U.S. patent application number 16/780475 was filed with the patent office on 2020-06-18 for methods and systems for fuel production.
The applicant listed for this patent is Prometheus Fuels, Inc. Invention is credited to Robert McGinnis.
Application Number | 20200190675 16/780475 |
Document ID | / |
Family ID | 69778951 |
Filed Date | 2020-06-18 |
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United States Patent
Application |
20200190675 |
Kind Code |
A1 |
McGinnis; Robert |
June 18, 2020 |
METHODS AND SYSTEMS FOR FUEL PRODUCTION
Abstract
The present disclosure provides systems and methods for
producing carbon products via electrochemical reduction from fluid
streams containing a carbon-containing material, such as, for
example, carbon dioxide. Electrochemical reduction systems and
methods of the present disclosure may comprise micro- or
nanostructured membranes for separation and catalytic processes.
The electrochemical reduction systems and methods may utilize
renewable energy sources to generate a carbon product comprising
one or more carbon atoms (C1+ product), such as, for example, fuel.
This may be performed at substantially low (or nearly zero) net or
negative carbon emissions.
Inventors: |
McGinnis; Robert; (Santa
Cruz, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Prometheus Fuels, Inc |
Santa Cruz |
CA |
US |
|
|
Family ID: |
69778951 |
Appl. No.: |
16/780475 |
Filed: |
February 3, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16503165 |
Jul 3, 2019 |
10590548 |
|
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16780475 |
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62781149 |
Dec 18, 2018 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25B 9/08 20130101; C25B
15/08 20130101; C25B 3/04 20130101 |
International
Class: |
C25B 3/04 20060101
C25B003/04 |
Claims
1. A system for generating a carbon product comprising one or more
carbon atoms (C1+ product), comprising: a first compartment; a
second compartment; and a separation unit separating said first
compartment and said second compartment, wherein said separation
unit comprises (i) an anode, (ii) a cathode, and (iii) a membrane
comprising a plurality of pores, wherein said plurality of pores
are configured to bring said first compartment in fluid
communication with said second compartment, wherein said cathode
and said anode are configured to reduce said carbon-containing
material to said C1+ product in said first compartment while a
voltage is applied between said cathode and said anode, and wherein
said plurality of pores are configured to direct said C1+ product
from said first compartment to said second compartment.
2. The system of claim 1, further comprising a gas contactor in
fluid communication with said first compartment, wherein said gas
contactor is configured to bring said carbon-containing material in
contact with water to yield a solution comprising said
carbon-containing material.
3. The system of claim 1, wherein said membrane comprises one or
more materials selected from the group consisting of carbon
nanotubes, carbon nanospheres, carbon nano-onions, graphene, and
porous pyrolyzed carbon.
4. The system of claim 1, wherein said cathode further comprises a
catalyst.
5. The system of claim 4, wherein said catalyst comprises a metal
nanoparticle.
6. The system of claim 5, wherein said metal nanoparticle comprise
a metal selected from the group consisting of copper, nickel,
platinum, iridium, ruthenium, palladium, tin, silver, and gold.
7. The system of claim 4, wherein said catalyst is N-doped.
8. The system of claim 1, further comprising a voltage source
configured to supply said voltage.
9. The system of claim 8, wherein said voltage source comprises a
renewable power source.
10. The system of claim 8, wherein said voltage source comprises
one or more members selected from the group consisting of a
photovoltaic power source, a wind power source, a geothermal power
source, a hydroelectric power source, a tidal power source, and
nuclear power.
11. The system of claim 1, further comprising an ion exchange
membrane between said cathode and said anode.
12. The system of claim 1, wherein said system is configured to
have a single pass selectivity for said C1+ product of at least
about 70%.
13. The system of claim 1, wherein a pore of said plurality of
pores has a pore size of less than or equal to about 5
micrometers.
14. The system of claim 13, wherein said pore size is less than or
equal to about 100 nanometers.
15. The system of claim 14, wherein said pore size is less than or
equal to about 10 nanometers.
16. The system of claim 1, wherein said C1+ product comprises one
or more members selected from the group consisting of methanol,
ethanol, propanol, and butanol.
17. The system of claim 1, wherein said first compartment comprises
said cathode and said second compartment comprises said anode.
18. The system of claim 1, wherein said first compartment comprises
said cathode and said membrane.
19. The system of claim 1, wherein said separation unit further
comprises an extractor.
20. The system of claim 19, wherein said extractor comprises said
second compartment and said second compartment said membrane.
Description
CROSS-REFERENCE
[0001] This application is a Continuation Application of U.S.
application Ser. No. 16/503,165, filed Jul. 3, 2019, which claims
the benefit of U.S. Provisional Patent Application No. 62/781,149,
filed Dec. 18, 2018, which is entirely incorporated herein by
reference for all purposes.
BACKGROUND
[0002] There is an increasing level of carbon-containing compounds,
such as carbon monoxide (CO) and carbon dioxide (CO.sub.2), in the
atmosphere. Such increase in level of carbon-containing compounds
may be adversely impacting the global temperature, leading to
global warming.
SUMMARY
[0003] Recognized herein is an increased need for efficient methods
of producing fuels and other chemical commodities from
non-petroleum sources. Such processes may utilize carbon monoxide
(CO) and/or carbon dioxide (CO.sub.2) as a carbon-source for the
production of organic molecules to minimize the carbon footprint of
the production and consumption of the produced fuels and chemicals.
The production of durable chemical products (e.g., polymers) may
even create net carbon sinks for products produced using
atmospheric carbon monoxide and/or carbon dioxide.
[0004] In an aspect, provided herein is a system for generating a
carbon product comprising one or more carbon atoms (C1+ product),
comprising a first compartment, a second compartment, and a
separation unit separating said first compartment and said second
compartment, wherein said separation unit comprises (i) an anode,
(ii) a cathode, and (iii) a membrane comprising a plurality of
pores, wherein said plurality of pores are configured to bring said
first compartment in fluid communication with said second
compartment, wherein said cathode and said anode are configured to
reduce said carbon-containing material to said C1+ product in said
first compartment while a voltage is applied between said cathode
and said anode, and wherein said plurality of pores are configured
to direct said C1+ product from said first compartment to said
second compartment.
[0005] In some embodiments, the system further comprises a gas
contactor in fluid communication with said first compartment,
wherein said gas contactor is configured to bring said
carbon-containing material in contact with water to yield a
solution comprising said carbon-containing material. In some
embodiments, the membrane comprises one or more materials selected
from the group consisting of carbon nanotubes, carbon nanospheres,
carbon nano-onions, graphene, and porous pyrolyzed carbon.
[0006] In some embodiments, the cathode further comprises a
catalyst. In some embodiments, the catalyst comprises a metal
nanoparticle. In some embodiments, the metal nanoparticle comprise
a metal selected from the group consisting of copper, nickel,
platinum, iridium, ruthenium, palladium, tin, silver, and gold. In
some embodiments, the catalyst is N-doped.
[0007] In some embodiments, the system further comprises a voltage
source configured to supply said voltage. In some embodiments, the
voltage source comprises a renewable power source. In some
embodiments, the voltage source comprises one or more members
selected from the group consisting of a photovoltaic power source,
a wind power source, a geothermal power source, a hydroelectric
power source, a tidal power source, and nuclear power.
[0008] In some embodiments, the system further comprises an ion
exchange membrane between said cathode and said anode.
[0009] In some embodiments, the system is configured to have a
single pass selectivity for said C1+ product of at least about 70%.
In some embodiments, a pore of said plurality of pores has a pore
size of less than or equal to about 5 micrometers. In some
embodiments, the pore size is less than or equal to about 100
nanometers. In some embodiments, the pore size is less than or
equal to about 10 nanometers.
[0010] In some embodiments, the C1+ product comprises one or more
members selected from the group consisting of methanol, ethanol,
propanol, and butanol.
[0011] In some embodiments, the first compartment comprises said
cathode and said second compartment comprises said anode. In some
embodiments, the first compartment comprises said cathode and said
membrane. In some embodiments, the separation unit further
comprises an extractor. In some embodiments, the extractor
comprises said second compartment and said second compartment said
membrane.
[0012] In another an aspect, provided is a method for using a
carbon-containing material to generate a carbon product comprising
one or more carbon atoms (C1+ product), comprising: (a) directing
an electrolyte solution comprising the carbon-containing material
into an electrochemical system comprising (i) an anode, (ii) a
cathode, and (iii) a micro- or nanostructured membrane, to bring
the electrolyte solution in contact with the cathode, wherein the
anode and/or cathode are associated with a catalyst(s), and wherein
the anode and the cathode are in electrical communication with one
another through the electrolyte; (b) reducing the carbon-containing
material in the electrolyte solution, using the cathode, to
generate the C1+ product; and (c) recovering the C1+ product from
the electrochemical system using the micro- or nanostructured
membrane.
[0013] In some embodiments, the carbon-containing material
comprises carbon monoxide (CO) and/or carbon dioxide
(CO.sub.2).
[0014] In some embodiments, the cathode comprises the
catalyst(s).
[0015] In some embodiments, the anode comprises the
catalyst(s).
[0016] In some embodiments, the electrolyte solution comprises an
aqueous species resulting from an interaction of the
carbon-containing material with water. In some embodiments, the
aqueous species comprises one or more members selected from the
group consisting of bicarbonate ions, carbonate ions, and formate
ions.
[0017] In some embodiments, the method further comprises, prior to
(b), introducing the carbon-containing material to water using a
gas contactor. In some embodiments, the gas contactor comprises a
membrane. In some embodiments, the membrane comprises one or more
nanomaterials selected from the group consisting of carbon
nanotubes, carbon nanospheres, carbon nano-onions, graphene, and
porous pyrolyzed carbon.
[0018] In some embodiments, the micro- or nanostructured membrane
comprises one or more materials selected from the group consisting
of carbon nanotubes, carbon nanospheres, carbon nano-onions,
graphene, and porous pyrolyzed carbon.
[0019] In some embodiments, the micro- or nanostructured membrane
further comprises a catalyst. In some embodiments, the catalyst
comprises metal nanoparticles. In some embodiments, the metal
nanoparticles comprise a metal selected from the group consisting
of copper, nickel, platinum, iridium, ruthenium, palladium, tin,
silver, and gold.
[0020] In some embodiments, the catalyst(s) is N-doped.
[0021] In some embodiments, the anode and the cathode are in
electrical communication with a voltage source, wherein the voltage
source comprises a renewable power source. In some embodiments, the
renewable power source comprises one or members selected from the
group consisting of photovoltaic power, wind power, geothermal
power, hydroelectric power, tidal power, and nuclear power.
[0022] In some embodiments, the method further comprises
introducing the carbon-containing material to the electrochemical
system by using hydroxides generated electrochemically.
[0023] In some embodiments, the cathode operates at a temperature
of about 10.degree. Celsius (C) to 40.degree. C.
[0024] In some embodiments, the C1+ product is recovered from the
electrochemical reduction system in absence of a distillation
unit.
[0025] In some embodiments, the electrochemical system further
comprises an ion exchange membrane configured to minimize a
distance between the cathode and the anode.
[0026] In some embodiments, the C1+ product is recovered from the
electrochemical reduction system at a single pass selectivity of at
least about 70%.
[0027] In some embodiments, the cathode comprises pores with pore
sizes of no more than about 5 microns.
[0028] In some embodiments, the C1+ product comprises one or more
members selected from the group consisting of methanol, ethanol,
propanol, and butanol.
[0029] Another aspect of the present disclosure provides a method
for using a carbon-containing material to generate a reduced carbon
product comprising one or more carbon atoms (C1+ product),
comprising: (a) directing an electrolyte solution comprising the
carbon-containing material into an electrochemical system
comprising an anode and a cathode comprising or being associated
with catalysts; (b) using the cathode to reduce the carbon
containing material to the C1+product in the electrolyte solution,
and (c) recovering the C1+ product from the electrochemical
reduction system with the aid of a micro- or nanostructured
membrane.
[0030] In some embodiments, the carbon-containing material
comprises CO and/or CO.sub.2. In some embodiments, the electrolyte
solution comprises aqueous species resulting from the interaction
of the carbon containing materials with water, including
bicarbonate, carbonate ions, and/or formate. In some embodiments,
the CO.sub.2 is from air. In some embodiments, the CO and/or
CO.sub.2 is from an effluent gas.
[0031] In some embodiments, the C1+ product comprises at least 50%
compounds in a molecular weight range from about C1 to about
C4.
[0032] In some embodiments, the membrane comprises one or more
materials selected from the group consisting of carbon nanotubes,
carbon nanospheres, carbon nano-onions, graphene, and a porous
pyrolyzed carbon.
[0033] In some embodiments, the catalyst comprises metal
nanoparticles. In some embodiments, the catalyst comprises one or
more materials that are N-doped. In some embodiments, the catalyst
is comprised of and/or associated with a micro- or nanostructured
membrane.
[0034] In some embodiments, the method further comprises separating
CO or CO.sub.2 from a gas stream using a membrane separator. In
some embodiments, the membrane separator comprises a micro- or
nanostructured membrane. In some embodiments, the membrane
separator comprises carbon nanotubes, carbon nanospheres, carbon
nano-onions, or a porous pyrolyzed carbon.
[0035] In some embodiments, the recovering the C1+ product
comprises separating the C1+ product using the membrane.
[0036] In some embodiments, the using of the cathode occurs at a
temperature of about 10.degree. C. to 40.degree. C.
[0037] In some embodiments, the cathode and the anode are in
electrical communication with a renewable power source. In some
embodiments, the renewable power source is selected from the group
consisting of a photovoltaic unit, wind turbine, geothermal unit,
hydroelectric unit, tidal power, nuclear power, and a combination
thereof.
[0038] In some embodiments, the introduction of carbon containing
materials to the system is facilitated by use of hydroxides
generated in the system.
[0039] Another aspect of the present disclosure provides an
electrochemical reduction system, comprising a housing comprising
(i) a cathode, and (ii) an anode, wherein the comprise or are
associated with catalysts, and wherein the housing is configured to
contain an electrolyte comprising a carbon-containing material in
contact with the cathode, and a voltage source configured to be in
electrical communication with the cathode and the anode, wherein
the electrochemical reduction system is configured to reduce the
carbon-containing material to a reduced carbon products comprising
one or more carbon atoms (C1+ product), wherein the reduced carbon
products are removed from the electrochemical reduction system with
the aid of a micro- or nanostructured membrane.
[0040] In some embodiments, the system further comprises a gas
contactor configured to introduce the carbon-containing material to
water. In some embodiments, the gas contactor comprises a membrane.
In some embodiments, the membrane comprises one or more
nanomaterials selected from the group consisting of carbon
nanotubes, carbon nanospheres, carbon nano-onions, and a porous
pyrolyzed carbon.
[0041] In some embodiments, the membrane comprises one or more
materials selected from the group consisting of carbon nanotubes,
carbon nanospheres, carbon nano-onions, and a porous pyrolyzed
carbon. In some embodiments, the one or more materials further
comprises a catalyst. In some embodiments, the catalyst comprises
metal nanoparticles. In some embodiments, the metal nanoparticles
comprise a metal selected from the group consisting of copper,
nickel, platinum, iridium, ruthenium, palladium, tin, silver, and
gold. In some embodiments, the one or more catalyst materials is
N-doped.
[0042] In some embodiments, the voltage source comprises a
renewable power source. In some embodiments, the renewable power
source is selected from the group consisting of photovoltaic, wind,
geothermal, hydroelectric, tidal power, nuclear power, and a
combination thereof.
