Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
APPARATUS AND PROCESSES OF INSTANTIATING THE SAME
RELATED APPLICATIONS
This application claims the benefit of priority under 35 USC 119(e) to U.S.
Patent
Application No. 63/241,697, filed September 8, 2021; and is a continuation-in-
part of U.S.
Patent Application No. 17/474,444, filed September 14, 2021 by Christopher J.
Nagel. The
entire teachings of the above applications are incorporated herein by
reference.
BACKGROUND OF THE INVENTION
Processes for producing hydrogen, including hydrogen on demand systems, are
described. For example, electrolyzers including a proton-exchange membrane, a
cathode
disposed on one surface, and an anode on a second surface of the membrane have
been used.
Such an anode can include an ionomer binder with dispersed particles having a
core and
catalytic layer, such as iridium or platinum. However, such systems can be
characterized by
high pressures and/or water-saturated gas. Therefore, there is a benefit to
improving such
processes to produce dry or substantially dry hydrogen gas.
SUMMARY OF THE INVENTION
The present invention relates to the discovery that apparatuses containing
carbon
matrices can be used to produce a variety of materials, such as gases,
hydrogen and small
organic molecules. The processes of the invention include the application of
electromagnetic
radiation, directly and/or indirectly, to gases, nano-porous carbon, or
compositions and
combinations thereof, thereby pre-treating the gas, and exposing a carbon
matrix to pre-
treated gas in an apparatus of the invention and recovering the products
produced therein.
The invention relates to apparatuses for instantiating materials and processes
for using
such apparatuses.
The invention includes processes comprising the steps of contacting a bed
comprising
nanoporous carbon with an activated gas while applying electromagnetic
radiation to the
nanoporous carbon for a time sufficient to cause instantiation of a gas and
collecting the gas.
The invention further relates to the gas produced by the process.
More specifically, the invention includes a process of instantiating a
material, such as
a gas composition (e.g., hydrogen) within a nanoporous carbon powder
comprising the steps
of:
(i) adding a nanoporous carbon powder into a reactor assembly (RA), as
described
below,
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(ii) adding a first gas composition to the reactor assembly;
(iii) powering one or more RA coils to a first electromagnetic energy level;
(iv) subjecting the nanoporous carbon powder (the terms nanoporous carbon
powder,
nanoporous carbon material and nanoporous carbon are used herein
interchangeably) to
harmonic patterning to instantiate a second gas composition (e.g, hydrogen)
thereby
producing a product gas composition;
(v) collecting the product gas composition and optionally separating the
second gas
composition or a component thereof (e.g., hydrogen).
In one embodiment, the RA coil surrounds a nanoporous carbon bed to establish
a
harmonic electromagnetic resonance in ultramicropores of the nanoporous carbon
powder.
The first gas composition can be, for example, air, oxygen, hydrogen, helium,
nitrogen, neon,
argon, krypton, xenon, carbon monoxide, carbon dioxide or mixtures thereof,
preferably
nitrogen or air. Preferably, the nanoporous carbon powder comprises graphene
having at
least 99.9% wt. carbon (metals basis), a mass mean diameter between 1 gm and 5
mm, and an
ultramicropore surface area between about 100 and 3000 m2/g.
More specifically, the invention includes a reactor assembly comprising:
(a) A reactor chamber containing a nanoporous carbon material;
(b) A second porous frit defining the ceiling of the reactor chamber; wherein
each porous frit has a porosity that is sufficient to allow a gas to permeate
into the reactor chamber and contain a nanoporous carbon material;
(c) A reactor head space disposed above the reactor cap;
(d) 1, 2, 3, 4, 5 or more RA coils surrounding the reactor chamber and/or
reactor head space operably connected to one or more RA frequency
generators and/or one or more power supplies;
(e) 0, 1, 2, 3, 4, 5 or more pairs of RA lamps wherein the pairs of RA lamps
are disposed circumferentially around the RA coils and define a space
between the pairs of RA lamps and the RA coils, when present;
(f) An optional x-ray source configured to expose the reactor chamber to x-
rays;
(g) One or more optional lasers configured to direct a laser towards (e.g.,
through or across) the reactor chamber or the gas within the reactor
assembly, when present; and
(h) A computer processing unit (CPU) configured to control the power supply,
frequency generator, x-ray source, lamps and/or lasers.
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As will be described in more detail below, the gas inlet of the reactor
assembly can be
in fluid connection with at least one gas supply selected from the group
consisting of air,
oxygen, hydrogen, helium, nitrogen, neon, argon, krypton, xenon, carbon
monoxide, carbon
dioxide and mixtures thereof; and/or (iii) the gas supply is directed through
a gas manifold
controlled by mass flow meters.
As will be described in more detail below, the nanoporous carbon powder
charged to
the reactor assembly can comprise graphene having at least 95% wt. carbon
(metals basis), a
mass mean diameter between 1 gm and 5 mm, and an ultramicropore surface area
between
about 100 and 3000 m2/g. The nanoporous carbon powder is preferably
characterized by acid
conditioning, wherein the acid is selected from the group consisting of HC1,
HF, HBr, HI,
sulfuric acid, phosphoric acid, carbonic acid, and nitric acid, and a residual
water content of
less than that achieved upon exposure to a relative humidity (RH) of less than
40% RH at
room temperature. In a preferred embodiment, the process contemplates
degassing the
nanoporous carbon powder prior to the process.
As will be described in more detail below, the reactor assembly can include a
plurality of devices that can impart electromagnetic fields, including x-ray
sources, coils,
lasers and lamps or lights, including pencil lamps, short wave and long wave
lamps. The
wavelengths generated by each device (e.g., lamps or lasers) can be
independently selected.
As will be described in more detail below, the RA coils can be made from the
same or
different electrically conducting materials. For example, a first RA coil
comprises a copper
wire winding, a second RA coil comprises a braiding of copper wire and silver
wire, and a
third RA coil is a platinum wire winding and each RA coil is configured to
create a magnetic
field and wherein each power supply independently provides AC and/or DC
current.
As will be described in more detail below, the reactor assembly can be
characterized
by (i) a first pair of RA lamps configured in a first plane defined by a
center axis and a first
radius of the reactor chamber, (ii) a second pair of RA lamps configured in a
second plane
defined by the center axis and a second radius of the reactor chamber and
(iii) a third pair of
RA lamps configured in a third plane defined by the center axis and a third
radius of the
reactor chamber. Preferably, each RA lamp is a pencil lamp characterized by a
tip
substantially equidistant from the central axis and each pair of RA lamps
comprises a vertical
RA lamp and a horizontal RA lamp. Preferably each pair of lamps is
equidistantly spaced
around the circumference of the reactor chamber.
As will be described in more detail below, the reactor assembly further
comprises an
electromagnetic embedding enclosure (E/MEE or EMEE), as defined more
specifically
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below. The E/MEE is typically located along a gas line upstream of the reactor
assembly gas
inlet. Typically, an electromagnetic embedding enclosure located upstream of
the gas inlet
comprises:
(a) a gas inlet;
(b) at least one E/MEE pencil lamp positioned below the internal gas line, at
least one E/MEE pencil lamp positioned above the internal gas line and at
least one E/MEE pencil lamp positioned to the side of the internal gas line;
wherein each E/MEE pencil lamp is independently rotatably mounted, located
along the length of the internal gas line, and
the lamps and/or coil(s) are powered by a power supply, preferably the power
supply of the reactor assembly;
the gas flow, lamps and/or coil(s) are preferably independently controlled by
one or more central processing units, preferably the central processing unit
(CPU) of
the reactor assembly. Typically, a CPU independently controls powering each
E/MEE pencil lamp and a rotation position of each E/MEE pencil lamp.
As will be described in more detail below, the E/MEE housing can be typically
closed
and opaque, the internal gas line can be transparent and external gas line in
fluid connection
with the housing outlet and gas inlet can be opaque. Typically, the internal
gas line is
between 50 cm and 5 meters or more and has a diameter between 2 mm and 25 cm
or more.
As will be described in more detail below, the apparatus can have at least 5
E/MEE
pencil lamps located along the internal gas line. Each E/MEE pencil lamp can
be
independently placed such that its longitudinal axis is (i) parallel to the
internal gas line, (ii)
disposed radially in a vertical plane to the internal gas line, or (iii)
perpendicular to the plane
created along the longitudinal axis of the internal gas line or along the
vertical axis of the
internal gas line. Each E/MEE pencil lamp can be independently affixed to one
or more
pivots that permit rotation between about 0 and 360 degrees with respect to
the x, y, and/or z
axis wherein (i) the x-axis is defined as the axis parallel to the gas line
and its vertical plane,
(ii) the y-axis defining the axis perpendicular to the gas line and parallel
to its horizontal
plane, and (iii) the z-axis is defined as the axis perpendicular to the gas
line and parallel to its
vertical plane.
As will be described in more detail below, at least one E/MEE pencil lamp can
be a
neon lamp, at least one E/MEE pencil lamp can be a krypton lamp, and at least
one E/MEE
pencil lamp can be an argon lamp. It can be desirable to match, or pair, one
or more E/MEE
pencil lamps with one or more (e.g., a pair) of RA lamps. Accordingly, at
least one pair of
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RA pencil lamps can be selected from the group consisting of a neon lamp, a
krypton lamp
and an argon lamp.
As will be described in more detail below, the invention also includes
nanoporous
carbon powder compositions and gas compositions produced in accordance with
the claimed
methods and processes.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, features and advantages of the invention will
be
apparent from the following more particular description of preferred
embodiments of the
invention, as illustrated in the accompanying drawings in which like reference
characters
refer to the same parts throughout the different views. The drawings are not
necessarily to
scale, emphasis instead being placed upon illustrating the principles of the
invention.
FIG. 1 is a perspective view of an E/MEE of the invention.
FIG. 2A and 2C show reactor assembly components. FIG. 2B is an expanded view
of
the reactor assembly components of FIG. 2A.
FIG. 3A, FIG. 3B, FIG. 3C, FIG. 3D and FIG. 3E provides five views of coils
which
can be used in a reactor assembly.
FIG. 4A is a perspective view of an E/MEE of the invention used in carbon
pretreatment. FIG. 4B shows reactor assembly components.
FIG. 5A illustrates one conformation for a standard coil. FIG. 5B illustrates
one
conformation for a reverse field coil.
FIG. 6A and 6B are illustrations of two examples of two composite reactor
assemblies. FIG. 6A illustrates a Composite Reactor with a copper body, carbon
graphite cup
and a carbon graphite cap. FIG. 6B illustrates a Composite Reactor with a
carbon graphite
body and cap and metal foil boundary.
FIGs. 7A-7I illustrate various reactor assembly views according to the
invention.
FIGs. 8A-8C and 9 are illustrations of reactor variations.
DETAILED DESCRIPTION
The invention relates to methods of instantiating materials, such as gases
and/or
hydrogen in nanoporous carbon powders. The invention includes methods
comprising the
steps of contacting a bed comprising a nanoporous carbon powder with a first
gas
composition, and optionally an electromagnetically activated gas, while
applying
electromagnetic radiation to the nanoporous carbon powder for a time
sufficient to cause
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instantiation within and/or from carbon nanopores. The process results in a
product gas
composition substantially distinct from the first gas composition. The
processes of the
invention have broad applicability in producing novel gas compositions, such
as hydrogen or
hydrogen on demand.
Nanoporous Carbon Powders
Nanoporous carbon powders or nanostructued porous carbons can be used in the
processes and methods of the invention. Nanoporous carbon powders or
nanostructued
porous carbons are also refered to herein as "starting material" or "charge
material". The
carbon powder preferably provides a surface and porosity (e.g., ultra-
microporosity) that
enhances metal deposition, including deposit, instantiation and growth.
Preferred carbon
powders include activated carbon, engineered carbon, graphite, and graphene.
For example,
carbon materials that can be used herein include graphene foams, fibers,
nanorods, nanotubes,
fullerenes, flakes, carbon black, acetylene black, mesophase carbon particles,
microbeads
and, grains. The term "powder" is intended to define discrete fine, particles
or grains. The
powder can be dry and flowable or it can be humidified and caked, such as a
cake that can be
broken apart with agitation. Although powders are preferred, the invention
contemplates
substituting larger carbon materials, such as bricks and rods including larger
porous carbon
blocks and materials, for powders in the processes of the invention.
The examples used herein typically describe highly purified forms of carbon,
such as
>99.995%wt. pure carbon (metals basis). Highly purified forms of carbon are
exemplified
for proof of principal, quality control and to ensure that the results
described herein are not
the result of cross-contamination or diffusion within the carbon source.
However, it is
contemplated that carbon materials of less purity can also be used. Thus, the
carbon powder
can comprise at least about 95% wt. carbon, such as at least about 96%, 97%,
98% or 99%
wt. carbon. In a preferred embodiment, the carbon powder can be at least
99.9%, 99.99% or
99.999% wt. carbon. In each instance, purity can be determined on either an
ash basis or on a
metal basis. In another preferred embodiment, the carbon powder is a blend of
different
carbon types and forms. In one embodiment, the carbon bed is comprised of a
blend of
different nano-engineered porous carbon forms. Carbon powders can comprise
dopants.
The carbon powder preferably comprises microparticles. The volume median
geometric particle size of preferred carbon powders can be between less than
about 1 gm and
5 mm or more. Preferred carbon powders can be between about 1 gm and 500 gm,
such as
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between about 5 gm and 200 gm. Preferred carbon powders used in the
exemplification had
median diameters between about 7 gm and 13 gm and about 30 gm and 150 gm.
The dispersity of the carbon particle size can improve the quality of the
products. It is
convenient to use a carbon material that is homogeneous in size or
monodisperse. Thus, a
preferred carbon is characterized by a polydispersity index of between about
0.5 and 1.5,
such as between about 0.6 and 1.4, about 0.7 and 1.3, about 0.8 and 1.2, or
between about 0.9
and 1.1. The polydispersity index (or PDI) is the ratio of the mass mean
diameter and
number average diameter of a particle population. Carbon materials
characterized by a
bimodal particle size can offer improved gas flow in the reactor.
