LICENSE AGREEMENT
EXHIBIT 10.1
License
Agreement made effective this 14th day of October, 2009 (the "Effective Date")
by and between Global Resource Corporation as Licensor (hereinafter called
"Licensor"), a Nevada corporation having a principal place of business at 0000
Xxxxxx Xxx, Xxxxx 000, Xxxxx Xxxxxx, Xxx Xxxxxx 00000 and Universal Alternative
Fuels, Inc., as Licensee (hereinafter called "Licensee"), a Nevada corporation
having a principal place of business at 0000 Xxx Xxxxxxx Xxxx, Xxxxx 000,
Xxxxxxxx, XX 00000.
WHEREAS,
Licensor has developed certain microwave technology for the recovery of
commercially usable energy or energy-producing materials, such as oil and gas,
together with by-products which may have commercial value, and Licensor has
filed certain patent applications for the protection of such technology, which
patent applications are pending;
WHEREAS,
Licensor continues, and has continued, directly, and indirectly through
contractors (e.g., Ingersoll Production Systems), to perform research and
development and has improved upon, added to, and enlarged its technology beyond
the content of the patents pending, and intends to continue to do
so;
WHEREAS,
Licensee desires to establish a business of (a) selling machines embodying the
microwave technology of Licensor as applied to oil shale and coal to recover
commercially usable energy, energy-producing materials and by-products from such
sources and (b) using such machines itself for the recovery of energy,
energy-producing materials and by-products from oil shale and/or coal and (c)
sub-licensing the use of the Technology, the pending Continuation Application
and the process hereinafter described within the Licensed Field of
Use;
WHEREAS,
Licensor has filed a continuation application with the U.S. Patent and Trademark
Office ("PTO") for the microwave processing of (i) oil shale and (ii) coal, a
true and complete copy of which is attached as Schedule A to this License
Agreement (the "Continuation Application");
WHEREAS,
Licensee desires to secure an exclusive, royalty-free world-wide license for the
application of the Licensor's Technology (now or hereafter acquired) and the
patents pending to the recovery of energy, energy-producing materials and
by-products from oil shale and/or coal, for the foregoing business
purposes;
WHEREAS,
Licensor is agreeable to licensing Licensee, on an exclusive and royalty-free
basis, world-wide, for the use of the Technology solely in the Licensed Field of
Use and the patents pending for the recovery of energy, energy-producing
materials and by-products from oil shale and/or coal, for the foregoing
business purposes of Licensee;
WHEREAS,
Licensee acknowledges that Licensor has entered into a JDA with Schlurnberger
for the development of the technology as applied to heavy oils, and Licensor and
Licensee agree that this License Agreement does not include any application
covered by the subject matter of the JDA with Schlumberger; and Licensee also
acknowledges its awareness of a Marketing and Licensing
Agreement (the "C6 Agreement") entered into by Licensor with C6 Energy Pty. Ltd
("C6") which is the subject of a termination notice by Licensor;
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WHEREAS,
the parties have negotiated and have reached certain
understandings, and desire a document to evidence and formalize such
understandings;
WHEREAS, in connection and simultaneous
with the execution of this License Agreement,
the
Licensor has executed a
Security Agreement (the "Security Agreement") granting
the Licensee security
interests in the Continuation
Application and
the
Existing Prototype Machine currently located at the Ingersoll
plant in Rockford, Illinois (together, the "Security
interests");
NOW,
THEREFORE, intending to be legally bound and in consideration of the mutual
promises and covenants contained
herein, and for other good and valuable consideration, the receipt and
adequacy of which are hereby
acknowledged, the
parties have agreed, and do hereby agree, as follows:
ARTICLE
I - DEFINITIONS
For the
purpose of this License Agreement, and solely for that purpose, the terms
set forth hereinafter shall be defined as follows:
(a) "Cost to Manufacture" shall mean all
direct costs the Licensor incurs in connection with the manufacture of any machine,
such as (i) raw materials, parts and sub-assemblies, (ii) direct, manufacturing labor, (iii)
utilities, and (iv) reasonable depreciation of directly-used tools, machines, and the
manufacturing facility but there shall be specifically excluded from this
calculation of cost all of
the following: any research and development expenses of Licensor and or its contractor(s) (e.g.,
Ingersoll Production Systems); the general and
administrative overhead (G&A) of Licensor and/or its contractor(s),
salaries and employee benefits of Licensor's and its contractor(s)'
employees
other than of those engaged directly in the manufacturing process; and
any and all
other non-manufacturing costs and expenses of Licensor and/its contractor(s).
(b) "Existing Prototype Machine"
shall mean that certain existing prototype machine of the Licensor at the
date hereof located
in Rockford, Illinois known as
the "PPS-TR Microwave Prototype Processor", as more
specifically described in Schedule B attached hereto and made a part
hereof.
(c) "Licensed Field of Use" shall
mean
microwave
energy applications relating to the recovery from (i)
oil shale and (ii) coal to recover commercially usable energy,
energy-producing
materials and by-products from
such sources, whether by its own use of machines embodying the Technology, the sale of
machines embodying the Technology or the sub-licensing of the
Technology in the
Licensed Field of Use.
(d) "Licensed Process" shall mean a method
or process in the Licensed Field of Use either covered by the Patent Rights or
by the Technology (now or hereafter acquired).
(e) "Licensed Product(s)" shall mean a
product in the Licensed Field of
Use that is covered by the Continuation Application, Patent Rights
and/or Technology.
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(f) "Licensed
Territory" shall mean all countries of the world.
(g) "Parties"
shall mean Licensor and Licensee, and "Party" shall mean Licensor or Licensee
as the text may dictate.
(h)
"Patent Rights" shall mean the patents and/or patent applications identified in
the Continuation Application, together with any divisional, continuation, or
continuation-in-part applications based thereon, any patents resulting from any
of said applications and any reissues or extensions that may be based on any of
said patents, and shall also include all improvements, modifications,
enlargements and extensions made to any of the Patent Rights during the term of
this License Agreement. For the avoidance of doubt, the Patent Rights relating
to the License shall be limited to the Licensed Field of Use.
(i) The phrase "covered by the Patent
Rights" and equivalent language as used herein shall mean covered by a valid claim of
an issued, unexpired patent within the Patent Rights or by a claim being presented in a pending
patent application within the Patent Rights. Any claim being presented in a pending
patent application shall
be deemed to be the equivalent of a valid claim of an issued, unexpired patent
for purposes of the grant of the License.
(j) "Seller"
shall mean one who sells.
(k)
"Sublicensee" shall mean a sublicensee pursuant to Article IV (a)
hereof;
(l)
"Technology" shall mean the microwave technology of Licensor as applied to oil
shale and/or coal only and shall include for this purpose not only the content
of the Patent Rights and the content of any future patents issued or applied for
in the Licensed Field of Use, but all improvements, modifications, enlargements
and extensions thereto, now or hereafter existing, whether or not Licensor seeks
additional patent protection thereon, together with all software programs used
to design, install and operate the machines, all proprietary data and trade
secrets, all know-how, inventions and discoveries (whether patentable or not),
invention disclosures, improvements, trade secrets, proprietary information,
know-how, technology,
technical data, supplier lists and customer lists and all documentation
relating to any of the foregoing; databases, data collections and content and
all rights therein, throughout the world (collectively "Data Collections"); all
computer software, including all source code, object code, firmware, development
tools, files, records data, and documentation (including design
documents, flowcharts and specifications therefor), and all media on which any
of the foregoing is recorded (collectively "Software");
(m) "Trademarks"
shall mean all trademarks, trade names, service marks, corporate
names
brand names, trade dress, designs and
logos and other source indicators, and all registrations and applications for
registration thereof and all other rights corresponding thereto throughout the
world, together with the goodwill of any business
symbolized thereby of the Licensor that relate to the Patent Rights in
the Licensed Field of Use; and
(n)
"Used" (or "Use") shall mean use of
the Patent Rights or the Technology within the Licensed Field of Use in return for
any form of consideration having monetary value including for this
purpose equity ownership or investment in any entity regardless of the
form of ownership or investment.
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ARTICLE
II - LICENSE
(a) (i)
Licensor hereby grants and agrees to grant to Licensee and Licensee hereby
accepts and agrees to accept from Licensor, upon the terms and conditions herein
specified, an exclusive, world-wide, royalty-free license, with right to
sublicense, in the Licensed Field of Use under the Patent Rights and the
Technology (i) to practice the Licensed Process as a service to others or for
the
Licensee itself, (ii) to make, to have made, to use in the practice of
the Licensed Process and to sell, offer to sell, lease, distribute, export and
import Licensed Products in the country or countries in which the Patent Rights
are or shall be in effect and in each such country's territories and
possessions, and (iii) to use the Licensor's Trademarks associated therewith, to
the full end of the term or terms for which the Patent Rights and the Technology
are or shall be issued, unless the license or this License Agreement
shall be sooner terminated as hereinafter provided.
(a) (ii)
Licensor agrees to indemnify and hold harmless Licensee and
each of
its respective members, managers, officers, directors, agents, employees
and affiliates (a "Licensee Party") from and against any and all losses, claims,
damages or liabilities, including penalties on reserves, to which it may
become subject that result from any claim asserted by any other party licensed
by or contracting with Licensor against Licensee
Party
arising out of, related to or in connection with any Licensor contract
regardless of how such claim is denominated or described, and
including all suits, actions, proceedings, demands, assessments,
judgments, costs, reasonable attorneys' fees and
expenses incident to any of the foregoing
matters, including those reasonable costs, charges and expenses
(including any expenses resulting from any
investigation or inquiry) with
respect to the participation of any Licensee
Party in defense thereof, whether or not the
Licensee
Party is named as
a party.
(b) The
foregoing grant and acceptance of the License is specifically made subject to an
option on
the part of the Licensor to repurchase the
License and retain the Existing Prototype Machine upon certain terms and
conditions as follows:
(i)
Contemporaneously with the execution
of this License Agreement, Licensee has given
Licensor a Purchase Order for an initial machine (Licensed
Product) embodying
the
technology
adapted for use with oil
shale (referred to in this
License Agreement as the
"initial machine" as differentiated from the
Existing Prototype Machine, as defined), Licensee shall have a "wait and
see" period of
hundred eighty
(180) days from the
date of this License Agreement)
to terminate that purchase order for the initial machine; but such right
is dependent upon
Licensor's failure, within one hundred fifty (150) days from the date of this
License Agreement,
to raise at least Three Million Four Hundred Thousand Dollars ($3,400,000)
in additional equity capital (which for this purpose shall include debt,
if convertible into common stock of the Licensor). If Licensor fails to achieve
such financing, Licensee shall
have the right (but not
the obligation) to terminate the Purchase Order. In the event that
Licensee so elects, then Licensor shall have a period of ten (10) days
in which to determine whether
it wishes to repurchase
this License and retain the Existing Prototype Machine in Rockford,
Illinois. The repurchase
and retention price shall be $1,700,000, including return of the Seven
Hundred Fifty Thousand Dollars ($750,000) paid as
license
fee
hereunder and reimbursement to Licensee of the $843,000
in costs incurred in connection
with this License Agreement. If Licensor
elects to repurchase and retain, it shall pay the sum of $1,700,000
within twenty (20) further days. If the repurchase/retention
is not timely accomplished by
Licensor, its option to repurchase/retain shall be null and void and of
no further effect.
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(ii) During the one hundred eight (180)
day "wait and see" period, Licensor and Licensee shall cooperate in
performing the necessary tests,
analyses, experiments, and research to determine the efficacy and efficicney
of the Technology to (i) oil shale and (ii) coal. If Licensee determines within its sole
discretion and
whether or not reasonably, that such Technology is not sufficiently
viable, efficacious or efficient within the Licensed Field of Use, then Licensee
shall have the
right (but not the
obligation), to terminate the Purchase Order. In the event that Licensee
so elects,
then Licensor shall have a period of ten (10) days in which to determine
whether it wishes to
repurchase this License and retain the Existing Prototype Machine in
Rockford. The repurchase price shall be
$1,700,000, including return of the Seven Hundred Fifty
Thousand
Dollars ($750,000) paid as
license fee hereunder and reimbursement to Licensee
of the $843,000 in costs incurred in connection with this
License Agreement. If Licensor elects to
repurchase
and retain, it shall pay
the sum of $1,700,000 within twenty (20) further days. If the
repurchase/retention is
not timely
accomplished by Licensor, its option to repurchase/retain shall be null and void and of no
further effect.
(c) In the event that Licensee exercises
its option to terminate the purchase order and Licensor either (i)
does not elect to repurchase this License Agreement and
retain the Existing Prototype Machine in Rockford, Illinois
or (ii) elects to repurchase and
retain but fails to timely
pay the $1,700,000, then
in such case Licensee shall retain the exclusive license for
which it has paid, shall
have the right to foreclose its security interest in and to the Patent Rights
and the Existing Prototype
Machine, pursuant to the contemporaneously granted Security Agreement,
and shall have the right
to take immediate and exclusive
possession and ownership of the Existing Prototype
Machine.
(d) In the
event that Licensee exercises its option to terminate the purchase order and
Licensor elects to repurchase
this License Agreement and retain the Existing Prototype Machine and
timely pays the $1,700,000, then this License Agreement shall
terminate
and (i) Licensee shall have no further rights hereunder and (ii)
Licensor's twenty
percent (20%) equity interest in Licensee shall terminate and be
rescinded ab initio, and (iii) all Security Interests on the Technology and
Existing Prototype Machine shall terminate and be released.
ARTICLE
III - EXCLUSIVITY
(a) Subject to the provisions of
Articles IV
and XIII hereof, the license herein granted under the Patent Rights shall
be exclusive to Licensee worldwide for a
period of time extending until the first to occur of
either: (i) termination of this License Agreement; or (ii) the expiration or lapsing of the last patent to expire
within the
Patent Rights in the respective countries in which applications for the
Patent Rights have been filed.
(b) The
Licensor shall manufacture all machines to be sold to
Licensee or
Sublicensees under
this License Agreement; provided, however, that in the event the Licensor
is unable to manufacture any machine for
any order hereunder within the time period allotted
for any specific contract of purchase, then the Licensee
shall
have the right to undertake to manufacture any such machine at its own
cost and expense for its own use or for resale to a Sublicensee,
and such action by the Licensee shall not constitute a breach of or
default under this Agreement. In any such ease, the Licensor shall not
be entitled to receive any payment under Article VI of this License Agreement.
All machines manufactured and delivered by Licensor shall
comply in all respects
with all governmental and regulatory permits and authorizations including but
not limited to
environmental and pollution matters, worker safety and fire and other hazards.
If Licensor's failure
to manufacture a machine in response to a Licensee order occurs more than
twice within any
successive 24 month period, then Licensee shall be
permitted to organize
its own methods for
manufacturing new machines and in such case, Licensor
shall not be entitled to receive any fixed payments for the
machines under Article VI.
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ARTICLE
IV - SUBLICENSING PROVISIONS
(a) Licensor
hereby grants and agrees to grant to Licensee, and Licensee hereby accepts and
agrees to accept from Licensor, upon the terms and conditions herein specified,
within the
Licensed Field of Use a nonassignable right and power
to
grant to others (Sublicensees"),
upon
reasonable
terms and conditions, nonassignable royalty-bearing or royalty-free
sublicenses under the Patent Rights to use or
resell the
Licensed Product and/or practice the
Licensed
Process in the
country or countries in which the Patent Rights are
or shall be in
effect
and in each
such country's
territories and possessions solely within the Licensed Field of
Use.
(b) Any Sublicense in effect at the
termination of this License Agreement shall remain in effect, but for the benefit of
Licensor and Licensee; providing the Sublicensee shall continue to make all reports and payments due
and owing under its sublicensing agreement and is not otherwise in breach or default
thereunder, such reports and payments then to be made to Licensor and
Licensee
rather than Licensee
alone.