[0043] In some embodiments, the introduction of carbon containing
materials to the system is facilitated by use of hydroxides
generated in the electrochemical process.
[0044] In some embodiments, the cathode is configured to operate at
a temperature of about 10.degree. C. to 40.degree. C.
[0045] In some embodiments, the electrochemical reduction system
comprises no distillation unit for the separation of reduced carbon
products.
[0046] Another aspect of the disclosure provides an electrochemical
reduction system, comprising a housing comprising (i) a cathode,
wherein the cathode comprises a membrane comprising pores and a
catalyst, and (ii) an anode, wherein the housing is configured to
contain an electrolyte comprising a carbon-containing material in
contact with the cathode, which electrolyte brings the cathode in
electrical communication with the anode, and a voltage source
configured to be in electrical communication with the cathode and
the anode, wherein the electrochemical reduction system is
configured to reduce the carbon-containing material to a reduced
carbon product comprising one or more carbon atoms (C1+
product).
[0047] In some embodiments, the carbon-containing materials are
introduced to the catalyst through the micro- or nanostructured
membrane. In some embodiments, the reduced carbon products are
removed through the micro- or nanostructured membrane as they are
produced at its surface. In some embodiments, the membrane
comprises one or more nanomaterials selected from the group
consisting of carbon nanotubes, carbon nanospheres, carbon
nano-onions, graphene, and porous pyrolyzed carbon.
[0048] In some embodiments, the catalyst comprises metal
nanoparticles. In some embodiments, the metal nanoparticles
comprise a metal selected from the group consisting of copper,
platinum, iridium, ruthenium, palladium, tin, silver and gold.
[0049] In some embodiments, the cathode comprises a membrane having
pores with sizes of less than or equal to about 5 micrometers. In
some embodiments, the material is N-doped.
[0050] In some embodiments, the voltage source comprises a
renewable power source. In some embodiments, the renewable power
source is selected from the group consisting of a photovoltaic
unit, wind turbine, geothermal unit, hydroelectric unit, tidal
power unit, nuclear power unit, and a combination thereof.
[0051] In some embodiments, the introduction of carbon containing
materials to the system is facilitated by use of hydroxides
generated by the reduction of the carbon-containing materials.
[0052] In some embodiments, the cathode operates at a temperature
of about 10.degree. C. to 40.degree. C.
[0053] In some embodiments, the electrochemical reduction system
comprises no distillation unit for the separation of reduced carbon
products.
[0054] Another aspect of the disclosure provide a method for using
a carbon-containing material to generate a reduced carbon product
comprising one or more carbon atoms (C1+ product), comprising (a)
directing an electrolyte solution comprising the carbon-containing
material into an electrochemical system comprising a housing
comprising (i) a cathode, wherein the cathode comprises a membrane
comprising pores and a catalyst, and (ii) an anode, wherein the
housing contains an electrolyte comprising the carbon-containing
material in contact with the cathode, which electrolyte brings the
cathode in electrical communication with the anode (b) at the
cathode, reducing carbon containing materials to the C1+product in
the electrolyte solution with aid of the catalyst, and (c)
recovering the C1+ product from the electrochemical reduction
system, wherein the C1+ product is removed through a micro- or
nanostructured membrane
[0055] In some embodiments, the carbon-containing material
comprises CO and/or CO.sub.2. In some embodiments, the aqueous
solution comprises species resulting from the interaction of CO or
CO.sub.2 with water, such as bicarbonate, carbonate, or formate
ions.
[0056] In some embodiments, the CO.sub.2 is from air. In some
instances, the CO and/or CO.sub.2 is from an effluent gas.
[0057] In some embodiments, the C1+ product comprises at least 50%
compounds in a molecular weight range from about C1 to about
C4.
[0058] In some embodiments, the membrane comprises one or more
materials selected from the group consisting of carbon nanotubes,
carbon nanospheres, carbon nano-onions, graphene, and porous
pyrolyzed carbon. In some instances, the one or more materials are
N-doped.
[0059] In some embodiments, the carbon-containing materials are
introduced to the catalyst through the micro- or nanostructured
membrane.
[0060] In some embodiments, the reduced carbon products are removed
through the micro-or nanostructured membrane as they are produced
at its surface. In some embodiments, the membrane comprises carbon
nanotubes, carbon nanospheres, carbon nano-onions, graphene, or
porous pyrolyzed carbon.
[0061] In some embodiments, the recovering the C1+ product
comprises separating the C1+ product using the membrane.
[0062] In some embodiments, the using of the cathode occurs at a
temperature of about 10.degree. C. to 40.degree. C.
[0063] In some embodiments, I the cathode and the anode are in
electrical communication with a renewable power source. In some
embodiments, the renewable power source is selected from the group
consisting of a photovoltaic unit, wind turbine, geothermal unit,
hydroelectric unit, tidal power unit, nuclear power unit, and a
combination thereof.
[0064] In some embodiments, the introduction of carbon containing
materials to the system is facilitated by use of hydroxides
generated in the system.
[0065] Another aspect of the present disclosure provides a
non-transitory computer readable medium comprising machine
executable code that, upon execution by one or more computer
processors, implements any of the methods above or elsewhere
herein.
[0066] Another aspect of the present disclosure provides a system
comprising one or more computer processors and computer memory
coupled thereto. The computer memory comprises machine executable
code that, upon execution by the one or more computer processors,
implements any of the methods above or elsewhere herein.
[0067] Additional aspects and advantages of the present disclosure
will become readily apparent to those skilled in this art from the
following detailed description, wherein only illustrative
embodiments of the present disclosure are shown and described. As
will be realized, the present disclosure is capable of other and
different embodiments, and its several details are capable of
modifications in various obvious respects, all without departing
from the disclosure. Accordingly, the drawings and description are
to be regarded as illustrative in nature, and not as
restrictive.
INCORPORATION BY REFERENCE
[0068] All publications and patent applications mentioned in this
specification are herein incorporated by reference to the same
extent as if each individual publication or patent application was
specifically and individually indicated to be incorporated by
reference.
BRIEF DESCRIPTION OF THE DRAWINGS
[0069] The novel features of the invention are set forth with
particularity in the appended claims. A better understanding of the
features and advantages of the present invention will be obtained
by reference to the following detailed description that sets forth
illustrative embodiments, in which the principles of the invention
are utilized, and the accompanying drawings (also "figure" and
"FIG." herein), of which:
[0070] FIG. 1A depicts a cross-sectional and face-oriented
schematic view of a micro- or nanostructured membrane material
comprising nanotubes. Arrows depict pore space that may permit the
selective passage of particular chemical species.
[0071] FIG. 1B depicts a cross-sectional and face-oriented
schematic view of a micro- or nanostructured membrane material
comprising nano-onions. Arrows depict pore space that may permit
the selective passage of particular chemical species.
[0072] FIG. 1C depicts a cross-sectional and face-oriented
schematic view of a micro- or nanostructured membrane material
comprising a pyrolyzed porous material. Arrows depict pore space
that may permit the selective passage of particular chemical
species.
[0073] FIG. 1D depicts a cross-sectional and face-oriented
schematic view of a micro- or nanostructured membrane material
comprising a graphene-like material. Arrows depict pore space that
may permit the selective passage of particular chemical
species.
[0074] FIG. 2 depicts an illustration of a carbon nanotube embedded
in a membrane material.
[0075] FIG. 3A depicts a micro- or nanostructured membrane
configured in a cylindrical fashion (such as a hollow fiber).
[0076] FIG. 3B shows a detailed illustration of a small region of
the membrane surface that comprises carbon nanotubes.
[0077] FIG. 4 illustrates a representative graphene-like material
of the present invention.
[0078] FIG. 5 shows an illustration of a catalyst nanoparticle
associated with a carbon nanotube as provided in the present
disclosure.
[0079] FIG. 6 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0080] FIG. 7 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0081] FIG. 8 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0082] FIG. 9 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0083] FIG. 10 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0084] FIG. 11 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0085] FIG. 12 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0086] FIG. 13 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0087] FIG. 14 depicts a schematic of another embodiment of an
electrochemical reduction system for the conversion of CO or
CO.sub.2 to hydrocarbons.
[0088] FIG. 15 illustrates a schematic of a computer system as
utilized for the present invention.
DETAILED DESCRIPTION
[0089] While various embodiments of the invention have been shown
and described herein, it will be obvious to those skilled in the
art that such embodiments are provided by way of example only.
Numerous variations, changes, and substitutions may occur to those
skilled in the art without departing from the invention. It should
be understood that various alternatives to the embodiments of the
invention described herein may be employed.
[0090] Whenever the term "at least," "greater than," or "greater
than or equal to" precedes the first numerical value in a series of
two or more numerical values, the term "at least," "greater than"
or "greater than or equal to" applies to each of the numerical
values in that series of numerical values. For example, greater
than or equal to 1, 2, or 3 is equivalent to greater than or equal
to 1, greater than or equal to 2, or greater than or equal to 3.
Whenever the term "no more than," "less than," or "less than or
equal to" precedes the first numerical value in a series of two or
more numerical values, the term "no more than," "less than," or
"less than or equal to" applies to each of the numerical values in
that series of numerical values. For example, less than or equal to
3, 2, or 1 is equivalent to less than or equal to 3, less than or
equal to 2, or less than or equal to 1.
[0091] The terms "C1+" and "C1+ compound," as used herein,
generally refer to a compound comprising one or more carbon atoms,
e.g., one carbon atom (C1), two carbon atoms (C2), etc. C1+
compounds include, without limitation, alkanes (e.g., methane,
CH.sub.4), alkenes (e.g., ethylene, C.sub.2H.sub.2), alkynes and
aromatics containing two or more carbon atoms. In some cases, C1+
compounds include aldehydes, ketones, esters and carboxylic acids.
Examples of C1+ compounds include, without limitation, methane,
ethane, ethylene, acetylene, propane, propene, butane, butylene,
etc.
[0092] The term "unit," as used herein, generally refers to a unit
operation, which is a basic operation in a process. Unit operations
may involve a physical change or chemical transformation, such as,
for example, separation, crystallization, evaporation, filtration,
polymerization, isomerization, transformation, and other reactions.
A given process may require one or a plurality of unit operations
to obtain the desired product(s) from a starting material(s), or
feedstock(s).
[0093] The term "carbon-containing material," as used herein,
generally refers to any material comprising at least one carbon
atom. In some example, a carbon-containing material is carbon
monoxide (CO), carbon dioxide (CO.sub.2), or a mixture of CO and
CO.sub.2. The carbon-containing material may be a material derived
from CO and/or CO.sub.2, such as bicarbonate or bicarbonate
ions.
[0094] Provided herein are systems and methods for producing
various chemical products, including hydrocarbon fuels, from a
source comprising a carbon-containing material, such as carbon
monoxide (CO) and/or carbon dioxide (CO.sub.2). The source may be a
gas source or a liquid source. In some instances, the gas source
comprising CO or CO.sub.2 may be air drawn directly from the
atmosphere. In other instances, the gas source comprising CO or
CO.sub.2 may be an effluent gas such as flue gas from a combustion
process. In the present invention, a gas stream comprising CO or
CO.sub.2 may be drawn into an electrochemical reduction system that
converts CO or CO.sub.2 into hydrocarbons. The described systems
may include one or more additional chemical conversion processes
that allow the conversion of the CO- or CO.sub.2-derived
hydrocarbons into other valuable chemical products.
[0095] Also provided herein are various configurations for an
electrochemical reduction system that converts CO or CO.sub.2 into
hydrocarbons. In some instances, the electrochemical reduction
system may operate at an ambient temperature. The electrochemical
reduction system may comprise one or more membranes that comprise a
micro- or nanostructured material such as carbon nanotubes (CNTs)
or graphene. In some instances, the micro- or nanostructured
membranes may be capable of selectively separating CO or CO.sub.2
from a mixed gas stream. In other instances, the micro- or
nanostructured membranes may be capable of selectively separating
certain hydrocarbons from a liquid or gaseous medium. Also provided
herein are micro- or nanostructured membranes that comprise
catalysts for the conversion of CO or CO.sub.2 into hydrocarbons.
In some instances, the micro- or nanostructured membrane may be
configured to comprise an anode or cathode in an electrochemical
reduction system.
[0096] Provided herein are various products that may be produced by
the systems and methods described herein. The electrochemical
reduction systems may produce alkanes, alkenes, alcohols, or other
organic molecules of varying chain lengths. The products of the
described electrochemical reduction systems may be further
processed into other fuel and chemical products, such as polymers.
The selectivity of the micro- or nanostructured membranes utilized
in the electrochemical reduction systems may allow chemical
products to be produced with tailored molecular weight ranges and
increased purity from processing byproducts (e.g. metals, salts and
other undesired inputs or products).
[0097] Also provided herein are systems of varying scale for
producing chemicals from a gas stream comprising CO or CO.sub.2. In
some instances, chemicals may be produced from a chemical plant
that comprises one or more CO or CO.sub.2 electrochemical reduction
systems. In other instances, chemicals may be produced from CO or
CO.sub.2 as a subsystem of a larger facility, for example as a
scrubber on a power-generation facility. In other instances,
chemicals may be produced using small-scale or even micro-scale
devices. In some instances, an electrochemical reduction system
utilizing a gas source comprising CO or CO.sub.2 may be coupled
with a renewable electrical generation sources (e.g. photovoltaics)
to create a fully sustainable method of chemical production. In
some instances, the system and methods described herein may be net
carbon negative (i.e. they sequester more carbon than they
produce). In some instances, the systems described herein may
decrease the energy input of a chemical production process by at
least about 50%.
Chemical Products
[0098] Described herein are various chemical products and reaction
mixtures generated via the electrochemical reduction of CO or
CO.sub.2 derived from a gas source. Chemical products may include
any process streams that is exported from a chemical processing
system or any process stream that undergoes no further reactive
processes. A reaction mixture may include any process mixture,
reagent, or compound within the confines of a chemical reactor,
reactor system, or in a process stream between chemical reactors or
reactor systems. The chemical products and reaction mixtures of the
present invention may include organic molecules where one or more
of the constituent carbon atoms are derived from CO or CO.sub.2. In
some instances a chemical product or reaction mixture may contain
only carbon atoms derived from CO or CO.sub.2. In other instances,
a chemical product may contain carbon atoms derived from CO or
CO.sub.2 and carbon atoms derived from other sources (e.g. fossil
fuels). In some instances, chemical products of the present
invention may have a distinct carbon isotope signature that is
consistent with the carbon isotope signature of CO or CO.sub.2
derived from the atmosphere. In some instances, chemical products
and reaction mixtures of the present invention may have a distinct
carbon isotope signature that is consistent with the carbon isotope
signature of CO or CO.sub.2 derived from a non-atmospheric source
such as the combustion of fossil fuels. The carbon isotope
signature of a chemical product or reaction mixture may be measured
by an isotopic ratio of .sup.14C:.sup.12C or .sup.13C:.sup.12C. In
some instances the isotopic signature of a chemical product or
reaction mixture may be measured as a percent difference between
the natural isotopic ratio of carbon and the measured isotopic
ratio. A percent difference between the natural isotopic ratio of
carbon and the measured isotopic ratio for .sup.14C,
.DELTA..sup.14C, may be calculated as:
.DELTA. 14 C = [ [ 14 C 12 C ] measured [ 14 C 12 C ] standard - 1
] .times. 1000 % ##EQU00001##
[0099] A percent difference between the natural isotopic ratio of
carbon and the measured isotopic ratio for .sup.13C,
.DELTA..sup.13C, may be calculated as:
.DELTA. 13 C = [ [ 13 C 12 C ] measured [ 13 C 12 C ] standard - 1
] .times. 1000 % ##EQU00002##
[0100] A chemical product or reaction mixture may have a
.DELTA..sup.14C of about -100%, -10%, 0%, 5%, 10%, 20%, 30%, 40%,
45%, 50% or about 100%. A chemical product or reaction mixture may
have a .DELTA..sup.13C of about -40%, -35%, -30%, -28%, -26%, -24%,
-22%, -20%, -15%, -10%, -8%, or about -5%.
