U.S. patent application number 14/992488 was filed with the patent office on 2016-05-05 for method and apparatus for a photocatalytic and electrocatalytic copolymer.
The applicant listed for this patent is Viceroy Chemical, Inc.. Invention is credited to Ed Chen, Tara Cronin.
Application Number | 20160122883 14/992488 |
Document ID | / |
Family ID | 49714410 |
Filed Date | 2016-05-05 |
United States Patent
Application |
20160122883 |
Kind Code |
A1 |
Cronin; Tara ; et
al. |
May 5, 2016 |
METHOD AND APPARATUS FOR A PHOTOCATALYTIC AND ELECTROCATALYTIC
COPOLYMER
Abstract
A method and apparatus for a photocatalytic and electrolytic
catalyst includes in various aspects one or more catalysts, a
method for forming a catalyst, an electrolytic cell, and a reaction
method.
Inventors: |
Cronin; Tara; (New York,
NY) ; Chen; Ed; (New York, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Viceroy Chemical, Inc. |
New York |
NY |
US |
|
|
Family ID: |
49714410 |
Appl. No.: |
14/992488 |
Filed: |
January 11, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13837372 |
Mar 15, 2013 |
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14992488 |
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61696608 |
Sep 4, 2012 |
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61657975 |
Jun 11, 2012 |
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Current U.S.
Class: |
205/340 ;
204/277; 205/431; 205/437; 205/440; 205/441; 205/444; 205/446;
205/448; 205/450; 205/461 |
Current CPC
Class: |
B01J 31/10 20130101;
C25B 9/00 20130101; B01J 2531/16 20130101; C25B 3/06 20130101; B01J
2531/845 20130101; B01J 2531/22 20130101; B01J 31/1616 20130101;
C25B 3/00 20130101; C25B 15/08 20130101; B01J 2531/025 20130101;
B01J 31/003 20130101; B01J 31/183 20130101; B01J 31/184
20130101 |
International
Class: |
C25B 3/00 20060101
C25B003/00; C25B 3/06 20060101 C25B003/06; C25B 9/00 20060101
C25B009/00 |
Claims
1. An electrolytic cell, comprising: at least one reaction chamber
into which, during operation, an aqueous electrolyte and a gaseous
feedstock are introduced, wherein the gaseous feedstock comprises a
carbon-based gas; and a pair of reaction electrodes disposed within
the reaction chamber, at least one of the reaction electrodes
including a catalyst comprising a first component selected from
protein enzymes, metabolic factors, organometallic compounds,
porphyrins and combinations thereof and a second component bonded
to the first component, wherein the second component is selected
from fluorinated sulfonic acid based polymers, polyaniline and
combinations thereof; wherein the catalyst, the aqueous electrolyte
and the gaseous feedstock, define a three-phase interface.
2. The electrolytic cell of claim 1, wherein the aqueous
electrolyte is selected from potassium chloride, potassium bromide,
potassium iodide, or hydrogen chloride.
3. The electrolytic cell of claim 1, wherein the carbon-based gas
comprises a non-polar gas, a carbon oxide, or a mixture of the
two.
4. The electrolytic cell of claim 1, wherein the non-polar gases
include a hydrocarbon gas.
5. The electrolytic cell of claim 1, wherein the carbon oxide
includes carbon monoxide, carbon dioxide, or a mixture of the
two.
6. The electrolytic cell of claim 1, wherein the gaseous feedstock
is a greenhouse gas.
7. The electrolytic cell of claim 1, wherein the first component
selected from chlorophyll, ribulose-1,5-bisphosphate carboxylase
oxygenase, chlorophyllin, azurite, tetramethoxyphenylporphyrin
hemoglobin, ferritin, co-enzyme Q, derivatives thereof and
combinations thereof.
8. The electrolytic cell of claim 1, wherein the metabolic factor
is selected from vitamins.
9. The electrolytic cell of claim 1, wherein the metabolic factor
is vitamin B12.
10. The electrolytic cell of claim 1 wherein the catalyst comprises
a film of the first component and the second component.
11. The electrolytic cell of claim 1, wherein the first component
is incorporated into a membrane formed of the second component.
12. The electrolytic cell of claim 1, wherein the catalyst further
comprises a support material.
13. The electrolytic cell of claim 12, wherein the support material
comprises a nanoparticle mixture.
14. The electrolytic cell of claim 12, wherein the support material
is selected from a plurality of fullerene molecules, a plurality of
quantum dots, graphite, a plurality of zeolites, and activated
carbon.
15. A method comprising: contacting a gaseous feedstock, an aqueous
electrolyte, and a solid catalyst in a reaction area, wherein the
catalyst comprises a first component selected from protein enzymes,
metabolic factors, organometallic compounds and combinations
thereof and a second component bonded to the first component,
wherein the second component is selected from fluorinated sulfonic
acid based polymers, polyaniline and combinations thereof; and
activating the gaseous feedstock in an aqueous electrochemical
reaction in the reaction area to yield a product.
16. The method of claim 15, wherein the product comprises a chain
modified hydrocarbon or organic component.
17. The method of claim 15, wherein the method is a continuous gas
capture process and further comprises sequestering the product.
18. The method of claim 15, wherein the gaseous feedstock is a
dilute, atmospheric greenhouse gas.
19. The method of claim 15, wherein the product comprises amino
acids, organic components, or a combination thereof.
20. The method of claim 15, wherein activating the gaseous
feedstock in an aqueous electrochemical reaction in the reaction
area comprises irradiating the reaction area.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. Non-Provisional
patent application Ser. No. 13/837,372, filed Mar. 15, 2013, which
claims priority to U.S. Provisional Patent Application Ser. No.
61/696,608, filed Sep. 4, 2012, and U.S. Provisional Patent
Application Ser. No. 61/657,975, filed Jun. 11, 2012, which are all
incorporated by reference, and to which priority are claimed.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
BACKGROUND
[0003] This section of this document introduces information about
and/or from the art that may provide context for or be related to
the subject matter described herein and/or claimed. below. It
provides background information to facilitate a better
understanding of the various aspects of the claimed subject matter.