ARTICLE
V - LICENSE FEE
(a)
Upon execution and delivery of this License Agreement, Licensee shall pay to
Licensor, an aggregate license fee
comprised of the following:
(1) a
one-time payment
of Seven Hundred
Fifty Thousand Dollars ($750,000);
(2) restricted shares
of Licensee equal to twenty percent (20%) of the
issued and
outstanding shares
of common stock of Licensee at the date
of
issuance (the "Ownership Percentage
Amount"). Licensee agrees to issue
additional shares of common stock to Licensor such that Licensor
always shall own that number of shares of Licensee common stock as is
equal
to the Ownership Percentage Amount at any time through and including the period
that ends one (1) year
after the "reorganization" of Licensee as defined in the next following
sentence. For a
period ending one (1) year after the Reorganization (the "Period") (except as
provided in
subsection (3) following), Licensor shall maintain its Ownership Percentage
Amount on the
reorganization of Licensee, whether by exchange agreement, merger, consolidation
or any other form of recapitalization or restructure into or with a public
corporation (the
"Reorganization").
Licensee shall take all actions reasonably necessary to ensure that Licensor
maintains its Ownership Percentage Amount in Licensee at the
Reorganization date and throughout the Period; provided, however, that
after the expiration of the Period
Licensor shall be subject to
dilution of its Ownership Percentage Amount together with all other stockholders of
Licensee.
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(3)
Licensor
acknowledges that Licensee
and any public corporation with
which it may engage in a Reorganization will be
required to seek either or both of private and/or public financing. In such event,
Licensor's Ownership Percentage
Amount shall be subject to
dilution pro
rata with all other
shareholders, notwithstanding any language to the contrary in subsection
(a)
(2) of this Article
V.
ARTICLE
VI - PURCHASE OF LICENSED PRODUCT; MANUFACTURE AND PURCHASE OF
PROTOTYPE AND MACHINES
(a) As
provided in Article III (b), subject to Licensor's ability to manufacture
machines for Licensee, whether for the use of the Licensee
or for resale by the Licensee, Licensor shall have the exclusive right to
manufacture all machines to be sold to Licensee
or
Sublicensees under
this License Agreement. Licensor's right to manufacture the machines may
be exercised
by the
Licensor directly or via the outsourcing of such
manufacture to one or more subcontractors as Licensor shall determine in
its sole and
absolute discretion.
(b) Contemporaneous
with the execution of this License Agreement, Licensee
shall place an order with Licensor for the manufacture of an initial
machine specifically
intended to be used on oil
shale. The Purchase Order for such machine shall be subject to
termination, as provided in Article II (b). The purchase price for such
initial machine shall be (1) the Licensor's Cost to Manufacture the Licensed
Product
plus (ii) twenty percent (20%) of the Licensor's Cost to manufacture
the
Licensed Product, plus (iii) such mutually
agreed amount for
research and development and testing, but not to exceed
Three Million Five Hundred Thousand Dollars ($3,500,000). Licensor
acknowledges that Licensee has
incurred various costs and expenses mutually
agreed to total Eight Hundred Forty Three Thousand Dollars ($843,000) in
preparation for this License Agreement and, accordingly, Licensor shall give
Licensee a credit of $843,000 against
the purchase price which shall be deducted from the final payment.
The
balance shall be
paid by
Licensee as follows:
(i) $500,000 at the end of six (6)
months from the date of the Purchase
Order,
(ii) $500,000
at the end of nine (9) months from the date of the
Purchase Order; and
(iii) the balance, after the application of the
$843,000 credit, upon completion of the initial machine, demonstration that it meets
the warranted purpose, and acceptance by
Licensee.
(c) The Purchase Order shall
be subject to the right of
Licensee to terminate the purchase order at the end of one hundred (180) days from the date of this License Agreement
as provided in
Article II (b).
Licensor's right to terminate shall he subject to Licensor's right to repurchase
this License Agreement and
retain the Existing Prototype Machine as further provided in Article II (b). Depending
upon the events that then
occur, the provisions of Articles II (c) and/or Article
shall be
applicable.
(d) During
such period that Licensor shall have the exclusive right to
manufacture machines,
Licensee shall order all machines, whether for its own use or for
resale to Sublicensees,
from Licensor and shall pay to Licensor therefor a purchase price
determined as follows:
(1) The Licensor's Cost to Manufacture
the Licensed
Product, and the lesser of
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(2)
either (i) fifty percent (50%) of the difference between the Licensor's Cost to
Manufacture the Licensed Product and the Licensor's actual sale price of the
Licensed Product to arm's length bona fide third party customers or (ii) twenty
percent (20%) of the Licensor's Cost to manufacture the Licensed
Product.
All
revenues of
the Licensee from the sale or resale of the Licensed Products to a third
party above the total of (1) and (2) shall belong to the Licensee.
Such
purchase price shall be paid by Licensee as follows:
(i) one-third
upon placement of the order;
(ii) one-third
upon completion by Licensor of fifty percent (50%) of the machine;
and
(iii)
one-third upon completion of the machine, demonstration that it meets the
warranted purpose, and acceptance by Licensee.
ARTICLE
VII - PATENT RIGHTS
(a) Licensor
shall
upon request of Licensee advise Licensee as to the status of any patents
and patent applications within the Patent Rights and the Technology as applicable
or potentially applicable within the Licensed Field of Use.
(b) In the event that
Licensor does not desire to file a particular patent application in the
Licensed Field of
Use or discontinues its responsibility for prosecution or maintenance of a
particular patent
application or applications or discontinues its responsibility for the
maintenance of a particular
patent in Patent Rights listed in Schedule A, Licensor shall
notify Licensee promptly in
writing of its intention and, in the case of
proposed discontinuances, at least sixty (60) days prior to the
effective date
thereof, in order
to permit Licensee to determine whether it wishes to assume the
responsibility therefor. Licensee shall have the
right and option, but not the obligation, to assume the
responsibility for filing, prosecution and maintenance of such patent
applications
and
patents therefor
which Licensor desires
not to prosecute or to
discontinue. Licensee
shall inform Licenser in writing
of
its decision to assume
the responsibility for filing, prosecution and maintenance of
such patent applications and patents, and Licensor
promptly execute
and deliver such
documents and take such actions as are reasonably necessary or
appropriate to assign such patent or patent application to Licensee and making
the inventor reasonably available to assist in the prosecution of any such
applications. Upon assignment of patent or patent application
to Licensee, said patent and/or patent application shall be removed from
the Patent Rights and no longer subject to this License Agreement.
(c) Licensor shall
promptly inform Licensee in writing of any Patent Rights in the Licensed
Field of Use that were filed with a Patent Office or invented subsequent to the
effective date of this License Agreement. Licensor covenants that Patent Rights
in the Licensed Field of
Use that were filed with a Patent Office or invented subsequent to the
effective date of this License Agreement shall be included in their entirety
within the scope of this License Agreement upon the same terms and
conditions and without any additional payment or
alteration of the existing fixed
payments or royalties payable by Licensee to Licensor under this
Agreement.
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(d)
Licensor shall upon request of Licensee inform Licensee of the issuance of all
licenses
granted by it to other Licensees under any of the Patent Rights in the event
that any such licenses shall be legally required to be granted.
ARTICLE
VIII - DEVELOPMENT AND
REGULATORY APPROVAL
(a)
Licensor will develop the Licensed Product and the Licensed Process for
commercialization at Licensor's sole and complete expense including the
research, planning, development and
manufacture
of prototypes and finished product working models of all Licensed Product
using the Licensed Process
and the Technology to be sold to Licensee or any Sublicensee. Licensor
shall also be responsible for
all costs of obtaining all regulatory and
governmental permits and authorizations
as may
be required. (b) Licensee shall control the process for
obtaining marketing licenses
and approvals for the Licensed Product and the Licensed Process. Licensee
shall bear the
complete costs for obtaining the regulatory and
marketing approvals for the Licensed Product and
the Licensed Process including all costs arising out of or related to modifying
or altering any machine
after it has been manufactured to conform to said requirements. (c)
Licensor will in good faith participate in and provide necessary information,
and data which may be necessary for obtaining regulatory and/or marketing approvals
for the Licensed Product and the Licensed Process, and
Licensee
agrees
to reimburse Licensor for all
commercially reasonable expense incurred
by such participation; provided, however, that all regulatory licenses and
approvals that require
modifications to the prototypes or any existing Licensed Products shall
future be at the sole cost and expense of the Licensor.
ARTICLE
IX - DILIGENCE
(a) Licensor shall
use
commercially
reasonable efforts in
developing, testing, and manufacturing
Licensed Products. Licensee shall use commercially reasonable efforts in
promoting,
advertising and selling the Licensed Products and
the
Licensed Process under this
License Agreement and in seeking responsible Sublicensees.
(b) Licensor
shall use reasonable efforts, at its expense, to prosecute any patent
applications
within the Licensed Field of Use, to obtain patents thereon and to
maintain any such patents.
(c) Licensor
shall
use reasonable efforts to submit
to
the appropriate authority in the
United States and
overseas patent claims related to the Patent Rights. Licensor shall promptly
provide Licensee
with copies of all patents, patent applications and other filings and
any communications
with the applicable patent office, including without limitation, all office
actions
and responses related to the Patent
Rights. Licensee
shall have no obligation to contribute,
in whole or part, to the costs of preparing, filing, prosecuting, issuing,
defending or maintaining
the
patents and patent
applications under this Article IX (c), except
as
otherwise
provided
in Article VII (b).
ARTICLE X - TERMINATION
(a)
Upon any breach of or default under this License Agreement by License, Licensor
may terminate this
License Agreement by sixty (60) days' written notice to
Licensee specifying
in
reasonable detail the nature of the default. Said notice shall become effective
at the end of said period, unless during said period Licensee shall
substantially cure such breach or default.
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(b) If the Licensor
dissolves, becomes insolvent or has a receiver appointed for all or any
part of its property, or makes
an assignment for the benefit of
creditors, or voluntarily commences or has filed
against it an involuntary proceeding under any bankruptcy or insolvency
laws which results in the
entry of an order for relief or which remains undismissed, undischarged
or unbonded for a period of 60 days or
more, and Licensee is unable to continue to use the license granted
hereunder for the Licensed Process or the Licensed Products, then (1) the Continuation
Application, the Patent Rights, the Technology and the Trademarks within
the Licensed Field of Use shall, ipso facto, and without any
additional documentation become the property of and ownership and title
shall vest in, the Licensee. In such a case, Licensee
shall, subject to
applicable federal bankruptcy and state insolvency laws, be permitted to
assume this
Agreement and to
perform
hereunder, and Licensor shall
cooperate in all respects and
furnish all assistance
reasonably necessary or required
to
enable Licensee to
continue to
obtain
the benefits of this License Agreement. Licensor hereby irrevocably
appoints Licensee as the Licensor's attorney-in-fact, with full authority in the
place and stead of Licensor and in the name of
Licensor or
otherwise, from time to time in Licensee's discretion, upon the Licensor's
failure or inability
to do
so, to take any action and
to execute any instrument and make any
filing with any regulatory authority or otherwise which Licensee may deem necessary
or advisable to accomplish the purposes of this Agreement,
including:
(i) To
modify, in its sole
discretion, this License Agreement without first obtaining Licensor's approval of
or signature to such modification by amending the definitions of Patents, Patent Rights,
Technology and Trademarks hereof, as appropriate within the Licensed
Field of Use, to include
reference to any right, title or interest in any Patents, Patent Rights, Technology and Trademarks
acquired by Licensor after the execution hereof or to delete any reference to any right, title or interest in any
Patents,
Patent Rights, Technology
and Trademarks in which
Licensor no longer has or claims any right, title or interest;
and
(ii) To file, in its sole discretion,
one or more financing or continuation statements
and amendments
thereto, or filings with
the U.S. Patent and Trademark Office or any similar foreign office performing a similar
function relative to any of the
foregoing without the
signature of
Licenser where permitted by law.
ARTICLE
XI - ASSIGNMENT
This
License Agreement shall not
be assigned by either party without the prior written consent of the other Party hereto;
provided, however, that a change of control of the Licensee, or its Reorganization with or into a
public company us provided in Article V, regardless of the form of the Reorganization, shall not
be deemed an assignment for purposes
of this License
Agreement.
10
ARTICLE
XII -
INFRINGEMENT
(a) (i)
In the event that any legal proceeding shall be instituted or threatened against
Licensee or any of its Sublicenses involving any claim of infringement
relating to the development, manufacture, import,
use, purchase
or sale of a Licensed
Product, or Licensed
Process, Licensee
will
notify Licenser thereof.
Licensor
shall have thirty (30) days after receipt
of the
above-mentioned notice to undertake, conduct
and control,
through counsel of its own choosing (subject to the consent of Licensee,
such consent not to be
unreasonably withheld) and at its expense, the settlement or
defense thereof, and the Licensee shall cooperate with Licensor in connection
therewith; provided that (i) Licensor shall not thereby permit to exist
any lien, encumbrance or other adverse
charge upon any asset of Licensee; (ii) in the event it appears likely,
in the reasonable judgment of the
Licensee, that different defenses are available to the Licensee or that a
conflict of interest may arise between the Licensee and the Licensor with
respect to such claim, the Licensee shall choose its own counsel, and the
reasonable fees and expenses of such counsel shall be home by the Licensor;
(iii) in the event
it appears that no conflict of interest will arise between the Licensee
and the Licensor and the Licensee desires to choose its counsel, the Licensor
shall permit the Licensee to participate in such settlement or defense through
such counsel chosen by the
Licensee, provided that the
fees and expenses of such counsel shall be borne
by the Licensee; and (iv) the
Licensor shall agree promptly to reimburse
the Licensee for the full amount
of any loss resulting from such claim and all
related
expenses incurred by the Licensee. So long as the Licensor is reasonably
contesting any such claim in
good faith, the Licensee shall not pay or settle any such claim.
Notwithstanding the foregoing, and provided that no rights of Licensor
are thereby in any way compromised or infringed, the Licensee shall have
the right to pay or
settle any such claim, provided that in such event the Licensee shall
waive any right to indemnity, contribution or any other form of repayment
therefor (however described) by the Licensor, and reimburse the Licensor for any
payments made to the date of the
settlement. If the Licensor does not notify the Licensee within thirty
(30) days after receipt of the
Licensee's notice of a claim of indemnity hereunder that it elects to
undertake the defense thereof, the
Licensee or its Sublicensee shall have the right to contest, settle or
compromise the claim in the exercise of its exclusive discretion at the expense
of the Licensor, and the reasonable
costs and expenses (including but not
limited to reasonable attorneys' fees and expenses) incurred by them in
connection with the defense
of such claim, at the expense of Licensor.
Licensee shall xxxx Licensor monthly for all costs and expenses incurred
in the defense of any
such claim, and Licensor
shall promptly remit payment of all such bills to Licensee Licensor's
failure to make such payment shall be a material default under
this License Agreement. Licensor shall be entitled to participate
in any such suit or action with its own counsel at its own expense. In
the event of any claim under this Article XII, each of Licensor and Licensee
shall (1) fully cooperate with each other in connection with any
such claim, (2) on
reasonable notice have any of its employees, officers, directors, agents
and other representatives testify when necessary,
and (3) on reasonable notice make available to each other as necessary
all relevant records, specimens, samples
and other information in its possession at its own expense.
(a) (ii) If,
as a result of any such claim described
in "(a)" above, Licensee or its Sublicensee is required by reason of an
order of a court, arbitration board or other similar body or by reason of a
settlement between the parties, to pay a royalty or make other similar payments
to a third party, on if as a result of such claim, Licensee or its Sublicensee
is obligated to pay damages
other than a royalty to a third party, Licensor shall be responsible for
all such damages,
and
shall defend, indemnify and hold harmless Licensee with respect
thereto.
(b) Licensee,
as exclusive Licensee, shall
have the power, but not the obligation, to institute,
prosecute
and settle, at its own expense, suits for infringement of the Patent Rights
and/or
Licensed Process
within the Licensed Field of Use,
and if,
required
by
law, Licensor
will join
as parry
plaintiff
in
such suits. Licensee shall be entitled
to all recoveries
in such suits.
11
Licensor shall
(1)
fully cooperate with
Licensee in connection with
any such
proceeding, (2) on reasonable notice
have any of its employees, officers, directors, agents and other representatives
testify when
necessary, and (3) on reasonable notice make available to Licensee as accessary
all relevant records,
specimens, samples and other information in its possession all at commercially
reasonable
expense of Licensee.
(c)
In the event
that Licensee
declines to pursue any claim of infringement
of
the Licensed Patents or Licensed Process brought to its attention by
Licensor within ninety (90) days following written notice from Licensor,
Licensor may thereafter, and at its sole cost and expense, pursue such
infringement independently of Licensee, and shall be entitled to retain
all resulting proceeds or recoveries.
