniques involve the reaction of a metal salt with the desired organic linker in a suitable solvent, usually organic, such as
dimethylformamide (DMF). High pressures and temperatures are commonly required to facilitate the reaction. Typical methods are disclosed in, for example, WO 2009/133366, WO 2007/023134, WO2007/090809 and WO 2007/118841.
The use of elevated temperatures and pressures not only increases the cost of the process but also means that scale-up to an industrial level poses many challenges. Apparatus suitable for withstanding the severe reaction conditions is often only compatible with small scale batch synthesis, rather than the continuous
processes favoured for large scale production. Employing high pressures also carries with it safety concerns, particularly when combined with the use of corrosive liquids. Moreover, the use of organic solvents as the reaction medium is undesirable as such solvents are harmful to the environment and are expensive.
As MOFs become increasingly employed as alternatives to, for example, zeolites, there is a need for the development of novel processes for their production which are applicable to use on an industrial scale. Replacement of the organic solvent with an aqueous medium is reported in, for example, US 7411081 and US 8524932. These processes routinely involve the use of a base or require an alkaline reaction medium.
Moreover, reactions conditions which are suitable for the production of certain MOFs may not be transferable to others where different metals are used. For example, conditions found to be optimal for the production of MOFs containing main group metals from the second or third groups of the periodic table (e.g.
magnesium or aluminium) are often not appropriate for the preparation of analogous frameworks wherein a transition metal is used.
Recently, continuous flow chemistry has been investigated for the synthesis of MOFs, however these processes often still require the use of high temperatures and/or pressure. For example, a continuous flow process is disclosed in WO
2014/013274, however this reaction uses supercritical fluids as solvents and thus requires extreme conditions to maintain the solvents in this state throughout the reaction. The use of microfluidics in combination with flow reactors has also been reported which involves the production of MOFs within oil droplets. Product quality is reported to be low for microfluidic processing and the requirement for both oil and water phases does not eliminate the need to use harmful and costly organic solvents.
The present invention is particularly directed towards Zr-MOFs. An aqueous-based process for producing a Zr-MOF is reported by Yang et al in Angew. Chem. Int. Ed. 2013, 52, 10316-10320. This process involves a two-step synthesis. The product is obtained as a gel which, to be isolated, must be washed and recrystallised. This adds to the costs and timescale of the process, making it unsuitable for use on a larger industrial scale.
There thus remains the need for the development of novel processes for the production of MOFs, and particularly Zr-MOFs, which are suitable for use on an industrial scale. The process should ideally be one which is "green" and thus considered environmentally friendly. It would also be advantageous to have a process which can be carried out quickly and cheaply and which offers
improvements in terms of complexity over those processes already known in the art. In particular, a process which involves fewer steps is desired. A process which avoids potential corrosion problems, such as the production of hydrochloric acid (HC1) as a by-product is particularly attractive. Ideally, a process which offers improvement in more than one of the above aspects would be developed.
The present inventors have surprisingly found that MOFs may be prepared in a straightforward continuous flow process utilising an aqueous solvent which avoids the need for high temperatures and pressures. In particular, the use of a flow reactor leads to a procedure which is applicable to use on an industrial scale and offers an environmentally friendly and cheap route to these valuable materials.
Summary of the Invention
Thus, in a first aspect, the invention provides a continuous flow process for preparing a metal organic framework (MOF), comprising the steps:
(i) preparing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent;
(ii) supplying said reaction mixture to a flow reactor at a temperature of less than 150 °C and a pressure of less than 20 bar; and (iii) optionally repeating steps (i) and (ii).
In a particularly preferable embodiment, the metal organic framework is a zirconium-based metal organic framework (Zr-MOF).
In a second aspect, the invention provides apparatus arranged to perform a process as hereinbefore defined comprising a flow reactor arranged to receive a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent, wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
Detailed Description
The present invention describes a continuous flow process for the
preparation of a metal organic framework (MOF). The process involves preparing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent and supplying said reaction mixture to a flow reactor at a particular temperature and pressure. The process typically involves subsequently collecting and isolating the MOF.
MOF
As used herein, the term "MOF" is intended to cover any metal organic framework. MOFs typically comprise at least one metal ion or cluster of metal ions and at least one organic linker compound.
The metal ion or cluster of metal ions may be any suitable metal selected from Groups 1 to 16 of the Periodic Table, preferably a metal selected from the group consisting of transition metals, alkaline earth metals, lanthanides and mixtures thereof. The metal ion may have any valence appropriate for the specific metal. In a particularly preferable embodiment, the metal ion is selected from the group consisting of copper, zirconium, scandium, nickel, magnesium, bismuth, gallium, cobalt, zinc, aluminium, iron, cadmium, cerium and yttrium. Most preferably, the metal ion is zirconium. Whilst it is possible for a mixture of metal ions to be used, it is preferable if the MOF contains only a single type of metal ion.