This is therefore a discussion of "related" art. That such art is
related in no way implies that it is also "prior" art. The related
art may or may not be prior art. The discussion in this section of
this document is to be read in this light, and not as admissions of
prior art.
[0004] Some common industrial processes involve the conversion of a
gas or components of a gaseous mixture into another gas. These
types of processes are performed at high pressures and
temperatures. Operational considerations such as temperature and
pressure requirements frequently make these types of processes
energy inefficient and costly. The industries in which these
processes are used therefore spend a great deal of effort in
improving the processes with respect to these kinds of
considerations. The art, however, is always receptive to
improvements or alternative means, methods and configurations.
Therefore the art will well receive the technique described
herein.
SUMMARY
[0005] In a first aspect, a catalyst comprises: a first component
selected from protein enzymes, metabolic factors, organometallic
compounds and combinations thereof; and a second. component bonded
to the first component, wherein the second component is selected
from fluorinated sulfonic acid based polymers, polyaniline and
combinations thereof.
[0006] In a second aspect, a method of forming a catalyst
comprising: contacting a first component selected from selected
from protein enzymes, metabolic factors, organometallic compounds
and combinations thereof with a second component selected from
fluorinated sulfonic acid based polymers, polyaniline and
combinations thereof.
[0007] In a third aspect, an electrolytic cell, comprises: at least
one reaction chamber into which, during operation, an aqueous
electrolyte and a gaseous feedstock are introduced, wherein the
gaseous feedstock comprises a carbon-based gas; and a pair of
reaction electrodes disposed within the reaction chamber. At least
one of the reaction electrodes includes a catalyst comprising: a
first component selected from protein enzymes, metabolic factors,
organometallic compounds and combinations thereof; and a second
component bonded to the first component, wherein the second
component is selected from fluorinated sulfonic acid based
polymers, polyaniline and combinations thereof; wherein the
catalyst, the aqueous electrolyte and the gaseous feedstock, define
a three-phase interface.
[0008] In a fourth aspect a method comprises: contacting a gaseous
feedstock, an aqueous electrolyte, and a catalyst in a reaction
area, the catalyst comprising a first component selected from
protein enzymes, metabolic factors, organometallic compounds and
combinations thereof; and a second component bonded to the first
component, wherein the second component is selected from
fluorinated sulfonic acid based polymers, polyaniline and
combinations thereof; and activating the gaseous feedstock in an
aqueous electrochemical reaction in the reaction area to yield a
product.
[0009] In a fifth aspect, a catalyst comprises: a first component
selected from protein enzymes, metabolic factors, organometallic
compounds and combinations thereof; and a second component selected
from fluorinated sulfonic acid based polymers, polyaniline and
combinations thereof, wherein the catalyst comprises a blend of the
first component and the second component, a multi-layer film of the
first component and the second component or a membrane formed from
incorporating the first component into a membrane formed from the
second component or a membrane formed from a blend of the first
component and second component.
[0010] The above presents a simplified summary of the presently
disclosed subject matter in order to provide a basic understanding
of some aspects thereof. The summary is not an exhaustive overview,
nor is it intended to identify key or critical elements to
delineate the scope of the subject matter claimed below. Its sole
purpose is to present some concepts in a simplified form as a
prelude to the more detailed description set forth below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The claimed subject matter may be better understood by
reference to the following description taken in conjunction with
the accompanying drawings, in which like reference numerals
identify like elements, and in which:
[0012] FIG. 1 depicts one particular embodiment of an electrolytic
cell in accordance with some aspects of the presently disclosed
technique.
[0013] FIG. 2 graphically illustrates a process in accordance with
other aspects of the presently disclosed technique.
[0014] FIG. 3A-FIG. 3B depict a gas diffusion electrode as may be
used in some embodiments.
[0015] FIG. 4-7 depict alternative embodiments of an electrolytic
cell in accordance with another aspect of the presently disclosed
technique.
[0016] While the invention is susceptible to various modifications
and alternative forms, the drawings illustrate specific embodiments
herein described in detail by way of example. It should be
understood, however, that the description herein of specific
embodiments is not intended to limit the invention to the
particular forms disclosed, but on the contrary, the intention is
to cover all modifications, equivalents, and alternatives falling
within the spirit and scope of the invention as defined by the
appended claims.
DETAILED DESCRIPTION
[0017] Illustrative embodiments of the subject matter claimed below
will now be disclosed. In the interest of clarity, not all features
of an actual implementation are described in this specification. It
will be appreciated that in the development of any such actual
embodiment, numerous implementation-specific decisions must be made
to achieve the developers' specific goals, such as compliance with
system-related and business-related constraints, which will vary
from one implementation to another. Moreover, it will be
appreciated that such a development effort, even if complex and
time-consuming, would be a routine undertaking for those of
ordinary skill in the art having the benefit of this
disclosure.
[0018] The presently disclosed technique provides a catalyst,
methods for manufacturing same, and uses therefore. The catalyst
described in further detail herein is either photocatalytic,
electrocatalytic or both photocatalytic and electrocatalytic. As
used herein, the term "photocatalytic" refers to the alteration of
the rate of a chemical reaction by light or other electromagnetic
radiation while the term "electrocatalytic" refers to a mechanism
which produces a speeding up of half-cell reactions at electrode
surfaces.
[0019] The catalyst generally includes a first component and a
second component bonded to the first component. The first
component, in various embodiments, may be selected from protein
enzymes, metabolic factors or organometallic compounds. In some
embodiments, the protein enzyme is a plant enzyme or a metabolic
enzyme. A non-limiting plant enzyme suitable for implementation is
a photosystem enzyme, including but not limited to, chlorophyll,
ribulose-1,5-bisphosphate carboxylase oxygenase (RuBisCO) and
derivatives thereof Non-limiting derivatives include, by way of
example, chlorophyllin and azurite. Other embodiments may use
metabolic enzymes. Non-limiting, exemplary metabolic enzymes
include hemoglobin, ferritin, co-enzyme Q and derivatives thereof.
