Metal-organic frameworks for aromatic hydrocarbon separations

Patent metadata

Field	Value
Publication number	US-10118877-B2
Application number	US-201514957494-A
Country	US
Kind code	B2
Filing date	Dec 2, 2015
Priority date	Dec 3, 2014
Publication date	Nov 6, 2018
Grant date	Nov 6, 2018

Abstract

The disclosure provides for metal organic frameworks (MOFs) that are selective adsorbents for aromatic hydrocarbons, devices comprising the MOFs thereof, and methods using the MOFS thereof for separating and/or storing aromatic hydrocarbons.

First claim

What is claimed is:

1. A metal-organic framework (MOF) comprising a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula III:

wherein,
R 5 -R 10 are independently selected from H, D, FG, optionally substituted (C 1 -C 12 )alkyl, optionally substituted hetero-(C 1 -C 12 )alkyl, optionally substituted (C 1 -C 12 )alkenyl, optionally substituted hetero-(C 1 -C 12 )alkenyl, optionally substituted (C 1 -C 12 )alkynyl, optionally substituted hetero-(C 1 -C 12 )alkynyl, optionally substituted (C 1 -C 12 )cycloalkyl, optionally substituted (C 1 -C 12 )cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, —C(R 11 ) 3 , —CH(R 11 ) 2 , —CH 2 R 11 , —C(R 12 ) 3 , —CH(R 12 ) 2 , —CH 2 R 12 , —OC(R 11 ) 3 , OCH(R 11 ) 2 , —OCH 2 R 11 , —OC(R 12 ) 3 , —OCH(R 12 ) 2 , OCH 2 R 12 ;
R 11 is selected from FG, optionally substituted (C 1 -C 12 )alkyl, optionally substituted hetero-(C 1 -C 12 )alkyl, optionally substituted (C 1 -C 12 )alkenyl, optionally substituted hetero-(C 1 -C 12 )alkenyl, optionally substituted (C 1 -C 12 )alkynyl, optionally substituted hetero-(C 1 -C 12 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; and
R 12 is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle;
wherein the MOF comprises coordinatively-unsaturated metal cation sites, and wherein the MOF is a selective adsorbent for aromatic hydrocarbons by having multiple unsaturated metal cation sites that can come into contact with an aromatic hydrocarbon to form multiple metal site-hydrocarbon molecule interactions.

2. The MOF of claim 1 , wherein the MOF comprises a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula III:

wherein,
R 5 -R 10 are independently selected from H, halo, amino, amide, imine, azide, methyl, cyano, nitro, nitroso, hydroxyl, aldehyde, carbonyl, ester, thiol, sulfinyl, sulfonyl, and thiocyanate.

3. The MOF of claim 1 , wherein M is selected from L + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Sc 2+ , Sc + , Y 3+ , Y 2+ , Y + , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , Hf 3+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ , Ta 5+ , Ta 4+ , Ta 3+ , Ta 2+ , Cr 6+ , Cr 5+ , Cr 4+ , Cr 3+ , Cr 2+ , Cr + , Cr, Mo 6+ , Mo 5+ , Mo 4+ , Mo 3+ , Mo 2+ , Mo + , Mo, W 6+ , W 5+ , W 4+ , W 3+ , W 2+ , W + , W, Mn 7+ , Mn 6+ , Mn 5+ , Mn 4+ , Mn 3+ , Mn 2+ , Mn + , Re 7+ , Re 6+ , Re 5+ , Re 4+ , Re 3+ , Re 2+ , Re + , Re, Fe 6+ , Fe 4+ , Fe 3+ , Fe 2+ , Fe + , Fe, Ru 8+ , Ru 7+ , Ru 6+ , Ru 4+ , Ru 3+ , Ru 2+ , Os 8+ , Os 7+ , Os 6+ , Os 5+ , Os 4+ , Os 3+ , Os 2+ , Os + , Os, Co 5+ , Co 4+ , Co 3+ , Co 2+ , Co + , Rh 6+ , Rh 5+ , Rh 4+ , Rh 3+ , Rh 2+ , Rh + , Ir 6+ , Ir 5+ , Ir 4+ , Ir 3+ , Ir 2+ , Ir + , Ir, Ni 3+ , Ni 2+ , Ni + , Ni, Pd 6+ , Pd 4+ , Pd 2+ , Pd + , Pd, Pt 6+ , Pt 5+ , Pt 4+ , Pt 3+ , Pt 2+ , Pt + , Cu 4+ , Cu 3+ , Cu 2+ , Cu + , Ag 3+ , Ag 2+ , Ag + , Au 5+ , Au 4+ , Au 3+ , Au 2+ , Au + , Zn 2+ , Zn + , Zn, Cd 2+ , Cd + , Hg 4+ , Hg 2+ , Hg + , B 3+ , B 2+ , B + , Al 3+ , Al 2+ , Al + , Ga 3+ , Ga 2+ , Ga + , In 3+ , In 2+ , In 1+ , Tl 3+ , Tl + , Si 4+ , Si 3+ , Si 2+ , Si + , Ge 4+ , Ge 3+ , Ge 2+ , Ge + , Ge, Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As 2+ , As + , Sb 5+ , Sb 3+ , Bi 5+ , Bi 3+ , Te 6+ , Te 5+ , Te 4+ , Te 2+ , La 3+ , La 2+ , Ce 4+ , Ce 3+ , Ce 2+ , Pr 4+ , Pr 3+ , Pr 2+ , Nd 3+ , Nd 2+ , Sm 3+ , Sm 2+ , Eu 3+ , Eu 2+ , Gd 3+ , Gd 2+ , Gd+, Tb 4+ , Tb 3+ , Tb 2+ , Tb+, Db 3+ , Db 2+ , Ho 3+ , Er 3+ , Tm 4+ , Tm 3+ , Tm 2+ , Yb 3+ , Yb 2+ , Lu 3+ , La 3+ , La 2+ , La + , and combinations thereof, including any complexes which contain the metals or metal ions, as well as any corresponding metal salt counter-anions.