ARTICLE XIII -
GENERAL
(a) This
License Agreement and the Security Agreement,
together with the Purchase Order, constitute the entire agreement between
the parties as to the Licensed Process, the Patent Rights, the Technology and
the Licensed Field of Use,
and all prior negotiations, representations, agreements
and understandings, written or oral, are merged into, extinguished by
and
completely expressed by it.
(b) Any notice required or permitted to be
given by this License Agreement shall be
given by
personal delivery, prepaid
overnight courier, prepaid registered or certified mail addressed to: Licensor: Global Resource
Corporation, 000 Xxxxxxxxxx Xxxxx., Xxxx # 0 Xxxx Xxxxxx, XX 00000, and Licensee: Universal
Alternative Fuel, Inc., 0000 Xxx Xxxxxxx Xxxx, Xxxxx 000, Xxxxxxxx, Xxx Xxxx
00000.
Such
addresses may be altered by notice so given.
(c) This
License Agreement and its effect are
subject to and shall be construed and
enforced in accordance with the law of the State of New York without
giving
effect to
any applicable conflicts
of laws principles, except as to any issue which by the law of New York
depends
upon the validity, scope or enforceability of any patent
within the Patent Rights, which issue shall be determined in accordance
with the
applicable parent laws of the country of such patent.
(d) Nothing
in
this License
Agreement shall be construed so as to require the commission of
any act contrary to law,
and wherever there is any
conflict between any provision of this License
Agreement or concerning the
legal
right of the parties
to
contract and
any statute, law, ordinance
or treaty, the latter shall prevail, but in such event the affected provisions
of this License
Agreement shall be curtailed and limited only to the extent necessary
to
bring it within the
applicable
legal requirements.
(e)
Licensee agrees to take all reasonable
and necessary steps
to register this License Agreement
in any country, other than the United States of America, where such is required
to permit
the transfer of funds and/or payment of royalties to Licensee hereunder
or
is
otherwise required
by the government
or
law of such country to effectuate or carry out this License
Agreement.
12
(f) It shall
be the full and sole responsibility of Licensor to use appropriate care in the
manufacture of any Licensed Product.
(g) Licensor
shall be required to provide Licensee, at no additional cost, with all know-how,
data, software operating programs, trade secrets, proprietary information or
operating instructions or other
information with respect to any such Licensed Process or Licensed
Product.
(h) Licensee
agrees to indemnify and hold harmless Licensor from and against any
and all claims, damages and liabilities asserted
by third parties (whether governmental or private) arising from
Licensee's and Sublicensee's practice of any Licensed Process or Use or Sale of
any Licensed Product or the use thereof by any third party unless any such
claim, damage or liability arises
in whole or in part from the willful recklessness, negligence or breach
of an obligation under
this License Agreement.
(i) As used
in this License Agreement, singular includes the plural and plural includes the
singular, wherever so required by the context. The headings appearing at the
beginning of the numbered Articles
hereof have been inserted for convenience
only and do not constitute a part of this License Agreement.
(j) The Licensee will maintain or cause
to be maintained, with financially sound and
reputable
insurers, appropriate products liability insurance with respect to
Licensed Products and Licensed Process in the Licensed Field of Use
against loss or damage of the kinds
customarily carried or maintained by corporations of established reputation
engaged in similar businesses.
ARTICLE
XIV - EXTENSION OF PATENT RIGHTS
(a) Licensor
shall seek any extension that is available or that becomes available in
respect of the term of any patent within the Patent Rights including
any patent
that may issue on a
patent application
within the Patent Rights.
(b) Upon
request Licensee shall reasonably cooperate with Licensor in
seeking any extension that is available or that becomes available with
respect to the term of any patent within the
Patent Rights including any patent
that may issue on a patent application within the Patent
Rights.
(c) Licensee
shall advise Licensor of any governmental approval to use or market Licensed
Products or to practice Licensed Process or any other governmental approval
obtained by or on behalf of Licensee or a Sublicensee that is material to any
such extension, and
Licensee shall supply Licensor with any pertinent
information and data in its possession or that
is in the possession of any Sublicensee.
(d) Licensee shall supply Licensor with
material information and data required to comply with 35 USC §156 Extension of Patent
Term (and any successor legislation) and any administrative rules or regulation
thereunder or required to comply with any corresponding laws and regulations that are or shall be in
effect in any country within the Patent Rights. Licensee
shall
require its Sublicensees to comply with this Article XIV, and each sublicensing
agreement
shall
include a clause essentially like this Article XIV.
13
ARTICLE
XV - EFFECTIVE DATE AND TERM
This
License Agreement shall become effective on the day and year first above written
and shall, unless terminated earlier by one of the parties in accord with its
terms, expire concurrently with the expiration, invalidation or lapsing of all
issued patents within the Patent Rights and/or the abandonment of pending patent
applications within the Patent Rights.
ARTICLE
XVI - CONFIDENTIALITY
The
Parties agree that each shall hold in confidence and refrain from disclosing to
others or using, in any activities other than those directly related to this
Agreement, information
which may be disclosed to each other which is marked "Confidential"
including this License Agreement. The Parties agree that each shall hold in
confidence and refrain from disclosing to others or using, in any activities
other than
those directly related to this Agreement, information that has been
disclosed to each other during the negotiation of this License Agreement that
either Party indicated was confidential at the time of disclosure to the other
Party. Such confidential information shall be disclosed in
writing, or if first communicated orally, confirmed in writing within
thirty (30) days of initial disclosure except with respect to confidential
information disclosed to each
other during the negotiation of this
License Agreement,
which shall be confirmed in
writing ten (10) days from the signing by
such Party of this License Agreement.
Without limiting the foregoing in any way, the Parties assume these
obligations in connection with information bearing on
the subject matter
of
this Agreement, including, but not limited to,
corporate business
plans and goals related hereto and the terms and conditions of this
License Agreement. The
provisions of the paragraph do not encompass information of the following
character:
(i) information
which at the time of disclosure to the party was or is generally known or which
later becomes known to others by publication or voluntary
disclosure;
(ii) information
which was already in the
party's possession
at the time of disclosure to such party; or
(iii) information
which is available to the party from a source other than the other party which
did not in the party's knowledge
have as its source for the information any company or individual bound to
secrecy by the other party; or
(iv) information
which the Licensor or the Licensee is required to disclose in connection
with compliance with
federal and state securities or similar disclosure laws applicable to
either of them, or as may be required in connection with any capital raising
activities of either Party. The provisions of this Article supersede any previous agreement or
confidentiality entered into by the parties, and shall
survive termination or expiration of this Agreement.
ARTICLE
XVII
- JURISDICTION
AND VENUE; WAIVER OF JURY TRIAL
(a)
Each Party hereto hereby irrevocably submits to the jurisdiction of any federal
or state
court sitting in the
City, County and State of New York, in any action or proceeding arising
out
of or relating to this
License Agreement, and each hereby irrevocably agrees that all claims
in
respect of such
action or proceeding may be heard and determined in any such federal
or
state
court.
Licensor accepts for itself and
in
respect of its property, generally
and unconditionally
the jurisdiction
and
venue of
the aforesaid courts. Licensor irrevocably consents
to
the service of
process
of any of the aforementioned courts in
any such action or proceeding by the mailing of copies
thereof by registered or certified mail, postage prepaid, to Licensor at its
address set forth in the first paragraph provided that the Licensee may serve
process in any other manner permitted by law. Each party hereto hereby
irrevocably waives any venue objection it may have to any such action or
proceeding arising out of or relating to this License
Agreement in any such venue
and
any objection on the grounds that any such action or proceeding in any
such court
has been
brought in any inconvenient forum. Nothing
herein shall affect the right or
any party hereto to
bring any action or proceeding against another party in
the courts of other jurisdictions.
14
(b) EACH PARTY
HEREBY WAIVES IRREVOCABLY ANY AND ALL RIGHT TO TRIAL BY JURY IN
ANY ACTION OR PROCEEDING ARISING OUT OF, RELATED TO OR IN
CONNECTION WITH THIS LICENSE AGREEMENT, AND THE ENFORCEMENT
THEREOF, WHETHER ALLEGED IN TORT, CONTRACT OR OTHERWISE AND
WHETHER ASSERTED
AS A CLAIM, COUNTERCLAIM, THIRD-PARTY
CLAIM OR IN ANY OTHER FORM.
ARTICLE
XVIII -
REPRESENTATIONS AND WARRANTIES
(a)
Licensor represents and warrants to Licensee as
of
the Effective Date, that:
(i)
Licensor has the right and the ability to license the Patent Rights, the
Technology
and the
Trademarks to Licensee;
(ii) to
the extent any Patent Rights are issued as of the Effective Date, such Patent
Rights are valid and enforceable, and with respect to Patent Rights for which an
application has been filed,
Licensor is not aware of any reason why such Patent Rights will not issue
into a
patent or will not be valid and enforceable;
(iii) the
Patent Rights
and the development, manufacture, import, export,
offer to sell,
use, distribution, licensing and sale of Licensed Products using the
Patent Rights or the Technology do not or will not interfere or infringe on any
intellectual
property rights owned
or possessed by any third party, nor would the use of the Patent Rights
or the
Technology
render Licensee Liable to a
third
party
for patent infringement.
Licensor is not aware of any
third party having superior rights that could reasonably be expected to
prevent Licensee from fulfilling its covenants and obligations
herein;
(iv) there
are no claims, judgments, pending or threatened claims or litigation,
or
settlements
against or owed
by Licensor or pending or threatened claims or litigation relating
to Patent Rights or Technology and Licensor does not know of any
reason for
such claims, judgments, settlements, or pending or threatened claims or
litigation;
(v) Licensor
has no knowledge of any circumstances that would adversely affect the
commercial utility
of the Patent
Rights or the Technology within the
scope of the licenses
granted under this License Agreement;
(vi) Licensor
owns all
right, title and interest in and to each of the Patent Rights listed on
Schedule
A free from all claims, encumbrances, mortgages, liens, taxes, pledges,
and similar defects of any kind; and
(vii) All
necessary
registration, maintenance and renewal fees in connection with 15
the
Patent Rights, the Technology and the Trademarks (and applications therefor)
have been paid and all necessary documents and certificates in connection with
such property have been
filed and all other necessary actions have been taken with the relevant
patent, copyright, trademark or other authorities in the United States or
foreign jurisdictions, as the case may be,
for the purposes of maintaining such property (and applications
therefor).
15
(b)
The Parties individually represent and warrant to each other that:
(i) this
License Agreement has been duly executed and delivered by each of them and
constitutes the legal, valid and binding obligation of each of them enforceable
in accordance with its terms; and
(ii) the
execution, delivery and performance by each of them of this License Agreement
have been duly authorized by all requisite corporate action and have not and will
not violate any provision of law or regulation, any
order, judgment., ruling,
writ, injunction, award or decree of
any court or other agency of government,
the Certificate of Incorporation or the By-Laws of such Party or any
provision of any indenture, agreement or other instrument to which they
are hound, or conflict with, result in a breach of or constitute (with due
notice of lapse of time or both) a default under any such indenture, agreement
or other instrument, or result in the creation or imposition of any lien,
charge, restriction, claim or encumbrance of any nature whatsoever upon any of
its properties or assets.
IN
WITNESS WHEREOF, the parties hereto have hereunto set their hands and seals
and duly executed this License Agreement on the date(s) indicated below,
to be effective the day and year first above written.
GLOBAL
RESOURCE CORPORATION
By:
/s/ Xxxxx X.
Xxxxxxxxxxx
Xxxxx
X. Xxxxxxxxxxx, Chairman and CEO
UNIVERSAL ALTERNATIVE FUELS, INC.
By:
/s/ Xxxx
Xxxxxxxx
Xxxx
Xxxxxxxx, President
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16
Schedule
A —
CONTINUATION APPLICATION FOR OIL SHALE AND COAL
17
18
Privacy
Act Statement
The Privacy Act of 1974 (P.L. 93-579)
requires that you be given certain information in connection with your
submission of the attached form related to a patent application or patent.
Accordingly, pursuant to the requirements of the Act, please be advised that:
(1) the general authority for the collection of this information is 35 U.S.C.
2(b)(2); (2) furnishing of the information solicited is voluntary; and (3) the
principal purpose for which the information is used by the U.S. Patent and
Trademark Office is to process and/or examine your submission related to a
patent application or patent. If you do not furnish the requested information,
the U.S. Patent and Trademark Office may not be able to process and/or examine
your submission, which may result in termination of proceedings or abandonment
of the application or expiration of the patent.
The
information provided by you in this form will be subject to the following
routine uses:
1.
|
The
information on this form will be treated confidentially to the extent
allowed under the Freedom of Information Act (5 U.S.C. 552) and the
Privacy Act (5 U.S.0 552a). Records from this system of records may be
disclosed to the Department of Justice to determine whether disclosure of
these records is required by the Freedom of Information
Act.
|
2.
|
A
record from this system of records may be disclosed, as a routine use, in
the course of presenting evidence to a court, magistrate, or
administrative tribunal, including disclosures to opposing counsel in the
course of settlement negotiations.
|
3.
|
A
record in this system of records may be disclosed, as a routine use, to a
Member of Congress submitting a request involving an individual, to whom
the record pertains, when the individual has requested assistance from the
Member with respect to the subject matter of the
record.
|
4.
|
A
record in this system of records may be disclosed, as a routine use, to a
contractor of the Agency having need for the information in order to
perform a contract. Recipients of information shall be required to comply
with the requirements of the Privacy Act of 1974, as amended, pursuant to
5 U.S.C. 552a(m).
|
5.
|
A
record related to an International Application filed under the Patent
Cooperation Treaty in this system of records may be disclosed, as a
routine use, to the International Bureau of the World Intellectual
Property Organization, pursuant to the Patent Cooperation
Treaty.
|
6.
|
A
record in this system of records may be disclosed, as a routine use, to
another federal agency for purposes of National Security review (35 U.S.C.
181) and for review pursuant to the Atomic Energy Act (42 U.S.C.
218(c)).
|
7.
|
A
record from this system of records may be disclosed, as a routine use, to
the Administrator, General Services, or his/her designee, during an
inspection of records conducted by GSA as part of that agency's
responsibility to recommend improvements in records management practices
and programs, under authority of 44 U.S.C. 2904 and 2906. Such disclosure
shall be made in accordance with the GSA regulations governing inspection
of records for this purpose, and any other relevant (i.e.,
GSA or Commerce) directive. Such disclosure shall not be used to
make determinations about
individuals.
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8.
|
A
record from this system of records may be disclosed, as a routine use, to
the public after either publication of the application pursuant to 35
U.S.C. 122(b) or issuance of a patent pursuant to 35 U.S.C. 151. Further,
a record may be disclosed, subject to the limitations of 37 CFR 1.14, as a
routine use, to the public if the record was filed in an application which
became abandoned or in which the proceedings were terminated and which
application is referenced by either a published application, an
application open to public inspection or an issued
patent.
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9.
|
A
record from this system of records may be disclosed, as a routine use, to
a Federal, State, or local law enforcement agency, if the USPTO becomes
aware of a violation or potential violation of law or
regulation.
|
19
20
21
22
23
Privacy
Act Statement
The
Privacy Act of 1974 (P.L. 93-579) requires that you be given certain
information in connection with your submission of the attached form
related to a patent application or patent Accordingly, pursuant to the
requirements of the Act, please be advised that: (1) the general authority
for the collection of this information Is 35 U.S.C. 2(b)(2); (2)
furnishing of the information solicited is voluntary; and (3) the
principal purpose for which the Information is used by the U.S. Patent and
Trademark Office is to process and/or examine your submission related to a
patent application or patent If you do not furnish the requested
information, the U.S. Patent and Trademark Office may not be able to
process and/or examine your submission, which may result in termination of
proceedings or abandonment of the application or expiration of the
patent
The
information provided by you in this form will be subject to the following
routine uses:
1. The
information on this form will be treated confidentially to the extent
allowed under the Freedom of Information Act (5 U.S.C. 552) and
the Privacy Act (5 U.S.C. 552a). Records from this system of records may
be disclosed to the Department of Justice to determine whether the Freedom
of Information Act requires disclosure of these records.
2. A
record from this system of records may be disclosed, as a routine use, in
the course of presenting evidence to a court, magistrate, or administrative
tribunal, including disclosures to opposing counsel In the course of
settlement negotiations.
