USOO8425659B2
`
`(12) United States Patent
`Matzger et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 8.425,659 B2
`Apr. 23, 2013
`
`(54) MICROPOROUS COORDINATION
`POLYMERS AS NOVEL, SORBENTS FOR GAS
`SEPARATION
`
`(58) Field of Classification Search ........ 95/96; 96/139,
`96/143
`See application file for complete search history.
`
`(75) Inventors: Adam J. Matzger, Ann Arbor, MI (US);
`Antek G. Wong-Foy, Ann Arbor, MI
`(US); Stephen Caskey, Franklin, WI
`(US)
`(73) Assignee: The Regents of The University of
`Michigan, Ann Arbor, MI (US)
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 393 days.
`12/744,709
`
`(21) Appl. No.:
`
`(*) Notice:
`
`Dec. 3, 2008
`PCT/US2008/085427
`
`(22) PCT Filed:
`(86). PCT No.:
`S371 (c)(1),
`(2), (4) Date: May 26, 2010
`(87) PCT Pub. No.: WO2009/073739
`PCT Pub. Date: Jun. 11, 2009
`
`(65)
`
`Prior Publication Data
`US 2010/O258004 A1
`Oct. 14, 2010
`
`Related U.S. Application Data
`(60) Provisional application No. 60/991,950, filed on Dec.
`3, 2007.
`
`(51) Int. Cl.
`BOID 59/26
`(52) U.S. Cl.
`USPC .................................... 95/96; 95/139; 95/143
`
`(2006.01)
`
`
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`5,378.440 A
`1/1995 Herbst et al.
`6,989,044 B2
`1/2006 Zhang et al.
`7,196,210 B2
`3/2007 Yaghi et al.
`8,163,949 B2 * 4/2012 Mueller et al. ................ 556,115
`OTHER PUBLICATIONS
`International Search Report from corresponding International Appli
`cation No. PCT/US2008/085427 (dated May 21, 2009).
`International Preliminary Report on Patentability and Written Opin
`ion of the International Searching Authority in counterpart Interna
`tional Application No. PCT/US2008/085427, dated Jun. 8, 2010 (5
`pgs.).
`Dietzel et al., “An In Situ High-Temperature Single-Crystal Investi
`gation of a Dehydrated Metal-Organic Framework Compound and
`Field-Induced Magnetization of One-Dimensional Metal-Oxygen
`Chains.” Angew. Chem. Int. Ed., 117:6512-16 (2005).
`Rosi et al., “Rod Packings and Metal-Organic Frameworks Con
`structed from Rod-Shaped Secondary Building Units.”.J. Am. Chem.
`Soc., 127: 1504-18 (2005).
`(Continued)
`Primary Examiner — Robert A Hopkins
`(74) Attorney, Agent, or Firm — Harness, Dickey & Pierce,
`P.L.C.
`ABSTRACT
`(57)
`A method of separating a target component from a chemical
`mixture comprising contacting a chemical mixture with a
`microporous coordination polymer. The microporous poly
`mer is described by the formula:
`M2(CH2O)
`where M is a transition metal, rare earth metal, or other
`element from the groups consisting of IIA through VB.
`24 Claims, 20 Drawing Sheets
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`US 8,425,659 B2
`Page 2
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`OTHER PUBLICATIONS
`Dietzel et al., “Hydrogen Adsorption in a Nickel Based Coordination
`Polymer with Open Metal Sites in the Cylindrical Cavities of the
`Desolvated Framework.” Chem. Commun., 959-61 (2006).
`Dietzel et al., “Base-Induced Formation of Two Magnesium Metal
`Organic Framework Compounds with a Bifunctional Tetratopic
`Ligand.” Eur: J. Inorg. Chem., 3624-32 (2008).
`
`Zhou et al., “Enhanced H. Adsorption in Isostructural Metal
`Orgainic Frameworks with Open Metal Sites: Strong Dependence of
`the Binding Strength on Metal Ions.” J. Am. Chem. Soc., 130:15268
`69 (2008).
`Glover et al., “MOF-74 Building Unit has a Direct Impact on Toxic
`Gas Adsorption.” Chem. Eng. Sci., 66:163-70 (2011).
