Note: Descriptions are shown in the official language in which they were submitted.
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APPLICATION FOR UNITED STATES LETTERS PATENT
FOR
BY
ED iTE CHEN
EFS-Web Transmission
37 C.F,R. 1.8
hereby certify that thi rrespnden s being transmitted via the U S. Patent
and Trademark Office (USPTO) electronic filing system (EFS-Web) to the
USPTO on March 1, 2013,
/Jeffrey A. Pyle/
Jeffrey A. Pyle
__________________________________________________________ =
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ELECTROLYTIC CELL INCLUDING A THREE-PHASE INTERFACE TO REACT
CARBON-BASED GASES IN AN AQUEOUS ELECTROLYTE
100911 The
priority of U.S. Application Serial No. 61/608,583, entitled, "An
Electrochemical Process for Direct one: step conversion of methane to Ethylene
on a Three
Phase GEts,.:Liquidõ Solid ftiterface"õ and filed March gõ.2012, in the nanie
of the inventor Ed
Chen is hereby claimed pursuant to 35 U.S.C. 019(4 This application is
commonly
assigned herewith and is also hereby iixorporated for all purposes as if set
forth verbatim
herein.
to (0002i
The priority of U.S. Application Serial No. 61/639,544, entitled,
"Electrochemical
Reactor for the use of Aqueous Electrolyte for High E.Mciency Reaction of on
Polar
Organic Gases"õ filed April 27, 2012, in the name of the inventor Ed Chen is
hereby claimed
pursuant to 35 U.S,C. ;11.19(0 This application is commonly assigned herewith
and is also
hereby incorporated for all purposes Its if set forth verbatim herein.
is 00031
The priority of US, Application Serial No, 6.1/606,398; entitled., .'"A.
Process,.
.Apparatus, and Components for the Pmduction of High Value Chemicals from
carbon
dioxide Using Modular, Electrochemical Reduction of C.02. on Three Phase.
Interphase Gas
Diffusion Electrode,. Med. klatch :3, 2912, in the Ilatile of the inventor Ed
Chen is hereby
claimed pursuam to 35 U.S.C. 1.1.9(e). This application is commonly assigned.
herewith and
2o is also hereby incorporated. for all purposes as if set forth verbatim
herein.
100041
The. priority of US. Application Serial No, 6.l171.3,487., entitled, 'A
Process for
Electrochemical Fischer Trospch', filed October 13,..20õ12, in the name of the
inventor Ed
Chen is hereby claimed pursuant to 35. U,S,C 1.19(e), This application is
commonly
assigned herewith and is also hereby incorporated for all puiToses as if set
forth verbaiiin
25 herein_
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CROSS-REFERENCE TO RELATED APPLICATIONS
10005) The technique described herein and illustrated in the appended
drawings is related
by overlapping disclosure to the following applications, each of which is
commonly assigned
herewith:
[00061 U.S. Application Serial No. 13/782,936, entitled "Chained
Modific.ation of
Gaseous iethane Using Aqueous Electrochemical. Activation at a. Three Phase
interface", in
the name of Ed Chen on an even date herewith (Attorney Docket No.
2039,000300).
STATEMENT REGARDING FEDERALLY SPONSORED
RESEARCH OR DEVELOPMENT
io 10007j Not applicable.
BACKGROUND
100081 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.
100091 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 at great deal of
effort in
improving the processes with respect to these kinds of considerations.
1001.01 Several configurations of electrolytic- cells are available to the.
art .many or all of
all of may be competent for their intended purposes. The art, however, is
always receptive to
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improvements or alternative means, methods and configurations. Therefore the
art will well
receive the launching tool described herein.
SUMMARY
NOM In
a first aspect, an electrolytic cell, comprises: at least one reaction chamber
into
which, during operation, a aqueous electrolyte and a gaseous feedstock
including 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 solid catalyst and defining, in conjunction with the
aqueous electrolyte
and the gaseous feedstock, a three-phase interfate.