3. A
record in this system of records may be disclosed, as a routine use, to a
Member of Congress submitting a request involving an individual,
to whom the record pertains, when the individual has requested assistance
from the Member with respect to the subject matter of the
record.
4. A
record in this system of records may be disclosed, as a routine use, to a
contractor of the Agency having need for the information in order
to perform a contract Recipients of information shall be required to
comply with the requirements of the Privacy Act of 1974, as amended,
pursuant to 5 U.S.C. 552a(m).
5. A
record related to an International Application filed under the Patent
Cooperation Treaty in this system of records may be disclosed,
as
a routine use, to the International Bureau of the World Intellectual
Property Organization, pursuant to the Patent Cooperation
Treaty.
6. A
record in this system of records may be disclosed, as a routine use, to
another federal agency for purposes of National Security review
(35 U.S.C. 181) and for review pursuant to the Atomic Energy Act (42
U.S.C. 218(c)).
7. A
record from this system of records may be disclosed, as a routine use, to
the Administrator, General Services, or his/her designee, during
an inspection of records conducted by GSA as part of that agency's
responsibility to recommend improvements in records management practices
and programs, under authority of 44 U.S.C. 2904 and 2906. Such disclosure
shall be made in accordance with the GSA regulations governing inspection
of records for this purpose, and any other relevant (i.e., GSA or
Commerce) directive. Such disclosure shall not be used to make
determinations about individuals.
8. A
record from this system of records may be disclosed, as a routine use, to
the public after either publication of the application pursuant
to
35 U.S.C. 122(b) or issuance of a patent pursuant to 35 U.S.C. 151.
Further, a record may be disclosed, subject to the limitations of 37 CFR
1.14, as a routine use, to the public if the record was filed in an
application which became abandoned or in which the proceedings were
terminated and which application is referenced by either a published
application, an application open to public inspections or an issued
patent.
9.A
record from this system of records may be disclosed, as a routine use, to
a Federal, State, or local law enforcement agency, if the USPTO
becomes aware of a violation or potential violation of law or
regulation.
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24
IN
THE UNITED STATES PATENT AND TRADEMARK OFFICE
In Re
Application of:
Xxxxx X.
Xxxxxxx; Xxxx Xxxxxxxxx; Xxxxxx
For
the
For:
MICROWAVE PROCESSING OF OIL SHALE AND COAL
Commissioner
for Patents X.X. Xxx 0000
Xxxxxxxxxx,
XX 00000-0000
Sir:
AUTHORIZATION
TO TREAT A REPLY AS INCORPORATING AN EXTENSION OF TIME
UNDER C.F.R. §1.136(a)(3)
The
Commissioner is hereby requested to grant an extension of time for the
appropriate length of time, should one be necessary, in connection with this
filing or any future filing submitted to the U.S. Patent and Trademark Office in
the above-identified application during the pendency of this application. The
Commissioner is further authorized to charge any fees related to any such
extension of time to Deposit Account No. 23-3050.
Date: October 2, 2009 | /s/ Xxxxxxx X. Rosedale
Xxxxxxx
X. Rosedale
Registration
No. 46,018
|
25
MICROWAVE
PROCESSING OF OIL SHALE AND COAL
CROSS-REFERENCE
TO RELATED APPLICATIONS
[0001] This application is a
continuation application of U.S. Patent Application No. 11/610,823,
"Microwave-Based Recovery of Hydrocarbons and Fossil Fuels", filed December 14,
2006, now allowed, which claims the benefit of U.S. Provisional Patent
Application No. 60/750,098, "Method for Using Microwave Radiation", filed
December 14, 2005, the entirety of each application is incorporated by reference
herein.
FIELD
OF THE INVENTION
[0002] The present invention
relates to methods and apparatuses for using microwave radiation and more
particularly, to methods and apparatuses for decomposing compositions comprising
petroleum-based materials.
BACKGROUND
OF THE INVENTION
[0003] Petroleum-based
materials are integral to the world's economy and demand for such fuels and
consumer products is increasing. As the demand rises, there is a need to
efficiently and economically extract petroleum-based materials to fulfill that
demand. As such, it would be advantageous to not only be able to extract
petroleum-based materials from the earth, but to also recycle consumer products
to recapture those petroleum-based materials.
[0004] Worldwide oil
consumption is estimated at seventy-three million barrels per day and growing.
Thus, there is a need for sufficient oil supplies. Tar sands, oil sands, oil
shales, oil cuttings, and slurry oil contain large quantities of oil, however,
extraction of oil from these materials is costly and time-consuming and
generally does not yield sufficient quantities of usable oil.
[0005] Soil contaminated with
petroleum products is an environmental hazard, yet decontamination of
petroleum-tainted soil is time-consuming and expensive.
[0006] Furthermore, it has
been estimated that 280 million gallons of oil-based products such as plastics
go into landfills each day in the United States. It would be desirable to
recapture and recycle the raw materials of these products.
26
[0007]
Scrap vehicle tires are a significant problem worldwide and their
disposal presents significant environmental and safety hazards, including fires,
overflowing landfills, and atmospheric pollution. While there are a number of
existing applications for these tires, including tire-derived fuels, road
construction, and rubber products, these applications are insufficient to
dispose of all the available scrap tires. The major components of tires are
steel, carbon black, and hydrocarbon gases and oils, which are commercially
desirable. As such, it is advantageous to develop processes for the recovery of
these products from scrap vehicles tires. Prior art methods of decomposing scrap
vehicle tires do not produce commercial-grade carbon black and require high
temperatures and extended exposure times for recovery of the hydrocarbon
components.
[0008]
Efforts to recycle tires using microwave technology has been described in
U.S. Patent Nos. 5,507,927 and 5,877,395 to Xxxxx. Efforts to recover petroleum
from petroleum-impregnated media has been described in U.S. Patent Nos.
4,817,711 and 4,912,971 to Jeambey. Efforts to decompose plastics using
microwave radiation has been described in U.S. Patent No. 5,084,140 to Holland.
The prior work has involved the use of single-frequency microwave radiation.
Single-frequency microwave radiation is a slow process that does not provide
uniform heating. Moreover, single-frequency microwave radiation typically
results in arcing on metal components.
[0009]
Thus, there is a need for methods and apparatuses for the recycling of
petroleum-based compositions and for the recovery of petroleum-based materials
from composites containing petroleum-based materials. The invention is directed
to these and other important needs.
SUMMARY
OF THE INVENTION
[0010]
The present invention provides methods for decomposing compositions
comprising carbon-based materials comprising subjecting the compositions to
microwave radiation for a time sufficient to at least partially decompose the
composition, wherein the microwave radiation comprises at least one frequency
component in the range of from about 4 GHz to about 18 GHz.
[0011]
The present invention provides methods for decomposing compositions
comprising petroleum-based materials comprising subjecting the compositions to
microwave radiation for a time sufficient to at least partially decompose the
composition, wherein the microwave radiation comprises at least one frequency
component in the range of from about 4 GHz to about 18 GHz.
27
[0012] The present invention
further provides methods for recovery of petroleum-based materials from
composites comprising those petroleum-based materials. The methods of the
present invention include subjecting the composite to microwave radiation for a
time sufficient to extract the petroleum-based material, wherein the microwave
radiation comprises at least one frequency component in the range of from about
4 GHz to about 18 GHz.
[0013] The present invention
also provides for products produced by the methods of the present
invention.
[0014] The present invention
additionally provides apparatuses for decomposing compositions comprising
petroleum-based materials. The apparatuses of the present invention comprise a
microwave radiation generator, wherein the generator is capable of applying
microwave radiation characterized as having at least one frequency component in
the range of from 4 GHz to about 18 GHz, and at least one container to collect
decomposed components from the compositions. The present invention further
provides apparatuses for extracting petroleum-based materials from composites
comprising the petroleum-based material. These apparatuses comprise a microwave
radiation generator, wherein the generator is capable of applying microwave
radiation characterized as having at least one frequency component in the range
of from 4 GHz to about 18 GHz, and at least one container to collect decomposed
components from the composite.
[0015] The general description
and the following detailed description are exemplary and explanatory only and
are not restrictive of the invention, as defined in the appended claims. Other
aspects of the present invention will be apparent to those skilled in the art in
view of the detailed description of the invention as provided
herein.
BRIEF
DESCRIPTION OF THE DRAWINGS
[0016] The summary, as well as
the following detailed description, is further understood when read in
conjunction with the appended drawings. For the purpose of illustrating the
invention, there are shown in the drawings exemplary embodiments of the
invention; however, the invention is not limited to the specific methods,
compositions, and devices disclosed. In addition, the drawings are not
necessarily drawn to scale. In the drawings:
[0017] FIGs. 1A — 1G
illustrate an embodiment of the present invention directed to processing
tire cuttings using microwaves to recover fuel oil;
[0018] FIG. 2A is an elevation
view, axial direction, of a microwave reactor suitable for processing oil
cuttings according to an aspect of the present invention;
[0019] FIG. 213 illustrates an
elevation view of the microwave reactor of FIG. 2A, longitudinal
direction;
28
[0020] FIG.2C illustrates an
elevation view of the microwave device and control room suitable
for generating microwaves and propagating the same through
waveguides;
[0021] FIGs. 3A - 3B
illustrate several embodiments of the present invention for extracting
petroleum-based materials from oil slurry;
[0022] FIG. 4A illustrates an
elevation view of a microwave reactor system suitable for processing shale rock,
tar sands, drill cuttings, and the like;
[0023] FIG. 4B provides a plan
view of FIG.
4A;
[0024] FIG. 5A is an
illustration of one embodiment of the present invention for extracting
petroleum-based materials from heavy oil contained in oil xxxxx;
[0025] FIG. 5B
is an illustration of one
embodiment of the present invention for extracting petroleum-based materials
from oil shale, in
situ;
[0026] FIG. 6 is an
illustration of one embodiment of the present invention for extracting
petroleum-based materials from tar sands, oil sands and shale rock;
[0027] FIG. 7 is an schematic
of one embodiment of the present invention for decomposing vehicle
tires;
[0028] FIG. 8A is a plan view
of an oil platform incorporating a drill cuttings microwave processing
unit;
[0029] FIG. 8B illustrates an
elevation view of the oil platform in FIG. 8A;
[0030] FIG. 8C illustrates a
vertical and horizontal configurations of the drill cuttings microwave
processing unit suitable for use in the oil platform illustrated in FIG. 8A;
[0031] FIG. 9A is a depiction
of an electron microscope photograph of carbon black produced
by the method of the present invention;
[0032] FIG. 9B is a depiction
of an electron microscope photograph of carbon black produced by the method of
the present invention;
[0033] FIG. 9C is a depiction
of an electron microscope photograph of carbon black produced by the method of
the present invention; and
[0034] FIGs. 10A-10E
illustrate an additional embodiment of a drum reactor system for
processing materials containing hydrocarbons.
DETAILED
DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0035] The present invention
may be understood more readily by reference to the following
detailed description taken in connection with the accompanying figures and
examples, which
form a part of this disclosure. It is to be understood that this invention is
not limited to the specific
devices, methods, applications, conditions or parameters described and/or shown
herein, and that
the terminology used herein is for the purpose of describing particular
embodiments by way of
example only and is not intended to be limiting of the claimed invention. Also,
as used in the specification including the appended claims, the singular forms
"a," "an," and "the" include the plural, and reference to a particular numerical
value includes at least that particular value, unless the context clearly
dictates otherwise. The term "plurality", as used herein, means more than one.
When a range of values is expressed, another embodiment includes from the one
particular value and/or to the other particular value. Similarly, when values
are expressed as approximations, by use of the antecedent "about," it will be
understood that the particular value forms another embodiment. All ranges are
inclusive and combinable.
29
[0036]
It is to be appreciated that certain features of the invention which are,
for clarity, described herein in the context of separate embodiments, may also
be provided in combination in a single embodiment. Conversely, various features
of the invention that are, for brevity, described in the context of a single
embodiment, may also be provided separately or in any subcombination. Further,
reference to values stated in ranges include each and every value within that
range.
[0037]
"Sweeping," as the term is used herein, is defined as the application of
a plurality of radiation frequencies over a period of time.
[0038]
"Pulsing," as used herein, means subjecting the composition to microwave
radiation for a period of time, followed by periods of time wherein the
composition is not subjected to microwave radiation.
[0039]
"Oil," as used herein, means any hydrocarbon or petroleum-based
oil.
[0040]
"Gas," as used herein, includes any hydrocarbon-based material that is in
the gaseous state at atmospheric temperature and pressure and includes, but is
not limited to, methane, ethane, propane, butane, isobutene, or mixtures
thereof.
[0041]
"Carbon black," as used herein, includes any grade of
commercially-acceptable carbon black, including, but not limited to, rubber
black.
[0042]
"Oil sands," also known as "tar sands," are deposits of bitumen, a heavy
black viscous oil.
[0043]
"Oil shale" is sedimentary rock containing a high proportion of Kerogen,
which, when heated, can be converted into oil.
[0044]
"Slurry oil" is refinery waste oil.
[0045]
"Oil cuttings" are the waste product generated during the drilling of oil
xxxxx. Examples of oiI cuttings include, but are not limited to, bits and pieces
of oil-soaked soil and rock.
[0046]
"Hydrocarbons" are compositions that comprise carbon and
hydrogen.
30
[0047] "Carbon-based" refers to matter that
comprises carbon.
[0048] "Decompose" and "decomposing" refers to
a process whereby matter is broken down to smaller constituents. For example,
solids can be broken down into particles, liquids, vapors, gases, or any
combination thereof; rubbery materials can be broken down into liquids, vapors,
gases, or any combination thereof; viscous liquids can be broken down to lower
viscosity liquids, vapors, gases, or any combination thereof; liquids can be
broken down to vapors, gases, or any combination thereof; composite materials
comprising inorganic solids and trapped organic matter can be broken down to
inorganic solids and released organic vapors and gases, and the
like.
[0049] 1 Torr = 1
mm Hg = 1 millimeter mercury.
[0050] Methods for decomposing compositions
comprising petroleum-based materials are set forth herein. The compositions used
in the present invention contemplate any composition comprised of
petroleum-based, carbon-based and various hydrocarbon materials. The
petroleum-based materials may be present in the composition in amounts ranging
from about 1% to 100%, by weight, based on the weight of the composition.
Preferably, the composition is a vehicle tire. In other embodiments, the
composition comprises plastic, which includes, but is not limited to ethylene
(co)polymer, propylene (co)polymer, styrene (co)polymer, butadiene (co)polymer,
polyvinyl chloride, polyvinyl acetate, polycarbonate, polyethylene
terephthalate, (meth)acrylic (co)polymer, or a mixture thereof. A variety of
natural and synthetic resins and rubbers can also be decomposed according to the
methods described herein. Various carbon-based materials that can also be
processed according to the inventions described herein include coal, such as
anthracite coal and bituminous coal.
[0051]
In one embodiment, the composition is subjected to microwave radiation
for a time sufficient to at least partially decompose the composition. The
microwave radiation can be in the range of from about 4.0 and about 12.0 GHz.
Other ranges can also be used, for example, in the range of from about 4 GHz to
about 18 GHz, and more preferably in the range of from about 12 GHz to about
18
GHz. For example, coal can be processed at frequencies in the range of
from about 4 GHz to about 18
GHz, and more preferably in the range of from about 12 GHz to about 18
GHz.
[0052]
In one embodiment, the composition is subjected to one or more
pre-selected microwave radiation frequencies. Preferably, the pre-selected
microwave radiation frequency will be the resonating microwave frequency, i.e,
the microwave radiation frequency at which the composition absorbs a maximum
amount of microwave radiation. It has been determined that different
compositions of the present invention will absorb more or less microwave
radiation, depending
on the frequency of the microwave radiation applied. It has also been determined
that the frequency at which maximum microwave radiation is absorbed differs by
composition. By using methods known in the art, a composition of the present
invention can be subjected to different frequencies of microwave radiation and
the relative amounts of microwave radiation absorbed can be determined.
Preferably, the microwave radiation selected is the frequency that comparatively
results in the greatest amount of microwave radiation absorption. In one
embodiment, microwave radiation frequency resulting in a comparative maximum
absorption of microwave radiation by the compositions of the present invention
is in the range of from about 4.0 and about 12.0 GHz. In others, particularly
with respect to vehicle tires, the microwave radiation frequency resulting in a
comparative maximum absorption of microwave radiation by the compositions of the
present invention is in the range of from about 4.0 and about 7.2 GHz.