`
`* cited by examiner
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 1 of 20
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`Figure
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 2 of 20
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`US 8.425,659 B2
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`
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`3040
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`1O
`
`Two-Theta (deg)
`
`Figure 2
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 3 of 20
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`US 8.425,659 B2
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`15OO
`
`1OOO
`
`10
`
`2O
`
`40
`30
`Two-Theta (deg)
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`50
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`60
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`70
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`Figure 3
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 4 of 20
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`US 8.425,659 B2
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`75
`
`so
`
`O
`
`2
`
`3.
`
`()
`Two-Theta (deg)
`
`SO
`
`s
`
`7
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`Figure 4
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 5 of 20
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`US 8.425,659 B2
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`
`
`83
`
`$3.3
`
`33.3
`
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`
`$3.8
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 6 of 20
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`US 8.425,659 B2
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`
`
`1. 2 O
`
`1. O O
`
`8 O
`
`6 O
`
`4. O
`
`2 O
`
`O
`
`-O-Adsorption CO2
`se-Desorption CO2
`
`O
`
`0.2
`
`0.4
`O,6
`Relative Pressure (P/PO)
`
`O.8
`
`1.
`
`Figure 6
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 7 of 20
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`US 8.425,659 B2
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`
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`CO2 Sorption for Mg-74 at 296 K
`
`ce-Adsorption CO2
`-e-Desorption CO2
`
`O
`
`0.2
`
`0.6
`O.4
`Relative Pressure (P/PO)
`
`O,8
`
`Figure 7
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 8 of 20
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`US 8.425,659 B2
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`
`
`Ethylene Sorption isotherm for Co-74 at 298 K
`
`-O-Ethylene Adsorption
`
`-e-Ethylene Desorption
`
`O.4
`0.6
`Relative Pressure (P/Po)
`
`Figure 8
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 9 of 20
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`US 8.425,659 B2
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`3:::: Ethylene sorption isotherm for Ni-74 at 298 K
`
`
`
`
`
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`Figure 9
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 10 of 20
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`US 8.425,659 B2
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`
`
`160 Ethylene Sorption isotherm for Zn-74 at 298 K
`
`$120
`E
`100
`E
`is 80
`ce
`9 60
`S 40
`
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`
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`
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`
`-e-Ethylene Desorption
`
`O.6
`O.4
`Relative Pressure (P/Po)
`
`Figure 10
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 11 of 20
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`US 8.425,659 B2
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`
`
`Ethane Sorption isotherm for Co-74 at 298 K
`
`ad
`
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`
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`O.6
`Relative Pressure (P/Po)
`
`Figure 11
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 12 of 20
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`US 8.425,659 B2
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`
`
`Ethane Sorption isotherm for Ni-74 at 298 K
`
`1. 2 O
`Sg
`1. O O
`ad
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`8 O
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`C
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`n
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`O
`
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`
`-e-Ethane Desorption
`
`0.4
`0.6
`Relative Pressure (P/Po)
`
`Figure 12
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 13 of 20
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`US 8.425,659 B2
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`
`
`1. 2 O
`s
`N
`1. O O
`E an
`(U
`E
`E.
`O
`Cs
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`al
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`
`Ethane Sorption isotherm for Zn-74 at 298 K
`
`-o-Ethane Adsorption
`
`e-Ethane Desorption
`
`O.6
`O.4
`Relative Pressure (P/Po)
`
`Figure 13
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 14 of 20
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`US 8.425,659 B2
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`0.0045 Separation of Ethane-Ethylene at 100 deg. C
`O.004
`
`O.OO35
`
`O.OO3
`
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`
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`10
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`
`2O
`
`25
`
`Figure 14
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 15 of 20
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`US 8.425,659 B2
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`Separation of Ethane-Ethylene by
`Temperature Ramp
`-Ramp Rate 5 deg. C/min
`
`O.OO45
`
`O.OO4
`
`O.OO35
`
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`
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`Time (min.)
`
`2O
`
`25
`
`Figure 15
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 16 of 20
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`US 8.425,659 B2
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`Separation of Ethane-Ethylene by
`Temperature Ramp
`
`-Ramp Rate 10 deg. C/min
`
`OOO5
`
`i
`
`O.OO2
`
`O.OO1
`
`O
`
`5
`
`1O
`
`15
`
`Time (min.)
