U.S. patent application number 15/849544 was filed with the patent office on 2018-09-27 for cracking of a process gas.
This patent application is currently assigned to Lyten, Inc.. The applicant listed for this patent is Lyten, Inc.. Invention is credited to Bryce H. Anzelmo, Ryan Balmores, Philip David Fulmer, Hossein-Ali Ghezelbash, Thomas Riso.
Application Number | 20180273379 15/849544 |
Document ID | / |
Family ID | 60813412 |
Filed Date | 2018-09-27 |
United States Patent
Application |
20180273379 |
Kind Code |
A1 |
Riso; Thomas ; et
al. |
September 27, 2018 |
CRACKING OF A PROCESS GAS
Abstract
A process gas (such as a hydrocarbon gas) is flowed through a
thermal cracking apparatus to crack the process gas into
constituent components (such as hydrogen gas and solid carbon
nano-particles, e.g., carbon nano-onions, necked carbon
nano-onions, carbon nanospheres, graphene, graphite, highly ordered
pyrolytic graphite, single walled nanotubes, and/or multi-walled
nanotubes). The thermal cracking apparatus has an elongated heating
element disposed within an inner volume along a longitudinal axis
thereof. The elongated heating element heats the process gas as it
flows within a longitudinal elongated reaction zone to thermally
crack molecules of the process gas into the constituent components
of the molecules.
Inventors: |
Riso; Thomas; (Elizabeth,
CO) ; Fulmer; Philip David; (San Jose, CA) ;
Balmores; Ryan; (Santa Clara, CA) ; Ghezelbash;
Hossein-Ali; (Santa Clara, CA) ; Anzelmo; Bryce
H.; (Mountain View, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Lyten, Inc. |
Sunnyvale |
CA |
US |
|
|
Assignee: |
Lyten, Inc.
Sunnyvale
CA
|
Family ID: |
60813412 |
Appl. No.: |
15/849544 |
Filed: |
December 20, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15470450 |
Mar 27, 2017 |
9862602 |
|
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15849544 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 2/006 20130101;
C01B 2203/0272 20130101; C01B 3/24 20130101; C01B 32/312 20170801;
C01B 32/16 20170801; C01B 2202/06 20130101; C01B 2203/085 20130101;
C10G 9/00 20130101; C01B 32/20 20170801; C01B 2203/1235 20130101;
C01B 32/18 20170801; C01B 32/184 20170801; C01B 2202/02 20130101;
C01B 32/33 20170801; C01B 32/05 20170801; C04B 35/62839
20130101 |
International
Class: |
C01B 3/24 20060101
C01B003/24; B01J 2/00 20060101 B01J002/00; C10G 9/00 20060101
C10G009/00; C04B 35/628 20060101 C04B035/628 |
Claims
1. A thermal cracking apparatus, comprising: a body having an inner
volume with a longitudinal axis, the inner volume having a reaction
zone concentric with the longitudinal axis; a feedstock process gas
inlet through which a feedstock process gas is flowed
longitudinally into the inner volume during thermal cracking
operations; and an elongated heating element disposed within the
inner volume along the longitudinal axis and being surrounded by
the reaction zone, wherein the elongated heating element is held in
tension by a biasing element; wherein, during the thermal cracking
operations, the elongated heating element is heated by electrical
power to a molecular cracking temperature to generate the reaction
zone, the feedstock process gas is heated by heat from the
elongated heating element, and the heat thermally cracks molecules
of the feedstock process gas that are within the reaction zone into
constituent components of the molecules.
2. The thermal cracking apparatus of claim 1, wherein: the body
further comprises a shell and a heating chamber disposed within the
shell; and the heating chamber defines the inner volume and
contains the reaction zone along the longitudinal axis.
3. The thermal cracking apparatus of claim 2, wherein: the shell
and the heating chamber define a preheating region in a space
between the shell and the heating chamber; the feedstock process
gas is flowed through the preheating region before it is flowed
into the inner volume during the thermal cracking operations; and
the feedstock process gas is preheated by heat transferred through
the heating chamber from the reaction zone during the thermal
cracking operations.
4. The thermal cracking apparatus of claim 3, wherein: the
feedstock process gas cools the heating chamber when flowed through
the preheating region during the thermal cracking operations.
5. The thermal cracking apparatus of claim 1, wherein: the
elongated heating element is disposed concentrically with the
longitudinal axis.
6. The thermal cracking apparatus of claim 1, wherein: the
elongated heating element further comprises a plurality of heating
filaments arranged symmetrically at locations around and parallel
to the longitudinal axis.
7. The thermal cracking apparatus of claim 1, wherein: the inner
volume has a cylindrical shape with a constant diameter along the
longitudinal axis.
8. The thermal cracking apparatus of claim 1, wherein: the inner
volume has a conical shape with an inwardly tapering diameter in a
direction of flow of the feedstock process gas along the
longitudinal axis.
9. A thermal cracking apparatus, comprising: a body having a
heating chamber disposed within a shell, the heating chamber
defining an inner volume with a longitudinal axis, the inner volume
having a reaction zone concentric with the longitudinal axis; an
elongated heating element disposed within the inner volume along
the longitudinal axis and being surrounded by the reaction zone;
electrodes electrically connected to the elongated heating element
to provide electrical power to the elongated heating element to
heat the elongated heating element to a molecular cracking
temperature to generate the reaction zone during thermal cracking
operations; a gas inlet through which a hydrocarbon gas is flowed
longitudinally into the inner volume, wherein the hydrocarbon gas
is heated by heat from the elongated heating element, which
thermally cracks molecules of the hydrocarbon gas that are within
the reaction zone into hydrogen and carbon nano-particles, during
the thermal cracking operations; and a gas preheating region
between the heating chamber and the shell through which the
hydrocarbon gas is flowed to preheat the hydrocarbon gas and cool
the heating chamber before the hydrocarbon gas is flowed into the
inner volume during the thermal cracking operations.
10.-27. (canceled)
28. The thermal cracking apparatus of claim 1, wherein the biasing
element comprises a spring.
29. The thermal cracking apparatus of claim 1, wherein the biasing
element is configured to compensate for thermal expansion or
contraction of the elongated heating element, maintaining the
elongated heating element in a position that is concentric with and
parallel to the longitudinal axis during the thermal cracking
operations.
30. The thermal cracking apparatus of claim 1, wherein the
elongated heating element comprises a plurality of wire filaments
twisted together.
31. The thermal cracking apparatus of claim 1, wherein the
constituent components include solid products.
32. The thermal cracking apparatus of claim 9, wherein the
elongated heating element is held in tension by a biasing
element.
33. The thermal cracking apparatus of claim 32, wherein the biasing
element comprises a spring.
34. The thermal cracking apparatus of claim 32, wherein the biasing
element is configured to compensate for thermal expansion or
contraction of the elongated heating element, maintaining the
elongated heating element in a position that is concentric with and
parallel to the longitudinal axis during the thermal cracking
operations.
35. The thermal cracking apparatus of claim 9, wherein the
elongated heating element comprises a plurality of wire filaments
twisted together.
36. The thermal cracking apparatus of claim 9, wherein the
constituent components include solid products.
Description
RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 15/470,450, filed Mar. 27, 2017, and entitled "Cracking of
a Process Gas," which is incorporated fully herein by
reference.
BACKGROUND
[0002] Hydrocarbons (e.g., methane, ethane, propane, etc.) can be
pyrolyzed or cracked to synthesize hydrogen and/or to produce solid
carbon materials, as well as higher order carbon substances.
However, many processes used to produce these higher-order carbon
substances require the use of catalysts, such as metal catalysts.
Additionally, many processes also result in the presence of
impurities or contaminants, such as metallic and/or corrosive
contaminants that foul the equipment. Furthermore, many processes
require additional complex steps to ensure a desired quality or
purity of the resulting products.
SUMMARY
[0003] In some embodiments, a thermal cracking apparatus for
cracking a feedstock process gas includes a body, a feedstock
process gas inlet, and an elongated heating element. The body has
an inner volume with a longitudinal axis. The inner volume has a
reaction zone concentric with the longitudinal axis. A feedstock
process gas is flowed into the inner volume through the feedstock
process gas inlet during thermal cracking operations. The elongated
heating element is disposed within the inner volume along the
longitudinal axis and is surrounded by the reaction zone. During
the thermal cracking operations, the elongated heating element is
heated by electrical power to a molecular cracking temperature to
generate the reaction zone, the feedstock process gas is heated
from the elongated heating element, and the heat thermally cracks
molecules of the feedstock process gas that are within the reaction
zone into constituent components of the molecules.
[0004] In some embodiments, a method for cracking a feedstock
process gas includes providing a thermal cracking apparatus having
an inner volume that has a longitudinal axis and an elongated
heating element disposed within the inner volume along the
longitudinal axis; heating the elongated heating element by
electrical power to a molecular cracking temperature to generate a
longitudinal elongated reaction zone within the inner volume;
flowing a feedstock process gas into the inner volume and through
the longitudinal elongated reaction zone, wherein the feedstock
process gas is heated by heat from the elongated heating element;
thermally cracking molecules of the feedstock process gas within
the longitudinal elongated reaction zone into constituent
components thereof (e.g., hydrogen gas and one or more solid
products) as the feedstock process gas flows through the
longitudinal elongated reaction zone; and collecting the
constituent components.
[0005] In some embodiments, the feedstock process gas includes a
hydrocarbon gas, and the constituent components include hydrogen
and carbon nano-particles (e.g., in a size range of 5-500 nm). In
some embodiments, the carbon nano-particles include necked carbon
nano-onions or at least one of: carbon nano-onions, carbon
nanospheres, graphene, graphite, highly ordered pyrolytic graphite,
single walled nanotubes, and multi-walled nanotubes. In some
embodiments, the feedstock process gas is preheated (e.g., to
100-500.degree. C.) by flowing the feedstock process gas through a
gas preheating region between a heating chamber and a shell of the
thermal cracking apparatus before flowing the feedstock process gas
into the inner volume. In some embodiments, a gas having
nano-particles therein is flowed into the inner volume and through
the longitudinal elongated reaction zone to mix with the feedstock
process gas; and a coating of a solid product (e.g., layers of
graphene) is formed around the nano-particles.
[0006] Other and further embodiments of the present disclosure are
described below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 depicts a simplified process flow diagram of a method
for cracking a feedstock process gas in accordance with at least
some embodiments.
[0008] FIG. 2 depicts a simplified schematic view of a cracking
apparatus in accordance with at least some embodiments.
[0009] FIG. 3 depicts a simplified cross-sectional view of a
cracking apparatus in accordance with at least some
embodiments.
[0010] FIG. 4 depicts a simplified isometric exploded view of a
cracking apparatus in accordance with at least some
embodiments.
[0011] FIG. 5 depicts a simplified isometric view of the cracking
apparatus shown in FIG. 3, in accordance with at least some
embodiments.
[0012] FIG. 6 depicts a simplified isometric view of the cracking
apparatus of FIG. 3, in accordance with at least some
embodiments.
[0013] FIG. 7 depicts a simplified schematic view of a cracking
apparatus in accordance with at least some embodiments.
[0014] FIGS. 8-12 depict example micrograph images of carbon
nano-particles, in accordance with at least some embodiments.
[0015] FIG. 13 depicts a simplified schematic view of a cracking
apparatus in accordance with at least some embodiments.
[0016] FIG. 14 depicts a simplified schematic view of a cracking
apparatus in accordance with at least some embodiments.
[0017] FIG. 15 depicts a simplified process flow diagram of a
method for cracking a feedstock process gas in accordance with at
least some embodiments.