The carbon powder is preferably porous. The pores, or cavities, residing
within the
carbon particles can be macropores, micropores, nanopores and/or ultra-
micropores. A pore
can include defects in electron distribution, compared to graphene, often
caused by changes
in morphology due to holes, fissures or crevices, corners, edges, swelling, or
changes in
surface chemistry, such as the addition of chemical moieties or surface
groups, etc. For
example, variation in the spaces that may arise between layers of carbon
sheets, fullerenes or
nanotubes are contemplated. It is believed that instantiation preferentially
occurs at or within
a pore or defect-containing pore and the nature of the surface characteristics
can impact
instantiation. For example, Micromeritics enhanced pore distribution analysis
(e.g., ISO
15901-3) can be used to characterize the carbon. It is preferred that the
carbon powder is
nanoporous. A "nanoporous carbon powder" is defined herein as a carbon powder
characterized by nanopores having a pore dimension (e.g., width or diameter)
of less than 100
nm. For example, IUPAC subdivides nanoporous materials as microporous (having
pore
diameters between 0.2 and 2 nm), mesoporous materials (having pore diameters
between 2
and 50 nm) and macroporous materials (having pore diameters greater than 50
nm).
Ultramicropores are defined herein as having pore diameters of less than about
1 nm.
Uniformity in pore size and/or geometry is also desirable. For example,
ultramicropores in preferred carbon materials (e.g., powders) account for at
least about 10%
of the total porosity, such as at least about 20%, at least about 30%, at
least about 40%, at
least about 50%, at least about 60%, at least about 70%, at least about 80%,
or at least about
90%. Preferred carbon materials (e.g., powders) are characterized with a
significant number,
prevalence or concentration of ultra-micropores having the same diameter,
thereby providing
predictable electromagnetic harmonic resonances and/or standing wave forms
within the
pores, cavities, and gaps. The word "diameter" in this context is not intended
to require a
spherical geometry of a pore but is intended to embrace a dimension(s) or
other characteristic
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distances between surfaces. Accordingly, preferred carbon materials (e.g.,
powders) are
characterized by a porosity (e.g., nanopores or ultramicropores) of the same
diameter account
for at least about 10% of the total porosity, such as at least about 20%, at
least about 30%, at
least about 40%, at least about 50%, at least about 60%, at least about 70%,
at least about
80%, or at least about 90%.
Measuring adsorption isotherm of a material can be useful to characterize the
surface
area, porosity, e.g., external porosity, of the carbon material. Carbon
powders having a
surface area between about 1 m2/g and 3000 m2/g are particularly preferred.
Carbon powders
having an ultramicropore surface area of at least about 50 m2/g, preferably at
least about 300
m2/g, at least about 400 m2/g, at least about 500 m2/g or higher are
particularly preferred.
Activated or engineered carbons, and other quality carbon sources, can be
obtained with a
surface area specification. Surface area can be independently measured by BET
surface
adsorption technique.
Surface area correlation with metal deposition was explored in a number of
experiments. Classical pore surface area measurements, using Micromeritics BET
surface
area analytical technique with nitrogen gas at 77K (-196.15C) did not reveal a
substantial
correlation in the deposition of metal elements at ?Sc confidence level, or
probability of
coincidence. However, a correlation with ultramicropores (pores having a
dimension or
diameter of less than 1 nm) was observed. Without being bound by theory,
instantiation is
believed to be correlated to resonating cavity features of the ultra-micropore
and
ultramicropore network such as the distance between surfaces or walls.
Features of the
ultramicropore, can be predicted from ultramicropore diameter as measured by
BET,
augmented by density function theory (DFT) models, for example. With the aid
of machine
learning, more precise relationships between ultramicropore size,
distribution, turbostratic
features, wall separation and diameter and elemental metal nucleation can be
established.
Carbon materials and powders can be obtained from numerous commercial
providers.
MSP-20X and MSC-30 are high surface area alkali activated carbon materials
with nominal
surface areas of 2,000-2,500 m2/g and >3,000 m2/g and median diameters of 7-13
gm and 60-
150 gm respectively (Kansai Coke & Chemicals Co). Norit GSX is a steam-washed
activated carbon obtained from Alfa Aesar. The purified carbon forms used in
the
experimental section all exceed >99.998wt% C (metals basis).
Modifying the surface chemistry of the carbon can also be desirable. For
example,
improved performance was observed when conditioning the carbon with an acid or
base.
Contacting the carbon with a dilute acid solution selected from the group
consisting of HC1,
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HF, HBr, HI, sulfuric acid, phosphoric acid, carbonic acid, and nitric acid
followed by
washing with water (such as deionized water) can be beneficial. The acid is
preferably in an
amount less than about 30%, less than about 25%, less than about 20% less than
about 15%,
less than about 10%, or less than about 5%, preferably less than or equal to
1% vol. The
preferred acid for an acid wash is an acid having a pKa of less than about 3,
such as less than
about 2. After washing, it can be beneficial to subject the carbon to a
blanket of a gas, such
as an inert gas, helium, hydrogen or mixtures thereof Alternative gases
include carbon
monoxide, carbon dioxide, nitrogen, argon, neon, krypton, helium, ammonia and
hydrogen.
The carbon can also be exposed to a base, such as KOH before or after an acid
treatment.
Controlling residual water content in the carbon which may include moisture
can
improve performance. For example, the carbon material can be placed in an oven
at a
temperature of at least about 100 C, preferably at least about 125 C, such as
between 125 C
and 300 C for at least 30 minutes such as about an hour. The oven can be at
ambient or
negative pressure, such as under a vacuum. Alternatively, the carbon material
can be placed
in an oven with high vacuum at a temperature of at least about 250 C,
preferably at least
about 350 C, for at least one hour, such as at least 2, 3, 4, 5, or 6 hours.
Alternatively, the
carbon material can be placed in an oven with high vacuum at a temperature of
at least about
700 C, preferably at least about 850 C, for at least one hour, such as at
least 2, 3, 4, 5, or 6
hours. Alternatively, the water or moisture can be removed by vacuum or
lyophilization
without the application of substantial heat. Preferably, the water, or
moisture, level of the
carbon is less than about 35%, 30%, 25%, 20%, 15%, 10%, 5%, such as less than
about 2%,
by weight carbon. In other embodiments, the carbon can be exposed to a
specific relative
humidity (RH) such as 0.5%, 1%, 2%, 5%, 12% RH or 40% RH or 70% RH or 80% RH
or
90% RH, for example, at 22 C.
Pre-treatment of the carbon material can be selected from one or more,
including all,
the steps of purification, humidification, activation, acidification, washing,
hydrogenation,
drying, chemistry modification (organic and inorganic), and blending. For
example, the
carbon material can be reduced, protonated or oxidized. The order of the steps
can be as
described, or two or more steps can be conducted in a different order.
For example, MSP-20X was exposed to an alkali (C:KOH at a molar ratio of
1:0.8),
activated at 700 C for 2 hours, washed with acid and then hydrogenated to form
MSP-20X
Lots 1000 when washed with HC1 and 105 when washed with HNO3. MSP-20X was
washed
with acid and then hydrogenated to form MSP-20X Lots 1012 when washed with HC1
and
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1013 when washed with HNO3. Activated carbon powder developed for the storage
of
hydrogen was HC1 acid washed, then subjected to HNO3 washing and hydrogenation
to form
APKI lots 1001 and 1002, as substantially described in Yuan, J. Phys. Chem.
B20081124614345-14357]. Poly(ether ether ketone) (PEEK, Victrex 450P) and
poly(ether
imide) (PEI, Ulteme 1000) was supplied by thermally oxidized in static air at
320 C for 15 h,
and carbonized at the temperature range of 550 ¨1100 C in nitrogen atmosphere,
at the
carbon yield of 50 ¨ 60 wt%. These carbons were then activated by the
following procedures:
(1) grind the carbonized polymer with KOH at KOH/carbon ¨ 1/1 ¨ 1/6 (w/w), in
the
presence of alcohol, to form a fine paste; (2) heat the paste to 600 ¨ 850 C
in nitrogen
atmosphere for 2 h; (3) wash and rinse with DI water and dry in vacuum oven.
PEEK/PEI
(50/50 wt) blend was kindly supplied by PoroGen, Inc. Likewise, the acid
washing sequence
of Lots 1001 and 1002 was reversed to form APKI lots 1003 and 1004. Universal
grade,
natural graphite, ¨200 mesh was purchased from Alfa Aesar, product number
40799.
Graphite lots R and Z were HC1 washed and hydrogenated to form R lot 1006 and
Z lot 1008,
respectively. Alfa Aesar graphite R and Z were nitric acid washed and
hydrogenated to form
R lot 1007 and Z lot 1009, respectively. MSC-30 (Kansai Coke and Chemicals)
was acid
washed and then hydrogenated to form MSC30 lots 1010 when washed with HC1 and
1011
when washed with HNO3. MSC-30 was exposed to an alkali (C:KOH at a molar ratio
of
1:0.8), activated at 700C for 2 hours, HC1 or nitric acid washed and then
hydrogenated to
form MSC-30 lots 1014 (HC1 washed) and 1015 (HNO3 washed), respectively. MSP-
20X,
MSC-30, Norit GSX and Alfa Aesar R were subjected to purification by MWI, Inc.
for MSP-
20X Lots 2000 and 2004, MSC-30 Lots 2001, 2006 and 2008, Norit GSX Lots 2005
and
2007, and Alfa Aesar R Lot 2009 respectively. MSP-20X Lot 2000 and MSC-30 2001
were
HC1 washed and hydrogenated to form MSP-20X Lot 2002 and MSC-30 Lot 2003,
respectively. Alfa Aesar R was washed with 1%, 5%, 10%, 15%, 20%, 25%, and 30%
HC1
(vol.) and then hydrogenated to for R Lot Graphite n% vol HC1, respectively.
Purified MSP-
20X (Lot 2006) was similarly washed by HC1, nitric acid, HF or H2SO4 to form
MSP-20X
1% HC1, MSP-20X 1% HNO3, MSP-20X 0.4% HF, MSP-20X 0.55% H2SO4 (Lot 1044),
respectively. Purified Norit GSX (Lot 2007) was similarly washed by nitric
acid, HF or
H2SO4 to form Norit GSX 1% HNO3 (Lot 1045), Norit-GSX 0.4% HF, Norit-GSX 0.55%
H2SO4, respectively. Purified MSC30 (Lot 2008) was similarly washed by HC1 and
H2SO4 to
form MSC30 1% HC1, and MSC30 5% H2SO4. Purified MSP2OX (Lot 2006), Norit GSX
(Lot 2007) and MSC30 (Lot 2008) were hydrogenated. Purified MSP-20X, Norit GSX
and
MSC30 were washed with 1% HC1 using methanol as a wetting agent. APKI-S-108
Lots
CA 03173512 2022- 9- 26
1021-1024 were recycled. The Ref-X Blend is a 40% Alfa Aesar R:60%MSP-20X (lot
2006)
850 C desorb then CO2 exposure at 138kPa (20 psi) for 5 days.
It is preferred to degas the nanoporous carbon powder prior to initiating the
process.
For example, the nanoporous carbon powder can be degassed by subjecting the
powder to a
vacuum. A range of vacuums can be used, with or without elevated temperatures.
It has
been found that applying a vacuum of about 10-2 torr to 10-6 ton was
sufficient. The powder
can be degassed prior to charging the powder into the reactor chamber.
Preferably the
powder can be degassed after the powder is charged into the reactor chamber.
In the
examples below, which are non-limiting, the carbon powder is charged into the
reactor
chamber, placed into the reactor assembly and the entire reactor assembly is
subjected to a
degassing step by maintaining the reactor assembly under vacuum. The degassing
step can
be performed at ambient temperature or an elevated temperature. For example,
good results
were achieved at a temperature of 400C. Other temperatures can be at least
50C, such as at
least 100C, at least 150C, at least 200C, or at least 300C. The degassing step
can be
maintained for at least 30 minutes, such as at least 45 minutes, at least 60
minutes, at least 4
hours, at least 6 hours, at least 12 hours, or at least 24 hours. Degassing
the carbon powder
ensures that contaminant elements have been removed from the system.
The carbon can be recycled or reused. In recycling the carbon, the carbon can
optionally be subjected to an acid wash and/or water removal one or more
times. In this
embodiment, the carbon can be reused one or more times, such as 2, 3, 4, 5,
10, 15, 20, or
about 25 or more times. The carbon can also be replenished in whole or in
part. It has been
discovered that recycling or reusing the carbon can enhance metal
nanostructure yields and
adjust nucleation characteristics enabling change in element selectivity and
resultant
distributions. Thus, an aspect of the invention is to practice the method with
recycled
nanoporous carbon powder, e.g., a nanoporous carbon powder that has been
previously
subjected to a method of the invention one or more times.
Nanoporous Carbon Compositions
The nanoporous carbon compositions produced by the processes described herein
possess several surprising and unique qualities. The nanoporosity of the
carbon powder is
generally retained during processing and can be confirmed, for example,
visually with a
scanning electron microscope or modeled by BET analysis. Visual inspection of
the powder
can identify the presence of elemental nanostructures residing within and
surrounding the
nanopores. The nanostructures are typically elemental metals. Visual
inspection of the
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CA 03173512 2022- 9- 26
powder can also identify the presence of elemental macrostructures residing
within and
surrounding the nanopores. The macrostructures are typically elemental metals
and often
contain interstitial and/or internal carbon, as generally described by
Inventor Nagel in US
Patent 10,889,892, which is incorporated herein by reference, in its entirety.
Methods for
instantiating gases are described in USSN 63/241,697 by Inventor Nagel, which
is
incorporated herein by reference in its entirety.
