U.S. patent application number 16/052016 was filed with the patent office on 2018-11-29 for processing hydrocarbons.
The applicant listed for this patent is XYLECO, INC.. Invention is credited to Marshall Medoff.
Application Number | 20180340405 16/052016 |
Document ID | / |
Family ID | 41430059 |
Filed Date | 2018-11-29 |
United States Patent
Application |
20180340405 |
Kind Code |
A1 |
Medoff; Marshall |
November 29, 2018 |
PROCESSING HYDROCARBONS
Abstract
Systems and methods that include providing, e.g., obtaining or
preparing, a material that includes a hydrocarbon carried by an
inorganic substrate, and exposing the material to a plurality of
energetic particles, such as accelerated charged particles, such as
electrons or ions.
Inventors: |
Medoff; Marshall;
(Wakefield, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
XYLECO, INC. |
Wakefield |
MA |
US |
|
|
Family ID: |
41430059 |
Appl. No.: |
16/052016 |
Filed: |
August 1, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15435508 |
Feb 17, 2017 |
10066470 |
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16052016 |
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14795422 |
Jul 9, 2015 |
9593564 |
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15435508 |
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14314834 |
Jun 25, 2014 |
9091165 |
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14795422 |
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13958130 |
Aug 2, 2013 |
8789584 |
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14314834 |
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13768593 |
Feb 15, 2013 |
8534351 |
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13958130 |
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13180717 |
Jul 12, 2011 |
8397807 |
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13768593 |
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12417786 |
Apr 3, 2009 |
8025098 |
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13180717 |
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61073665 |
Jun 18, 2008 |
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61106861 |
Oct 20, 2008 |
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61139324 |
Dec 19, 2008 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 1/00 20130101; E21B
43/2401 20130101; E21B 43/281 20130101; C10G 1/04 20130101; E21B
43/24 20130101; C10G 2300/1033 20130101; C10G 15/08 20130101; E21B
43/2403 20130101; C10G 2300/807 20130101; C10G 15/10 20130101; C10G
2300/4037 20130101 |
International
Class: |
E21B 43/24 20060101
E21B043/24; C10G 1/04 20060101 C10G001/04; C10G 15/08 20060101
C10G015/08; C10G 15/10 20060101 C10G015/10; E21B 43/28 20060101
E21B043/28; C10G 1/00 20060101 C10G001/00 |
Claims
1. A method comprising: exposing a material comprising a
hydrocarbon carried by an inorganic substrate to at least 0.5
megarads of radiation.
2. The method of claim 1, wherein the inorganic substrate comprises
exterior surfaces, and wherein the hydrocarbon is carried on at
least some of the exterior surfaces.
3. The method of claim 1, wherein the inorganic substrate comprises
interior surfaces, and wherein the hydrocarbon is carried on at
least some of the interior surfaces.
4. The method of claim 1, wherein the material comprises oil
shale.
5. The method of claim 1, wherein the material comprises oil
sand.
6. The method of claim 1, wherein the inorganic substrate comprises
a material having a thermal conductivity of less than 5 W m.sup.-1
K.sup.-1.
7. The method of claim 1, wherein the inorganic substrate comprises
at least one of an aluminosilicate material, a silica material, and
an alumina material.
8. The method of claim 7, wherein the substrate further comprises a
noble metal, such as platinum, iridium, or rhodium.
9. The method of claim 7, wherein the substrate comprises a zeolite
material.
10. The method of claim 9, wherein the zeolite material has a base
structure selected from the group consisting of ZSM-5, Zeolite Y,
Zeolite Beta, mordenite, ferrierite, and mixtures of any two or
more of these structures.
11. The method of claim 1 wherein the radiation is in the form of
energetic particles.
12. The method of claim 1 wherein exposing the hydrocarbon to
radiation reduces the molecular weight by at least about 25%.
13. The method of claim 12 wherein the hydrocarbon initially has a
molecular weight of from about 300 to about 2000, and after
irradiation the hydrocarbon has a molecular weight of from about
190 to about 1750.
14. The method of claim 1 further comprising delivering radiation
to a site where the material is found.
Description
RELATED APPLICATIONS
[0001] This application is a continuation of pending U.S. Ser. No.
15/434,508, filed Feb. 17, 2017, which is a continuation of U.S.
Ser. No. 14/795,422, filed Jul. 9, 2015, now U.S. Pat. No.
9,593,564, issued Mar. 14, 2017, which is a continuation of U.S.
Ser. No. 14/314,834, filed Jun. 25, 2014, now U.S. Pat. No.
9,091,165, issued Jul. 28, 2015, which is a continuation of U.S.
Ser. No. 13/958,130, filed Aug. 2, 2013, now U.S. Pat. No.
8,789,584, issued Jul. 29, 2014, which is a continuation of U.S.
Ser. No. 13/768,593, filed Feb. 15, 2013, now U.S. Pat. No.
8,534,351, issued Sep. 17, 2013, which is a continuation of U.S.
Ser. No. 13/180,717, filed Jul. 12, 2011, which is now U.S. Pat.
No. 8,397,807, issued Mar. 19, 2013, which is a continuation of
U.S. Ser. No. 12/417,786, filed Apr. 3, 2009, which is now U.S.
Pat. No. 8,025,098, issued Sep. 27, 2011, which claims priority
from U.S. Provisional Application Ser. No. 61/073,665, filed Jun.
18, 2008, 61/106,861, filed Oct. 20, 2008, and 61/139,324, filed
Dec. 19, 2008. The full disclosure of each of these applications is
incorporated by reference herein.
TECHNICAL FIELD
[0002] This disclosure relates to processing hydrocarbon-containing
materials.
BACKGROUND
[0003] Processing hydrocarbon-containing materials can permit
useful products to be extracted from the materials. Natural
hydrocarbon-containing materials can include a variety of other
substances in addition to hydrocarbons.
SUMMARY
[0004] Systems and methods are disclosed herein for processing a
wide variety of different hydrocarbon-containing materials, such as
light and heavy crude oils, natural gas, bitumen, coal, and such
materials intermixed with and/or adsorbed onto a solid support,
such as an inorganic support. In particular, the systems and
methods disclosed herein can be used to process (e.g., crack,
convert, isomerize, reform, separate) hydrocarbon-containing
materials that are generally thought to be less-easily processed,
including oil sands, oil shale, tar sands, and other
naturally-occurring and synthetic materials that include both
hydrocarbon components and solid matter (e.g., solid organic and/or
inorganic matter).
[0005] In some cases, the methods disclosed herein can be used to
process hydrocarbon-containing materials in situ, e.g., in a
wellbore, hydrocarbon-containing formation, or other mining site.
In some implementations, this in situ processing can reduce the
energy required to mine and/or extract the hydrocarbon-containing
material, and thus improve the cost-effectiveness of obtaining
products from the hydrocarbon-containing material.
[0006] The systems and methods disclosed herein use a variety of
different techniques to process hydrocarbon-containing materials.
For example, exposure of the materials to particle beams (e.g.,
beams that include ions and/or electrons and/or neutral particles)
or high energy photons (e.g., x-rays or gamma rays) can be used to
process the materials. Particle beam exposure can be combined with
other techniques such as sonication, mechanical processing, e.g.,
comminution (for example size reduction), temperature reduction
and/or cycling, pyrolysis, chemical processing (e.g., oxidation
and/or reduction), and other techniques to further break down,
isomerize, or otherwise change the molecular structure of the
hydrocarbon components, to separate the components, and to extract
useful materials from the components (e.g., directly from the
components and/or via one or more additional steps in which the
components are converted to other materials). Radiation may be
applied from a device that is in a vault.
[0007] The systems and methods disclosed herein also provide for
the combination of any hydrocarbon-containing materials described
herein with additional materials including, for example, solid
supporting materials. Solid supporting materials can increase the
effectiveness of various material processing techniques. Further,
the solid supporting materials can themselves act as catalysts
and/or as hosts for catalyst materials such as noble metal
particles, e.g., rhodium particles, platinum particles, and/or
iridium particles. The catalyst materials can increase still
further the rates and selectivity with which particular products
are obtained from processing the hydrocarbon-containing
materials.
[0008] In a first aspect, the disclosure features methods that
includes exposing a material that includes a hydrocarbon carried by
an inorganic substrate to a plurality of energetic particles, such
as accelerated charged particles, such as electrons or ions, to
deliver a level or dose of radiation of at least 0.5 megarads,
e.g., at least 1, 2.5, 5, 10, 25, 50, 100, 250, or even 300 or more
megarads to the material.
[0009] Embodiments can include one or more of the following
features.
[0010] The inorganic substrate can include exterior surfaces, and
the hydrocarbon can be carried, e.g., adsorbed, on at least some of
the exterior surfaces. The inorganic substrate can include interior
surfaces, and the hydrocarbon can be carried, e.g., adsorbed, on at
least some of the interior surfaces. The material can include oil
shale and/or oil sand.
[0011] The substrate can include a material having a thermal
conductivity of less than 5 W m.sup.-1 K.sup.-1. The inorganic
substrate can include at least one of an aluminosilicate material,
a silica material, and an alumina material. The substrate can
include a noble metal, such as platinum, iridium, or rhodium. The
substrate can include a zeolite material. The zeolite material can
have a base structure selected from the group consisting of ZSM-5,
zeolite Y, zeolite Beta, Mordenite, ferrierite, and mixtures of any
two or more of these base structures.