In yet
others, the microwave radiation frequency resulting in a comparative maximum
absorption of microwave radiation by the compositions of the present invention
is in the range of from about 4.0 and about 6.0 GHz.
31
[0053]
The present invention also provides methods for subjecting a composition
to a sweeping range of microwave radiation frequencies for a time sufficient to
at least partially decompose the composition. Preferably, variable frequency
microwave ("VFM") is used to sweep the compositions. VFM is described in U.S.
Patent No. 5,321,222 to Bible, et al. and U.S. Patent No. 5,521,360 to Xxxxxxx,
et al., incorporated herein by reference in their entireties. Unlike single
frequency microwave radiation, VFM produces a bandwidth of microwave radiation
frequencies that are applied sequentially to the composition. Consequentially,
the field distribution with VFM is substantially more uniform than the field
distribution of single microwave frequency radiation. The more uniform field
distribution of VFM produces fewer hot spots, resulting in more uniform heating
of the composition. Moreover, generally, no single frequency is applied for
longer than about 25 p.s. The short duration of each applied frequency produces
no build-up of charge, thus eliminating discharge, or arcing, typically observed
during single frequency microwave irradiation.
[0054] In some embodiments, particularly with
respect to vehicle tires, the range of microwave radiation frequencies swept is
in the range of from about 4.0 GHz to about 12.0 GHz. In certain embodiments,
the range of microwave radiation frequencies swept is in the range of from about
5.8 GHz to about 7.0 GHz. In still others, the range of microwave radiation
frequencies swept is in the range of from about 7.9 GHz and 8.7 GHz. In some
embodiments, range of microwave radiation frequencies is in the C-Band frequency
range, the C-Band frequency range encompassing microwave frequencies in the
range of from about 4.0 GHz to about 8.0
GHz. In other embodiments, the range of microwave radiation frequencies is in
the X- Band frequency range, the X-band frequency range encompassing microwave
frequencies in the range of from about 8.0 GI-Iz to about 12.0 GHz.
[0055] Preferably, the
sweeping of the range of microwave radiation frequencies encompasses a
pre-selected, resonating microwave radiation frequency characterized as having
at least one frequency component in the range of from about 4.0 GHz to about
12.0 GElz. This frequency can be selected by using the methods described herein
and techniques known in the art. Preferably, the bandwidth of the sweeping range
of microwave radiation is about 4.0 GHz. More preferably, the range of microwave
frequencies with which the composition is swept, is about +1- 2 GHz of the
pre-selected microwave radiation frequency. For example, if the preselected
microwave radiation frequency is 7.2 GHz, the composition would be swept with
the range of microwave radiation frequencies encompassing from about 5.2 to
about 9.2 GHz. The microwave frequencies can also be swept at about +1- 1.5 GHz,
or even +/- 1.0 GHz, or even +10.5 GHz of the preselected microwave
frequency.
[0056] Upon decomposition of
the compositions subjected to the methods and apparatuses of the invention,
flammable hydrocarbon-based gases are released. To reduce the risk of ignition,
it is preferred that the method be performed in an oxygen-deprived atmosphere.
Preferably, the composition is exposed to less than about 12% oxygen. More
preferably, the composition is exposed to less than about 8% oxygen. Even more
preferably, the composition is exposed to less than about 5%
oxygen.
32
[0057] In one embodiment, the
composition is exposed an inert gas atmosphere. Preferably, the inert gas is
nitrogen, argon, or mixtures thereof.
[0058] In some embodiments,
the composition is exposed to less than atmospheric pressure. Preferably, the
composition is exposed to less than about 40 Ton.
More preferably, the composition is exposed to less than about 20 Ton.
Even more preferably, the composition is exposed to less than about 5 Torr.
Without being bound by any particular thery or operation, it is believed that
operating at sub-atmospheric pressures helps to recover hydrocarbon-based gases
and prevents over-heating.
[0059] In one embodiment, the
composition of the present invention forms a vehicle tire. Using the methods of
the present invention, the tire can be decomposed to produce at least one of
oil, gas, steel, sulfur, and carbon black.
[0060] Over-exposure to
microwave radiation and over-heating of the composition of the present invention
may result in the recovery of non-commercially-acceptable carbon black.
Controlling the temperature of the composition during microwave irradiation
prevents such over exposure
and over-heating to produce commercially-acceptable carbon black. Preferably,
the temperature of the composition does not exceed about 700 °F. More
preferably, the temperature of the composition does not exceed about 500 °F.
Even more preferably, the temperature of the composition does not exceed about
465 °F.
[0061]
In one embodiment, the temperature of the composition can be controlled
while performing the method of the present invention by pulsing the microwave
radiation subjection. For example, microwave radiation can be applied until the
composition temperature reaches about 465 °F, at which time, the application of
microwave radiation can be stopped for a time sufficient for the composition to
cool between about 5 to 25 degrees. Once the composition has cooled, the
application of microwave radiation can be resumed. This process can be repeated,
as necessary, until the composition is sufficiently decomposed.
[0062]
Decomposition products obtained from the compositions using the methods
of the present invention may be refined and/or purified using techniques known
in the art.
[0063]
The present invention also provides methods for extracting
petroleum-based materials from composites comprising the petroleum-based
materials by subjecting the composites to microwave radiation for a time
sufficient to extract the petroleum-based material. Preferably, the microwave
radiation is in the range of from about 4.0 and about 12.0 GHz.
[0064]
The composites are any material comprising petroleum-based materials,
including, but not limited to, at least one of oil sands, oil shale, slurry oil,
oil cuttings, and soil or sand contaminated with petroleum-based materials. As
used herein, "composites" also includes, but is not limited to, oil
xxxxx.
33
[0065]
In one embodiment, the composite is subjected to oneor more pre-selected
microwave radiation frequencies. Preferably, the pre-selected microwave
radiation frequency will be the resonating microwave frequency, i.e, the
microwave radiation frequency at which the composite absorbs a maximum amount of
microwave radiation. It has been determined that different composites of the
present invention will absorb more or less microwave radiation, depending on the
frequency of the microwave radiation applied. It has also been determined that
the frequency at which maximum microwave radiation is absorbed differs by
composite. By using methods known in the art, a composite of the present
invention can be subjected to different frequencies of microwave radiation and
the relative amounts of microwave radiation absorbed can be determined.
Preferably, the microwave radiation selected is the frequency that comparatively
results in the greatest amount of microwave radiation absorption. In one
embodiment, microwave radiation frequency resulting in a comparative maximum
absorption of microwave radiation by the composite of the present invention is
in the range of from about 4.0 and about
12.0 GHz. In others, the microwave radiation frequency resulting in a
comparative maximum absorption of microwave radiation by the composite of the
present invention is in the range of from about7.9 and about 12.0 GHz. In yet
others, the microwave radiation frequency resulting in a comparative maximum
absorption of microwave radiation by the composite of the present invention is
in the range of from about 7.9 and about 8.7 GHz.
[0066]
The present invention also provides methods for recovery of
petroleum-based materials from composites comprising those petroleum-based
materials, by subjecting the composite to a sweeping range of microwave
radiation frequencies for a time sufficient to extract the petroleum-based
material, and wherein the range of frequencies of the microwave radiation is in
the range of from about 4.0 GHz to about 12.0 GHz. The composites are any
material comprising petroleum-based materials, including, but not limited to, at
least one of oil sands, oil shale, slurry oil, oil cuttings and soil or sand
contaminated with petroleum-based materials.
[0067]
Preferably, variable frequency microwave ("VFM") is used to sweep the
composites. VFM is described in U.S. Patent No. 5,321,222 to Bible, et al. and
U.S. Patent No. 5,521,360 to Xxxxxxx, et al., incorporated herein by reference
in their entireties. Unlike single frequency microwave radiation, VFM produces a
bandwidth of microwave radiation frequencies that are applied sequentially to
the composite. Consequentially, the field distribution with VFM is substantially
more uniform than the field distribution of single microwave frequency
radiation. The more uniform field distribution of VFM produces fewer hot spots,
resulting in more uniform heating of the composite. Moreover, generally, no
single frequency is applied for longer than about 25 usr, or no longer than
about 20 us,
or no longer than about 15us, or even no longer than about 10 us. The
short duration of each applied frequency produces no build-up of charge, thus
eliminating discharge, or arcing, typically observed during single frequency
microwave irradiation.
[0068]
In certain embodiments, the range of microwave radiation frequencies is
in the range of from about 7.9 GHz to about 12.0 GHz. In still others, the range
of microwave radiation frequencies is in the range of from about 7.9 GHz and 8.7
GHz. In some embodiments, range of microwave radiation frequencies is in the
C-Band frequency range, the C-Band frequency range encompassing microwave
frequencies in the range of from about 4.0 GHz to about 8.0 GHz. In other
embodiments, the range of microwave radiation frequencies is in the X- Band
frequency range, the X-band frequency range encompassing microwave frequencies
in the range of from about 8.0 GHz to about 12.0 GHz.
34
[0069]
Preferably, the sweeping of the range of microwave radiation frequencies
encompasses one or more pre-selected microwave radiation frequencies in the
range of from about 4.0
GHz to about 12.0 GHz. This frequency can be selected by using the methods
described herein and techniques known in the art. In one embodiment, the
pre-selected microwave radiation frequency is in the range of from about 7.9 and
about 8.7 GHz. In other
embodiments, the bandwidth of the sweeping range of microwave radiation is about
4.0 GHz. More preferably, the range of microwave frequencies with which the
composition is swept, is about +/- 2 GHz of the pre-selected microwave radiation
frequency. For example, if the preselected microwave radiation frequency is
7.2 GHz, the composition would be swept with the range of microwave radiation
frequencies encompassing from about 5.2 to about 9.2 GHz.
[0070] Upon
extraction, flammable hydrocarbon-based gases are released. To reduce the risk
of ignition, it is preferred that the method be performed in an oxygen-deprived
atmosphere. Preferably, the composite is exposed to less than about 12% oxygen.
More preferably, the composite is exposed to less than about 8% oxygen. Even
more preferably, the composite is exposed to less than about 5%
oxygen.
[0071] In one
embodiment, the composite is exposed to an inert gas atmosphere. Preferably, the
inert gas is nitrogen, argon, or mixtures thereof.
[0072] In
some embodiments, the composite is exposed to less than atmospheric pressure.
Preferably, the composite is exposed to less than about 40 Torr. More
preferably, the composite is exposed to less than about 20 Torn Even more
preferably, the composite is exposed to less than about 5 Torr.
[0073] In one
embodiment, the composite is subjected to microwave radiation sufficient to heat
the petroleum-based material to its boiling point temperature. Boiling point
temperatures of petroleum-based materials are known in the art. Reducing the
pressure at which the composite is exposed will result in a decrease in the
boiling point temperature of the petroleum-based material. Those of skill in the
art will be able to determine the boiling point temperatures of petroleum-based
materials at different pressures.
[00741 In
some embodiments, the methods of the present invention may be used in
situ to extract petroleum-based materials from composites located in the
field. In
other embodiments, inert gases may be flowed, in
situ, onto the composites. In one embodiment, the pressure surrounding
the composite may be reduced to below atmospheric pressure.
[0075] Using
the methods of the present invention, oil and/or gases can be recovered from the
composite.
[0076] The
petroleum-based material extracted using the methods of the present invention
may be refined and/or purified using techniques known in the art.
[0077] The present invention also provides for
apparatuses for decomposing a composition comprising a petroleum-based material.
In one embodiment, the apparatuses of the present invention comprise a microwave
radiation generator, wherein the generator is capable of applying microwave
radiation characterized as having at least one frequency component in the range
of from about 4.0 and about 12.0 GHz, and at least one container to collect
decomposed components from the composition. In one embodiment, the microwave
radiation generator is capable of applying a microwave radiation frequency
between about 4.0 and about 12.0 GHz.
35
[0078] In other embodiments, the apparatuses of
the present invention comprise a microwave radiation generator, wherein the
generator is capable of applying a sweeping range of frequencies of microwave
radiation characterized as having at least one frequency component in the range
of from about 4.0 GHz to about 12.0 GHz, and at least one container to collect
decomposed components from the composition. In other embodiments, microwave
radiation generator is capable of applying sweeping microwave radiation in the
C-Band frequency range. In yet other embodiments, microwave radiation generator
is capable of applying sweeping microwave radiation in the X-Band frequency
range. In yet other embodiments, microwave radiation generator is capable of
applying sweeping microwave radiation in the Ku-Band frequency range (about 12
GHz to about 18 GHz). In further embodiments, the microwave radiation generator
is capable of applying sweeping microwave radiation in the range of about 5.8
GHz to about 7.0 GHz. In yet other embodiments, the microwave radiation
generator is capable of applying sweeping microwave radiation in the range of
about 7.9 GHz to about 8.7 GHz.
[0079] In another embodiment, the chamber is
open to the outside atmospheric conditions. In other embodiments, the chamber is
closed to the outside atmosphere. In yet other embodiments, the chamber has an
internal pressure of less than atmospheric pressure. Preferably, the chamber is
capable of operating at a pressure of less than about 40 Torr. More preferably,
the chamber is capable of operating at a pressure of less than about 20 Ton.
Even more preferably, the chamber is capable of operating a pressure of less
than about 5 Ton.
[0080]
The present invention also provides for apparatuses for extracting a
petroleum- based material from a composite comprising the petroleum-based
material. In one embodiment, the apparatuses of the present invention comprise a
microwave radiation generator, wherein the generator is capable of applying
microwave radiation characterized as having at least one frequency component in
the range of from about 4.0 GHz to about 12.0 GHz, and at least one container to
collect the extracted petroleum-based material. In some embodiments, the
microwave radiation generator is capable of applying a microwave radiation
frequency of characterized
as having at least one frequency component in the range of from about 4.0 and
about 12.0 GI-lz.
[0081] In other embodiments,
the apparatuses of the present invention comprise a microwave radiation
generator, wherein the generator is capable of applying a sweeping range of
frequencies of microwave radiation characterized as having at least one
frequency component in the range of from about 4.0 GHz to about 12.0 GHz, and at
least one container to collect the extracted petroleum-based material. In some
embodiments, the microwave radiation generator is capable of applying sweeping
microwave radiation in the C-Band frequency range. In yet other embodiments,
microwave radiation generator is capable of applying sweeping microwave
radiation in the X-Band frequency range. In further embodiments, the microwave
radiation generator is capable of applying sweeping microwave radiation in the
range of about 5.8 GHz to about 7.0 GHz. In yet other embodiments, the microwave
radiation generator is capable of applying sweeping microwave radiation in the
range of about 7.9 GHz to about 8.7 GHz.
[0082] In some embodiments,
the apparatuses of the present invention may be used in
situ to extracted petroleum-based materials from composites located in
the field.
36
[0083] In other embodiments,
the apparatuses further comprise at least one chamber for holding the composite.
In another embodiment, the chamber is open to the outside atmospheric
conditions. In other embodiments, the chamber is closed to the outside
atmosphere. In yet other embodiments, the chamber has an internal pressure of
less than atmospheric pressure. Preferably,
the chamber is capable of operating at a pressure of less than about 40 Torr.
More preferably, the chamber is capable of operating at a pressure of less than
about 20 Ton.
Even more preferably, the chamber is capable of operating at a pressure
of less than about 5 Torr.
[0084] In other embodiments,
the apparatuses further comprise at least one chamber for holding the
composition. The volume of the compositions of the present invention may reduce
during decomposition. In some embodiments, the chamber may have a conveyor
having a perforated bottom such that decomposed materials may fall out of the
chamber once reaching a particular size, so as not to over-expose the materials
to microwave radiation. The conveyor may be adapted to be
oscillated.