Typically, the porosity of the nanoporous carbon compositions will be at least
about
70% of the porosity attributed to ultramicropores of the nanoporous carbon
powder starting,
or charge, material and having a total void volume that is about 40% or more
of the bulk
material volume. The pores, or cavities, residing within the carbon particles
can be
macropores, micropores, nanopores and/or ultra-micropores. A pore can include
defects in
electron distribution, compared to graphene, often caused by changes in
morphology due to
holes, fissures or crevices, edges, corners, swelling, dative bonds, or other
changes in surface
chemistry, such as the addition of chemical moieties or surface groups, etc.
For example, the
spaces that may arise between layers of carbon sheets, fullerenes, nanotubes,
or intercalated
carbon are contemplated. It is believed that instantiation preferentially
occurs at or within a
pore and the nature of the surface characteristics can impact the deposit. For
example,
Micromeritics enhanced pore distribution analysis (e.g., ISO 15901-3) can be
used to
characterize the carbon. It is preferred that the carbon powder is nanoporous.
It has now
been surprisingly found that gases and other light materials can be
instantiated and collected
in the gas stream.
=
METHODS AND APPARATUS
Conceptually, the apparatus for baseline experimentation can be broken into
two
primary areas: Gas Processing and Reactor Assembly.
Gas Processing:
The gas processing section controls gas composition and flow rate, with the
optional
embedding of electromagnetic (e.g., light) information or electromagnetic gas
pre-treatment
to the reactor. The invention includes an electromagnetic embedding enclosure
(E/MEE or
EMEE), or apparatus, for processing a gas (feed gas or first gas composition,
used
interchangeably herein) comprising or consisting of:
a central processing unit and power supply;
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one or more gas supplies;
a housing having a housing inlet and housing outlet;
an upstream gas line that is in fluid connection with each gas supply and the
housing inlet;
an internal gas line in fluid connection with the housing inlet and housing
outlet;
a downstream gas line in fluid connection with the housing outlet;
at least one pencil lamp positioned below the internal gas line, at least one
pencil lamp positioned above the internal gas line and/or at least one pencil
lamp
positioned to the side of the internal gas line;
an optional short wave lamp and/or a long wave lamp; and
an optional coil wrapped around the internal gas line, operably connected to a
frequency generator;
wherein each lamp is independently rotatably mounted, located along the
length of the internal gas line, and powered by the power supply; and
wherein the central processing unit independently controls powering the
frequency generator, if present, and each lamp and the rotation position of
each lamp.
Feed gases can preferably be research grade or high purity gases, for example,
as
delivered via one or more gas supplies, such as a compressed gas cylinder.
Examples of
gases that can be used include, for example, air, oxygen, nitrogen, hydrogen,
helium, neon,
argon, krypton, xenon, ammonium, carbon monoxide, carbon dioxide and mixtures
thereof.
Preferred gases include nitrogen, helium, argon, carbon monoxide, carbon
dioxide and
mixtures thereof. Nitrogen, air and helium are preferred. In the examples
below, a highly
purified nitrogen gas was used. The use of highly purified nitrogen gas
facilitated product
gas analysis. The feed gas can be added continuously or discontinuously,
throughout the
process.
One or more gases (e.g., 2, 3, 4, 5, or more gases) can optionally pass
through a gas
manifold comprising mass flow meters to produce a first gas composition, also
called the
reactor feed gas. The reactor feed gas may then either by-pass an
electromagnetic (EM)
embedding enclosure (E/MEE) or pass through one or more E/MEEs. The E/MEE
exposes
the reactor feed gas to various electromagnetic field (EMF) sources. Flow
rates,
compositions, and residence times can be controlled. The rate of flow of the
reactor feed gas
can be between 0.01 standard liters per minute (SLPM) and 10 SLPM, or 100 SLPM
or more.
A constant flow of gas can maintain a purged environment within the reactor.
The
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schematics shown in FIG. 1 depicts a flow path for the gases through a sample
E/MEE. The
sample E/MEE comprises a series of lights and coils that can optionally expose
the reactor
feed gas to EM radiation. EMF sources within the E/MEE can be energized
simultaneously
or in sequence or a combination thereof.
FIG. 1 is an illustration of an E/MEE of the invention. Gas enters the E/MEE
via the
inlet 101, or entrance, in line 102 and exits at the outlet, or exit, 110. The
inlet 101 and outlet
110 may optionally have valves.
Line 102 can be made of a transparent or translucent material (glass is
preferred)
and/or an opaque or non-translucent material, such as stainless steel or non-
translucent plastic
(such as TYGON manufactured by Saint-Globain Performance Plastics) or a
combination
thereof Using an opaque material can reduce or eliminate electromagnetic
exposure to the
gas as the gas resides within the line. The length of line 102 can be between
50 cm and 5
meters or longer. The inner diameter of line 102 can be between 2 mm and 25 cm
or more.
Line 102 can be supported on and/or enclosed within a housing or substrate
111, such as one
or more plates, with one or more supports 112. For example, substrate 111 can
be configured
as a plane or floor, pipe or box. Where the substrate is a box, the box can be
characterized by
a floor, a ceiling and side walls. The box can be closed to and/or insulated
from ambient EM
radiation, such as ambient light.
One or more lamps (such as 2, 3, 4, 5, 6, 7, 8, 9, 10 lamps or more) can be
configured
within the E/MEE. Lamps (numbered individually) are preferably pencil lamps
characterized
by an elongated tube with a longitudinal axis. The pencil lamps can
independently be placed
such that its longitudinal axis is (i) parallel to the line 102, (ii) disposed
radially in a vertical
plane to the line 102, or (iii) perpendicular to the plane created along the
longitudinal axis of
the line 102 or along the vertical axis of the line 102.
Each lamp can, independently, be fixed in its orientation by a support 112.
Each lamp
can, independently, be affixed to a pivot 113 to permit rotation from a first
position. For
example, the lamps can be rotated between about 0 and 360 degrees, such as
about 45, 90,
135, 180, 225 or 270 degrees, preferably about 90 degrees relative to a first
position. The
rotation can be with respect to the x, y, and/or z axis wherein (i) the x-axis
is defined as the
axis parallel to the gas line and its vertical plane, (ii) the y-axis defining
the axis
perpendicular to the gas line and parallel to its horizontal plane, and (iii)
the z-axis is defined
as the axis perpendicular to the gas line and parallel to its vertical plane.
Referring to the specific pencil lamps within an E/MEE, line 102 is configured
along
the E/MEE with gas flowing from the inlet 101 and exiting at the outlet 110.
Lamp 103, a
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CA 03173512 2022- 9- 26
neon lamp, is first and is shown above line 102 oriented to be along the z-
axis and
perpendicular to line 102, with the tip of the lamp pointed towards line 102.
Lamp 109, a
krypton lamp, is shown below line 102 oriented to be parallel to the x-axis,
with the tip
pointing towards the outlet 110. Lamps 104 and 105, a long wave and short wave
lamp,
respectively, are shown parallel to line 102 oriented to be along the x-axis
with the tips
pointing towards the inlet. Lamp 122, an argon lamp, is shown to be below line
102 oriented
to be parallel to the x-axis, with the tip pointing towards the inlet 101 at
approximately the
same distance from the inlet as lamps 104 and 105. Lamp 106, a neon lamp, is
downstream
at about the midpoint of the E/MEE, is above line 102 with the tip pointing
down. Lamp 107,
a xenon lamp, is shown downstream of lamp 106 above line 102, parallel to the
x axis of line
102 and points toward the outlet 110. Lamp 108, an argon lamp, is below line
102 and the tip
is pointing toward line 102 along the z-axis. Optional coil 120 is wrapped
around line 102.
Each of these lamps can be independently rotated, for example, 90 degrees
along any axis.
Each lamp is connected to a power supply or power source to turn on or off the
power. Each
lamp can be independently rotated 1, 2, 3, 4 or more times during the process.
For
convenience, each lamp is held by a pivot that can be controlled by a central
processing unit,
such as a computer programmed to rotate the pivot and provide power to each
lamp. For the
ease of describing the experimental procedures, each orientation of each lamp
is called
"position n" wherein n is 0, 1, 2, 3, 4, or more. As the procedure is
conducted, each lamp can
be powered for specific periods of time at specific amperage(s) and positioned
or
repositioned.
In the exemplification described below, the initial bulb position for each
lamp is
described with a degree. A zero degree (0 ) reference point is taken as the 12
o'clock
position on the glass pipe when looking down the gas pipe in the direction of
intended gas
flow (e.g., when looking at the E/MEE exit). The length of the glass pipe or
line is taken as
the optical length (e.g., in this instance 39 inches). For example, 6 inches
from the end is
defined as 6 inches from the optical end of pipe.
The lamps can be placed above, below, or to the side (for example, level with
the
longitudinal axis or a plane parallel to (above or below) the longitudinal
axis), for example,
of line 102. The lamps can be independently placed between 5 and 100 cm from
the center of
the line 102 in the vertical plane, as measured from the tip of the lamp to
the center of line
102. One or more lamps can be placed in the same vertical plane along line
102, as
illustrated by lamps 122, 104, and 105. Two lamps are in the same vertical
plane if they (as
CA 03173512 2022- 9- 26
defined by the tip or base of the lamp) are the same distance from the inlet
101. Preferably,
lamp 105 can be placed in a plurality of (e.g., 2, 3, 4, 5 or more) vertical
planes along the
length of line 102 within the E/MEE. Further, one or more lamps can be placed
in the same
horizontal plane above, below or through line 102, as shown with lamps 104 and
105. Two
lamps are in the same horizontal plane if they (as defined by the tip or base
of the lamp) are
the same distance from the center of line 102. Preferably, lamps can be placed
in a plurality
of (e.g., 2, 3, 4, 5 or more) horizontal planes along the length of line 102
within the E/MEE,
as generally illustrated.
It is understood that "pencil lamps," as used herein, are lamps filled with
gases or
vapor that emit specific, calibrated wavelengths upon excitation of the vapor.
For example,
pencil lamps include argon, neon, xenon, and mercury lamps. For example, one
or a plurality
of lamps can be selected from argon, neon, xenon or mercury or a combination
thereof.
Preferably, at least one lamp from each of argon, neon, xenon and mercury are
selected.
Wavelengths between 150 nm and 1000 nm can be selected. One example of a
pencil lamp
is a lamp characterized by an elongated tube having a tip and a base.
Long wave and/or short wave ultraviolet lamps can also be used. Pencil lamps
used
in the E/MEE were purchased from VWRTM under the name UVP Pen_Ray rare gas
lamps,
or Analytik Jena in the case of the UV short wave lamps.
A power supply is operably connected to independently to each lamp, E/MEE
coil,
and frequency generator. The power supply can be AC and/or DC.
The E/MEE can be open or enclosed. Where the E/MEE is enclosed, the enclosure
is
typically opaque and protects the gas from ambient light. The enclosure can be
made of a
plastic or resin or metal. It can be rectangular or cylindrical. Preferably,
the enclosure is
characterized by a floor support.
In baseline experimentation the feed gas can by-pass the E/MEE section and are
fed
directly to the reactor assembly. The energy levels and frequencies provided
by the EM
sources can vary.
FIG. 4A provides a second illustration of an E/MEE of the invention. Gas
enters the
E/MEE at inlet 401 and exits at outlet 409 along line 410. Pencil lamp 402 and
Pencil lamp
403 are shown parallel to and above line 410 along the vertical plane through
line 410 axis.
Pencil lamps 404 and 405 are parallel to and below line 410 in the same
horizontal plane
equidistant from the vertical plane through line 410. Pencil lamp 406 is shown
above and
perpendicular to line 410, positioned along the z axis. An optional coil 407
is a conductive
coil wrapped around line 410. Pencil lamp 408 is shown below and perpendicular
to line 410
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CA 03173512 2022- 9- 26
along the y axis. Substrate 411 provides a base for supports 412. Pivots 413
control the
position of each pencil lamp and permit rotation along axis x, y and z. An
optional x-ray
source 429 is also shown directed towards the coil 407.
The coil 407 is preferably made of conducting material and is connected to a
power
supply and, optionally, a frequency generator. The coil can comprise copper,
aluminum,
platinum, silver, rhodium, palladium or other metals or alloys (including
braidings, platings
and coatings) and can optionally be covered with an insulating coating, such
as glyptal. It
can be advantageous to use a braid of 1, 2, 3 or more metal wires. The coil
can be
manufactured from wire typically used in an induction coil and can vary in
size and the
number of turns. For example, the coil can comprise, 3, 4, 5, 6, 7, 8, 9, 10
or more turns.
The inner diameter of the coil can be between 2 cm and 6 cm or more and
preferably snugly
fits the line 410. The wire used can have a diameter of between 5 mm and 2 cm.
An x-ray source 429 can included in the E/MEE. For example, the x-ray source
can
be directed at line 410 along the line between the inlet 401 and outlet 409.
For example, it
can be advantageous to direct the x-ray source at coil 407, where present.
Reactor Assembly (RA):
The invention further relates to a reactor assembly comprising:
A gas inlet and one or more gas outlets;
A reactor chamber, preferably containing a nanoporous carbon material or
powder;
A first porous frit defining a floor of the reactor chamber,
A second porous frit defining the ceiling of the reactor chamber; wherein each
porous frit has a porosity that is sufficient to allow a gas to permeate into
the reactor chamber
and contain a nanoporous carbon material;
An optional reactor cup defining side walls of the reactor chamber;
An optional reactor cap positioned above the second porous frit;
A reactor body disposed below the first porous frit;
A reactor head space disposed above the reactor cap;
An optional foil disposed between the reactor chamber and reactor cup;
One or more coils surrounding the reactor body and/or the reactor chamber
operably connected to a power supply and/or frequency generator;
An optional x-ray source configured to expose the reactor head space to x-
rays;
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CA 03173512 2022- 9- 26
One or more optional lasers configured to direct a laser towards a frit and/or
through the reactor chamber;
A computer processing unit configured to control the power supply, frequency
generator, lamps, lasers and x-ray source, when present.