[0012] Irradiating can in some cases reduce the molecular weight of
the hydrocarbon, e.g., by at least 25%, at least 50%, at least 75%,
or at least 100% or more. For instance, irradiation can reduce the
molecular weight from a starting molecular weight about 300 to
about 2000 prior to irradiation, to a molecular weight after
irradiation of about 190 to about 1750, or from about 150 to about
1000.
[0013] Embodiments can also include any of the other features or
steps disclosed herein.
[0014] In another aspect, the disclosure features methods for
processing a hydrocarbon material. The methods include combining
the hydrocarbon material with a solid supporting material, exposing
the combined hydrocarbon and solid supporting materials to a
plurality of charged particles or photons to deliver a dose of
radiation of at least 0.5 megarads, e.g., at least 1, 2.5, 5, 10,
25, 50, 100, 250, or even 300 or more megarads, and processing the
exposed combined hydrocarbon and solid supporting materials to
obtain at least one hydrocarbon product.
[0015] Embodiments can include one or more of the following
features.
[0016] The solid supporting material can include at least one
catalyst material. The at least one catalyst material can include
at least one material selected from the group consisting of
platinum, rhodium, osmium, iron, and cobalt. The solid supporting
material can include a material selected from the group consisting
of silicate materials, silicas, aluminosilicate materials,
aluminas, oxide materials, and glasses. The solid supporting
material can include at least one zeolite material.
[0017] The processing can include exposing the combined hydrocarbon
and solid supporting materials to ultrasonic waves. The processing
can include oxidizing and/or reducing the combined hydrocarbon and
solid supporting materials.
[0018] The plurality of charged particles can include ions. The
ions can be selected from the group consisting of positively
charged ions and negatively charged ions. The ions can include
multiply charged ions. The ions can include both positively and
negatively charged ions. The ions can include at least one type of
ions selected from the group consisting of hydrogen ions, noble gas
ions, oxygen ions, nitrogen ions, carbon ions, halogen ions, and
metal ions. The plurality of charged particles can include
electrons. The plurality of charged particles can include both ions
and electrons.
[0019] The processing can include exposing the combined hydrocarbon
and solid supporting materials to additional charged particles. The
additional charged particles can include ions, electrons, or both
ions and electrons. The additional charged particles can include
both positively and negatively charged ions. The additional charged
particles can include multiply charged ions. The additional charged
particles can include at least one type of ions selected from the
group consisting of hydrogen ions, noble gas ions, oxygen ions,
nitrogen ions, carbon ions, halogen ions, and metal ions.
[0020] The plurality of charged particles can include catalyst
particles. The additional charged particles can include catalyst
particles.
[0021] The methods can be performed in a fluidized bed system. The
method can be performed in a catalytic cracking system. Exposing
the combined materials to charged particles can heat the combined
materials to a temperature of 400 K or more.
[0022] The methods can include exposing the combined hydrocarbon
and solid supporting materials to reactive particles. Exposing the
combined hydrocarbon and solid supporting materials to reactive
particles can be performed during the processing. Exposing the
combined hydrocarbon and solid supporting materials to reactive
particles can be performed during the exposure to charged
particles. The reactive particles can include one or more types of
particles selected from the group consisting of oxygen, ozone,
sulfur, selenium, metals, noble gases, and hydrogen. Exposing the
combined hydrocarbon and solid supporting materials to reactive
particles can be performed in a catalytic cracking system.
[0023] The hydrocarbon material can include oil sand. The
hydrocarbon material can include oil shale.
[0024] Embodiments can also include any of the other features or
steps disclosed herein.
[0025] In a further aspect, the disclosure features methods for
processing a heterogeneous material that includes at least one
hydrocarbon component and at least one solid component. The methods
include combining the heterogeneous material with at least one
catalyst material to form a precursor material, exposing the
precursor material to a plurality of charged particles to deliver a
dose of radiation of at least 0.5 megarads (or higher as noted
herein), and processing the exposed precursor material to obtain at
least one hydrocarbon product.
[0026] Embodiments of these methods can include one or more of the
features discussed above.
[0027] The methods can also include combining the precursor
material with a solid supporting material. The solid supporting
material can include at least one zeolite material. The solid
supporting material can include at least one material selected from
the group consisting of silicate materials, silicas,
aluminosilicate materials, aluminas, oxide materials, and glasses.
The solid supporting material can include the at least one catalyst
material.
[0028] In some implementations, the methods disclosed herein
include providing the material by excavating a site where the
material is found, and exposing the material includes delivering a
source of radiation to the site where the material is found.
[0029] In a further aspect, the invention features a method that
includes forming a wellbore in a hydrocarbon-containing formation;
delivering a radiation source into the wellbore; irradiating at
least a portion of the formation using the radiation source; and
producing a hydrocarbon-containing material from the wellbore.
[0030] The method may further include thermally treating the
irradiated formation, e.g., with steam, to extract the
hydrocarbon-containing material therefrom.
[0031] The full disclosures of each of the following U.S. Patent
Applications, which are being filed concurrently herewith, are
hereby incorporated by reference herein: U.S. application Ser. No.
12/417,707, filed Apr. 3, 2009, now U.S. Pat. No. 7,867,358, issued
Jan. 11, 2011; U.S. application Ser. No. 12/417,720, filed Apr. 3,
2009, now U.S. Pat. No. 7,846,295, issued Dec. 7, 2010; U.S.
application Ser. No. 12/417,699, filed Apr. 3, 2009, now U.S. Pat.
No. 7,931,784, issued Apr. 26, 2011; U.S. application Ser. No.
12/417,840, filed Apr. 3, 2009; U.S. application Ser. No.
12/417,731, filed Apr. 3, 2009; U.S. application Ser. No.
12/417,900, filed Apr. 3, 2009; U.S. application Ser. No.
12/417,880, filed Apr. 3, 2009, now U.S. Pat. No. 8,212,087, issued
Jul. 3, 2012; U.S. application Ser. No. 12/417,723, filed Apr. 3,
2009; U.S. application Ser. No. 12/417,904, filed Apr. 3, 2009, now
U.S. Pat. No. 7,867,359, issued Jan. 11, 2011.
[0032] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this disclosure belongs.
Although methods and materials similar or equivalent to those
described herein can be used in the practice or testing of the
present disclosure, suitable methods and materials are described
below. All publications, patent applications, patents, and other
references mentioned herein are incorporated by reference in their
entirety for all that they each contain. In case of conflict, the
present specification, including definitions, will control. In
addition, the materials, methods, and examples are illustrative
only and not limiting.
[0033] The details of one or more embodiments are set forth in the
accompanying drawings and description. Other features and
advantages will be apparent from the description, drawings, and
claims.
DESCRIPTION OF DRAWINGS
[0034] FIG. 1 is a schematic diagram showing a sequence of steps
for processing hydrocarbon-containing materials.
[0035] FIG. 2 is a schematic diagram showing another sequence of
steps for processing hydrocarbon-containing materials.
[0036] FIG. 3 is a schematic illustration of the lower portion of a
well, intersecting a production formation and having a system for
injecting radiation into the formation.
[0037] FIG. 3A is a schematic illustration of the lower portion of
the same well, showing injection of steam and/or chemical
constituents into the formation and producing the well via a
production conduit of the well.
DETAILED DESCRIPTION
[0038] Many embodiments of this application use Natural Force.TM.
Chemistry. Natural Force.TM. Chemistry methods use the controlled
application and manipulation of physical forces, such as particle
beams, gravity, light, etc., to create intended structural and
chemical molecular change. In preferred implementations, Natural
Force.TM. Chemistry methods alter molecular structure without
chemicals or microorganisms. By applying the processes of Nature,
new useful matter can be created without harmful environmental
interference.
[0039] While petroleum in the form of crude oil represents a
convenient source of hydrocarbon materials in the world economy,
there exist significant alternative sources of
hydrocarbons--materials such as oil sands, oil shale, tar sands,
bitumen, coal, and other such mixtures of hydrocarbons and
non-hydrocarbon material--which also represent significant
hydrocarbon reserves. Unfortunately, conventional processing
technologies focus primarily on the refining of various grades of
crude oil to obtain hydrocarbon products. Far fewer facilities and
technologies are dedicated to the processing of alternative sources
of hydrocarbons. Reasons for this are chiefly economic--the
alternative sources of hydrocarbons noted herein have proved to be
more difficult to refine and process, resulting in a smaller margin
of profit (if any at all) per unit of hydrocarbon extracted. There
are also technical difficulties associated with the extraction and
refining of hydrocarbon materials from such sources. Many technical
difficulties arise from the nature (e.g., the chemical and physical
structure) of the hydrocarbons in the alternative materials and the
low weight percentage of hydrocarbons in the hydrocarbon-containing
material. For example, in certain hydrocarbon-containing materials
such as tar sands, hydrocarbons are physically and/or chemically
bound to solid particles that can include various types of sand,
clay, rock, and solid organic matter. Such heterogeneous mixtures
of components are difficult to process using conventional
separation and refinement methods, most of which are not designed
to effect the type of component separation which is necessary to
effectively process these materials. Typically, processing methods
which can achieve the required breakdown and/or separation of
components in the hydrocarbon-containing materials are
cost-prohibitive, and only useful when shortages of various
hydrocarbons in world markets increases substantially the per-unit
price of the hydrocarbons. It can also be difficult and costly to
remove some hydrocarbon-containing materials, e.g., oil sands and
bituminous compounds, from the formations where they are present.