[0101] A chemical product or reaction mixture of the present
invention may include gaseous, liquid, or solid substances.
Chemical products and reaction mixtures of the current invention
may include one or more organic compounds. Chemical products and
reaction mixtures may be miscible or immiscible in water. Chemical
products and reaction mixtures may be polar or nonpolar. Chemical
products and reaction mixtures may be acidic, basic, or neutral.
Organic compounds may include alkanes, alkenes, alkynes,
cycloalkanes, cycloalkenes, cycloalkynes, substituted alkanes,
substituted alkenes, substituted alkynes, alcohols, esters,
carboxylic acids, ethers, amines, amides, aromatics,
heteroaromatics, sulfides, sulfones, sulfates, thiols, aldehydes,
ketones, amides, and halogenated compounds. Chemical products and
reaction mixtures may include branched or linear compounds.
Chemical products and reaction mixtures may comprise oxygen,
methane, ethane, ethylene, propane, butane, hexanes, octanes,
decanes, carbon monoxide, methanol, ethanol, propanol, butanol,
hexanol, octanol, and formate. Chemical products and reaction
mixtures may include organometallic compounds. Chemical products
and reaction mixtures of the present disclosure may include
compounds intended for consumer use or industrial use, such as
fuels, solvents, additives, polymers, food additives, food
supplements, pharmaceuticals, fertilizers, agricultural chemicals,
coatings, lubricants, and building materials. Chemical products and
reaction mixtures of the present disclosure may comprise a
precursor, component, substituent, or substrate for a product
produced by further processing.
[0102] An organic compound of the present disclosure may comprise
one or more carbon atoms. In some instances, an organic compound
may comprise about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35,
40, 45, 50, 55, 60, 65, or about 70 carbon atoms. In some
instances, an organic compound may comprise at least about 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,
22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, or
about 70 or more carbon atoms. In some instances, an organic
compound may comprise no more than about 70, 65, 60, 55, 50, 45,
40, 35, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16,
15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or less carbon
atoms. An organic compound of the present disclosure may comprise
one or more carbon atoms derived from CO or CO.sub.2. In some
instances, an organic compound may comprise about 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,
24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, or about 70
carbon atoms that are derived from CO or CO.sub.2. In some
instances, an organic compound may comprise at least about 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,
22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, or
about 70 or more carbon atoms that are derived from CO or CO.sub.2.
In some instances, an organic compound may comprise no more than
about 70, 65, 60, 55, 50, 45, 40, 35, 30, 29, 28, 27, 26, 25, 24,
23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6,
5, 4, 3, 2 or less carbon atoms that are derived from CO or
CO.sub.2.
[0103] A chemical product or reaction mixture of the present
disclosure may comprise more than one chemical species. A chemical
product or reaction mixture may be a mixture of about 2, 3, 4, 5,
6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,
24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,
85, 90, 95 or about 100 detectable chemical compounds. A chemical
product or reaction mixture may be a mixture of at least about 2,
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,
21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, 80, 85, 90, 95 or about 100 or more detectable chemical
compounds. A chemical product or reaction mixture may be a mixture
of no more than about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50,
45, 40, 35, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17,
16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, or no more than about
3 or less detectable chemical compounds.
[0104] A chemical product or reaction mixture of the present
disclosure may comprise a particular compound at a particular
weight percentage or molar percentage of the total chemical product
or reaction mixture. For example, a particular chemical product may
include at least about 50 wt % ethanol. In another example, a
particular chemical product may include no more than about 1 wt %
water. In some instances, at least about 10%, 15%, 20%, 25%, 30%,
35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%,
96%, 97%, 98%, 99% or more of a chemical product or reaction
mixture may be a specific chemical compound on a weight or molar
basis. In some instances, no more than about 99%, 98%, 97%, 96%,
95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%,
30%, 25%, 20%, 15%, or no more than about 10% or less of a chemical
product or reaction mixture be a specific chemical compound on a
weight or molar basis.
[0105] A chemical product or reaction mixture of the present
disclosure may include compounds within a particular range of
molecular weights or carbon numbers. In some instances, at least
about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%,
70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or more of a
chemical product or reaction mixture may include compounds within a
particular molecular weight range or carbon number range. In some
instances, no more than about 99%, 98%, 97%, 96%, 95%, 90%, 85%,
80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%,
15%, or no more than about 10% or less of a chemical product or
reaction mixture may include compounds within a particular
molecular weight range or carbon number range. A chemical product
or reaction mixture may include compounds within a molecular weight
range from about 15 g/mol to about 30 g/mol, about 15 g/mol to
about 60 g/mol, about 15 g/mol to about 100 g/mol, about 15 g/mol
to about 200 g/mol, about 15 g/mol to about 400 g/mol, about 15
g/mol to about 600 g/mol, about 15 g/mol to about 1000 g/mol, about
30 g/mol to about 60 g/mol, about 30 g/mol to about 100 g/mol,
about 30 g/mol to about 200 g/mol, about 30 g/mol to about 400
g/mol, about 30 g/mol to about 600 g/mol, about 30 g/mol to about
1000 g/mol, about 60 g/mol to about 100 g/mol, about 60 g/mol to
about 200 g/mol, about 60 g/mol to about 400 g/mol, about 60 g/mol
to about 600 g/mol, about 60 g/mol to about 1000 g/mol, about 100
g/mol to about 200 g/mol, about 100 g/mol to about 400 g/mol, about
100 g/mol to about 600 g/mol, about 100 g/mol to about 1000 g/mol,
about 200 g/mol to about 400 g/mol, about 200 g/mol to about 600
g/mol, about 200 g/mol to about 1000 g/mol, about 400 g/mol to
about 600 g/mol, about 30 g/mol to about 1000 g/mol, about 30 g/mol
to about 100 g/mol, about 30 g/mol to about 200 g/mol, about 30
g/mol to about 400 g/mol, about 30 g/mol to about 600 g/mol, about
400 g/mol to about 1000 g/mol, or about 600 g/mol to about 1000
g/mol. A chemical product or reaction mixture may include compounds
within a carbon number range from about C1 to about C2, about C1 to
about C3, about C1 to about C4, about C1 to about C5, about C1 to
about C6, about C1 to about C8, about C1 to about C10, about C1 to
about C20, about C1 to about C30, about C1 to about C40, about C2
to about C3, about C2 to about C4, about C2 to about C5, about C2
to about C6, about C2 to about C8, about C2 to about C10, about C2
to about C20, about C2 to about C30, about C2 to about C40, about
C3 to about C4, about C3 to about C5, about C3 to about C6, about
C3 to about C8, about C3 to about C10, about C3 to about C20, about
C3 to about C30, about C3 to about C40, about C4 to about C5, about
C4 to about C6, about C4 to about C8, about C4 to about C10, about
C4 to about C20, about C4 to about C30, about C4 to about C40,
about C5 to about C6, about C5 to about C8, about C5 to about C10,
about C5 to about C20, about C5 to about C30, about C5 to about
C40, about C6 to about C8, about C6 to about C10, about C6 to about
C20, about C6 to about C30, about C6 to about C40, about C8 to
about C10, about C8 to about C20, about C8 to about C30, about C8
to about C40, about C10 to about C20, about C10 to about C30, about
C10 to about C40, about C20 to about C30, about C20 to about C40,
or about C30 to about C40.
[0106] A chemical product or reaction mixture of the present
disclosure may comprise one or more impurities. Impurities may
derive from reactant streams, reactor contaminants, breakdown or
decomposition products of produced organic compounds, catalyst
compounds, or side reactions in the electrochemical reduction
system or other chemical conversion systems described herein. A
chemical product or reaction mixture may comprise one or more
organic impurities such as formate or higher molecular weight
alcohols. A chemical product or reaction mixture may include carbon
or non-carbon nanomaterial impurities. A chemical product or
reaction mixture may comprise one or more inorganic impurities
derived from sources such as catalyst degradation or leaching and
corrosion of processing equipment. An inorganic impurity may
comprise sodium, magnesium, potassium, calcium, titanium, vanadium,
chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum,
silicon, yttrium, zirconium, niobium, molybdenum, ruthenium,
rhodium, palladium, silver, cadmium, indium, tin, antimony,
tantalum, tungsten, osmium, platinum, gold, mercury, and lead.
Inorganic impurities may be present in oxidized or reduced
oxidation states. Inorganic impurities may be present in the form
of organometallic complexes. An impurity in a chemical product or
reaction mixture may be detectable by any common analysis technique
such as gas or liquid chromatography, mass spectrometry, IR or
UV-Vis spectroscopy, Raman spectroscopy, X-ray photoelectron
spectroscopy, X-ray diffraction, or other methods. One or more
impurities may be detectable at an amount of at least about 1 part
per billion (ppb), 5 ppb, 10 ppb, 50 ppb, 100 ppb, 250 ppb, 500
ppb, 750 ppb, 1 part per million (ppm), 5 ppm, 10 ppm, 50 ppm, 100
ppm or more. One or more impurities may be detectable at an amount
of no more than about 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 750
ppb, 500 ppb, 250 ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb, or no more
than about 1 ppb or less.
[0107] A chemical product may have a particular level of purity. In
some instances, a chemical product may have sufficient purity to
achieve a particular grade or standard. A chemical product may be
ACS grade, reagent grade, USP grade, NF grade, laboratory grade,
purified grade or technical grade. A chemical product may have a
purity that exceeds an azeotropic composition, e.g. >95%
ethanol. A gaseous chemical product of the current invention may
have a purity rating of about N1.0, N2.0, N3.0, N4.0, N5.0, N6.0 or
greater. A chemical product may achieve a purity level according to
a defined international standard. E.g. the ASTM D-1152/97 standard
for methanol purity.
[0108] In some instances a chemical product or reaction mixture
from an electrochemical reduction system may have no detectable
amount of certain impurities. In some instances, a chemical product
or reaction mixture may have no detectable amount of biological
molecules or derivatives thereof. A chemical product or reaction
mixture may contain no detectable amount of lipids, saccharides,
proteins, nucleic acids, amino acids, spores, bacteria, viruses,
protozoa, fungi, animal or plant cells, or any component
thereof.
Chemical Feeds
[0109] The electrochemical conversion systems and related systems
may require one or more feed streams. Feed streams may comprise
solids, liquids or gases. Feed streams may comprise slurries,
pastes, powders, particles, or bed materials. In some instances, a
feed stream may comprise one or more chemical reactants. In other
instances, a feed stream may comprise a catalyst, a co-catalyst, an
activator, an inhibitor, a buffer, or a reactive scavenger. In some
instances, a feed stream may comprise an inert species.
[0110] A feed stream may comprise a gas or a mixture of gases. In
some instances, a gas stream may comprise CO, CO.sub.2, nitrogen, a
nitrogen oxide, oxygen, ozone, argon, hydrogen, helium, methane,
ethane, ethylene, propane, propylene, hydrogen sulfide, a sulfur
oxide, silanes, aromatics, chlorine, hydrochloric acid, sulfuric
acid, nitric acid, water vapor, and other gases. In some instances,
a gas stream may comprise air drawn directly from the atmosphere.
In other instances, a gas stream may comprise effluent gases from
an industrial or other source. In some instances, a gas stream may
comprise suspended particulates such as soot, pollen, spores, dust,
and mineral matter or ash. A gas stream may comprise an aerosol. A
gas stream may be filtered or scrubbed to remove particulates or
unwanted chemical species. A gas stream may be subjected to one or
more operations before entering a chemical conversion process or
other process to alter its composition or otherwise prepare the gas
stream for utilization. A gas stream may be separated or purified
to enrich for a particular component (e.g. CO.sub.2) or remove an
unwanted component (e.g. hydrogen sulfide).
[0111] A feed stream may comprise a liquid or a mixture of liquids.
In some instances, a liquid stream may comprise a chemical
reactant. In other instances, a liquid stream may comprise a
solvent carrying a chemical reactant. A liquid stream may comprise
a buffered solution, e.g. bicarbonate solution. A liquid stream may
comprise one or more of alkanes, alkenes, alkynes, cycloalkanes,
cycloalkenes, cycloalkynes, substituted alkanes, substituted
alkenes, substituted alkynes, alcohols, esters, carboxylic acids,
ethers, amines, amides, aromatics, heteroaromatics, sulfides,
sulfones, sulfates, thiols, aldehydes, ketones, amides, and
halogenated compounds.
[0112] A liquid feed stream may comprise an aqueous solution. An
aqueous solution may be buffered to maintain a particular pH. A
feed stream may have a pH of about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, or about 14. A feed stream may have a pH of at
least about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or
more. A feed stream may have a pH of no more than about 14, 13, 12,
11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0 or less.
[0113] A feed stream may be a multi-phase stream. A feed stream may
comprise gas entrained in a liquid or a solid entrained in a
liquid, such as a slurry. A feed stream may exist in a phase
equilibrium between solid and liquid, liquid and gas, or solid and
gas.
[0114] A feed stream may comprise one or more impurities or tracer
compounds. Impurities in a feed stream may arise from the processes
that produced them or transportation methods used to convey the
feed stream matter from production to the systems of the present
disclosure. Impurities may include organic or inorganic chemical
species, particulates (e.g. dirt, dust, rust, or ash), and
biological materials. An impurity may be detrimental to the
performance of an electrochemical reduction system or related
system. An inorganic impurity may comprise sodium, magnesium,
potassium, calcium, titanium, vanadium, chromium, manganese, iron,
cobalt, nickel, copper, zinc, aluminum, silicon, yttrium,
zirconium, niobium, molybdenum, ruthenium, rhodium, palladium,
silver, cadmium, indium, tin, antimony, tantalum, tungsten, osmium,
platinum, gold, mercury, and lead. Inorganic impurities may be
present in oxidized or reduced oxidation states. Inorganic
impurities may be present in the form of organometallic complexes.
A feed stream may be purified before use to remove one or more
impurities before utilization in an electrochemical reduction
system or a related system. A tracer compound may comprise a
chemical species that exists at a low but detectable level within a
feed stream. A tracer compound may be come in a particular feed
stream reagent or may be added to a feed stream prior to the feed
stream entering a conversion or other process. A tracer compound
may be an inert species. A tracer compound may be a compound that
is selectively converted, separated, or otherwise altered in
certain processes and is unaffected by other processes. An impurity
or a tracer compound may have a measured concentration in a feed
stream. An impurity or a tracer compound in a chemical product may
be detectable by any common analysis technique such as gas or
liquid chromatography, mass spectrometry, IR or UV-Vis
spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy,
X-ray diffraction, or other methods. One or more impurities or
tracer compounds may be detectable at an amount of at least about 1
ppb, 5 ppb, 10 ppb, 50 ppb, 100 ppb, 250 ppb, 500 ppb, 750 ppb, 1
ppm, 5 ppm, 10 ppm, 50 ppm, 100 ppm or more. One or more impurities
or tracer compounds may be detectable at an amount of no more than
about 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, 750 ppb, 500 ppb, 250
ppb, 100 ppb, 50 ppb, 10 ppb, 5 ppb, or no more than about 1 ppb or
less.