The invention also includes a reactor assembly comprising:
A gas inlet and one or more gas outlets;
A reactor chamber, preferably containing a nanoporous carbon material;
A first porous frit defining a floor of the reactor chamber,
A second porous frit defining the ceiling of the reactor chamber; wherein each
porous frit has a porosity that is sufficient to allow a gas to permeate into
the reactor
chamber and contain a nanoporous carbon material;
A reactor head space disposed above the reactor cap;
2, 3, 4, 5 or more RA coils surrounding the reactor chamber and/or reactor
head space operably connected to an RA frequency generator and power supply;
2, 3, 4, 5 or more pairs of lamps wherein the pairs of lamps are disposed
circumferentially around the RA coils and define a space between the pairs of
lamps
and the RA coils;
An optional x-ray source configured to expose the reactor chamber to x-rays;
One or more optional lasers configured to direct a laser through the reactor
chamber; and
A computer processing unit configured to control the power supply, frequency
generator and the optional x-ray source and lasers.
The invention also includes a reactor assembly comprising:
A gas inlet and one or more gas outlets;
A reactor chamber, preferably containing a nanoporous carbon material;
A first porous frit defining a floor of the reactor chamber,
A second porous frit defining the ceiling of the reactor chamber; wherein each
porous frit has a porosity that is sufficient to allow a gas to permeate into
the reactor
chamber and contain a nanoporous carbon material;
A reactor head space disposed above the reactor chamber;
An induction coil surrounding the reactor chamber and/or reactor head space
operably connected to a power supply;
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CA 03173512 2022- 9- 26
A computer processing unit configured to control the power supply. The
reactor chamber can optionally contain a cap and/or cup to contain the carbon
material.
As shown in FIG. 2A and 2B, the reactor assembly comprises a reactor body 202
and
starting, or charge, material 204 (which is generally a nanoporous carbon
powder) and is
located downstream of the gas sources 221 and E/MEE 222, as shown in FIG. 2A.
As
described above, it is possible for reactor feed gas to bypass the E/MEE. The
reactor body
202 can be a packed bed tubular micro-reactor surrounded by one or more
conducting coils
208, as illustrated in FIG. 2B, a cross section of the reactor assembly.
The conducting coil 208 can be manufactured from electrically conducting
material,
such as copper, aluminum, platinum, silver, rhodium, palladium or other metals
or alloys
(including braidings, platings and coatings) and can optionally be covered
with an insulating
coating, such as glyptal. The coil can be manufactured from wire typically
used in an
induction coil and can vary in size and the number of turns. For example, the
coil can
comprise 3, 4, 5, 6, 7, 8, 9, 10 or more turns. The inner diameter of the coil
can be between 2
cm and 6 cm or more and preferably snugly fits the reactor body containment
207. The wire
used can have a diameter of between 5 mm and 2 cm.
Each conducting coil 208 (or coil) can generate inductive heat and,
optionally, a
magnetic field. Standard induction coils or reverse field induction coils
(coils that have a
lower and upper sections connected through an extended arm that allows the
sections to be
wound in opposite directions, thereby producing opposing magnetic fields) are
preferred. The
coil 208 can be water-cooled via a heat exchanger. The coil can be connected
to a power
flange 210, which can be water cooled as well and in turn can connect to a
power supply,
such as an Ambrell 10kW 150-400kHz power supply. In baseline experimentation a
standard
coil was used with simple copper windings. The windings can form a coil such
that the
connection to the power supply is at opposite ends of the coil FIG. 5A or the
coil can return
such that the connection to the power supply are adjacent, as shown in FIG.
5B.
The reactor assembly can optionally further comprise one or more coils 208,
preferably surrounding the reactor body and its containment system. For
example, the reactor
assembly can comprise 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 or more coils, also
called RA coils. As
shown in FIG. 2B, one or more electromagnetic (E/M) coils can be used to
provide magnetic
fields. Preferably, 1, 2, 3, 4, or 5 or more E/M coils can be used, more
preferably 3, 4, or 5
E/M coils. FIG. 3 shows groupings of three coils, for example, which can
generally be
numbered 1, 2, or 3, from top to bottom. A grouping of coils, as shown in FIG.
3A-3E, can
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CA 03173512 2022- 9- 26
be called a boundary. Where a plurality of groupings is used, the number of
coils used is
independently selected. Further, the groupings can be equidistantly spaced
along or
irregularly spaced.
Coils can be manufactured from electrically conducting materials, such as
copper,
platinum, silver, rhodium, palladium and, wire braids or coated wires of two
or more
materials. Each coil in a grouping may be made of the same material or
different. For
example, a grouping can be made such that each coil is made of a different
material. For
example, a braiding of copper wire and silver wire can be used. Silver plated
copper wire can
be used. A first RA coil can be made of a copper winding. A second RA coil can
be a
copper/silver braid. A third RA coil can be a platinum wire winding. An RA
coil can be
configured to create a magnetic field and wherein each power supply
independently provides
AC and/or DC current. Any one or all RA coils can be optionally lacquered.
The coils are preferably circular in geometry. However, other geometries, such
as
rounded shapes, ellipses and ovoids can be used. The wire diameter can be
between about
0.05 mm (> about 40 gauge) and about 15 mm (about 0000 gauge) or more. For
example, the
wire diameter can be between about 0.08 mm (about 40 gauge) and about 0.8 mm
(about 20
gauge) wire. Excellent results have been obtained using 0.13 mm (36 gauge)
wire. Coils can
be wire windings (e.g., the wire can be wound in 1, 2, 3, 4, 5, 6, 7, 8, 9,
20, or more turns or
can be a single turn. When the coil is made with a single winding, the
diameter or width of
the wire can preferably be 10 mm or more in diameter. In this context, a
"wire" can also be
considered a band where the width of the material is greater than the depth.
FIG. 3 provides
illustrations or views of various coils and groupings of coils. A wire coil
can be made of a
single wire, a wire alloy or two or more wires. For example, two wires
comprising different
metals can be wound or braided together.
The inner diameter (or dimension(s) where the coil is not a circle) of each
coil can be
the same or different and can be between 2 and 200 cm.
Coils 208 can independently be connected to one or more power supplies, such
as an
AC or DC power supply or combination thereof. For example, an AC current can
be supplied
to alternating (1, 3, and 5, for example) or adjacent coils (1, 2 and/or 4, 5,
for example) while
DC current is supplied to the remaining coils. Current can be provided
(independently) in a
frequency, such as in a patterned frequency, e.g., triangle, square or sine
pattern or
combination thereof. The frequency supplied to each coil can be the same or
different and
between 0 to 50 MHz or higher. While the coils 208 can generate and transfer
thermal
energy, or heat, to the reactor feed gas they are predominantly used to create
a magnetic field.
CA 03173512 2022- 9- 26
The power supply can be an AC and/or DC power supply or combination thereof.
Current can be provided (independently) in a frequency, such as in a patterned
frequency, e.g.,
triangle, square or sine pattern or combination thereof The frequency supplied
to each coil
can be the same or different and between 0 to 50 MHz or higher, such as
between 1 Hz to 50
Mhz.
As described above, the RA coils typically surround the reactor chamber and/or
reactor head space. For example, a first RA coil can be aligned with the first
(or bottom) frit.
A second RA coil can be aligned with the reactor chamber or nanoporous carbon
bed. A
third RA coil can be aligned with the second (or top) frit. Where present, a
fourth RA coil
can be disposed between the first RA and the second RA coil. When present, a
fifth RA coil
can be disposed between the second RA coil and third RA coil. When two or more
reactor
chambers, or nanoporous carbon beds are present, it can be desirable to add
additional RA
coils, also aligned with a second or additional reactor chambers or nanoporous
carbon beds.
Additional RA coils can be added to align with additional frits when present.
The RA coils can typically be supported in a support or stator to maintain a
fixed
distance between each coil. The support, when present, can be transparent. In
one
embodiment, the RA coils can be configured in a cartridge that can be removed
or moved.
The RA coils can, additionally or alternatively, be aligned with the reactor
headspace.
The reactor headspace can typically be a volume above the second, or top,
frit. It is
understood that where the reactor assembly is positioned horizontally (or at
some other angle
than vertical), the geometry of the spaces is maintained, albeit rotated. The
reactor headspace
can typically be an enclosed volume. For example, the reactor assembly can be
inserted into
a closed ended transparent (e.g., glass) tube, vial or bottle. The reactor
assembly can be
movably engaged with the RA coils (or boundary), thereby permitting each RA
coil to align
to a different element within the reactor assembly. For example, the first RA
coil can be
realigned with the reactor chamber.
Reactor body 202 can also be a packed, moving or fluidized bed or other
configuration characterized by one or more chambers that receive the charge
material 204 and
facilitates transfer of a reactor feed gas through the charge material 204 and
can transfer
thermal and/or electromagnetic energy to the charge material 204. The reactor
body 202 is
generally contained within a housing, e.g., closed end tube, 207 and frits
203, which function
to contain the charge material 204. It can be advantageous to use a reactor
within a
translucent or transparent housing, such as quartz or other materials
characterized by a high
melting point. The volume of the reactor bed can be fixed or adjustable. For
example, the
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CA 03173512 2022- 9- 26
reactor bed can contain about 1 gram, or less of starting material, between
about 1 g to 1 kg
of starting material or more. Where the reactor assembly comprises two or more
reactor
chambers, the reactor chambers are preferably directly or indirectly stacked,
preferably
having a common central axis and can be separated by one or two frits.
The reactor body 202 can be made of a thermally conductive material, such as
graphite, copper, aluminum, nickel, molybdenum, platinum, iridium, cobalt, or
niobium, or
non-thermally conducting material, such as quartz, plastic (e.g., acrylic), or
combinations
thereof An optional cup 206 capped with cap 205 can be advantageous. The cup
and cap
material can be independently selected. For example, a graphite cup can be
combined with a
graphite cap, which is the selection for the examples below. A copper cup can
be combined
with a graphite cap. A graphite cup can be combined with a copper cap. A
copper cup can
be combined with a copper cap and so on.
The reactor assembly can also receive the gas line through the entrance, or
inlet, 201
and to provide an exhaust through an exit, or outlet, 209, optionally
controlled by valves. A
head space defined by a closed end tube 207 can be configured above the
reactor body. The
reactor body is preferably made of graphite, copper, or other inorganic rigid
material. The gas
line is preferably made of an inert tubing, such as glass, acrylic,
polyurethane, plexiglass,
silicone, stainless steel, and the like can also be used. Tubing can,
optionally, be flexible or
rigid, translucent or opaque. The inlet is generally below the charge
material. The outlet can
be below, above or both.
Frits 203 used to define the chamber containing the charge material are also
shown.
The frits can be made of a porous material which permits gas flow. The flits
will preferably
have a maximum pore size that is smaller than the particle size of the
starting material. Pore
sizes of between 2 and 50 microns, preferably between 4 and 15 microns can be
used. The
thickness of the frits can range satisfactorily between 1 and 10 mm or more.
The flits are
preferably made of an inert material, such as silica or quartz. Porous frits
from Technical
Glass Products (Painesville Tp., Ohio) are satisfactory. On the examples
below, fused quartz
#3 porous flits (QPD10-3) with a pore size between 4 and 15 microns and a
thickness of 2-3
microns and fused quartz frits with a pore size between 14 and 40 microns
(QPD10-3) were
used. The purity of the frits exemplified herein was very high, 99.99%wt, to
ensure that the
results obtained cannot be dismissed as the result of contamination. Frits of
lower purity and
quality can also be used. The diameter of the porous frit is preferably
selected to permit a
snug fit within the reactor interior, or cup. That is, the diameter of the
porous frit is
approximately the same as the inner diameter of the reactor or cup, if
present.
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Referring to FIG. 6A and 6B, a foil can optionally encase the chamber
containing the
charge material on the inside and/or outside of the frits and/or cup, thereby
creating a metal
boundary surrounding the starting material. The foil can be a metal, such as
copper,
platinum, niobium, cobalt, gold, silver, or alloys thereof The foil can also
be graphite or the
like. The foil can be between 0 and 0.5 cm thick, preferably 1-10 mm. The
profile of the
reactor can be linear or it can be configured to contain a constriction below
the lower frit,
providing the general appearance of a lollipop. The gas line 102 is also
shown.
The reactor chamber is sized to contain the desired amount of charge material
204. For
the experiments described herein, the chamber is designed to contain between
20 mg to 100
grams of nanoporous carbon powder. Larger reactors can be scaled up.
The reactor assembly may be augmented with additional forms of electromagnetic
radiation, such as light. FIG. 4B exemplifies light sources 426 and 427 that
generate light
directed through the reactor housing 415 and starting material contained
therein. Preferred
light sources 426 and 427 can be lasers and/or can emit light in a wavelength
between 10 nm
and 1 mm. The light is optionally subjected to one or more filters 428, as
shown in the use of
light sources (beams) in FIG. 4B. Preferably, the reactor assembly comprises
2, 3, 4, 5 or
more pairs of lamps disposed circumferentially around the RA coils. Pencil
lamps, such as
the lamps used within the E/MEE which is incorporated herein by reference from
above, are
preferred. The pairs of lamps preferably define a boundary surrounding the
coil and are not
touching or otherwise adjacent to the coils. Two lamps are considered paired
where they are
proximal to each other, such as within the same plane with the center axis of
an RA coil.
Paired lamps can be parallel or orthogonal to each other and the RA coil
center axis. Lamps
can be considered proximal to each other if the space between any two points
between the
lamp tip and base is within 10 cm, preferably within 5 cm. Lamps that are
positioned
orthogonally to the RA coil center axis are generally positioned along the
line defined by the
radius of one or more RA coils.
The RA lamps, e.g., the pencil lamps proximal to the reactor body, can be
matched, or
paired, to one or more E/MEE lamps, e.g., the pencil lamps residing within the
E/MEE
housing and proximal to the gas line. For example, where an E/MEE pencil lamp
is a neon
lamp, a pair of RA lamps can be neon pencil lamps. Additionally, where an
E/MEE pencil
lamp is a neon lamp, a pair of RA lamps can be neon pencil lamps. Such matched
lamps can
emit light characterized by substantially the same wavelength. This can be
conveniently
achieved by using lamps from the same manufacturer with the same
specifications.