In a particularly preferred embodiment, the process of the invention is used to prepare zirconium-based metal organic frameworks (Zr-MOFs). As used herein, the term "Zr-MOF" is intended to cover any metal organic frameworks (MOFs) which comprise at least one zirconium metal ion. The Zr-MOFs of the invention have "cornerstones" which are zirconium inorganic groups. Typical zirconium inorganic groups include zirconium ions connected by bridging oxygen or hydroxide groups. These inorganic groups are further coordinated to at least one organic linker compound. In some cases, the inorganic groups may be further connected to non-
bridging modulator species, complexing reagents or ligands (e.g. sulfates or carboxylates such as formate, benzoate or acetate) and/or solvent molecules. The zirconium oxide unit is usually based on an idealized octahedron of Zr-ions which are μ3-bridged by 02~ and/or OH" ions via the faces of the octahedron and further saturated by coordinating moieties containing O-atoms like carboxylate groups. The idealised Zr oxide cluster is considered to be a Zr6032-cluster which comprises between 6 and 12 (preferentially as close as possible to 12) carboxylate groups. However, in practice, there is a degree of flexibility in the structure of the cluster. The cluster may be represented by the formula Zr6Ox(OH)8_x wherein x is in the range 0 to 8. For example, the cluster may be represented by the formula
Zr6(0)4(OH)4,
Zr-MOFs are well known in the art and cover structures in which the zirconium cornerstone is linked to an at least bidentate organic linker compound to form a coordinated network. The structures may be one- two- or three-dimensional. The Zr-MOF usually comprises pores which are present in the voids between the coordinated network of zirconium ions and organic linker compounds. The pores are typically micropores, having a diameter of 2 nm or less, or mesopores, having a diameter of 2 to 50 nm.
The Zr-MOF may comprise additional metal ions other than zirconium, such as hafnium, titanium, or cerium, however preferably zirconium is the only metal ion present. If additional metal ions are present these may be present in an amount of up 50 wt% relative to total amount of metal ions, preferably up to 25 wt%, more preferably up to 10 wt%, e.g. up to 5 wt%.
The Zr-MOFs of the invention particularly preferably have cornerstones having at least 12 coordination sites for the organic linkers, e.g. 12-24, preferably at least 14, 16 or 18, most especially 24. In this way at least 6, more preferably at least 8, especially at least 12 bidentate ligand groups of the organic linkers can bind to each cornerstone.
In all embodiments, the surface area of the MOF is preferably at least 400 m2/g, more preferably at least 500 m2/g, especially at least 700 m2/g, such as at least 1020 m2/g, for example at least 1050 m2/g, e.g. at least 1200 m2/g. The surface area may be up to 10000 m2/g, especially up to 5000 m2/g. It will be understood that,
where functionalised organic linker compounds are used, the presence of additional, and often bulky, groups may affect (i.e. reduce) the surface area of the MOF.
In addition to the at least one metal ion or cluster of metal ions, the MOFs of the invention comprise at least one organic linker compound.
The organic linker compound is typically at least bidentate, i.e. has at least two functional groups capable of coordinating to the metal ion. The organic linker compound may also be tridentate (i.e. containing three functional groups) or tetradentate (i.e. containing four functional groups).
The MOF may have a metal ion to organic linker molecule ratio of from 1 :0.45 to 1 :0.55, especially l :0.49 to 1 :0.51, particularly 1 :0.5. Other preferred metal ion to organic linker molecule ratios are 0.5 : 1 , 1 : 1, 3: 1 and 1 :3, especially 1 : 1.
The organic linker compounds of the MOFs of the invention may be any organic linker molecule or molecule combination capable of binding to at least two inorganic cornerstones and comprising an organic moiety. By "organic" moiety we mean a carbon based group which comprises at least one C-H bond and which may optionally comprise one or more heteroatoms such as N, O, S, B, P, Si. Typically, the organic moiety will contain 1 to 50 carbon atoms.
The organic linker compound may be any of the linkers conventionally used in MOF production. These are generally compounds with at least two cornerstone binding groups, e.g. carboxylates, optionally with extra functional groups which do not bind the cornerstones but may bind metal ions on other materials it is desired to load into the MOF. The introduction of such extra functionalities is known in the art and is described for example by Campbell in JACS 82:3126-3128 (1960).
The organic linker compound may be in the form of the compound itself or a salt thereof, e.g. a disodium 1 ,4-benzenedicarboxylate salt or a monosodium 2- sulfoterephthalate salt.