DETAILED DESCRIPTION
[0018] Embodiments of the present disclosure provide thermal
cracking apparatuses and methods for refining, pyrolyzing,
dissociating or cracking feedstock process gases into constituent
components to produce solid products (e.g., carbon nano-particles)
and gaseous products (e.g., hydrogen gas and/or lower order
hydrocarbon gases). The feedstock process gases generally include,
for example, hydrogen gas (H.sub.2), carbon dioxide (CO.sub.2),
C1-10 hydrocarbons, other hydrocarbon gases, natural gas, methane,
ethane, propane, butane, isobutane, unsaturated hydrocarbon gases,
ethene, propene, C.sub.2H.sub.2, C.sub.2H.sub.4, C.sub.2H.sub.6,
H.sub.2S, SiH.sub.4, etc. and mixtures thereof. The carbon
nano-particles generally include, for example, carbon nano-onions
(CNOs), necked CNOs, carbon nanospheres, graphene, graphite, highly
ordered pyrolytic graphite, single walled nanotubes, multi-walled
nanotubes, and/or other solid carbon products.
[0019] Some embodiments comprise thermal cracking methods that use,
for example, an elongated longitudinal heating element optionally
enclosed within an elongated casing, housing or body of a thermal
cracking apparatus. The body generally includes, for example, one
or more tubes or other appropriate enclosures made of stainless
steel, titanium, graphite, quartz, or the like. In some
embodiments, the body of the thermal cracking apparatus is
generally cylindrical in shape with a central elongate longitudinal
axis arranged vertically and a feedstock process gas inlet at or
near a top of the body. The feedstock process gas flows
longitudinally down through the body or a portion thereof. In the
vertical configuration, for embodiments in which the gas flow
direction is downward, both gas flow and gravity assist in the
removal of the solid products from the body of the thermal cracking
apparatus. In some embodiments, the gas flow direction is upward in
the vertical configuration.
[0020] The heating element generally includes, for example, a
heating lamp, one or more resistive wires or filaments, twisted
wire filaments, metal filaments, flat metallic strips, cylindrical
rods, and/or other appropriate thermal radical generators or
elements that can be heated to a specified temperature (i.e., a
molecular cracking temperature) sufficient to thermally crack
molecules of the feedstock process gas. The heating element is
generally disposed, located or arranged to extend centrally within
the body of the thermal cracking apparatus along the central
longitudinal axis thereof. For example, if there is only one
heating element, then it is placed at or concentric with the
central longitudinal axis, and if there is a plurality of the
heating elements, then they are spaced or offset generally
symmetrically or concentrically at locations near and around and
parallel to the central longitudinal axis.
[0021] Thermal cracking is generally achieved by passing the
feedstock process gas over, in contact with, or within the vicinity
of, the heating element within a longitudinal elongated reaction
zone generated by heat from the heating element and defined by and
contained inside the body to heat the feedstock process gas to or
at a specified molecular cracking temperature as discussed further
below. The reaction zone is considered to be the region surrounding
the heating element and close enough to the heating element for the
feedstock process gas to receive sufficient heat to thermally crack
the molecules thereof. The reaction zone is thus generally axially
aligned or concentric with the central longitudinal axis of the
body. In some embodiments, the thermal cracking is performed under
a specified pressure. In some embodiments, the feedstock process
gas is circulated around or across the outside surface of a
container of the reaction zone or a heating chamber in order to
cool the container or chamber and preheat the feedstock process gas
before flowing the feedstock process gas into the reaction
zone.
[0022] In some embodiments, the carbon nano-particles and/or
hydrogen gas are produced without the use of catalysts. In other
words, the process can be catalyst-free.
[0023] Some embodiments provide a standalone system that can
advantageously be rapidly scaled up or scaled down for different
production levels as desired. For example, some embodiments are
scalable to provide a standalone hydrogen and/or carbon
nano-particle producing station system, a hydrocarbon source or a
fuel cell station. Some embodiments can be scaled up to provide
higher capacity systems, e.g., for a refinery or the like.
[0024] FIG. 1 depicts a simplified process flow diagram of a method
100 for cracking a feedstock process gas according to at least some
embodiments. In some embodiments, the method obtains desired
hydrogen and/or carbon products by thermally dissociating or
cracking the feedstock process gas, e.g., gaseous hydrocarbon
feedstocks. The particular steps, combination of steps, and order
of steps are shown for illustrative and explanatory purposes only.
Other embodiments may include other steps, combinations of steps,
and/or orders of steps to achieve generally similar results.
[0025] The method 100, and variations thereof, may be carried out
in any suitable thermal cracking apparatus as disclosed herein
capable of control in accordance with the teachings provided
herein. Illustrative, but non-limiting, examples of embodiments of
a suitable apparatus are described below with respect to FIGS. 2-7
and 13.
[0026] The method 100 can produce one or more desired hydrogen
and/or carbon products in accordance with some embodiments. In some
embodiments, the desired products generally include gaseous
products, hydrocarbon liquids, and/or solid products. The gaseous
products generally include hydrogen gas and/or hydrocarbon gases.
Such gaseous products can be used, for example, for a hydrogen fuel
station, as a raw material source for a process requiring hydrogen
gas, and/or other appropriate uses. The solid products generally
include the carbon nano-particles mentioned herein. Such solid
products can be used in, for example, batteries, fuel cells,
digital displays, lubricants, tires, biomedical applications,
various industrial products, and other applications, or
combinations thereof.
[0027] The method 100 generally starts at 102, wherein an inner
volume of a thermal cracking apparatus, such as the apparatus
described below with respect to FIGS. 2-7, is at least partially
purged of contaminants, for example, air and moisture, for example,
by pulling a vacuum. Alternatively or in combination, a purge gas
is flowed into the inner volume of the thermal cracking apparatus
and optionally removed therefrom. The purge gas may be any suitable
gas or gaseous mixture inert to the process and processing
environment or that is a feedstock process gas for the process.
Examples of suitable purge gases include one or more inert gases,
such as noble gases, among others. In some embodiments, the purge
gas is flowed into the inner volume of the thermal cracking
apparatus at a flow rate of about 0.5 to about 10 slm (standard
liter per minute). In some embodiments, the thermal cracking
apparatus can be seasoned prior to processing the feedstock process
gas by purging the inner volume of the thermal cracking apparatus
with one or more purge gases, for example, at the flow rates
disclosed above and with the heating element at a temperature of
about 600.degree. C. to about 3000.degree. C., or 1600-2200.degree.
C. (e.g., at the molecular cracking temperature), for about 5 to
about 80 minutes, e.g., about 35 minutes. In some embodiments, the
seasoning temperature may be the same temperature as the subsequent
processing temperature used to process the feedstock process gas.
In some embodiments, methane, compressed/clean natural gas, or
pipeline quality natural gas (or any other suitable feedstock
process gas) is flowed into the inner volume of the thermal
cracking apparatus for a few seconds, optionally heated, and purged
from the thermal cracking apparatus.
[0028] At 104, the feedstock process gas is flowed into the inner
volume of the thermal cracking apparatus and into contact with (or
immediately surrounding or in the vicinity of) the heating element,
i.e., a reaction zone. The feedstock process gas generally has
little or no oxygen, sulfur, chlorine, or metal attached to the
molecules thereof. As used herein, little or no means less than 0.5
molar percent of the total feedstock process gas. In some
embodiments, the feedstock process gas comprises less than 0.5
molar % oxygen or C.sub.xO.sub.y complexes. (Some embodiments, on
the other hand, use a significant percentage of oxygen in the
feedstock process gas, depending on process parameters and desired
products.) The feedstock process gas is generally delivered at a
known, predetermined flow rate for continuous processing
embodiments. In some embodiments, before delivery to the thermal
cracking apparatus or before processing, the feedstock process gas
is optionally preheated (e.g., by heating delivery conduits or
staging vessels). Alternatively or in combination the gaseous
hydrocarbon feedstock may be heated within the thermal cracking
apparatus (e.g., by providing a heat jacket or other energy source
outside the thermal cracking apparatus, etc.). In some embodiments,
the feedstock process gas is provided from a liquid source, and the
liquid therefrom is brought to a temperature and pressure suitable
to maintain the feedstock process gas in a gaseous state when
introduced into the inner volume of the thermal cracking apparatus.
In some embodiments, the feedstock process gas is heated to about
100 to about 500.degree. C. before delivering the gaseous
hydrocarbon feedstock to the inner volume.
[0029] In some embodiments, the feedstock process gas within the
inner volume of the thermal cracking apparatus may be maintained at
a relatively low pressure. Various example alternative pressure
ranges generally include: about 0.5-10 atmospheres, about 1-10
atmospheres, less than about 5 atmospheres, about 1 to 3
atmospheres, and about 1 to 2 atmospheres. The low pressure
advantageously allows the use of less expensive equipment compared
with typical refining equipment, which operates at about 10 to
about 50 atmospheres.
[0030] At 106, the feedstock process gas is thermally cracked,
e.g., by heating with thermal energy provided by the heating
element disposed within the inner volume of the thermal cracking
apparatus. The thermal cracking apparatus thus provides sufficient
thermal energy to the feedstock process gas to break or overcome at
least some molecular bonds thereof to break down or fragment the
reactants of the feedstock process gas into smaller components,
i.e., various solid and gaseous products. To do so, for example,
the heating element is heated to a temperature of about 600.degree.
C. to about 3000.degree. C., or 1600-2200.degree. C. Without
intending to be bound by theory, it is believed that the feedstock
process gas becomes radicalized and fragmented into various
moieties by the thermal energy provided by the heating element. For
example, in the case in which a hydrocarbon is the feedstock
process gas, the hydrocarbon molecules are heated by the heating
element, which cracks the hydrocarbon molecules into, for example,
hydrogen ions and charged carbon atoms (and/or other hydrocarbons).
The hydrogen ions can associate to form diatomic hydrogen gas. The
charged carbon atoms form the carbon nano-particles. The desired
products are thus produced.
[0031] In some embodiments, either or both of the carbon
nano-particles or the hydrogen gas (or other desired products) can
be produced without the use of catalysts, i.e., catalyst-free,
using some or all of the methods and apparatus described herein.
The absence of catalysts from the methods described herein avoids
the use of expensive catalysts and also avoids introducing
impurities or contaminants, such as metallic or other corrosive
contaminants, into the carbon nano-particles or other desired
products. In addition, metals, as are present in many catalysts,
may be highly combustible in hydrogen gas, so the catalyst-free
process avoids such situations.
[0032] In some embodiments, the carbon nano-particles may comprise
a specified size and/or geometry as described more fully below.
Also, partially or fully activated carbon nano-particles and
gaseous products may be advantageously produced in the absence of a
catalyst.
[0033] Moreover, the size of the carbon nano-particles, for
example, the diameter of the particles, may be controlled. Some
embodiments comprise the production of carbon nano-particles (such
as carbon nano-onions) ranging in diameter from, for example,
approximately 5 nanometers (nm) to approximately 300 nm in diameter
or larger.
[0034] Carbon nano-particle geometry or size or the amount of
hydrogen conversion may be controlled, at least in part, by
controlling residence time of the feedstock process gas within the
reaction zone, or within the vicinity of the heating element.
Residence time in the reaction zone can be controlled, for example,
by controlling the length of the reaction zone, the flow rate of
the feedstock process gas, or combinations thereof. Examples of
suitable residence time include between about 0.1 to about 100
seconds. In some embodiments, the feedstock process gas has a
residence time greater than about two seconds. Also, in some
embodiments, networks of partially and/or fully activated
integrated fullerene allotropes are produced. For example,
Carbon-60, i.e., "Buckyballs" further comprise layers, such as
substantially concentric layers of single-walled nanotubes (SWNT)
and multi-walled nanotubes (MWNT), to form carbon nano-onions. At
least one example is a Carbon-60 structure surrounded by a
Carbon-320 structure of graphene.