23
CA 03173512 2022- 9- 26
The reactor can be in a closed or open housing 415 and can be supported
therein by
reactor supports. The reactor feed gas is directed to the reactor inlet frit,
or bottom frit,
directed through the starting material contained within the housing 415 and
exits the reactor
at the reactor exit frit, or top frit. The reactor feed gas can then be
exhausted or recycled,
optionally returning to the E/MEE for further treatment.
The reactor can further comprise an x-ray source 211 (FIG. 2C) or 424 (FIG.
4B)
and/or one or more lasers 212 (FIG. 2C) or 426 and 427 (FIG. 4B). Preferred x-
ray sources
include a mini-x. The x-ray is preferably directed through the reactor towards
a gas
headspace, or target holder 213, above the charge material. The x-ray can be
directly or
indirectly provided from the source, such as by reflecting the x-ray from a
foil disposed
above or below a frit.
FIG. 7A illustrates a top view of a preferred reactor assembly. Pencil lamp
1501,
pencil lamp 1502 and pencil lamp 1503 are shown with the tip directed towards
a center axis
of the reactor assembly along a radius of the reactor assembly. Pencil lamp
1504, pencil
lamp 1505 and pencil lamp 1506 are shown directed parallel to a center axis of
the reactor
assembly and are disposed in a plane along a radius of the reactor assembly.
Pencil lamp
1501, together with pencil lamp 1504, form a first RA lamp pair. Pencil lamp
1502, together
with pencil lamp 1505, form a second RA lamp pair. Pencil lamp 1503, together
with pencil
lamp 1506, form a third RA lamp pair. As with the E/MEE pencil lamps, each RA
lamp can
be rotated along its x, y or z axis. Each pair can optionally reside within
the same radial
plane, as shown. Outer support 15109 provides support for the pencil lamps
1501, 1502 and
1503. Inner support 15110 provides support for the pencil lamps 1504, 1505 and
1506. The
outer and inner supports are preferably made of non-conductive materials (such
as polymers
or resins) and are preferably transparent. An optional x-ray source 1507 is
shown directing x-
rays towards the center axis of the reaction chamber 1508. Reactor connector
15111 is also
shown.
FIG. 7B is a perspective view of this reactor assembly. Pencil lamp 1509,
pencil lamp
1510 and pencil lamp 1511 are shown directed with the tip towards a center
axis of the
reactor assembly along a radius of the reactor assembly. The tip of each lamp
aligns with the
center, or third, RA coil 1517 and is in the same horizontal plane. Pencil
lamp 1512, pencil
lamp 1513 and pencil lamp 1514 are shown directed parallel to a center axis of
the reactor
assembly, disposed in a plane along a radius of the reactor assembly and is
charaterized by a
tip pointing towards top of the reactor, away from the gas inlet 1520. These
lamps are
illustrated above the horizontal pencil lamps. The length of each pencil lamp
align with RA
24
CA 03173512 2022- 9- 26
coils 1516, 1517 and 1518. Outer support 15109 and inner support 15110 support
the pencil
lamps. An optional x-ray source 1515 is shown directing x-rays towards the
center axis of
the reactor assembly above the third RA coil 1516. Disposed within the reactor
assembly can
be a reflecting plate to direct the x-ray towards the reaction chamber.
Reactor connector
15111 is also shown, as well as other non-material connectors and spacers. Gas
inlet 1520
and gas outlet 1519 are also shown.
FIG. 7C is a second perspective view of a reactor assembly. Pencil lamp 1521,
pencil
lamp 1522 and pencil lamp 1523 are shown directed with the tip towards a
center axis of the
reactor assembly along a radius of the reactor assembly. Pencil lamp 1524,
pencil lamp 1525
and pencil lamp 1526 are shown directed parallel to a center axis of the
reactor assembly,
disposed in a plane along a radius of the reactor assembly and is charaterized
by a tip
pointing towards the bottom of the reactor, towards the gas inlet 1532. These
vertical lamps
are shown above the horizontal lamps and, again, each pair of lamps can
optionally lie in the
same radial plane. The tip of each pencil lamp aligns with the third RA coil
1528. Outer
support 15109 and inner support 15110 support the pencil lamps. Three RA coils
1528, 1529
and 1530 are shown. An optional x-ray source 1527 is shown directing x-rays
towards the
center axis of the reactor assembly. Disposed within the reactor assembly can
be a reflecting
plate to direct the x-ray towards the reaction chamber. Reactor connector
15111 is also
shown, as well as other non-material connectors and spacers. Gas inlet 1532
and gas outlet
1531 are also shown.
FIG. 7D is a cross sectional side view of the reactor assembly, stripped of
the pencil
lamps and x-ray source. Gas enters at the inlet 1541 and exits at the outlet
1540. RA coils
1537, 1538 and 1539 are shown. The first, or bottom, frit 1535 and the second,
or top, frit
1533 contain the reaction chamber 1534, which can be charged with nanoporous
carbon
powder. The reactor body 1536 is also shown. Other non-material spacers and
connectors
remain unlabeled.
FIG. 7E is a second cross sectional side view of a reactor assembly, stripped
of the
pencil lamps and x-ray source. Gas enters at the inlet 1551. RA coils 1545,
1546 and 1547
are shown. The first, or bottom, frit 1544 and the second, or top, frit 1542
contain the
reaction chamber 1543, which can be charged with nanoporous carbon powder. The
reactor
body 1548 is also shown. X-ray source 1549 directs x-rays towards the center
axis of the
reacto assembly which is then deflected towards the reactor chamber with
element 1550.
Other non-material spacers and connectors remain unlabeled.
CA 03173512 2022- 9- 26
FIG. 7F is a second cross sectional side view of a reactor assembly with the
pencil
lamps and x-ray source. Gas enters at the inlet 1564. RA coils 1555, 1556 and
1557 are
shown. The first, or bottom, frit 1554 and the second, or top, frit 1552
contain the reaction
chamber 1553, which can be charged with nanoporous carbon powder. The reactor
body
1558 is also shown. Vertical pencil lamps 1560 and 1561 are shown as are
horizontal pencil
lamps 1560 and 1559. X-ray source 1562 directs x-rays towards the center axis
of the reacto
assembly which is then deflected towards the reactor chamber with element
1563. Other non-
material spacers and connectors remain unlabeled.
FIG. 7G is a perspective view of a reactor assembly with the pencil lamps and
x-ray
source. Gas enters at the inlet 1577 and exits at outlet 1578. A first laser
1575 and a second
laser 1576 directing radiation towards the reaction chamber along the axis of
the reactor
assembly is shown. RA coils 1571, 1572 and 1573 are shown. In this embodiment
pencil
lamps 1565, 1566, 1567, 1568, 1569, and 1570 are all shown horizontally
disposed in pairs
along the radius towards the reactor assembly central axis. Tips are proximal
to RA coils
1571, 1572 and 1573. X-ray source 1574 directs x-rays towards the center axis
of the reactor
assembly. Support 15109 supports all of the horizontal pencil lamps. Other non-
material
spacers and connectors remain unlabeled.
FIG. 711 is a perspective view of a reactor assembly with the pencil lamps and
x-ray
source. Gas enters at the inlet 1591 and exits at outlet 1592. A first laser
1589 and a second
laser 1590 directing radiation towards the reaction chamber along the axis of
the reactor
assembly is shown. RA coils 1585, 1586 and 1587 are shown. In this emodiment
pencil
lamps 1579, 1580, 1581, 1582, 1583, and 1584 are all shown vertically disposed
in pairs in
radial planes aligned with the RA coils. Tips are proximal to RA coils 1585,
1586 and 1587.
X-ray source 1588 directs x-rays towards the center axis of the reactor
assembly. Supports
15109 and 15110 support the pencil lamps. Other non-material spacers and
connectors
remain unlabeled.
FIG. 71 is a perspective view of a reactor assembly illustrating 5 RA coils,
horizontal
pencil lamps and an x-ray source. Gas enters at the inlet 15107 and exits at
outlet 15108. A
first laser 15105 and a second laser 15106 directing radiation towards the
reaction chamber
along the axis of the reactor assembly is shown. RA coils 1599, 15100, 15101,
15102 and
15103, defining a cyndrical boundary, are shown. In this embodiment pencil
lamps 1593,
1594, 1595, 1596, 1597, and 1598 are all shown horizontally disposed in pairs
in radial
planes aligned with the RA coils. Tips are proximal to RA coils 1599 and
15103. X-ray
26
CA 03173512 2022- 9- 26
source 15104 directs x-rays towards the center axis of the reactor assembly.
Support 15109
support the pencil lamps. Other non-material spacers and connectors remain
unlabeled.
Ni-1 Reactor:
Referring to FIG. 8A, the reactor body (1702) is based on a high purity nickel
(Ni)
rod. The Ni rod, with an outside diameter of 15.873 mm (OD) is bored through
then
machined with a female thread on one end. The inside diameter allows for the
installation of
upper and lower frit and carbon bed. The carbon reaction medium is housed
inside the reactor
body (1702). To load the reactor, the reactor body (1702) is positioned with
the gas discharge
opening (1706) facing down on a flat surface. A quartz frit (1705) is placed
inside the reactor
body (1702) to form the upper containment. 100 mg of carbon is then loaded
into the reactor
body (1702). After loading of the graphite bed inside the reactor body (1702),
a second quartz
frit (1703) is installed. A reactor pole (1701), machined out of a high purity
graphite rod with
matched male threads for the reactor body (1702), is then screwed onto the
reactor body
(1702). The reactor pole (1701) is designed to provide the identical graphite
bed compression
as that provided by the cup design (1708).
NiPtG Reactor:
Referring to FIG. 8B, in the NiPtG Reactor embodiment, the reactor body (1707)
is
based on a high purity nickel (Ni) rod. The Ni rod, with an outside diameter
of 15.873 mm
(OD) is bored through then machined on one end to have an inside diameter of
11.68 mm
(ID). The inside diameter allows for the installation of a graphite cup (1708)
and an optional
0.025 mm platinum (Pt) foil (1713). The graphite cup provides for reactor wall
and foil
isolation from the carbon bed. The carbon reaction medium is housed inside a
99.9999wt%
pure graphite cup (1708). To load the reactor, a quartz frit (1709) is placed
inside the graphite
cup (1708) to form the bottom containment. 100 mg of carbon (1710) is then
loaded into the
cup (1708). After loading of the graphite bed inside the cup, a second quartz
frit (1711) is
installed; this system is defined as the cup assembly. Prior to installing the
cup assembly, the
foil (1713) is used to line the inside surface of the reactor wall. The cup
assembly is then
placed within the nickel reactor body (1707) and foil (1713). After the cup
assembly is
installed, a 99.9999wt% pure graphite cap (1712) is screwed onto the reactor
body. The cap
secures the cup from movement after assembly. The figure additionally is
illustrative of the
GG Reactor configuration.
27
CA 03173512 2022- 9- 26
PtIrGG Reactor:
Referring to FIG. 8C, the reactor body (1714) is based on a high purity
graphite rod.
The graphite rod, with an outside diameter of 15.873 mm (OD) is bored through
then
machined on one end to have an inside diameter of 11.68 mm (ID). The inside
diameter
allows for the installation of a graphite cup (1715) for reactor wall
isolation from the carbon
bed. The carbon reaction medium is housed inside a 99.9999wt% pure graphite
cup (1715). To
load the reactor, a quartz frit (1716) is placed inside the graphite cup to
form the bottom
containment. 100 mg of carbon (1717) is then packed into the cup. After
loading of the
graphite bed inside the cup, a second quartz frit (1718) is installed; this
system is defined as
the cup assembly. The cup assembly is then placed within the graphite reactor
body (1714).
After the cup assembly is installed, a cap (1719) composed of platinum and
10%wt iridium is
screwed onto the reactor body. The cap secures the cup from movement after
assembly.
The residence time of the starting material within the reactor is effective to
instantiate
product into the starting material and can be between 0 and 15 minutes.
Referring to FIG 9, the reactor body (905) has an outside diameter and an
inside
diameter. The inside diameter allows for the installation of a graphite cup
(901) for reactor
wall isolation from the carbon bed. The carbon reaction medium is housed
inside a graphite
cup (901). To load the reactor, a lower frit (904) is placed inside the
graphite cup to form the
bottom containment. Carbon (903) is then packed into the cup. After loading of
the graphite
bed inside the cup, an upper frit (902) is installed; this system is defined
as the cup assembly.
The cup assembly is then placed within the reactor body (905). After the cup
assembly is
installed, a cap (901) is screwed onto the reactor body. The cap secures the
cup from
movement after assembly. Gas can be transported via the Gas Transport (906)
from the gas
inlet (907). The gas exits at the gas exit (908), optionally to a manifold for
collection. The
gas can be energized with a shortwave ultraviolet (SUV) lamp (909). The
reactor body
and/or cup can be wrapped with an electromagnetic (E/M) Coil (911) as
previously described.
Preferred reactors used in the methods of the invention are shown in the table
below.
Reactor Cup Cap Reactor Pole
Boundary Chamber Coil Type
ID Material Material Material Material
Capacity
Cu, Ni
CgF N/A N/A or Mo or graphite N/A
100 mg Induction
graphite
Induction
CuG Graphite graphite Cu quartz N/A
100 mg or
Frequency
PtIrGG Graphite Pt/Ir graphite quartz N/A
100 mg Induction
28
CA 03173512 2022- 9- 26
Reactor Cup Cap Reactor Pole
Boundary Chamber Coil Type
ID Material Material Material Material
Capacity
Induction
GPtG Graphite graphite graphite quartz Pt
100 mg or
Frequency
GPtGPtG Graphite graphite graphite quartz 2X Pt
100 mg Induction
Induction
100 mg-
GG-EL Graphite graphite graphite quartz N/A
or
3g
Frequency
Induction
Foil (Pt) Graphite graphite graphite quartz Pt
100 mg or
Frequency
b
Induction
N,
GZ Foil Graphite graphite graphite quartz PtCo
100 mg or
or
Frequency
Induction
nZG Foil Graphite Any Z* graphite quartz Ir
100 mg or
Frequency
Induction
NiG Graphite graphite Ni quartz
N/A 100 mg or
Frequency
NiPtG Graphite graphite Ni quartz Pt
100 mg Induction
Pd/Ru or
ZG N/A graphite quartz
N/A 100 mg Induction
any Z
Ref-X Graphite graphite graphite quartz N/A 1-20g Frequency
*Any Z is intended to mean any material
The invention further relates to methods of instantiating materials in
nanoporous
carbon powders. It has been surprisingly found that light elements, such as
hydrogen,
oxygen, helium, and the like are instantiated. Instantiating is defined herein
to include the
nucleation and assembly of atoms within carbon structures, particularly,
ultramicropores.