1.00121 In a second aspect, a method fir chain modification of hydrocarbons
and organic
compounds comprises: contacting a gaseous feedstock including a carbon-based
gas, an
aqueous electrolyte, and a catalyst in a reaction area; andactivating the
carbon-based gas in an
aqueous electrochemical reaction at the reaction electrode and yield a
product,
(00131 In
a third aspect, a method for chain modification of hydrocarbons and organic
compounds comprises: contacting an aqueous electrolyte with a a catalyst and a
gaseous
feedstock including a carbon-based gas within a reaction area; and reacting
the aqueous
electrolyte, the catalyst, and the gaseous feedstock at temperatures in the
range of C to
1000 C and at 'pressures in the range of .1 ATM to 100 ATM to yield a long
chained
hydrocarbon.
'20 100141
In a third aspect, a gas diffusion electrode, comprises: a hydrophobic layer
porous
to carbon dioxide and impermeable to aqueous electrolytes; a hydrophilic layer
bonded to the
hydrophObic layer; and. a cuprous halide coating disposed. about the bonded
hydrophobic and
hydrophilic layers.
(00151 In
a fourth aspect, a -method for fabricating a gas diffusion electrode,
comprising:
23 bonding
a hydrophobic layer porous to carbon dioxide and impemeable to aqueous
electrolytes to a hydrophilic layer supporting a copper catalyst; and treating
the copper
catalyst to create a cuprous halide.
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10016) The
above presents.a simplified summary of the presently disclosed -subject matter
in order to. provide a basic understandina of some, aspects thereof The
summary is not an
exhaustive overview, -nor is it intended to .i.d.entify 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
F00171 The
claimed subject matter may be better understood by reference to the following
deseription taken in conjunction with the accompanying draWings,. in .which
like, femme.
numerals identify like elements, and in which:
io 1.0018]
Figure l depicts one particular embodiment of an electrolytic cell. in
accordance
with some aspects of the presently .disclosed technique.
10019]
Figure 2 graphically illustrates the electrochemical Fischer-Tropsch process
in
accordance with other aspects of the presently disclosed technique.,
100201
Figure :.1A-Figure 3B depict a copper mesh reaction electrode as .may be used
in
is some embodiments..
1002 I
Figure 41-A-Figure. 4-B depict a gas diffusion electrode as may be used in
some
embodiments.
10022)
Figure 5A-Fi.i.gire 5B depict a gas diffusion electrode as may be used in some
embodiments.
20 10023i
.Figure 6 depicts a portiori. of an embodiment: in Nvhich the electrodes are
electrically short. ci reui ted
[00241
Figure I graphically illustrates the process .917..carbon dioxide to ethylene
in
accordancewith one particular embodiment of the presently disclosed technique.
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(0025j
Figure 8 depicts another embodiment of an electrolytic cell in accordance with
another aspect of the presently disclosed technique.
(0026j
Figure 9 depicts another embodiment of an electrolytic cell in accordance with
another aspect of the presently disclosed technique.
100271 Figure I OA-Figure 1013 depict another embodiment of an electrolytic
celi in
accordance with another aspect of the.presently disclosed technique.
[00281
Figure I I depicts another embodiment of an electrolytic cell in accordance
with
another aspect of the presently disclosed technique.
(00291
While the invention is susceptible to various modifications and al.temati.ve
forms,
in 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
inte.nded 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
f00301
Illustrative embodiments of the subject matter claimed below will now be
disclosed. hi the interest of clarity, not all features of an actual
implementation are described
in this specification. it will be appreciated tb,at in the development of any
such actual
embodiment, numerous implementation-specific decisions must be made to achieve
the
2o
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.
(0031j The
presently disclosed technique is a. process for converting carbon-based gases
25 such as
non-polar organic eases 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
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organic compounds. in general, the method is for chain modification of
hydrocarbons and
organic compounds, including Chain lengthening, and eventual conversion into
liquids
including, bat not limited to, hydrocarbons, alcohols, and other organic
co.mpounds.