[0035] Without intending to be limited by theory, it is believed
that thermal gradients are created within the thermal cracking
apparatus. For example, the temperature within the inner volume of
the thermal cracking apparatus is hottest at or near the heating
element and relatively cooler near a wall of the thermal cracking
apparatus, wherein a thermal gradient is formed therebetween. It is
further believed that at higher temperatures within the thermal
gradient, and/or higher residence times, hollow and/or necked
carbon nano-onions are formed, having smaller diameters, e.g.,
approximately an average of 5 nm to approximately 90 nm. At
relatively lower temperature regions of the gradient, i.e., near a
wall of the thermal cracking apparatus, and at shorter residence
times, larger carbon nano-particles are formed, e.g., an average of
150-500 nm. Additionally, shorter residence times generally result
in lower hydrogen conversion. Between these extremes of the
gradient, other sized carbon nano-particles are formed, e.g.,
approximately 100 nm. Thus, typical ranges for the sizes of the
carbon nano-onions are 5-500 nm, 5-90 nm, 5-100 nm, 100-150 nm,
100-500 nm, and 150-500 nm, among others, depending on process
parameters for preheat temperature, heating element temperature,
pressure, flow rate, residence time, etc.
[0036] At 108, one or more solid products, such as the carbon
nano-particles, are collected in any suitable manner. For example,
the carbon nano-particles may be separated from the gas stream and
collected via cyclonic separation, filtering, or other appropriate
collection or separation technique. In some embodiments, the carbon
nano-particles are collected via a collector, such as any of the
collectors discussed further below with respect to FIGS. 2-7. The
collector may be placed at a location suitable to collect the
carbon nano-particles from the inner volume of the thermal cracking
apparatus. In some embodiments, a charge may be applied to the
collector to electrostatically attract the carbon
nano-particles.
[0037] At 110, gaseous desired products, such as hydrogen gas or
hydrocarbon gas, are optionally collected. Various gaseous
products, for example, mixtures of hydrogen gas and other
hydrocarbons, having various boiling points, can be independently
collected, for example, by collecting and delivering the gaseous
product to a distillation apparatus to separate desired products
based upon their respective boiling points. In some embodiments,
the gaseous output is collected and stored for later use. For
example, in some embodiments, the output gas may be hydrogen
(H.sub.2) and the hydrogen may be stored, in tanks or other
suitable canisters, e.g., for later use on site or at a different
location. Alternatively, in some embodiments, the thermal cracking
apparatus may be a point of use generator of a desired product and
the gaseous output is routed to another apparatus for use therein.
In some embodiments, some gaseous output may be routed to another
apparatus for immediate use, while a remaining portion of the
gaseous output may be collected and stored.
[0038] Upon completion of collection of the desired products (e.g.,
at 108 and/or 110), the method 100 generally ends. However, the
method 100 may include variations and/or additional processing
techniques. For example, the method 100 may include a plurality of
thermal cracking apparatuses, operating at the same or different
conditions (e.g., varying temperatures, flow rates, and/or
pressures). For example, in such embodiments, the method 100 may
further comprise at least one additional thermal cracking apparatus
in fluid communication with the inner volume downstream of the
thermal cracking apparatus. Also, a plurality of thermal cracking
apparatuses may be in fluid communication in parallel or in
series.
[0039] Furthermore, some embodiments of the method 100 comprise the
use of micro gas chromatograph analysis, such that the output of
hydrogen gas can be measured, as well as providing data regarding
the particle size, e.g., length and/or diameter of carbon
nano-particles and/or the morphology of the carbon nano-particles.
For example, an in-situ feedback loop may be provided by feeding
data corresponding to the micro gas chromatograph results to a
controller to control process parameters such as one or more of
flow rate of the feedstock process gas, power provided to the
heating element, power provided to gas preheating elements, flow
rates of heat transfer fluids used for heating the feedstock
conduits or the housing of the thermal cracking apparatus, or other
potential parameters.
[0040] The method 100 may be a continuous process capable of
operating continuously and/or automatically. Alternately, the
method 100 may be a batch process to process a pre-determined
amount of the feedstock process gas. Also, a controller may be
coupled to the thermal cracking apparatus to control operation of
the thermal cracking apparatus. In some embodiments, the controller
may further be configured to communicate with a remote computer
network. In some embodiments, the controller may further be
configured to communicate with and control operation of one or more
additional thermal cracking apparatuses to control operation of the
plurality of thermal cracking apparatuses.
[0041] Various example and non-limiting embodiments of the method
100 are disclosed herein and all features of any embodiment may be
incorporated within any other embodiment without limitation. For
example, in some embodiments, the method 100 for cracking a
feedstock process gas includes flowing a feedstock process gas to
an inner volume of the thermal cracking apparatus and into contact
with or in the vicinity of the heating element (i.e., the reaction
zone) of the thermal cracking apparatus, thereby thermally cracking
the feedstock, producing a carbon product and hydrogen gas, as
described above, without the use of catalysts, i.e.,
catalyst-free.
[0042] In some embodiments, the method 100 for cracking a feedstock
includes flowing a purge gas, as described above, into the inner
volume of the thermal cracking apparatus to remove contaminants
therefrom, flowing the feedstock process gas to the inner volume of
the thermal cracking apparatus and into contact with or in the
vicinity of the heating element to thermally crack the feedstock
process gas, producing a carbon product and hydrogen gas, without
the use of catalysts, i.e., catalyst-free, wherein the feedstock
process gas contains little to no C.sub.xO.sub.y complexes, for
example, wherein the feedstock process gas comprises approximately
less than 0.50 molar % oxygen.
[0043] In some embodiments, the method 100 for cracking a feedstock
process gas includes flowing a purge gas, as described above, into
the inner volume of the thermal cracking apparatus to remove
contaminants therefrom, flowing the feedstock process gas to the
inner volume of the thermal cracking apparatus and into contact
with or in the vicinity of the heating element to thermally crack
the feedstock process gas, to produce carbon nano-particles (e.g.,
solid carbon nano-onions, hollow carbon nano-onions and/or necked
carbon nano-onions) that further may comprise additional layers of
single-walled nanotubes, multi-walled nanotubes, and/or
combinations thereof and/or graphene and/or highly ordered
pyrolytic graphite, or the like, wherein varying process
conditions, such as feedstock process gas flow rate, thermal
cracking apparatus geometry, preheat temperatures, heating element
operating temperatures and pressures, and/or feedstock process gas
concentration, permits controlled modulation of the diameter of the
carbon nano-particles, without the use of catalysts, i.e.,
catalyst-free. Also, the methods comprise the manufacture of
hydrogen gas as a product gas.
[0044] In some embodiments, the method 100 utilizes a first thermal
cracking apparatus, as described above, and a second thermal
cracking apparatus, wherein the first thermal cracking apparatus
and the second thermal cracking apparatus are fluidly coupled. In
some embodiments, the method 100 utilizes a first thermal cracking
apparatus, a second thermal cracking apparatus, and at least one
additional thermal cracking apparatus situated between the first
and second thermal cracking apparatuses, wherein the first thermal
cracking apparatus, the second thermal cracking apparatus and the
at least one additional thermal cracking apparatus are fluidly
coupled. In some embodiments, the thermal cracking apparatuses may
be fluidly coupled in series, in parallel, or combinations thereof.
Embodiments further comprising more than one thermal cracking
apparatus are capable of mitigating and/or eliminating undesirable
by-products as well as controlling the output of products, e.g.,
hydrogen gas and carbon nano-particles.
[0045] FIG. 2 depicts a simplified schematic view of a thermal
cracking apparatus 200 in accordance with at least some embodiments
and suitable for performing the method 100 described above. The
thermal cracking apparatus 200 generally includes a body 202, a lid
204, a collector 206, a process gas supply 208, a gas inlet 210, a
gas outlet 212, a lower channel 211, an upper channel 213, a heat
transfer source 215, a first electrical terminal 216, a second
electrical terminal 218, a heating element 222, and a support rod
223, among other possible components not shown for simplicity.
[0046] The body 202 generally defines an inner volume 224, within a
portion of which the heating element 222 is disposed. The body 202
is thus the heating chamber or reaction tube of the thermal
cracking apparatus 200. In some embodiments, the heating element
222 may be axially symmetrically disposed within the inner volume
224 near or concentrically arranged around a central longitudinal
axis of the body 202 of the thermal cracking apparatus 200. The
portion of the inner volume 224 through which the heating element
222 extends is considered to contain a reaction zone 226 that is
generated by the heating element 222 during thermal cracking
operations. The reaction zone 226 may include the entire inner
volume 224 or only that portion of the inner volume 224 that is
within a certain distance of the heating element 222, e.g., as
indicated by the dashed line.
[0047] Although the reaction zone 226 (or the inner volume 224) is
depicted in FIG. 2 as being conical in shape, the reaction zone 226
may have other geometries as well. For example, conical,
cylindrical, or Venturi-shaped reaction zones may be used, among
other geometries. Any of these configurations can have multiple
inlet or outlet ports disposed at different locations along the
length of the reaction zone to control the length of travel of the
feedstock process gas through the reaction zone.
[0048] In some embodiments, the heating element 222 is one or more
resistive or conductive wires or filaments, metal filaments, flat
conductive strips, and/or other appropriate thermal radical
generators or elements that can be heated to a specified
temperature. The heating element 222 may be fabricated from
suitable process-compatible conductive materials such as tungsten,
tantalum, or the like. The number, diameter, spacing, geometry,
arrangements, material composition, etc., of the heating element
222 may be changed as desired to control the temperature, zones,
reaction kinetics, resulting products, etc.
[0049] In some embodiments, the heating element 222 represents a
single wire or a twisted wire filament. The twisted wire filament
is also known as a bundled wire, which is formed of a bundle of
multiple individual wire filaments twisted together. Any
appropriate number of individual wire filaments can be used in the
twisted wire filament, e.g., 4 individual wire filaments or 2-8
individual wire filaments. In some embodiments, the individual wire
filaments of the twisted wire filament generally have any
appropriate diameter, e.g., a diameter of 0.5 mm or 0.5-12 mm.
[0050] In some embodiments, the heating element 222 is a flat
strip, instead of a round wire. For example, a flat strip having a
rectangular cross section with a width of 1-15 mm and a thickness
of 1-4 mm have been shown to provide a sufficient surface area to
enable appropriate heat transfer to the feedstock process gas to
crack the reactants into the desired products.
[0051] The heating element 222 is made of any appropriate
electrically resistive material capable of the desired temperature
level with an appropriate level of applied electrical power.
Relevant factors for selecting an appropriate material generally
include a lower thermal expansion coefficient, a higher
resistivity, and a higher melting point temperature. In some
embodiments, for example, the heating filament 222 is made of
tungsten (W), tantalum (Ta), molybdenum (Mo), iridium (Ir), rhenium
(Re), ruthenium (Ru), nichrome alloys, or graphite. Tungsten and
tantalum have relatively high melting points, which generally
render them more suitable as heating element materials herein.
Tantalum carbides have an even higher melting point than tantalum
alone has; whereas, tungsten carbides have a lower melting point
than tungsten alone has. Tantalum has a higher resistivity, but
also a higher thermal expansion coefficient, than does tungsten.
Under some thermal cracking conditions, tungsten is more likely to
crack or form graphitic spheres or nodules on its surface. The
preferred heating element material thus generally depends on the
particular operating parameters and thermal cracking device
configuration for a desired thermal cracking operation.
