Exxonmobil Research and Engineering Company

Exxonmobil Technology and Engineering Company

Exxonmobil Chemical Patents Inc.

University of California

Georgia Tech Research Corporation

Exxonmobile Research and Engineering Company

Exxonmobil Oil Corporation

Mobil Corporation

Simon Christopher Weston

Mobae Afeworki

Hilda B Vroman

Joseph M Falkowski

Karl Gottlieb Strohmaier

David Charles Calabro

Allen Wayne Burton

Ivy Dawn Johnson

Ross Mabon

Mary S Abdulkarim

Wieslaw J Roth

Jeffrey R Long

Quanchang Li

Paul Podsiadlo

Michael Charles Kerby

Thomas Yorke

Wenyih Frank Lai

David Lawrence Stern

Scott Jeffrey Weigel

Ramesh Gupta

Kirk D Schmitt

Hans Thomann

Sandeep Singh Dhingra

Carter W Abney

Michael A Marella

Phillip J Milner

Rebecca L Siegelman

David A Griffin

Lei Zhang

Yi Du

John Zengel

Hugo S Caram

Zheng Ni

Kiara M Benitez

Jean Willem Lodewijk Beeckman

Meghan Nines

Jeffrey D Martell

Stephen John McCarthy

Charles T Kresge

Narasimhan Sundaram

Franklin F Mittricker

Preeti Kamakoti

Matu J Shah

Matthew Scott Ide

Loren K Starcher

Mohan Kalyanaraman

Himanshu Gupta

Ryan Paul Lively

Douglas Lewis Dorset

Yogesh V Joshi

Fengyi Zhang

Yang Liu

Randall J Meyer

Matthew James Realff

William W Lonergan

Hannah E Holmes

Wenying Quan

Anna C Ivashko

James C Vartuli

Margaret M Wu

Arthur W Chester

Jose G Santiesteban

Terry Eugene Helton

William John Koros

Jane C Cheng

Shifang Luke Luo

Jean Willem Beeckman

David Stern

Xiaochun Xu

Bhupender S Minhas

Richard F Socha

Bal K Kaul

Tilman W Beutel

Frank C Wang

Arun K Sharma

Darryl Donald Lacy

J Thomas Ippoliti

Hye Kyung C Timken

Joseph E Gatt

James William Gleeson

Kanmi Mao

Aaron Sattler

Robert A Crane, Jr

Nadya A Hrycenko

Glenn R Sweeten

Michael Alan Steckel

Michele L Paccagnini

Theodore E Datz

Wesley Sattler

Machteld Maria Wilfried Mertens

Richard T Spissell

Matthew T Kapelewski

Bradley Wooler

Aaron W Peters

Manoj Kumar Chaudhury

Gerardo J Majano Sanchez

Keith C Gallow

Philip Trotto

Doug F Colmyer

Kristen Colwell

Ink compositions are provided for using solvent-based additive manufacturing (SBAM) techniques to form contactor structures and/or structures for use in an adsorption or absorption contactor. Methods forming a contactor using SBAM are also provided. The ink compositions can include a substantial content of adsorbent particles to provide enhanced adsorption by a contactor. Metal organic framework (MOF) structures and zeotype framework structures are examples of types of adsorbent particles that can be incorporated into an ink composition for forming a contactor structure by SBAM. The ink can further include a polymeric component that can serve as the structural component of a polymeric structural material produced by the additive manufacturing method. Such a structural material can correspond to a polymeric material with incorporated adsorbent particles. In some aspects, the polymeric structural material and/or the adsorbent particles can have selectivity for adsorption of COfrom a process fluid flow.

Additive manufacturing techniques and ink formulations for incorporating adsorbent particles

Provided herein are adsorption materials comprising a metal-organic framework comprising metal ions of metals, a plurality of organic linkers and one or more modulator where each modulator forms a localized defect. Each organic linker in the plurality of organic linkers creates a bridge between metal ions. Each modulator is connected to only one metal chain. The adsorption material further comprises one or more ligands. Each ligand in the plurality of ligands can be an amine or other Lewis base (electron donor) appended to a metal ion of the metal-organic framework.