100321
This process .tnore particularly uses aqueous electrolytes to act as a
reducing or
3 oxidizing atmosphere and hydrogen and oxygen source for hydrocarbon
gases. The process in
the disclosed technique is a chain modification of hydrocarbons and organic
compounds
using aqueous electrochemical activation of carbon based gases at three-phase
interface of a
gas-liquid-solid electrode surface. This process aims hydrocarbon gases
including, but not
limited to, gaseous methane, natural gas, other hydrocarbons, carbon monoxide,
carbon
to dioxideõ and/or other organic gases into Cri- hydrocarbons, alcohols,
and other organic
compounds.One exemplary product is ethylene (C21-14) and alcohols. The process
may also
turn carbon dioxide (CO2) into one or more of isopropyl alcohol, hydroxy1-3-
methy1-2-
butanone, tetrahydrofuran, toluene, 2-heptanone, 2-butoxy ethanol, 1-butoxy-2-
propanolõ
benzaldehyde, 2-ethyl-hexanol, methyl.-undecanol, methyl-octanol, 2-hoptene,
nonan.ol,
is diethyl-dodecanol, dimethyl-cyclooctane, dimethyl octane', dodecanol,
ethyl-I, 4-dimethyl-
cyclohexane, dimethyl-octanol, bexadecene, ethyl-1-propenyl ether, dimethyl-
silanediol,
toluene, hexanal, methy1-2-hexatione, xylene isomer, methyl-hexanone,
heptanal, methyl-
hepttmone, benz.aldehyde, octanal, 2-ethyl-hexanol, nominal, 'hexerte-2õ 5-
diol, dodecanal, 3,
7-dimethyl-octanol, methyl-2, 2-dimethy1-1-(2-hydroxy-I-methylethyl)propyl
ester propanoic
2o acid, methy1-3- hydroxy-2, 4, 4-trimethylpentyl ester propanoic acid,
phthalic anhydride.
100331 The
reaction of carbon based eases may be successfully achieved with an aqueous
electrochemical solution serving as a liquid ion source along with the supply
for hydrogen or
singlet oxygen being provided by the aqueous source through acids and bases.
By creating a
three phase gas, solid, liquid interface between the carbon-based gases with
an electrolyte at a
25 solid phase catalyst which is connected to the reaction electrode of an
electrolytic cell. The
reaction may also be adjusted with different pHs or any kind of additive in
the electrolytic
solution.
[0034f The
reaction. utilizes a three phase interface which defines a reaction area. A
catalyst, a liquid, and a gas are contacted in the reaction area and an
electric potential is
3o applied to make electrons available to the reaction site. When
hydrocarbons are used as the
reactant gas it is possible to create hydrocarbon radicals which dien join
with other molecules
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or parts of molecules or themselves to create longer Chained hydrocarbons
andlor organic
molecules. The reaction site can also cause branched chain production by
reacting with a
newly created moh...cule and building on that or continuous chain building.
Thus from the
simple molecule of propane (CAW chains of molecules can be built by activating
the propane
molecule, Existing chained molecules can be lengthened, and existing chained
molecules can
be branched. A simple example is methane (CII4), can be converted to propanol
(C31I7(011)).
Different voltages create different reaction product distributions or
facilitate different reaction
types.
(00351
This aqueous electrochemical reaction includes a reaction that proceeds at
room
to temperature and pressure, although higher temperatures and pressures may
be used. In
general, temperatures may range front -IOC to 240C., or from -I 0C to 1000C,
and pressures
may range from .1 ATM to 10 ATM, or front .1 ATM to 100 ATM. The process
aenerates
reactive activated carbon-based gases through the reaction on the reaction
electrodes. On the
reaction electrode, the production of activated carbon-based gases occurs.
10036l In general, the method introduces a liquid ion source and a gaseous
feedstock into
a chamber in contact with a catalyst supporting reaction electrode submerged
in an
electrolyte. The reaction electrode is powered.
100371 In
the embodiments illustrated herein, the technique employs an electrochemical
cell such as the one illustrated in Figure 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 'natter of
polarity that can vary by implementation. In the illustrated embodiment, the
electrode 115 is
the anode and the electrode HO 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, the reaction electrode is considered to be
either or both of the
electrode 115 and electrode 116.