Surface mining requires enormous energy expenditure and is
environmentally damaging, while in situ thermal recovery with steam
is also energy-intensive. The use of processes described herein
can, for example, reduce the temperature and/or pressure of steam
required for in situ thermal recovery.
[0040] Methods and systems are disclosed herein that provide for
efficient, inexpensive processing of hydrocarbon-containing
materials to extract a variety of different hydrocarbon products.
The methods and systems are particularly amenable to processing the
alternative sources of hydrocarbons discussed above, but can also
be used, more generally, to process any type of naturally-occurring
or synthetic hydrocarbon-containing material. These methods and
systems enable extraction of hydrocarbons from a much larger pool
of hydrocarbon-containing resources than crude oil alone, and can
help to alleviate worldwide shortages of hydrocarbons and/or
hydrocarbon-derived or -containing products.
[0041] The methods disclosed herein typically include exposure of
hydrocarbon-containing materials carried by solid substrate
materials (organic or inorganic) to one or more beams of particles
or high energy photons. The beams of particles can include
accelerated electrons, and/or ions. Solid materials--when combined
with hydrocarbons--are often viewed as nuisance components of
hydrocarbon mixtures, expensive to separate and not of much use.
However, the processing methods disclosed herein use the substrate
materials to improve the efficiency with which hydrocarbon
containing-materials are processed. Thus, the solid substrate
materials represent an important processing component of
hydrocarbon-containing mixtures, rather than merely another
component that must be separated from the mixture to obtain purer
hydrocarbons. If desired, after recovery of the hydrocarbon
component, the solid substrate may be used as a separate product,
e.g., as an aggregate or roadbed material. Alternatively, the solid
substrate may be returned to the site.
[0042] FIG. 1 shows a schematic diagram of a technique 100 for
processing hydrocarbon-containing materials such as oil sands, oil
shale, tar sands, and other materials that include hydrocarbons
intermixed with solid components such as rock, sand, clay, silt,
and/or solid organic material. These materials may be in their
native form, or may have been previously treated, for example
treated in situ with radiation as described below. In a first step
of the sequence shown in FIG. 1, the hydrocarbon-containing
material 110 can be subjected to one or more optional mechanical
processing steps 120. The mechanical processing steps can include,
for example, grinding, crushing, agitation, centrifugation, rotary
cutting and/or chopping, shot-blasting, and various other
mechanical processes that can reduce an average size of particles
of material 110, and initiate separation of the hydrocarbons from
the remaining solid matter therein. In some embodiments, more than
one mechanical processing step can be used. For example, multiple
stages of grinding can be used to process material 110.
Alternatively, or in addition, a crushing process followed by a
grinding process can be used to treat material 110. Additional
steps such as agitation and/or further crushing and/or grinding can
also be used to further reducing the average size of particles of
material 110.
[0043] In a second step 130 of the sequence shown in FIG. 1, the
hydrocarbon-containing material 110 can be subjected to one or more
optional cooling and/or temperature-cycling steps. In some
embodiments, for example, material 110 can be cooled to a
temperature at and/or below a boiling temperature of liquid
nitrogen. More generally, the cooling and/or temperature-cycling in
step 130 can include, for example, cooling to temperatures well
below room temperature (e.g., cooling to 10.degree. C. or less,
0.degree. C. or less, -10.degree. C. or less, -20.degree. C. or
less, -30.degree. C. or less, -40.degree. C. or less, -50.degree.
C. or less, -100.degree. C. or less, -150.degree. C. or less,
-200.degree. C. or less, or even less). Multiple cooling stages can
be performed, with varying intervals between each cooling stage to
allow the temperature of material 110 to increase. The effect of
cooling and/or temperature-cycling material 110 is to disrupt the
physical and/or chemical structure of the material, promoting at
least partial de-association of the hydrocarbon components from the
non-hydrocarbon components (e.g., solid non-hydrocarbon materials)
in material 110. Suitable methods and systems for cooling and/or
temperature-cycling of material 110 are disclosed, for example, in
U.S. Provisional Patent Application Ser. No. 61/081,709, filed on
Jul. 17, 2008, the entire contents of which are incorporated herein
by reference.
[0044] In a third step 140 of the sequence of FIG. 1, the
hydrocarbon-containing material 110 is exposed to charged particles
or photons, such as photons having a wavelength between about 0.01
nm and 280 nm. In some embodiments, the photons can have a
wavelength between, e.g., 100 nm to 280 nm or between 0.01 nm to 10
nm, or in some cases less than 0.01 nm. The charged particles
interact with material 110, causing further disassociation of the
hydrocarbons therein from the non-hydrocarbon materials, and also
causing various hydrocarbon chemical processes, including chain
scission, bond-formation, and isomerization. These chemical
processes convert long-chain hydrocarbons into shorter-chain
hydrocarbons, many of which can eventually be extracted from
material 110 as products and used directly for various
applications. The chemical processes can also lead to conversion of
various products into other products, some of which may be more
desirable than others. For example, through bond-forming reactions,
some short-chain hydrocarbons may be converted to
medium-chain-length hydrocarbons, which can be more valuable
products. As another example, isomerization can lead to the
formation of straight-chain hydrocarbons from cyclic hydrocarbons.
Such straight-chain hydrocarbons may be more valuable products than
their cyclized counterparts.
[0045] By adjusting an average energy of the charged particles
and/or an average current of the charged particles, the total
amount of energy delivered or transferred to material 110 by the
charged particles can be controlled. In some embodiments, for
example, material 110 can be exposed to charged particles so that
the energy transferred to material 110 (e.g., the energy dose
applied to material 110) is 0.3 Mrad or more (e.g., 0.5 Mrad or
more, 0.7 Mrad or more, 1.0 Mrad or more, 2.0 Mrad or more, 3.0
Mrad or more, 5.0 Mrad or more, 7.0 Mrad or more, 10.0 Mrad or
more, 15.0 Mrad or more, 20.0 Mrad or more, 30.0 Mrad or more, 40.0
Mrad or more, 50.0 Mrad or more, 75.0 Mrad or more, 100.0 Mrad or
more, 150.0 Mrad or more, 200.0 Mrad or more, 250.0 Mrad or more,
or even 300.0 Mrad or more).
[0046] In general, electrons, ions, photons, and combinations of
these can be used as the charged particles in step 140 to process
material 110. A wide variety of different types of ions can be used
including, but not limited to, protons, hydride ions, oxygen ions,
carbon ions, and nitrogen ions. These charged particles can be used
under a variety of conditions; parameters such as particle
currents, energy distributions, exposure times, and exposure
sequences can be used to ensure that the desired extent of
separation of the hydrocarbon components from the non-hydrocarbon
components in material 110, and the extent of the chemical
conversion processes among the hydrocarbon components, is reached.
Suitable systems and methods for exposing material 110 to charged
particles are discussed, for example, in the following U.S.
Provisional Patent Applications: Ser. No. 61/049,406, filed on Apr.
30, 2008; Ser. No. 61/073,665, filed on Jun. 18, 2008; and Ser. No.
61/073,680, filed on Jun. 18, 2008. The entire contents of each of
the foregoing provisional applications are incorporated herein by
reference. In particular, charged particle systems such as
inductive linear accelerator (LINAC) systems can be used to deliver
large doses of energy (e.g., doses of 50 Mrad or more) to material
110.
[0047] In the final step of the processing sequence of FIG. 1, the
processed material 110 is subjected to a separation step 150, which
separates the hydrocarbon products 160 and the non-hydrocarbon
products 170. A wide variety of different processes can be used to
separate the products. Exemplary processes include, but are not
limited to, distillation, extraction, and mechanical processes such
as centrifugation, filtering, and agitation. In general, any
process or combination of processes that yields separation of
hydrocarbon products 160 and non-hydrocarbon products 170 can be
used in step 150. A variety of suitable separation processes are
discussed, for example, in PCT Publication No. WO 2008/073186
(e.g., in the Post-Processing section), the entire contents of
which are incorporated herein by reference.
[0048] The processing sequence shown in FIG. 1 is a flexible
sequence, and can be modified as desired for particular materials
110 and/or to recover particular hydrocarbon products 160. For
example, the order of the various steps can be changed in FIG. 1.
Further, additional steps of the types shown, or other types of
steps, can be included at any point within the sequence, as
desired. For example, additional mechanical processing steps,
cooling/temperature-cycling steps, particle beam exposure steps,
and/or separation steps can be included at any point in the
sequence. Further, other processing steps such as sonication,
chemical processing, pyrolysis, oxidation and/or reduction, and
radiation exposure can be included in the sequence shown in FIG. 1
prior to, during, and/or following any of the steps shown in FIG.
1. Many processes suitable for inclusion in the sequence of FIG. 1
are discussed, for example, in PCT Publication No. WO 2008/073186
(e.g., throughout the Detailed Description section).
[0049] As an example, in some embodiments, material 110 can be
subjected to one or more sonication processing steps as part of the
processing sequence shown in FIG. 1. One or more liquids can be
added to material 110 to assist the sonication process. Suitable
liquids that can be added to material 110 include, for example,
water, various types of liquid hydrocarbons (e.g., hydrocarbon
solvents), and other common organic and inorganic solvents.