Without being bound by theory, it is believed instantiation is related to,
inter alia, degrees of
freedom of the electromagnetic field as expressed by quantum field theory. By
exposing a
gas to harmonic resonances, or harmonics, of electromagnetic radiation within
one or more
ultramicropores, vacuum energy density is accessed and allows for the
nucleation and
assembly of atoms. Electromagnetic energy that is within the frequencies of
light, x-rays,
and magnetic fields subjected to frequency generators can enhance the
formation and
maintenance of such harmonics. Modifying the boundaries of the system, by
selecting the
reactor materials and adding a foil layer can also enhance the harmonics.
29
CA 03173512 2022- 9- 26
In particular, the invention includes processes of producing, or
instantiating,
nanoporous carbon compositions comprising the steps of:
adding a nanoporous carbon powder into a reactor assembly as described herein;
adding a feed gas to the reactor assembly;
powering the one or more RA coils to a first electromagnetic energy level;
heating the nanoporous carbon powder;
harmonic patterning the nanoporous carbon powder between a first
electromagnetic
energy level and a second electromagnetic energy level for a time sufficient
to instantiate a
material in a nanopore and, optionally, collecting the material.
The invention includes a process for producing a product gas comprising the
steps of:
(a) adding a feed gas to an electromagnetic embedding apparatus:
(b) exposing the feed gas to at least one E/MEE light source;
(c) directing the feed gas from step (b) to a reactor assembly comprising:
A gas inlet and one or more gas outlets;
A reactor chamber containing a nanoporous carbon disposed within a cup and,
optionally, covered with a cap;
A first porous frit defining a floor of the reactor chamber disposed within
the
cup,
A second porous frit defining the ceiling of the reactor chamber; wherein each
porous frit has a porosity that is sufficient to allow a gas to permeate into
the
reactor chamber;
A reactor head space disposed above the reactor chamber;
At least one RA coil surrounding the reactor chamber and/or reactor head
space operably connected to a power supply, wherein the computer processing
unit is
configured to control the power supply to the RA coil;
(d) subjecting the nanoporous carbon powder to harmonic patterning to
instantiate a
material;
(f) collecting the product gas comprising the material; and
(g) isolating the material from the product gas.
The term "harmonic patterning" is defined herein as oscillating between two or
more
energy levels (or states) a plurality of times. The energy states can be
characterized as a first,
or high, energy level and a second, or lower, energy level. The rates of
initiating the first
energy level, obtaining the second energy level and re-establishing the first
energy level can
be the same or different. Each rate can be defined in terms of time, such as
over 1, 2, 3, 4, 5,
CA 03173512 2022- 9- 26
6, 7, 8, 9, 10 or more seconds. Each energy level can be held for a period of
time, such as 1,
2, 3, 4, 5, 6, 7, 8, 9, 10 or more seconds. Harmonic patterning is continued
until instantiation
is achieved.
Where two more electromagnetic radiation sources are present (e.g., coils, x-
ray
source, lasers, and/or lamps), each can be subjected to harmonic patterning
and the patterning
can occur independently, simultaneously or sequentially.
The process further comprises independently powering any additional
electromagnetic
radiation source, as described above in the E/MEE apparatus or reactor
assembly. For
example, the process further comprises the step(s) of powering RA frequency
generator(s)
connected to one or more RA coils, one or more lamps or lasers, x-ray sources,
induction
coils, E/MEE coils, and the like substantially as described above.
The invention particularly relates to the identification and collection of a
product gas
produced by the methods. The product gas can be collected from the process in
a continuous,
semi-continuous or batch manner. The product gas typically comprises the feed
gas (or first
gas composition, as discussed above) and a second gas composition, e.g.,
comprising
hydrogen. The second gas composition is distinct from the first gas
composition and
preferably contains one or more gases not present in the feed gas. For
example, where the
feed gas is pure nitrogen (e.g., a gas comprising at least 99% vol nitrogen,
such as at least
99.9% vol nitrogen), such as a nitrogen gas with less than 1% hydrogen, the
product gas will
contain one or more other materials (e.g., elements or molecules that exist in
gas form under
ambient conditions), preferably hydrogen. The feed gas can also include air.
The product
gas can comprise a gas such as hydrogen, helium, water, neon, nitrogen, carbon
monoxide,
oxygen, argon, carbon dioxide, fluorocarbons, ammonia, krypton, xenon, methane
and other
hydrocarbons or organics and mixtures thereof. "Product gas" is defined herein
as being
compositionally distinct different from the term "Feed gas" and explicitly
excludes air.
Preferred product gases comprise hydrogen and/or oxygen. Typically, the
concentration of hydrogen and/or oxygen in the product gas will exceed the
concentration of
hydrogen and/or oxygen, respectively, in the feed gas. For example, the
product gas can
comprise at least about 1%vol (preferably at least about 4%vol) hydrogen. In
another
example, the product gas can comprise at least about 20%vol (preferably at
least about
40%vol) oxygen. In yet another example, the product gas comprises at least
1%vol.
(preferably at least about 3%vol) water. Preferably, product gases will
further comprise
neon, helium, argon and combinations thereof Typically, the product gas will
further
comprise the components found in the feed gas (e.g., nitrogen and hydrogen or
air), however,
31
CA 03173512 2022- 9- 26
in concentrations distinct therefrom. A preferred product gas comprises
nitrogen, hydrogen
and a gas selected from neon, helium, argon and combinations thereof. A
preferred product
gas comprises nitrogen, hydrogen, oxygen and a gas selected from neon, helium,
argon and
combinations thereof A preferred product gas comprises at least 1%vol helium,
argon, neon
and combinations.
The invention permits the manufacture of green gas, such as product gas that
has less
than 0.5%vol CO2, such as less than 100 ppm CO2.
Hydrogen can be isolated from, or purified, the product gas, thereby producing
a high
concentration hydrogen gas. An example of a purification system utilizing a
hydrogen-
selective membrane. Examples of suitable materials for membranes include
palladium and
palladium alloys, and especially thin films of such metals and metal alloys.
Palladium alloys
are particularly effective, especially palladium with 35 weight % to 45 weight
% copper.
Another effective alloy is palladium with 2 weight % to 10 weight % gold, such
as palladium
with 5 weight % gold. Hydrogen-selective membranes can be configured to be a
foil.
Alternatively or additionally a pressure swing adsorption system can be used
to concentrate
hydrogen and remove unwanted gases. Such processes use activated carbon,
silica or
zeolites.
Ex. 1: Energy/Light Combed Activation (E/LC)
One hundred milligrams (100 mg) of powdered carbon was placed in a GG-EL
graphite tubular reactor (15.875 mm) OD, with ID machined to ¨9 mm). This
reactor was
inserted into a reactor assembly FIG 2A and then placed into a high vacuum
oven for
degassing according to the Degassing Procedure (See Profile 1 or Profile 2).
After degassing,
the reactor assembly is transferred to a test cell for processing. Research-
grade Nitrogen
(N2) was delivered at 2 SLPM to purge the system for a minimum of 25 seconds
or more.
The gases were fed through the E/MEE in a horizontal and level gas line, as
described above.
During purging, gas sampling lines are also purged. TEDLAR sealed bags, when
used, are
connected to the sampling lines during the purge cycle.
Referring to FIG. 1, the argon "KC" light 108 located in position 0 (vertical
lamp
orientation; 7.62 cm from inlet or entrance flange; at 180'; bulb tip pointing
up 2.54 cm from
the outer diameter of the gas line) was turned on at the onset while
simultaneously energizing
the power supply to 5 amps. This light was kept on for a minimum hold time of
9 sec. Next
light 109 in position 1 (109; horizontal lamp orientation; 7.62 cm from inlet
or entrance
32
CA 03173512 2022- 9- 26
flange; at 1800; bulb tip facing exit plate; bulb glass base at the optical
entrance; 5.08 cm,
from the outer diameter of the gas line), a krypton light, was turned on and
the power is
increased to 10 amps on the power supply. This was held for 3 seconds, light
107, in position
1 (107; horizontal lamp orientation; at 0'; bulb tip at the optical exit
facing the exit plate; 5.04
cm from the outer diameter of the gas line), a xenon light was turned on and
held for 9
seconds and the power was increased to 15 amps. After these 3 lights have been
sequentially
turned on, the sealed TEDLAR bags are opened for gas collection, and the
amperage
delivered to reactor was adjusted to 100 amps and held for a minimum of 30
seconds.
Immediately after the power was increased light 103 in position 1 (103;
vertical lamp
orientation; 7.62 cm from inlet or entrance flange; at 0'; bulb tip pointing
down 2.54 cm from
the outer diameter of the gas line), a neon light, was turned on.
Amperage harmonic patterning was then initiated on the reactor. With each
amperage
pattern (oscillation), the gases fed to the reactor can treated by the same or
different light
sequence. In one embodiment of the experimental protocol, the amperage of the
reactor was
increased to 78.5 amps over 1 second, the high-end harmonic pattern point. The
amperage of
the reactor was then decreased to 38.5 amps over 9 seconds and held at 38.5
amps for 3
seconds. Immediately at the start of the 3 second hold, an argon light 122 in
position 1 (122;
horizontal lamp orientation; at 180'; bulb tip pointing towards entrance plate
at the optical
entrance; 5.04 cm from the outer diameter of the gas line) was turned on.
After the 3 second
hold, amperage to the reactor was then ramped up to 78.5 amps over 9 seconds
with a 3
second hold upon reaching 78.5 amps before a downward ramp was initiated. The
reactor
amperage was decreased to 38.5 amps, over 9 seconds and then held for 3
seconds.
Immediately at the start of the 3 second hold, light 103 (103), a neon light
in position 1, was
turned on. The reactor amperage was again ramped up to 78.5 amps over 9
seconds, held
there for 3 seconds, and then again ramped down to 38.5 amps over 9 seconds. A
long-wave
ultraviolet lamp (104; horizontal lamp orientation; at 90'; bulb tip facing
entrance plate at the
optical entrance; 5.04 cm from the outer diameter of the gas line) in position
1 was turned on.
The reactor was again ramped up to 78.5 amps over 9 seconds, held for 3
seconds,
then decreased to 38.5 amps over another 9 seconds. Next a short-wave
ultraviolet lamp (105
horizontal lamp orientation; 7.62 cm from inlet or entrance flange; at 270';
bulb tip at the
optical entrance and facing the entrance plate; 5.04 cm from the outer
diameter of the gas
line) in the E/MEE (position 1) E/MEE section light was turned on and held for
3 seconds.
The reactor was again ramped up to 78.5 amps over 9 seconds and held for 3
seconds. After
33
CA 03173512 2022- 9- 26
the 3 second hold, the reactor amperage was decreased to 38.5 amps over
another 9 seconds.
The reactor was then held at 38.5 amps for 3 seconds, before another ramp up
to 78.5 amps
over 9 seconds was initiated. At 3 seconds into this ramp, lamp 107, in
position 1 (107) was
turned on and held there for the remaining 6 seconds of the 9 second total
ramp. The reactor
was held for 3 seconds in this condition.
The lights were turned off simultaneously in the E/MEE section as follows:
(103),
(108), (106), (105) and (104) and the reactor was deenergized. The reactor was
held at this
state, with continuous gas flow for 27 seconds during which the TEDLAR bags
are closed
and removed. All remaining lights were turned off and gas flow continues for
240 seconds.
Example 2: Degassing Profile 1
One hundred milligrams (100 mg) of powdered carbon was placed in a graphite
tubular reactor (15.875 mm) OD, with ID machined to ¨9 mm), as described above
and
loaded into a closed end system. After ten closed end set-ups have been
completed, each
individual unit was loaded into the degassing oven openings and all incoming
and outgoing
lines were connected to the closed end systems. Isolated each incoming line to
each reactor
while maintaining the outgoing lines in an open position. Started the vacuum
system until the
vacuum gauge reads at least 750 mmHg. Upon reaching 750 MmHg, closed all
outgoing line
valves from the closed end systems and secured the vacuum pump. Performed a 30-
minute
leak test of the system. After successfully passing the leak check, opened
each incoming line
to the closed end system one at a time at 0.4 slpm N2. Once all incoming lines
were open and
the vacuum gauge reached a slight positive pressure, opened the outgoing gas
line on the
degassing oven. Started the degassing oven profile ramping from Tamb to 400 C
over 1 hour
while maintaining N2 flow. After the 1-hour ramp, maintained flow for an
additional hour for
temperature stabilization while maintaining gas flow. After the temperature
stabilization was
complete, secured all incoming gas flows and isolated the degassing oven vent
line.
Immediately started the vacuum pump and begin the degassing protocol.
Maintained the
temperature and vacuum for 12 hours. After the 12 hours, allowed the oven to
cool prior to
closed end unit removal.
Example 3: Degassing Profile 2
One hundred milligrams (100 mg) of powdered carbon was placed in a graphite
tubular reactor (15.875 mm) OD, with ID machined to ¨9 mm), as described above
and
34
CA 03173512 2022- 9- 26
loaded into a closed end system. After ten closed end set-ups have been
completed, each
individual unit was loaded into the degassing oven openings and connected all
incoming and
outgoing lines to the closed end systems. Isolated each incoming line to each
reactor while
maintaining the outgoing lines in an open position. Started the vacuum system
until the
vacuum gauge reads at least 750 mmHg. Upon reaching 750 MmHg, closed all
outgoing line
valves from the closed end systems and secured the vacuum pump. Performed a 30-
minute
leak test of the system. After successfully passing the leak check, opened
each incoming line
to the closed end system one at a time at 0.4 SLPM N2. Once all incoming lines
were open
and the vacuum gauge reached a slight positive pressure, opened the gas
outgoing gas line on
the degassing oven. Started the degassing oven profile ramping from 200 C 50
C to 400 C
over 1 hour while maintaining N2 flow. After the 1-hour ramp, maintained flow
for an
additional hour for temperature stabilization while maintaining gas flow.