100381
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
carborp.based gas, for
example, non-polar organic gases, carbon-based oxides, or some mixture of the
two. The two
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Chanibers 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.
100391
Catalysts will be implementation specific depending, at least in part, on the
implementation of the reaction electrode 1.16. Depending on the embodiment,
suitable
catalysts may include, but are not limited. to, nickel, copper, iron, tin,
zinc, ruthenium,
palladiuin, rhenium, or any of the other transition or lanthanide and actinide
metals, or a
it) noble metal such as platinum, palladium, gold, or silver. They may also
include products
thereof, including for example cuprous chloride or cuprous oxide, other
inorganic compounds
of catalytic metals, as well as organometallic compounds. Exemplary
organometallic
coin.pounds include, but are not limited to, tetracarbonyl nickel,
lithiumdiphenylcu.prate,
pentamesitylpentacopper, and etharatedimer.
1100401 The electrolyte 120 will also be implementation specific depending,
at least in
part, on the implementation of the reaction electrode 1.16. Exemplary liquid
ionic substances
include, but are not limited to, Polar Organic Compounds, such as Glacial
...Acetic Acid, Alkali
or alkaline :Earth salts, sucb as halides, sulfates, sulfites, orbonates,
nitrates, or nitrites. The
electrolyte 120 may therefore be, depending upon the embodiment, magnesium
sulfate
(MgS), sodium chloride (NaCI), sulfuric acid (112SO4), potassium chloride
(K.C.1), hydrogen
chloride MCI), hydrogen bromide (HBr), hydrogen fluoride (H.F), potassium
chloride (KCI),
potassium bromide (Ki3r..), and potassium iodide (K1), or any other suitable
electrolyte and
acid. or base known to the art.
0o411 The
pH of the electrolyte .120 may range from -4 to 14 and concentrations of
ZS between 0.1M. and 3N1 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. In some embodiments, the electrolyte 120 is a halide to benefit
catalyst lifetime.
100421 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
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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 0,1 AT to 10 ATM, or fro.m .1 ATM to 100 ATW.t,
and the
selected pressure may be, for example, between .01 V and .10 V.
1.00431 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
Figure 6. 'The reaction products 160 are generated in both the electrolyte 120
and in the
to chamber 125 and may be collected in a vessel 165 of some kind in any
suitable 'timer
k-nown to the art. hi 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.
[00441 The embodiment of Figure 1 includes only a single reactor 105.
However, in
alternative embodiments. multiple units of these may be arranged for greater
efficiencies. In a
larger single chamber, pressure would more likely have to be adjusted. with
electrolyte level
rather than changes in the pressure of the gaseous feedstock 130 in the
chamber 125.
(00451
Those in the art will appreciate that some implementation specific details are
omitted from 'Figure 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 em.bodiments. Such instrinnenuition is used in
conventional
fashion to achieve, monitor, and maintain various operational parameters of
die process.
Exemplary operational parameters include, but are not limited to, pressures,
temperatures,
ZS 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.
(0046j The
reaction is conceptually illustrated in Figure 2. In this embodiment 200, the
feedstock 1.30' is natural gas and the electrolyte 1.20' is Sodium. Chloride.
Reactive hydrogen
ions ai4) are fed to the natural gas stream 130' through the electrolyte 120'
with an applied
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cathode potential of The molecules may also in turn react with water on the
interface to form
alcohols, ox.ygenates, and ketones. In one example of this reaction, the
reaction occurs at
room temperature and with an applied cathode potential of 0Ø1V versus SHE to
I .99V
versus SHE.