[0050] Material 110 is sonicated by introducing the material into a
vessel that includes one or more ultrasonic transducers. A
generator delivers electricity to the one or more ultrasonic
transducers, which typically include piezoelectric elements that
convert the electrical energy into sound in the ultrasonic range.
In some embodiments, the materials are sonicated using sound waves
having a frequency of from about 16 kHz to about 110 kHz, e.g.,
from about 18 kHz to about 75 kHz or from about 20 kHz to about 40
kHz (e.g., sound having a frequency of 20 kHz to 40 kHz).
[0051] The ultrasonic energy (in the form of ultrasonic waves) is
delivered or transferred to material 110 in the vessel. The energy
creates a series of compressions and rarefactions in material 110
with an intensity sufficient to create cavitation in material 110.
Cavitation disaggregates the hydrocarbon and non-hydrocarbon
components of material 110, and also produces free radicals in
material 110. The free radicals act to break down the hydrocarbon
components in material 110 by initiating bond-cleaving
reactions.
[0052] Typically, 5 to 4000 MJ/m.sup.3, e.g., 10, 25, 50, 100, 250,
500, 750, 1000, 2000, or 3000 MJ/m.sup.3, of ultrasonic energy is
delivered or applied to material 110 moving at a rate of about 0.2
m.sup.3/s (about 3200 gallons/min) through the vessel. After
exposure to ultrasonic energy, material 110 exits the vessel and is
directed to one or more additional process steps.
[0053] As discussed briefly previously, in step 140 of the sequence
of FIG. 1, exposure to charged particles or photons is performed in
the presence of various solid components in material 110. The solid
components can carry the hydrocarbon components in a variety of
ways. For example, the hydrocarbons can be adsorbed onto the solid
materials, supported by the solid materials, impregnated within the
solid materials, layered on top of the solid materials, mixed with
the solid materials to form a tar-like heterogeneous mixture,
and/or combined in various other ways. During exposure of material
110 to charged particles, the solid components enhance the
effectiveness of exposure. The solid components can be composed
mainly of inorganic materials having poor thermal conductivity
(e.g., silicates, oxides, aluminas, aluminosilicates, and other
such materials).
[0054] When material 110 is exposed to charged particles or
photons, the charged particles or photons act directly on the
hydrocarbons to cause a variety of chemical processes, as discussed
above. However, the charged particles also transfer kinetic energy
in the form of heat to the solid components of material 110.
Because the solid components have relatively poor thermal
conductivity, the transferred heat remains in a region of the solid
material very close to the position at which the charged particles
are incident. Accordingly, the local temperature of the solid
material in this region increases rapidly to a large value. The
hydrocarbon components, which are in contact with the solid
components, also increase rapidly to a significantly higher
temperature. At elevated temperature, the rates of reactions
initiated in the hydrocarbons by the charged particles--chain
scission (e.g., cracking), bond-forming, isomerization, oxidation
and/or reduction--are typically enhanced, leading to more efficient
separation of the hydrocarbons from the solid components, and more
efficient conversion of the hydrocarbons into desired products.
[0055] Overall, the solid components present in material 110
actually promote, rather than discourage, the separation and
conversion of the hydrocarbons in the material using the methods
disclosed herein. In some embodiments, material 110 is heated
during exposure to charged particles to an average temperature of
300 K or more (e.g., 325 K or more, 350 K or more, 400 K or more,
450 K or more, 500 K or more, 600 K or more, 700 K or more).
Further, when the solid components include one or more types of
metal particles (e.g., dopants), the rates and/or efficiencies of
various chemical reactions occurring in material 110 can be still
further enhanced, for example due to participation of the metals as
catalysts in the reactions.
[0056] To further increase the rate and/or selectivity of the
process shown in FIG. 1, one or more catalyst materials can also be
introduced. Catalyst materials can be introduced in a variety of
ways. For example, in some embodiments, in step 140 (or another
comparable step in which material 110 is treated with charged
particles), the charged particles can include particles of
catalytic materials in addition to, or as alternatives to, other
ions and/or electrons. Exemplary catalytic materials can include
ions and/or neutral particles of various metals including platinum,
rhodium, osmium, iron, and cobalt.
[0057] In certain embodiments, the catalytic materials can be
introduced directly into the solid components of material 110. For
example, the catalytic materials can be mixed with material 110
(e.g., by combining material 110 with a solution that includes the
catalytic materials) prior to exposure of material 110 to charged
particles in step 140.
[0058] In some embodiments, the catalytic materials can be added to
material 110 in solid form. For example, the catalytic materials
can be carried by a solid supporting material (e.g., adsorbed onto
the supporting material and/or impregnated within the supporting
material) and then the solid supporting material with the catalytic
materials can be combined with material 110 prior to exposure step
140. As a result of any of the processes of introducing the
catalyst material into the solid components of material 110, when
material 110 is exposed to charged particles in step 140, the
hydrocarbon components are carried by one or more solid materials
that include one or more catalytic materials. In general, the
catalytic materials can be carried (e.g., adsorbed) on internal
surfaces of the solid supporting material, on external surfaces of
the solid supporting material, or on both internal and external
surfaces of the solid supporting material.
[0059] In certain embodiments, additional solid material can be
added to material 110 prior to exposing material 110 to charged
particles. The added solid material can include one or more
different types of solid materials. As discussed above, by adding
additional solid materials, local heating of the hydrocarbon
components can be enhanced, increasing the rate and/or selectivity
of the reactions initiated by the charged particles.
[0060] Typically, the added solid materials have relatively low
thermal conductivity, to ensure that local heating of the
hydrocarbons in material 110 occurs, and to ensure that heat
dissipation does not occur too quickly. In some embodiments, the
thermal conductivity of one or more solid materials added to
material 110 prior to a step of exposing material 110 to charged
particles is 5 W m.sup.-1 K.sup.-1 or less (e.g., 4 W m.sup.-1
K.sup.-1 or less, 3 W m.sup.-1 K.sup.-1 or less, 2 W m.sup.-1
K.sup.-1 or less, 1 W m.sup.-1 K.sup.-1 or less, or 0.5 W m.sup.-1
K.sup.-1 or less). Exemplary solid materials that can be added to
material 110 include, but are not limited to, silicon-based
materials such as silicates, silicas, aluminosilicates, aluminas,
oxides, various types of glass particles, and various types of
stone (e.g., sandstone), rock, and clays, such as smectic clays,
e.g., montmorillonite and bentonite.
[0061] In some embodiments, one or more zeolite materials can be
added to material 110 prior to exposure of material 110 to charged
particles. Zeolite materials are porous, and the pores can act as
host sites for both catalytic materials and hydrocarbons. A large
number of different zeolites are available and compatible with the
processes discussed herein. Methods of making zeolites and
introducing catalytic materials into zeolite pores are disclosed,
for example, in the following patents, the entire contents of each
of which are incorporated herein by reference: U.S. Pat. No.
4,439,310; U.S. Pat. No. 4,589,977; U.S. Pat. No. 7,344,695; and
European Patent No. 0068817. Suitable zeolite materials are
available from, for example, Zeolyst International (Valley Forge,
Pa., http://www.zeolyst.com).
[0062] In certain embodiments, one or more materials can be
combined with material 110 prior to exposing material 110 to
charged particles. The combined materials form a precursor
material. The one or more materials can include reactive substances
that are present in a chemically inert form. When the reactive
substances are exposed to charged particles (e.g., during step
140), the inert forms can be converted to reactive forms of the
substances. The reactive substances can then participate in the
reactions of the hydrocarbon components of material 110, enhancing
and rates and/or selectivity of the reactions. Exemplary reactive
substances include oxidizing agents (e.g., oxygen atoms, ions,
oxygen-containing molecules such as oxygen gas and/or ozone,
silicates, nitrates, sulfates, and sulfites), reducing agents
(e.g., transition metal-based compounds), acidic and/or basic
agents, electron donors and/or acceptors, radical species, and
other types of chemical intermediates and reactive substances.
[0063] In some embodiments, solid materials can be added to
material 110 until a weight percentage of solid components in
material 110 is 2% or more (e.g., 5% or more, 10% or more, 15% or
more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or
more, 70% or more, or 80% or more). As discussed above, in certain
embodiments, exposing the hydrocarbons to charged particles when
the hydrocarbons are carried by solid materials can enhance the
rate and/or selectivity of the reactions initiated by the charged
particles.
[0064] In some embodiments, an average particle size of the solid
components of material 110 can be between 50 .mu.m and 50 mm (e.g.,
between 50 .mu.m and 65 mm, between 100 .mu.m and 10 mm, between
200 .mu.m and 5 mm, between 300 .mu.m and 1 mm, between 0.06 mm and
2 mm, or between 500 .mu.m and 1 mm). In general, by controlling an
average particle size of the solid components, the ability of the
solid components to support hydrocarbon-containing materials can be
controlled. In some instances, catalytic activity of the solid
components can also be controlled by selecting suitable average
particle sizes.
[0065] The average particle size of the solid components of
material 110 can be controlled via various optional mechanical
processing techniques in step 120 of FIG. 1. For example, in some
embodiments, the average particle size of material 110 can be
reduced sufficiently so that material 110 is pourable and flows
like granulated sugar, sand, or gravel.