[0052] An advantage of the twisted wire filament over a single wire
filament is that the twisted wire filament has a larger surface
area for radiating heat to the surrounding feedstock process gas
during thermal cracking operations. Overall thermal cracking
efficiency or conversion when using the twisted wire filament is
thus improved or increased, thereby resulting in greater production
of desired gaseous and solid products. In some embodiments, a
twisted wire filament demonstrated greater than a 50% improvement
over a single wire filament for thermal cracking of methane.
Another advantage of the twisted wire filament over a single wire
filament is that the twisted wire filament is less prone to
breakage, particularly after repeated thermal cycling for multiple
thermal cracking operations.
[0053] In the illustrated embodiment, the heating element 222 is a
wire, twisted wire filament or flat strip whose ends are coupled to
electrodes 228 and 230. The heating element 522 is stretched from
the first electrode 228, down under the support rod 223, and back
up to the second electrode 230. The support rod 223 is coupled to
the lid 204 for mechanical stability and extends longitudinally
down into the reaction zone 226 (or the inner volume 224).
[0054] In some embodiments, the heating element 222 is coupled to a
power supply to cause the generation of heat by conduction of
electrical energy from the power supply through the heating element
222. Electrical power may be provided to the heating element 222
from a power supply 232 via the first and second electrical
terminals 216, 218. The electrical terminals 216, 218 are
electrically coupled to the electrodes 228 and 230 (and thus to the
ends of the heating element 222) and to the power supply 232. The
heating element 222 is configured to be heated by the electrical
power to a suitable temperature to dissociate the feedstock process
gas passing through the reaction zone 226 of the thermal cracking
apparatus 200. For example, in some embodiments, the heating
element 222 may be heated to a temperature of about 600.degree. C.
to about 3000.degree. C., or 1600-2200.degree. C. The electrical
power level or the temperature may be selected dependent upon at
least one of the type of the feedstock process gas to be
dissociated or the type of the desired products to be produced.
[0055] In some embodiments, the electrical power provided to the
heating element 222 by the power supply 232 is adjusted by a
feedback loop during thermal cracking operations in order to
maintain the desired power level. For some types of heating element
materials, the conductivity (or resistivity) of the heating element
222 changes due to carbon buildup on, or carbonization of, the
heating element material. Tantalum, for example, reacts with the
carbon to form carbon tantalum, which has a different resistivity
than tantalum. The feedback loop thus detects changes in the
resistance of the heating element 222 and adjusts the voltage
and/or amperage output level of the power supply 232 to maintain a
relatively constant power level, thereby maintaining a relatively
constant operating temperature for the reaction zone.
[0056] The inlet 210 and the outlet 212 are fluidly coupled to the
body 202 or the lid 204 to access the inner volume 224 proximate a
larger diameter end of the inner volume 224 (e.g., proximate the
top of the upwardly expanding cone, assuming a conical shape). The
process gas supply 208 is coupled to the inlet 210 to provide the
feedstock process gas to the inner volume 224. In some embodiments,
the collector 206 is coupled to the bottom of the body 202 of the
thermal cracking apparatus 200 proximate the smaller diameter end
of the inner volume 224 (e.g., proximate the bottom of the upwardly
expanding cone, assuming a conical shape).
[0057] In use during processing, the feedstock process gas is
delivered into the inner volume 224 via the inlet 210. The
feedstock process gas is then heated by the thermal energy provided
by the heating element 222 sufficiently to at least partially
dissociate the molecules thereof. Resultant gaseous products from
the thermal dissociation exit the thermal cracking apparatus 200
through the outlet 212. In embodiments where solid products of the
dissociation are created, such as carbon nano-particles, the carbon
nano-particles flow, fall, or are pushed down toward the bottom of
the inner volume 224 and move into the collector 206, where they
are retained.
[0058] In some embodiments, the thermal cracking apparatus 200
includes a heat transfer apparatus to facilitate cooling the outer
components of the thermal cracking apparatus 200, such as the body
202. For example, in some embodiments, channels are disposed within
the body 202 to flow a heat transfer medium, such as a coolant,
supplied by the heat transfer source 215. As illustrated for
example in FIG. 2, the lower channel 211 and the upper channel 213
are provided as shown for this purpose. However, other numbers of
channels or configurations of channels may be used as well.
Alternatively or in combination, an external cooling jacket may be
coupled to the body 202 to facilitate removal of excess heat from
the body 202. Alternatively or in combination, the thermal cracking
apparatus 200 includes thermal insulation around the body 202 to
maintain the outer surfaces thereof at or below a desired
temperature, for example, to facilitate safe handling of the
thermal cracking apparatus 200 or to minimize undesired reactions,
explosion, or other hazards that may be triggered or accelerated
due to thermal energy.
[0059] In some embodiments, the lid 204 is coupled to the top of
the body 202 of the thermal cracking apparatus 200. For example,
the lid 204 may be removably coupled to the body 202 to provide
internal access for cleaning, maintenance, or the like. Various
components, such as the inlet 210 and the outlet 212 may be
disposed in the lid 204, as discussed in greater detail below.
[0060] FIG. 3 depicts a simplified cross-sectional view of a
thermal cracking apparatus 500 in accordance with some embodiments.
The thermal cracking apparatus 500 is substantially similar to the
thermal cracking apparatus 200 described above except as indicated
to the contrary below. The thermal cracking apparatus 500 generally
includes a body 502 having an inner volume 503, a lid 504 coupled
to the top of the body 502, and a collector 506 coupled to the
bottom of the body 502. The inner volume 503 is generally defined
by an inner surface 508 of walls 509. In some embodiments, the
walls 509 are reinforced with stiffening elements 507. In some
embodiments, the walls 509 and stiffening elements 507 are part of
an insert disposed within (i.e., inserted within) an outer shell of
the body 502. In use during processing, a longitudinal reaction
zone 510 is formed within the inner volume 503 and includes all or
part of the inner volume 503, e.g., similar to the reaction zones
mentioned above. The reaction zone 510 is generated by a heating
element 522 during thermal cracking operations. The body 502 is
thus the heating chamber or reaction tube of the thermal cracking
apparatus 500.
[0061] In some embodiments, the thermal cracking apparatus 500
further includes a first housing 516 encapsulating a first
electrode 517 and a second housing 518 encapsulating a second
electrode 519. The first and second housings 516, 518 are coupled
to the lid 504 as shown (or an upper portion of the body 502). The
first and second electrodes 517, 519 are coupled to an external
power source (not shown) and extend into an upper portion of the
inner volume 503 and are coupled to corresponding wire lugs (first
and second wire lugs 520 and 521, respectively) of the heating
element 522. The heating element 522 extends into the reaction zone
503 generally along, and spaced or offset generally symmetrically
or concentrically at locations near and around, a central
longitudinal axis of the thermal cracking apparatus 500 or the body
502 thereof. The thermal cracking apparatus 500 functions similarly
to the thermal cracking apparatus 200, as described above.
[0062] In some embodiments, the heating element 522 represents a
single wire, a twisted wire filament or a flat strip whose ends are
coupled to the wire lugs 520 and 521. The heating element 522 is
stretched from the first wire lug 520, down under a quartz rod 523,
and back up to the second wire lug 521. The quartz rod 523 is
coupled to a ceiling 505 of the lid 504 for mechanical stability.
In some embodiments, the heating element 522 is similar to the
heating element 222, as described above.
[0063] FIG. 4 illustrates some variations on the embodiments shown
in FIGS. 2 and 3 with an exploded view of a portion of a thermal
cracking apparatus 400 (e.g., similar in some respects to a portion
of the thermal cracking apparatus 200 and 500). The thermal
cracking apparatus 400 generally includes a body 402 with an outer
shell 404 and an insert 406. In some embodiments, cooling channels
are provided to circulate a heat transfer medium (e.g., a coolant)
from a coolant source through the cooling channels. The cooling
channels are disposed within the body 402, for example, between the
outer shell 404 and the insert 406. In some embodiments, the insert
406 has an outer surface with an outer profile that defines,
together with the inner surface of the outer shell 404, one or more
channels for the heat transfer medium to flow. In some embodiments,
a lower annular channel 408 and an upper annular channel 410 are
provided. In some embodiments, the lower annular channel 408 and
the upper annular channel 410 are fluidly coupled within the body
402. For example, one or more openings may be provided in each of
the lower annular channel 408 and the upper annular channel 410 to
couple each of the lower annular channel 408 and the upper annular
channel 410 to each other via an intermediate volume disposed
within the body 402 between the lower annular channel 408 and the
upper annular channel 410 and between the insert 406 and the outer
shell 404. In some embodiments, the insert 406 has a plurality of
external fins 412, which may be disposed within the intermediate
volume between the lower and upper annular channels 408, 410 to
facilitate heat transfer from the insert 406 to the heat transfer
medium flowing between the lower annular channel 408 and the upper
annular channel 410 and through the intermediate volume. In some
embodiments, the fins 412 are an integral part of the insert
406.
[0064] The heat transfer medium can be flowed from the lower
annular channel 408 to the upper annular channel 410 or from the
upper annular channel 410 to the lower annular channel 408 to
facilitate heat transfer from the insert 406 to the heat transfer
medium. When present, the fins 412 further facilitate heat transfer
from the insert 406 to the heat transfer medium. A heat transfer
supply line (not shown) may be coupled to a heat transfer inlet 414
and a heat transfer return line (not shown) may be coupled to a
heat transfer outlet 416 of the body 402 (or the outer shell 404)
to facilitate flow of the heat transfer medium to/from the thermal
cracking apparatus 400.
[0065] FIG. 5 depicts a simplified isometric view of the thermal
cracking apparatus 500 (or 200). As illustrated in FIG. 5, the
thermal cracking apparatus 500 may be supported on a plurality of
legs 720. Although not shown in FIG. 3, the thermal cracking
apparatus 500 includes a heat transfer inlet 702, a gas inlet 710,
and a gas outlet 712, which function similarly to the heat transfer
inlet 414, the gas inlet 210, and the gas outlet 212, respectively,
of the thermal cracking apparatus 500 or 200, as described above.
Additionally, the thermal cracking apparatus 500 generally includes
a heat transfer outlet (not shown), e.g., similar to the heat
transfer outlet 416 described above.
[0066] FIG. 6 depicts an alternative simplified isometric view of
the thermal cracking apparatus 500 (or 200). As illustrated in FIG.
6, the thermal cracking apparatus 500 (or 200) may be supported on
a plurality of legs 602.
[0067] FIG. 7 depicts a simplified schematic view of a thermal
cracking apparatus 900 in accordance with at least some embodiments
and suitable for performing the method 100 described above. The
thermal cracking apparatus 900 generally includes an upper housing
902, a lower housing 904, and a collector 906. The upper and lower
housings 902 and 904 are collectively referred to as "the body" in
this embodiment. The body 902/904 and the collector 906 are formed
of stainless steel, e.g., SST 316 or SST 304, or other appropriate
material. In some embodiments, the upper and lower housings 902 and
904 are formed as one integral piece of material. In some
embodiments, the upper and lower housings 902 and 904 are removably
coupled to one another to facilitate ease of access to an interior
of each housing 902 and 904.
[0068] The upper housing 902 generally includes an interior into
which an insert 910 is disposed, so that the upper housing 902 and
the insert 910 are considered a dual wall structure. The insert 910
includes inner walls that define an inner volume 908, all or part
of which includes a longitudinal reaction zone generated by a
heating element 948 during thermal cracking operations. The upper
housing 902 or the insert 910 is thus considered the heating
chamber or reaction tube of the thermal cracking apparatus 900.