Metal-organic frameworks having localized defects for gas separations

A method can include heating an aqueous reaction mixture comprising a silicon source and a boron source and/or an aluminum source in the presence of a quaternary structure directing agent to a temperature of at least 75° C. to produce a zeolite. A composition can include a borosilicate zeolite, an aluminosilicate zeolite, or an aluminoborosilicate zeolite having a framework symmetry of C2/m and a unit cell with measurements of a of 3.5 Å to 4.5 Å, b of 20.1 Å to 21.1 Å, c of 15.5 to 16.5 Å, and β of 97° to 98°.

Zeolite syntheses using diquaternary structure directing agents

Contactor structures are provided that can allow for improved heat management while reducing or minimizing the potential for contamination of process gas streams with heat transfer fluids. The contactor structures can include one or more sets of flow channels for process gas flows, such as gas flows introduced to allow adsorption of components from a gas stream or gas flows introduced to facilitate desorption of previously adsorbed components into a purge gas stream. The process gas flow channels can correspond to flow channels defined by a structural material of unitary structure. The unitary structure can correspond to the entire contactor, or the unitary structure can correspond to a monolith that forms a portion of the contactor. The contactor structures can also include one or more sets of flow channels for heat transfer fluids. The heat transfer flow channels can also be defined by the structural material of a unitary structure.

Advantaged adsorption contactors

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. Crystallization may be problematic in some instances when secondary binding sites are present in the multidentate organic ligand. Multidentate organic ligands comprising first and second binding sites bridged together with a third binding site comprising a diimine moiety may alleviate these issues, particularly when using a preformed metal cluster as a metal source to form a MOF. Such MOFs may comprise a plurality of metal centers, and a multidentate organic ligand coordinated to the plurality of metal centers to define an at least partially crystalline network structure having a plurality of internal pores, and in which the multidentate organic ligand comprises first and second binding sites bridged together with a third binding site comprising a diimine moiety. Particular MOFs may comprise N,N'-di(1H-pyrazol-4-yl)ethane-1,2-diimine as a multidentate organic ligand.

Metal-organic framework materials comprising a diimine scaffold and methods for production thereof

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. Some highly porous MOFs lack stability at ambient conditions. MOFs having ambient condition stability may comprise a plurality of metal clusters (MO clusters, M=a metal), and a plurality of 4-(1H-pyrazol-4-yl)benzoate ligands coordinated to the plurality of metal clusters to define an at least partially crystalline network structure having a plurality of internal pores. Methods for synthesizing these MOFs may comprise combining a metal source, such as a preformed metal cluster, with 4-(1H-pyrazol-4-yl)benzoic acid, and reacting the preformed metal cluster with the 4-(1H-pyrazol-4-yl)benzoic acid to form a MOF having an at least partially crystalline network structure with a plurality of internal pores defined therein and comprising a plurality of metal clusters coordinated to a multidentate organic ligand comprising 4-(1H-pyrazol-4-yl)benzoate.

Metal-organic framework materials comprising a pyrazolylbenzoate ligand and methods for production thereof

This disclosure relates to EMM-41 materials, methods for making it, and processes for its use. This disclosure also relates to the structure directing agents used in the methods for making the EMM-41 material as well as the synthesis method used to prepare such structure directing agents.

EMM-41 composition, methods of making and uses thereof

Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers. MOFs having ambient condition stability may comprise a plurality of metal clusters comprising one or more MO clusters (M is a metal), and a plurality of 4-pyrazolecarboxylate ligands coordinated to the plurality of metal clusters to define an at least partially crystalline network structure having a plurality of internal pores. The MOFs may have a Pa3 symmetry, which upon activation may convert into Fm3m symmetry. Methods for synthesizing the MOFs may comprise combining a metal source, such as a preformed metal cluster, with 4-pyrazolecarboxylic acid, and reacting the preformed metal cluster with the 4-pyrazolecarboxylic acid to form a MOF having an at least partially crystalline network structure with a plurality of internal pores defined therein and comprising a plurality of metal clusters coordinated to a multidentate organic ligand comprising 4-pyrazolecarboxylate.