Structured Membranes
[0115] The present disclosure may provide reactor and separation
systems that comprise micro- or nanostructured membranes. A micro-
or nanostructured membrane may be utilized to perform a selective
separation of one or more chemical species from a mixture
comprising more than one chemical species. A micro- or
nanostructured membrane may also provide additional utility in a
chemical processing system including physically separating product
streams and comprising a component of an electrical cathode or
anode in an electrochemical system.
[0116] A micro- or nanostructured membrane may comprise one or more
microscale or nanoscale materials features (e.g., including
positive features, such as microscale or nanoscale structures,
and/or negative features, such as microscale and nanoscale pores or
microscale and nanoscale depressions). In some instances, a
membrane may comprise carbon nanotubes, carbon nanospheres, carbon
nano-onions, graphene-like materials, or pyrolyzed porous carbon
materials (see FIGS. 2 and 4). A membrane may comprise micro- or
nanostructured material synthesized from non-carbon materials. A
membrane may comprise carbon nanomaterials doped with other
elements such as nitrogen, sulfur, and boron. A micro- or
nanostructured material may be embedded, fixed, or otherwise bound
to one or more other substrates or materials to construct a
membrane. A micro- or nanostructured material embedded in a
substrate or material may create pores within the structured
membrane. The pores may permit the selective passage of certain
chemical species. Other substrates or materials in the membrane may
be selected for material properties including rigidity, strength,
and electrical conductivity. Other substrates or materials in a
micro- or nanostructured membrane may include polymers, e.g.
polysulfones, metals, and ceramics. The microscale or nanoscale
features may have a maximum dimension of at least about 0.4
nanometers (nm), 0.6 nm, 0.8 nm, 1 nm, 1.2 nm, 1.4 nm, 1.6 nm, 1.8
nm, 2.0 nm, 2.5 nm, 3.0 nm, 3.5 nm, 4.0 nm, 4.5 nm, 5.0 nm, 5.5 nm,
6.0 nm, 6.5 nm, 7.0 nm, 7.5 nm, 8.0 nm, 8.5 nm, 9.0 nm. 9.5 nm. 10
nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm,
200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1
micrometer, 10 micrometers, 100 micrometers or larger. In some
instances, the maximum dimension may be at most about 100
micrometers, 10 micrometers, 1 micrometer, 900 nm, 800 nm, 700 nm.
600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70
nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 10 nm, 9.5 nm, 9.0 nm, 8.5
nm, 8 nm, 7.5 nm, 7.0 nm, 6.5 nm, 6.0 nm, 5.5 nm, 5.0 nm, 4.5 nm,
4.0 nm, 3.5 nm, 3.0 nm, 2.5 nm, 2.0 nm, 1.8 nm, 1.6 nm, 1.4 nm, 1.2
nm, 1.0 nm, 0.8 nm, 0.6 nm, or 0.4 nm or less.
[0117] A micro- or nanostructured membrane may comprise a
particular shape, structure depending upon its application. In some
instances, a membrane may have a cylindrical structure (see FIG. 3A
and 3B) such as with a hollow fiber membrane format, or have a
substantially flat sheet structure. A membrane may partially or
fully enclose a volume or void space. The surface area of a
membrane disposed toward an enclosed or void space may be defined
as a lumen side of the membrane. In some instances, mass transfer
across a membrane may be driven by chemical potential, pressure
difference, or temperature difference between a lumen side and a
non-lumen side of a membrane. A membrane may further comprise
additional structures such as frames or fittings that secure the
membrane to other portions of the described systems.
[0118] A micro- or nanostructured membrane may be composed with
micro- or nanomaterials embedded so as to create pores within the
membrane. The micro- or nanomaterial may be chosen based upon a
characteristic pore size that it may create. Without wanting to be
bound by theory, a pore may be defined as a void space or volume
within a solid material through which a liquid or gas molecule may
flow or diffuse. A chemical species may pass through a pore created
by the internal diameter space in a carbon nanotube (see FIG. 1A),
through spaces between nanoparticles e.g. clustered nanotubes or
nano-onions (see FIG. 1B), through the pores of a porous carbon
(see FIG. 1C), or through the space between layers of graphene-like
material (see FIG. 1D). A micro- or nanomaterial may have a
characteristic length scale such as a diameter, pore size, or layer
spacing that is sufficient to permit the passage of chemical
species through a void space in the material. In some instances, a
characteristic length may be at least about 0.4 nanometers (nm),
0.6 nm, 0.8 nm, 1 nm, 1.2 nm, 1.4 nm, 1.6 nm, 1.8 nm, 2.0 nm, 2.5
nm, 3.0 nm, 4.0 nm, 5.0 nm or larger. In some instances, a
characteristic length may be no more than about 5.0 nm, 4.0 nm, 3.0
nm, 2.5 nm, 2.0 nm, 1.8 nm, 1.6 nm, 1.4 nm, 1.2 nm, 1.0 nm, 0.8 nm,
0.6 nm, or about 0.4 nm or less. A pore may have a larger diameter
than length. A pore may have a larger length than diameter. A pore
may have a length to width ratio of about 1:10, 1:5, 1:2, 1:1, 2:1,
5:1, 10:1, 100:1, or about 1000:1. A pore may have a length to
width ratio of at least about 1:10, 1:5, 1:2, 1:1, 2:1, 5:1, 10:1,
100:1, or about 1000:1. A pore may have a length to width ratio of
no more than about 1000:1, 100:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, or
about 1:10 or less. A pore may comprise a substantially straight
path such as a carbon nanotube or the space between layers of
horizontal graphene-like materials. A pore may have a diagonal,
skewed, or tortuous path in some materials, such as meso- or
nanoporous carbons.
[0119] A membrane may comprise a material with a characterized
porous structure. Materials may include nanopores, mesopores, and
micropores. In some instances, nanopores may be characterized as
having an average diameter of about 2 nm or less. In some
instances, mesopores may be characterized as having an average
diameter of between about 2 nm and about 20 nm. In some instances,
micropores may be characterized as having an average diameter of
about 20 nm or more. A membrane may comprise structures with pore
sizes across a range of pores sizes (e.g., nanopores and
mesopores). A membrane may comprise structures with pores sizes
from within a particular classification of pores sizes (e.g., only
mesopores). A membrane may comprise pores (e.g., micropores or
nanopores) with an average diameter of at least about 0.5 nm, 1 nm,
5 nm, 10 nm, 15 nm, 20 nm, 30 nm, 40 nm, 50 nm, 100 nm, 250 nm, 500
nm, 1 micron .mu.m), or at least about 5 .mu.m. A membrane may
comprise pores with an average diameter of no more than about 5
.mu.m, 1 .mu.m, 500 nm, 250 nm, 100 nm, 50 nm, 40 nm, 30 nm, 20 nm,
15 nm, 10 nm, 5 nm, 1 nm, 0.5 nm or less.
[0120] A membrane comprising a micro- or nanostructured material
may permit mass transport of one or more chemical species across
the membrane. A membrane comprising a micro- or nanostructured
material may be selective for particular species. In some
instances, a membrane comprising micro- or nanostructured materials
may selectively transfer CO or CO.sub.2 from a gas stream. In some
instances, a membrane comprising micro- or nanostructured materials
may selectively transfer gaseous ethylene or ethanol from a gas
mixture. In some instances, a membrane comprising micro- or
nanostructured materials may selectively transfer hydrocarbons from
an aqueous liquid mixture. A membrane comprising a micro- or
nanostructured material may transfer particular chemical species by
diffusive or convective mass transport. In some instances, mass
transfer may be enhanced by the application of an external force or
field. In particular instances, mass transfer may be driven or
enhanced by the application of a magnetic or electrical field. In
other instances, mass transfer may be driven by a pressure gradient
(e.g. pulling a vacuum on one side of the membrane). In some
instances, the selectivity of a membrane can be reversed by
reversing an applied field or force. In other instances, a membrane
may have a unidirectional or invariant mass transfer
selectivity.
[0121] A micro- or nanostructured membrane may have an optimal or
preferred operation temperature and operation pressure. In some
instances, a system comprising a micro- or nanostructured membrane
may be operated at an ambient pressure or temperature. In some
instances, a system comprising a micro- or nanostructured membrane
may be operated at an elevated pressure or under a vacuum or
reduced pressure. A pressure gradient may be utilized to drive mass
transfer across a membrane system. A micro- or nanostructured
membrane may be utilized in a system with an operating temperature
of about -30.degree. C., -20.degree. C., -10.degree. C., 0.degree.
C., 5.degree. C., 10.degree. C., 15.degree. C., 20.degree. C.,
25.degree. C., 30.degree. C., 35.degree. C., 40.degree. C.,
50.degree. C., 60.degree. C., 70.degree. C., or about 80.degree. C.
A micro- or nanostructured membrane may be utilized in a system
with an operating temperature of at least about -30.degree. C.,
-20.degree. C., -10.degree. C., 0.degree. C., 5.degree. C.,
10.degree. C., 15.degree. C., 20.degree. C., 25.degree. C.,
30.degree. C., 35.degree. C., 40.degree. C., 50.degree. C.,
60.degree. C., 70.degree. C., or about 80.degree. C. or more. A
micro- or nanostructured membrane may be utilized in a system with
an operating temperature of no more than about 80.degree. C.,
75.degree. C., 70.degree. C., 65.degree. C., 60.degree. C.,
55.degree. C., 50.degree. C., 45.degree. C., 40.degree. C.,
35.degree. C., 30.degree. C., 25.degree. C., 20.degree. C.,
15.degree. C., 10.degree. C., 5.degree. C., 0.degree. C.,
-5.degree. C., -10.degree. C., -20.degree. C., or about -30.degree.
C. or less.
[0122] A micro- or nanostructured membrane may be utilized in a
system with an operating pressure of about 0 bar, 1 bar, 2 bar, 3
bar, 4, bar, 5 bar, 6 bar, 7 bar, 8 bar, 9 bar, 10 bar, 15 bar, 20
bar, 30 bar, 40 bar, 50 bar or more. A micro- or nanostructured
membrane may be utilized in a system with an operating pressure of
at least about 1 bar, 2 bar, 3 bar, 4, bar, 5 bar, 6 bar, 7 bar, 8
bar, 9 bar, 10 bar, 15 bar, 20 bar, 30 bar, 40 bar, 50 bar or more.
A micro- or nanostructured membrane may be utilized in a system
with an operating pressure of no more than about 50 bar, 40 bar, 30
bar, 20 bar, 15 bar, 10 bar, 9 bar, 8 bar, 7 bar, 6 bar, 5 bar, 4
bar, 3 bar, 2 bar, 1 bar or less.
[0123] A micro- or nanostructured membrane may be capable of
permitting a particular flux of CO or CO.sub.2 across the membrane.
A flux of CO or CO.sub.2 may be driven by a pressure gradient
across the membrane. In some instances, a pressure gradient may be
driven by a gas stream comprising CO or CO.sub.2 at a pressure
elevated above ambient pressure. In other instances, a pressure
gradient may exist by pulling a vacuum on one side of the membrane,
e.g. the lumen side. A micro- or nanostructured membrane may permit
a CO or CO.sub.2 flux of about 0.1 kilogram gas/m.sup.2 of
membrane/hr (kg/m.sup.2/hr), 0.5 kg/m.sup.2/hr, 1 kg/m.sup.2/hr, 2
kg/m.sup.2/hr, 3 kg/m.sup.2/hr, 4 kg/m.sup.2/hr, 5 kg/m.sup.2/hr, 6
kg/m.sup.2/hr, 7 kg/m.sup.2/hr, 8 kg/m.sup.2/hr, 9 kg/m.sup.2/hr,
or about 10 kg/m.sup.2/hr. A micro- or nanostructured membrane may
permit a CO or CO.sub.2 flux of at least about 0.1 kg/m.sup.2/hr,
0.5 kg/m.sup.2/hr, 1 kg/m.sup.2/hr, 2 kg/m.sup.2/hr, 3
kg/m.sup.2/hr, 4 kg/m.sup.2/hr, 5 kg/m.sup.2/hr, 6 kg/m.sup.2/hr, 7
kg/m.sup.2/hr, 8 kg/m.sup.2/hr, 9 kg/m.sup.2/hr, or at least about
10 kg/m.sup.2/hr. A micro- or nanostructured membrane may permit a
CO or CO.sub.2 flux of no more than about 10 kg/m.sup.2/hr, 9
kg/m.sup.2/hr, 8 kg/m.sup.2/hr, 7 kg/m.sup.2/hr, 6 kg/m.sup.2/hr, 5
kg/m.sup.2/hr, 4 kg/m.sup.2/hr, 3 kg/m.sup.2/hr, 2 kg/m.sup.2/hr, 1
kg/m.sup.2/hr, 0.5 kg/m.sup.2/hr, or about 0.1 kg/m.sup.2/hr or
less.
[0124] A micro- or nanostructured membrane may be capable of
permitting a particular flux of hydrocarbons across the membrane. A
flux of hydrocarbons may be driven by a pressure gradient across
the membrane. In some instances, a pressure gradient may be driven
by a gas or liquid stream comprising hydrocarbons at a pressure
elevated above ambient pressure. In other instances, a pressure
gradient may exist by pulling a vacuum on one side of the membrane,
e.g. the lumen side. A micro- or nanostructured membrane may permit
a hydrocarbon flux of about 0.1 kilogram hydrocarbon/m.sup.2 of
membrane/hr (kg/m.sup.2/hr), 0.5 kg/m.sup.2/hr, 1 kg/m.sup.2/hr, 2
kg/m.sup.2/hr, 3 kg/m.sup.2/hr, 4 kg/m.sup.2/hr, 5 kg/m.sup.2/hr, 6
kg/m.sup.2/hr, 7 kg/m.sup.2/hr, 8 kg/m.sup.2/hr, 9 kg/m.sup.2/hr,
or about 10 kg/m.sup.2/hr. A micro- or nanostructured membrane may
permit a hydrocarbon flux of at least about 0.1 kilogram
kg/m.sup.2/hr, 0.5 kg/m.sup.2/hr, 1 kg/m.sup.2/hr, 2 kg/m.sup.2/hr,
3 kg/m.sup.2/hr, 4 kg/m.sup.2/hr, 5 kg/m.sup.2/hr, 6 kg/m.sup.2/hr,
7 kg/m.sup.2/hr, 8 kg/m.sup.2/hr, 9 kg/m.sup.2/hr, or at least
about 10 kg/m.sup.2/hr. A micro- or nanostructured membrane may
permit a hydrocarbon flux of no more than about 10 kg/m.sup.2/hr, 9
kg/m.sup.2/hr, 8 kg/m.sup.2/hr, 7 kg/m.sup.2/hr, 6 kg/m.sup.2/hr, 5
kg/m.sup.2/hr, 4 kg/m.sup.2/hr, 3 kg/m.sup.2/hr, 2 kg/m.sup.2/hr, 1
kg/m.sup.2/hr, 0.5 kg/m.sup.2/hr, or about 0.1 kg/m.sup.2/hr or
less.
[0125] A membrane with an enhanced selectivity for one or more
chemical species may enhance the chemical conversion rate or phase
equilibrium of a conversion system. Without wanting to be bound to
theory, selective enrichment for one or more chemical species
within the void or pore space of the micro- or nanostructured
component of a membrane may increase the volumetric concentration
of the one or more chemical species within the void or pore space.