[0085] An exemplary embodiment
of the present invention is depicted in FIGS. IA- 1G. Figures 1A-1G demonstrates one
apparatus wherein tire fragments are placed on a first conveyor belt that
carries the tire pieces through three, differently-sized xxxxxxxx of the
apparatus. In a first chamber, the tire pieces are exposed to microwave
radiation using the methods described herein. As the tire fragments decompose,
the smaller pieces will fall through perforations in the first conveyor and drop
to a second conveyor. The second conveyor is not exposed
to microwave radiation in the first chamber. The second conveyor carries the
pieces to a second
chamber, wherein they are exposed to microwave radiation using the methods
described herein. As the pieces decompose, the smaller pieces fall through the
perforations in the second conveyor to a third conveyor. The perforations in the
second conveyor are smaller than the perforations in the first conveyor. The
third conveyor is not exposed to microwave radiation in the second chamber. The
third conveyor carries the pieces to a third chamber, wherein they are exposed
to microwave radiation using the methods described herein. As the pieces
decompose, the smaller pieces fall through the perforations in the third
conveyor to a fourth conveyor. The perforations in the third conveyor are
smaller than the perforations in the second conveyor. Decomposition will be
essentially complete after exposure in the third chamber and the material
remaining on the fourth conveyor will be mainly steel, carbon black, and ash,
which can be further processed using techniques known in the
art.
37
[0086]
FIG. 1 comprises FIGS.
1A-1F, along with inset FIG.
1G. The orientation of
FIGs.
IA through FIG.
IF arc set forth in the inset in FIG.
1. Referring to FIGs.
lA - 1G, there is provided an embodiment of the present invention
directed to processing tire cuttings using microwaves to recover fuel oil. The
processing equipment described herein is commercially available from one or more
process equipment manufacturing companies.
[0087]
FIG. IA illustrates an elevation view of the beginning section of a tire
cuttings plant layout according to an aspect of the present invention. This
illustration shows two tire processing lines side-by-side in a parallel
configuration. Tires from automobiles and trucks are first cut into suitable
chips, e.g., 4 x 4 or 5 x 5 chips (not shown). The tire chips are transported
using incline belt conveyor 120 to accumulation silos 102. The tire chips are
then conveyed from the accumulation silos 102 to a pre-washer screw wash section
122. Tire chips are then conveyed to a pressure washer hot water sonic washer
105. Dirt, stones, gravel and other debris is cleaned off of the tire chips to
minimize contamination of the process further downstream. The tire chips are
then dried using forced air dryer system 106. FIG.
IB is a plan view of the beginning section of a tire cuttings plant
layout corresponding to FIG.
1A. Cleaned and dried tire chips are then conveyed up another conveyor
120, as set forth in FIGs.
1C and 1D,
below.
[0088]
FIG. 1C is an elevation view of the midsection of the tire cuttings plant
layout described here. Cleaned and dried chips are transported to accumulation
silo 112, which are then transported along transport conveyor 120 to microwave
room 124. The details of the microwave room 124 or further described in FIG.
1G below. In this elevation view, a dual wall tank with enclosed high
high-capacity heat exchanger 118 is shown in dotted lines. This high- capacity
heat exchanger receives hydrocarbon vapor produced by the microwave
reactors
38
residing
within the microwave room 124. The position of the dual wall tank with enclosed
high- capacity heat exchanger 118 is illustrated further in FIG. 1D.
[0089] FIG. ID is a plan view
of the midsection of the tire cuttings plant layout described here. Accumulation
silos 112 feed tire chips via incline belt conveyor 120 and screw feed in-feed
section 117 to a series of microwave reactors within hermetically sealed reactor
room 116 with filtration system and vacuum pumps. Tire chips in the screw feed
in-feed section 117 are fed into a first microwave reactor 150 (see FIG. 1G) residing within the
microwave room 116. The microwave room is depicted in FIG. ID containing two sets of
microwave reactors side-by-side. Additional microwave reactors and additional
lines can also be added. Hydrocarbon vapors generated in the microwave reactors
from the irradiated tire chips are collected out of the top of each of the
microwave reactors. The hydrocarbon vapors are then transported, under vacuum
(e.g. at a pressure less than ambient) to heat exchanger 118. The heat exchanger
is capable of further separating hydrocarbon vapors to oil and high carbon gases
by cooling to a liquid or a vapor, depending on the vaporization temperature of
the hydrocarbon vapors.
[0090] The microwave reactor
room 116 is also depicted having refrigeration equipment 123 for maintaining
constant room temperature. Processed tire chips exit the microwave reactor 154
(Fig. 1G) by a screw
feed discharge section 115. Processed tire chips exit the final microwave room
hot and are subsequently cooled using cooler 114. The cooled processed tire
chips (below about 110°F) then enter a pregrader grinder system 113, where
processed carbon containing materials are separated from metallic materials
(e.g., metal tire cords). Metal materials are separated using a suitable
magnetic conveyor take away system, as shown in 121 in FIGs. lE and 1F. Organic particles (e.g.
carbon black) can further be shipped to bulk feed trucks equipped to handle fine
particles, other packaging, as well as rail cars. The resulting organic
particles are composed primarily of carbon. In some embodiments, the organic
particles can be used as electronic activators, as described
herein.
[0091] FIGs. 1E and 1F illustrate the magnetic
conveyor take away system 121 for separating metal particles from nonmagnetic
organic matter. Metal is stored in a metal storage unit 140 while nonmagnetic
organic matter (e.g., carbon particles) is transported via incline belt conveyor
120 to silo and grinder 130. Carbon particles prepared according to the
processes of the present invention are suitable for use as electron activators
for the microwave processing of heavy residual refinery oil and other materials
(e.g., residual oil from the bottom of a hydrocarbon distillation apparatus that
is traditionally unable to be further processed). In one embodiment, the tire
sidewalls can be separated from the tire treads. Tire treads typically have
a
39
greater
amount of carbon black than the sidewalls. Accordingly, the amount of carbon
black recovered from the treads is greater than that of the sidewalls. In one
aspect, carbon black can be accumulated to form electron activator by processing
the treads. Electron activator that can be further used in processing heavy
viscous oil feedstocks. Also present is a sifter system with grinder return 111
for preparing controlled particle size carbon material. The matter in the silo
and grinder 130 is transported by a pneumatic tube conveyor system 119 and
auxiliary pump 136 toward sifter 132, and then to sorter 134, and finally to a
super sack gantry system 138. The super sack entry system 109 is suitable for
loading and unloading using forklift delivery. Also shown is electrical
enclosure 108 containing control panels, a centrifugal feeder/sorter system 110
for managing fine particles.
[0092]
As shown in FIGs.
1D and 1G,
the microwave reactor room contains two series of three reactors each
(one series is illustrated in FIG.
1G). Tire pieces enter first reactor 150 via screw feed infeed section
117. This reactor is the largest reactor of the series. 4 x 4 or 5 x 5 inch tire
chips are first exposed to microwaves in the first reactor 150 by operation of
the microwave antennas
in the first microwave chamber 160. In this first stage, the tire pieces "pop"
or explode into smaller pieces when exposed to the microwaves. The smaller
pieces are separated through a mesh belt 170, and then transported onto another
transportation mesh belt 172. The mesh is designed to keep the microwaves in the
first reactor from getting through and over heating the tire chips. Typically,
the temperature of the tire chips is maintained at about 465°F or less. The mesh
size in the larger reactor will have an opening of approximately 2 inches, the
mesh size in the midsized reactor is approximately 0.5 inches, and the mesh size
opening for the smallest reactor is approximately 1/16".
[0093]
Microwaves are generally generated outside of the microwave room and
transported into the microwave room by a suitable microwave conduit, e.g.
stainless steel wire. The design and interconnection of the three microwave
reactors in series is provided so that the location of the tire chips in the
microwave radiation zone is maintained so that the tire chips do not exceed
465°F. Initially, "popping" of the tire begins in the first reactor 150 when the
temperature of the tire chips is in the range of from about 300°F to about
450°F. It has been surprisingly found that once the temperature exceeds about
450°F, the carbon black residing within the tires can be charred and overcooked
and the efficiency of the process for recovering hydrocarbon fuel oils
diminishes drastically. Accordingly temperature is desirably maintained below
about 465°F, or even below about 550°F. Without being bound by any particular
theory of operation, it appears that the tire chips pop because the reactors are
under vacuum and a lot of gas within the tire chips is being released suddenly
upon irradiation with microwaves.
40
[0094] Suitable operating
pressures are the range of up to about 20 mm of mercury, or even up to about 40
mm of mercury, or even up to about 100 mm of mercury. Accordingly, tire chips
processed in the first microwave reactor 150 are then transported to the second
microwave reactor 152, where the processed chips are further irradiated under
vacuum using microwave antennas
162. The tire chips are further reduced in size, and fall through mesh 174, and
then transported to the third microwave reactor 154. In the third microwave
reactor 154, the processed
chips are further irradiated using microwave antenna 164. Processed chips are
finally transported by a screw feed discharge section 118 and exit the microwave
reactors from screw feed discharge section 166, and through airlock (not shown)
and onto conveyor 156.
[0095] Each of the microwave
reactors are fed with microwave conduits terminating in a suitable cone or
nozzle. The first microwave reactor has more microwave nozzles 160 as it is
larger than the other two microwave reactors. The second microwave reactor is
shown with microwave nozzles 162, and the third microwave reactor is shown with
microwave nozzles 164. Each of the microwave reactors contains vacuum lines 180
to transport the resulting hydrocarbon gases to the high-capacity heat exchanger
118 (shown in dotted lines). Also shown in the microwave room 124 are
refrigeration equipment 123 to maintain the temperature of the ambient
conditions in the microwave room, and support structures 158 for supporting the
microwave reactors.
[0096] Suitable microwave
ranges for the processing of tire chips includes using X-band microwave
radiation generators (not shown) transmitted via conduit in tubes at various
frequencies to each of the reactors. Microwave frequencies for tire processing
varies from X-band down towards C-Band radiation. X-band is 5.2 to 10.9 GHz;
C-band is 3.9 to 6.2 GHz. K-band radiation is also useful in some embodiments.
K-band is 10.9 GHz to 35 GHz, which includes the sub-bands Ku (15.35 GHz to
17.25 GHz) and Ka (33.0 GHz to 36.0 GHz). Typically separate microwave antenna
tubes are separated in frequency by approximately 0.2 gigahertz. In the
embodiment shown in FIG. 1G, a total of approximately 36 microwave antenna tubes
are transported from a microwave source (not shown) to the microwave reactors.
The largest microwave reactor 150 has the greatest number of tubes, for example
about 18. The second microwave reactor 152 has fewer tubes, approximately 12.
The third microwave reactor 154 has the fewest number of tubes, approximately
60. Each of the tubes are capable of operating at different frequencies, which
frequencies in certain preferred embodiments varies between about 7.0 and 6.4
GHz. The ends of the microwave antenna from which the microwave radiation exits
into the reactor xxxxxxxx are fitted with a suitable cone antenna. Each of the
cone antennae emits microwave radiation at a separate frequency, which is
typically about 0.2 GHz
41
different
than the others that irradiate into each of the microwave reactors. Microwaves
are typically fixed in frequency but they may also be capable of being swept in
a varying frequency manner, for example, by using a variable frequency microwave
generator. A number of different frequency combinations are envisioned, for
example each of the cone antennas may be fixed in frequency, vary in frequency,
or any combination thereof. As the tire chips are irradiated, volatile
hydrocarbon vapors are emitted from the tire chips and collected by vacuum
tubing. Hydrocarbon vapors are then transported to a heat exchanger condenser.
Highly volatile gases and vapors that are not conveniently liquefied can be
separately recovered as a high BTU gas product.
[0097]
The plant layout described in FIGS.
1A-1G is operated at a product speed (per line) of approximately 30 tires
per minute on average. Hourly production rate is approximately 36000 pounds per
hour or approximately 1300 ft.3 per hour. This
is based upon a used automobile tire weight of approximately 20 pounds (9.1 kg).
Or alternatively a used truck tire about 40 pounds (18.2 kg). The shredded tire
chip sizes can be in the range of from about 3 to about 5 inches. Average loose
density of the chips is approximately 24 pounds per cubic foot to about 33
pounds per cubic foot. Heat values generated at atmospheric pressure range from
approximately 12,000 BTUs per pound to about 15,000
BTUs per pound.
[0098]
FIG. 2A is an elevation view, axial direction, of a microwave reactor
suitable for processing oil cuttings according to an aspect of the present
invention, Oil cuttings comprise dirt, rock, water, carbon deposits, and the
like, which oil cuttings are obtained during drilling operations. Drilling
operations include drilling from an oil rig, drilling from a deep-sea oil
platform, as well as mining of shale rock and coal deposits. During drilling,
rock that is rich in hydrocarbons is typically reached prior to hitting a pocket
of oil. This hydrocarbon rich rock is transported up to the surface and can
comprise up to 15% oil, and even up to 25% oil. The consistency can also be
similar to oil shale. Hydrocarbon rich rock can be considered hazardous waste
and would need to be disposed of properly. It cannot be sent to a landfill, and
accordingly it has traditionally been handled by combustion. This is
particularly a problem on an oil rig in the middle of the ocean, where it may be
forbidden to dump oil drillings comprising greater than 1% hydrocarbon content.
Accordingly, the process of the present invention can also be used to recover
hydrocarbons from drill cuttings, thereby permitting the drill cuttings to be
placed back in the environment after the hydrocarbons have been substantially
removed. As used herein the term "substantially removed" refers to a composition
comprising less than 1% by weight hydrocarbon content. Oil drill cuttings having
less than 0.01% by weight hydrocarbon has been produced using the processes
described herein. Accordingly, the methods suitably provide drill
42
cuttings
that comprise less than 1 percent, or even less than 0.5 percent, or even less
than 0.2 percent, or even less than 0.1 percent, or even less than 0.05 percent,
or even less than 0.02 percent, or even less than 0.01 percent by weight hydrocarbons
based on weight oil cuttings. Suitable oil cuttings enter into the system
through in-feed grinder system 201. Oil cuttings are ground to a suitable size,
then fed into the microwave reactor chamber (vacuum sealed reactor tank 216) via
in feed screw 202. The vacuum sealed reactor tank 216 contains a helical mixer
element 203 for mixing and stirring the ground oil cuttings. The reactor tank is
typically filled to about 40% of its total volume. The microwaves irradiate the
contents of the reactor via antennas that are oriented in an orbital arrangement
emanating from the top of the reactor. The microwave antennas are desirably
flexible and irradiate from several slides from the top the reactor towards the
mixing material below. A helical mixer element is turned using a motor 210.
Microwaves emanating from a cone antenna or a plurality of cone antennas (not
shown) irradiate the oil cuttings with suitable microwave radiation. Hydrocarbon
gases and oil vapor exit towards the top vacuum tubing towards vacuum pump and
collected in a suitable heat exchanger vapor condensing unit. Hydrocarbon vapor
gases produced by the process of irradiating the oil cuttings with microwaves
exit via a vacuum discharge tube (not shown). Residual geologic material and
unreacted carbon deposits settled towards the bottom of the reactor. The
unvaporized matter is discharged from the microwave reactor 216 via screw feed
discharge section 204, and exits the system via discharge system 206. Material
exiting the system is suitably clean of hydrocarbons so as to be considered
nonhazardous waste. For example, material exiting the reactor can be returned to
the ocean after drilling, or can be returned to the land after drilling. Also
shown is reactor support structure 205 for holding the components as set forth
in the system.
[0099] FIG. 2B illustrates an
elevation view of the microwave reactor of FIG. 2A, longitudinal
direction. Oil cuttings are added to the system as in-feed via an airlock at
201, which oil cuttings are then transported to the reactor 216 via in-feed
screw 202. Depicted in this diagram is conduit 214 for pulling vacuum on the
airlock, and on the vacuum sealed reactor tank 216, using vacuum pumps 207.
Microwave waveguides 212 are shown entering the vacuum sealed reactor tank 216.
Microwaves emanating from a suitable microwave cone antenna radiates the oil
cuttings within the reactor tank. A helical mixer element 203 rotates to mix the
oil cuttings, convey the oil cuttings, and reflects microwaves throughout the
volume of the chamber. After suitable microwave processing at a particular
residence time, the reacted oil cuttings exits the reactor through screw feed
discharge section 204 and exits via a suitable airlock 206 of the discharge
system. Also shown is reactor support structure 205.
43
[0100] FIG. 2C
illustrates an elevation view of the microwave device and control room
suitable for generating microwaves and propagating the same through waveguides.
The microwave device and control room 208 is depicted as comprising an
electrical panel and a series of six individual microwave generators (222, 226,
230, 234, 238, and 242) each connected to a series of microwave antennas (220,
224, 228, 232, 236, and 240). The antennas are combined into a combined antenna
conduit 212 which exits the microwave device control room 208 and leads towards
the vacuum sealed reactor tank 216 as shown in FIG. 2B.