Metal-organic framework materials comprising a pyrazolylcarboxylate ligand and methods for production thereof

A method can include heating an aqueous reaction mixture comprising a silicon source and a boron source and/or an aluminum source in the presence of a diquaternary structure directing agent to a temperature of at least 75° C. to produce a zeolite. A composition can include a borosilicate zeolite, an aluminosilicate zeolite, or an aluminoborosilicate zeolite having a framework symmetry of C2/m and a unit cell with measurements of a of 3.5 Å to 4.5 Å, b of 20.1 Å to 21.1 Å, c of 15.5 to 16.5 Å, and β of 97° to 98°.

Provided herein are methods of novel methods of synthesizing a metal-organic framework system by vapor-phase appending of a plurality of ligands appended to a metal-organic framework. Also, provided are methods of recycling metal-organic framework systems by detaching the ligand and re-appending the same ligand or appending a different ligand to the metal-organic framework to provide a recycled or repurposed metal-organic framework system.

Methods of synthesizing and recycling metal-organic framework systems

The present application relates to absorbents comprising tetraamine ligands grafted onto metal-organic frameworks and a method for using same for CO2 capture from fossil fuel combustion sources to reduce emissions. In particular, this application relates to capturing >90% by volume, preferable >99% by volume, CO2 emissions such that the emissions are negative, essentially removing CO2 from the combustion air.

Metal-organic frameworks for carbon dioxide capture

Primary, secondary (1&#xb0;,2&#xb0;) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for COcapture 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 Mg(dotpdc) (dotpdc=4,4&#x2033;-dioxido-[1,1':4&#x2032;,1&#x2033;-terphenyl]-3,3&#x2033;-dicarboxylate), yields diamine-appended adsorbents displaying a single COadsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg(pc-dobpdc) (pc-dobpdc=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single COadsorption step with bulky diamines. By relieving steric interactions between adjacent ammonium carbamate chains, these frameworks enable step-shaped COadsorption, decreased water co-adsorption, and increased stability to diamine loss. Variants of Mg(dotpdc) and Mg(pc-dobpdc) functionalized with large diamines such as N-(n-heptyl)ethylenediamine have utility as adsorbents for carbon capture applications.

Overcoming two carbon dioxide adsorption steps in diamine-appended metal organic frameworks

Disclosed are zeolitic imidazolate framework (ZIF) compositions in which at least a portion of the ligands in its shell have been exchanged with other ligands, and methods of making such shell-ligand-exchanged ZIFs. Also disclosed is the use of such shell-ligand-exchanged ZIFs in hydrocarbon separation processes.

Ligand-exchanged zeolite imidazolate frameworks

Systems and methods for concentration of a sorbate in a feedstream and subsequent adsorption utilizing a Type V adsorbent are provided.

Use of Type V adsorbent and gas concentration for gas adsorption and capture

Methods of synthesizing crystalline metal-organic frameworks (MOFs) comprising polytopic organic linkers and cations, where each linker is connected to two or more cations, are provided. In the disclosed methods, the linkers are reacted with a compound of formula MX, where M is cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf, X is anionic, n and m are integers. The reacting is buffered by a buffer devoid of metal coordinating functionality when the pKa of the anion is below a threshold related to the lowest pKa of the linker. The reacting is optionally not buffered when the pKa of the anion is at or above this threshold. The disclosed methods lead to product phase MOF in which crystal growth is controlled leading to control over molecular diffusion.

Metal-organic framework phase and crystallite shape control

Growing community of inventors

Annandale, NJ, United States of America

Simon Christopher Weston