100471 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. These specific examples may or may not he
reflective of
the actual product yield and are meant only to illustrate how a product
produced can be
altered with a change in voltage.
io 100481
Figure 7 graphically illustrates the process of carbon dioxide to ethylene in
accordance with one particular embodiment of the presently disclosed
technique. The aaseotis
feedstock 730 is carbon dioxide. A voltage is applied across the cathode 716
and the anode
715 or a electrically short circuited reaction electrode illustrated in Figure
1 l. The
electrochemical interface in this reactor prevents the deactivation of carbon
dioxide by
is providing sufficient reactants to the surface of the catalyst to
consistently produce the desired
products without -the buildup of carbon black. In one example of this
reaction, the reaction
occurs at a temperature of -.10C to 210C and a pressure of.. ATM to. 10 ATM to
yield
ethylene product 765 found in 'both the gas and electrolyte
(00491
Returning now to Figure 1, additional attention will now be directed to the
20 electrochemical cell 100. .As noted above, the reactor 105 can be
fabricated from
conventional .materials using conventional fabrication techniques. Notably,
the presently
disclosed technique operates at room temperatures and pressures whereas
conventional
processes are performed at temperatures and pressines much higher. Design
considerations
pertaining to temperature and pressure therefore can be relaxed relative to
conventional
ZS practice. However, conventional reactor designs may nevertheless be used in
some
embodiments.
100501 The
presently disclosed technique admits variation in the implementation of the
electrode at whiclì the reaction occurs, hereafter referred to as the
"reaction electrode". As set
forth above, either the electrode 1.15 or the electrode 1.16, or both, may be
considered to be
30 the reaction electode depending upon the embodiment.
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(00511 in
one embodiment, an 80 mesh copper ineSh is used. This mesh may be plated
.with high current densities to produce thetal foam structures with high
surface areas which
may be utilized as catalysts in this reaction. More particularly, the catalyst
305 is supported
on a copper mesh 310 embedded in an ion exchange resin 300 as shown in Figure
3A. The
catalyst 305 can be a plated catalyst or powdered catalyst. The metal catalyst
305 is a
catalyst capable of reducing carbon-based gases to products of interest.
Exemplary metals
include, but are not limited to, metals such as copper, silver, gold, iron,
tin, zinc,
ruthenium, platinum, palladium, rhenium, or any of the other transition or
lanthanide and
actinide metals. In one embodiment, the -metal catalyst is silver, copper,
copper chloride or
to copper oxide. Ion exchange resins are well known in the art and any
suitable ion exchange
resin known to the art .may be used. In one particular embodiment, the ion
exchange resin. is
NAFION 117 by Dupont.
100521 The
copper wire .mesh 310 can be used to structure the catalyst 305 within the
resin 300 or it may,' be used without a resin. The assembly 315 containing the
catalyst 305 can
be deposited onto or otherwise structurally associated with an electrically
conducting paper
320, as shown in Figure 3B, Electrical leads (not shown) can then be attached
to the copper
.wire mesh 310 in conventional fashion. The reaction electrode 320 is but one
implementation
of the reaction electrode 116 in Figere 1. The eleatical leads may also be
connected to short
circuit the electrodes. Alternative implementations will be discussed below.
100531 -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 305 forms
one part of the three-phase interlace 155. When electricity is applied to
electrodes 115, 116,
electrochemical reduction discussed above takes place to produce hydrocarbons
and organic
chemicals. The reaction electrode 320 receives the electrical power and
catalyzes a reaction
.25 between the hydrogen in the electrolyte 120 and the gaseous feedstock
130.
(0054) .As
mentioned above, the copper mesh 310 in the illustrated embodiment is a mesh
in the range of .1- 400 mesh.
(00551 In
a second embodiment shown in Figure 4A-Figure 4B, a gas diffusion electrode
400 comprises a hydrophobic layer 405 that is porous to carbon-based gases but
impermeable
or nearly impermeable to aqueous electrolytes, in one e.mbodiment of the
electrode 400, a
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lmil thick advcarb carbon paper 410 treated with TEFLON* (i.e.,
polytetrafluoroethylene)
dispersion (not separately shown) is coated with activated carbon 415 with
copper 420
deposited in the pores of the activated carbon 415. The copper 420 may he
deposited through
a wet impregnation method, electrolytic reduction, or other means of reduction
of copper,
silver other transition metals into the porous carbon material.
1.00561
This material is then mixed with a hydrophilic binding agent (not shown), such
as
polyvinyl alcohol (PVA), 'polyvinyl acetate (PVAc), or Nation. An ink is made
from the
mixture of impregnated graphite, binding agent, and alcohol or other organic
solvent. The ink
is painted onto the hydrophobic layer 405 and then bonded through any means,
such as
to atmospheric drying, heat press, or other means of application of heat.