The organic linker compound is preferably water soluble. By water soluble we mean that it preferably has a solubility in water which is high enough to enable the formation of a homogenous solution in water. The solubility of the organic linker compound in water may be at least 1 g/L at room temperature (i.e. 18 to 30 °C) and pressure (i.e. 0.5 to 3 bar) (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
The organic linker compound typically comprises at least two functional groups capable of binding to the inorganic cornerstone. By "binding" we mean linking to the inorganic cornerstone by donation of electrons (e.g. an electron pair) from the linker to the cornerstone. Preferably, the linker comprises two, three or four functional groups capable of such binding.
Typically, the organic linker comprises at least two functional groups selected from the group of carboxylate (COOH), amine (NH2), nitro (N02), anhydride and hydroxyl (OH) or a mixture thereof. In a preferable embodiment, the linker comprises two, three or four carboxylate or anhydride groups, most preferably carboxylate groups.
The organic linker compound comprising said at least two functional groups may be based on a saturated or unsaturated aliphatic compound or an aromatic compound. Alternatively, the organic linker compound may contain both aromatic and aliphatic moieties.
In one embodiment, the aliphatic organic linker compound may comprise a linear or branched Ci_2o alkyl group or a C3_i2 cycloalkyl group. The term "alkyl" is intended to cover linear or branched alkyl groups such as all isomers of propyl, butyl, pentyl and hexyl. In all embodiments, the alkyl group is preferably linear. Particularly preferred cycloalkyl groups include cyclopentyl and cyclohexyl.
In a particularly preferred embodiment, the organic linker compound comprises an aromatic moiety. The aromatic moiety can have one or more aromatic rings, for example two, three, four or five rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in condensed form. The aromatic moiety particularly preferably has one, two or three rings, with one or two rings being particularly preferred, most preferably one ring. Each ring of said moiety can independently comprise at least one heteroatom such as N, O, S, B, P, Si, preferably N, O and/or S.
The aromatic moiety preferably comprises one or two aromatic C6 rings, with the two rings being present either separately or in condensed form. Particularly preferred aromatic moieties are benzene, naphthalene, biphenyl, bipyridyl and pyridyl, especially benzene.
Examples of suitable organic linker compounds include oxalic acid, ethyloxalic acid, fumaric acid, 1,3,5-benzene tribenzoic acid (BTB), benzene tribiphenylcarboxylic acid (BBC), 5, 15 -bis (4-carboxyphenyl) zinc (II) porphyrin (BCPP), 1,4-benzene dicarboxylic acid (BDC), 2-amino-l,4-benzene dicarboxylic acid (R3-BDC or H2N BDC), 1,2,4,5-benzene tetracarboxylic acid, 2-nitro- 1,4- benzene dicarboxylic acid Ι,Γ-azo-diphenyl 4,4'-dicarboxylic acid, eye lo butyl- 1,4- benzene dicarboxylic acid (R6-BDC), 1,2,4-benzene tricarboxylic acid, 2,6- naphthalene dicarboxylic acid (NDC), Ι,Γ-biphenyl 4,4'-dicarboxylic acid (BPDC), 2,2'-bipyridyl-5, 5 '-dicarboxylic acid, adamantane tetracaboxylic acid (ATC), adamantane dibenzoic acid (ADB), adamantane teracarboxylic acid (ATC), dihydroxyterephthalic acid (DHBDC), biphenyltetracarboxylic acid (BPTC), tetrahydropyrene 2,7-dicarboxylic acid (HPDC), pyrene 2,7-dicarboxylic acid (PDC), pyrazine dicarboxylic acid, acetylene dicarboxylic acid (ADC), camphor dicarboxylic acid, fumaric acid, benzene tetracarboxylic acid, 1 ,4-bis(4- carboxyphenyl)butadiyne, nicotinic acid, terphenyl dicarboxylic acid (TPDC), 1,4- cyclohexane dicarboxylic acid (H2CDC) and N,N'- piperazinebis(methylenephosphonic acid). Other acids besides carboxylic acids, e.g. boronic acids may also be used.
Anhydrides may also be used, particularly those which are converted to dicarboxylic acids under the aqueous conditions used in the invention.
In a particularly preferred embodiment, the organic linker compound is selected from the group consisting of 1 ,4-benzene dicarboxylic acid (BDC), 2- amino- 1,4-benzene dicarboxylic acid, 1,2,4-benzene tricarboxylic acid, 1,2,4,5- benzene tetracarboxylic acid and 2-nitro- 1,4-benzene dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid (H2CDC), N,N'-piperazinebis(methylenephosphonic acid) or mixtures thereof.
A mixture of two or more of the above-mentioned linkers may be used. It is preferable, however, if only one type of linker is used.
