# US 10,118,877 B2 · Metal-organic frameworks for aromatic hydrocarbon separations

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- Number: US 10,118,877 B2
- Document ID: US10118877B2
- Status: Granted
- Kind: B2
- Application number: 14/957,494
- Filed: 2015-12-02
- Published: 2016-06-09
- Granted: 2018-11-06
- Earliest claimed: 2014-12-03
- Assignees: The Regents of the University of California
- Applicants: The Regents of the University of California
- Inventors: Jeffrey R. Long; Eric D. Bloch; Matthew Kapelewski; Miguel Carlos I. Gonzalez
- Web page: https://patentgrep.com/patent/US10118877B2

## CPC

- C07C 7/12: by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- B01D 15/08: Selective adsorption, e.g. chromatography
- B01D 15/3828: {Ligand exchange chromatography, e.g. complexation, chelation or metal interaction chromatography}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01D 53/04: with stationary adsorbents {(B01D53/025 takes precedence)}
- B01J 20/226: {Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- C07F 15/065: {without a metal-carbon linkage}
- C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03}
- B01D 53/0462: {Temperature swing adsorption}
- B01D 53/047: Pressure swing adsorption
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2257/7027: Aromatic hydrocarbons
- Y02C 20/40: of CO2
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## 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.

## Claims

### Claim 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,
R5-R10 are independently selected from H, D, FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, optionally substituted (C1-C12)cycloalkyl, optionally substituted (C1-C12)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, —C(R11)3, —CH(R11)2, —CH2R11, —C(R12)3, —CH(R12)2, —CH2R12, —OC(R11)3, OCH(R11)2, —OCH2R11, —OC(R12)3, —OCH(R12)2, OCH2R12;
R11 is selected from FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; and
R12 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.

### Claim 2 (depends on 1)

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,
R5-R10 are independently selected from H, halo, amino, amide, imine, azide, methyl, cyano, nitro, nitroso, hydroxyl, aldehyde, carbonyl, ester, thiol, sulfinyl, sulfonyl, and thiocyanate.

### Claim 3 (depends on 1)

The MOF of claim 1, wherein M is selected from L+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Sc2+, Sc+, Y3+, Y2+, Y+, Ti4+, Ti3+, Ti2+, Zr4+, Zr3+, Zr2+, Hf4+, Hf3+, V5+, V4+, V3+, V2+, Nb5+, Nb4+, Nb3+, Nb2+, Ta5+, Ta4+, Ta3+, Ta2+, Cr6+, Cr5+, Cr4+, Cr3+, Cr2+, Cr+, Cr, Mo6+, Mo5+, Mo4+, Mo3+, Mo2+, Mo+, Mo, W6+, W5+, W4+, W3+, W2+, W+, W, Mn7+, Mn6+, Mn5+, Mn4+, Mn3+, Mn2+, Mn+, Re7+, Re6+, Re5+, Re4+, Re3+, Re2+, Re+, Re, Fe6+, Fe4+, Fe3+, Fe2+, Fe+, Fe, Ru8+, Ru7+, Ru6+, Ru4+, Ru3+, Ru2+, Os8+, Os7+, Os6+, Os5+, Os4+, Os3+, Os2+, Os+, Os, Co5+, Co4+, Co3+, Co2+, Co+, Rh6+, Rh5+, Rh4+, Rh3+, Rh2+, Rh+, Ir6+, Ir5+, Ir4+, Ir3+, Ir2+, Ir+, Ir, Ni3+, Ni2+, Ni+, Ni, Pd6+, Pd4+, Pd2+, Pd+, Pd, Pt6+, Pt5+, Pt4+, Pt3+, Pt2+, Pt+, Cu4+, Cu3+, Cu2+, Cu+, Ag3+, Ag2+, Ag+, Au5+, Au4+, Au3+, Au2+, Au+, Zn2+, Zn+, Zn, Cd2+, Cd+, Hg4+, Hg2+, Hg+, B3+, B2+, B+, Al3+, Al2+, Al+, Ga3+, Ga2+, Ga+, In3+, In2+, In1+, Tl3+, Tl+, Si4+, Si3+, Si2+, Si+, Ge4+, Ge3+, Ge2+, Ge+, Ge, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As2+, As+, Sb5+, Sb3+, Bi5+, Bi3+, Te6+, Te5+, Te4+, Te2+, La3+, La2+, Ce4+, Ce3+, Ce2+, Pr4+, Pr3+, Pr2+, Nd3+, Nd2+, Sm3+, Sm2+, Eu3+, Eu2+, Gd3+, Gd2+, Gd+, Tb4+, Tb3+, Tb2+, Tb+, Db3+, Db2+, Ho3+, Er3+, Tm4+, Tm3+, Tm2+, Yb3+, Yb2+, Lu3+, La3+, La2+, La+, and combinations thereof, including any complexes which contain the metals or metal ions, as well as any corresponding metal salt counter-anions.