In some instances, a kinetic rate enhancement or shift in phase
equilibrium for a particular chemical reaction may be driven by one
or more chemical species having higher volumetric concentrations
within the membrane than may be predicted by their bulk phase
concentrations on either side of the membrane. In a particular
instance, the selective mass transfer of one or more chemical
species through a membrane may cause an increased concentration of
the one or more chemical species in a boundary layer adjacent to
the surface of the membrane. An increase in the boundary layer
concentration of the one or more chemical species may increase the
availability of one or more chemical species to a catalyst
deposited at the surface of the membrane. In another instance, a
catalyst may be deposited within the void or pore space of a micro-
or nanostructured material within a membrane, allowing direct
transfer of an increased mass transfer of one or more chemical
species to the catalyst by bulk flow.
[0126] The mass transfer selectivity of a membrane for one or more
chemical species may cause a measurable enhancement of the rate of
reaction for one or more chemical reactions in a chemical
conversion system that comprises such a membrane. In some
instances, the rate of reaction for one or more chemical reactions
may increase by at least about 5%, 10%, 20%, 30%, 40%, 50%, 75%,
100%, 150%, 200%, 500%, or about 1000% or more. In some instances,
the rate of reaction for one or more chemical reactions may be
higher than may be predicted by the use of measured reactant
concentrations due to other synergistic effects such as electric
field enhancement of catalyst activity. In some instances, the mass
transfer selectivity of a membrane for one or more chemical species
may cause a measurable reduction in the rate of reaction for one or
more chemical unwanted reactions (e.g. side reactions, degradation
reactions) in a chemical conversion system that comprises such a
membrane. In some instances, the rate of reaction for one or more
unwanted chemical reactions may decrease by at least about 5%, 10%,
20%, 30%, 40%, 50%, 75%, 100%, 150%, 200%, 500%, or about 1000% or
more.
[0127] A membrane comprising a micro- or nanostructured material
may further comprise one or more catalyst materials. A catalyst
material may be attached, bonded, deposited or functionalized to
the surface of a micro- or nanostructured material. In some
instances, a catalyst may be located on a surface of a membrane. A
catalyst may be localized in particular areas of a membrane or on
particular areas of a micro- or nanostructured material to control
where a catalyzed chemical reaction may occur. A catalyst may be
located within a pore or pore-like structure in a membrane. A
chemical reaction catalyzed by a catalyst may occur on a particular
area of the membrane or within the pore or pore-like space of the
membrane. A catalyst may comprise a metal atom, metal complex, or
metal particle. A catalyst may comprise a metal such as titanium,
vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc,
aluminum, silicon, yttrium, zirconium, niobium, molybdenum,
ruthenium, rhodium, palladium, silver, cadmium, indium, tin,
antimony, tantalum, tungsten, osmium, platinum, gold, mercury, or
lead. In some instances, a doped carbon nanomaterial may comprise a
catalyst. In a particular instance, N-doped carbon nanotubes may
comprise a catalyst. In another instance, carbon nanotubes with
electrodeposited platinum, nickel, or copper nanoparticles may
comprise a catalyst (see FIG. 5). A membrane may comprise more than
one catalyst. In some instances, one or more catalysts may be
deposited on one or more areas or surfaces of a membrane, and one
or more differing catalysts may be deposited on one or more
differing areas or surfaces of a membrane. A membrane may be
capable of catalyzing one or more chemical reactions when mass
transfer occurs in a particular direction across the membrane, and
may be capable of catalyzing one or more differing chemical
reactions when mass transfer occurs in a differing direction across
the membrane.
[0128] An electrochemical reduction process utilizing a micro- or
nanostructured catalyst membrane may utilize methods or components
to minimize catalyst poisoning. A micro- or nanostructured membrane
comprising a catalyst may be refreshed or regenerated to mitigate
the impact of catalyst poisoning and the deposition of other
unwanted species. In some instances, a membrane may be removed from
an electrochemical reduction system for catalyst regeneration. In
other instances, a membrane may be flushed with acid to dissolve or
remove catalyst particles, followed thereafter by deposition of new
catalyst particles on the membrane surface or nanoparticle
surface.
[0129] A membrane comprising a micro- or nanostructured material
may have enhanced electrical properties. In some aspects, the
membranes may be conductive, due to the electrical properties of
the micro- or nanostructured materials. In some instances, a
membrane may be semiconducting (e.g. carbon nanotubes of a
particular chirality). A membrane may be configured to act as an
electrode in an electrochemical system. A membrane may allow an
electrical current to be conveyed to one or more catalysts
associated with it. An electrical current may enhance the
reactivity of a catalyst for particular catalyzed chemical
reactions. In some instances, the selective mass transfer of
particular chemical species across a micro- or nanostructured
membrane may increase the current density achieved at the membrane
electrode.
[0130] A membrane comprising a micro- or nanostructured material
may be utilized for various purposes. In some instances, a membrane
may permit mass transfer of a chemical species from a first gas
mixture into a second gas mixture. In some instances, a membrane
may permit mass transfer of a chemical species from a gas phase
into a liquid phase. In some instances, a membrane may permit mass
transfer of a chemical species from a first liquid mixture into a
second liquid mixture. In some instances, a membrane may permit
mass transfer of a chemical species to a catalytic site where a
chemical reaction may occur. In some instances, a membrane may be
utilized to perform both chemical separations and catalysis. In
some instances, a membrane may be cycled between separation and
catalysis by the directional application of electric fields or
other fields or forces. In other instances, a membrane may be
capable of simultaneously catalyzing and performing a chemical
separation.
Chemical Conversion Systems
[0131] The invention of the present disclosure includes chemical
conversion systems for the conversion of carbon dioxide into other
chemical species via electrochemical reduction. Numerous
embodiments of the present invention may be conceived over a wide
range of processing scales. CO or CO.sub.2 conversion systems may
include microscale fuel production devices, standalone chemical
production systems that produce specific chemicals or fuels at the
scale of tens to hundreds of kilograms per day, or industrial-scale
production of chemicals or fuels at the scale of thousands of
kilograms per day or more.
[0132] A chemical conversion system may utilize one or more micro-
or nanostructured membranes to perform the electrochemical
reduction of carbon dioxide. A chemical conversion system may
include one or more micro- or nanostructured membranes to perform a
separation of carbon dioxide from a gas stream and supply the
carbon dioxide to a chemical reactor. A chemical conversion system
may include one or more micro- or nanostructured membranes to
perform a separation of a chemical mixture resulting from a unit
operation of a chemical conversion system. A chemical conversion
system may include one or more micro- or nanostructured membranes
to perform a catalyzed electrochemical reduction of carbon dioxide
to another chemical species (e.g. formate, methanol, ethanol). A
chemical conversion system may include one or more micro- or
nanostructured membranes to perform one or more catalyzed
conversion reactions of one or more species formed via
electrochemical reduction of carbon dioxide (e.g. further reduction
of CO or CO.sub.2 reduced products, such as formate to methanol or
ethanol, methanol and ethanol to propanol, ethanol to butanol, etc;
dehydration of ethanol to ethylene).
[0133] A chemical conversion system may comprise one or more unit
operations for separating chemical species using a membrane
comprising a micro- or nanostructured material. A chemical
conversion system may comprise one or more unit operations for
reacting one or more chemical species using a membrane comprising a
micro- or nanostructured material. In some instances, a chemical
conversion system may utilize micro- or nanostructured membrane
unit operations for distinct operations, such as the reaction of
one or more chemical species or the separation of one or more
chemical species. In some instances, a chemical conversion system
may utilize a single micro- or nanostructured membrane unit
operation for multiple operations, such as simultaneous reaction
and separation of one or more chemical species. In some instances,
a chemical conversion system may comprise a plurality of unit
operations comprising a membrane that comprises a micro- or
nanostructured material. In some instances, a plurality of unit
operations may be working redundantly on a particular process, for
example multiple CO or CO.sub.2 to formate chemical reactors. In
other instances, a plurality of unit operations may be performing a
range of processes, for example chemical reactors tailored to
produce hydrocarbons with varying molecular weight ranges.
[0134] Any unit operation in a chemical conversion system may be
designed to operate in a batch, semi-batch, or continuous mode. Any
unit operation in a chemical conversion system may have one or more
feed streams. Any unit operation in a chemical conversion system
may have one or more product streams. A unit operation in a
chemical conversion system may utilize one or more recycle or purge
streams to control its function. In some instances, a unit
operation capable of multiple processes (e.g. reaction and
separation) may operate continuously. In some instances, a unit
operation capable of multiple processes may operate cyclically
between modes of operation.
[0135] A chemical conversion system of the present invention may
comprise any number of additional operations beyond the
membrane-based unit operations. A chemical conversion system may
comprise one or more unit operations for separations. Separation
unit operations may include distillation columns, reactive
distillation columns, gas absorption columns, stripping columns,
additional catalysis operations, such as with catalyst packed
columns, flash tanks, humidifiers, leaching units, liquid-liquid
extraction units, dryers, adsorption systems, ion-exchange columns,
membrane separation units, filtration units, sedimentation units,
and crystallization units. A chemical conversion system may
comprise one or more unit operations for heat transfer. Heat
transfer unit operations may include mantle heaters, cartridge
heaters, tape heaters, pad heaters, resistive heaters, radiative
heaters, fan heaters, shell-and-tube heat exchangers, plate-type
heat exchangers, extended-surface heat exchangers, scraped-surface
heat exchangers, condensers, vaporizers, and evaporators. A
chemical conversion system may comprise one or more unit operations
for fluid transfer. Fluid transfer devices may include piping,
tubing, fittings, valves, pumps, fans, blowers, compressors,
stirrers, agitators, and blenders. Pumping equipment may be
operated at pressures above atmospheric pressure or used to draw a
vacuum. A chemical conversion system may comprise one or more
chemical reaction units aside from an electrochemical reduction
reactor. Chemical reaction units may include plug flow reactors,
continuous-stirred tank reactors, packed bed columns, fluidized bed
reactors, and batch reactors. Chemical reactors may be utilized for
various upgrading and conversions including dehydrogenation,
hydrogenation, cracking, dehydration, decarboxylation,
carboxylation, amination, deamination, alkylation, dealkylation,
oxidation, reduction, polymerization, and depolymerization.
[0136] A chemical conversion system may have one or more pieces of
equipment for process control or process safety. A chemical
conversion system may contain one or more thermocouples,
temperature gauges, pressure gauges, rotameters, mass flow
controllers, pH probes, chemical analyzers, velocity gauges,
infrared sensors, flow sensors, PID control devices, PLC control
devices, purge valves, purge lines, and recycle lines. A chemical
conversion system may be under operative control by one or more
computers or computer systems.
[0137] Any unit operation within a chemical conversion system,
including a central electrochemical reduction unit, may have at
least one feed or input stream. Any unit operation within a
chemical conversion system, including a central electrochemical
reduction unit, may have at least one product or outlet stream. Any
feed or input stream and product or outlet stream may comprise one
or more inline unit operations for processes such as fluid
transfer, heat transfer, mass transfer, chemical reaction, or
process control.
[0138] A chemical conversion system comprising one or more micro-
or nanostructured membranes may reduce or eliminate the energy
consumption associated with one or more unit operations. For
example, a gas separator comprising one or more micro- or
nanostructured membranes may eliminate the need for a distillation
column or separate adsorption system to separate CO or CO.sub.2
from air. In some instances, the utilization of unit operations
comprising micro- or nanostructured membranes may eliminate one or
more pumps, compressors, heat exchangers, separators, or reactors
from an electrochemical reduction system. The utilization of one or
more micro-or nanostructured membranes may reduce the energy
consumption of a processing step or processing component by at
least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%,
60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99% or more.
[0139] A chemical conversion system may comprise one or more energy
generation devices. Energy generation devices may comprise
renewable energy generation devices such as photovoltaic cells,
solar concentration heaters, wind turbines, water turbines, biomass
combustion systems, and biomass gasifiers. A chemical conversion
system may be in direct electrical connection with an energy source
such as a nuclear power source or a geothermal power source. A
renewable energy source may provide the electrical energy source
necessary to electrochemically reduce CO or CO.sub.2 to other
chemicals. A renewable energy source may provide the electrical
energy source necessary to perform any other unit operation
necessary to produce a chemical product. A renewable energy source
may include solar power sources (e.g. photovoltaic cells)
geothermal power sources, hydroelectric power sources, nuclear
power sources, tidal power sources, wind power sources, biomass
power sources, or any combination thereof. In some instances, a
chemical conversion system may be entirely self-sustaining, i.e. no
external power supply is necessary. In other instances, a chemical
conversion system may reduce the external power demand of a
chemical production process when compared to a conventional
production method. In some cases, power generation systems may be
employed to make use of non-target byproducts, such as with a fuel
cell for conversion of hydrogen, methane, or CO with oxygen to
create electricity, which may be used in the electrochemical
process.
[0140] A chemical conversion system may reduce the external power
demand of a chemical process by at least about 5%, 10%, 15%, 20%,
25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%,
90%, 95%, 96%, 97%, 98%, 99% or more. In some instances, a chemical
conversion system may generate fuels with a greater energy content
than the total external energy consumed to produce the fuels. A
chemical conversion system may reduce the carbon footprint for the
production of one or more chemicals.
[0141] A chemical conversion system may reduce the net carbon
emissions of a chemical production process. The total carbon
emissions of a chemical production process may decrease by at least
about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%,
65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or more. In
some instances, a chemical production process may be net carbon
negative, i.e. more carbon is sequestered in a product than is
released by the production of the product. A chemical conversion
system may be utilized to reduce the net carbon emissions of
another chemical process. In some instances, a chemical conversion
system may be coupled to an effluent gas source (e.g. a power plant
flue gas stream) to minimize the total carbon dioxide release from
the effluent gas source. A chemical conversion system may reduce
the total carbon emissions of another system or source by at least
about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%,
65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or more.
Chemical Reduction Systems and Methods
[0142] The present disclosure provides chemical conversion systems
that convert CO or CO.sub.2 to other chemicals via an
electrochemical reduction system. In some instances, the
electrochemical conversions system may produce hydrocarbons in the
liquid phase via the electrochemical reduction of bicarbonate ions
that are produced by the reaction of CO or CO.sub.2 with water. The
electrochemical reduction system may generate bicarbonate ions via
the capture of CO or CO.sub.2 from various sources, including
atmospheric carbon dioxide and effluent gases from an industrial or
chemical process. In some instances, the chemical reduction system
may reduce the energy consumption of a CO or CO.sub.2 reduction
process by at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%,
45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%,
98%, 99% or more. In some instances, a CO or CO.sub.2 reduction
system may utilize a feed stream comprising carbon dioxide without
the need for further purification. In some instances, a CO or
CO.sub.2 reduction system may utilize a feed stream comprising CO
or CO.sub.2 without the need for additional separation processes
that enrich the CO or CO.sub.2 composition of the feed stream. A
feed stream to an electrochemical reduction system may comprise
carbon dioxide on a molar basis of about 0.01%, 0.02%, 0.03%,
0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.5%, 1%, 5%,
10%, 20%, 50%, 90%, 95% or more. A feed stream to an
electrochemical reduction system may comprise carbon dioxide on a
molar basis of at least about 0.01%, 0.02%, 0.03%, 0.04%, 0.05%,
0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.5%, 1%, 5%, 10%, 20%,
50%, 90%, 95% or more. A feed stream to an electrochemical
reduction system may comprise carbon dioxide on a molar basis of no
more than about 95%, 90%, 50%, 20%, 10%, 5%, 1%, 0.5%, 0.2%, 0.1%,
0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, or 0.01% or
less.