`
`Figure 16
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 17 of 20
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`US 8.425,659 B2
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`Separation of Propane-Propylene at 100 deg. C
`
`O.OO2
`O.OO18
`
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`
`50
`
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`Time (mins.)
`
`150
`
`Figure 17
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 18 of 20
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`US 8.425,659 B2
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`O.O.05 Separation of Propane-Propylene at 150 deg. C
`
`OOO45
`
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`
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`
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`
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`25
`
`30
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`Figure 18
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 19 of 20
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`US 8.425,659 B2
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`0.006
`
`O.OO5
`
`Separation of Propane-Propylene by
`Temperature Ramp
`Ramp Rate 5 deg. C/min
`
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`
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`
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`
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`
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`
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`
`2O
`
`25
`
`Figure 19
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`U.S. Patent
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`Apr. 23, 2013
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`Sheet 20 of 20
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`US 8.425,659 B2
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`Separation of Propane-Propylene by
`Temperature Ramp
`-Ramp Rate 10 deg. C/min
`
`O.OO9
`
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`
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`
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`Figure 20
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`US 8,425,659 B2
`
`1.
`MCROPOROUS COORONATION
`POLYMERS AS NOVELSORBENTS FOR GAS
`SEPARATION
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`This application claims the benefit of U.S. provisional
`application Ser. No. 60/991,950 filed Dec. 3, 2007.
`
`10
`
`BACKGROUND OF INVENTION
`
`2
`thesized and the effect on CO2 uptake is investigated leading
`to a very high affinity CO material.
`Currently known MCPs have relatively unexceptional
`uptake of CO at low relative pressure. The best performance
`achieved previously by a material in this class is 21.4 wt % at
`1.1 bar and 298 K by MOF-74. This material is difficult to
`synthesize and activate to high Surface area. Also, the activa
`tion/evacuation conditions required to achieve porosity are
`relatively harsh (vacuum, 270° C., 16 hours). HKUST-1 Cus
`(BTC), BTC-benzene-1,3,5-tri-carboxylate or trimesylate
`is another MCP with relatively strong affinity for CO. The
`adsorption of CO on HKUST-1 was first reported in 2002 to
`achieve ~4.2 mol CO/kg. MCP or ~18 wt % at ~1 bar and 295
`K. This was substantiated in 2005 by a report of 17.9 wt % at
`1 bar and 298 K. The most recent report of a relatively strong
`affinity CO material was in 2007 using FeO(BTB),
`which displayed -95 mL CO/g or ~19 wt % at 273 Kand ~48
`mL CO/g or -9.4 wt % at 298 K. Thus, currently known
`MCPs are comparable to 13x Zeolite in low pressure CO
`uptake at room temperature and there remains a great need for
`higher affinity CO2 uptake materials and especially those that
`function well below one bar.
`The separations of close boiling mixtures of ethane/ethyl
`ene or propane?propylene are among the most energy-inten
`sive separations carried out in the chemical and petrochemi
`cal industry. Because of the relatively close boiling points
`within the two pairs of compounds, cryogenic distillation at
`Super pressures in trayed fractionators is still used to separate
`them on a large scale. Other approaches that are potentially
`less energy intensive involve an absorption/stripping method
`based on aqueous silver nitrate solutions and adsorption on a
`solid sorbent. Zeolites or molecular sieves and L-complex
`ation sorbents are types of Sorbents have been examined to
`accomplish these separations. Among the former materials
`that have been studied are activated carbon, 4A zeolite, 13x
`molecular sieve and the aluminophosphate AlPO-14
`molecular sieve. JL-Complexation Sorbents are normally
`based on silica gel and activated alumina that are impregnated
`with transition metal salts such as AgNO or CuCl. Other
`materials that have been examined for light olefin/paraffin
`separations are metal-containing facilitated transport mem
`branes.
`
`15
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`
`1. Field of the Invention
`metal-organic
`to
`The present invention relates
`microporous coordination polymers and their use in chemical
`separation of gases.
`2. Background Art
`The development of materials with high adsorption of car
`bon dioxide at low relative pressure and ambient temperature
`has been a significant challenge to materials chemistry. Physi
`cal adsorption of carbon dioxide is an emergent technology.