[0069] Although the insert 910 is shown with the inner volume 908
being cylindrical, the insert 910 may alternatively have a
downwardly and inwardly tapering conically shaped inner surface
similar to that described above for the inner volume 224 of the
body 202. The insert 910 is formed of a thermally reflective
material such as, for example, stainless steel, titanium, graphite,
quartz, or the like.
[0070] Upper and lower ring supports 912 and 914 support the insert
910 and facilitate coupling, or fixing, of the insert 910 to the
interior of the upper housing 902. In some embodiments, the upper
and lower ring supports 912 and 914 are formed of a thermally
insulative material, such as a ceramic. Alternatively, or in
combination, the upper and lower ring supports 912 and 914 are
configured to limit a physical surface contact between the upper
and lower ring supports 912 and 914 and the insert 910 in order to
reduce thermal transfer via conduction of heat from the insert 910
to the ring supports 912 and 914, the upper housing 902, and/or
other surrounding components.
[0071] In some embodiments, outer surfaces of the upper and lower
ring supports 912 and 914 include threads that mate with
corresponding threads on an interior wall of the upper housing 902.
In some embodiments, a fastening element (e.g., a screw) is
alternatively used to couple the upper and lower ring supports 912
and 914 to the interior of the upper housing 902.
[0072] In some embodiments, a thermal insulator 916 is disposed
between the insert 910 and the interior wall of the upper housing
902. The thermal insulator 916 is formed of a thermally insulative
material, e.g., ceramic.
[0073] In some embodiments, the thermal cracking apparatus 900
further generally includes a lid 920. In some embodiments, the lid
920 is permanently or removably coupled to, or integrally formed
with, an upper portion of the upper housing 902. The lid 920
includes an inlet 918 to which a gas source is coupled to provide
the feedstock process gas into an inner volume 928 of the lid 920
to provide a generally laminar flow of the feedstock process gas in
the thermal cracking apparatus 900. Although the inlet 918 is shown
at the top of the lid 920, in some embodiments, the inlet 918 may
alternatively be disposed in a side of the lid 920 to provide a
rotational gas flow.
[0074] In some embodiments, the feedstock process gas is provided
in a generally downwardly directional flow into the insert 910. To
improve this flow, the thermal cracking apparatus 900 optionally
includes a shower plate 966 having a plurality of through holes 968
(depicted as lines) to allow the feedstock process gas to pass
therethrough.
[0075] In some embodiments, the lid 920 further includes a through
hole 922 through which a first bulkhead fitting 924 is disposed. An
electrical feedthrough 926 (e.g., a first electrode) extends
through the first bulkhead fitting 924 and into the inner volume
928 of the lid 920.
[0076] The lower housing 904 is disposed beneath the upper housing
902 and may either be removably coupled to the upper housing 902 or
formed integrally with the upper housing 902. The lower housing 904
generally includes a ceiling 930 having an opening 932 that is open
to the inner volume 908 and the reaction zone of the upper housing
902, thereby fluidly connecting the inner volume 908 of the upper
housing 902 to an inner volume 933 of the lower housing 904.
[0077] The lower housing 904 further includes a hole 934 through
which a second bulkhead fitting 936 extends. An arm 938 (e.g., a
second electrode) extends through the second bulkhead fitting 936
into the inner volume 933 of the lower housing 904. The arm 938 is
formed of an electrically conductive material. In some embodiments,
the second bulkhead fitting 936 is formed of an electrically
insulative material to electrically insulate the lower housing 904
from the arm 938. In some embodiments, an insulative material may
alternatively be disposed in the hole 934 between the bulkhead
fitting 936, which may or may not be metallic or electrically
conducting, and the lower housing 904 to electrically insulate the
lower housing 904 from the arm 938. The arm 938 generally includes
a shaft 940 having a base 942 at a first end 944. The ceiling 930
generally shields at least a portion of the arm 938 from the
accumulation of byproducts of the thermal cracking process.
[0078] One or more heating elements 948 (one shown) of any
appropriate type described above are coupled at one end (the top)
to the electrical feedthrough 926 and at an opposite end (the
bottom) to the base 942 at or concentric with a central
longitudinal axis of the body 902/904. To flow electricity through
the heating element 948, a power supply (not shown) is coupled to
the electrical feedthrough 926 and a second end 946 of the arm 938
is coupled to ground (or vice versa). In some embodiments, the
current flowed through the heating element 948 is controlled to
control the temperature of the heating element 948. In addition,
the length of the heating element 948 is selected to provide a
length of the reaction zone in the inner volume 908 that, in
combination with the flow rate of the feedstock process gas,
controls or determines the residence time of the feedstock process
gas in the reaction zone. Thus, to achieve dissociation of a
particular feedstock process gas and produce the desired products,
the length of the heating element 948, the power provided to the
heating element 948, and the flow rate of the feedstock process gas
are controlled, in some embodiments, to provide a predetermined
residence time of the feedstock process gas at a predetermined
temperature within the reaction zone.
[0079] The first bulkhead fitting 924 and the base 942 keep the
heating element 948 taut. However, during operation, the heating
element 948 may experience thermal expansion/contraction.
Therefore, in some embodiments, a biasing element 950, such as a
spring, is coupled to an end of the heating element 948 that
extends through the base 942 to compensate for any thermal
expansion/contraction of the heating element 948 and maintain
tension on the heating element 948.
[0080] In some embodiments, the lower housing 904 may further
include a sampling port 952 to facilitate access to the inner
volume 933 of the lower housing 904 for sampling of byproducts of
the process. For example, a gas chromatograph or mass spectrometer
may be coupled to the sampling port 952 to sample the byproducts
and provide information for controlling the amount or rate of the
feedstock process gas supplied and/or the temperature of the
heating element 948.
[0081] The collector 906 includes an inner volume 954, in which a
mesh filter 960 is disposed. To facilitate placement of the filter
960 within the inner volume 954, the collector 906 includes a
ceiling 958 having an opening 956 through which the filter 960
extends. The filter 960 may include a collar 962 having a diameter
greater than the opening 956 so that the collar 962 rests on the
ceiling 958. The filter 960 includes a plurality of holes 961
through which the cracked gaseous product flows. Each of the
plurality of holes 961 may have a diameter sized to allow the
gaseous product to flow therethrough and to prevent the solid
product of the thermal cracking process from passing therethrough.
In some embodiments, for example, each hole 961 has a diameter that
is less than 1 micron. The collector 906 further includes a gas
outlet 964 disposed beneath the filter 960 to flow out the gaseous
product of the thermal cracking process.
[0082] In operation, the feedstock process gas enters the thermal
cracking apparatus 900 through the inlet 918 and flows through the
insert 910. As the feedstock process gas flows past the heating
element 948, the feedstock process gas is dissociated into
constituent elements or molecules thereof. The solid products of
the dissociation are collected in or on the filter 960, while the
gaseous product flows through the plurality of holes 961 and
through the gas outlet 964.
[0083] Although the gas outlet 964 is illustrated at the bottom of
the thermal cracking apparatus 900, the gas outlet 964 may
alternatively be disposed in the lid 920 in a plane above a plane
of the inlet 918. In such an embodiment, the inner volume 928 of
the lid 920 generally includes a partition (not shown) to separate
the incoming feedstock process gas from the outgoing gaseous
product of the dissociation/cracking process. Also, in such an
embodiment, the filter 960 may be excluded and the collector 906
electrically biased to attract the solid products of the
dissociation process.
[0084] FIGS. 8-12 depict example micrograph images of carbon
nano-particles (e.g., carbon nano-onions) having differing sizes.
Each of the different types of carbon nano-particles can be
produced by the thermal cracking apparatuses described herein by
tuning various operating parameters thereof, e.g., temperature of
the heating element, temperature of the preheated feedstock process
gas, pressure within the inner volume, feedstock process gas flow
rate, etc. In some embodiments, groupings of integrated carbon
nano-particles are fused to create solid carbon nano-particles,
hollow carbon nano-particles, and/or necked carbon nano-particles
that comprise one or more of spherical or oblong shapes. Moreover,
the carbon nano-particles may form highly ordered pyrolytic
graphite, partially or fully activated fullerenes that are
single-walled nanotubes, multi-walled nanotubes, and/or
combinations thereof, such as solid carbon nano-onions, hollow
carbon nano-onions and/or necked carbon nano-onions that further
comprise additional layers of single-walled nanotubes, multi-walled
nanotubes, and/or combinations thereof, and/or graphene, optionally
producing novel carbon allotropes. In some embodiments, multi-wall
fullerene nanospheres may be integrated with at least one
single-walled nanotube, multi-walled nanotube, or both to form
integrated fullerene allotropes. In some embodiments, groupings of
integrated fullerene allotropes may be randomly fused, creating
networks of activated carbon multi-wall fullerene nanospheres.
[0085] FIG. 8 depicts a micrograph image 1000 of carbon nano-onions
formed by the thermal cracking apparatus and methods described
herein, according to some embodiments. FIG. 8 was taken by
transmission electron microscopy (TEM) techniques. The image 1000
shows a first small carbon nano-onion 1002 having a diameter of
approximately 13 nm and a second small carbon nano-onion 1004
having a diameter of approximately 5.6 nm, which are comprised of a
plurality of graphene molecules 1006 disposed in a concentric
manner.
[0086] FIG. 9 depicts a micrograph image 1100 of a medium-sized
carbon nano-onion 1102 formed by the thermal cracking apparatus and
methods described herein, according to some embodiments. The carbon
nano-onion 1102 has a diameter of approximately 95 nm and a center
1104. FIG. 9 was taken by TEM techniques. The image 1100 also shows
that the medium-sized carbon nano-onion 1102 comprises a plurality
of graphene molecules 1106 disposed in a concentric manner around
the center 1104.
[0087] FIG. 10 depicts a micrograph image 1200 of a necked carbon
nano-onion 1201 formed by the thermal cracking apparatus and
methods described herein, according to some embodiments. FIG. 10
was taken by TEM techniques. The necked carbon nano-onion 1201
comprises a first carbon region 1202 and a second carbon region
1204, where the first carbon region 1202 and the second carbon
region 1204 are joined by a necked region 1206 with single-walled
nanotubes and/or multi-walled nanotubes, forming a conjoined or
necked carbon nano-onion having a barbell shape.
[0088] FIG. 11 depicts a micrograph image 1300 of a large carbon
nano-onion 1302 formed by the thermal cracking apparatus and
methods described herein, according to some embodiments. FIG. 11
was taken by TEM techniques. The large carbon nano-onion 1302 has a
spherical shape and a diameter of approximately 300 nm. Although
the graphene molecules cannot be seen because the image 1300 is
taken from a further distance, the large carbon nano-onion 1302
nonetheless comprises a plurality of graphene molecules, as is
discussed above with respect to the small carbon nano-onions 1002,
1004 and the medium-sized carbon nano-onion 1102.
[0089] FIG. 12 depicts a micrograph image 1400 of at least one
necked carbon nano-onion 1401 formed by the thermal cracking
apparatus and methods described herein, according to some
embodiments. FIG. 12 was taken by TEM techniques. The necked carbon
nano-onion 1401 comprises a number of carbon nano-onions 1402
joined together as if in a string or necklace. The carbon
nano-onions 1402 are generally connected together by necked regions
(generally too small to distinguish at the scale of the micrograph
image 1400), such as single-walled nanotubes and/or multi-walled
nanotubes.
[0090] FIG. 13 depicts a simplified schematic view of a thermal
cracking apparatus 1500, in accordance with at least some
embodiments. The thermal cracking apparatus 1500 generally includes
a body 1502, a top cap assembly 1504, a bottom cap assembly 1506, a
heating element 1508, a feedstock process gas preheat inlet 1512, a
secondary feedstock process gas inlet 1514, one or more cooling gas
inlets and outlets 1516 and 1518, a cooling fluid inlet and outlet
1520 and 1522, and a product outlet 1524, among other components
shown (but not labeled) or not shown for simplicity and ease of
illustration and description.