Where the MOF is a Zr-MOF, it is preferably of UiO-66 type. UiO-66 type Zr-MOFs cover structures in which the zirconium inorganic groups are
ΖΓ6(0)4(ΟΗ)4 and the organic linker compound is 1 ,4-benzene dicarboxylic acid or a derivative thereof. Derivatives of 1 ,4-benzene dicarboxylic acid used in UiO-66
type Zr-MOFs include 2-amino-l,4-benzene dicarboxylic acid, 2-nitro-l,4-benzene dicarboxylic acid, 1,2,4-benzene tricarboxylic acid and 1,2,4,5-benzene
tetracarboxylic acid.
When the linker is 1 ,4-benzene dicarboxylic acid, the resulting MOF may be referred to as UiO-66(Zr). When the linker is 2-amino-l,4-benzene dicarboxylic acid, the resulting MOF may be referred to as UiO-66(Zr)-NH2. When the linker is 1,2,4-benzene tricarboxylic acid, the resulting MOF may be referred to as UiO- 66(Zr)-COOH. When the linker is 1,2,4,5-benzene tetracarboxylic acid, the resulting MOF may be referred to as UiO-66(Zr)-2COOH.
A mixture of linkers may be used to introduce one or more functional groups within the pore space, e.g. by using aminobenzoic acid to provide free amine groups or by using a shorter linker such as oxalic acid. This introduction of functionalised linkers is facilitated by having a MOF with inorganic cornerstones with a high number of coordination sites. Where the number of these coordination sites exceed the number required to form the stable 3D MOF structure, functionalisation of the organic linkers may be effected, e.g. to carry catalytic sites, without seriously weakening the MOF structure.
By "functionalised MOF" we mean a MOF wherein one or more of the backbone atoms of the organic linkers carries a pendant functional group or itself forms a functional group. Functional groups are typically groups capable of reacting with compounds entering the MOF or acting as catalytic sites for reaction of compounds entering the MOF. Suitable functional groups will be apparent to a person skilled in the art and in preferred embodiments of the invention include amino, nitro, thiol, oxyacid, halo (e.g. chloro, bromo, fluoro) and cyano groups or heterocyclic groups (e.g. pyridine), each optionally linked by a linker group, such as carbonyl. The functional group may also be a phosphorus-or sulfur-containing acid.
A particularly preferred functional group is halo, most preferably a fluoro group.
Preferably, the functionalised MOF has a surface area of at least 400 m2/g, more preferably at least 500 m2/g, especially at least 700 m2/g, such as at least 1020 m2/g.
Process
The process of the invention is a continuous flow process for preparing a metal organic framework (MOF), comprising the steps:
(i) preparing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent;
(ii) supplying said reaction mixture to a flow reactor at a temperature of less than 150 °C and a pressure of less than 20 bar; and
(iii) optionally repeating steps (i) and (ii).
By "continuous flow process" we mean one in which a chemical reaction is run in a continuously flowing stream rather than in a batch. Thus, it may be contrasted with a "batch process".
By "slurry" we mean a suspension of solid particles in a liquid, i.e. a heterogenous mixture of at least one solid and at least one liquid. Thus a "slurry" may be contrasted with a "solution", which is a homogenous mixture.
The organic linker compound may be any organic linker as hereinbefore defined. It will be understood that the organic linker described in the context of the MOF produced by the processes of the invention is the same organic linker which is used as a starting material in step (i) of the process of the invention, albeit that once bound to the metal ion or metal ion cluster the organic linker will be deprotonated. Thus all preferable embodiments defined above relating to the organic linker in the context of the MOF apply equally to this compound as a starting material.
The metal ions may be provided in any conventional way, and thus any conventional source of metal ions may be used. However, the metal ions will typically be provided in the form of at least one metal salt, which may or may not be in its hydrated form. Whilst the use of a mixture of two or more different salts is encompassed by the invention, it is preferable if one salt is used.
Where a metal salt is used, the salt is usually water soluble, i.e. preferably having a solubility of at least 1 g/L at room temperature (i.e. 18 to 30 °C) and pressure (i.e. 0.5 to 3 bar) (RTP), preferably at least 2 g/L, more preferably at least 5 g/L.
Preferable metal ions are discussed above in the context of the MOF and all embodiments discussed therein apply equally here. Suitable counter-ions will be familiar to the skilled worker and may include halides (e.g. chlorides), acetates, nitrates, oxides, acrylates, carboxylates, sulfates, hydroxides, oxynitrates and oxychlorides. Examples of metal salts include zirconium sulfate, zirconium hydroxide, zirconium chloride (ZrC ) and zirconyl chloride (ΖΓ0Ο2·ηΗ20, wherein n is an integer from 1 to 10, preferably 8).