Still other embodiments may use metabolic factors. These may
include, but are not limited to, vitamins, such as B12 and its
derivatives, although other vitamins and metabolic factors may be
used. And still other embodiments may use an organometallic
component, such as a porphyrin complexed with a metal. The metal
may include a variety of metals, such as ferromagnetic metals,
including cobalt, iron, nickel and combinations thereof. One
suitable porphyrin complexed with a metal is cobalt
tetramethoxyphenylporphyrin and derivatives thereof, although other
porphyrins and other organometallic components may also be
suitable
[0020] The second component generally includes an electroconductive
polymer. The electroconductive polymer may include, depending on
the embodiment, a fluorinated sulfonic acid based polymer or
polyalinine. One suitable fluorinated sulfonic acid based polymer
is a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.
One particular sulfonated tetrafluoroethylene based
fluoropolymer-copolymer suitable for use is sold under the trade
name NAFION.RTM. by DuPont. Thus, in some embodiments, the second
component may he an ion exchange resin such as NAFION.RTM..
However, other suitable electroconductive polymers may become
apparent to those skilled in the art having the benefit of this
disclosure and may be used in alternative embodiments.
[0021] The second component may be bonded to the first component
via any method suitable for bonding such components to one another.
However, such bonding process generally results in a bond that does
not dissociate upon immersion or contact with water. For example,
the bond may be ionic, covalent or combinations thereof. While
techniques for manufacturing the catalyst are presented herein, it
is understood that other techniques may be used. Similarly, while
some exemplary uses are disclosed and claimed herein, the catalyst
may be applied to other uses.
[0022] The catalyst may be formed in a variety of manners. For
example, the catalyst may include a blend of the first component
and the second component. Alternatively, the catalyst may include a
multi-layer film of the first component and the second component.
In one or more embodiments, the first component may be incorporated
into a membrane formed from the second component. In yet another
embodiment, the first component and the second component are
blended and formed into a membrane.
[0023] In one or more embodiments, the catalyst includes from 20
wt. % to 80 wt. % first component and from 20 wt. % to 80 wt. %
second component. For example one may use 5 grams of Chlorophyllin
mixed with 20 grams of NAFION.RTM., 10 grams of ferritin with 20
grams of NAFION.RTM. or 20 grams of B12 mixed with 5 grams of
NAFION.RTM..
[0024] In one or more embodiments, the catalyst is bound to a
support material to form a supported catalyst. Typical support
materials may include talc, inorganic oxides, clays and clay
minerals, ion-exchanged layered components, diatomaceous earth
components, zeolites or a resinous support material, such as a
polyolefin, for example. Specific inorganic oxides include silica,
alumina, magnesia, titania and zirconia, for example. In one or
more embodiments, the support material includes a nanoparticulate
material. The term "nanoparticulate material" refers to a material
having a particle size smaller than 1,000 nm. Exemplary
nanoparticulate materials include, but are not limited to, a
plurality of fullerene molecules (i.e., molecules composed entirely
of carbon, in the form of a hollow sphere (e.g., buckyballs),
ellipsoid or tube (e.g., carbon nanotubes), a plurality of quantum
dots (e.g., nanoparticles of a semiconductor material, such as
chalcogenides (selenides or sulfides) of metals like cadmium or
zinc (CdSe or ZnS, for example)), graphite, a plurality of
zeolites, or activated carbon. In addition to the non-limiting,
exemplary supports listed above, any catalyst support known to
those skilled in the art may be used depending upon
implementation-specific design considerations. Accordingly, other
embodiments may employ other supports for the catalyst.
[0025] In another aspect, the technique presents a process for
forming the catalyst described previously herein. One particular
embodiment of the process includes contacting the first component
with the second component. Such contact may include a variety of
processes, such as blending the components or forming a multi-layer
film with the components, for example. One particular embodiment
includes blending the first component with the second component. In
one or more embodiments, the first component and the second
component are contacted in a solution of alcohol and water. The
solution may include from 3 wt. % to 97 wt. % alcohol and from 3
wt. % to 97 wt. % water, for example. The contact may last for a
time sufficient to bond or blend the first and second component.
For example, the contact may last for a time of from 30 minutes to
24 hours.
[0026] The resulting mixture may be dried to yield a crystalized
catalyst. The act of drying the solution mentioned above may be
performed by permitting the solution to dry by evaporation.
However, some embodiments may facilitate or accelerate drying by
heating the solution. However, care should be taken to avoid
damaging the solution components with the heat. Thus, embodiments
which include heating in the drying should heat the solution to a
temperature below the breakdown or boiling temperatures of the
components, i.e., the first and second component, alcohol, and
water.
[0027] In one particular embodiment, the first component and the
second component are blended in substantially equal molar amounts.
However, this is product dependent and not all embodiments will mix
in equal molar amounts. Alternative embodiments may employ
different ratios for the mixture to adjust for kinetics, catalyst
lifetime, and yields of products. For example, one or more
embodiments may include contacting the first component and the
second component in a molar ratio of from 0.8:1 to 1.2:1. Some
embodiments contact and crystalize the components as described
above and then add water to the crystallized catalyst to test the
catalyst for water solubility. If the crystallized catalyst is
still water soluble, the crystallized catalyst can be reconstituted
with an alcohol/water mixture along with further first and second
component and the process repeated as described above until the
crystallized catalyst is no longer water soluble.
[0028] Preparing the mixture in solution may also find variation
across embodiments. In one embodiment, preparing the mixture in
solution includes dissolving the mixture with the alcohol and
water. In another embodiment, preparing the mixture in solution
includes dispersing the mixture in a colloidal suspension in the
alcohol and water. Those in the art having the benefit of this
disclosure may find still other alternatives for the preparation of
the mixture in solution.