[0143] An electrochemical reduction system may produce hydrocarbons
at a specific rate based upon the available surface area for
electrochemical reduction. An electrochemical reduction system may
produce hydrocarbons at a rate of about 10 kilograms/meter
squared/hour (kg/m.sup.2/hr), 20 kg/m.sup.2/hr, 30 kg/m.sup.2/hr,
40 kg/m.sup.2/hr, 50 kg/m.sup.2/hr, 60 kg/m.sup.2/hr, 70
kg/m.sup.2/hr, 80 kg/m.sup.2/hr, 90 kg/m.sup.2/hr, 100
kg/m.sup.2/hr, 150 kg/m.sup.2/hr, or about 200 kg/m.sup.2/hr. An
electrochemical reduction system may produce hydrocarbons at a rate
of about 10 kg/m.sup.2/hr, 20 kg/m.sup.2/hr, 30 kg/m.sup.2/hr, 40
kg/m.sup.2/hr, 50 kg/m.sup.2/hr, 60 kg/m.sup.2/hr, 70
kg/m.sup.2/hr, 80 kg/m.sup.2/hr, 90 kg/m.sup.2/hr, 100
kg/m.sup.2/hr, 150 kg/m.sup.2/hr, or about 200 kg/m.sup.2/hr or
more. An electrochemical reduction system may produce hydrocarbons
at a rate of no more than about 200 kg/m.sup.2/hr, 150
kg/m.sup.2/hr, 100 kg/m.sup.2/hr, 90 kg/m.sup.2/hr, 80
kg/m.sup.2/hr, 70 kg/m.sup.2/hr, 60 kg/m.sup.2/hr, 50
kg/m.sup.2/hr, 40 kg/m.sup.2/hr, 30 kg/m.sup.2/hr, 20
kg/m.sup.2/hr, or 10 kg/m.sup.2/hr or less.
[0144] An electrochemical reduction system may have a selectivity
for the conversion of CO or CO.sub.2 to one or more chemical
species. In some instances, a selectivity may be defined as the
percentage of carbon atoms entering a reactor, system, or unit that
are converted to a product species. For example, a selectivity of
50% may indicate that 50% of entering CO or CO.sub.2 molecules were
converted to a hydrocarbon species in a reactor, system or unit. In
some instances, a selectivity may be defined as the percentage of
carbon atoms entering a reactor, system, or unit that are converted
to a chemical species within a particular class, weight range,
carbon number range, or other characteristic. For example, a
selectivity of 50% C1-C4 may indicate that 50% of entering CO or
CO.sub.2 molecules were converted to a C1 to C4 hydrocarbon
product. A selectivity may be a single-pass selectivity. A
single-pass selectivity may be defined as the percentage of carbon
atoms entering a reactor, system, or unit that are converted to a
hydrocarbon product on a single pass through the reactor, system,
or unit. A selectivity may be a recycled selectivity. A recycled
selectivity may be defined as the percentage of carbon atoms
entering a reactor, system, or unit that are converted to a
hydrocarbon product on two or more passes through the reactor,
system, or unit.
[0145] An electrochemical reduction system may have a selectivity
of about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or about
99%. An electrochemical reduction system may have a selectivity of
at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or
about 99% or more. An electrochemical reduction system may have a
selectivity of no more than 99%, 95%, 90%, 80%, 70%, 60%, 50%, 40%,
30%, 20%, or 10% or less.
[0146] An electrochemical reduction system for the conversion of CO
or CO.sub.2 into other chemicals may comprise various components
that may be necessary for the reduction of CO or CO.sub.2.
Components may include cathodes, anodes, contactors, extractors,
pumps, vapor-liquid separators, and ion exchange membranes. In some
instances, some components may be included or excluded from a
chemical reduction system depending upon the preferred embodiment
of the device. In some instances, a chemical reduction system may
be a single, stand-alone, or fully integrated system that performs
all processes in the electrochemical reduction of CO or CO.sub.2.
In other instances, an electrochemical reduction system may
comprise at least two or more operatively linked unit operations
that collectively perform the necessary processes in the
electrochemical reduction of CO or CO.sub.2.
[0147] An electrochemical reduction system may comprise a housing.
The housing may provide various functions to the electrochemical
reduction system, including without limitation: securing components
(e.g., membranes), physically containing fluids, separating
differing fluids within a single unit, retaining temperature or
pressure, and/or providing insulation. The housing may comprise any
suitable material, including metals, ceramics, refractories,
insulations, plastics, and glasses. The housing may comprise one
unit of an electrochemical reduction system (e.g., a cathode). The
housing may comprise two or more units of an electrochemical
reduction system (e.g., a cathode and anode). A complete
electrochemical reduction system may be contained within a single
housing.
[0148] The housing may include one or more walls. The housing may
include one or more compartments. The housing may have a
cross-section that is circular, triangular, square, rectangular,
pentagonal, hexagonal, or partial shapes or combinations of shapes
thereof. The housing may be single-piece or formed of multiple
pieces (e.g., pieces welded together). The housing may include a
coating on an interior portion thereof. Such coating may prevent
reaction with a surface in the interior portion of the housing,
such as corrosion or an oxidation/reduction reaction with the
surface.
[0149] An electrochemical reduction system may comprise a cathode,
an anode and an electrolyte solution that collectively provide the
necessary components for the reduction of carbon dioxide to other
chemical species. The electrolyte may comprise an aqueous salt
solution that is composed with an optimal ionic strength and pH for
the electrochemical reduction of CO or CO.sub.2. An electrolyte may
comprise an aqueous salt solution comprising bicarbonate ions. In
some instances, an electrolyte may comprise an aqueous solution of
sodium bicarbonate or potassium bicarbonate. In some instances,
bicarbonate ions may dissociate in the presence of one or more
catalysts to produce CO or CO.sub.2 molecules for a reduction
reaction. The dissolution of CO or CO.sub.2 into the electrolyte
solution may regenerate or maintain the optimal concentration of
bicarbonate ions.
[0150] An electrochemical reduction system may be configured to
operate at an optimal processing temperature. An electrochemical
reduction system or any component thereof may have an operating
temperature of about -30.degree. C., -20.degree. C., -10.degree.
C., 0.degree. C., 5.degree. C., 10.degree. C., 15.degree. C.,
20.degree. C., 25.degree. C., 30.degree. C., 35.degree. C.,
40.degree. C., 50.degree. C., 60.degree. C., 70.degree. C., or
about 80.degree. C. An electrochemical reduction system or any
component thereof may have an operating temperature of at least
about -30.degree. C., -20.degree. C., -10.degree. C., 0.degree. C.,
5.degree. C., 10.degree. C., 15.degree. C., 20.degree. C.,
25.degree. C., 30.degree. C., 35.degree. C., 40.degree. C.,
50.degree. C., 60.degree. C., 70.degree. C., or about 80.degree. C.
or more. An electrochemical reduction system or any component
thereof may have an operating temperature of no more than about
80.degree. C., 75.degree. C., 70.degree. C., 65.degree. C.,
60.degree. C., 55.degree. C., 50.degree. C., 45.degree. C.,
40.degree. C., 35.degree. C., 30.degree. C., 25.degree. C.,
20.degree. C., 15.degree. C., 10.degree. C., 5.degree. C.,
0.degree. C., -5.degree. C., -10.degree. C., -20.degree. C., or
about -30.degree. C. or less.
[0151] An electrochemical reduction system may be configured to
operate at an optimal voltage for the reduction of CO or CO.sub.2
to reduced products. An electrochemical reduction system may be
arranged in a stack or series configuration to tailor the system
voltage to an optimal value. An electrochemical reduction system
may have an operating voltage of about 0.1 volts (V), 0.2V, 0.3V,
0.4V, 0.5V, 0.75V, 1.0V, 2.0V, 3.0V, 4.0V, 5.0V, 10 V, 15V, or
about 20V. An electrochemical reduction system may have an
operating voltage of at least about 0.1 volts (V), 0.2V, 0.3V,
0.4V, 0.5V, 0.75V, 1.0V, 2.0V, 3.0V, 4.0V, 5.0V, 10 V, 15V, or
about 20V or more. An electrochemical reduction system may have an
operating voltage of no more than about 20V, 15V, 10V, 5.0V, 4.0V,
3.0V, 2.0V, 1.0V, 0.75V, 0.5V, 0.4V, 0.3V, 0.2V, or about 0.1V or
less.
[0152] An electrochemical reduction system may have an optimal
cathode current density. In some instances, the cathode current
density may determine the rate of CO or CO.sub.2 reduction at the
cathode. A cathode may be characterized by an overall
electrochemical efficiency. An overall electrochemical efficiency
may be defined as the percentage of electrical energy converted
into chemical energy. A cathode may have a cathode current density
of about 10 milliAmps/square centimeter (mA/cm.sup.2), 50
mA/cm.sup.2, 100 mA/cm.sup.2, 150 mA/cm.sup.2, 200 mA/cm.sup.2, 250
mA/cm.sup.2, 300 mA/cm.sup.2, 350 mA/cm.sup.2, 400 mA/cm.sup.2, 450
mA/cm.sup.2, 500 mA/cm.sup.2, 600 mA/cm.sup.2, 700 mA/cm.sup.2, 800
mA/cm.sup.2, 900 mA/cm.sup.2, or about 1000 mA/cm.sup.2. A cathode
may have a cathode current density of at least about 10
mA/cm.sup.2, 50 mA/cm.sup.2, 100 mA/cm.sup.2, 150 mA/cm.sup.2, 200
mA/cm.sup.2, 250 mA/cm.sup.2, 300 mA/cm.sup.2, 350 mA/cm.sup.2, 400
mA/cm.sup.2, 450 mA/cm.sup.2, 500 mA/cm.sup.2, 600 mA/cm.sup.2, 700
mA/cm.sup.2, 800 mA/cm.sup.2, 900 mA/cm.sup.2, or about 1000
mA/cm.sup.2 or more. A cathode may have a cathode current density
of no more than about 1000 mA/cm.sup.2, 900 mA/cm.sup.2, 800
mA/cm.sup.2, 700 mA/cm.sup.2, 600 mA/cm.sup.2, 500 mA/cm.sup.2, 450
mA/cm.sup.2, 400 mA/cm.sup.2, 350 mA/cm.sup.2, 300 mA/cm.sup.2, 250
mA/cm.sup.2, 200 mA/cm.sup.2, 150 mA/cm.sup.2, 100 mA/cm.sup.2, 50
mA/cm.sup.2, 0 mA/cm.sup.2 or less.
[0153] A cathode in an electrochemical reduction system may have an
overall electrochemical efficiency. A cathode may have an overall
electrochemical efficiency of about 5%, 10%, 15%, 20%, 25%, 30%,
35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or
more. A cathode may have an overall electrochemical efficiency of
at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%,
55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or more. A cathode may
have an overall electrochemical efficiency of no more than about
95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%,
30%, 25%, 20%, 15%, 10%, 5% or less.
[0154] An electrolyte may comprise a solution with a particular
ionic strength or molarity. An electrolyte may have an ionic
strength of about 0.01moles/liter (M), 0.05M, 0.1M, 0.2M, 0.3M,
0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1.0M, 1.1M, 1.2M, 1.3M, 1.4M,
1.5M, 2.0M, 2.5M, or about 3.0M. An electrolyte may have an ionic
strength of at least about 0.01M, 0.05M, 0.1M, 0.2M, 0.3M, 0.4M,
0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M,
2.0M, 2.5M, or at least about 3.0M or more. An electrolyte may have
an ionic strength of no more than about 3.0M, 2.5M 2.0M, 1.5M,
1.4M, 1.3M, 1.2M, 1.1M, 1.0M, 0.9M, 0.8M, 0.7M, 0.6M, 0.5M, 0.4M,
0.3M, 0.2M, 0.1M, 0.05M, or no more than about 0.01M or less. A
salt in an electrolyte may have a molarity of about 0.01moles/liter
(M), 0.05M, 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M,
1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 2.0M, 2.5M, or about 3.0M.A
salt in an electrolyte may have a molarity of at least about 0.01M,
0.05M, 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1.0M,
1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 2.0M, 2.5M, or at least about 3.0M or
more. A salt in an electrolyte may have a molarity of no more than
about 3.0M, 2.5M 2.0M, 1.5M, 1.4M, 1.3M, 1.2M, 1.1M, 1.0M, 0.9M,
0.8M, 0.7M, 0.6M, 0.5M, 0.4M, 0.3M, 0.2M, 0.1M, 0.05M, or no more
than about 0.01M or less. A salt in an electrolyte may have a
molarity in a range from about 0.01M to about 0.1M, about 0.01M to
about 0.2M, about 0.01M to about 0.5M, about 0.01M to about 1.0M,
about 0.01M to about 3.0M, about 0.1M to about 0.2M, about 0.1M to
about 0.5M, about 0.1M to about 1.0M, about 0.1M to about 3.0M,
about 0.2M to about 0.5M, about 0.2M to about 1.0M, about 0.2M to
about 3.0M, about 0.5M to about 1.0M, about 0.5M to about 3.0M, or
about 1.0M to about 3.0M.
[0155] An electrolyte may have an optimal pH for the
electrochemical reduction of CO.sub.2. An electrolyte may have a pH
of about 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or about 14.
An electrolyte may have a pH of at least about 0, 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14 or more.
[0156] An electrolyte may have a pH of no more than about 14, 13,
12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0 or less. An electrolyte
may have a pH in a range from about 0 to about 2, about 0 to about
3, about 0 to about 4, about 0 to about 5, about 0 to about 7,
about 0 to about 10, about 0 to about 14, about 2 to about 3, about
2 to about 4, about 2 to about 5, about 2 to about 7, about 2 to
about 10, about 2 to about 14, about 3 to about 4, about 3 to about
5, about 3 to about 7, about 3 to about 10, about 3 to about 14,
about 4 to about 5, about 4 to about 7, about 4 to about 10, about
4 to about 14, about 5 to about 7, about 5 to about 10, about 5 to
about 14, about 7 to about 10, about 7 to about 14, or from about
10 to about 14.
[0157] An electrolyte in an electrochemical reduction system may be
a non-aqueous electrolyte. In some instances, an electrolyte may
comprise an ionic liquid with a dissolved salt. An ionic liquid may
include, but is not limited to, midazolium-based fluorinated anion
ionic liquids, midazolium acetates, midazolium fluoroacetates,
pyrrolidinium ionic liquids, or any combination thereof.
[0158] An anode may comprise an elemental metal such as nickel,
tin, or gold. An anode may comprise a wire mesh, metal foam or
other permeable structure of the chosen anode material. An anode
material may be in operative contact with an anion exchange
membrane material or another physical separator that prevents
contact with the cathode.
[0159] A cathode may comprise any appropriate material. In some
instances a cathode may comprise copper nanoparticles and/or
N-doped carbon nanomaterials. In some instances, a cathode may
comprise a micro- or nanostructured membrane material. In some
instances, a cathode may comprise one or more catalysts for the
electrochemical reduction of CO or CO.sub.2 or other chemical
reactions. A cathode material may be in operative contact with an
anion exchange membrane material or another physical separator that
prevents contact with the cathode. In some instances, the distance
between the cathode and anode may be minimized to reduce
resistance. In some instances, forced convective flow of
electrolyte between the electrodes may further reduce electrical
resistance and/or may allow for greater distance between the
electrodes. In some instances the electrodes may be in different
housings. In some instances, the anode and cathode may have a
minimal distance with an ion selective membrane between them. In
some instances no ion selective membrane may be used.