[00571 The
copper 420 impregnated into the ion electrode 400 is then made into a
cuprous halide through any suitable procedure. One erritxxliment of the
procedure to make
the cuprous halide is to submerge the electrode in a solution of hydrochloric
acii and cupric
chloride, heat to 100C for 2 hours. Another embodiment stibmerges the
impregnated
electrode 400 in 3 M KBr or 3 M la and run a 4 V pulse of electricity to the
electrode 400 in
order tc.) form a thin film of cuprous halide 425, shown in cross-section
Figure 48, in the
electrode 400.
100581 In
another embodiment, the copper particles in the electrode are first plated.
with
silver by electroless plating or another -method, creating a thin film of
silver over the copper.
Copper may then he plated onto the silver and transformed into a halide
through procedure
previously described. in another embodiment, silver particles are deposited
into the
hydrophilic layer, coated with copper electrolytically, and then the same
procedure for the
conversion of the copper layer to a copper halide layer is conducted.
[0059] In
another embodiment, the gas diffusion electrode uses nanoparticles reduced
as from a
solution of Cupric Chloride with an excess of a.scarbic acid and 10 grams of
carbon
graphite. The amalgam was heated to .t 00C .fir eight hours. It is then mixed
with equal
amounts in weight of a hydrophilic binder.
(0060i in
another embodiment, a high mesh copper of 200 mesh is allowed. to form
cuprous chloride in a solution of cuptic chloride and hydrochloric acid. This
layer of halide
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on the surface of the catalyst material allows for catalyst regeneration. This
accounts for the
abnormally high lifetime of the three phase reaction. The result is then
treated in a .1 to 3M
solution of Cupric Chloride heated to 100 C. This treatment is not necessary
for the wire
mesh catalyst to function.
3 100611
In one embodiment the electrode 400 therefore includes a covering or coating
425
'of cuprous chloride to prevent "poisoning" or .fouling of the electrode 400
during operation.
The electrodes in this embodiment nmst be copper so that no other metals foul
the reaction by
creating intermediate products wh.ich ruin the efficacy of the surface of the
copper. Some
embodiments also treat the copper with a high surface area powder by
electroplating, which
to will allow .for the generation of greater microturbulence, thereby
creating more contact and
release between the three phase reaction surface. Furthermore, contrary to
conventional
:practice, rather than separate the cathode arid anode, the cathode and anode
are allowed to
remain in the same electrolyte in this embodiment (The electrolyte is
filtered. through a pump
not shown.) The electrolyte is therefore contacted directly to the gas
diffusion electrode 400
15 rather than through the intercession of a polymer exchange membrane.
10062]
Catalysts in this particular embodiment may include copper, silver, gold,
iron, tin,
inc, ruthenium, platinum., palladium, rhenium, or any of the other transition
or lanthanide
and actinide metals. In addition, the catalysts may be formed into a metal
foam or
alternatively it may be deposited through electroless or electrolytic
deposition onto a porous
24 support 'with a hydrophobic. and hydrophilic layer.
[00631 In
one particular embodiment, the electrodes are electrically short circuited
("shorted") within the electrolyte while maintaining a three phase interface
between carbon-
based gases and electrolyte 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.
2.
Figure 6 depicts a portion 600 of an embodiment in which the electrodes are
shorted. In this
drawing., only a single electrode 605 is shown but the electric potential is
drawn across the
electrode 605. The companion electrode (not shown) is similarly shorted.
[0064{ So,
turning now to the process again ancl referring to Figure 1, carbon-based
gases
or electrolyte gaseous mixture including gaseous feedstock 130 is introduced
into the reaction
14
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of the column of electrolyte, which depends on the height of the electrolyete,
to induce the
reaction. 'The exemplary embodiments discussed below all include the following
design
characteristics: (1.) a three-phase catalytic interface 155 for solid
catalyst, gaseous feedstock
130, and. liquid ion source (e.g, a liquid electrolyte) 120, (2) a cathode 116
and anode 115 in
the same, or a shorted reaction electrode, filtered electrolyte 120, and (3)
an electrolyte 120
contacted directly -to the reaction electrode, which is the cathode 116.