In a preferable embodiment, the metal ions are zirconium metal ions. These zirconium metal ions may be provided in the form of a zirconium salt selected from the group consisting of hydroxide, sulfate or mixtures thereof. Most preferably, the salt is zirconium hydroxide (e.g. Zr(OH)4) or zirconium sulfate (e.g. Zr(S04)2 or Zr(S04)2.4H20), especially zirconium sulfate. The zirconium ions will typically be in the +4 oxidation state, i.e. Zr4+ ions.
The use of zirconium salts such as sulfate and hydroxide has cost advantages because these starting materials are relatively cheap to obtain. Moreover, these preferable salts are safer to handle than certain other common salts and do not lead to the production of highly corrosive hydrochloric acid as a side-product.
A slurry reaction mixture of the metal salt and the at least one organic linker compound is prepared in aqueous solvent, i.e. a solvent comprising water. The pH of the aqueous solvent is preferably acidic, i.e. having a pH less than 7, more preferably pH 0-5, such as pH 0-3. In one embodiment, the aqueous solvent consists of water. Alternatively, the aqueous solvent may comprise a mixture of water and acetic acid. The water and acetic acid may be present in a volume ratio of between 1 :5 and 5: 1, more preferably 1 :2 to 2: 1 , most preferably 1 : 1.
In all embodiments of the invention it is preferred if the slurry reaction mixture does not comprise an organic solvent.
The reaction mixture prepared in step (i) of the processes of the invention is typically prepared by mixing the various components together in the aqueous solvent. Mixing may be carried out by any known method in the art, e.g.
mechanical stirring. Alternatively, the mixture may be prepared by mixing a first component comprising an aqueous solvent and the metal salt and a second
component comprising an aqueous solvent and the at least one organic linker compound. The mixing may occur in a mixing vessel such as a beaker.
The mixing is preferably carried out at room temperature, i.e. 18 to 30 °C. Usually, step (i) is carried out at or around atmospheric pressure, i.e. 0.5 to 3 bar, especially 1 bar.
In step (ii) of the process, the reaction mixture prepared in step (i) is supplied to a flow reactor at a temperature of less than 150 °C and a pressure of less than 20 bar.
Flow reactors are well known in the art. They carry material as a flowing stream. Reactants are continuously fed into the reactor and emerge as continuous stream of product. The flow reactor of the present invention may be any suitable type of flow reactor known in the art, but is typically tube-like and is made from a material which will not react with the reagents of the continuous flow process. Examples of suitable materials include stainless steel, glass and polymers.
The flow reactor is at a temperature of less than 150 °C. Preferably, the temperature is less than 120 °C, more preferably less than 110 °C, such as less than 100 °C. The temperature may be at least 35 °C, preferably at least 40 °C, more preferably at least 50 °C. An example temperature is 85 °C.
The pressure of the flow reactor in step (ii) of the process is preferably less than 15 bar, more preferably less than 10 bar, even more preferably less than 5 bar, such as 0.5 to 3 bar, especially 1 to 2 bar.
The method of heating may be by any known method in the art, such as heating in a conventional oven, a microwave oven or heating in an oil bath.
In step (ii), the reaction mixture is typically supplied to the flow reactor by way of at least one pump, which pumps the mixture through the flow reactor.
Preferably, a single pump is used. Where more than one pump is present, they are preferably connected in series.
It will be appreciated that a suitable pump speed may be chosen to achieve a desired flow rate through the reactor and thus the residence time (i.e. reaction time) in the flow reactor. Naturally, the residence time is also dependent upon the volume of the flow reactor. The skilled man would be able to select appropriate values based on the desired reaction time.
The volume of the flow reactor may be in the range 100 ml to 5 litres, preferably 250 ml to 3 litres, more preferably 500 ml to 2 litres, such as 1.5 litres.
Typical pumping speeds would be in the range 4 ml/min to 300 ml/min, preferably 8 ml/min to 150 ml/min, more preferably 10 ml/min to 50 ml/min, such as 20 ml/min.
The residence time (i.e. reaction time/heating time) may be from 10 minutes to 10 hours, preferably 30 minutes to 5 hours, more preferably 45 minutes to 2 hours, such as 75 minutes.
As an example, for a flow reactor with a volume of 1.5 litres a pump speed of 20 ml/min may be used, giving a reaction time of 75 minutes.
The mild reactions conditions used in the process of the invention offer numerous advantages over those of previous methods wherein organic solvents were used as the reaction medium. The processes may be carried out in the absence of high pressures, temperatures or reaction times. This offers improvements in terms of costs, safety and suitability for industrial scale-up.
Moreover, the use of a slurry reaction mixture means that a wider range of starting materials may be employed compared with processes which require homogenous solutions. The process is thus potentially compatible with a large variety of MOFs. There is also a cost and time advantage, since slurries may be cheaper and easier to prepare than solutions.