[0066] In certain embodiments, a surface area per unit mass of
solid materials added to material 110 is 250 m.sup.2 per g or more
(e.g., 400 m.sup.2 per g or more, 600 m.sup.2/g or more, 800
m.sup.2/g or more, 1000 m.sup.2/g or more, 1200 m.sup.2/g or more).
Generally, by adding solid materials with higher surface areas, the
amount of hydrocarbon material that can be carried by the solid
components of material 110 increases. Further, the amount of
catalyst material that can be carried by the solid components of
material 110 also increases, and/or the number of catalytic sites
on the solid materials increases. As a result of these factors, the
overall rate and selectivity of the chemical reactions initiated by
charged particle exposure can be enhanced.
[0067] In some embodiments, a weight percentage of catalyst
material in the solid components of material 110 can be 0.001% or
more (e.g., 0.01% or more, 0.1% or more, 0.3% or more, 0.5% or
more, 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.0%
or more, or 10.0% or more). The catalyst material can include a
single type of catalyst, or two or more different types of
catalysts.
[0068] In general, a wide variety of different types of charged
particles can be used to expose material 110. The charged particles
can include, for example, electrons, negatively charged ions, and
positively charged ions. The charged particles can include ions of
hydrogen, oxygen, carbon, nitrogen, noble metals, transition
metals, and a variety of other monatomic and polyatomic ions. The
ions can be singly-charged and/or multiply-charged.
[0069] In certain embodiments, one or more different types of
reactive particles can be introduced into the process prior to,
during, or following one or more charged particle exposure steps.
Suitable reactive particles include oxygen, ozone, sulfur,
selenium, various metals, noble gases (including noble gas ions),
and hydride ions. Reactive particles assist in further enhancing
the rate and selectivity of processes initiated by the charged
particles (e.g., chain scission, bond forming, functionalization,
and isomerization).
[0070] In some embodiments, the steps shown in FIG. 1 can be
performed without adding any liquids, e.g., solvents, during
processing. There can be significant advantages to processing
material 110 without adding liquids; these include no need for used
liquid disposal and/or recycling problems and equipment, no need
for a fluid pumping and transport system for moving material 110
through the processing system, and simpler material handling
procedures. Further, liquid-free (e.g., solvent-free) processing of
material 110 can also be significantly less expensive than
liquid-based processing methods when large volumes of material 110
are processed.
[0071] In certain other embodiments, some or all of the steps shown
in FIG. 1 can be performed in the presence of a liquid such as a
solvent, an emulsifier, or more generally, one or more liquids that
are mixed with material 110. For example, in some embodiments, one
or more liquids such as water, one or more liquid hydrocarbons,
and/or other organic and/or inorganic solvents of hydrocarbons can
be combined with material 110 to improve the ability of material
110 to flow. By mixing one or more liquids with material 110, a
heterogeneous suspension of solid material in the liquids can be
formed. The suspension can be readily transported from one location
to another in a processing facility via conventional pressurized
piping apparatus. The added liquids can also assist various
processes (e.g., sonication) in breaking up the solid material into
smaller particles during processing.
[0072] In certain embodiments, the methods disclosed herein can be
performed within conventional crude oil processing apparatus. For
example, some or all of the processing steps in FIG. 1 can be
performed in a fluidized bed system. Material 110 can be subjected
to mechanical processing and/or cooling/thermal-cycling steps and
introduced into a fluidized bed. Charged particles can be delivered
into the fluidized bed system, and material 110 can be exposed to
the charged particles. The charged particles can include one or
more different types of catalytic particles (e.g., particles of
metals such as platinum, rhodium, osmium, iron, cobalt) which can
further enhance the rate and/or selectivity of the chemical
reactions initiated by the charged particles. Reactive particles
can also be delivered into the fluidized bed environment to promote
the reactions. Exemplary reactive particles include, but are not
limited to, oxygen, ozone, sulfur, selenium, various metals, noble
gas ions, and hydride ions.
[0073] In some embodiments, the methods disclosed herein can be
performed in catalytic cracking apparatus. Following processing of
material 110 (e.g., via mechanical processing steps and/or
cooling/temperature-cycling), material 110 can be introduced into a
catalytic cracking apparatus. Charged particles can be delivered to
the catalytic cracking apparatus and used to expose material 110.
Further, reactive particles (as discussed above in connection with
fluidized bed systems) can be introduced into the catalytic
cracking apparatus to improve the rate and/or selectivity of the
reactions initiated by the charged particles. Hydrocarbon
components of material 110 can undergo further cracking reactions
in the apparatus to selectively produce desired products.
[0074] In other embodiments, the methods disclosed herein can be
performed in situ, e.g., in a wellbore or other mining site. For
example, in some implementations a source of radiation is
introduced into a wellbore to irradiate a hydrocarbon-containing
material within the wellbore. The source of radiation can be, for
example an electron gun, such as a Rhodotron.RTM. accelerator.
[0075] In some cases, for example if a plurality of lateral
wellbores are drilled in the formation and electrons are introduced
through each lateral, the electron gun may be used by itself. In
such instances, while the electrons do not penetrate deeply into
the formation surrounding the laterals, they penetrate relatively
shallowly over the entire length of each lateral, thereby
penetrating a considerable area of the formation. It is important
that electrons be able to penetrate into the formation.
Accordingly, for example, the lateral wellbores may be unlined, may
be lined after irradiation, may be lined with a liner that is
perforated sufficiently to allow adequate penetration of radiation,
or may be lined with a liner that transmits radiation, e.g., a PVC
pipe.
[0076] In other cases, when deeper penetration is desired, the
source of radiation can be configured to emit x-rays or other high
energy photons, e.g., gamma rays that are able to penetrate the
formation more deeply. For example, the source of radiation can be
an electron gun used in combination with a metal foil, e.g., a
tantalum foil, to generate bremssthrahlung x-rays. Electron guns of
this type are commercially available, e.g., from IBA Industrial
under the tradename eXelis.RTM..
[0077] Typically, such devices are housed in a vault, e.g., of lead
or concrete.
[0078] Various other irradiating devices may be used in the methods
disclosed herein, including field ionization sources, electrostatic
ion separators, field ionization generators, thermionic emission
sources, microwave discharge ion sources, recirculating or static
accelerators, dynamic linear accelerators, van de Graaff
accelerators, and folded tandem accelerators. Such devices are
disclosed, for example, in U.S. Provisional Application Ser. No.
61/073,665, the complete disclosure of which is incorporated herein
by reference.
[0079] Alternatively, cobalt 60 can be used to generate gamma rays.
However, for safety reasons it is important that the cobalt 60 be
shielded when it could be exposed to humans. Thus, in such
implementations the cobalt 60 should generally be shielded when it
is not confined in a wellbore or other closed formation.
[0080] Referring to FIGS. 3 and 3A, a subsurface formation
production system is shown generally at 10 and includes one or more
primary wellbores 12 that are lined with a string of well casing
14. The primary wellbores 12 intersect a subsurface production
formation 16 from which hydrocarbon-containing materials are to be
produced.
[0081] An injection tubing string 18 extends from the surface
through the well or casing 14 and is secured in place by packers 20
and 22 or by any other suitable means for support and orientation
within the wellbore. The lower, open end 24 of the injection tubing
string 18 is in communication with an injection compartment 26
within the well or casing which is isolated, e.g., by packers 22
and 28 that establish sealing within the well or casing.
[0082] An array of laterally oriented injection passages 30 and 32
that are formed within the production formation 16 extend from the
isolated injection compartment 26. Passages 30, 32 extend from
openings or windows 34 and 36 that are formed in the well or casing
14 by a suitable drilling, milling or cutting tool or by any other
suitable means.
[0083] Referring to FIG. 3, the formation can be irradiated by
passing a source of radiation through the injection tubing string
18, for example an electron gun as discussed above. Irradiation of
the formation will cause a reduction in the molecular weight of the
hydrocarbon-containing materials in the formation, thereby reducing
the viscosity of the hydrocarbons.
[0084] A downhole pump can be provided for pumping the collected
production fluid to the surface; however in many cases production
of the well is caused by injection pressure or steam pressure.
[0085] Accordingly, if desired, steam may be used after irradiation
to aid in production of the hydrocarbon-containing materials from
the wellbore. Referring now to FIG. 3A, in some implementations
steam from a suitable source located at the surface (not shown) can
be injected through the injection tubing string 18 into the
injection compartment 26 of the well or casing 14. From the
injection compartment 26 the steam enters the array of injection
passages 30 and 32 and enters the subsurface production formation
where it heats the hydrocarbon-containing material and reduces its
viscosity and also pressurizes the production formation. The
formation pressure induced by the pressure of the steam causes the
heated and less viscous hydrocarbon-containing material to migrate
through the formation toward a lower pressure zone where it can be
acquired and produced.
[0086] While only two radially or laterally oriented injection
passages 30 and 32 are shown in FIG. 3A, it will be apparent that
any suitable number of injection passages or bores may be formed.
The injection passages may be formed through the use of various
commercially available processes.
[0087] In many applications, to minimize the potential for
sloughing of formation material into previously jetted lateral
passages it is desirable to conduct post jetting liner washing
operations where a perforate i.e., slotted liner is washed into
place to provide formation support and to also provide for
injection of fluid and provide for flow of formation fluid to the
wellbore for production. As discussed above, if the liner is
inserted prior to the irradiation step discussed above, it is
important that the liner be constructed to allow the radiation to
penetrate into the formation.