`This system may replace the currently used processes, such as
`chemical adsorption by a bed of amine, which are costly to
`operate. Microporous coordination polymers (MCPs) offer
`advantages as high Surface area materials yet the challenge
`that is addressed here is the development of an MCP with a
`strong affinity for CO. Such a material provides high adsorp
`tion at low relative pressures and ambient temperature.
`Amines are presently materials of choice for sequestration of
`CO. Flue gas, for example from coal combustion, is bubbled
`through a solution of amine that reacts with the CO. The
`product of this reaction can then be pumped to another vessel
`and heated to release the CO, and recycle the amine. The
`process however is inefficient and costly in terms of energy
`required to recycle the amine. Physisorption, as opposed to
`this chemisorption, is likely to be a more efficient and less
`expensive method of sequestration of CO if high affinity CO
`materials are developed. In general, physisorption provides
`ready release of the Sorbed gas with moderate changes in
`pressure or temperature unlike chemisorption which gener
`ally requires more vigorous conditions.
`In light of this, adsorbent materials or molecular sieves
`such as Zeolites have been investigated extensively for CO.
`uptake. Zeolite syntheses often require high temperature con
`ditions for both syntheses and calcinations. In most cases, the
`45
`nature of Zeolites does not provide the opportunity for Syn
`thetic flexibility and/or ready functionalization. Yet to this
`point zeolites have been among the best materials for CO.
`uptake. Zeolite 13X (UOP) has been the traditionally used
`sorbent for CO storage and has been reported to provide
`uptake of 4.7 mmol CO/g sorbent (20.7 wt %) at 1 bar and
`298 K.
`A new class of materials known as MCPs offer many
`advantages to Zeolites in the ease of synthesis, flexibility in
`functionalization and alteration, and characterization due to
`crystallinity. MCPs are composed of multifunctional organic
`linkers and metal-containing secondary building units
`(SBUs). Synthetic procedures are easily altered by modifica
`tion of the linker Such that functional groups can be added to
`the framework or the framework can be expanded. Substitu
`tion of the metal in the synthesis of MCPs has generally led to
`different SBUs which in turn leads to global changes to the
`resulting structure and porosity. Thus, careful examination of
`the metal effects alone has not been possible due to differ
`ences in structure of the resulting networks. There is a need to
`examine the effects of only the metal on the resulting prop
`erties of the MCP Here isostructural MCPs have been syn
`
`SUMMARY OF THE INVENTION
`
`The present invention solves one or more of the issues
`related to the separation of gases not addressed in the prior art.
`In an embodiment of the present invention, exceptionally
`high affinity CO materials are provided. These materials
`include microporous coordination polymers containing Co.
`Ni, Mg, and/or Zn and an organic linker. The materials dis
`closed here, referred to as Co-74, Ni-74, and Mg-74, are
`particularly high affinity CO materials with exceptional
`uptake of CO at low relative pressures and ambient tempera
`tures.
`In another embodiment, a method of separating olefin/
`paraffin using a high affinity olefin-adsorbing material is pro
`vided. Such affinity olefin-adsorbing materials include
`microporous coordination polymers containing Co, Ni, Mg,
`and/or Zn and an organic linker. These material show good
`selectivities for olefin compounds over paraffin compounds.
`Co-74, Ni-74, and Mg-74 are useful in the chemical separa
`tion of unsaturated molecules from Saturated molecules, and
`in particular olefins from paraffins. Ethylene and ethane can
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`BRIEF DESCRIPTION OF THE DRAWINGS
`
`10
`
`15
`
`25
`
`30
`
`3
`be separated using Co-74, Ni-74, Mg-74, and/or Zn-74. Pro
`pylene and propane can be separated using Co-74, Ni-74,
`Mg-74, and/or Zn-74.
`
`4
`invention, which constitute the best modes of practicing the
`invention presently known to the inventors. The Figures are
`not necessarily to scale. However, it is to be understood that
`the disclosed embodiments are merely exemplary of the
`invention that may be embodied in various and alternative
`forms. Therefore, specific details disclosed herein are not to
`FIG. 1 provides the X-ray crystal structure for Co-74.