In the context of Zr-MOFs it has surprisingly been found that the specific combination of zirconium ions and sulfate ions in the reaction mixture enable the direct formation of the Zr-MOF as an easy-to-handle powder. Thus, the preparation process may take place over significantly shorter timescales compared to the methods of the prior art.
The molar ratio of total metal ions to total organic linker compound(s) present in the reaction mixture prepared in step (i) is typically 1 : 1, however in some embodiments an excess of the organic linker compound may be used. Thus, in some embodiments, the molar ratio of total metal ions to total organic linker compound(s) in the reaction mixture is in the range 1 : 1 to 1 :5, such as 1 :4.
It will be appreciated that the MOF product forms during step (ii) of the process.
The processes of the invention additional comprise step (iii) in which steps (i) and (ii) are optionally repeated. Steps (i) and (ii) may be repeated once or more than once, depending on factors such as the scale of the reaction or the nature of the apparatus employed. Step (iii) may be used when the reaction is performed on an industrial scale, for example, when large tanks or hoppers are refilled with the slurry reaction mixture to enable a continuous flow of said mixture to the flow reactor.
The processes of the invention usually comprise a further step (iv) of isolating the MOF.
Advantageously, the MOF is usually formed as a crystalline product which can be isolated quickly and simply by methods such as filtration, or centrifugation. This offers an improvement over some methods of the prior art which produce an amorphous or gel-like product which must be further recrystallized before it can be isolated. The processes of the present invention thus preferably eliminate the need for these additional steps.
The isolation step (iv) is typically carried out by filtration, but isolation may also be performed by processes such as centrifugation, solid-liquid separations or extraction. After isolation, the MOF is preferably obtained as a fine crystalline powder having crystal size of 0.1 to 100 μιη, such as 10 to 50 μιη.
In addition to steps (i), (ii), (iii) and (iv), the processes of the invention may comprise additional steps, such as drying and/or cooling. Typically, there will be a cooling step prior to step (iv). Cooling usually involves bringing the temperature of the reaction mixture back to room temperature, i.e. 18-30 °C.
In all embodiments of the invention, it is preferred the process is carried out in the absence of a base.
In a further embodiment, the invention relates to a metal organic framework
(MOF) produced or formable by the processes as herein described.
Apparatus The present invention also relates to an apparatus arranged to perform the processes as hereinbefore defined. The apparatus comprises a flow reactor arranged to receive a slurry reaction mixture comprising a metal salt and at least one organic
linker compound in an aqueous solvent, wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
It will be appreciated that all embodiments relating to the nature of the flow reactors such as pump speed, volume, temperature and pressure etc. discussed above in the context of the process of the invention apply equally to the apparatus of the invention. Similarly, all embodiments discussed above relating to the metal salt, organic linker and solvent apply equally to the apparatus embodiment.
Typically, the flow reactor comprises tubing in fluid communication with at least one pump, which pumps the reaction mixture through the reactor. The pump may be placed at one end of the tubing or part way along the length of the tubing. Preferably a single pump is used. If more than one pump is present, they are preferably connected in series.
In one embodiment, the apparatus comprises at least one pump connected via a first tube to a reaction vessel containing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent, and a second tube to a flow reactor.
Thus, in a particularly preferred embodiment, the invention relates to an apparatus arranged to perform the process as hereinbefore defined, wherein said apparatus comprises:
(i) a reaction vessel containing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent; (ii) a first tube in fluid communication with the reaction vessel and at least one pump so as to allow the reaction mixture to flow from the reaction vessel to the at least one pump;
(iii) a second tube in fluid communication with the at least one pump and a flow reactor so as to allow the reaction mixture to flow from the at least one pump to the reactor;
wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
Typically, in this embodiment, the flow reactor is heated using an oven or microwave reactor. The pump may be a magnetic membrane pump. An example of this embodiment of the apparatus of the invention is shown in Figure 1.
In all embodiments, the apparatus of the invention may further comprise other components such as a sonicator, which can be used to enhance mixing.
Preferably, the apparatus of the invention does not comprise a back pressure regulator. This is because the apparatus is most preferably operated at atmospheric pressure, e.g. 1 to 3 bar.
Applications
The MOF produced or formable by the processes of the present invention may be employed in any known application for such materials. Applications therefore include, but are not restricted to, electrode materials, drug reservoirs, catalyst materials, adsorbents and cooling media.
Figures
Figure 1: Example apparatus of the invention
Figure 2: Powder X-ray diffraction pattern measured with a wavelength of 1.5406 A of UiO-66-COOH prepared as described in the first example.
Figure 3: Powder X-ray diffraction pattern measured with a wavelength of 1.5406 A of UiO-66-COOH prepared as described in the second example.