Suitable microwaves for processing oil drill cuttings have frequencies in
the range of about 11.2 to about 11.8 GHz, typically about 11.5 GHz. Oil shale
can also be processed using the equipment and processes described herein at a
microwave frequency in the range of from about 10.6 to about 11.2 GHz, and
typically about 10.9 GHz. Tar sands can be appropriately processed using
microwaves 4 to about 12 GHz. Tar sands can also be processed in the K-band,
preferably in the Ku band. Anthracite coal deposits can also be processed in the
KU band as well. A vacuum is maintained within the microwave reactor chamber
using suitable vacuum and hydrocarbon vapor condensation equipment, for example
at pressures less than about 100 mm of mercury, and even at pressures of less
than about 40 mm of mercury, or even at pressures of less than about 20 mm of
mercury. Maintaining such low operating pressures helps to keep the overall
process temperatures below about 465°F or even a temperatures less than about
450°F so as to prevent overheating and efficient recovery of hydrocarbon vapors.
A large proportion of the hydrocarbon vapors can be condensed into liquid fuel
oil at ambient temperatures.
[0101] The
system described in FIGs. 2A-2C
can be suitably adapted and scaled to process oil cuttings at a
throughput of up to about 2 tons per hour to even up to about 10 tons per hour.
It should be readily apparent to the skilled person how to increase the size and
power of the microwave reactor chamber to yield higher throughputs.
[0102] The
system described in FIGs. 2A-2C
can also be suitably adapted in scale to process oil shale rock. The
processing of oil shale rock includes irradiating it with suitable microwaves at
power sufficient to increase the temperature of the oil shale rock to within a
range of from about 500°C to about 600°C. Without being bound by any theory of
operation, it is believed that these processing temperatures are considerably
hotter than compared to tire cuttings for the reason that more energy needs to
be applied to the rocks to volatile lies the hydrocarbons. This is in contrast
to softer, substantially higher concentration hydrocarbon, tires that readily
absorb the microwave energy. Suitable shale rocks are broken down into small
pieces after being mined For example, shale rock pieces are suitably smaller
than an inch cube, even smaller than a half inch cube, or even smaller than
about 3/8" cube, even smaller than about a
44
half inch
cube, or even smaller than about 1/4" cube. The hydrocarbon content of the oil
shale rock typically comprises hydrocarbons comprising from about CIO to about
C25, or even from about CM to about C22. Oil shale rock can contain up to about
5% by weight hydrocarbons, or even up to about 15% by weight hydrocarbons, or
even up to about 25% by weight hydrocarbons. In some cases, shale rock can
contain up to about 70% by weight hydrocarbons.
[0103] FIGs. 3A and 3B depicts several embodiments of the present
invention for recovering petroleum-based materials and hydrocarbons from oil
slurry. FIG. 3A and 3B are schematic illustrations of two
embodiments of a microwave assisted system for the distillation and recovery of
heavy oil bottoms, e.g., oil slurry, from a distillation plant. FIG. 3A shows the following elements of a
traditional hydrocarbon distillation plant: 302 distillation tower 360 unrefined
inlet into distillation tower; 304 vapor line; 306 natural gas line; 308 gas
separator; 310 pump; 312 LPG line; 314 gasoline lines; 316 jet fuel (kerosene)
line; and 318 inset: close-up view of the liquid vapor contact caps with an a
distillation tower. This distillation system can be modified using the microwave
process of the present invention as follows. An electron activator 320 is added
using an electron activator pump 322 into residual oil 362. Hot residual oil
line (e.g., heavy oil) 362 is pumped into the microwave reactor 330 and atomized
using an atomizer 334. Microwave waveguide antenna 336 is powered from the
microwave room and control system 340, which control system includes microwave
generators 342 and microwave waveguides 344. The microwaves exit the waveguide
antenna 336 at cone nozzles within the microwave reactor so as to radiate the
atomized residual oil above the atomizer 334. Vacuum pumps 350 connected to the
vacuum line 332 maintains pressure of less than about 20 mmHg, or even less than
about 40 mmHg, or even less than about 100 mmHg. The irradiation of the atomized
residual oil gives rise to cracking of the residual heavy oil, which in turn
produces hydrocarbon vapors such as natural gas 352 and heavier hydrocarbon
vapors such as diesel and heating oil 354. In the microwave reactor 330,
residual oil 362 is removed from the bottom of a distillation tower 302,
combined with electron activator 320 and processed by microwave after
atomization. We have discovered that addition of the electron activator to the
residual oil, for example about 2% by weight based on residual oil of carbon
small particles, gives rise to a much faster, more efficient absorption of the
microwaves to yield more efficient cracking of the residual oil. Accordingly,
electron activator made using microwave processing of tire chips as described
supra is useful for making electron activator. Suitable electron activator is
provided as a fine powder, for example of about a hundred mesh, or finer. The
electron activator may be coarser than 100 mesh, depending on the precise
application and handling requirements. Without
being limited by any particular theory of operation, the electron activator
enhances the
45
absorption of microwaves by the residual oil, which gives rise to faster processing and more efficient processing of the heavy oil. As a result, the electron activator, which comprises carbon powder particulates, are capable of absorbing microwave radiation. Solid particles containing residual hydrocarbons, such as electron activator, result in popping (as in popcorn) when irradiated. Without being bound by any particular theory of operation, it is believed that the popping action of the small electron activator particles within the residual oil enhances the microwave processing of the residual oil. In certain embodiments, the electron activator functions as a catalyst for effectuating the microwave cracking process.
[0104] Suitable microwave
radiation frequency ranges from about 8.0 to about 8.8 GHz, or
in the range of from about 8.1 GHz to about 8.7 GHz, or even in the range of
from about 8.2 GHz
to about 8.6 GHz, or even in the range of from about 8.3 GHz to about 8.5 GHz,
or even about 8.4 GHz. The microwave reactor contains a series of microwave cone
antennas that radiate the atomized residual oil with microwaves. These microwave
cone antennas can each receive the same or different microwave frequencies. When
the frequencies differ, they typically are separated by increments of about 0.2
GHz. Ranges of microwave frequencies are typically useful for processing the
atomized residual oil in this manner. Accordingly multiple microwave antennas
344 receive microwaves generated by a plurality of microwave generators 342
provided in the microwave control system 340. Microwaves are transmitted through
microwave antennas 344 to the microwave antenna conduit 336. Microwaves then
enters the microwave reactor. Typically the residual oil 362 is pre-heated to a
temperature of about 350°C so that it is capable of flowing under pressure and
atomized. The use of microwaves has been demonstrated to effectively crack the
hydrocarbon chains in the heavy residual oil. Atomization helps to increase the
surface area of the residual oil and decrease particle size, thereby
effectuating absorption of the microwaves and cracking of the hydrocarbon
chains. The residual oil is suitably heated to temperatures sufficient that can
flow under pressure and atomized. Suitable temperatures are at least about
250°C, or even at least about 300° C, or even at least about 350° C, or even at
least about 400°C, or even at least about 450°C, or even at least about 500°C.
The residual oil may be preheated using any of a variety of heating methods, for
example convection, conduction, or irradiation, e.g. microwaves. The heavy
residual oil chains crack at least several times.
[0105] Processes according to
the present invention are capable of producing combustible gases. The processes
according to the present invention are also capable of producing at least
several different weights of oils. These oil products range from carbon content
of hydrocarbon chains comprising from 14 carbons up to about 25 carbons. The
starting residual oils comprise hydrocarbon chains having at least 25 carbons or
even at least 28 carbons. The
46
hydrocarbons
in the residual oil do not necessarily need to be linear hydrocarbon chains, for
example cyclic and branched hydrocarbons are also envisioned. Instead of
atomization, hot flowing residual oil can be formed into a thin film and
irradiated with microwaves, or can be ejected into a shooting stream and
irradiated with microwaves, or can be broken into droplets under force of
pressure and irradiated with microwaves. Similar related processes give rise to
narrow dimension residual oil droplets. In certain embodiments the products of
microwave radiation within the microwave reactor 330 illustrated in FIG. 3A can
be recycled back to the distillation tower 302 for further
processing.
[0106] FIG. 38 is a schematic of another embodiment of
a microwave assisted distillation and recovery unit for
heavy oil bottoms from a distillation plant. This embodiment is similar to that
described in FIG. 3B,
with the exception that
this embodiment further includes a reboiler 348 for heating the bottoms
coming from distillation tower 302 by a transfer line 370. The reboiler heats the bottoms which
are distilled in vacuum tower 340. Residual oil 346 from the vacuum tower is combined with
electron activator 320 using electron activator pump 322 to provide a mixture of residual oil in
electron activator 362. This mixture is then atomized in microwave reactor in
330. The operation of the microwave reactor is similar to that discussed supra
in FIG.
3A.
[0107] FIG. 4A
illustrates an elevation view of a microwave reactor system suitable for
processing shale rock, tar sands, drill cuttings, and the like. Inlet feed screw
402 is suitable for transporting shale rock and other hydrocarbon containing
cuttings and the like into microwave reaction chamber 412. Helical screw mixing
flights 408 arc mounted to an axle 406 which is rotated using a motor. Helical
screw mixing flights mix and transport the material, such as shale rock pieces,
in the microwave reaction chamber interior 404. Microwave antennas 410 enter the
interior of the microwave reaction chamber 404. The material within the
microwave reaction chamber interior is stirred and irradiated. Vapors are
removed using a vacuum recovery system and condensing unit (not shown). Material
depleted of hydrocarbon vapor is discharged through the exit discharged from
feed system 416. Also shown is a support structure 414.
[0108] FIG. 4B
provides a plan view of FIG. 4A,
wherein the direction of the material is shown entering the microwave
reaction chamber via onlet feed screw 402 mixing within the microwave reaction
chamber by a helical screw mixing flights 408, and finally exiting via exit
discharge screw feed system 416. FIG. 4C is an
elevation view of the microwave reactor system along the axis 406, the near end
being the exit discharge screw feed system section 416. FIG. 4D
illustrates a suitable microwave device control room, waveguides, and
vacuum pumps suitable for use with the system illustrated in FIG. 4A. FIG. 4E
illustrates an optional xxxxxx
47
elevator
for transporting material into the inlet feed section 402. FIGs. 4F and 4G illustrate three horizontal
microwave reactor systems operating in parallel. FIG. 4H illustrates additional
microwave generators, waveguides and vacuum pumps for operating the three
horizontal microwave reactors illustrated in FIGs. 4F and 4G. The
processing of hydrocarbon containing materials, such as shale rock, tar sands,
drill cuttings and the like, is conducted in a vacuum environment, less than
about 20 mm of mercury, or less than about 40 mm of mercury, or even about less
than 100 mm of mercury. The hydrocarbon containing materials are subject to
heating by the microwaves and other heating means, up to about 350°C, or even up
to about 450°C, or even up to about 550°C, or even up to about 600°C. The
hydrocarbon containing materials are removed from the microwave reactor chamber
via a suitable vacuum plumbing system. The hydrocarbons are recovered using a
suitable heat exchange or condensing system (not shown).
[0109] FIG. 5A depicts an
exemplary embodiment of the present invention for extracting petroleum-based
materials, carbon-based materials and hydrocarbon-based materials in
situ. A probe capable of generating microwave radiation (e.g., cone,
antennae or nozzle) according to the methods of the present invention can be
lowered into drilled oil xxxxx. Using the methods of the present invention, the
petroleum-based materials can be vaporized and collected at surface-level and
processed using techniques known in the art. FIG. 5A illustrates a
schematic view of a microwave system for in situ recovery of oil from geologic
deposits. A suitable geologic deposit 526 includes an oil well, a capped oil
well, a shale rock deposit, a tar sand deposit, a coal deposit, and the like.
This illustration depicts a vacuum recovery unit 502 (e.g., a Venturi type
system) for recovering geologic hydrocarbons such as fossil fuels from a capped
oil well. This system comprises casing 504 extending from the surface of the
ground to the geologic carbon deposits at 526. A microwave waveguide is
delivered through the casing to the geologic carbon deposit 526. A microwave
antenna nozzle 510 resides at the end of the microwave waveguide 506 proximate
to the geologic carbon deposit, into which microwaves radiate. On the ground
surface is illustrated portable electric generator 522, portable pumping system
524, and portable microwave generation station control unit 520. Hydrocarbon
vapors generated by the microwaves in the geologic carbon deposit 526 are
transported under vacuum as vaporized geologic carbon deposit (e.g., oil vapor)
508 to the vacuum recovery unit on the surface ground. Capped oil xxxxx contain
hydrocarbons that can be cracked to oil, suitable for use as diesel fuel. This
involves opening up capped oil xxxxx, optionally adding electron activator into
the xxxxx (which aid in absorbing the microwaves and converting the heavy oil in
the xxxxx to hydrocarbon vapor), and irradiating the heavy hydrocarbons with
microwaves. Once vaporized, the hydrocarbons are readily transported to the
surface using suitable vacuum piping,
48
or other
plumbing means 528. The vacuum recovery unit 502 is also capable of
fractionating the hydrocarbons into other hydrocarbon products. Oils that are
difficult to recover using normal pumping means can be recovered according to
the processes.
[0110] FIG. 5B
depicts an apparatus of the present invention for recovering petroleum-
based materials from oil shale, in situ. A probe capable of
generating microwave radiation according to the methods of the present
invention, can be lowered into oil shale deposits. Using the methods of the
present invention, the petroleum-based materials can be vaporized and collected
at surface level and processed using techniques known in the art. FIG. 5B
illustrates a schematic view of a microwave system for recovering
hydrocarbons below ground. In this embodiment, one or more microwave antennae
are shown capable of traveling horizontally underground with respect to the
ground surface. The microwave antennae are illustrated comprising one or more
microwave nozzles for vaporizing hydrocarbon geological deposits in a vacuum
environment. FIG. 5B
illustrates two conduits (on the left portion of the figure), each
containing a plurality of waveguides that terminate it into a suitable microwave
nozzle or cone emitter. Suitable microwave cones emitters are commercially
available. This process is adapted for recovering residual oil in capped oil
xxxxx, and can also be adapted to other geological hydrocarbon deposits such as
tar sands and shale rock. If the oil well is "dry" with mainly heavy viscous
hydrocarbon material remaining in the well, a microwave antenna is transported
down into the oil well and the antenna-end can reside in one or more of the
openings. Microwave radiation is directed towards the geologic material in the
vicinity of the antenna.
[0111]
Various hydrocarbon geological deposits can be processed underground
using this technology at various depths. Piping for the xxxxx can start at a
diameter of about 24 inches at the surface, which diameter is progressively
narrower and narrower as sections of piping are added as the depth increases. At
a depth of approximately 3000 feet, a typical opening (diameter) of the piping
is about 6 inches. For example oil shale deposits in the Western part of the
United States are relatively shallow, i.e., near the surface. Strip mines are
also relatively shallow, and other deposits may be as deep as 2000 feet or more.
Previously pumped oil xxxxx often have xxxxxxxx of oil that are not readily
accessible but require opening by an additional explosive or drilling operation.
Certain xxxxxxxx can also be opened by irradiating the sealing rock material
with microwaves. In a laboratory setting, it has been discovered that oil shale
pops and reduces in size when irradiated with microwaves. As the oil shale
releases hydrocarbons (i.e. oil), the oil shale "pops" like popcorn.
Accordingly, directionalizing microwaves within the geological xxxxxxxx can give
rise to breakdown of the geological formation (i.e. the rocks pop, break apart,
and fall down and fill the cavity). Accordingly, the antennas can be moved
around
49
within
geological formations to aid in recovering hydrocarbon material. In some
embodiments microwave antennas are placed down about 5000 feet or more, and then
are directionalized to travel on the order of approximately 100 yards or so
horizontally.
[0112] Any type of hydrocarbon
material present within the geological formation can be cracked to gas and
recovered at the surface using fractionalization condensation units. For
example, any carbon suitable for use as diesel fuel can be made by irradiating
oil shale. Resulting diesel fuel is suitably used as Cat Diesel Engine Oil.
Sometimes oil xxxxx are drilled using directional drilling technologies.
Suitable directional drilling technologies are capable of bending at a rate of a
degree a foot to create an angle. Accordingly, flexible microwave antennas are
suitable for use in such oils. Accordingly, the process includes uncapping a
capped oil well. This can be accomplished by drilling out a concrete plug used
to cap the well, if present.