[0160] An electrochemical reduction system may comprise one or more
extractor units. An extractor unit may comprise any unit operation
or separation unit that selectively separates one or more chemical
species from a feed stream. In some instances, an extractor may
comprise a membrane separator. In some instances, an extractor may
comprise a micro- or nanostructured membrane. In some instances, an
extractor may extract one or more chemical species derived from the
reduction of carbon dioxide. In some instances, an extractor may
extract one or more chemical species derived from the reduction of
CO or CO.sub.2 from an electrolyte solution. In other instances, an
extractor may separate one or more chemical species derived from
the subsequent reaction of carbon dioxide electrochemical reduction
products.
[0161] An electrochemical reduction system may comprise one or more
contactor units. A contactor unit may comprise any unit operation
or separation unit that selectively separates one or more chemical
species from a feed stream. In some instances, a contactor may
comprise a gas adsorption column. In other instances, a contactor
may comprise packing to increase a liquid solutions surface area
and a fan to increase gas passage at the liquid interface. Such
contactors may share design features with cooling towers. In other
instances, an extractor may comprise a membrane separator. In some
instances, an extractor may comprise a micro- or nanostructured
membrane. In some instances, a contactor may extract one or more
chemical species from a feed stream. In some instances, a contactor
may extract carbon dioxide from a feed stream. In some instances, a
contactor may separate CO or CO.sub.2 from a feed stream and
dissolve the CO or CO.sub.2 in an electrolyte solution. In some
cases a feed stream may be air. In some cases the feed stream may
be filtered prior to use. Such filtering may in some cases remove
particulate matter and/or volatile organic materials and/or
undesired materials of various kinds. The uptake of CO or CO.sub.2
in a gas contactor may be enhanced by the presence of hydroxide
ions generated within the electrochemical reduction system.
[0162] An electrochemical reduction system may comprise one or more
ion exchange membranes. An ion exchange membrane may comprise a
cation exchange membrane, an anion exchange membrane, or a bipolar
membrane. An ion exchange membrane may be in operative contact with
a cathode, an anode, or both a cathode and anode. In some
instances, an electrochemical reduction system may comprise no ion
exchange membranes.
[0163] Various embodiments of chemical reduction systems utilizing
micro- or nanostructured membranes may be conceived. In an
embodiment, depicted in FIG. 6, an electrolyte solution with an
optimal pH (1) may be introduced to a chemical reduction unit (2),
where CO.sub.2 is introduced to the electrolyte and reduced by a
catalyst to useful reduced carbon products (RCPs). In some
instances, CO.sub.2 is captured in a separate unit operation and
introduced into the chemical reduction unit as a gas. In some
instances, CO.sub.2 is captured in a separate unit operation and
introduced as a component of the electrolyte. In some instances,
the chemical reduction unit may consist of various housings, tanks,
pumps, or other elements used to operate the unit. In some cases,
separate catholyte and anolyte reservoirs may be used. In some
cases, pumping may be used to circulate catholyte and anolyte to an
electrolysis stack. In some instances, the catholyte reservoir may
also be a vapor liquid separator. In some instances, heat
exchangers and cooling or heating systems may be used to maintain
desired temperatures in the various reservoirs, stack, or other
unit elements. In some instances, the chemical reduction unit (2)
may comprise a micro- or nanostructured membrane. The micro- or
nanostructured membrane may comprise one or more catalysts. In
other instances, a catalysis process may comprise a conventional
electrochemical "stack", comprising an anode and cathode within the
same housing. In some instances, an ion exchange membrane may be
used. In some instances, various catalytic membranes may be used,
or otherwise achieve the desired reduction of CO.sub.2 by other
methods of reduction. Oxygen or other oxidized species may also be
produced by such a process and released to the atmosphere or
directed to beneficial use. An stream containing RCPs (3) is
directed to an extractor (4), where the RCPs are extracted. In some
instances, the RCP stream is a liquid electrolyte. In some
instances, the RCP stream is a vapor. In some instances, the RCP
stream is a vapor collected from the gas space above the
electrolyte. In some instances the gas space is integral to the
chemical reduction unit. In some cases, the gas space is part of a
vapor liquid separator which may be in a separate casing. In some
instances the vapor liquid separator may also be the catholyte
reservoir. In some instances, the extractor may comprise a membrane
extractor. A membrane extractor may comprise a micro- or
nanostructured membrane material. RCPs may be extracted through the
pores or channels of the micro- or nanostructured membrane due to
pressure or chemical potential differences (for example, as
produced by a vacuum downstream of the lumen or backing side of the
membrane), producing an RCP product stream (5) which is condensed
or otherwise collected by a collector unit. A collector unit may
comprise a condenser. In some instance, a collector unit may
comprise a heat exchange condenser, an adsorption unit or other
capture processes. In other instances, the collector system may be
understood to mean any of a variety of product capture and/or
further processing steps, which may include, by way of non-limiting
examples, condensation, adsorption, re-pressurization, further
reactions (such as further catalysis for polymerization or other
formation of longer chain hydrocarbons, etc). The collected RCPs
may be directed to further processes or uses in stream (7). A
stream of any non-condensable, non-collectable, or intentionally
not collected gases (8) may be recompressed by a vacuum pump (9)
and ejected to the environment or collected for further usage in a
product stream (10). In some cases, non-collected gases may include
reduced matter such as H.sub.2, CO, CH.sub.4 or other gases,
including alcohols. In some cases, non-collected gases may be put
to beneficial use. In some instances, beneficial use may include
generation of electricity in a fuel cell or other unit operation,
which may use O.sub.2 generated by the chemical reduction process.
In some instances, non-collected gases may be used prior to a
vacuum pump. In some instances, non-collected gases may be sold or
used to make secondary products. After RCP extraction, the RCP
containing stream, which may be substantially depleted of RCPs or
may have a baseline recirculated concentration of RCPs (as may be
needed to optimize various features or operations of the process,
such as, for example, extraction) is returned to the chemical
reduction unit as a feed stream (1).
[0164] In another embodiment, depicted in FIG. 7, an electrolyte
solution (1) may be directed to a chemical reduction unit (2),
where CO or CO.sub.2 is reduced to RCPs. An electrolyte solution
containing RCPs (3) is directed to an extractor (4), where the RCPs
are extracted. In some instances, the extractor may employ a vapor
liquid separator such that RCPs may be extracted from the vapor
stream above the electrolyte. In some instances, the extractor may
comprise a membrane extractor. A membrane extractor may comprise a
micro- or nanostructured membrane material. RCPs may be extracted
through the pores or channels of the micro- or nanostructured
membrane due to pressure or chemical potential differences (for
example, as produced by a vacuum downstream of the lumen or backing
side of the membrane), producing an RCP product stream (5) which is
condensed or otherwise collected by a collector unit. A collector
unit may comprise a condenser. In some instance, a collector unit
may comprise a heat exchange condenser, an adsorption unit or other
capture processes. In other instances, the collector system may be
understood to mean any of a variety of product capture and/or
further processing steps, which may include, by way of non-limiting
examples, condensation, adsorption, re-pressurization, further
reactions (such as further catalysis for polymerization or other
formation of longer chain hydrocarbons, etc). The collected RCPs
may be directed to further processes or uses in stream (7). A
stream of any non-condensable or otherwise non-collectable gases
(8) may be recompressed by a vacuum pump (9) and ejected to the
environment or collected for further usage in a product stream
(10). The electrolyte stream which may be either largely depleted
of RCPs or has some recirculating concentration thereof, is
directed to a contactor (12). The contactor may comprise a membrane
for separating one or more gases from a gas feed stream, or utilize
any other approach for contacting a gas with an electrolyte stream.
A contactor membrane may comprise a micro- or nanostructured
membrane. A gas feed stream may comprise air, an effluent gas, or
any other gas stream comprising CO or CO.sub.2 (13). In some
instances, the hydroxides formed in the electrolyte in the chemical
reduction unit may be the primary adsorbing species in the
electrolyte to capture CO or CO.sub.2. In some instances, the
electrolyte stream in a contactor may have its pH controlled for
optimal CO or CO.sub.2 adsorption by the addition of hydroxide
species, such as sodium hydroxide or potassium hydroxide. A CO or
CO.sub.2 depleted air stream may be directed to an atmospheric
purge of another use. An electrolyte solution with the desired pH
and concentration of carbonate species may be returned as a feed
stream (1) for reuse in the chemical reduction system.
[0165] In another embodiment, depicted in FIG. 8, an electrolyte
stream is directed to a cathode unit. In some instances, the
cathode unit may comprise a micro- or nanostructured membrane. In
some instances, the cathode unit may comprise a micro- or
nanostructured membrane comprising nitrogen doped carbon
nanomaterials with copper nanoparticles (which may include further
deposition of NCMs to the membrane surface during its fabrication
or thereafter to facilitate improved electrical conductivity or
other characteristics). At the cathode unit, CO or CO.sub.2 may be
reduced to RCPs. The RCPS may be extracted by the a membrane
(through the membrane to the backing layer, or lumen) (2),
producing an RCP product stream (3) which is collected in a
condenser (4), and produced as an RCP product stream (5). Any
non-condensable gases (6) may be recompressed by a vacuum pump (7)
to maintain system vacuum or otherwise processed, and ejected to
the environment or subsequently put to some other use (8). The
cathode electrolyte outlet stream (9) is directed to a contactor
(10), which may contacts the electrolyte solution with air, an
effluent gas, or any other gas stream comprising CO or CO.sub.2
(11), allowing the electrolyte to adsorb CO or CO.sub.2. CO- or
CO.sub.2-depleted air is directed to an outlet stream (12). The
electrolyte stream containing adsorbed CO or CO.sub.2 (13) is
directed to an anode unit (14). In some instances, the anode unit
is in the same housing as the cathode unit. In some instances, the
distance between the cathode and anode are minimized. In some
cases, an ion exchange membrane is used between the cathode and
anode. An anode may comprise a membrane. In some instances, an
anode may comprise a micro- or nanostructured material that may be
of any type, such as a membrane comprising a carbon nanomaterial
with reduced nanoparticle platinum or a similar catalyst (such as
nickel, indium oxide or others with similar performance
characteristics, for example). The electrolyte solution may be
directed from one side of the membrane to the other to increase
mass transfer to the catalyst sites. Oxygen and hydrogen (in the
form of hydronium, lowering pH) may be produced in the anode unit,
completing the electrocatalytic circuit. The anode unit and the
cathode may be electrically connected. In some instance, the anode
and cathode units may be incorporated within a single chemical
reduction unit. If any residual RCPs are in stream (13), they may
be oxidized in the anode unit. In some instances, it may be optimal
to have some amount of oxidized RCP species available in the
post-anode electrolyte stream to optimize system cost or
performance. Electrolyte solution containing oxygen and any CO or
CO.sub.2 that may have been released by the lowering of the pH of
the solution (15) may be directed to a vapor liquid separator unit
(VLS) (16), where gases are directed to stream (17), and liquids to
stream (18). Liquids produced from a VLS unit may be directed back
to the cathode unit for reuse. In this and other embodiments in
which an anode and contactor are present, the relative order of
these two operations is often interchangeable, in that the
contactor may come before the anode, or after, as desired. If the
contactor comes after the anode, oxygen release and CO or CO.sub.2
capture may potentially be achieved in the same unit operation.
[0166] In another embodiment, depicted in FIG. 9, an electrolyte
solution (1) is directed to a cathode unit (2). In some instances,
the cathode unit may comprise a micro- or nanostructured membrane.
In some instances, the cathode unit may comprise a micro- or
nanostructured membrane comprising nitrogen doped carbon
nanomaterials with copper nanoparticles. The cathode unit membrane
may have an external electric field applied axially to the
direction of water transport in the nanopores or channels, such
that RCPs are substantially rejected by the membrane, such that
largely RCP-depleted electrolyte is directed to stream (3), and an
electrolyte stream with an increased concentration of RCPs is
produced as stream (4). The RCP concentration of stream (4) may be
increased with a longer cathode membrane feed channel (removing
electrolyte solution while retaining RCPs which are continuously
produced at the membrane surface). The RCP containing electrolyte
stream (4) may be directed to an extractor (5). In some instances,
the extractor may comprise a membrane extractor. A membrane
extractor may comprise a micro- or nanostructured membrane
material. RCPs may be extracted through the pores or channels of
the micro- or nanostructured membrane due to pressure or chemical
potential differences (for example, as produced by a vacuum
downstream of the lumen or backing side of the membrane), producing
an RCP product stream (5) which is condensed or otherwise collected
by a collector unit, producing an RCP product stream (8). Any
non-condensable gases (9) may be recompressed by a vacuum pump (10)
to maintain system vacuum, or subjected to any other processing
method, and ejected to the environment or subsequently put to some
beneficial use (11). The extractor electrolyte product stream (12)
is directed to an anode (13), where oxygen generation and pH
reduction may occur. In some instances, the anode unit is in the
same housing as the cathode unit. In some instances, the distance
between the cathode and anode are minimized. In some cases, an ion
exchange membrane is used between the cathode and anode. An oxygen
containing stream (14) may be directed to a VLS (15), producing a
gas outlet stream (16) and a liquid outlet stream (17). The
RCP-depleted electrolyte stream (3) may be directed to a contactor
(18), where it is contacted with air, and effluent gas, or any
other gas stream comprising CO.sub.2 (19), causing adsorption of CO
or CO.sub.2 to the electrolyte, facilitated by the increase in pH
that occurs during the CO or CO.sub.2 reduction. CO or CO.sub.2
reduced or depleted air may be directed to an outlet stream (20).
Electrolyte solution containing RCPs and adsorbed CO or CO.sub.2
(21) may be combined or mixed with stream (17), forming an
electrolyte stream (1) for reuse in the cathode unit.
[0167] In another embodiment, shown in FIG. 10, an electrolyte
stream (1) is directed to a cathode unit comprising a membrane (2).
In some instances, the cathode may comprise a micro-or
nanostructured membrane. A gas feed stream comprising CO or
CO.sub.2 (3) is introduced to the electrolyte from the back of the
membrane, such that it may become readily available to the catalyst
at the membrane surface. The CO or CO.sub.2 may be substantially
pure, and may be from a variety of sources, including capture from
a combustion source, geothermal source, direct air capture, or
other sources, as may be desired. An RCP-containing electrolyte
stream (4) may be directed to an extractor (5), where RCPs (6) are
extracted to a collector (7) and produced as stream (8).
Non-condensable gases (NCGs) (9) are directed to a vacuum pump (10)
and directed to stream (11). Post-extractor electrolyte solution
(12) may be directed to an anode (13). In some instances, the anode
unit is in the same housing as the cathode unit. In some instances,
the distance between the cathode and anode are minimized. In some
cases, an ion exchange membrane is used between the cathode and
anode. Oxygen-containing solution (14) produced at the anode may be
directed to a VLS (15), producing and outlet gas stream (16) and an
outlet liquid stream (17), which may be recycled to the cathode
unit.