100651 The
method of operation generally comprises introducinn 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
to enoutth pressure -to overcome the gravitational pressure of the column
of electrolyte, which
depends on the height of the electrolyte, to induce the reactionto 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 eeneml context, the following examples are
implemented.
100661 Above the second chamber 125, but attached to it, is an area for the
introduction
of a cathode reaction electrode 1.16 where the three-phase interface 155 will
form. Catalysts
supported by the reaction electrode .1.16 include copper, silver, gold, iron,
tin, zinc,
ruthenium, platinum, palladium, rhenium, or any of the other transition or
lanthanide and
actinide metals. In addition, the catalysts may be -fanned into a metal foam
or alternatively it
2o may be deposited through electroless or electrolytic deposition onto a
porous support with a
hydrophobic and hydrophilic layer as previously described above. The
electrolyte 120 may
compriseõ for example, potassium chloride (KC1), potassium bromide (KBr),
potassium
iodide (KJ), or any other suitable electrolyte known to the art.
100671
This particular embodiment implements the reaction electrode 116 as the gas
diffusion electrode described above with the cuprous halide coating.
Alternative
embodiments may use another cuprous halide coating the surface of the metal.
Cuprous
Oxide, Cupric Oxide, and other varying valence states of copper will also work
in the
reaction.
100681 By
maintaining a three phase interface between the gaseous feedstock 130 and the
3o electrolyte 120, the carbon-based gases will .fonn organic Chemicals and
form a nearly
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complete conversion when there is continuous contact to the gaseous feedstock
130 on the
three phase interfhces 155 between the liquid electrolyte 120, the solid
catalyst, and the
gaseous feedstock 1.30.
100691 For
carbon dioxide, this reaction mechanism also produces organic compounds
3 such as
ethers, epoxides, and C5+ alcohols, among other compounds such as ethers,
epoxies
and. long C5+ hydrocarbons which have not been reported in the prior art.
Iwo] The
electrolyte 120 should be relatively concentrated at .1M-3.1v1 and should be 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
Hi
electrolyte 120 on the other side, the higher the conversion rates. Operating
pressures could
be ranged from only 10000 pascals or . I atm to 10 atm, though Standard
Temperature and
Pressures (STP) were sufficient for the reaction.
[00711 in
one embodiment of the gas diffusion electrode (GDE) an antioxidant layer of
ascorbic acid is mixed with the ODE high porosity carbon.. The high porosity
carbon includes
is
nanotubes, fullerines, and other specialized formations of carbon as described
above. The
high porosity carbon is impregnated through reduction of cupric Chloride, or
other form of
carbon. It is then made into a halide by treatment with a diloride solution
under the proper
pH. and temperature of E11.417 conditions. It also includes a reaction in the
solid polymer phase.
A paste is made from the -impregnated carbon, ascorbic acid, and a hydrophilic
binding agent.
zo This paste is painted onto a hydrophobic layer.
100721 The
principles discussed above can readily be scaled up to achieve higher yield.
Four such embodinumts are shown in Figure 8-Figure 11.
100731 For
example, those in the art having the benefit of the disclosure associated with
Figure 1 will realize that the gaseous feedstock 130 and the electrolyte 120
need liot
25
necessarily be introduced into separate Chambers. One such example is shown in
Figure 8. In
this stacked embodiment 800, reactants 805 (e.g., gaseous feedstock and liquid
electrolyte, or
gaseous feedstock and a slurry of the catalyst and liquid electrolyte) enter a
chamber 810 in
which they are mix -ed, the resulting, mixture 835 then entering a reaction
chamber 840. A
plurality of alternating anodes 820 and cathodes 815 (only one of each
indicated) are
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positioned in the reaction chamber 840. Each of the anodes 820, cathodes 815
is a reaction
electrode at which a three-phase reaction area forms as described above. The
resultant
product 845 is collected in the chamber 825, a portion of which is then
recirculated back to
the chamber 810 via the line 830,
3 100741
In the stacked embodiment 900, Shown in Figure 9, the gaseous feedstock 915
and
liquid electrolyte 920 are separately introduced at the bottom of the reaction
chamber 925. A
plurality of chambers 930 only one indicated) are disposed between respective
anodes 820
and cathodes 815. Gaseous feedstock 935 and liquid electrolyte 940 are then
reacted in the
chambers 930 and the resultant gas product 905 and fouled electrolyte 910 are
drawn off the
it) top.