[0088] For production of the well, a production tubing string 38
extends from the surface through an open hole or through the casing
string 14 and is secured by the packer 20 or by any suitable anchor
device. The lower open end 40 of the production tubing string
extends below the packer 20 and is open to a production compartment
42 within the well or casing 14 that is isolated by the packers 20
and 22. Typically, a pump will be located to pump collected
formation fluid from the production compartment and through the
production tubing to the surface; however in some cases the
formation pressure, being enhanced by steam or injected fluid
pressure will cause flow of the production fluid to the surface to
fluid handling equipment at the surface.
[0089] A plurality of lateral production passages or bores, two of
which are shown at 44 and 46, extend into the production formation
16 from openings or windows 48 and 50 that are formed in the well
or casing. The production passages may be un-lined as shown in FIG.
3, or lined by a flexible perforated liner as is well known,
depending on the characteristics of the production formation. The
lateral production passages 44 and 46 are open to the production
compartment 42 of the well or casing. The heat and formation
pressure induced by the pressure of the steam causes the heated and
therefore less viscous hydrocarbon-containing materials to migrate
through the formation to the lateral production passages 44 and 46
which conduct the produced materials through the openings or
windows 48 and 50 into the production compartment 42 of the well
casing. When a pump is not employed, the produced material is then
forced by the formation pressure into the production tubing 38
which conducts it to the surface where it is then received by
surface equipment "P" for further processing and for storage,
handling or transportation.
[0090] In some cases, for example if the hydrocarbon-containing
material is near the surface, it may not be necessary to apply
steam or other heat to extract the hydrocarbon. For example, in
some instances the hydrocarbon-containing material can be
irradiated in situ and then removed without heating, e.g., by strip
mining.
[0091] The hydrocarbons 160 produced from the process shown in FIG.
1 are typically less viscous and flow more easily than original
material 110 prior to the beginning of processing. Accordingly, the
process shown in FIG. 1 permits extraction of flowable components
from material 110, which can greatly simplify subsequent handling
of the hydrocarbons. However, not all of the steps shown in FIG. 1
are required for processing material 110 to obtain hydrocarbon
components 160, depending upon the nature of material 110. For some
materials, for example, direct exposure to charged particles (step
140), followed by separation (step 150) is a viable route to
obtaining hydrocarbons 160. For certain materials, direct exposure
to catalytic particles (e.g., neutral particles and/or ions of
materials such as platinum, rhodium, osmium, iron and cobalt) in
step 140, followed by separation (step 150) can be used to obtain
hydrocarbons 160.
[0092] Although the preceding discussion has focused on processing
of materials that include both hydrocarbons and non-hydrocarbon
components, the methods disclosed herein can also be used to
processed materials that include, at least nominally, primarily
hydrocarbons, such as various grades of crude oil. FIG. 2 is a
schematic diagram showing a series of steps 200 that can be used to
process such materials. In a first step 220, hydrocarbon 210 is
combined with a quantity of solid material to form a heterogeneous
mixture. The solid material can include any one or more of the
solid materials disclosed herein. The solid material(s) can also
include any one or more of the catalyst materials disclosed herein.
The added solids form a carrier for hydrocarbon 210, and also
provide an active surface for any catalytic steps.
[0093] In step 230, hydrocarbon 210 is exposed to charged particles
(e.g., electrons and/or ions). Local heating due to charged
particle exposure and relatively slow thermal dissipation due to
the poor thermal conductivity of the added solid materials
increases the temperature of hydrocarbon 210, leading to enhanced
rates and selectivity of the reactions initiated by the charged
particles. Catalytic particles, present in the added solid
materials and/or the charged particles, further enhance reaction
rates and specificity. In general, the conditions during the
exposure step 230 can be selected according to the discussion of
step 140 in FIG. 1 above. In the final step 240 of FIG. 2,
hydrocarbon products 250 and non-hydrocarbon products 260 are
separated using any one or more of the procedures discussed above
in connection with step 150 of FIG. 1.
[0094] Hydrocarbon products, whether extracted from
hydrocarbon-containing materials with solid components (e.g.,
process 100) or extracted from hydrocarbon sources such as crude
oils (e.g., process 200), can be further processed via conventional
hydrocarbon processing methods. Where hydrocarbons were previously
associated with solid components in materials such as oil sands,
tar sands, and oil shale, the liberated hydrocarbons are flowable
and are therefore amenable to processing in refineries.
[0095] In general, the methods disclosed herein can be integrated
within conventional refineries to permit processing and refining of
hydrocarbons from alternative sources. The methods can be
implemented before, during, and/or after any one or more
conventional refinery processing steps. Further, certain aspects of
the methods disclosed herein, including exposure of hydrocarbons to
charged particles, can be used to assist conventional refining
methods, improving the rate and selectivity of these methods. In
the following discussion, further refining methods that can be used
to process hydrocarbons 160 and/or 250 (e.g., the mixtures of
products obtained from processes 100 and 200) are described.
[0096] Hydrocarbon refining comprises processes that separate
various components in hydrocarbon mixtures and, in some cases,
convert certain hydrocarbons to other hydrocarbon species via
molecular rearrangement (e.g., chemical reactions that break
bonds). In some embodiments, a first step in the refining process
is a water washing step to remove soluble components such as salts
from the mixtures. Typically, the washed mixture of hydrocarbons is
then directed to a furnace for preheating. The mixture can include
a number of different components with different viscosities; some
components may even be solid at room temperature. By heating, the
component mixture can be converted to a mixture that can be more
easily flowed from one processing system to another (and from one
end of a processing system to the other) during refining.
[0097] The preheated hydrocarbon mixture is then sent to a
distillation tower, where fractionation of various components
occurs with heating in a distillation column. The amount of heat
energy supplied to the mixture in the distillation process depends
in part upon the hydrocarbon composition of the mixture; in
general, however, significant energy is expended in heating the
mixture during distillation, cooling the distillates, pressurizing
the distillation column, and in other such steps. Within limits,
certain refineries are capable of reconfiguration to handle
differing hydrocarbon mixtures and to produce products. In general,
however, due to the relatively specialized refining apparatus, the
ability of refineries to handle significantly different feedstocks
is restricted.
[0098] In some embodiments, pretreatment of hydrocarbon mixtures
using methods disclosed in the publications incorporated herein by
reference, such as ion beam pretreatment (and/or one or more
additional pretreatments), can enhance the ability of a refining
apparatus to accept hydrocarbon mixtures having different
compositions. For example, by exposing a mixture to incident ions
from an ion beam, various chemical and/or physical properties of
the mixture can be changed. Incident ions can cause chemical bonds
to break, leading to the production of lighter molecular weight
hydrocarbon components with lower viscosities from heavier
components with higher viscosities. Alternatively, or in addition,
exposure of certain components to ions can lead to isomerization of
the exposed components. The newly formed isomers can have lower
viscosities than the components from which they are formed. The
lighter molecular weight components and/or isomers with lower
viscosities can then be introduced into the refinery, enabling
processing of mixtures which may not have been suitable for
processing initially.
[0099] In general, the various components of hydrocarbon mixtures
distill at different temperature ranges, corresponding to different
vertical heights in a distillation column. Typically, for example,
a refinery distillation column will include product streams at a
large number of different temperature cut ranges, with the lowest
boiling point (and, generally, smallest molecular weight)
components drawn from the top of the column, and the highest
boiling point, heaviest molecular weight components, drawn from
lower levels of the column. As an example, light distillates
extracted from upper regions of the column typically include one or
more of aviation gasoline, motor gasoline, naphthas, kerosene, and
refined oils. Intermediate distillates, removed from the middle
region of the column, can include one or more of gas oil, heavy
furnace oil, and diesel fuel oil. Heavy distillates, which are
generally extracted from lower levels of the column, can include
one or more of lubricating oil, grease, heavy oils, wax, and
cracking stock. Residues remaining in the still can include a
variety of high boiling point components such as lubricating oil,
fuel oil, petroleum jelly, road oils, asphalt, and petroleum coke.
Certain other products can also be extracted from the column,
including natural gas (which can be further refined and/or
processed to produce components such as heating fuel, natural
gasoline, liquefied petroleum gas, carbon black, and other
petrochemicals), and various by-products (including, for example,
fertilizers, ammonia, and sulfuric acid).
[0100] Generally, treatment of hydrocarbon mixtures using the
methods disclosed (including, for example, ion beam treatment,
alone or in combination with one or more other methods) can be used
to modify molecular weights, chemical structures, viscosities,
solubilities, densities, vapor pressures, and other physical
properties of the treated materials. Typical ions that can be used
for treatment of hydrocarbon mixtures can include protons, carbon
ions, oxygen ions, and any of the other types of ions disclosed
herein. In addition, ions used to treat hydrocarbon mixtures can
include metal ions; in particular, ions of metals that catalyze
certain refinery processes (e.g., catalytic cracking) can be used
to treat hydrocarbon mixtures. Exemplary metal ions include, but
are not limited to, platinum ions, palladium ions, iridium ions,
rhodium ions, ruthenium ions, aluminum ions, rhenium ions, tungsten
ions, and osmium ions.
