公开(公告)号：US20210370267A1

公开(公告)日：2021-12-02

申请号：US17178177

申请日：2021-02-17

Applicant: The Regents of the University of California ,  ExxonMobil Research and Engineering Company

Inventor： Jeffrey R. Long ,  Simon Christopher Weston ,  Phillip J. Milner ,  Jeffrey D. Martell ,  Rebecca L. Siegelman

IPC: B01J20/22 ,  B01J20/28 ,  B01D53/02 ,  B01J31/16 ,  B01D53/62 ,  B01D53/82 ,  B01D53/96 ,  C07F3/02 ,  C10L3/10

Abstract: Primary, secondary (1°,2°) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for CO2 capture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimzing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4−=4,4″-dioxido-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate), yields diamine-appended adsorbents displaying a single CO2 adsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4−=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single CO2 adsorption step with bulky diamines. By relieving steric interactions between adjacent ammonium carbamate chains, these frameworks enable step-shaped CO2 adsorption, decreased water co-adsorption, and increased stability to diamine loss. Variants of Mg2(dotpdc) and Mg2(pc-dobpdc) functionalized with large diamines such as N-(n-heptyl)ethylenediamine have utility as adsorbents for carbon capture applications.

公开(公告)号：US10780388B2

公开(公告)日：2020-09-22

申请号：US16054800

申请日：2018-08-03

Applicant: The Regents of the University of California ,  ExxonMobil Research and Engineering Company

Inventor： Jeffrey R. Long ,  Simon Christopher Weston ,  Phillip J. Milner ,  Rebecca L. Siegelman

IPC: B01J20/22 ,  B01D53/14 ,  B01D53/04 ,  B01D53/02 ,  B01D53/047 ,  C07F3/02

Abstract: Achieving the selective and reversible adsorption of CO2 from humid, low partial pressures streams such as the flue gas resulting from the combustion of natural gas in combined cycle power plants (4% CO2) is challenging due to the need for high thermal, oxidative, and hydrolytic stability as well as moderate regeneration conditions to reduce the energy of adsorption/desorption cycling. Appending cyclic primary, secondary diamines, exemplified by 2-(aminomethyl)piperidine (2-ampd), to the metal-organic frameworks Mg2(dobpdc) (dobpdc4−=4,4-dioxidobiphenyl-3,3-dicarboxylate), Mg2(dotpdc) (dotpdc4−=4,4″-dioxido-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate) or Mg2(pc-dobpdc) (pc-dobpdc4−=dioxidobiphenyl-4,4′-dicarboxylate) produces adsorbents of the classes EMM-44, EMM-45, and EMM-46, respectively, that display step-shaped adsorption of CO2 at the partial pressures required for 90% capture from natural gas flue gas at temperatures up to or exceeding 60° C. Using a cyclic diamine in place of a diamine functionalized with bulky alkyl groups enables fast adsorption/desorption kinetics with sharp CO2 adsorption and desorption steps.