4. The MOF of claim 3 , wherein M is selected from Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 2+ , Y 2+ , Ti 2+ , Zr 2+ , V 2+ , Nb 2+ , Ta 2+ , Cr 2+ , Mo 2+ , W 2+ , Mn 2+ , Re 2+ , Fe 2+ , Ru 2+ , Os 2+ , Co 2+ , Rh 2+ , Ir 2+ , Ni 2+ , Pd 2+ , Pt 2+ , Cu 2+ , Ag 2+ , Au 2+ , Zn 2+ , Cd 2+ , Hg 2+ , B 2+ , Al 2+ , Ga 2+ , In 2+ , Si 2+ , Ge 2+ , Sn 2+ , Pb 2+ , As 2+ , Te 2+ , La 2+ , Ce 2+ , Pr 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Gd 2+ , Tb 2+ , Db 2+ , Tm 2+ , Yb 2+ , and La 2+ , including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions.

5. The MOF of claim 4 , wherein M is Co 2+ .

6. The MOF of claim 1 , wherein the MOF comprises a repeating core of Co 2 (dobpdc) (dobpdc=4,4′-dioxido-3,3′-biphenyldicarboxylate).

7. The MOF of claim 1 , wherein the MOF comprises 1-D hexagonal channels with a high density of 5-coordinate metal centers with a sixth, vacant coordination site pointing into the pores.

8. The MOF of claim 1 , wherein the MOF is reacted with a post framework reactant that adds at least one effect to a MOF selected from:
modulating the aromatic hydrocarbon storage and/or separation ability of the MOF;
modulating the sorption properties of the MOF;
modulating the pore size of the MOF; and
modulating the metal-metal separation distance of the MOF.

9. A device comprising a MOF of claim 1 used for separating and/or storing aromatic hydrocarbons.

10. A method of separating and/or storing one or more aromatic hydrocarbons from a mixture comprising aromatic hydrocarbons comprising contacting the mixture with a MOF comprising a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula I, II and/or Formula III:

wherein,
R 1 -R 10 are independently selected from H, D, FG, optionally substituted (C 1 -C 12 )alkyl, optionally substituted hetero-(C 1 -C 12 )alkyl, optionally substituted (C 1 -C 12 )alkenyl, optionally substituted hetero-(C 1 -C 12 )alkenyl, optionally substituted (C 1 -C 12 )alkynyl, optionally substituted hetero-(C 1 -C 12 )alkynyl, optionally substituted (C 1 -C 12 )cycloalkyl, optionally substituted (C 1 -C 12 )cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, —C(R 11 ) 3 , —CH(R 11 ) 2 , —CH 2 R 11 , —C(R 12 ) 3 , —CH(R 12 ) 2 , —CH 2 R 12 , —OC(R 11 ) 3 , OCH(R 11 ) 2 , —OCH 2 R 11 , —OC(R 12 ) 3 , —OCH(R 12 ) 2 , OCH 2 R 12 ;
R 11 is selected from FG, optionally substituted (C 1 -C 12 )alkyl, optionally substituted hetero-(C 1 -C 12 )alkyl, optionally substituted (C 1 -C 12 )alkenyl, optionally substituted hetero-(C 1 -C 12 )alkenyl, optionally substituted (C 1 -C 12 )alkynyl, optionally substituted hetero-(C 1 -C 12 )alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; and
R 12 is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle;
wherein the MOF comprises coordinatively-unsaturated metal cation sites, and wherein the MOF is a selective adsorbent for aromatic hydrocarbons by having multiple unsaturated metal cation sites that can come into contact with an aromatic hydrocarbon to form multiple metal site-hydrocarbon molecule interactions.

11. The method of claim 10 , wherein the mixture comprises reformates from a catalytic reforming process.

12. The m

Assignees

• Univ California

Inventors

• Long Jeffrey R
• Bloch Eric D
• Kapelewski Matthew
• Gonzalez Miguel Carlos I

Classifications

• B01D15/08

  Selective adsorption, e.g. chromatography · CPC title

• B01D53/0462

  Temperature swing adsorption · CPC title

• C07C15/073

  Ethylbenzene · CPC title

• B01D15/3828

  Ligand exchange chromatography, e.g. complexation, chelation or metal interaction chromatography · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title