`be interpreted as limiting, but merely as a representative basis
`FIG. 2 provides a powder X-ray diffraction (“PXRD)
`for any aspect of the invention and/or as a representative basis
`pattern for Co-74.
`for teaching one skilled in the art to variously employ the
`FIG. 3 provides a powder X-ray diffraction (“PXRD)
`present invention.
`pattern for Ni-74.
`FIG. 4 provides a powder X-ray diffraction (“PXRD)
`Except in the examples, or where otherwise expressly indi
`pattern for Mg-74.
`cated, all numerical quantities in this description indicating
`FIG. 5 provides a carbon dioxide sorption isotherm for
`amounts of material or conditions of reaction and/or use are to
`Co-74 measured at 296 K.
`be understood as modified by the word “about in describing
`FIG. 6 provides a carbon dioxide sorption isotherm for
`the broadest scope of the invention. Practice within the
`Ni-74 measured at 296 K.
`numerical limits stated is generally preferred. The description
`FIG. 7 provides a carbon dioxide sorption isotherm for
`of a group or class of materials as Suitable or preferred for a
`Mg-74 measured at 296 K.
`given purpose in connection with the invention implies that
`FIG. 8 provides an ethylene sorption isotherm for Co-74
`mixtures of any two or more of the members of the group or
`measured at 298 K.
`FIG. 9 provides an ethylene sorption isotherm for Ni-74
`class are equally Suitable or preferred; description of constitu
`measured at 298 K.
`ents in chemical terms refers to the constituents at the time of
`FIG. 10 provides an ethylene sorption isotherm for Zn-74
`addition to any combination specified in the description, and
`measured at 298 K.
`does not necessarily preclude chemical interactions among
`FIG. 11 provides an ethane sorption isotherm for Co-74
`the constituents of a mixture once mixed; the first definition of
`measured at 298 K.
`an acronym or other abbreviation applies to all Subsequent
`FIG. 12 provides an ethane sorption isotherm for Ni-74
`uses herein of the same abbreviation and applies mutatis
`measured at 298 K.
`mutandis to normal grammatical variations of the initially
`FIG. 13 provides an ethane sorption isotherm for Zn-74
`defined abbreviation; and, unless expressly stated to the con
`measured at 298 K.
`trary, measurement of a property is determined by the same
`FIG. 14 provides an isothermal gas chromatogram of the
`technique as previously or later referenced for the same prop
`separation of ethane and ethylene at 100° C. over a 50:50 wt.
`erty.
`mixture of celite and Ni-74. Ethane elutes first at 2.7 minutes
`It is also to be understood that this invention is not limited
`while ethylene elutes at 12.6 minutes.
`to the specific embodiments and methods described below, as
`FIG. 15 provides a gas chromatogram of the separation of
`specific components and/or conditions may, of course, vary.
`ethane and ethylene by a temperature ramp program from 50°
`35
`Furthermore, the terminology used herein is used only for the
`C. to 175° C. at a rate of 5°C/min over a 50:50 wt. mixture of
`purpose of describing particular embodiments of the present
`celite and Ni-74. Ethane elutes first at 5.9 minutes while
`invention and is not intended to be limiting in any way.
`ethylene elutes at 15.3 minutes.
`It must also be noted that, as used in the specification and
`FIG. 16 provides a gas chromatogram of the separation of
`the appended claims, the singular form “a,” “an and “the
`ethane and ethylene by a temperature ramp program from 50°
`40
`comprise plural referents unless the context clearly indicates
`C. to 200° C. at a rate of 10° C./min over a 50:50 wt. mixture
`otherwise. For example, reference to a component in the
`of celite and Ni-74. Ethane elutes first at 4.8 minutes while
`singular is intended to comprise a plurality of components.
`ethylene elutes at 9.9 minutes.
`Throughout this application, where publications are refer
`FIG. 17 provides a gas chromatogram of the separation of
`enced, the disclosures of these publications in their entireties
`propane and propylene at 100° C. over a 50:50 wt. mixture of
`45
`are hereby incorporated by reference into this application in
`celite and Ni-74. Propane elutes first at 14.9 minutes while
`their entirety to more fully describe the state of the art to
`propylene elutes at 93.9 minutes.