[0091] The body 1502 generally includes an outer shell or housing
1526, a secondary shell 1528, an inner reactor tube (an insert or
heating chamber) 1530, and an outer reactor tube 1532. The body
1502 is considered a dual wall structure or dual tube reactor
because it generally includes both of the reactor tubes 1530 and
1532 disposed within the shells 1526 and 1528. (In some
embodiments, the outer reactor tube 1532 is considered to be
another shell surrounding the inner reactor tube 1530.) The shells
1526 and 1528 and the reactor tubes 1530 and 1532 are generally
cylindrical in shape with a central longitudinal axis arranged
vertically. The inner reactor tube 1530 is generally made of
quartz, alumina, or other appropriate material for withstanding the
operational temperatures of the reaction zone. The shells 1526 and
1528 and the outer reactor tube 1532 are generally made of steel,
titanium, or other appropriate materials.
[0092] The top cap assembly 1504 and the bottom cap assembly 1506
are generally made of steel or other appropriate materials. The top
cap assembly 1504 and the bottom cap assembly 1506 are mounted or
attached to the top and bottom, respectively, of the shells 1526
and 1528 to hold the shells 1526 and 1528 in a generally concentric
arrangement or relationship to each other with a space 1534 there
between. The space 1534 between the shells 1526 and 1528 defines a
cooling fluid region.
[0093] A top and bottom plug, cap or insert 1536 and 1538 are
disposed within the secondary shell 1528 near the top and bottom,
respectively, of the body 1502. The top and bottom plugs 1536 and
1538 are generally made of steel or other appropriate materials.
The bottom plug 1538 is mounted or set within the secondary shell
1528 down against an inner surface or flange of the bottom cap
assembly 1506 and engages bottom ends of the reactor tubes 1530 and
1532. The top plug 1536 is mounted or set within the secondary
shell 1528 near a top end of the secondary shell 1528 and engages
top ends of the reactor tubes 1530 and 1532. A compression spring
assembly 1540 engages the top plug 1536 and an inner surface or
flange of the top cap assembly 1504 to press the top plug 1536 to
the reactor tubes 1530 and 1532, the reactor tubes 1530 and 1532 to
the bottom plug 1538, and the bottom plug 1538 to the inner surface
or flange of the bottom cap assembly 1506, thereby holding the
reactor tubes 1530 and 1532 in place. The top and bottom plugs 1536
and 1538 generally hold the reactor tubes 1530 and 1532 in a
generally concentric arrangement or relationship to each other and
to the secondary shell 1528, with a space 1542 between the outer
reactor tube 1532 and the secondary shell 1528, and a space 1544
between the inner reactor tube 1530 and the outer reactor tube
1532. The space 1542 between the outer reactor tube 1532 and the
secondary shell 1528 defines a gas coolant region. The space 1544
between the inner reactor tube 1530 and the outer reactor tube 1532
defines a feedstock gas preheating region.
[0094] The heating element 1508 is any appropriate type described
above and extends along, generally concentrically with, and
parallel to, the central longitudinal axis of the body 1502 or the
inner reactor tube 1530. The heating element 1508 is mounted or
attached at a top end to a top electrode assembly 1546 that is
mounted or attached to the body 1502 and extends through the shells
1526 and 1528 above the top plug 1536. In the illustrated
embodiment, the heating element 1508 is mounted or attached at a
bottom end to a bottom electrode assembly 1548 and a spring bias
assembly 1550. The bottom electrode assembly 1548 is mounted or
attached to a lower portion 1552 of the bottom cap assembly 1506
and extends through the lower portion 1552 to contact the heating
element 1508 through a hole in the bottom electrode assembly 1548.
The spring bias assembly 1550 includes a spring 1554 within a
cylindrical housing 1556 that is attached or mounted to the
underside of the lower portion 1552 of the bottom cap assembly
1506. The heating element 1508 extends through a hole in the bottom
cap assembly 1506 and the hole in the bottom electrode assembly
1548 down to the bottom of the spring 1554. The heating element
1508 is attached to the bottom of the spring 1554 and is held in
tension by the spring 1554 acting against the underside of the
bottom electrode assembly 1548. Thus, when the heating element 1508
heats up during gas processing or thermal cracking operations and
cools down afterwards, any thermal expansion or contraction of the
heating element 1508 is compensated for by the spring bias assembly
1550, which maintains the heating element 1508 in tension, so that
the heating element 1508 remains generally concentric and parallel
to the central longitudinal axis of the body 1502 or the inner
reactor tube 1530.
[0095] An interior surface of a wall of the inner reactor tube 1530
defines an inner volume, all or part of which includes a
longitudinal elongated reaction zone generated in the vicinity of
the heating element 1508 during gas processing or thermal cracking
operations. The inner reactor tube 1530 is thus the heating or
reaction chamber of the thermal cracking apparatus 1500, and the
central longitudinal axis of the body 1502 or the inner reactor
tube 1530 is also considered to be a central longitudinal axis of
the longitudinal elongated reaction zone.
[0096] Electrical power is provided to the heating element 1508
through the top electrode assembly 1546 and the bottom electrode
assembly 1548 during gas processing operations. The top electrode
assembly 1546 electrically connects to, or near, the top of the
heating element 1508. The bottom electrode assembly 1548
electrically connects to, or near, the bottom of the heating
element 1508, either directly to the heating element 1508 (within
the hole therein) or through an electrical connection to the spring
1554.
[0097] The feedstock process gas preheat inlet 1512 is fluidly
connected to a feedstock process gas source (not shown). The
feedstock process gas preheat inlet 1512 is also attached or
mounted to the shells 1526 and 1528 to be in fluid communication
with the feedstock gas preheating region (space 1544) via apertures
or holes through the shells 1526 and 1528, the bottom plug 1538,
and the outer reactor tube 1532. During gas processing operations,
the feedstock process gas is flowed from the source through the
feedstock process gas preheat inlet 1512 and into the feedstock
process gas preheating region (space 1544). The feedstock process
gas then circulates across the outer surface of the inner reactor
tube 1530. The inner reactor tube 1530 is typically very hot due to
the thermal gas processing occurring therein. The circulation of
the feedstock process gas around the inner reactor tube 1530, thus,
serves the dual purpose of cooling the inner reactor tube 1530 and
preheating the feedstock process gas with residual heat transferred
through the wall of the inner reactor tube 1530 from the reaction
zone. For embodiments in which the gas flow direction is downward,
a series of holes or apertures 1558 in the wall of the inner
reactor tube 1530 near the top of the feedstock gas preheating
region (space 1544) allow the preheated feedstock process gas to
flow into the inner volume of the inner reactor tube 1530, i.e.,
the reaction zone. Within the inner volume or the reaction zone,
the preheated feedstock process gas circulates around the heating
element 1508, which further heats the feedstock process gas in the
vicinity thereof to thermally crack the feedstock process gas into
constituent elements and/or lower order molecules, i.e., the
gaseous and solid products. For embodiments in which the gas flow
direction is upward, on the other hand, the series of holes or
apertures 1558 in the wall of the inner reactor tube 1530 are
placed near the bottom of the feedstock gas preheating region
(space 1544) and the feedstock process gas preheat inlet 1512 is
placed near the top of the feedstock gas preheating region.
[0098] In some embodiments, the secondary feedstock process gas
inlet 1514 is fluidly connected to a source (not shown) of a gas
(e.g., a second feedstock process gas) having additional particles
(e.g., nano-particles of Silicon (Si), Silicon Carbide (SiC), or
other appropriate materials able to withstand the high temperatures
of the process without melting) floating or suspended therein. The
secondary feedstock process gas inlet 1514 is attached or mounted
to the shells 1526 and 1528 to be in fluid communication with the
inner volume of the inner reactor tube 1530 via apertures through
the shells 1526 and 1528, the top plug 1536, and the inner reactor
tube 1530. During gas processing operations, the feedstock process
gas with additional particles is flowed from the source through the
secondary feedstock process gas inlet 1514, through a series of
holes or apertures 1560 (in the wall of the inner reactor tube 1530
near the top thereof), and into the inner volume of the inner
reactor tube 1530, i.e., the reaction zone. Within the inner volume
or the reaction zone, the feedstock process gas with additional
particles mixes with the preheated feedstock process gas. In some
embodiments, the additional particles have a melting point at or
above about 500-1000.degree. C. The temperature to which the
additional particles are heated generally depends on various
process parameters, such as the temperature of the heating element
1508, the flow rate of the feedstock process gas, the longitudinal
length of the reaction zone, and the time that the additional
particles spend within the reaction zone. Therefore, since the
process parameters are set so that the additional particles are
heated to a temperature lower than their melting point when they
pass through the reaction zone, the solid carbon product (e.g., the
graphene) produced from the feedstock process gas (e.g., the
methane, natural gas, or other hydrocarbons) generally forms a
coating around the additional particles. The coating generally
includes one or more layers of the solid carbon product, such as
one or more concentric layers of graphene, surrounding each
additional particle. In this manner, carbon-coated nano-particles
are formed within the reaction zone. Additionally, in some
embodiments, the additional particles act as a catalyst in the
thermal cracking of the feedstock process gas in the reaction
zone.
[0099] In some embodiments, the feedstock process gas having
additional particles, the secondary feedstock process gas inlet
1514, and the series of holes or apertures 1560 are considered
optional or are not included in the thermal cracking apparatus
1500.
[0100] In some embodiments, the cooling gas inlet and outlet 1516
and 1518 are attached or mounted to the shells 1526 and 1528 to be
in fluid communication with the gas coolant region, i.e., the space
1542 between the outer reactor tube 1532 and the secondary shell
1528, via apertures or holes through the shells 1526 and 1528.
During gas processing operations, a coolant gas (e.g., air,
nitrogen, a noble gas, etc.) is flowed from a source thereof,
through the cooling gas inlet 1516, and into the gas coolant region
(space 1542). The coolant gas thus circulates within the gas
coolant region, absorbs some of the heat from the outer reactor
tube 1532 (thereby serving to cool the outer reactor tube 1532),
and exits through the outlet 1518 to be cooled, recycled, discarded
or stored.
[0101] In some other embodiments, the space 1542 between the outer
reactor tube 1532 and the secondary shell 1528 is filled with a
thermally insulating or conducting material, rather than having a
coolant gas flow therein. In various embodiments, the use or
selection of the coolant gas or the thermally insulating or
conducting material for the space 1542 generally depends on the
thermal requirements for the overall configuration of the thermal
cracking apparatus 1500, the type of the feedstock process gas, the
type or characteristics of the desired solid and/or gaseous
products, and/or the process parameters of the gas processing
operations. Different embodiments, in other words, generally have
different thermal requirements.
[0102] In some embodiments, the cooling fluid inlet and outlet 1520
and 1522 are attached or mounted to the outer shell 1526 to be in
fluid communication with the cooling fluid region, i.e., the space
1534 between the shells 1526 and 1528, via apertures or holes
through the outer shell 1526. During gas processing operations, a
coolant fluid (e.g., water, etc.) is flowed from a source thereof,
through the cooling fluid inlet 1520, and into the cooling fluid
region (space 1534). The coolant fluid thus circulates within the
cooling fluid region, absorbs some of the heat from the secondary
shell 1528 (thereby cooling the secondary shell 1528), and exits
through the outlet 1522 to be cooled, recycled, discarded or
stored. In this manner, the action of the coolant fluid, or the
combined action of the coolant fluid and the coolant gas, ensures
that the outer surface of the thermal cracking apparatus 1500
(i.e., of the body 1502 or the outer shell 1526) remains cool, or
does not become too hot to pose a danger to nearby equipment or
personnel.