Figure 4: Sorption isotherm of nitrogen measured at 77 K on UiO-66-COOH prepared as described in the second example.
Figure 5: Powder pattern from [Al(OH)(FUM)] synthesised in a flow reactor.
Figure 6: N2-Isotherme of [Al(OH)(FUM)] synthesised in a flow reactor.
Examples
In order to pump a defined amount of slurry through the flow reactor, a pressure transmitting medium is necessary. Here, water was utilized and prior to the reaction the reactor was filled with water and preheated to the temperature given. After pumping the slurry into the reactor, additional water was again used to push the slurry to the end of the reactor. In a fully continuous mode the pressure transmitting medium would be the slurry itself.
Example 1
Trimellitic acid (16.8 g) and Zr(S04)2»4H20 (7.1 g) were mixed with 100 mL water using a magnetic stirrer. The resulting slurry was transferred into the reactor using a magnetic membrane pump into the reactor which was preheated to 85 °C. Adjusting the pumping frequency (12 per minute) and the idle stroke (50 %) to suitable values, a residence time of 75 minutes in the reactor was achieved (Volume 1850 mL). The product was first collected in a beaker and separated by filtration while still hot. Afterwards the raw material was mixed with water (50 mL par 5 g) and heated for 15 minutes to 85 °C in order to remove residual linker molecules. The slurry was again filtrated while still hot and dried under ambient conditions. The PXRD pattern is shown in Figure 2. Example 2
Trimellitic Anhydride (15.4 g) was thoroughly ground. The fine powder and Zr(S04)2»4H20 (7.1 g) were mixed with 100 mL water using a magnetic stirrer. The resulting slurry was transferred into the reactor using a magnetic membrane pump into the reactor which was preheated to 85 °C. Adjusting the pumping frequency (12 per minute) and the idle stroke (50 %) to suitable values, a residence time of 75 minutes in the reactor was achieved (Volume 1850 mL). The product was first collected in a beaker and separated by filtration while still hot. Afterwards the raw material was mixed with water (50 mL par 5 g) and heated for 15 minutes to 85 °C in order to remove residual linker molecules. The slurry was again filtrated while still hot and dried under ambient conditions. 6.1 g of a white powder were obtained. The PXRD pattern is shown in Figure 3. The sorption isotherm measured with
nitrogen at 77 K after activation at 120 °C in vacuum (0.1 mbar) is shown in Figure 4. The apparent specific surface area evaluated with the BET method is 760 m2/g.
Example 3
Terephtalic acid (0.42 g), NaOH (0.2 g) and Α1(Ν03)3·9 H20 (0.94 g) were mixed with 25 mL water using a magnetic stirrer. The resulting solution was transferred into the reactor using a magnetic membrane pump into the reactor which was preheated to 80 °C. Adjusting the pumping frequency (65 per minute) and the idle stroke (50 %) to suitable values, a residence time of 15 minutes in the reactor was achieved (Volume 1850 mL). The product was first collected in a beaker and separated by filtration while still hot.
Example 4
Fumaric acid (H2FUM, 2.9 g), NaOH (3 g) and A1(S04)2- 18 H20 (8.33 g) were mixed with 50 mL water using a magnetic stirrer. The resulting solution was transferred into the reactor using a magnetic membrane pump into the reactor which was preheated to 80 °C. Adjusting the pumping frequency (65 per minute) and the idle stroke (50 %) to suitable values, a residence time of 15 minutes in the reactor was achieved (Volume 1850 mL). The product was first collected in a beaker and separated by filtration while still hot. The PXRD pattern is shown in Figure 5. The sorption isotherm measured with nitrogen at 77 K after activation at 120 °C in vacuum (0.1 mbar) is shown in Figure 6.
Claims
1. A continuous flow process for preparing a metal organic framework (MOF), comprising the steps:
(i) preparing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent;
(ii) supplying said reaction mixture to a flow reactor at a temperature of less than 150 °C and a pressure of less than 20 bar; and
(iii) optionally repeating steps (i) and (ii).
2. A process as claimed in claim 1, wherein the metal salt comprises a metal ion selected from the group consisting of copper, zirconium, scandium, nickel, magnesium, bismuth, gallium, cobalt, zinc, aluminium, iron, cadmium, cerium and yttrium, preferably zirconium.
3. A process as claimed in claim 1 or 2, wherein the metal salt is selected from the group consisting of zirconium sulfate, zirconium hydroxide, zirconium chloride and zirconyl chloride.
4. A process as claimed in any of claims 1 to 3, wherein the temperature of the flow reactor is less than 120 °C, preferably less than 110 °C, more preferably less than 100 °C.
5. A process as claimed in any of claims 1 to 4, wherein the pressure of the flow reactor is less than 15 bar, preferably less than 10 bar, more preferably less than 5 bar.