`which this invention pertains.
`FIG. 18 provides a gas chromatogram of the separation of
`As used herein “linking ligand’ means a chemical species
`propane and propylene at 150° C. over a 50:50 wt. mixture of
`(including neutral molecules and ions) that coordinate two or
`celite and Ni-74. Propane elutes first at 4.5 minutes while
`50
`more metal atoms or metal clusters resulting in an increase in
`propylene elutes at 13.7 minutes.
`their separation, and the definition of void regions or channels
`FIG. 19 provides a gas chromatogram of the separation of
`in the framework that is produced. Examples include, but are
`propane and propylene by a temperature ramp program from
`not limited to, 4,4'-bipyridine (a neutral, multiple N-donor
`75° C. to 200° C. at a rate of 5° C.Amin over a 50:50 Wt.
`molecule) and benzene-1,4-dicarboxylate (a polycarboxylate
`mixture of celite and Ni-74. Propane elutes first at 12.2 min
`55
`anion). In an embodiment of the present invention, a method
`utes while propylene elutes at 20.25 minutes.
`of separating a target component from a chemical mixture is
`FIG. 20 provides a gas chromatogram of the separation of
`provided. The method of this embodiment comprises contact
`propane and propylene by a temperature ramp program from
`ing a chemical mixture with a microporous polymer to form
`75° C. to 250° C. at a rate of 10° C.Amin over a 50:50 Wt.
`mixture ofcelite and Ni-74. Propane elutes first at 8.7 minutes 60 a modified chemical composition and to separate out a target
`component. Specifically, at least a portion of the target com
`while propylene elutes at 12.7 minutes.
`ponent is adsorbed to the microporous coordination polymer.
`In an optional Subsequent step, the modified chemical com
`position is collected. The microporous polymer comprising
`monomer units having formula:
`
`DETAILED DESCRIPTION OF THE PREFERRED
`EMBODIMENT(S)
`Reference will now be made in detail to presently preferred
`compositions, embodiments and methods of the present
`
`65
`
`M2(CH2O)
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`US 8,425,659 B2
`
`5
`wherein M is a transition metal, rare earth metal, or other
`element from the groups consisting of IIA through VB. It
`should be appreciated that M is typically a metalion (cation)
`while (CH2O) is anionic. Specific examples of metal ions
`used include one or more ions selected from the group con
`sisting Be?", Mg, Ca", Sr.", Ba?", Sc", Y", Ti, Zr",
`Hi?t, V5+, v4+, v3+, v2+, Nb5*, Nb", Tast, Tast, Cró", Cr3+,
`Mo", Mo", W6", W3", Mn", Mn?", Re", Re?", Fe", Fe?",
`Ru", Ru?", Os", Os?", Co", Co?", Rh", Rh?", Rh", Irs",
`Ir", Ni", Ni, Pd*, Pd?", Pt", Pt?", Cu2+, Cut, Ag", Au",
`Au", Zn?", Cd?", Hg", A1", Ga", In", T13+. Si", Si?",
`Ge", Ge?", Sn", Sn?", Pb, Pb2+, Ass", Ast, As", Sb,
`Sb", Sb, Bi", Bi", Bi", and combinations thereof. In a
`particularly useful variation, Mis Co, Ni, Mg, or Zn. Particu
`larly useful materials for the separation of gases are the mate
`rials named Co-74, Ni-74, Mg-74, and Zn-74 and are
`described below in more detail. In a variation, the structure of
`(CH2O) is given by the following formula:
`
`10
`
`15
`
`CO
`
`do.9
`
`In a variation, a portion of the metal M is substituted with
`a different metal. In this variation, this different metal can be
`Co, Ni, Mg, or Zn, or any other metal compatible with the
`lattice of the microporous coordination polymers.
`In another variation of the present embodiment, the
`microporous coordination polymers comprising monomer
`units having formula:
`
`25
`
`30
`
`35
`
`6
`component may be separated based on shape or size. In one
`refinement, the target component is CO and the microporous
`material has a high affinity for CO. Examples of such mate
`rials include Co-74, Ni-74, and Mg-74.7. In a refinement of
`this variation, CO, uptake at 1 bar and 296 K is from about 20
`to about 45 wt % (i.e., weight increase of the microporous
`material). In another refinement, the uptake of CO at 0.1 bar
`and 296 K1 is from about 5 to about 30 wt %.