[0029] Some embodiments may reconstitute the crystallized polymer
for reasons other than testing for water solubility. For example,
in some embodiments, the crystallized polymer may be reconstituted
for the purpose of fabricating it into a membrane or as otherwise
described herein. In this case, the crystallized polymer may be
reconstituted by, for example, adding pure alcohol or another
non-water based solvent such as napthalene or hexane. The use of
such membranes is helpful in implementing some of the end uses
described further below.
[0030] In a third aspect, the catalyst as described above may be
implemented in an electrolytic cell. Such an electrolytic cell may
comprise at least one reaction chamber and a pair of reaction
electrodes. During operation, an aqueous electrolyte and a gaseous
feedstock are introduced into at least one chamber, the gaseous
feedstock comprising a carbon-based gas. The pair of reaction
electrodes are disposed within the reaction chamber. At least one
of the reaction electrodes includes the catalyst as described above
adapted to catalyze reaction between the electrolyte and the
gaseous feedstock.
[0031] In some embodiments, the catalyst, in conjunction with the
aqueous electrolyte and the gaseous feedstock, defines a
three-phase interface. However, the presently disclosed. technique
is not so limited. The catalyst will also operate in liquid/liquid
and gas/gas reactions. With respect to gas/gas reactions, these
will be between gas phase reactants.
[0032] The aqueous electrolyte may comprise any ionic substance
that dissociates in aqueous solution. In various embodiments, the
aqueous electrolyte is selected from potassium chloride, potassium
bromide, potassium iodide, hydrogen chloride, magnesium sulfate,
sodium chloride, sulfuric acid, sea salt, or brine. However, other
embodiments may employ other aqueous electrolytes.
[0033] The carbon-based gas of the gaseous feedstock may comprise a
non-polar gas, a carbon oxide, or a mixture of the two. Suitable
non-polar gases include a hydrocarbon gas. Suitable carbon oxides
include carbon monoxide, carbon dioxide, or a mixture of the two.
These examples are non-limiting and other non-polar gases and
carbon oxides may be used in other embodiments. In some
embodiments, the gaseous feedstock comprises one or more greenhouse
gases.
[0034] In a fourth aspect, an electrolytic cell in which the
catalyst has been deployed as described above may be used to
implement one or more methods for chain modification of
hydrocarbons and organic components. The method comprises
contacting a gaseous feedstock including a carbon-based gas, an
aqueous electrolyte, and the catalyst in a reaction area. The
carbon-based gas is then activated in an aqueous electrochemical
reaction in the reaction area to yield a product.
[0035] As described above, the aqueous electrolyte may comprise any
ionic substance that dissociates in aqueous solution. In various
embodiments, the aqueous electrolyte is selected. from potassium
chloride, potassium bromide, potassium iodide, hydrogen chloride,
magnesium sulfate, sodium chloride, sulfuric acid, sea salt, or
brine. However, other embodiments may employ other aqueous
electrolytes.
[0036] Also as described above, the carbon-based gas of the gaseous
feedstock may comprise a non-polar gas, a polar gas, a carbon
oxide, or a mixture of the two. Suitable non-polar gases include a
hydrocarbon gas. Suitable carbon oxides include carbon monoxide,
carbon dioxide, or a mixture of the two. These examples are
non-limiting and other gases and inorganic gases may be used in
other embodiments. In some embodiments, the gaseous feedstock
comprises one or more greenhouse gases.
[0037] The apparatus and method of the third and fourth aspect
above may be adapted from the apparatus and methods disclosed in,
for example, International Application PCT/U.S. Ser. No. 13/28748
through the addition of the catalyst disclosed herein. To further
clarify how this adaptation may be, and to help illustrate the
presently disclosed technique, portions of that disclosure will now
be reproduced, albeit modified with the adaptation.
[0038] The presently disclosed technique is, in this particular
embodiment, a process for converting carbon-based gases such as
non-polar organic gases and carbon oxides to longer chained organic
gases such as liquid hydrocarbons, longer chained gaseous
hydrocarbons, branched-chain liquid hydrocarbons, branched-chain
gaseous hydrocarbons, as well as chained and branched-chain organic
components. In general, the method is for chain modification of
hydrocarbons and organic components, including chain lengthening,
and eventual conversion into liquids including, but not limited to,
hydrocarbons, alcohols, and other organic components.
[0039] This process turns hydrocarbon gases including, but not
limited to, gaseous methane, natural gas, other hydrocarbons,
carbon monoxide, carbon dioxide, and/or other organic gases into
C.sub.2+ hydrocarbons, alcohols, and other organic components. One
exemplary product is ethylene (C.sub.2H.sub.4) and alcohols. The
process may also turn carbon dioxide (CO.sub.2) into one or more of
isopropyl alcohol, hydroxyl-3-methyl-2-butanone, tetrahydrofuran,
toluene, 2-heptanone, 2-butoxy ethanol, 1-butoxy-2-propanol,
benzaldehyde, 2-ethyl-hexanol, methyl-undecanol, methyl-octanol,
2-heptene, nonanol, di ethyl-dodecanol, dimethyl-cyclooctane,
dimethyl octanol, dodecanol, ethyl-1, 4-dimethyl-cyclohexane,
dimethyl-octanol, hexadecene, ethyl-1-propenyl ether,
dimethyl-silanediol, toluene, hexanal, methyl-2-hexanone, xylene
isomer, methyl-hexanone, heptanal, methyl-heptanone, benzaldehyde,
octanal, 2-ethyl-hexanol, nonanal, hexene-2, 5-diol, dodecanal, 3,
7-dimethyl-octanol, methyl-2, 2-dimethyl-1-(2-hydroxy-1
methylethyl)propyl ester propanoic acid, methyl-3-hydroxy-2, 4,
4-trimethylpentyl ester propanoic acid, phthalic anhydride.