After the
temperature stabilization was complete, secured all incoming gas flows and
isolated the
degassing oven vent line. Immediately started the vacuum pump and began the
degassing
protocol. Maintained the temperature and vacuum for 12 hours. After the 12
hours, allowed
the oven to cool prior to closed end unit removal.
Example 4: Gas analysis
For the chemical analysis of gas samples in TEDLAR bags, a test protocol was
developed based on the standard test method established for internal gas
analysis of
hermetically-sealed devices. Prior to sample measurement, system background
was
determined by following exact measurement protocol that is used for sample
gas. For system
background and sample, a fixed volume of gas was introduced to the Pfeiffer
QMA 200M
quadrupole mass spectrometer (QMS) system through a capillary. Through a
capillary, a
fixed volume of gas was introduced to the Pfeiffer QMA 200M quadrupole mass
spectrometer (QMS) system. After sample gas introduction, the ion current for
specific
masses (same as masses analyzed for system background) were measured. During
background and sample gas analyses total pressure of the QMS system was also
recorded,
allowing for correction of the measured ion current.
Table 1: Gases analyzed for the test method and measured masses used in
deconvolution.
Gas Masses used for deconvolution
1. Hydrogen 2, 18, 55, 57
2. Helium (3) 2,4
CA 03173512 2022- 9- 26
3. Helium (4) 4
4. Methane 14,15
5. Water 18,32,40
6. Neon (20) 18,20,40
7. Neon (22) 20
8. Nitrogen 14
9. Carbon Monoxide 14, 28
10. Oxygen 32
11. Argon 40,41,43
12. Carbon Dioxide 44
13. Tot. HC and Org. 55, 57
14. Fluorocarbons 69
15. Ammonia 17,18
16. Krypton 84
17. Xenon 132
Data analysis:
Measurements of the ion current for each mass were corrected to the average of
measured background contributions corrected for pressure difference.
Subsequent to the
background correction, individual corrected mass signals were averaged and
corrected to a
known gas standard to determine the percent volume of 17 gas species. All
corrections were
determined using nitrogen and nitrogen-hydrogen mixture reference gases
analyzed to match
selected process gas for test samples using the developed protocol based on
the standard test
method, in accordance with Military Standard (MIL-STD-883) Test Method 1018,
Microcircuits, Revision L, FSC/Area: 5962 (DLA, 16 September 2019). Results
below:
1%=10,000 ppm, Volume values for gas blanks and samples were produced using
the
developed gas analysis test method and validated using a gas mixture standard
of 99.98%
nitrogen and 0.02% hydrogen. All analytical performed by EAG Laboratories,
Liverpool, NY
using standard TEDLAR bag gas sampling protocols and specified mass
spectrometry
methods.
Mass Analyzer: Quadrupole mass spectrometer (Pfeiffer QMA 200M)
Measurement mode: Analog scan for selected masses
No. of channels used: 64
Mass resolution: Unit resolution
Maximum detectable concentration: 100%
Minimum detectable concentration: 1 ppb
Background vacuum: <2 x 10-6 Torr
36
CA 03173512 2022- 9- 26
Results:
Protocol 1:
Gases Analyzed (Vol %) Ill. 1 Ill. 2 Ill. 3 Ill. 4 Ill.
5
Hydrogen 0.7678 0.2405 0 0 0.0162
Helium (4) 0.1923 0.2963 0.1928 0.5476 0.1254
Methane (CHO 0 0 0 0 0
Water (1420) 0.4054 1.0773 0 0 0
Neon (20) 0.036 0.03 0.0417 0.1789 0.0345
Neon (22) 0.0036 0.003 0.0042 0.0179 0.0035
Nitrogen 95.276 89.3705 99.347 88.2306 99.6251
Carbon Monoxide (CO) 0 0 0 0 0
Oxygen 3.1604 8.5606 0.3796 10.945 0.1826
Argon 0.0676 0.349 0.0003 0.08 0
Carbon Dioxide (CO2) 0.0138 0 0 0 0
Total Hydrocarbons and 0.0269 0 0.0175 0 0
Organics
Fluorocarbons 0.0261 0.0417 0.0162 0 0.0127
Ammonia (NH3) 0 0.031 0 0 0
Krypton 0.0242 0 0 0 0
Xenon 0 0 0 0 0
Protocol 1 (cont.)
Gases Analyzed (Vol %) Ill. 6 Ill 7 Ill. 8 Ill. 9
Hydrogen 1.027 0 0 4.0494
Helium (4) 0.364 2.6033 0.2145 25.118
Methane (CHO 0 0 0 0
Water (H20) 0 0 0 0
Neon (20) 0.1093 0.4736 0.0308 5.6369
Neon (22) 0.0109 0.0474 0.0031 0.5637
Nitrogen 97.1911 94.6204 95.9834 56.538
Carbon Monoxide (CO) 0 0 0 0
Oxygen 1.2975 2.2553 3.7604 4.1726
37
CA 03173512 2022- 9- 26
Gases Analyzed (Vol %) Ill. 6 Ill 7 Ill. 8 Ill. 9
Argon 0 0 0.0078 0
Carbon Dioxide (CO2) 0 0 0 0
Total Hydrocarbons and 0 0 0 1.0654
Organics
Fluorocarbons 0 0 0 1.9565
Ammonia (NH3) 0 0 0 0
Krypton 0 0 0 0.8997
Xenon 0 0 0 0
Protocol 2:
Gases Analyzed Ill. 10 Ill. 11 Ill. 12 Ill. 13
Ill. 14 Ill. 15
(Vol.%)
Hydrogen 0 1.0428 1.3437 0
1.6249 1.7941
Helium (4) 0.4679 0.3492 0.4409 0.8074 0.4888 0.6406
Methane (CHO 0 0 0 0 0 0
Water (H2O) 0 2.3924 3.1436 0
4.4032 2.4182
Neon (20) 0.1598 0 0 0 0 0
Neon (22) 0.016 0 0 0 0 0
Nitrogen 76.7986 79.9798 94.2126 51.1046 92.2167 75.6209
Carbon Monoxide 0 0 0 0 0 0
(CO)
Oxygen 22.079 15.565 0.8348 48.088 1.239 18.7733
Argon 0.4639 0.5717 0 0 0 0.721
Carbon Dioxide 0 0.0991 0.0244 0
0.0274 0.0319
(CO2)
Total Hydrocarbons 0 0 0 0 0 0
and Organics
Fluorocarbons 0.0147 0 0 0 0 0
Ammonia (NH3) 0 0 0 0 0 0
Krypton 0 0 0 0 0 0
Xenon 0 0 0 0 0 0
38
CA 03173512 2022- 9- 26
Standard (Nitrogen):
Gases Analyzed Vol%
Standard
99.98 vol% N2
/ 200 ppm H2
Hydrogen 0.0223
Helium (3) 0.0000
Helium (4) 0.0000
Methane (CHO 0.0000
Water (H20) 0.0000
Neon (20) 0.0000
Neon (22) 0.0000
Nitrogen 99.9777
Carbon Monoxide 0.0000
(CO)
Oxygen 0.0000
Argon 0.0000
Carbon Dioxide (CO2) 0.0000
Total Hydrocarbons 0.0000
and Organics
Fluorocarbons 0.0000
Ammonia (NH3) 0.0000
Krypton 0.0000
Xenon 0.0000
Example 5: Energy/Light Combed Activation (E/LC)
One hundred milligrams (100 mg) of powdered carbon was placed in a GG-EL
graphite tubular reactor (15.875 mm) OD, with ID machined to ¨9 mm). In one
iteration the
placement of the powder carbon was performed in the presence of a visible
emissions
spectrum containing ultraviolet light. This reactor was inserted into a
reactor assembly FIG
2A and then placed into a high vacuum oven for degassing according to the
Degassing
Procedure (See Profile 1 or Profile 2). After degassing, the reactor assembly
is transferred to
a test cell for processing. Research-grade Nitrogen (N2) was delivered at 2
SLPM to purge
the system for a minimum of 25 seconds or more. The gases were fed through the
E/MEE in
a horizontal and level gas line, as described above. One iteration of the run
can include the
use of a SUV light on the incoming gas lines. When used and prior to run start-
up, referring
to FIG. 9, the SUV light 909 located horizontal on the incoming gas line is
turned on and
allowed to heat-up for 5 minutes prior to run commencement for E/M
stabilization. This light
is on throughout the entire run. During purging, gas sampling lines are also
purged. Tedlarg
sealed bags, when used, are connected to the sampling lines during the purge
cycle.
39
CA 03173512 2022- 9- 26
Referring to FIG. 1, the argon "KC" light 108 located in position 0 (vertical
lamp
orientation; 7.62 cm from inlet or entrance flange; at 180'; bulb tip pointing
up 2.54 cm from
the outer diameter of the gas line) was turned on at the onset while
simultaneously energizing
the power supply to 5 amps. This light was kept on for a minimum hold time of
9 sec. Next
light 109 in position 1 (109; horizontal lamp orientation; 7.62 cm from inlet
or entrance
flange; at 180'; bulb tip facing exit plate; bulb glass base at the optical
entrance; 5.08 cm,
from the outer diameter of the gas line), a krypton light, was turned on and
the power is
increased to 10 amps on the power supply. This was held for 3 seconds, light
107, in position
1 (107; horizontal lamp orientation; at 0'; bulb tip at the optical exit
facing the exit plate; 5.04
cm from the outer diameter of the gas line), a xenon light was turned on and
held for 9
seconds and the power was increased to 15 amps. After these 3 lights have been
sequentially
turned on, the sealed Tedlai'9 bags are opened for gas collection, and the
amperage delivered
to reactor was adjusted to 100 amps and held for a minimum of 30 seconds.
Immediately
after the power was increased light 103 in position 1 (103; vertical lamp
orientation; 7.62 cm
from inlet or entrance flange; at 0'; bulb tip pointing down 2.54 cm from the
outer diameter
of the gas line), a neon light, was turned on.
CA 03173512 2022- 9- 26
Amperage harmonic patterning was then initiated on the reactor. With each
amperage
pattern (oscillation), the gases fed to the reactor can treated by the same or
different light
sequence. In one embodiment of the experimental protocol, the amperage of the
reactor was
increased to 78.5 amps over 1 second, the high-end harmonic pattern point. The
amperage of
the reactor was then decreased to 38.5 amps over 9 seconds and held at 38.5
amps for 3
seconds. Immediately at the start of the 3 second hold, an argon light 122 in
position 1 (122;
horizontal lamp orientation; at 1800; bulb tip pointing towards entrance plate
at the optical
entrance; 5.04 cm from the outer diameter of the gas line) was turned on.
After the 3 second
hold, amperage to the reactor was then ramped up to 78.5 amps over 9 seconds
with a 3
second hold upon reaching 78.5 amps before a downward ramp was initiated. The
reactor
amperage was decreased to 38.5 amps, over 9 seconds and then held for 3
seconds.
Immediately at the start of the 3 second hold, light 103 (103), a neon light
in position 1, was
turned on. The reactor amperage was again ramped up to 78.5 amps over 9
seconds, held
there for 3 seconds, if two gas samples were collected in a single cycle, the
first Tedlarg bags
are closed and the second bag is opened for gas collection at this point and
then power again
ramped down to 38.5 amps over 9 seconds. A long-wave ultraviolet lamp (104;
horizontal
lamp orientation; at 90'; bulb tip facing entrance plate at the optical
entrance; 5.04 cm from
the outer diameter of the gas line) in position 1 was turned on.
The reactor was again ramped up to 78.5 amps over 9 seconds, held for 3
seconds,
then decreased to 38.5 amps over another 9 seconds. Next a short-wave
ultraviolet lamp (105
horizontal lamp orientation; 7.62 cm from inlet or entrance flange; at 270';
bulb tip at the
optical entrance and facing the entrance plate; 5.04 cm from the outer
diameter of the gas
line) in the E/MEE (position 1) E/MEE section light was turned on and held for
3 seconds.
The reactor was again ramped up to 78.5 amps over 9 seconds and held for 3
seconds. After
the 3 second hold, the reactor amperage was decreased to 38.5 amps over
another 9 seconds.
The reactor was then held at 38.5 amps for 3 seconds, before another ramp up
to 78.5 amps
over 9 seconds was initiated. At 3 seconds into this ramp, lamp 107, in
position 1 (107) was
turned on and held there for the remaining 6 seconds of the 9 second total
ramp. The reactor
was held for 3 seconds in this condition.
41
CA 03173512 2022- 9- 26
The lights were turned off simultaneously in the E/MEE section as follows:
(103),
(108), (106), (105) and (104) and the Tedlar Bags are closed prior to the
reactor being
deenergized. The reactor was deenergized. The reactor was held at this state,
with continuous
gas flow for 27 seconds. All remaining lights were turned off and gas flow
continues for 240
seconds.
The purpose of the hydrogen gas analysis herein was to collect gas samples
under
multiple experimental conditions and analyze the contents for targeted
species, particularly
hydrogen (112). Eight experimental conditions were chosen and sampled with the
goals of 1)
increasing/altering hydrogen production, 2) providing differential gas
sampling to identify
change in hydrogen production within experimental timing, and 3) reducing
carrier gas flow
to show a greater fraction of hydrogen production. The experimental conditions
included
variation on run plan base of GSA or LA M/M, cold or hot degassing oven
starts, and use of a
shortwave ultraviolet (SUV) lamp. For each experimental condition, ten MSP-20X
Lot 2006
carbon samples (100 mg each) were run. One or two gas samples were collected
during each
run into a Tedlar bag (3 or 12 L). Twenty-eight experimental gas samples and
two standard
gas samples were pumped into stainless steel (SS) canisters for independent
analysis at
Airborne Labs (Somerset, NJ) using gas chromatograph discharge ionization
detector (GC-
DID) methodology.