### Claim 4 (depends on 3)

The MOF of claim 3, wherein M is selected from Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc2+, Y2+, Ti2+, Zr2+, V2+, Nb2+, Ta2+, Cr2+, Mo2+, W2+, Mn2+, Re2+, Fe2+, Ru2+, Os2+, Co2+, Rh2+, Ir2+, Ni2+, Pd2+, Pt2+, Cu2+, Ag2+, Au2+, Zn2+, Cd2+, Hg2+, B2+, Al2+, Ga2+, In2+, Si2+, Ge2+, Sn2+, Pb2+, As2+, Te2+, La2+, Ce2+, Pr2+, Nd2+, Sm2+, Eu2+, Gd2+, Tb2+, Db2+, Tm2+, Yb2+, and La2+, including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions.

### Claim 5 (depends on 4)

The MOF of claim 4, wherein M is Co2+.

### Claim 6 (depends on 1)

The MOF of claim 1, wherein the MOF comprises a repeating core of Co2(dobpdc) (dobpdc=4,4′-dioxido-3,3′-biphenyldicarboxylate).

### Claim 7 (depends on 1)

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.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 1)

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

### Claim 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,
R1-R10 are independently selected from H, D, FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, optionally substituted (C1-C12)cycloalkyl, optionally substituted (C1-C12)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, —C(R11)3, —CH(R11)2, —CH2R11, —C(R12)3, —CH(R12)2, —CH2R12, —OC(R11)3, OCH(R11)2, —OCH2R11, —OC(R12)3, —OCH(R12)2, OCH2R12;
R11 is selected from FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; and
R12 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.

### Claim 11 (depends on 10)

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

### Claim 12 (depends on 10)

The method of claim 10, wherein the mixture comprises aromatic hydrocarbons selected from toluene, ethylbenzene, benzene, para-xylene, meta-xylene, ortho-xylene, durene, mesitylene, biphenyl, naphthalene, anthracene, phenanthrene, and any combination thereof.

### Claim 13 (depends on 12)

The method of claim 12, wherein the mixture comprises aromatic hydrocarbons selected from ethylbenzene, para-xylene, meta-xylene, and ortho-xylene.

### Claim 14 (depends on 10)

The method of claim 10, 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 I, II and/or Formula III:
wherein,
R1-R10 are independently selected from H, halo, amino, amide, imine, azide, methyl, cyano, nitro, nitroso, hydroxyl, aldehyde, carbonyl, ester, thiol, sulfinyl, sulfonyl, and thiocyanate.

### Claim 15 (depends on 10)

The method of claim 10, wherein M is selected from Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc2+, Y2+, Ti2+, Zr2+, V2+, Nb2+, Ta2+, Cr2+, Mo2+, W2+, Mn2+, Re2+, Fe2+, Ru2+, Os2+, Co2+, Rh2+, Ir2+, Ni2+, Pd2+, Pt2+, Cu2+, Ag2+, Au2+, Zn2+, Cd2+, Hg2+, B2+, Al2+, Ga2+, In2+, Si2+, Ge2+, Sn2+, Pb2+, As2+, Te2+, La2+, Ce2+, Pr2+, Nd2+, Sm2+, Eu2+, Gd2+, Tb2+, Db2+, Tm2+, Yb2+, and La2+, including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions.

### Claim 16 (depends on 15)

The method of claim 15, wherein M is Co2+.

### Claim 17 (depends on 10)

The method of claim 10, wherein the MOF comprises a repeating core of Co2(dobdc), Co2(m-dobdc) or Co2(dobpdc) (dobdc=2,5-dioxido-1,4-benzenedicarboxylate, m-dobdc=4,6-dioxido-1,3-benzenedicarboxylate, dobpdc=4,4′-dioxido-3,3′-biphenyldicarboxylate).

### Claim 18 (depends on 17)

The method of claim 17, wherein the MOF comprises a repeating core of Co2(dobdc).

### Claim 19 (depends on 1)

The method of claim 1, wherein the metal-metal separation distance of the MOF is from about 7.7 Å to about 12.7 Å.

### Claim 20 (depends on 10)

The method of claim 10, 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.