[0040] This aqueous electrochemical reaction includes a reaction
that proceeds at room temperature and pressure, although higher
temperatures and pressures may be used. In general, temperatures
may range from -10.degree. C. to 240.degree. C., or from
-10.degree. C. to 1000.degree. C., and pressures may range from 0.1
ATM to 10 ATM, or from 0.1 ATM to 100 ATM. The process generates
reactive activated carbon-based gases through the reaction on the
reaction electrodes. On the reaction electrode, the production of
activated carbon-based gases occurs.
[0041] In the embodiments illustrated herein, the technique employs
an electrochemical cell such as the one illustrated in FIG. 1 The
electrochemical cell 100 generally comprises a reactor 105 in one
chamber 110 of which are positioned two electrodes 115, 116, a
cathode and an anode, separated by a liquid ion source, i.e., an
electrolyte 120. Those in the art will appreciate that the identity
of the electrodes 115, 116 as cathode and anode is a matter of
polarity that can vary by implementation. In the illustrated
embodiment, the electrode 115 is the anode and the electrode 116 is
the cathode. Because of the interchangeability between electrode
115 and 116 and because in some embodiments of the design the
electrodes are electrically short circuited ("shorted"), the
reaction electrode is considered to be either or both of the
electrode 115 and electrode 116.
[0042] There is also a second chamber 125 into which a gaseous
feedstock 130 is introduced as described below. The gaseous
feedstock 130 may be a carbon-based gas, for example, non-polar
organic gases, carbon-based oxides, or some mixture of the two. The
two chambers are joined by apertures 135 through the wall 140
separating the two chambers 110, 125. The reactor 105 may be
constructed in conventional fashion except as noted herein. For
example, materials selection, fabrication techniques, and assembly
processes in light of the operational parameters disclosed herein
will be readily ascertainable to those skilled in the art.
[0043] The electrolyte 120 will also be implementation specific
depending, at least in part, on the implementation of the reaction
electrode 116. Exemplary liquid ionic substances include, but are
not limited to, Polar Organic Components, such as Glacial Acetic
Acid, Alkali or alkaline Earth salts, such as halides, sulfates,
sulfites, carbonates, nitrates, or nitrites. The electrolyte 120
may therefore be, depending upon the embodiment, magnesium sulfate
(MgS), sodium chloride (NaCl), sulfuric acid (H.sub.2SO.sub.4),
potassium chloride (KCl), hydrogen chloride (HCl), hydrogen bromide
(HBr), hydrogen fluoride (HF), potassium chloride (KCl), potassium
bromide (KBr), and potassium iodide (KI), or any other suitable
electrolyte and acid or base known to the art.
[0044] The pH of the electrolyte 120 may range from -4 to 14 and
concentrations of between 0 M and 3M inclusive may be used. Some
embodiments may use water to control pH and concentration, and such
water may be industrial grade water, brine, sea water, or even tap
water. The liquid ion source, or electrolyte 120, may comprise
essentially any liquid ionic substance.
[0045] In addition to the reactor 105, the electrochemical cell 100
includes a gas source 145 and a power source 150, and an
electrolyte source 163. The gas source 145 provides the gaseous
feedstock 130 while the power source 150 is powering the electrodes
115, 116 at a selected voltage sufficient to maintain the reaction
at the three phase interface 155. The three phase interface 155
defines a reaction area. In one example, the reaction pressure
might be, for example, 10000 pascals or from 0.1 ATM to 10 ATM, or
from 0.1 ATM to 100 ATM, and the selected pressure may be, for
example, between 0.01 V and 10 V.
[0046] The electrolyte source 163 provides adequate levels of the
electrolyte 120 to ensure proper operations. The three phases at
the interface 155 are the liquid electrolyte 120, the solid
catalyst of the reaction electrode 116, and the gaseous feedstock
130 as illustrated in FIG. 6. The reaction products 160 are
generated in both the electrolyte 120 and in the chamber 125 and
may be collected in a vessel 165 of some kind in any suitable
manner known to the art. In some embodiments, the products 160 may
be forwarded to yet other processes either after collection or
without ever being collected at all. In these embodiments, the
products 160 may be streamed directly to downstream processes using
techniques well known in the art.
[0047] Those in the art will appreciate that some implementation
specific details are omitted from FIG. 1. For example, various
instrumentation such as flow regulators, mass regulators, a pH
regulator, and sensors for temperatures and pressures are not shown
but will typically be found in most embodiments. Such
instrumentation is used in conventional fashion to achieve,
monitor, and maintain various operational parameters of the
process. Exemplary operational parameters include, but are not
limited to, pressures, temperatures, pH, and the like that will
become apparent to those skilled in the art. However, this type of
detail is omitted from the present disclosure because it is routine
and conventional so as not to obscure the subject matter claimed
below.
[0048] The reaction is conceptually illustrated in FIG. 2. In this
embodiment 200, the feedstock 130' is natural gas and the
electrolyte 120' is Sodium Chloride. Reactive hydrogen ions
(H.sup.+) are fed to the natural gas stream 130' through the
electrolyte 120' with an applied cathode potential of the molecules
may also in turn react with water on the interface to form
alcohols, oxygenates, and ketones. In one example of this reaction,
the reaction occurs at room temperature and with an applied cathode
potential of 0.01V versus SHE to 4.99V versus SHE.
[0049] The voltage level can be used to control the resulting
product. A voltage of 0.01V may result in a methanol product
whereas a 0.5V voltage may result in butanol as well as higher
alcohols such as dodecanol. A voltage of 2 volts may results in the
production of ethylene or polyvinyl chloride precursors. These
specific examples may or may not be reflective of the actual
product yield and are meant only to illustrate how a product
produced can be altered with a change in voltage.