[0101] In some embodiments, multiple ion exposure steps can be
used. A first ion exposure can be used to treat a hydrocarbon
mixture to effect a first change in one or more of molecular
weight, chemical structure, viscosity, density, vapor pressure,
solubility, and other properties. Then, one or more additional ion
exposures can be used to effect additional changes in properties.
As an example, the first ion exposure can be used to convert a
substantial fraction of one or more high boiling, heavy components
to lower molecular weight compounds with lower boiling points.
Then, one or more additional ion exposures can be used to cause
precipitation of the remaining amounts of the heavy components from
the component mixture.
[0102] In general, a large number of different processing protocols
can be implemented, according to the composition and physical
properties of the mixture. In certain embodiments, the multiple ion
exposures can include exposures to only one type of ion. In some
embodiments, the multiple ion exposures can include exposures to
more than one type of ion. The ions can have the same charges, or
different charge magnitudes and/or signs.
[0103] In certain embodiments, the mixture and/or components
thereof can be flowed during exposure to ion beams. Exposure during
flow can greatly increase the throughput of the exposure process,
enabling straightforward integration with other flow-based refinery
processes.
[0104] In some embodiments, the hydrocarbon mixtures and/or
components thereof can be functionalized during exposure to ion
beams. For example, the composition of one or more ion beams can be
selected to encourage the addition of particular functional groups
to certain components (or all components) of a mixture. One or more
functionalizing agents (e.g., ammonia) can be added to the mixture
to introduce particular functional groups. By functionalizing the
mixture and/or components thereof, ionic mobility within the
functionalized compounds can be increased (leading to greater
effective ionic penetration during exposure), and physical
properties such as viscosity, density, and solubility of the
mixture and/or components thereof can be altered. By altering one
or more physical properties of the mixture and/or components, the
efficiency and selectivity of subsequent refining steps can be
adjusted, and the available product streams can be controlled.
Moreover, functionalization of hydrocarbon components can lead to
improved activating efficiency of catalysts used in subsequent
refining steps.
[0105] In general, the methods disclosed herein--including ion beam
exposure of hydrocarbon mixtures and components--can be performed
before, during, or after any of the other refining steps disclosed
herein, and/or before, during, or after any other steps that are
used to obtain the hydrocarbons from raw sources. The methods
disclosed herein can also be used after refining is complete,
and/or before refining begins.
[0106] In some embodiments, when hydrocarbon mixtures and/or
components thereof are exposed to one or more ion beams, the
exposed material can also be exposed to one or more gases
concurrent with ion beam exposure. Certain components of the
mixtures, such as components that include aromatic rings, may be
relatively more stable to ion beam exposure than non-aromatic
components. Typically, for example, ion beam exposure leads to the
formation of reactive intermediates such as radicals from
hydrocarbons. The hydrocarbons can then react with other less
reactive hydrocarbons. To reduce the average molecular weight of
the exposed material, reactions between the reactive products and
less reactive hydrocarbons lead to molecular bond-breaking events,
producing lower weight fragments from longer chain molecules.
However, more stable reactive intermediates (e.g., aromatic
hydrocarbon intermediates) may not react with other hydrocarbons,
and can even undergo polymerization, leading to the formation of
heavier weight compounds. To reduce the extent of polymerization in
ion beam exposed hydrocarbon mixtures, one or more radical
quenchers can be introduced before, during, and/or after ion beam
exposure. The radical quenchers can cap reactive intermediates,
preventing the re-formation of chemical bonds that have been broken
by the incident ions. Suitable radical quenchers include hydrogen
donors such as hydrogen gas.
[0107] In certain embodiments, reactive compounds can be introduced
during ion beam exposure to further promote degradation of
hydrocarbon components. The reactive compounds can assist various
degradation (e.g., bond-breaking) reactions, leading to a reduction
in molecular weight of the exposed material. An exemplary reactive
compound is ozone, which can be introduced directly as a gas, or
generated in situ via application of a high voltage to an
oxygen-containing supply gas (e.g., oxygen gas or air) or exposure
of the oxygen-containing supply gas to an ion beam and/or an
electron beam. In some embodiments, ion beam exposure of
hydrocarbon mixtures and/or components thereof in the presence of a
fluid such as oxygen gas or air can lead to the formation of ozone
gas, which also assists the degradation of the exposed
material.
[0108] Prior to and/or following distillation in a refinery,
hydrocarbon mixtures and/or components thereof can undergo a
variety of other refinery processes to purify components and/or
convert components into other products. In the following sections,
certain additional refinery steps are outlined, and use of the
methods disclosed herein in combination with the additional
refinery steps will be discussed.
(I) Catalytic Cracking
[0109] Catalytic cracking is a widely used refinery process in
which heavy oils are exposed to heat and pressure in the presence
of a catalyst to promote cracking (e.g., conversion to lower
molecular weight products). Originally, cracking was accomplished
thermally, but catalytic cracking has largely replaced thermal
cracking due to the higher yield of gasoline (with higher octane)
and lower yield of heavy fuel oil and light gases. Most catalytic
cracking processes can be classified as either moving-bed or
fluidized bed processes, with fluidized bed processes being more
prevalent. Process flow is generally as follows. A hot oil
feedstock is contacted with the catalyst in either a feed riser
line or the reactor. During the cracking reaction, the formation of
coke on the surface of the catalyst progressively deactivates the
catalyst. The catalyst and hydrocarbon vapors undergo mechanical
separation, and oil remaining on the catalyst is removed by steam
stripping. The catalyst then enters a regenerator, where it is
reactivated by carefully burning off coke deposits in air. The
hydrocarbon vapors are directed to a fractionation tower for
separation into product streams at particular boiling ranges.
[0110] Older cracking units (e.g., 1965 and before) were typically
designed with a discrete dense-phase fluidized catalyst bed in the
reactor vessel, and operated so that most cracking occurred in the
reactor bed. The extent of cracking was controlled by varying
reactor bed depth (e.g., time) and temperature. The adoption of
more reactive zeolite catalysts had led to improved modern reactor
designs in which the reactor is operated as a separator to separate
the catalyst and the hydrocarbon vapors, and control of the
cracking process is achieved by accelerating the regenerated
catalyst to a particular velocity in a riser-reactor before
introducing it into the riser and injecting the feedstock into the
riser.
[0111] The methods disclosed herein can be used before, during,
and/or after catalytic cracking to treat hydrocarbon components
derived from alternative sources such as oil shale, oil sands, and
tar sands. In particular, ion beam exposure (alone, or in
combination with other methods) can be used to pre-treat
hydrocarbons prior to injection into the riser, to treat
hydrocarbons (including hydrocarbon vapors) during cracking, and/or
to treat the products of the catalytic cracking process.
[0112] Cracking catalysts typically include materials such as
acid-treated natural aluminosilicates, amorphous synthetic
silica-alumina combinations, and crystalline synthetic
silica-alumina catalysts (e.g., zeolites). During the catalytic
cracking process, hydrocarbon components can be exposed to ions
from one or more ion beams to increase the efficiency of these
catalysts. For example, the hydrocarbon components can be exposed
to one or more different types of metal ions that improve catalyst
activity by participating in catalytic reactions. Alternatively, or
in addition, the hydrocarbon components can be exposed to ions that
scavenge typical catalyst poisons such as nitrogen compounds, iron,
nickel, vanadium, and copper, to ensure that catalyst efficiency
remains high. Moreover, the ions can react with coke that forms on
catalyst surfaces to remove the coke (e.g., by processes such as
sputtering, and/or via chemical reactions), either during cracking
or catalyst regeneration.
(II) Alkylation
[0113] In petroleum terminology, alkylation refers to the reaction
of low molecular weight olefins with an isoparaffin (e.g.,
isobutane) to form higher molecular weight isoparaffins. Alkylation
can occur at high temperature and pressure without catalysts, but
commercial implementations typically include low temperature
alkylation in the presence of either a sulfuric acid or
hydrofluoric acid catalyst. Sulfuric acid processes are generally
more sensitive to temperature than hydrofluoric acid based
processes, and care is used to minimize oxidation-reduction
reactions that lead to the formation of tars and sulfur dioxide. In
both processes, the volume of acid used is typically approximately
equal to the liquid hydrocarbon charge, and the reaction vessel is
pressurized to maintain the hydrocarbons and acid in a liquid
state. Contact times are generally from about 10 to 40 minutes,
with agitation to promote contact between the acid and hydrocarbon
phases. If acid concentrations fall below about 88% by weight
sulfuric acid or hydrofluoric acid, excessive polymerization can
occur in the reaction products. The use of large volumes of strong
acids makes alkylation processes expensive and potentially
hazardous.
[0114] The methods disclosed herein can be used before, during,
and/or after alkylation to treat hydrocarbon components derived
from alternative sources such as oil shale, oil sands, and tar
sands. In particular, ion beam exposure (alone, or in combination
with other methods) during alkylation can assist the addition
reaction between olefins and isoparaffins. In some embodiments, ion
beam exposure of the hydrocarbon components can reduce or even
eliminate the need for sulfuric acid and/or hydrofluoric acid
catalysts, reducing the cost and the hazardous nature of the
alkylation process. The types of ions, the number of ion beam
exposures, the exposure duration, and the ion beam current can be
adjusted to preferentially encourage 1+1 addition reactions between
the olefins and isoparaffins, and to discourage extended
polymerization reactions from occurring.