[0168] In another embodiment, shown in FIG. 11, an electrolyte
solution (1) may introduced to a cathode unit comprising a membrane
from the back or lumen side. In some instances, the cathode unit
membrane may comprise a micro- or nanostructured membrane. The
electrolyte solution may flow to an active catalyst surface, where
CO or CO.sub.2 is reduced to RCPs. High efficiency utilization of
catalyst use may be expected by introducing reactants at an ideal
pH directly to the catalyst site in this manner. The RCP-containing
electrolyte stream (3) is directed to an extractor (4), where RCPs
(5) are extracted to a collector (6), and produced as an RCP
product stream (7). Non-condensable gases (NCGs) (8) are directed
to a vacuum pump (9) and directed to an outlet stream (10).
Post-extractor electrolyte solution (11) is directed to an anode
unit (12). In some instances, the anode unit is in the same housing
as the cathode unit. In some instances, the distance between the
cathode and anode are minimized. In some cases, an ion exchange
membrane is used between the cathode and anode. Oxygen-containing
solution that may be produced in the anode unit (13) is directed to
a VLS (14), producing a gas outlet stream (15) and a liquid outlet
stream (16), which becomes a recycled feed stream (1) for
reuse.
[0169] In another embodiment, shown in FIG. 12, an electrolyte
solution comprising CO or CO.sub.2 (1) is directed to an extracting
catalytic membrane (2), where RCPs may be produced. An
RCP-containing electrolyte stream (3) may be directed to a
condenser (4), and produced as an RCP product stream (5). NCGs (6)
are directed to a vacuum pump (7) and become outlet stream 8. A
post-extractor electrolyte solution, which may be largely depleted
of RCPs or have a desired minimum recirculating concentration of
RCPs, is directed to an ion exchange membrane (10), to allow for
exchange of either OH- anions (in the case of an anion exchange
membrane), or H+ ions (in the case of a proton (or cation) exchange
membrane), from stream (11) to equilibrate the pH as required for
the continued operation of the catalysis circuit, and to protect
RCPs in stream (9) from oxidation that may be expected to occur in
contact with the anode or its immediate environment. An
ion-exchanged electrolyte stream may be directed to an anode unit
(17). In some instances, the anode unit is in the same housing as
the cathode unit. In some instances, the distance between the
cathode and anode are minimized. In some cases, an ion exchange
membrane is used between the cathode and anode. In some instances,
the flows indicated are diffusive. In some instances, the flows
indicated are recirculating flows intended to assist in the
reduction of boundary layers and improve mass transport. This
configuration allows a high circulating concentration of RCPs, if
desired, which may improve the RCP extraction and/or offer other
benefits. The pH equilibrated stream (13) is directed to a
contactor (14), where CO or CO.sub.2 is adsorbed from air, an
effluent gas, or any other gas stream comprising CO or CO.sub.2
(15). CO or CO.sub.2 depleted air may be directed to outlet stream
(16). The reconstituted electrolyte stream (1) may be directed for
reuse in the cathode unit. In the anode system, oxygen may be
produced and pH may be reduced. Oxygen-containing solution (18) may
be directed to a VLS (19), producing outlet product gases (20) and
outlet liquids (21), which may be recycled as stream (11) for
reuse. In this and other embodiments where both a contactor and an
ion exchange membrane are used, the relative order of these
operations may be changed, for example having the contactor prior
to the ion exchange or vice versa, as may be beneficial to system
optimization.
[0170] In another embodiment, shown in FIG. 13, an electrolyte
solution (1) is directed to a cathode unit (2) where RCPs may be
produced. In some instances, the cathode unit may comprise a micro-
or nanostructured membrane. In some instances, the cathode unit may
comprise a catalyst comprising nitrogen doped carbon nanomaterials
with copper nanoparticles. In some instances, the cathode unit may
comprise a micro- or nanostructured membrane comprising nitrogen
doped carbon nanomaterials with copper nanoparticles. An RCP
bearing electrolyte stream (3) is directed to an extractor (4). A
substantially purified RCP stream (5) is directed to a collector,
producing a product stream (7). NCGs or other non-collected
substances (8) are directed to a subsequent separation unit(s) or
process, such as a vacuum pump (9), becoming outlet stream (10).
Post-extractor electrolyte solution (11) is directed to an ion
exchange (IX) membrane (12), where pH is equilibrated between
streams (11) and (13), producing electrolyte streams (14) (cathode
side), and (15) (anode side). Stream (15) is directed to an anode
unit (16) that may produce an oxidized species-rich stream (17),
which is directed to a separator device (here denoted VLS) (18),
separating the oxidized species from the electrolyte stream (20),
which is reused as stream (13). Stream (14) is directed to a
contactor, where it is contacted with a CO or CO.sub.2 source (22),
resulting in a CO or CO.sub.2 depleted outlet stream (23), and an
electrolyte stream with desired characteristics (24) for recycle to
the cathode unit. In some instances, the anode unit is in the same
casing as the cathode unit. In some instances, the distance between
the cathode and anode are minimized. In some cases, an ion exchange
membrane is used between the cathode and anode. In some instances,
the flows indicated are diffusive. In some instances, the flows
indicated are recirculating flows intended to assist in the
reduction of boundary layers and improve mass transport.
[0171] In another embodiment, shown in FIG. 14, an electrolyte
solution (1) is directed to a cathode unit (2) where RCPs may be
produced. In some instances, the cathode unit may comprise a micro-
or nanostructured membrane. In some instances, the cathode unit may
comprise a micro- or nanostructured membrane comprising nitrogen
doped carbon nanomaterials with copper nanoparticles. An RCP
containing electrolyte stream (3) may be directed to an extractor
(4). A substantially-purified RCP stream (5) may be directed to a
collector (6), producing an RCP product stream (7). NCGs or other
non-collected substances (8) may be directed to a subsequent
separation unit(s) or process, such as a vacuum pump (9), becoming
outlet stream (10). A post-extractor electrolyte stream (11) may be
directed to an ion exchange (IX) membrane (12), where pH may be
equilibrated between streams (11) and (13), producing streams (14)
(cathode side), and (15) (anode side). Stream (15) may be directed
to an anode unit (16), producing oxidized species rich stream (17),
which may be directed to a separator device (here denoted VLS)
(18), separating the oxidized species from the electrolyte stream
(20), which may be reused as stream (13). Stream (14) becomes an
electrolyte stream with desired characteristics (14) for reuse. A
CO or CO.sub.2 source (21), which may be substantially pure, may be
introduced to the cathode membrane such that it is introduced to
the active catalytic sites from the backing or lumen side of a
membrane, which may result in a high availability and efficient
utilization of the reactant at the catalyst sites. . In some
instances, the anode unit is in the same housing as the cathode
unit. In some instances, the distance between the cathode and anode
are minimized. In some cases, an ion exchange membrane is used
between the cathode and anode. In some instances, the flows
indicated are diffusive. In some instances, the flows indicated are
recirculating flows intended to assist in the reduction of boundary
layers and improve mass transport.
[0172] It shall be understood that the systems and processes for
any described embodiment of the chemical reduction system may be
utilized in any other embodiment of the chemical reduction system.
For example, a particular cathode, anode, collector, extractor,
contactor or vapor-liquid system may be applied to any embodiment
of the chemical reduction system when appropriate. In some
instances, the differences in system configuration for various
embodiments may favor the selection of differing system components
to produce optimal system performance and processing
conditions.
Computer Systems
[0173] The present disclosure provides computer systems that are
programmed to implement methods of the disclosure. FIG. 15 shows a
computer control system 1501 that is programmed or otherwise
configured to control a chemical reduction system or a process
within a chemical reduction system (e.g. controlling and balancing
the pH of an electrolyte stream). The computer control system 1501
can regulate various aspects of the methods of the present
disclosure, such as, for example, methods of producing a reduced
carbon product or monitoring for potentially hazardous operating
conditions. The computer control system 1501 can be implemented on
an electronic device of a user or a computer system that is
remotely located with respect to the electronic device. The
electronic device can be a mobile electronic device.
[0174] The computer system 1501 includes a central processing unit
(CPU, also "processor" and "computer processor" herein) 1505, which
can be a single core or multi core processor, or a plurality of
processors for parallel processing. The computer control system
1501 also includes memory or memory location 1510 (e.g.,
random-access memory, read-only memory, flash memory), electronic
storage unit 1515 (e.g., hard disk), communication interface 1520
(e.g., network adapter) for communicating with one or more other
systems, and peripheral devices 1525, such as cache, other memory,
data storage and/or electronic display adapters. The memory 1510,
storage unit 1515, interface 1520 and peripheral devices 1525 are
in communication with the CPU 1505 through a communication bus
(solid lines), such as a motherboard. The storage unit 1515 can be
a data storage unit (or data repository) for storing data. The
computer control system 1501 can be operatively coupled to a
computer network ("network") 1530 with the aid of the communication
interface 1520. The network 1530 can be the Internet, an internet
and/or extranet, or an intranet and/or extranet that is in
communication with the Internet. The network 1530 in some cases is
a telecommunication and/or data network. The network 1530 can
include one or more computer servers, which can enable distributed
computing, such as cloud computing. The network 1530, in some cases
with the aid of the computer system 1501, can implement a
peer-to-peer network, which may enable devices coupled to the
computer system 1501 to behave as a client or a server.
[0175] The CPU 1505 can execute a sequence of machine-readable
instructions, which can be embodied in a program or software. The
instructions may be stored in a memory location, such as the memory
1510. The instructions can be directed to the CPU 1505, which can
subsequently program or otherwise configure the CPU 1505 to
implement methods of the present disclosure. Examples of operations
performed by the CPU 1505 can include fetch, decode, execute, and
writeback.
[0176] The CPU 1505 can be part of a circuit, such as an integrated
circuit. One or more other components of the system 1501 can be
included in the circuit. In some cases, the circuit is an
application specific integrated circuit (ASIC).
[0177] The storage unit 1515 can store files, such as drivers,
libraries and saved programs. The storage unit 1515 can store user
data, e.g., user preferences and user programs. The computer system
1501 in some cases can include one or more additional data storage
units that are external to the computer system 1501, such as
located on a remote server that is in communication with the
computer system 1501 through an intranet or the Internet.
[0178] The computer system 1501 can communicate with one or more
remote computer systems through the network 1530. For instance, the
computer system 1501 can communicate with a remote computer system
of a user (e.g., a user controlling the manufacture of a slurry
coated substrate). Examples of remote computer systems include
personal computers (e.g., portable PC), slate or tablet PC's (e.g.,
Apple.RTM. iPad, Samsung.RTM. Galaxy Tab), telephones, Smart phones
(e.g., Apple.RTM. iPhone, Android-enabled device, Blackberry.RTM.),
or personal digital assistants. The user can access the computer
system 1501 via the network 1530.
[0179] Methods as described herein can be implemented by way of
machine (e.g., computer processor) executable code stored on an
electronic storage location of the computer system 1501, such as,
for example, on the memory 1510 or electronic storage unit 1515.
The machine executable or machine readable code can be provided in
the form of software. During use, the code can be executed by the
processor 1505. In some cases, the code can be retrieved from the
storage unit 1515 and stored on the memory 1510 for ready access by
the processor 1505. In some situations, the electronic storage unit
1515 can be precluded, and machine-executable instructions are
stored on memory 1510.
[0180] The code can be pre-compiled and configured for use with a
machine having a processer adapted to execute the code, or can be
compiled during runtime. The code can be supplied in a programming
language that can be selected to enable the code to execute in a
pre-compiled or as-compiled fashion.
[0181] Aspects of the systems and methods provided herein, such as
the computer system 401, can be embodied in programming. Various
aspects of the technology may be thought of as "products" or
"articles of manufacture" typically in the form of machine (or
processor) executable code and/or associated data that is carried
on or embodied in a type of machine readable medium.
Machine-executable code can be stored on an electronic storage
unit, such as memory (e.g., read-only memory, random-access memory,
flash memory) or a hard disk. "Storage" type media can include any
or all of the tangible memory of the computers, processors or the
like, or associated modules thereof, such as various semiconductor
memories, tape drives, disk drives and the like, which may provide
non-transitory storage at any time for the software programming.
All or portions of the software may at times be communicated
through the Internet or various other telecommunication networks.
Such communications, for example, may enable loading of the
software from one computer or processor into another, for example,
from a management server or host computer into the computer
platform of an application server. Thus, another type of media that
may bear the software elements includes optical, electrical and
electromagnetic waves, such as used across physical interfaces
between local devices, through wired and optical landline networks
and over various air-links. The physical elements that carry such
waves, such as wired or wireless links, optical links or the like,
also may be considered as media bearing the software. As used
herein, unless restricted to non-transitory, tangible "storage"
media, terms such as computer or machine "readable medium" refer to
any medium that participates in providing instructions to a
processor for execution.
[0182] Hence, a machine readable medium, such as
computer-executable code, may take many forms, including but not
limited to, a tangible storage medium, a carrier wave medium or
physical transmission medium. Non-volatile storage media include,
for example, optical or magnetic disks, such as any of the storage
devices in any computer(s) or the like, such as may be used to
implement the databases, etc. shown in the drawings. Volatile
storage media include dynamic memory, such as main memory of such a
computer platform. Tangible transmission media include coaxial
cables; copper wire and fiber optics, including the wires that
comprise a bus within a computer system. Carrier-wave transmission
media may take the form of electric or electromagnetic signals, or
acoustic or light waves such as those generated during radio
frequency (RF) and infrared (IR) data communications. Common forms
of computer-readable media therefore include for example: a floppy
disk, a flexible disk, hard disk, magnetic tape, any other magnetic
medium, a CD-ROM, DVD or DVD-ROM, any other optical medium, punch
cards paper tape, any other physical storage medium with patterns
of holes, a RAM, a ROM, a PROM and EPROM, a FLASH-EPROM, any other
memory chip or cartridge, a carrier wave transporting data or
instructions, cables or links transporting such a carrier wave, or
any other medium from which a computer may read programming code
and/or data. Many of these forms of computer readable media may be
involved in carrying one or more sequences of one or more
instructions to a processor for execution.
[0183] The computer system 1501 can include or be in communication
with an electronic display 1535 that comprises a user interface
(UI) 1540 for providing, for example, parameters for producing a
reduced carbon product. Examples of UI's include, without
limitation, a graphical user interface (GUI) and web-based user
interface.
[0184] Methods and systems of the present disclosure can be
implemented by way of one or more algorithms. An algorithm can be
implemented by way of software upon execution by the central
processing unit 1505. The algorithm can, for example, regulate the
flow rate of a gas stream comprising CO.sub.2 through a contactor
unit to optimize the pH or bicarbonate concentration of an
electrolyte solution. As another example, the algorithm can
regulate the electric field applied to a micro- or nanostructured
membrane to control the selectivity of the membrane for a
particular chemical species.
[0185] While preferred embodiments of the present invention have
been shown and described herein, it will be obvious to those
skilled in the art that such embodiments are provided by way of
example only. It is not intended that the invention be limited by
the specific examples provided within the specification. While the
invention has been described with reference to the aforementioned
specification, the descriptions and illustrations of the
embodiments herein are not meant to be construed in a limiting
sense. Numerous variations, changes, and substitutions will now
occur to those skilled in the art without departing from the
invention. Furthermore, it shall be understood that all aspects of
the invention are not limited to the specific depictions,
configurations or relative proportions set forth herein which
depend upon a variety of conditions and variables. It should be
understood that various alternatives to the embodiments of the
invention described herein may be employed in practicing the
invention. It is therefore contemplated that the invention shall
also cover any such alternatives, modifications, variations or
equivalents. It is intended that the following claims define the
scope of the invention and that methods and structures within the
scope of these claims and their equivalents be covered thereby.
* * * * *