[0103] In the illustrated embodiment, the product outlet 1524 is
mounted or attached to the lower portion 1552 of the bottom cap
assembly 1506 for embodiments in which the gas flow direction is
downward. (For embodiments in which the gas flow direction is
upward, on the other hand, the product outlet 1524 is mounted or
attached near the top of the inner volume of the inner reactor tube
1530.) The solid and gaseous products generally flow out the bottom
cap assembly 1506, e.g., through a series of passageways through
the bottom cap assembly 1506 leading to the product outlet 1524,
and then to an appropriate storage apparatus, hopper, or other
receiving mechanism 1562. In some embodiments, the gaseous and
solid products enter the hopper 1562 and are exhausted with a
Venturi assist and a flow of nitrogen gas. The solid products are
removed by detaching the hopper 1562 from the product outlet 1524
and pouring them out. The gaseous products are removed by flowing
through a gaseous product outlet 1564 from the hopper 1562. The
gaseous product outlet 1564 is mounted or attached to the hopper
1562 to provide a fluid connection to the interior of the hopper
1562. The gaseous product outlet 1564 is also fluidly connected to
a downstream storage apparatus or further gas processing apparatus.
The gaseous products are thus flowed out through the gaseous
product outlet 1564 to the downstream storage apparatus or further
gas processing apparatus. Some embodiments incorporating an
alternative exhaust system technique that may be used with the
thermal cracking apparatus 1500, with appropriate adjustments or
modifications thereto, are described below with respect to FIG. 14.
Additionally, in some embodiments, different hoppers (e.g., having
the same or different design or configuration) are used for
different applications. For example, one hopper is used when
producing the solid carbon products, and a different hopper is used
when producing the carbon-coated nano-particles. Thus, the bottom
cap assembly 1506 and the connection to the product outlet 1524
and/or the hopper 1562 are designed for removal and replacement of
the hopper 1562, so that a clean or different hopper 1562 can be
attached for each application.
[0104] In some situations, some of the solid products can
accumulate within the inner volume of the inner reactor tube 1530,
e.g., on the interior surface of the wall of the inner reactor tube
1530 and/or the heating element 1508. Some embodiments may also use
any appropriate structures or subassemblies for forcibly removing
the solid products or cleaning the reaction zone.
[0105] FIG. 14 depicts a simplified schematic view of a thermal
cracking apparatus 1600, in accordance with at least some
embodiments. Some of the features described for the thermal
cracking apparatus 1600 can be applied to the embodiment shown for
the thermal cracking apparatus 1500 in FIG. 13, and some of the
features described above for the thermal cracking apparatus 1500
can be applied to the embodiment for the thermal cracking apparatus
1600, as will be described below.
[0106] The thermal cracking apparatus 1600 generally includes a
body 1602, a top cap assembly 1604, a bottom cap assembly 1606, a
heating element 1608, a feedstock process gas inlet 1612, a
secondary feedstock process gas inlet 1614, one or more cooling gas
inlets and outlets 1616 and 1618, a cooling fluid inlet and outlet
1620 and 1622, a gaseous product outlet 1624, and a solid product
outlet 1626, among other components shown (but not labeled) or not
shown for simplicity and ease of illustration and description.
[0107] The body 1602 generally includes an outer shell or housing
1628, a secondary shell 1630, and a reactor tube (heating chamber)
1632. The body 1602 is considered a single wall structure or single
tube reactor because it generally includes only the single reactor
tube 1632 disposed within the shells 1628 and 1630. The single wall
structure or single tube reactor embodiment of FIG. 14 is, thus, an
alternative to the dual wall structure or dual tube reactor
embodiment of FIG. 13. The shells 1628 and 1630 and the reactor
tube 1632 are generally cylindrical in shape with a central
longitudinal axis arranged vertically. The reactor tube 1632 is
generally made of quartz, alumina, or other appropriate material
for withstanding the operational temperatures of the reaction zone.
The shells 1628 and 1630 are generally made of steel, titanium, or
other appropriate materials.
[0108] The top cap assembly 1604 and the bottom cap assembly 1606
are generally made of steel or other appropriate materials. The top
cap assembly 1604 and the bottom cap assembly 1606 are mounted or
attached to the top and bottom, respectively, of the shells 1628
and 1630 to hold the shells 1628 and 1630 in a generally concentric
arrangement or relationship to each other with a space 1634 there
between. The space 1634 between the shells 1628 and 1630 defines a
cooling fluid region.
[0109] A top and bottom plug, cap or insert 1636 and 1638 are
disposed within the secondary shell 1630 near the top and bottom,
respectively, of the body 1602. The top and bottom plugs 1636 and
1638 are generally made of steel or other appropriate materials.
The bottom plug 1638 is mounted or set within the secondary shell
1630 down against an inner surface or flange of the bottom cap
assembly 1606 and engages a bottom end of the reactor tube 1632.
The top plug 1636 is mounted or set within the secondary shell 1630
near a top end of the secondary shell 1630 and engages a top end of
the reactor tube 1632. The reactor tube 1632 and the top and bottom
plugs 1636 and 1638 are generally held in place by any appropriate
means, e.g., such as that described above for FIG. 13. The top and
bottom plugs 1636 and 1638 generally hold the reactor tube 1632 in
a generally concentric arrangement or relationship to the secondary
shell 1630, with a space 1640 between the reactor tube 1632 and the
secondary shell 1630. The space 1640 between the reactor tube 1632
and the secondary shell 1630 defines a gas coolant region.
[0110] The heating element 1608 is any appropriate type described
above and extends along, generally concentrically with, and
parallel to, the central longitudinal axis of the body 1602 or the
reactor tube 1632. The heating element 1608 (at or near the top end
thereof) contacts a top electrode assembly 1642 that is mounted or
attached to the body 1602 and extends through the shells 1628 and
1630 above the top plug 1636. Additionally, the heating element
1608 is mounted or attached at a top end to a tensioning assembly
1644 (e.g., a pneumatic tensioning device, a spring biasing
assembly, etc.) through a hole in the top electrode assembly 1642
and a hole in a lower portion of the top cap assembly 1604. The
heating element 1608 is also mounted or attached at a bottom end to
a bottom electrode assembly 1646. The bottom electrode assembly
1646 is mounted or attached to a lower portion 1648 of the bottom
cap assembly 1606 and extends through the lower portion 1648 to
connect to the heating element 1608 at a point along a longitudinal
axis of the lower portion 1648, which is coaxial with the
longitudinal axis of the body 1602 or the reactor tube 1632. The
heating element 1608 extends through a hole in a flange 1650 of the
bottom cap assembly 1606 down to the bottom electrode assembly
1646. The heating element 1608 is held in tension by the tensioning
assembly 1644 acting against an upper portion of the top cap
assembly 1604. Thus, when the heating element 1608 heats up during
gas processing or thermal cracking operations and cools down
afterwards, any thermal expansion or contraction of the heating
element 1608 is compensated for by the tensioning assembly 1644,
which maintains the heating element 1608 in tension, so that the
heating element 1608 remains generally concentric and parallel to
the central longitudinal axis of the body 1602 or the reactor tube
1632.
[0111] The technique described for FIG. 14 for mounting or
attaching the heating element 1608 using the top and bottom
electrodes 1642 and 1646 and the tensioning assembly 1644 is an
alternative embodiment that can be applied to the overall
embodiment shown in FIG. 13, given appropriate modifications to
support this alternative structure. On the other hand, the
technique described for FIG. 13 for mounting or attaching the
heating element 1508 using the top and bottom electrodes 1546 and
1548 and the spring bias assembly 1550 is an alternative embodiment
that can be applied to the overall embodiment shown in FIG. 14,
given appropriate modifications to support this alternative
structure.
[0112] An interior surface of a wall of the reactor tube 1632
defines an inner volume, all or part of which includes a
longitudinal elongated reaction zone generated in the vicinity of
the heating element 1608 during gas processing or thermal cracking
operations. The reactor tube 1632 is thus the heating or reaction
chamber of the thermal cracking apparatus 1600, and the central
longitudinal axis of the body 1602 or the reactor tube 1632 is also
considered to be a central longitudinal axis of the longitudinal
elongated reaction zone.
[0113] Electrical power is provided to the heating element 1608
through the top electrode assembly 1642 and the bottom electrode
assembly 1646 during gas processing operations. The top electrode
assembly 1642 electrically connects to, or near, the top of the
heating element 1608. The bottom electrode assembly 1646
electrically connects to, or near, the bottom of the heating
element 1608.
[0114] The feedstock process gas inlet 1612 is fluidly connected to
a feedstock process gas source (not shown). The feedstock process
gas inlet 1612 is also attached or mounted to the shells 1628 and
1630 to be in fluid communication with the inner volume of the
reactor tube 1632 via apertures or holes through the shells 1628
and 1630, the top plug 1636, and the reactor tube 1632. During gas
processing operations, the feedstock process gas is flowed from the
source through the feedstock process gas inlet 1612 and into the
inner volume (the reaction zone) of the reactor tube 1632 through a
series of holes or apertures 1652 in the wall of the reactor tube
1632 near the top of the reactor tube 1632, for embodiments in
which the gas flow direction is downward. Within the inner volume
or the reaction zone, the feedstock process gas circulates around
the heating element 1608, which heats the feedstock process gas in
the vicinity thereof to thermally crack the feedstock process gas
into constituent elements and/or lower order molecules, i.e., the
gaseous and solid products. For embodiments in which the gas flow
direction is upward, on the other hand, the feedstock process gas
inlet 1612 and the series of holes or apertures 1652 in the wall of
the reactor tube 1632 are placed near the bottom of the reactor
tube 1632.
[0115] In some embodiments, the secondary feedstock process gas
inlet 1614 is fluidly connected to a source (not shown) of a second
feedstock process gas having additional particles (e.g.,
nano-particles) floating therein. The secondary feedstock process
gas inlet 1614 is attached or mounted through the shells 1628 and
1630 and the top plug 1636 to be in fluid communication with the
inner volume of the reactor tube 1632 via apertures or holes
through the shells 1628 and 1630 and the top plug 1636. During gas
processing operations, the feedstock process gas with additional
particles is flowed from the source through the secondary feedstock
process gas inlet 1614 into the inner volume of the reactor tube
1632, i.e., the reaction zone. Within the inner volume or the
reaction zone, the feedstock process gas with additional particles
mixes with the feedstock process gas from the feedstock process gas
inlet 1612. The additional particles (e.g., nano-particles of
Silicon, silicon carbide, etc.)
[0116] assist in the heating, and thus the thermal cracking, of the
feedstock process gas in the reaction zone. In some embodiments,
the feedstock process gas having additional particles and the
secondary feedstock process gas inlet 1614 are considered optional
or are not included in the thermal cracking apparatus 1500.
[0117] The technique described for FIG. 14 for providing the
feedstock process gas with additional particles through the
secondary feedstock process gas inlet 1614 is an alternative
embodiment that can be applied to the overall embodiment shown in
FIG. 13, given appropriate modifications to support this
alternative structure. On the other hand, the technique described
for FIG. 13 for providing the feedstock process gas with additional
particles through the secondary feedstock process gas inlet 1514 is
an alternative embodiment that can be applied to the overall
embodiment shown in FIG. 14, given appropriate modifications to
support this alternative structure.