`In another variation, the microporous materials have a high
`affinity for ethylene. Examples of such materials include
`Co-74, Ni-74, Mg-74, and Zn-74. The adsorption selectivity
`for ethylene over ethane is important for the separation of
`these gases.
`In another variation of the present invention, materials with
`the ability to separate olefins and paraffins are provided by use
`of microporous coordination polymers. The materials that are
`useful in the separation of gases are specifically named
`Co-74, Ni-74, Mg-74, and Zn-74. For example, the
`microporous coordination polymers adsorb olefins in prefer
`ence to paraffins from about 0 to 50 bar and from about 200K
`to 473 K while possessing reversible adsorption and desorp
`tion characteristics. Of particular importance are the separa
`tion of ethylene from ethane and the separation of propylene
`from propane.
`In the embodiments and variations set forth above, the
`microporous coordination polymers are used as Sorbents. In
`one refinement, the Sorbents are used in fixed or moving bed
`adsorption systems for separation or sequestration of the tar
`get component. In another variation, the sorbents are used in
`pressure- or thermal-swing adsorption systems for separation
`or sequestration of the target component.
`Co-74 is conveniently formed by a hydrothermal reaction
`of Co(NO)6H2O and 2,5-dihydroxyterephthalic acid. Pre
`ferred solvents for this reaction are mixtures of a formamide
`with an alcohol and water. The most preferred solvent is a
`1:1:1 (v/v/v) mixture of N,N-dimethylformamide:ethanol:
`water. The reaction temperature is from about 50 to about
`200° C., preferably 100° C. Ni-74 is conveniently formed by
`hydrothermal reaction of Ni(NO)6HO and 2,5-dihy
`droxyterephthalic acid. Examples of solvents for this reaction
`are mixtures of a formamide with an alcohol and water. A
`particularly useful solvent is a 1:1:1 (v/v/v) mixture of N.N-
`dimethylformamide:ethanol: water. The reaction temperature
`is from about 50 to about 200° C. A reaction temperature of
`about 100° C. is particularly useful. Mg-74 is conveniently
`formed by hydrothermal reaction of Mg(NO), .6HO and
`2,5-dihydroxyterephthalic acid. Examples of solvents for this
`reaction are mixtures of a formamide with an alcohol and
`water. A particularly useful solvent is a 15:1:1 (v/v/v) mixture
`of N,N-dimethylformamide:ethanol: water. The reaction tem
`perature is from about 50 to about 200° C. A reaction tem
`perature of about 125°C. is particularly useful. The structure
`of 2,5-dihydroxyterephthalic acid is presented in Formula I:
`
`40
`
`45
`
`50
`
`M2(CH2O).(solvent),
`wherein M is a metal as set forth above and X is a real number.
`In a refinement, X is from 1 to 6.
`The microporous coordination polymers may further
`include one or more non-linking ligands. Useful non-linking
`ligands include, for example, a ligand selected from the group
`consisting of O', sulfate, nitrate, nitrite, sulfite, bisulfite,
`phosphate, hydrogen phosphate, dihydrogen phosphate,
`diphosphate, triphosphate, phosphite, chloride, chlorate, bro
`mide, bromate, iodide, iodate, carbonate, bicarbonate, Sul
`fide, hydrogen Sulphate, selenide, selenate, hydrogen sel
`enate, telluride, tellurate, hydrogen tellurate, nitride,
`phosphide, arsenide, arsenate, hydrogen arsenate, dihydro
`gen arsenate, antimonide, antimonate, hydrogen antimonate,
`dihydrogen antimonate, fluoride, boride, borate, hydrogen
`borate, perchlorate, chlorite, hypochlorite, perbromate, bro
`mite, hypobromite, periodate, iodite, hypoiodite; and mix
`55
`tures thereof.
`In a variation of the present embodiment, the chemical
`mixture used in the separation includes a plurality of compo
`nents. An example of Such a chemical mixture is air. Advan
`tageously, the contact with the microporous polymer results
`in preferential removal of one component of the mixture. In a
`refinement of the present embodiment, the temperature at
`which the chemical mixture is contacted is from about 233 K
`to about 473 K.