[0050] Returning now to FIG. 1, additional attention will now be
directed to the electrochemical cell 100. As noted above, the
reactor 105 can be fabricated from conventional materials using
conventional fabrication techniques. Notably, the presently
disclosed technique may operate at room temperatures and pressures
whereas conventional processes are performed at temperatures and
pressures much higher. Design considerations pertaining to
temperature and pressure therefore can be relaxed relative to
conventional practice. However, conventional reactor designs may
nevertheless be used in some embodiments.
[0051] The presently disclosed technique admits variation in the
implementation of the electrode at which the reaction occurs,
hereafter referred to as the "reaction electrode". As set forth
above, either the electrode 115 or the electrode 116, or both, may
be considered to be the reaction electrode depending upon the
embodiment.
[0052] The counter electrode 115 and the reaction electrode 116 are
disposed within a reactor 105 so that, in use, it is submerged in
the electrolyte 120 and the catalyst forms one part of the
three-phase interface 155. When electricity is applied to
electrodes 115, 116, electrochemical reduction discussed above
takes place to produce hydrocarbons and organic chemicals. The
reaction electrode 116 receives the electrical power and catalyzes
a reaction between the hydrogen in the electrolyte 120 and the
gaseous feedstock 130.
[0053] In an embodiment shown in FIG. 3A-FIG. 3B, a gas diffusion
electrode 300 comprises a hydrophobic layer 305 that is porous to
carbon-based gases but impermeable or nearly impermeable to aqueous
electrolytes. In one embodiment of the electrode 300, a 1 mil thick
advcarb carbon paper 310 treated with TEFLON.RTM. (i.e.,
polytetrafluoroethylene) dispersion (not separately shown) is
coated with the photocatalytic and electrocatalytic membrane 315 by
any means, such as painting, dipping or spray coating.
[0054] So, turning now to the process again and referring to FIG.
1, carbon-based gases or electrolyte gaseous mixture including
gaseous feedstock 130 is introduced into the reaction chamber 125
of the reactor 105 under enough pressure to overcome the
gravitational pressure of the column of electrolyte, which depends
on the height of the electrolyte, to induce the reaction.
[0055] The method of operation generally comprises introducing the
electrolyte 120 into the reaction chamber 110 into direct contact
with the powered electrode surfaces 115 and 116. The gaseous
feedstock 130 is then introduced into the second chamber 125 under
enough pressure to overcome the gravitational pressure of the
column of electrolyte, which depends on the height of the
electrolyte, to induce the reaction to induce the reaction. During
the reaction, the electrolyte 120 is filtered, the gaseous
feedstock 130 is maintained at a selected pressure to ensure its
presence at the three phase interface 155, and the product 165 is
collected. Within this general context, the following examples are
implemented.
[0056] By maintaining a three phase interface between the gaseous
feedstock 130 and the electrolyte 120, the carbon-based gases will
form organic chemicals and form a nearly complete conversion when
there is continuous contact to the gaseous feedstock 130 on the
three phase interfaces 155 between the liquid electrolyte 120, the
solid catalyst, and the gaseous feedstock 130.
[0057] For carbon dioxide, this reaction mechanism also produces
organic components such as ethers, epoxides, and C.sub.5+ alcohols,
among other components such as ethers, epoxies and long C.sub.5+
hydrocarbons which have not been reported in the prior art.
[0058] The electrolyte 120 may be relatively concentrated at 0.1
M-3 M and may he a halide electrolyte as discussed above to
increase catalyst lifetime. The higher the surface area between the
reaction electrode 116 and the gaseous chamber 125 on one side and
the liquid electrolyte 120 on the other side, the higher the
conversion rates. Operating pressures may range from 10000 pascals
or from 0.1 atm to 10 atm, though standard temperature and
pressures (STP) are sufficient for the reaction.
[0059] The principles discussed above can readily be scaled up to
achieve higher yield. Four such embodiments are shown in FIG.
4-FIG. 6.
[0060] For example, those in the art having the benefit of the
disclosure associated with FIG. 1 will realize that the gaseous
feedstock 130 and the electrolyte 120 need not necessarily be
introduced into separate chambers. One such example is shown in
FIG. 4. In this stacked embodiment 400, reactants 405 (e.g.,
gaseous feedstock and liquid electrolyte, or gaseous feedstock and
a slurry of the catalyst and liquid electrolyte) enter a chamber
410 in which they are mixed, the resulting mixture 435 then
entering a reaction chamber 440. A plurality of alternating anodes
420 and cathodes 415 (only one of each indicated) are positioned in
the reaction chamber 440. Each of the anodes 420, cathodes 415 is a
reaction electrode at which a three-phase reaction area forms as
described above. The resultant product 445 is collected in the
chamber 425, a portion of which is then recirculated back to the
chamber 410 via the line 430.
[0061] In the stacked embodiment 500, shown in FIG. 5, the gaseous
feedstock 515 and liquid electrolyte 520 are separately introduced
at the bottom of the reaction chamber 525. A plurality of chambers
530 (only one indicated) are disposed between respective anodes 820
and cathodes 415. Gaseous feedstock 535 and liquid electrolyte 540
are then reacted in the chambers 530 and the resultant gas product
505 and fouled electrolyte 510 are drawn off the top.
[0062] Another stacked embodiment 600 is shown in FIG. 6. A mixture
605 of gaseous feedstock and liquid electrolyte is introduced into
a chamber 610, from which it is then introduced into a reaction
chamber 630 in which a plurality of alternating anodes 616 and
cathodes 615 are stacked. When the anodes 616 and cathodes 615 are
powered, they are shorted together. Those in the art will
appreciate that, at this point, they lose their identity as a
"cathode" or an "anode" because they all have the same polarity and
instead all become reaction electrodes. As the mixture 605 rises in
the reaction chamber 630, it forms a three-phase reaction at each
reaction electrode. The gas product 605 and the fouled electrolyte
610 are drawn from the chamber 625 at the top of the embodiment
600.