[0118] In some embodiments, the cooling gas inlet and outlet 1616
and 1618 are attached or mounted to the shells 1628 and 1630 to be
in fluid communication with the gas coolant region, i.e., the space
1640 between the reactor tube 1632 and the secondary shell 1630,
via apertures or holes through the shells 1628 and 1630. During gas
processing operations, a coolant gas (e.g., air, nitrogen, a noble
gas, etc.) is flowed from a source thereof, through the cooling gas
inlet 1616, and into the gas coolant region (space 1640). The
coolant gas thus circulates within the gas coolant region, absorbs
some of the heat from the reactor tube 1632 (thereby serving to
cool the reactor tube 1632), and exits through the outlet 1618 to
be cooled, recycled, discarded or stored.
[0119] In some other embodiments, the space 1640 between the
reactor tube 1632 and the secondary shell 1630 is filled with a
thermally insulating or conducting material, rather than having a
coolant gas flow therein. In various embodiments, the use or
selection of the coolant gas or the thermally insulating or
conducting material for the space 1640 generally depends on the
thermal requirements for the overall configuration of the thermal
cracking apparatus 1600, the type of the feedstock process gas, the
type or characteristics of the desired solid and/or gaseous
products, and/or the process parameters of the gas processing
operations. Different embodiments, in other words, generally have
different thermal requirements.
[0120] In some embodiments, the cooling fluid inlet and outlet 1620
and 1622 are attached or mounted to the outer shell 1628 to be in
fluid communication with the cooling fluid region, i.e., the space
1634 between the shells 1628 and 1630, via apertures or holes
through the outer shell 1628. During gas processing operations, a
coolant fluid (e.g., water, etc.) is flowed from a source thereof,
through the cooling fluid inlet 1620, and into the cooling fluid
region (space 1634). The coolant fluid thus circulates within the
cooling fluid region, absorbs some of the heat from the secondary
shell 1630 (thereby cooling the secondary shell 1630), and exits
through the outlet 1622 to be cooled, recycled, discarded or
stored. In this manner, the action of the coolant fluid, or the
combined action of the coolant fluid and the coolant gas, ensures
that the outer surface of the thermal cracking apparatus 1600
(i.e., of the body 1602 or the outer shell 1628) remains cool, or
does not become too hot to pose a danger to nearby equipment or
personnel.
[0121] In the illustrated embodiment, the thermal cracking
apparatus 1600 further includes a primary hopper 1656 and a
secondary hopper 1658. (As mentioned above for the hopper 1562, in
some embodiments, different hoppers 1656 and/or 1658 are used for
different applications, so the thermal cracking apparatus 1600 is
designed with an attachment mechanism for removal and replacement
of the hopper 1656 and/or 1658, so that a clean or different hopper
1656 and/or 1658 can be attached for each application.) The primary
hopper 1656 is mounted or attached to the lower portion 1648 of the
bottom cap assembly 1606. The primary hopper 1656 generally has
lower and upper portions 1660 and 1662 and lower and upper filters
1664 and 1666. The lower portion 1648 of the bottom cap assembly
1606 extends through the upper portion 1662 and the upper filter
1666 down to the lower portion 1660 to provide a fluid connection
between the inner volume of the reactor tube 1632 and the lower
portion 1660. The upper filter 1666 generally separates the lower
and upper portions 1660 and 1662. The lower filter 1664 is disposed
at or near the bottom of the lower portion 1660 at the solid
product outlet 1626. The solid product outlet 1626 is mounted or
attached to the lower portion 1660, at or near a bottom thereof.
The gaseous product outlet 1624 is mounted or attached to the upper
portion 1662 (at or near a side thereof) to provide a fluid
connection between the upper portion 1662 and the secondary hopper
1658.
[0122] During gas processing operations, the gaseous and solid
products fall or flow down from the inner volume of the reactor
tube 1632, through the hole in the flange 1650, through the lower
portion 1648 of the bottom cap assembly 1606, and into the lower
portion 1660 of the primary hopper 1656, for embodiments in which
the gas flow direction is downward. The solid products generally
continue to fall and pass out through the solid product outlet
1626. The desired solid product is typically the carbon
nano-particles described above; however, some larger aggregate
particles, debris or flake material can also sometimes form within
the reactor tube 1632 and fall down into the primary hopper 1656.
The lower filter 1664 is generally designed or selected to be
capable of catching these larger particles and allowing the desired
solid product to pass through to the solid product outlet 1626. The
larger particles are periodically removed from the primary hopper
1656. For embodiments in which the gas flow direction is upward, on
the other hand, the solid products flow out of the reactor tube
1632 near the top thereof, unless the solid products are heavy
enough to fall against the gas flow, in which case the solid
product outlet can be placed near the bottom of the reactor tube
1632, similar to that described previously.
[0123] For embodiments in which the gas flow direction is downward,
the gaseous product is generally forced to flow (in the direction
of arrows 1668) down from the reactor tube 1632, into the lower
portion 1660 of the primary hopper 1656, up through the upper
filter 1666, into the upper portion 1662, and out through the
gaseous product outlet 1624. (For embodiments in which the gas flow
direction is upward, on the other hand, the gaseous product is
generally forced to flow out of the reactor tube 1632 near the top
thereof.) Some of the solid product (such as the smaller particles)
can potentially be swept up in the flow of the gaseous product,
instead of falling to the bottom of the primary hopper 1656 as
mentioned above. The upper filter 1666 is generally designed or
selected to be capable of catching these particles, which
eventually are removed with the other solid products through the
solid product outlet 1626. An ultrasonic port 1670 (mounted or
attached to the upper portion 1662) provides an ultrasonic or
mechanical vibrational assist for removing these particles by the
upper filter 1666. The gaseous product is exhausted with a Venturi
assist and a flow of nitrogen gas through the gaseous product
outlet 1624 to the secondary hopper 1658. Most of the solid product
has been removed from the gaseous product at this point, but some
can still remain. Thus, additional gas/solid separation via cyclone
or electrical precipitation is implemented for further separation
at the secondary hopper 1658. The gaseous products are then removed
by flowing through a gaseous product outlet 1672 from the secondary
hopper 1658. The gaseous product outlet 1672 is mounted or attached
to the secondary hopper 1658 to provide a fluid connection to the
interior of the hopper 1658. The gaseous product outlet 1672 is
also fluidly connected to a downstream storage apparatus or further
gas processing apparatus. The gaseous products are thus flowed out
through the gaseous product outlet 1564 to the downstream storage
apparatus or further gas processing apparatus.
[0124] The exhaust system technique described for FIG. 14 for
exhausting and separating the gaseous and solid products through
the hoppers 1656 and 1658 is an alternative embodiment that can be
applied to the overall embodiment shown in FIG. 13, given
appropriate modifications to support this alternative structure. On
the other hand, the exhaust system technique described for FIG. 13
for exhausting and separating the gaseous and solid products
through the hopper 1562 is an alternative embodiment that can be
applied to the overall embodiment shown in FIG. 14, given
appropriate modifications to support this alternative
structure.
[0125] In some situations, some of the solid products can
accumulate within the inner volume of the reactor tube 1632, e.g.,
on the interior surface of the wall of the reactor tube 1632 and/or
the heating element 1608. Some embodiments may also use any
appropriate structures or subassemblies for forcibly removing the
solid products or cleaning the reaction zone.
[0126] FIG. 15 depicts a simplified process flow diagram of a
method 1800 for cracking a feedstock process gas in accordance with
at least some embodiments, which may be an alternative embodiment
to, or a more detailed embodiment of, the method 100 shown in FIG.
1, so that the steps of the method 1800 are performed in addition
to or in place of some or all of the steps of method 100. The
particular steps, combination of steps, and order of steps are
shown for illustrative and explanatory purposes only. Other
embodiments may include other steps, combinations of steps, and/or
orders of steps to achieve generally similar results.
[0127] The method 1800, and variations thereof, may be carried out
in any suitable thermal cracking apparatus as disclosed herein
capable of control in accordance with the teachings provided
herein. Illustrative, but non-limiting, examples of embodiments of
a suitable apparatus are described above with respect to FIGS. 2-7,
13 and 14.
[0128] Upon starting the method 1800 (at 1802), the feedstock
process gas source (or sources with and without the additional
nano-particles) is turned on and the thermal cracking apparatus is
allowed to heat up to an operating temperature (e.g., so that the
temperature of the inner wall of the reactor tube, or heating
chamber, reaches at least 200.degree. C.). In some embodiments, the
product separation and exhaust components or assembly (e.g., from
the point at which the desired products exit the heating chamber to
the downstream storage or further processing components) is also
heated to, and maintained at, a temperature of about 300.degree.
C., or other appropriate temperature that prevents volatile organic
material or compounds from being absorbed in the collected solid
product. In some embodiments, the purge gas is flowed through the
inner volume of the thermal cracking apparatus, i.e., of the
heating chamber, as described above at this time.
[0129] For embodiments that incorporate the preheating features
shown in FIG. 13 (or other suitable preheating structure), the
feedstock process gas (without additional nano-particles) is fed
(at 1804) into the thermal cracking apparatus (e.g., at the bottom,
as shown in FIG. 13) for pre-heating before entering the reaction
zone. The feedstock process gas thus circulates around the heating
chamber (e.g., reaction tube or insert of the body of the thermal
cracking apparatus) to cool the heating chamber and preheat the
feedstock process gas.
[0130] The preheated feedstock process gas (or the non-preheated
feedstock process gas, for embodiments that do not include the
preheating features) then enters the reaction zone of the heating
chamber and (at 1806) is cracked thermally within the reaction zone
surrounding the heating element. In some embodiments, the thermal
cracking is performed with the heating element at a molecular
cracking temperature greater than 1600.degree. C. and less than
2200.degree. C. the gas flow at a rate greater than 1 slm (standard
liter per minute), and a minimum temperature of the wall of the
heating chamber (i.e., of the inner volume) of 200.degree. C. Other
embodiments may use other values for these operating parameters
(e.g., as mentioned herein), depending on the thermal requirements
for the overall configuration of the thermal cracking apparatus,
the type of the feedstock process gas, the type or characteristics
of the desired solid and/or gaseous products, and/or the process
parameters of the gas processing operations, among other potential
considerations.
[0131] A reaction zone cleaning cycle is implemented (at 1808),
e.g., by activating an appropriate solid product removal mechanism.
In some embodiments, the cleaning cycle is performed every few
seconds or minutes, e.g., at a minimum of 100 seconds to a maximum
of 600 seconds or other appropriate time interval (dependent on
carbon deposition rate), to ensure that the inner surface of the
heating chamber and the heating element are kept relatively clean.
Experiments have shown that the overall operating efficiency of the
thermal cracking apparatus is substantially higher when the
cleaning cycle is performed regularly, thereby resulting in a
substantially greater production rate for the gaseous and solid
products, even at lower temperatures and higher flow rates,
compared to an example process in which no cleaning cycle is
performed. In some embodiments, the improvement in the operating
efficiency or production rate is on the order of about 25-30%.
[0132] The gaseous products and the solid products flow out of, or
are collected from, (at 1810) the thermal cracking apparatus either
through separate gaseous and solid product outlets or the same
combined product outlet. In some embodiments, the gaseous and solid
products enter the hopper, are filtered with an ultrasonic or
mechanical vibrational assist, and are exhausted with a Venturi
assist and a flow of nitrogen gas. In some embodiments, additional
gas/solid separation is performed (at 1812) via cyclone or
electrical precipitation downstream of an initial separation
hopper. In some embodiments, un-abated gas/solid material is sent
(at 1814) to a wet and/or dry scrubber.
[0133] Although a few example embodiments have been described in
detail above, those skilled in the art will appreciate that many
modifications are possible in embodiments without materially
departing from the teachings disclosed herein. Any and all such
modifications are intended to be included within the embodiments of
the invention, and other embodiments may be devised without
departing from the scope thereof.
* * * * *