`In a variation of the present embodiment, the target com
`65
`ponent is an inorganic or organic molecule having a prede
`termined degree of unsaturation. Alternatively, the target
`
`60
`
`CO2H
`
`OH
`
`HO
`
`CO2H
`
`In a variation of the present invention, the microporous
`coordination polymer is activated by immersion in a low
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`US 8,425,659 B2
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`7
`boiling solvent (e.g., methanol) followed by evacuation under
`vacuum at a temperature from 0° C. to about 325° C. A
`temperature of about 250° C. is particularly useful. In another
`variation, the microporous coordination polymer is activated
`by immersion in a low boiling solvent (e.g., methanol) fol
`lowed by passing an inert gas Such as nitrogen, carbon diox
`ide, helium, neon, argon, krypton, or Xenon through the Sor
`bent material while heating for about 12 hours. Particularly
`useful gases include nitrogen or helium. Typically, this acti
`Vation is carried out at an elevated temperature from about
`100 to 350° C. A particularly useful temperature is 250° C.
`The composition of Co-74 is described as a combination of
`Co" ions and the tetraanion of 2,5-dihydroxyterephthalic
`acid. The composition of Ni-74 is described as a combination
`of Ni" ions and the tetraanion of 2,5-dihydroxyterephthalic
`acid. The composition of Mg-74 is described as a combina
`tion of Mg" ions and the tetraanion of 2,5-dihydroxytereph
`thalic acid. The tetraanion of 2,5-dihydroxyterephthalic acid
`(i.e., an example of (CHO)) is described by Formula II:
`
`II
`
`CO
`
`do.
`
`A variation of a method of preparing Co-74 for use as a
`sorbent is to first immerse the product crystals in methanol.
`The methanol is decanted and replaced four times over two
`days. Co-74 is then dried and evacuated under vacuum at
`elevated temperature (e.g. about 250° C.), for 5 hours.
`Samples of Co-74 are then handled and stored under vacuum
`or an inert atmosphere (e.g., N), but can be handled for brief
`periods under air, for example less than 1 minute. Other
`methods of preparing the Co-74 may include different sol
`vents, numbers of washes, or thermal treatments.
`A variation of a method of preparing Ni-74 for use as a
`sorbent is to first immerse the product crystals in methanol.
`The methanol is decanted and replaced four times over two
`days. Ni-74 is then dried and evacuated under vacuum at
`elevated temperature (e.g., about 250° C.) for 5 hours.
`Samples of Ni-74 are then handled and stored under vacuum
`or an inert atmosphere (e.g., N), but can be handled for brief
`periods under air, for example less than 1 minute. Other
`methods of preparing the Ni-74 may include different sol
`vents, numbers of washes, or thermal treatments.
`A variation of a method of preparing Mg-74 for use as a
`sorbent is to first immerse the product crystals in methanol.
`The methanol is decanted and replaced four times over two
`days. Mg-74 is then dried and evacuated under vacuum at
`elevated temperature (e.g., about 250° C.) for 5 hours.
`Samples of Mg-74 are then handled and stored under vacuum
`or an inert atmosphere (e.g., N.) but can be handled for brief
`periods under air, for example less than 1 minute. Other
`methods of preparing the Mg-74 may include different sol
`vents, numbers of washes, or thermal treatments.
`The structural diagram for Co-74 is presented in FIG. 1.
`This structure is a three-dimensional framework with one
`dimensional channels as depicted. The isostructural nature of
`Co-74, Ni-74, and Mg-74 is presented in FIGS. 2, 3, and 4 due
`to the approximate equivalence of the powder X-ray diffrac
`tion patterns.
`
`8
`These materials, Co-74, Ni-74, and Mg-74, display very
`strong affinity for CO. Carbon dioxide sorption isotherms
`are presented in FIGS. 5, 6, and 7 for Co-74, Ni-74, and
`Mg-74, respectively. High affinity for CO at low partial pres
`sures and ambient temperatures is preferable for certain
`applications. The uptake of CO for Co-74 at 0.1 bar and 296
`K is 11.74 wt.%. It is understood that value obtained from an
`adsorption experiment should be used in an app