[0063] In this particular embodiment, the electrodes 615, 616 are
electrically short circuited within the liquid electrolyte (not
shown) while maintaining a three phase interface between
carbon-based gases and electrolyte at each of the electrodes 615,
616 in a mixed slurry pumped through the reactor. In this
embodiment, the catalyst in powder form is mixed with the
electrolyte to make a slurry. FIG. 7 depicts a portion 700 of the
embodiment 600 in which the electrodes are shorted. In this
drawing, only a single electrode 705 is shown but the electric
potential is drawn across the electrode 705. The companion
electrode (not shown) is similarly shorted.
[0064] The catalyst disclosed above, when incorporated into a
suitable apparatus, can be used for a wide variety of end uses,
such as to deodorize water or to produce ethylene from air for use
in fruit ripening production. It can also be used to remove carbon
dioxide from air while simultaneously fixing the carbon dioxide in
a useful form. It also may be used to capture swamp gasses, farm
gasses, and other dilute gasses, and concentrate them in aqueous
form. For example, a catalyst membrane can be constituted upon a
floating porous substance, such as Teflon treated paper of any
substance. One example is Teflon treated conductive carbon fiber
paper. It can then be floated on the surface of a body of water and
exposed to sunlight while electricity is applied. Or,
alternatively, floating a painted electrode on aqueous electrolyte
and then adding electricity.
[0065] The catalyst disclosed above can also be used for the
conversion of greenhouse gases to aqueous sequestered chemicals
such as amino acids and organic components. Such greenhouse gases
may include, for example, Hydrogen Sulfide (H.sub.2S), sulfur
oxides (SO.sub.x), nitrogen oxides (NO.sub.x) (common environmental
pollutants in the air) and other polar and non polar gases both
organic and inorganic. For example, a catalyst membrane can be laid
out on a solid surface or floated on the surface of water and
exposing to sunlight, or alternatively, floating a painted
electrode on aqueous electrolyte, and then adding electricity.
[0066] Note that the process catalyzes the same reaction whether
through shining light on the membrane/resin or by applying
electricity. Shining a light will only give a single reaction
product since sunlight can only provide a fixed voltage to the
membrane, while applying electricity will allow one to vary the
products and reaction speeds. However, the catalyst works with both
sources of energy (i.e., the catalyst is photocatalytic and
electrocatalytic).
[0067] Note that not all embodiments will manifest all these
characteristics and, to the extent they do, they will not
necessarily manifest them to the same extent. Thus, some
embodiments may omit one or more of these characteristics entirely.
Furthermore, some embodiments may exhibit other characteristics in
addition to, or in lieu of, those described herein.
[0068] The phrase "capable of" as used herein is a recognition of
the fact that some functions described for the various parts of the
disclosed apparatus are performed only when the apparatus is
powered and/or in operation. Those in the art having the benefit of
this disclosure will appreciate that the embodiments illustrated
herein include a number of electronic or electro-mechanical parts
that, to operate, require electrical power. Even when provided with
power, some functions described herein only occur when in
operation. Thus, at times, some embodiments of the apparatus of the
invention are "capable of" performing the recited functions even
when they are not actually performing them i.e., when there is no
power or when they are powered but not in operation.
[0069] The following patent, applications, and publications are
hereby incorporated by reference for all purposes as if set forth
verbatim herein:
[0070] U.S. Application Ser. No. 61/657,975, entitled, "Catalytic
Membrane for the Continuous Air Capture and Simultaneous Fixation
of CO2", filed Jun. 11, 2012, in the name of the inventors Tara
Cronin and Ed Chen and commonly assigned herewith.
[0071] U.S. Application Ser. No. 61/698,608, entitled, "Protein and
Enzyme Cofactors Immobilized Nafion or Other Electroconducting
Polymer Co-membrane", filed Sep. 8, 2012, in the name of the
inventors Tara Cronin and Ed Chen and commonly assigned
herewith.
[0072] U.S. application Ser. No. 13/783,102, entitled, "Method and
Apparatus for an Electrolytic Cell Including a Three-Phase
interface to React Carbon-Based Gases in an Aqueous Electrolyte",
filed Mar. 1, 2013, in the name of the inventor Ed Chen and
commonly assigned herewith.
[0073] International Application Serial No. PCT/U.S. Ser. No.
13/28748, entitled, "Method and Apparatus for an Electrolytic Cell
Including a Three-Phase Interface to React Carbon-Based Gases in an
Aqueous Electrolyte", filed Mar. 1, 2013, in the name of the
inventor Ed Chen and commonly assigned herewith.
[0074] U.S. application Ser. No. 13/782,936, entitled, "Chain
Modification of Gaseous Methane Using Aqueous Electrochemical
Activation at a Three-Phase Interface", filed Mar. 1, 2013, in the
name of the inventor Ed Chen and commonly assigned herewith.
[0075] International Application Serial No. PCT/U.S. Ser. No.
13/28728, entitled, "Chain Modification of Gaseous Methane Using
Aqueous Electrochemical Activation at a Three-Phase Interface",
filed Mar. 1, 2013, in the name of the inventor Ed Chen and
commonly assigned herewith.
[0076] To the extent that any patent, patent application, or other
reference incorporated herein by reference conflicts with the
present disclosure set forth herein, the present disclosure
controls.
EXAMPLES
[0077] Example 1
[0078] A number of samples were analyzed with an Extech infrared
CO.sub.2 monitor to determine the effect of the contact of various
catalyst samples upon a gaseous feedstock comprising CO.sub.2. The
samples included chlorophyllin (15 by weight %) mixed with a
NAFION.RTM. dispersion with 85% by weight. The resulting mixture
was diluted in a 70% ethanol/30% water mixture, which was stirred
until the Chlorophyllin was fully dissolved. This mixture was
allowed to dry in open air all water and alcohol was evaporated.
