US-12616930-B2 - Composite 3D-printed reactors for gas absorption, purification, and reaction

US12616930B2US 12616930 B2US12616930 B2US 12616930B2US-12616930-B2

Abstract

A composite material for gas capture including CO 2 capture and capture of other gases. The composite material includes solid or liquid reactive material, filler material, and a gas-permeable polymer coating such that the reactive material forms micron-scale domains in the filler material.

Inventors

Du T. Nguyen
Sarah E. Baker
William L. Bourcier
Joshua K. Stolaroff
Congwang Ye
Maxwell R. Murialdo
Maira R. Cerón Hernández
Jennifer M. Knipe

Assignees

LAWRENCE LIVERMORE NATIONAL SECURITY, LLC

Dates

Publication Date: 20260505
Application Date: 20220310

Claims (13)

1 . A reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases, comprising: an extruded composite able to be flowed through a print nozzle of an extrusion system onto a surface; said extruded composite comprising a monolithic block and being formed by: a filler; and units of sorbent material in said extruded composite with said filler; and a gas-permeable polymer coating layer formed around said extruded composite; a plurality of spaced apart gas flow channels arranged in a grid and extending fully throughout the monolithic block.
2 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 , wherein said units of sorbent material are units of carbon dioxide stripping material.
3 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said units of sorbent material are units of stripping material for stripping other gasses than carbon dioxide.
4 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said units of sorbent material are liquid units of carbon dioxide stripping material.
5 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said units of sorbent material are liquid droplets of carbon dioxide stripping material encapsulated in capsules.
6 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said units of sorbent material are solid units of carbon dioxide stripping material.
7 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said units of sorbent material are solid droplets of carbon dioxide stripping material encapsulated in capsules.
8 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said extruded composite forms filaments of said extruded composite with said filler in said filaments, with said units of sorbent material in said filaments with said filler; and with said gas-permeable polymer coating layer around said filaments and wherein said filaments form an entangled mass of filaments.
9 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said extruded composite forms filaments of said extruded composite with said filler in said filaments, with said units of sorbent material in said filaments with said filler; and with said gas-permeable polymer coating layer around said filaments and wherein said filaments form a layered mass of filaments.
10 . The reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases of claim 1 wherein said extruded composite forms filaments of said extruded composite with said filler in said filaments, with said units of sorbent material in said filaments with said filler; and with said gas-permeable polymer coating layer around said filaments and wherein said filaments form a woven mass of filaments.
11 . The reactor of claim 1 , wherein the monolithic structure further comprises a plurality of cooling tubes extending throughout the monolithic structure.
12 . A reactor product that removes a single gas or multiple gases from a gas stream containing the single gas or the multiple gases, comprising: units of sorbent material; a gas-permeable polymer; said units of sorbent material and said gas-permeable polymer forming a composite material; and wherein composite material that is a mixture of said units of sorbent material and said gas-permeable polymer is in the form of a web with openings.
13 . A reactor for removing a single gas or multiple gases from a gas stream containing the single gas or the multiple gases, comprising: an extruded composite; a filler in said extruded composite; units of sorbent material in said extruded composite with said filler; a gas-permeable polymer coating layer around said extruded composite; and wherein said extruded composite forms filaments of said extruded composite with said filler in said filaments, with said units of sorbent material in said filaments with said filler; and with said gas-permeable polymer coating layer around said filaments and wherein said filaments form a layered mass of filaments.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This present application is a Division of application Ser. No. 16/384,520 filed Apr. 15, 2019, which is a continuation-in-part of U.S. patent application Ser. No. 15/468,297 filed Mar. 24, 2017 titled composite 3D-printed reactors for gas absorption, purification, and reaction which is incorporated by reference herein. STATEMENT AS TO RIGHTS TO APPLICATIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT This invention was made with Government support under Contract No. DE-AC52-07NA27344 awarded by the United States Department of Energy. The Government has certain rights in the invention. BACKGROUND Field of Endeavor The present application relates to reactors for gas absorption, purification, and/or reaction and more particularly to composite 3-D printed reactors for gas absorption, purification, and/or reaction. State of Technology This section provides background information related to the present disclosure which is not necessarily prior art. The exchange of gas into or out of a liquid is a common problem in the absorption of gases into a solvent for industrial chemical processes, gas purification, and water purification. The potentially largest scale application is for the absorption of CO2 for carbon capture and storage from power plants. Other applications include purification of natural gas, purification of biogas, and various industrial gas-to-liquid reactions. The most common method for gas absorption is the use of a “packed tower” absorption column. The absorption column is typically a cylindrical reactor filled with a packing material. Liquid solvent is pumped to the top of the tower and allowed to flow down over the packing while gas is blown from the bottom of the tower in the opposite direction. The liquid solvent forms a film over the wetted parts of the packing material, resulting in a gas-liquid interface where the exchange between CO2 and solvent takes place. A major limitation of these tower packings is that the surface-area to volume ratio of the liquid is limited by the thickness of the liquid film. This thickness is determined by the properties of the solvent, but is typically around 1 mm. Additional area can be put into the tower using finer packings, but this leads to higher holdup of liquid, and impeded gas flow. Solid sorbents are an alternative to liquid solvents in many applications, including large-scale CO2 capture. Solid sorbents are preferred for air purification for, e.g. small submarines and personal underwater rebreathers and removal of volatile organic compounds emitted from certain industrial processes. Solid sorbents include mineral CO2 sorbents like soda-lime, designer gas sorbents like metal-organic frameworks (MOFs), zeolites, and activated carbons. Solid sorbents are typically prepared in a powder, and must be pelletized or formed into monoliths with a binder, reducing accessible surface area and yielding sub-optimal gas flow. SUMMARY Features and advantages of the disclosed apparatus, systems, and methods will become apparent from the following description. Applicant is providing this description, which includes drawings and examples of specific embodiments, to give a broad representation of the apparatus, systems, and methods. Various changes and modifications within the spirit and scope of the application will become apparent to those skilled in the art from this description and by practice of the apparatus, systems, and methods. The scope of the apparatus, systems, and methods is not intended to be limited to the particular forms disclosed and the application covers all modifications, equivalents, and alternatives falling within the spirit and scope of the apparatus, systems, and methods as defined by the claims. The inventor's apparatus, systems, and methods provide a composite material for gas capture, notably CO2 capture and storage. The composite material includes a mixture of a solid or liquid reactive filler and a gas-permeable polymer (e.g. silicone), such that the reactive filler forms micron-scale domains in the polymer matrix. In contrast to typical absorption schemes based on liquid solvents or solid sorbent powders, the composite materials can be fabricated into arbitrary fixed shapes via additive or conventional manufacturing. The gas-permeable polymer matrix acts as a gas-permeable support while the reactive filler acts as a gas sorbent or catalyst for chemical reactions. Control over the material shape allows for the patterning of high surface-area-to-volume ratio structures for fast reactivity while minimizing pressure drops typically associated with high surface area materials and packings. The inventor's apparatus, systems, and methods can be used for the absorption of gases or catalyzing chemical reactions involving a gas. This use can be tailored for specific applications such as CO2 capture from power plants, CO2 utilization, natural gas purification, biogas purification, and underwater rebrea