6. A process as claimed in any of claims 1 to 5, wherein the at least one organic linker compound comprises at least two functional groups selected from the group consisting of carboxylate (COOH), amine (NH2), anhydride and hydroxyl (OH) or a mixture thereof.
A process as claimed in any of claims 1 to 6, wherein the at least one organic linker compound comprises a linear or branched Ci_2o alkyl group, a C3-12 cycloalkyl group and/or an aromatic moiety, preferably an aromatic moiety such as benzene, naphthalene, biphenyl, bipyridyl or pyridyl.
A process as claimed in any of claims 1 to 7, wherein the organic linker compound is selected from the group consisting of 1 ,4-benzene dicarboxylic acid (BDC), 2-amino-l ,4-benzene dicarboxylic acid, 1 ,2,4-benzene tricarboxylic acid, 2-nitro-l ,4-benzene dicarboxylic acid and 1 ,2,4,5-benzene tetracarboxylic acid, or mixtures thereof.
A process as claimed in any of claims 1 to 8, wherein the aqueous solvent consists of water or is a mixture of water and acetic acid.
A process as claimed in any of claims 1 to 9, wherein the reaction mixture does not comprise an organic solvent.
A process as claimed in any of claims 1 to 10, wherein the molar ratio of total metal ions to total organic linker compound(s) in the reaction mixture is in the range 1 : 1 to 1 :5.
12. A metal organic framework (MOF) produced or formable by the process as defined in any of claims 1 to 1 1.
13. Apparatus arranged to perform the process as defined in any of claims 1 to 1 1 , comprising a flow reactor arranged to receive a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent, wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
14. Apparatus as claimed in claim 13, wherein said apparatus comprises
apparatus comprises:
(i) a reaction vessel containing a slurry reaction mixture comprising a metal salt and at least one organic linker compound in an aqueous solvent;
(ii) a first tube in fluid communication with the reaction vessel and at least one pump so as to allow the reaction mixture to flow from the reaction vessel to the at least one pump;
(iii) a second tube in fluid communication with the at least one pump and a flow reactor so as to allow the reaction mixture to flow from the at least one pump to the reactor;
wherein the flow reactor is operated at a temperature of less than 150 °C and a pressure of less than 20 bar.
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Cited By (4)
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CN108287187A (en) * | 2018-03-30 | 2018-07-17 | 北京大学 | A kind of electrochemical luminescence sensor |
CN108607611A (en) * | 2018-04-19 | 2018-10-02 | 上海理工大学 | A kind of Cu-Ce-Zr mixed metal oxide catalysts |
CN110862550A (en) * | 2019-12-04 | 2020-03-06 | 安徽师范大学 | Cobalt-metal organic framework material and preparation method and application thereof |
EP3783633A1 (en) * | 2019-08-23 | 2021-02-24 | Technische Universität Berlin | Supercapacitors comprising phosphonate and arsonate metal organic frameworks (mofs) as active electrode materials |
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US20090198079A1 (en) * | 2006-04-18 | 2009-08-06 | Basf Se | Process for preparing metal organic frameworks comprising metals of transition group iv |
WO2014013274A2 (en) * | 2012-07-20 | 2014-01-23 | The University Of Nottingham | Metal-organic frameworks |
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US20090198079A1 (en) * | 2006-04-18 | 2009-08-06 | Basf Se | Process for preparing metal organic frameworks comprising metals of transition group iv |
WO2014013274A2 (en) * | 2012-07-20 | 2014-01-23 | The University Of Nottingham | Metal-organic frameworks |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108287187A (en) * | 2018-03-30 | 2018-07-17 | 北京大学 | A kind of electrochemical luminescence sensor |
CN108287187B (en) * | 2018-03-30 | 2020-03-31 | 北京大学 | Electrochemical luminescence sensor |
CN108607611A (en) * | 2018-04-19 | 2018-10-02 | 上海理工大学 | A kind of Cu-Ce-Zr mixed metal oxide catalysts |
EP3783633A1 (en) * | 2019-08-23 | 2021-02-24 | Technische Universität Berlin | Supercapacitors comprising phosphonate and arsonate metal organic frameworks (mofs) as active electrode materials |
WO2021037428A1 (en) * | 2019-08-23 | 2021-03-04 | Technische Universität Berlin | Supercapacitors comprising phosphonate and arsonate metal organic frameworks (mofs) as active electrode materials |
CN110862550A (en) * | 2019-12-04 | 2020-03-06 | 安徽师范大学 | Cobalt-metal organic framework material and preparation method and application thereof |
CN110862550B (en) * | 2019-12-04 | 2021-09-28 | 安徽师范大学 | Cobalt-metal organic framework material and preparation method and application thereof |
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