(III) Catalytic Reforming and Isomerization
[0115] In catalytic reforming processes, hydrocarbon molecular
structures are rearranged to form higher-octane aromatics for the
production of gasoline; a relatively minor amount of cracking
occurs. Catalytic reforming primarily increases the octane of motor
gasoline.
[0116] Typical feedstocks to catalytic reformers are heavy
straight-run naphthas and heavy hydrocracker naphthas, which
include paraffins, olefins, naphthenes, and aromatics. Paraffins
and naphthenes undergo two types of reactions during conversion to
higher octane components: cyclization, and isomerization.
Typically, paraffins are isomerized and converted, to some extent,
to naphthenes. Naphthenes are subsequently converted to aromatics.
Olefins are saturated to form paraffins, which then react as above.
Aromatics remain essentially unchanged.
[0117] During reforming, the major reactions that lead to the
formation of aromatics are dehydrogenation of naphthenes and
dehydrocyclization of paraffins. The methods disclosed herein can
be used before, during, and/or after catalytic reformation to treat
hydrocarbon components derived from alternative sources such as oil
shale, oil sands, and tar sands. In particular, ion beam exposure
(alone, or in combination with other methods) can be used to
initiate and sustain dehydrogenation reactions of naphthenes and/or
dehydrocyclization reactions of paraffins to form aromatic
hydrocarbons. Single or multiple exposures of the hydrocarbon
components to one or more different types of ions can be used to
improve the yield of catalytic reforming processes. For example, in
certain embodiments, dehydrogenation reactions and/or
dehydrocyclization reactions proceed via an initial hydrogen
abstraction. Exposure to negatively charged, basic ions can
increase the rate at which such abstractions occur, promoting more
efficient dehydrogenation reactions and/or dehydrocyclization
reactions. In some embodiments, isomerization reactions can proceed
effectively in acidic environments, and exposure to positively
charged, acidic ions (e.g., protons) can increase the rate of
isomerization reactions.
[0118] Catalysts used in catalytic reformation generally include
platinum supported on an alumina base. Rhenium can be combined with
platinum to form more stable catalysts that permit lower pressure
operation of the reformation process. Without wishing to be bound
by theory, it is believed that platinum serves as a catalytic site
for hydrogenation and dehydrogenation reactions, and chlorinated
alumina provides an acid site for isomerization, cyclization, and
hydrocracking reactions. In general, catalyst activity is reduced
by coke deposition and/or chloride loss from the alumina support.
Restoration of catalyst activity can occur via high temperature
oxidation of the deposited coke, followed by chlorination of the
support.
[0119] In some embodiments, ion beam exposure can improve the
efficiency of catalytic reformation processes by treating catalyst
materials during and/or after reformation reactions occur. For
example, catalyst particles can be exposed to ions that react with
and oxidize deposited coke on catalyst surfaces, removing the coke
and maintaining/returning the catalyst in/to an active state. The
ions can also react directly with undeposited coke in the
reformation reactor, preventing deposition on the catalyst
particles. Moreover, the alumina support can be exposed to suitably
chosen ions (e.g., chlorine ions) to re-chlorinate the surface of
the support. By maintaining the catalyst in an active state for
longer periods and/or scavenging reformation by-products, ion beam
exposure can lead to improved throughput and/or reduced operating
costs of catalytic reformation processes.
(IV) Catalytic Hydrocracking
[0120] Catalytic hydrocracking, a counterpart process to ordinary
catalytic cracking, is generally applied to hydrocarbon components
that are resistant to catalytic cracking. A catalytic cracker
typically receives as feedstock more easily cracked paraffinic
atmospheric and vacuum gas oils as charge stocks. Hydrocrackers, in
contrast, typically receive aromatic cycle oils and coker
distillates as feedstock. The higher pressures and hydrogen
atmosphere of hydrocrackers make these components relatively easy
to crack.
[0121] In general, although many different simultaneous chemical
reactions occur in a catalytic hydrocracker, the overall chemical
mechanism is that of catalytic cracking with hydrogenation. In
general, the hydrogenation reaction is exothermic and provides heat
to the (typically) endothermic cracking reactions; excess heat is
absorbed by cold hydrogen gas injected into the hydrocracker.
Hydrocracking reactions are typically carried out at temperatures
between 550 and 750.degree. F., and at pressures of between 8275
and 15,200 kPa. Circulation of large quantities of hydrogen with
the feedstock helps to reduce catalyst fouling and regeneration.
Hydrocarbon feedstock is typically hydrotreated to remove sulfur,
nitrogen compounds, and metals before entering the first
hydrocracking stage; each of these materials can act as poisons to
the hydrocracking catalyst.
[0122] Most hydrocracking catalysts include a crystalline mixture
of silica-alumina with a small, relatively uniformly distributed
amount of one or more rare earth metals (e.g., platinum, palladium,
tungsten, and nickel) contained within the crystalline lattice.
Without wishing to be bound by theory, it is believed that the
silica-alumina portion of the catalyst provides cracking activity,
and the rare earth metals promote hydrogenation. Reaction
temperatures are generally raised as catalyst activity decreases
during hydrocracking to maintain the reaction rate and product
conversion rate. Regeneration of the catalyst is generally
accomplished by burning off deposits which accumulate on the
catalyst surface.
[0123] The methods disclosed herein can be used before, during,
and/or after catalytic hydrocracking to treat hydrocarbon
components derived from alternative sources such as oil shale, oil
sands, and tar sands. In particular, ion beam exposure (alone, or
in combination with other methods) can be used to initiate
hydrogenation and/or cracking processes. Single or multiple
exposures of the hydrocarbon components to one or more different
types of ions can be used to improve the yield of hydrocracking by
tailoring the specific exposure conditions to various process
steps. For example, in some embodiments, the hydrocarbon components
can be exposed to hydride ions to assist the hydrogenation process.
Cracking processes can be promoted by exposing the components to
reactive ions such as protons and/or carbon ions.
[0124] In certain embodiments, ion beam exposure can improve the
efficiency of hydrocracking processes by treating catalyst
materials during and/or after cracking occurs. For example,
catalyst particles can be exposed to ions that react with and
oxidize deposits on catalyst surfaces, removing the deposits and
maintaining/returning the catalyst in/to an active state. The
hydrocarbon components can also be exposed to ions that correspond
to some or all of the metals used for hydrocracking, including
platinum, palladium, tungsten, and nickel. This exposure to
catalytic ions can increase the overall rate of the hydrocracking
process.
(V) Other Processes
[0125] A variety of other processes that occur during the course of
crude oil refining can also be improved by, or supplanted by, the
methods disclosed herein. For example, the methods disclosed
herein, including ion beam treatment of crude oil components, can
be used before, during, and/or after refinery processes such as
coking, thermal treatments (including thermal cracking),
hydroprocessing, and polymerization to improve the efficiency and
overall yields, and reduce the waste generated from such
processes.
Particle Beam Exposure in Fluids
[0126] In some cases, the hydrocarbon-containing materials can be
exposed to a particle beam in the presence of one or more
additional fluids (e.g., gases and/or liquids). Exposure of a
material to a particle beam in the presence of one or more
additional fluids can increase the efficiency of the treatment.
[0127] In some embodiments, the material is exposed to a particle
beam in the presence of a fluid such as air. Particles accelerated
in any one or more of the types of accelerators disclosed herein
(or another type of accelerator) are coupled out of the accelerator
via an output port (e.g., a thin membrane such as a metal foil),
pass through a volume of space occupied by the fluid, and are then
incident on the material. In addition to directly treating the
material, some of the particles generate additional chemical
species by interacting with fluid particles (e.g., ions and/or
radicals generated from various constituents of air, such as ozone
and oxides of nitrogen). These generated chemical species can also
interact with the material, and can act as initiators for a variety
of different chemical bond-breaking reactions in the material. For
example, any oxidant produced can oxidize the material, which can
result in molecular weight reduction.
[0128] In certain embodiments, additional fluids can be selectively
introduced into the path of a particle beam before the beam is
incident on the material. As discussed above, reactions between the
particles of the beam and the particles of the introduced fluids
can generate additional chemical species, which react with the
material and can assist in functionalizing the material, and/or
otherwise selectively altering certain properties of the material.
The one or more additional fluids can be directed into the path of
the beam from a supply tube, for example. The direction and flow
rate of the fluid(s) that is/are introduced can be selected
according to a desired exposure rate and/or direction to control
the efficiency of the overall treatment, including effects that
result from both particle-based treatment and effects that are due
to the interaction of dynamically generated species from the
introduced fluid with the material. In addition to air, exemplary
fluids that can be introduced into the ion beam include oxygen,
nitrogen, one or more noble gases, one or more halogens, and
hydrogen.
Process Water
[0129] In the processes disclosed herein, whenever water is used in
any process, it may be grey water, e.g., municipal grey water, or
black water. In some embodiments, the grey or black water is
sterilized prior to use. Sterilization may be accomplished by any
desired technique, for example by irradiation, steam, or chemical
sterilization.
Other Embodiments
[0130] A number of embodiments of the invention have been
described. Nevertheless, it will be understood that various
modifications may be made without departing from the spirit and
scope of the invention. Accordingly, other embodiments are within
the scope of the following claims.
* * * * *
References