The resulting solid crystal compound of Chlorophyllin bounded
membrane was then reconstittted by adding a 97% isopropyl alcohol
and 3% water mixture into a paint, and painted onto the surface of
a porous conducting carbon paper. This paper was placed on the
surface of a container of 2 Molar Sodium Sulfite aqueous
electrolyte and connected to a power source set to 0.5 volts with
30 square centimeters of surface area exposed to the rest of the
enclosed atmosphere. The samples were exposed to CO.sub.2 in a 16
liter closed container with 30 square cm of contact area between
the carbon paper painted with the catalytic membrane and the power
source was switched on. Upon powering of the electrode floating on
the surface of the water and contacting the enclosed air, the level
of CO2 was monitored and recorded in Table 1 below. Such contact
occurred at ambient room temperatures and pressures. It was
observed that after only 8 minutes, the resultant level of CO2 had
been lowered to 350 ppm (see, Table 1), the level determined as the
maximum, which would prevent catastrophic climate change.
TABLE-US-00001 TABLE 1 Minutes CO.sub.2 ppm 1 750 2 700 3 600 4 520
5 450 6 400 7 400 8 350 9 300 10 250 11 200 12 160 13 128 14 102 15
80 16 64 17 51 18 41 19 33 20 27 21 22 22 18
Example 2
[0079] A number of samples were analyzed by Gas Chromotography/Mass
Spectroscopy to determine the effect of the contact of catalyst
samples upon a gaseous feedstock over time. The gaseous feedstock
is methane, while the catalyst is formed from B12 impregnated
within a NAFION.RTM. membrane in approximately equal molar amounts.
This formed a catalyst was supported on a support material
comprising 50% equal mixture by weight magnesium oxide, graphite
and copper nanoparticles and 50% by weight of the B-12 NAFION
membrane that was painted onto a porous conductive carbon paper.
The samples were exposed to gaseous feedstock at various electrical
pulse levels for a varied period of time to determine the resultant
products formed (shown in Table 2) from the contact of the gaseous
feedstock with the catalyst. Such contact occurred at ambient room
temperature and pressure. It was observed that the reaction
produced longer chained molecules than that of the gaseous
feedstock, in this example, methane. It was further observed that
the length of the retention time could be tailored to form the
length of the chain and position of substituents on the product. In
the first set of experiments a one second pulse of 2 Volts was used
with no reverse pulse over a period of 1 hour as methane was fed to
the interface between the painted carbon paper electrode and the
liquid electrolyte consisting of 3 molar KO. In the second set of
experiments, 2 millisecond pulses were used with a reverse pulse of
100 microseconds. In the third experiment, no reverse pulse was
used and a continuous 2 volt potential was applied to the
electrode. In the final set of experiments, labeled FT Cold Trap,
the methane gas with a 1 second pulse followed by a2 ms reverse
pulse was passed over a cold trap to gather condensate.
TABLE-US-00002 TABLE 2 RETENTION ELECTRICAL PULSE TIME (MIN) BEST
SPECTRAL MATCH 1 SECOND 4.001 ACETYL CHLORIDE 1 SECOND 5.072
ACETONE 1 SECOND 5.147 ISOPROPYL ALCOHOL 1 SECOND 6.204 1-PROPANOL
1 SECOND 6.761 2-BUTANONE 1 SECOND 7.519 ACETIC ACID 1 SECOND
15.287 DIMETHYL- BENZENEMETHANOL 2 MS 4.007 METHYL HYDROGEN
DISULFIDE 2 MS 5.185 ISOPROPYL ALCOHOL 2 MS 8.660 2-(METHYLTHIO)-
ETHANAMINE 2 MS 9.504 UNIDENTIFIED NONE 3.925 ACETYL CHLORIDE NONE
5.153 ISOPROPYL ALCOHOL NONE 5.540 ACETALDOXIME NONE 6.764
2-BUTANONE NONE 6.885 2-BUTANOL 1 S Pulse, 2 ms Reverse 3.821
ACETALDEHYDE 1 S Pulse, 2 ms Reverse 4.657 ETHANOL 1 S Pulse, 2 ms
Reverse 5.080 ACETONE 1 S Pulse, 2 ms Reverse 5.160 ISOPROPYL
ALCOHOL 1 S Pulse, 2 ms Reverse 5.382 ACETIC ACID METHYL ESTER 1 S
Pulse, 2 ms Reverse 6.184 1-PROPANOL 1 S Pulse, 2 ms Reverse 6.768
2-BUTANONE 1 S Pulse, 2 ms Reverse 6.872 2-BUTANOL 1 S Pulse, 2 ms
Reverse .440 2-METHYL-1-PROPANOL 1 S Pulse, 2 ms Reverse 7.526
ACETIC ACID 1 S Pulse, 2 ms Reverse 8.138 1-BUTANOL 1 S Pulse, 2 ms
Reverse 9.678 3-METHYL-1-BUTANOL 1 S Pulse, 2 ms Reverse 10.307
1-PENTANOL 1 S Pulse. 2 ms Reverse 11.605 4-METHYL-1-PENTANOL 1 S
Pulse, 2 ms Reverse 11.779 1-HEXANOL 1 S Pulse, 2 ms Reverse 12.108
1-HEPTANOL 1 S Pulse, 2 ms Reverse 13.562 1-(2-METHOXY-1-
METHYLETHOXY)-2- PROPANOL 1 S Pulse, 2 ms Reverse 13.981
1-(2-METHOXY-1- METHYLETHOXY)-2- PROPANOL 1 S Pulse, 2 ms Reverse
14.019 1-(2-METHOXYPROPOXY)- 2-PROPANOL 1 S Pulse, 2 ms Reverse
14.189 1-OCTANOL
[0080] This concludes the detailed description. The particular
embodiments disclosed above are illustrative only, as the invention
may be modified and practiced in different but equivalent manners
apparent to those skilled in the art having the benefit of the
teachings herein. Furthermore, no limitations are intended to the
details of construction or design herein shown, other than as
described in the claims below. It is therefore evident that the
particular embodiments disclosed above may be altered or modified
and all such variations are considered within the scope and spirit
of the invention. Accordingly, the protection sought herein is as
set forth in the claims below.
* * * * *