All gas samples were collected using a Tedlar bag (3 L or 12 L). All Tedlar
bags
were filled with carrier gas (N2 or Ar/Kr) and emptied via vacuum, 3 times,
approximately
24-72 hours prior to sample collection. After each bag is emptied the final
time, it is sealed
until ready for gas collection. This process primes the sampling vessel by
removing any
residual gas from manufacturing inside the Tedlar bags.
During the experiment runs, sampling lines were purged for a minimum of 25
seconds. Sealed and primed Tedlar bags were attached to the sampling lines
during that
period. Each bag was opened after the 25 second purge period and remained open
during a
designated collection length, depending on the run plan. Experimental runs
where two gas
samples were collected, a second sampling line was used. The valve on the
first bag was
closed and the valve on the second bag was opened to begin collection.
Select samples were purged through, then pumped into a 500 cubic centimeters
(cc)
SS canister provided by Airborne Labs using a small micro diaphragm pump.
These cylinders
were sent filled with helium at 2-5 psig. This was in error from Airborne Labs
as vacuum
evacuated cylinders were requested.
42
CA 03173512 2022- 9- 26
During collection, gas was pumped from the Tedtar bag into a SS cannister. A
pressure gauge was attached to measure the maximum pressure of the cannister
and tube
vessel. Approximately 1 L of gas was allowed to flow through the SS canister
to purge the
containers before the valves were closed to pressurize the systems. Purging
the system with
sample gas reduces the likelihood of contamination.
Gas chromatography (GC) employs two states of matter to separate compounds: a
stationary phase, which generally is a solid, and a gas mobile phase. When an
unknown
mixture is introduced to the system, the mixture has components that have
different affinities
for the two phases and thus move through the system at different rates. A
component with a
high affinity for the mobile phase moves more quickly through the
chromatographic system
relative to other species, whereas one with a high affinity for the solid
phase moves more
slowly.
The stationary phase used in this application was a molecular sieve. The
molecular
sieve was composed of a crystalline material that has a large internal volume,
which permits
gas molecules to be "absorbed" into the internal structure of the material.
Smaller molecules
move in and out of this internal structure relatively quickly, larger
molecules less so. This
difference in mobility allows smaller molecules to move through the column
faster than the
larger molecules and are separated in a reproduceable fashion, separating one
from another.
Thermal conductivity detectors (TCD) create an electrical signal-based
differential
thermal conduction of a gas flow over a heated filament. The electronics
maintain a constant
current across the filament. Changes in gas composition causes variation of
that current that
increases or decreases in order to maintain a constant temperature. This
differential in current
can be measured and expressed in chromatography as a curve, or peak. The
measured area
under the peak is calculated and expressed as an amount chosen by the
operator.
Discharge ionization detectors (DID) use an electric current to ionize a gas
species
(e.g., helium) and produce characteristic photons. The photons irradiate
incoming gas species
from a sample. With a gas chromatography column different gas species are
separated before
they arrive at the ionization chamber. Electrons produced by the interaction
of the photons
and the ionizable gas molecules are attracted to a collector and detector. The
detector then
measures the change in current during sample analysis.
Gas samples were analyzed by Airborne Labs, Inc. (Somerset, NJ) using a
generalized
test for noncombustible gases (NCG). The NCG protocol involved the use of GC-
DID for
components <5000 ppm in mixture and GC-TCD for components >5000 ppm in mixture
43
CA 03173512 2022- 9- 26
using a helium carrier gas. Results from Airborne Labs are certified under
ISO/IEC
17025:2017.
Ten 100 milligram (mg) carbon samples were processed under eight different
experimental conditions using a variation in run plan, use of SUV, and carrier
gas type and
flow. Of the 80 total carbon samples, a total of 120 gas samples were
collected for analysis
using Tedlar bags (3 L or 12 L).
A total of 30 gas samples were collected during the three GSA runs. Gas
collection
began after a 25 second purge of the gas lines. Collection duration alternated
between 35
seconds to capture the gas during the change in EM fields and 4 minutes to
capture the gas
during the entire vacuum period. Only one sample was collected per carbon
sample under
these first three condition types. Four of the GSA samples were submitted to
Airborne Labs
for further NCG testing.
A total of 50 gas samples were collected during the three LA M/M run plans
using
nitrogen as a carrier gas. A total of 40 gas samples were collected during the
two LA M/M
run plans using an argon-krypton mixture as a carrier gas. Gas collection
began after a 25
second purge of the gas lines. If a single sample was collected the duration
lasted 173
seconds. If two samples were collected the first was for 85 seconds and the
second was for 88
seconds.
Out of 116 viable experimental gas samples, 28 were submitted to Airborne Labs
for
further quantitative analysis for hydrogen, oxygen, nitrogen, argon, and
krypton using a
noncombustible gas generalized test. Of these 28 production gas samples sent
to Airborne
Labs for NCG testing 12 samples resulted in significant hydrogen
concentrations, from 7.7 ¨
27 ppm for nitrogen samples (Table 4) and 1-10 ppm for argon samples (Table
5). These
results differ from reported atmospheric concentrations of hydrogen at ¨0.6
ppm. Hydrogen
concentrations exceeded the reported 2 ppm impurity limit on the certificate
of analysis for
nitrogen gas in 9 of 20 samples analyzed. Of the 20 N2 gas samples, 15 had
argon levels <100
ppm, within the allowed concentration for research grade nitrogen. In an
argon/krypton
mixture, no hydrogen concentration is reported as an impurity for the
certificate of analysis
for these two gases.
Of the total 20 N2 sample SS gas canisters with tested two were rejected. The
ratio of
argon to oxygen in the results was used to detect possible atmospheric
contamination in
nitrogen gas samples. Samples with an argon to oxygen concentrations of 0.934
0.002 %vol
Ar : 20.95 0.32 %vol 02 were rejected. These bounds were established using
observed
variation in atmospheric sample sets analyzed for oxygen and argon
concentrations. The
44
CA 03173512 2022- 9- 26
rejected samples had argon concentrations >100 ppm and oxygen concentrations
>1 %vol.
The blank that was rejected also had open valves on the SS canister when
shipped from
Airborne Labs. Neither the sample nor gas blank rejected had reported hydrogen
concentrations >2 ppm.
Reported data indicate some repeatability in hydrogen detection among LA M/M
runs
in nitrogen with shortwave ultraviolet treatment. The highest reported
hydrogen
concentration of 27 ppm corresponds with a reported oxygen concentration of 24
%vol, more
than 3% greater than atmospheric oxygen, and 4700 ppm argon, nearly half of
atmospheric
concentrations. The results for this one sample highlight atmosphere is an
unlikely source of
reported gas species. For two sets of sample splits from the same run (i.e.,
GH8030A/B,
GH8050A/B), hydrogen and oxygen concentrations were significantly greater in
the last 88
seconds than the first 85 seconds.
For experiments run using an argon/krypton gas mixture increased hydrogen
concentrations (> 1 ppm) were only observed under 1/2 flow conditions. Three
of four total
runs sampled for analysis at Airborne Labs yielded hydrogen detection. It's
worth noting that
the largest concentration was measured in the first 83 seconds of collection
of the run, in
alternate observation to what was seen in the nitrogen gas runs.
Follow-up conversations with Airborne Labs indicated a variable and, at times,
high
presence of helium. After secondary review of all results, they assured that
all data reported
from DID and TCD met passing standards for QA/QC.
Table: Experimental sample results from nitrogen gas runs with hydrogen
detection
reported from GC-DID (Airborne Labs, Inc.). From NCG testing of 20 samples, 9
samples
resulted in significant concentrations of hydrogen (>2 ppm). The nitrogen
blank and one
sample were rejected due to argon:oxygen ratios, total concentrations, and a
known valve
integrity problem with the blank sample canister.
Sample Experimental Protocol Hydrogen Argon:Oxygen
ppm
GH8008 GSA, N2, Hot, SUV 0.7
4/89 (1/22.25)
GH8014 GSA, N2, Hot, SUV 0.9
<0
GH8021 GSA, N2, Hot, No SUV 0.3
<0
GH8023 GSA, N2, Hot, No SUV 1.2
3/77
GH8030A LA M/M, N2, Cold, SUV <0.2
<0
GH8030B LA M/M, N2, Cold, SUV 27
1/52
GH8031A LA M/M, N2, Cold, SUV 14
<0
GH8031B LA M/M, N2, Hot, SUV 11
<0
GH8038 LA M/M, N2, Hot, SUV 1.2
<0
GH8039 LA M/M, N2, Hot, SUV 9.7
<0
GH8040 LA M/M, N2, Hot, SUV 10
<0
CA 03173512 2022- 9- 26
Sample Experimental Protocol Hydrogen
Argon:Oxygen
PPm
GH8041 LA M/M, N2, Hot, SUV 7.7
<0
GH8042 LA M/M, N2, Hot, SUV 11
<0
GH8044 LA M/M, N2, Hot, SUV 9.2
<0
GH8048A LA M/M, N2, Hot, No SUV 0.6
<0
GH8048B LA M/M, N2, Hot, No SUV 0.5
2/55
GH8049A LA M/M, N2, Hot, No SUV 0.6
0
GH8049B LA M/M, N2, Hot, No SUV <0.2
<0
GH8050A LA M/M, N2, Hot, No SUV 0.5
<0
GH8050B LA M/M, N2, Hot, No SUV 9.8
<0
GH071522BLK1 N2 Blank <0.2
1/6
Table 2: Experimental sample results from argon/krypton gas runs with hydrogen
detection reported from GC-DID (Airborne Labs, Inc.). From NCG testing of 8
samples, 3
samples resulted in significant concentrations of hydrogen (? 1 ppm).
Sample Experimental Protocol Hydrogen
Krypton
PPm
PPm
GH8058A LA M/M, Ar/Kr, Hot, SUV <0.2
23000
GH8058B LA M/M, Ar/Kr, Hot, SUV <0.2
18000
GH8059A LA M/M, Ar/Kr, Hot, SUV <0.2
21000
GH8059B LA M/M, Ar/Kr, Hot, SUV <0.2
25000
GH8068A LA M/M, Ar/Kr, Hot, SUV, 1/2 Flow <0.2
22000
GH8068B LA M/M, Ar/Kr, Hot, SUV, 1/2 Flow 1
26000
GH8069A LA M/M, Ar/Kr, Hot, SUV, 1/2 Flow 10
23000
GH8069B LA M/M, Ar/Kr, Hot, SUV, 1/2 Flow 1
25000
GH071522BLK2 Ar/Kr Blank <0.2
27000
More results are provided in the Table below:
46
CA 03173512 2022- 9- 26
,
.
u.,
F-,
J
U.,
VI
F-,
0
4)
0
Run Gas TEDLAR
Collection H Ar Kr
Sample II Plan Matrix Hot/Cold SUV/No Flow
Sim Length N ppm 0 ppm ppm ppm ppm
0/Ar
GH8014 GSA N2 Hot SUV 2 L/min 3 L 35
sec N/A 760 0.9 18 N/A 42
3L
GI-18021 GSA N2 Hot No SUV 2 Li/min 4
rnin N/A 1,400 0.3 35 N/A 40
3L
GI-18023 GSA N2 Hot No SUV 2 Li/min 4
rnin N/A 1,800 1.2 170 N/A 11
3L
GI-18030A LA MN N2 Cold SW 2 Lirnin 85
sec N/A 1,200 <0.2 39 WA 31
3L
GH8030B LA MN N2 Cold SUV 2 Limin 161
sec N/A 240,000 27 4,700 N/A 51
3L
GH8031A LA WM N2 Cold SUV 2 Limin 85
sec N/A 760 14 50 N/A 15
3L
GH8031B LA WM N2 Cold SUV 2 Li/min 161
sec N/A 1,700 11 55 N/A 31
-4
GI-18014 GSA N2 Hot SUV 2 Limin 3 L 35
sec N/A 760 0.9 18 N/A 42
GR9039 LA Ivlifv1 N2 Hot SUV 2 L/min 12 L
173 sec N/A 800 9.7 51 11/41,1A 16
12 L
G H8040 LA MINI N2 Hot SUV 2 L/min 173
sec N/A 510 10 40 N/A 13
12 L
GH8041 LA MN N2 Hot SW 2 L/min 173
sec N/A 550 7.7 35 N/A 16
12 L
G H8042 LA MN N2 Hot SW 2 L/min 173
sec N/A 560 11 44 N/A 13
12 L
G H8044 LA MN N2 1-1 ot SIN 2 Limin 173
sec N/A 490 9.2 41 N/A 12
3L
GI-18021 GSA N2 Hot No SUV 2 Limin 4
rnin N/A 1,400 0.3 35 N/A 40
3L
GI-18023 GSA N2 Hot No SUV 2 Li/min 4 min
N/A 1,800 1.2 170 N/A 11
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48
CA 03173512 2022 9 26
The patent and scientific literature referred to herein establishes the
knowledge that is
available to those with skill in the art. All United States patents and
published or unpublished
United States patent applications cited herein are incorporated by reference.
All published
foreign patents and patent applications cited herein are hereby incorporated
by reference. All
other published references, documents, manuscripts and scientific literature
cited herein are
hereby incorporated by reference.
While this invention has been particularly shown and described with references
to
preferred embodiments thereof, it will be understood by those skilled in the
art that various
changes in form and details may be made therein without departing from the
scope of the
invention encompassed by the appended claims. Numerical values where presented
in the
specification and claims are understood to be approximate values (e.g.,
approximately or
about) as would be determined by the person of ordinary skill in the art in
the context of the
value. For example, a stated value can be understood to mean within 10% of the
stated value,
unless the person of ordinary skill in the art would understand otherwise,
such as a value that
must be an integer.
49
CA 03173512 2022- 9- 26