100751 .A
cylindrical embodiment 1000 is shown in Figure 10A-Figure 1011 A mixture
1005 of gaseous feedstock and liquid electrolyte is introduced into the bottom
of the
embodiment 1000, The embodiment includes a plurality of alternating, nested
anodes 101.6
and cathodes 1015 (only one of each indicated). As the mixture 1005 bubbles up
it reacts
J5 with
the catalyst (not shown) on the anodes 1016 and cathodes 1015 that define a
plurality of
three-phase interface as discussed above. Eventually, the product and fouled
electrolyte 1020
are drawn Off the top.
100761
Another stacked embodiment 1100 is shown in Figure 11. A mixture 1105 of
gaseous feedstock and liquid electrolyte is introduced into a chamber 1110,
from which it is
20 then
introduced into a reaction chamber 1130 in which a plurality of alternating
anodes 1016
and cathodes 1015 are stacked. When the anodes 1016 and cathodes 1015 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 elt..ctrodes. As the mixture 1105 rises in the reaction chamber 1130,
it forms a three-
phase reaction at each reaction electrode The gas product 1405 and the fouled
electrolyte
1410 are drawn from the chamber 1125 at the top of the embodiment 1100.
100771
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
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embodiments may exhibit other characteristics in addition to, or in lieu of,
those described
herein.
[00781 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
3 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
lumber 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
to ...................................................................
'recited &actions even when they are not actually perfbrming them i.e.,
when there is no
power or when they are powered but not in operation.
100791 The
following patent, applications, and publications are hereby incorporated by
reference for all purposes as if set forth verbatim herein:
[00801
U.S. .Application Serial No.. 61/608,583, erititled,'"An Electrochemical
Process for
is Direct
one step conversion of methane to Ethylene on a Three Phase Gas, Liquid, Solid
Interface", and filed March 8, 2012, in the name of the inventor Ed Chen and
commonly
assigned herewith.
100811
U.S. Application Serial No. 61/639,544, entitled,".Electrochemical Reactor for
the
use of Aqueous Electrolyte for High 'Efficiency Reaction of Non Polar Organic
Gases", filed
zo April 27, 2012, in the name of the inventor Ed Chen and commonly
assigned herewith.
100821
U.S. Application Serial No. 61/606,398, entitled, "A Process, Apparatus, and
Components for the Production of High Value Chemicals from carbon dioxide
Using
Modular, Electrochemical .Reduction of CO2 on Three Phase Interphase Gas
Diffusion
Electrode", filed March 3, 201.2, in the name of the inventor Ed Chen and
commonly
25 assigned herewith.
100831
U.S. Application Serial No. 61/713,487, entitled, "A Process for
'Electrochemical
Fischer Trospch", -filed October 13, 20.12, in the name of the inventor Ed
Chen and
commonly assigned here-with.
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10084)
'International ApplicatiOnSerial No, PCTIUS2011/004589, entitlek-Porous Metal
Deildrites for EliLJi Efficiency Aqn.
eous Reduction of CO2 to fiydrocarbone',: filed Dixerriber
13, -2011, in the name of the inventor Ed. Chen and assigned to The 'Trustees
of Columbia.
:University in the City of New York..
[00851 To
die:extent that any patent, patent applicatiOn. Or other reference
incorporated
herein by ;reference conflicts With the prekm disclostire set forth herein,
the present.
disclosure controls,
1:00861
:This concludes the detailed description. The .particular embodiments
disclosed
above are illustrative only, as the invention may be rnodified 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 de-tails 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 inventionõNrcordinay, the
protection sought
is herein is as set forth in the claims below,
19
