Solid-state copper(i) sorbents for olefin separations

Patent metadata

Field	Value
Publication number	US-2021387134-A1
Application number	US-201917285524-A
Country	US
Kind code	A1
Filing date	Oct 15, 2019
Priority date	Oct 15, 2018
Publication date	Dec 16, 2021
Grant date	—

Abstract

Disclosed herein is a process for separating a hydrocarbon feed gas mixture comprising constituents including ethylene to produce a separated ethylene product. The disclosed process employs a solid-state ethylene sorbent and temperature and/or pressure swing adsorption and membrane separation and demonstrates a methodology to reduce the net heat of reaction during the adsorption of ethylene onto an adsorbent.

First claim

1 . A process comprising:
exposing a trinuclear copper(I) pyrazolate complex to a hydrocarbon feed gas mixture comprising one or more alkenes comprising ethylene, propylene, butene, pentene, or isobutylene and one or more alkanes comprising ethane, methane, propane, butane, or pentane, to form a product comprising a dinuclear copper(I)-alkene complex.

2 . (canceled)

3 . (canceled)

4 . (canceled)

5 . (canceled)

6 . The process of claim 1 , wherein the one or more alkenes comprise ethylene, wherein the one or more alkanes comprise ethane, and wherein the formed product comprises a dinuclear copper(I)-ethylene complex.

7 . The process of claim 6 , further comprising a step of separating ethylene from ethane.

8 . The process of claim 6 , wherein the dinuclear copper(I)-ethylene complex is formed by adsorption of ethylene on the trinuclear copper(I) pyrazolate complex.

9 . The process of claim 8 , further comprising a step of desorption of ethylene from the dinuclear copper(I)-ethylene complex at a temperature from about −50° C. to about 150° C. and a pressure from about 0 bar to about 500 bar.

10 . (canceled)

11 . The process of claim 9 , wherein the ethylene desorption forms a regenerated trinuclear copper(I) pyrazolate complex.

12 . The process of claim 1 , wherein the trinuclear copper(I) pyrazolate complex is a [3,4,5-tris(trifluoromethyl)pyrazolyl)Cu] 3 complex ([(3,4,5-(CF 3 ) 3 Pz)Cu] 3 , ([Cu 3 ]).

13 . The process of claim 6 , wherein the dinuclear copper(I)-ethylene complex is a [3,4,5-tris(trifluoromethyl)pyrazolyl)Cu(C 2 H 4 )] 2 ([3,4,5-(CF 3 ) 3 Pz)Cu(C 2 H 4 )] 2 complex, ([Cu 2 .(C 2 H 4 ) 2 ]).

14 . (canceled)

15 . The process of claim 8 , wherein at least a portion of the ethylene adsorption occurs at a ‘step’ pressure of about 2 kPa to about 30 kPa and a temperature from about 20° C. to about 75° C. (from about 293 K to about 348 K).

16 . The process of claim 12 , wherein the step of exposing comprises exposing a solid-state [Cu 3 ] or a dichloromethane solution of [Cu 3 ] to the hydrocarbon feed gas mixture.

17 . (canceled)

18 . The process of claim 11 , wherein the ethylene desorption from dinuclear copper(I)-ethylene complex to regenerate trinuclear copper(I) pyrazolate complex is performed in a solid-state.

19 . The process of claim 13 , wherein the step of exposing results in a reversible solid-state structural transformation [Cu 3 ] to [Cu 2 .(C 2 H 4 ) 2 ].

20 . (canceled)

21 . The process of claim 12 , wherein an adsorption selectivity of ethylene/ethane on [Cu 3 ] is from about 1:1 to about 136:1 when measured at a temperature of 20° C. and an equilibrium loading at 1 atm or wherein an adsorption selectivity of ethylene/ethane on [Cu 3 ] is from about 1:1 to about 131:1 when measured at a temperature of 70° C. and an equilibrium loading at 1 atm.

22 . (canceled)

23 . The process of claim 12 , wherein the process exhibits a decrease of a heat of adsorption by 50 to 85% when compared to a substantially identical reference process comprising a copper (I) complex that is not [Cu 3 ].

24 . The process of claim 12 , wherein [Cu 3 ] is formed by:
a) reacting copper (I) oxide with a precursor 3,4,5-(CF 3 ) 3 pyrazole (3,4,5-(CF 3 ) 3 PzH) in a solvent-free process to form a product comprising a [3,4,5-tris(trifluoromethyl)pyrazolyl)Cu] 3 complex ([(3,4,5-(CF 3 ) 3 Pz)Cu] 3 , ([Cu 3 ]); b) extracting [Cu 3 ] with a solvent.

25 . (canceled)

26 . The process of claim 24 , further comprising removing the solvent to form a solid-state [Cu 3 ].

27 . A composition comprising a trinuclear copper(I) pyrazolate complex, wherein the composition is reversibly transformed to a dinuclear copper(I)-alkene complex, when exposed to a hydrocarbon feed gas mixture comprising one or more alkenes comprising ethylene, propylene, butene, pentene, or isobutylene and one or more alkanes comprising ethane, methane, propane, butane, or pentane.

28 . (canceled)

29 . (canceled)

30 . (canceled)

31 . (canceled)

32 . The composition of claim 27 , wherein the trinuclear copper(I) pyrazolate complex comprises a [3,4,5-tris(trifluoromethyl)pyrazolyl)Cu] 3 complex ([(3,4,5-(CF 3 ) 3 Pz)Cu] 3 , ([Cu 3 ]), wherein the composition is reversibly transformed to the dinuclear copper(I)-alkene complex comprising a [3,4,5-tris(trifluoromethyl)pyrazolyl)Cu(C 2 H 4 )] 2 ([3,4,5-(CF 3 ) 3 Pz)Cu(C 2 H 4 )] 2 , ([Cu 2 (C 2 H 4 ) 2 ]) when exposed to a hydrocarbon feed gas mixture comprising ethylene and one or more alkanes comprising ethane.

33 . The composition of claim 32 , wherein [Cu 2 (C 2 H 4 ) 2 ] is formed by an ethylene adsorption on [Cu 3 ].

34 . The composition of claim 32 , wherein an ethylene desorption transforms [Cu 2 (C 2 H 4 ) 2 ] to [Cu 3 ].

35 . The composition of claim 32 , wherein the composition exhibits an adsorption selectivity of ethylene/ethane on [Cu 3 ] of from about 1:1 to about 136:1 when measured at a temperature of 20° C. and an equilibrium loading at 1 atm or wherein the composition exhibits an adsorption selectivity of ethylene/ethane on [Cu 3 ] of from about 1:1 to about 131:1 when measured at a temperature of 70° C. and an equilibrium loading at 1 atm.

36 . (canceled)

37 . The composition of claim 32 , wherein the reversible transformation is an endothermic structural rearrangement of [Cu 3 ].

38 . The composition of claim 32 , wherein the reversible transformation is a solid-state transformation.

Assignees

• Univ Texas
• Univ Colorado Regents

Inventors

• Dias Rasika
• Jayaratna Naleen B
• Noble Richard D
• Cowan Matthew G
• Parasar Devaborniny

Classifications

• C07F1/08 Primary

  Copper compounds · CPC title

• B01D2253/204

  Metal organic frameworks (MOF's) · CPC title

• B01D2257/7022

  Aliphatic hydrocarbons · CPC title

• B01D2256/24

  Hydrocarbons · CPC title

• B01D53/0462 Primary

  Temperature swing adsorption · CPC title