[0113] The system can include
a number of auxiliary equipment located on the surface of the ground. Such
equipment includes, for example, well drilling equipment, vacuum pump vehicle,
fuel tank vehicles, a generator vehicle, and microwave control vehicle that
includes microwave generators, microwave waveguides, and associated equipment.
The vacuum pump vehicle can contain a vacuum pump that is capable of applying
intermittent vacuum pulse technology to raise hydrocarbon gases to the surface.
The hydrocarbon gases are recovered and collected in a suitable distillation
tower or fractionation tower that is fitted with heat exchanger and condensing
unit. Suitable oil xxxxx and other hydrocarbon geological deposits residing in
the ground are accessed via a tube to provide a sealed system with the vacuum
pump vehicle for producing the vacuum environment needed for recovering a
hydrocarbon vapors. Suitable vacuums include absolute pressures of less than
about 20 mm of mercury, or even less than about 40 mm of mercury, or even less
than about 100 mm of mercury. The microwave control vehicle contains suitable
flexible microwave waveguides and generators. Typically the end of the microwave
waveguides (e.g., antennas) are fitted with a suitable microwave cone emitter
(e.g., nozzle). The antennas are placed into the mahogany zone in Earth in situ
and microwaves are used to radiate tar sands, or oil shale, or other hydrocarbon
deposits. The microwaves cause vaporization and gasification of the otherwise
viscous and solid-like hydrocarbon and carbon geological sources within the
ground. One or more antenna fitted with one or more cone emitter devices can be
used.
[0114] Generated hydrocarbon
gases (e.g., take off gases) are transported to a suitable fractionation tower
capable of separating the gas, as illustrated in FIG. 5C. Geological material
such as sand and rock from which hydrocarbons have been removed remain within
the geological formation. In some embodiments, an in situ microwave process is
provided. Other
50
embodiments
do not require in situ microwave irradiation of the geological formation, e.g.,
geological material containing hydrocarbons that are mined and provided via
separate feed mechanism into a suitable microwave reactor. Geological material
such as sand and rock can be substantially totally gasified (i.e., depleted of
hydrocarbons and carbons) according to the processes of the present invention,
which geological material is then returned to the environment substantially free
of hydrocarbons. Finally, fuel and other hydrocarbons recovered form the
geological source can be stored in a suitable tanker vehicle and shipped for
delivery, further processing, and so on. The recovered hydrocarbons may also be
transported by pipeline, rail car, and the like. Optionally, the hydrocarbon
vapor recovered from geological sources may be fractionalized on-site using a
suitable distillation tower, as illustrated in FIG. 5A. The process of operating a
distillation tower is suitably described in FIG.
5C, which illustration shows the separation of crude oil using a
fractionating tower into its component products.
[0115] FIG. 6 depicts one embodiment
for extracting petroleum-based materials from shale and tar sands and oil sands.
The tar sands can be loaded into the top of the apparatus, which can be under
reduced pressure. Using gravity and shaking, the tar sands move through the
apparatus while being exposed to microwave radiation as described herein.
Vaporized petroleum-based materials can be captured and collected in separate
vessels and refined using methods known in the art. After the material has
passed through the apparatus, it will be essentially free of petroleum-based
materials. FIG. 6 provides an elevation
view of a multiple microwave reactor system suitable for high volume recovery of
petroleum, carbon and hydrocarbons (e.g. diesel oil) from mined material, e.g.,
oil shale, oil sands, coal slag, and tar sands. This system is illustrated
having the following equipment: microwave waveguide 602; microwave antennas 620;
vacuum gas line 604; microwave reactors 606 - a total of five connected in
series; connecting pipe 608 between microwave reactors 606; top airlock 610
adjacent to in-feed of surface shale and tar sand material; airlock 612 adjacent
to discharge of depleted material; baffles 614 within vertically oriented
microwave reactors 606; support structure 630 to support multiple microwave
reactors connected in series and adjacent to source of surface shale and/or tar
sands. Mined material enters the system at airlock in-feed 610, which minimizes
the amount of air entering the system. The system is also fitted with a suitable
vacuum gas line 604 to maintain a vacuum environment (vacuum pumping equipment
not shown) of up to about 20 mm of mercury, or even up to about 40 mm of
mercury, or even up to about 100 mm of mercury. Material enters the first
microwave reactors 606 adjacent to the airlock, which material is transported
along baffles 614 while being irradiated with microwave radiation through
microwave antennas 620 (as illustrated in the second through fourth
51
microwave
reactors 606). Microwaves irradiate, heat, and crack the hydrocarbons, which
hydrocarbons exit the system via a vacuum gas line 604 (connections between the
microwave reactors 606 in the vacuum gas line 604 not shown). Geological
material leaves the topmost microwave reactor 606 and enters a first connecting
pipe 608, which partially reacted material is transported to a second microwave
reactor 606. The process is repeated and the material is subsequently
transported and irradiated with microwaves as it progresses along the series of
microwave reactors and connecting tubes. The processed material eventually
arrives at the bottom discharge, where it exits the system through an airlock
612.
[0116] Another embodiment of
an apparatus of the present invention is depicted in FIG. 7. FIG. 7 is a schematic
view of a microwave reactor chamber and system for recovering fuel oil from a
hydrocarbon-containing source, such as used tires. The system includes the
following equipment and features: nitrogen supply 702 ; nitrogen regulator 704;
nitrogen flow valve 706; nitrogen inlet 708 to microwave reactor chamber 710 ;
microwave reactor chamber 710; infrared thermocouple 712 to measure average
temperature over irradiated area ; nitrogen flow meter 714 for infrared
thermocouple purge (low flow) ; microwave scattering reflector 716; motor 718
for microwave scattering reflector 716 ; platform 720 for holding hydrocarbon
containing materials; irradiation area 722; vacuum outlet 724; vacuum gauge 726;
opening 728 to microwave antennae; microwave source 730 (TVT or magnetron);
temperature gauge 732; vapor transfer tube 734; condenser tube 736; cooling coil
740; oil collector 742; valve drain 744; vacuum bypass valve 746; vacuum pump
748; flow meter 750 for TWT nitrogen purge (flow); nitrogen supply lines 752;
exhaust 754; exhaust gas flow meter 756; reactor chamber 758; reactor chamber
door 760.
[0117] FIGs. 8A, 8B and 8C illustrate an embodiment of
the present invention for incorporating a microwave processing system to process
drilling cuttings on an oil drilling platform. FIG. 8A is a plan view of an exemplary oil
platform incorporating a drill cuttings microwave processing unit. A suitable
placement of a microwave processing unit (further illustrated in FIG. 8C) is provided . FIG. 8B illustrates an
elevation view of the oil platform in FIG. 8A. FIG. 8C illustrates a
vertical and horizontal configurations of the drill cuttings microwave
processing unit suitable for use in the oil platform illustrated in FIG. 8A.
[0118] FIGs. 9A-9C are
electron microscope photographs at 60,000 times magnification of pyrolytic
carbon black material obtained according to Example 3 and using the system
illustrated in FIG. 7. The production of
this material is further described in Example 3, below.
52
[0119] FIGs. 10A-10E
illustrate an additional embodiment of a system for processing materials
containing hydrocarbons. Suitable materials include shale rock, drilling
cuttings, tar sands, plastics, polymeric materials, recycled
hydrocarbon-containing materials, refuse, residual oil, slurry oil, hydrocarbon
distillation bottoms, and the like. These figures illustrate the following
equipment and features: 1001 microwave tubes, amplifier and waveguides; reactor
drum 1004; sealed material in-feed 1002 through reactor drum 1004; in-feed screw
1003; rotating discharge screw 1005; control panel 1006; vacuum pumps 1007;
hydraulic drive transmission system 1008 for rotating reactor drum 1004;
shipping container 1009; vacuum release support 1010; drum bearing seal 1012;
roller bearings 1014; vacuum port 1016; microwave waveguides 1018 entering
rotating reactor drum 1004; mixing flight bars 1020 for mixing materials within
the rotating reactor drum 1004; bearings 1022 by which mechanism the drum
slidably rotates; rotating reactor drum axel 1024 by which mechanism the reactor
drum rotates through actuation with the hydraulic drive transmission center
1008.
[0120] FIG. 10A is an
elevation view of a rotating drum reactor system. Material enters the in-feed
1002 via a suitable source, for example a xxxxxx for receiving chips or chunks
of material. The material then enters into the in-feed screw 1003, which meters
the material into reactor drum 1004. The material is stirred and mixed using
mixing flight bars 1020. The drum is rotated using the hydraulic drive system
1008. The drum reactor is maintained under vacuum by means of vacuum pumps 1007
and vacuum gas line. The reactor drum is vacuum sealed by means of a drum
bearing seal 1012 as shown in the inset of FIG. 10D. Microwaves are
generated at 1001 and transmitted by a waveguides 1018 into the drum reactor
1004. Hydrocarbon vapors are removed through the vacuum gas line and collected
for further processing as described herein above.
[0121] FIG. 10B is a plan view
of the rotating drum reactor portion depicted in FIG. 10A. The rotating drum 1004 is
shown comprising a drum bearing seal 1012, which drum slidably rotates against
end caps comprising ports for microwave antenna and vacuum connections. The
reactor drum slides via roller bearings 1014 in the top and bottom end caps. The
drum reactor 1004 resides within shipping container 1009. Screw conveyor 1003
conveys material into the drum reactor 1004. FIG. 10C is a plan view of an
alternative embodiment of a rotating drum reactor system. FIG. 10D is a cross-sectional
view of a drum bearing seal used in the rotating drum reactor
system.
[0122] FIG. 10E is an
elevation view of the rotating drum reactor portion depicted in FIG. 10A. FIG. 10E further
illustrates the in-feed screw 1003 for metering the material into reactor drum
1004, which material is stirred and mixed using mixing flight bars 1020 as
the
53
drum is
rotated using the hydraulic drive system 1008. The drum reactor is maintained
under vacuum by means of vacuum pumps 1007 and vacuum gas line. The reactor drum
is vacuum sealed by means of a drum bearing seal 1012 as shown in the inset of
FIG.
10D. Microwaves are generated at 1001 and transmitted by waveguides 1018
into the drum reactor 1004. Mixing flight bars 1020 are used for mixing
materials within the rotating reactor drum 1004. Bearings 1022 are used for
slidably rotating the drum while maintaining the vacuum and microwave antenna
connections. The reactor drum rotates by means of axel 1024 through actuation
with the hydraulic drive transmission center 1008. Hydrocarbon vapors are
removed through the vacuum gas line 1016 and collected for further processing as
described herein above. Spent materials substantially depleted of hydrocarbons
exit to discharge screw 1005.
[0123]
As an example, a suitable microwave rotating reactor drum system for
extracting hydrocarbons from materials such as drill cuttings and fluids can
comprise the following equipment:
[0124]
A suitable microwave control center includes a number of hydrocarbon
specific modular microwave generators, high power amplifiers, master controller
module, slave driven power modules, thermal sensors, safety 1/0 devices for
vacuum, interlocks, and emergency shut down, manifold banked configuration of
flexible waveguides/windows/adapter plates, thermal metrology gear microwave
power measurement instruments and computer control station as per
schedule.
[0125]
A suitable 4'-0" diameter rotating in-feed channel drum unit with vacuum
seal provisions comprises 3/8" stainless steel welded frame construction and
bolt on stainless steel (replaceable) hardened steel troughs driven by a direct
coupled, 5-hp NEMA-4 variable speed (VFD driven) indexing servo-motor to
transfer metered product into the feed screw.
[0126]
A suitable 2'-6" diameter x 12'-6" long in-feed screw assembly comprises
heavy-duty stainless steel 2" square tubing frame supporting 3/8" stainless
steel skins with hardened helical screw driven by a direct coupled, 2-hp NEMA-4
variable speed (VFD) servomotor to transfer metered product into the reactor
vessel.
[0127]
A suitable 5'-0" diameter x 3/8" horizontal seamlessly welded stainless
steel and jaciceted sub-baric vessel is constructed with internal angular flight
bars, (length varies depending on composition of the intended process to) with
two - 24" long x 3/8" stainless steel end cap sections, hardened steel
circum-centerline rack & pinion hydraulic transmission driven by a variable
speed gear-head motor. Includes a maintenance access door, piping as required to
heat vessel jacket, microwave antenna mountings, vacuum port, pressure/flow
meters and gauges as required, power transmission is stainless steel guarded.
Reactor tank and peripheral equipment
54
is
supported by heavy duty stainless steel formed structural channels and heavy
duty external bearing wheels.
[0128] A
suitable 2'-6" diameter x 12'-6" long discharge screw assembly
comprises heavy-duty stainless steel 2" square tubing frame supporting 3/8"
stainless steel skins with hardened helical screw driven by a direct coupled,
2-hp NEMA-4 variable speed (VFD) servomotor to transfer metered product
into the reactor vessel.
[0129] A
suitable NEMA 4 electrical motor control panel, 480v/3ph/60Hz - 24 volt
control circuits controls all motors and devices, directly mounted to shipping
container wall, includes Xxxxx-Xxxxxxx PLC, touch screen diagnostics, VFD drive
components, I/O racks, rigid conduit with all marine wire specs, color coded,
tagged and match-marked for easy identification.
[0130] A
suitable vacuum system comprises Dual to Quad (which varies according to
throughput) 1.5-hp oil-lubricated, rotary vane vacuum pumps system for -20in.Hg.
continuous duty operation. A vacuum release port system is mounted on the
discharge screw section.
[0131] Electron
activator. It has been discovered that microwave radiation in the
frequency range of from about 4 GHz to about 12 GHz is useful for selectively
recovering hydrocarbon materials from geological petroleum and mineral sources,
as well as manufactured materials such as automobile and truck tires. It has
further been found that such materials can comprise carbon particles that absorb
energy when irradiated with microwave radiation. The heat from the energized
carbon particles is released to the adjacent hydrocarbon materials, and when
sufficient heat is released, the hydrocarbons are reduced in molecular weight,
i.e., "cracked", and vaporized. Unlike the prior art, the present discovery
discloses a particular range of frequencies that is efficacious for the
electromagnetic stimulation and heating of carbon particles for recovering
hycrocarbons, such as diesel fuel, from difficult to recover hydrocarbon
sources.
[0132]
Disclosed are methods for microwave treatment of difficult-to-recover
hydrocarbon source materials comprising contacting the hydrocarbon source
material with particles comprising carbon, and subjecting the hydrocarbon source
material to microwave radiation. Also disclosed are methods for microwave
treatment of hydrocarbon source material comprising contacting the hydrocarbon
source material with material having a resonating frequency in the range of from
about 4 GHz to about 12 GHz, and subjecting the hydrocarbon source material to
microwave radiation characterized as having at least one frequency component
that corresponds to the resonating frequency of the material. As used herein,
carbon particles or material having a resonating frequency corresponding to the
applied microwave radiation frequency are collectively referred to as "electron
activator".
55
[0133]
In preferred embodiments of the disclosed methods, the microwave
radiation is one or more pre-selected microwave radiation frequencies.
Preferably, the pre-selected microwave radiation frequency will be the
resonating microwave frequency, i.e., the microwave radiation frequency at which
the particles comprising carbon absorb a maximum amount of microwave radiation.
It has been determined that different compositions of the present invention will
absorb more or less microwave radiation, depending on the frequency of the
microwave radiation applied. It has also been determined that the frequency at
which maximum microwave radiation is absorbed differs by composition. By using
methods known in the art, a composition of the present invention can be
subjected to different frequencies of microwave radiation and the relative
amounts of microwave radiation absorbed can be determined. Preferably, the
microwave radiation selected is the frequency that comparatively results in the
greatest amount of microwave radiation absorption. In one embodiment, the
pre-selected microwave radiation frequency is characterized as having at least
one frequency component in the range of from about 4 GHz to about 12 GHz. In
other embodiments, the pre-selected microwave radiation frequency is
characterized as having at least one frequency component in the range of from
about 5 GHz to about 9 GHz, from about 6 GHz to about 8 GHz, or from about 6.5
GHz to about 7.5 GHz.
[0134]
The particles comprising carbon are preferably carbon substances that
have a resonating microwave frequency of from about 4 GHz to about 12 GHz. Many
forms of carbon are known by those skilled in the art, and, while not intending
to exclude other carbon types, it is contemplated that any form of carbon having
a resonating microwave frequency of from about 4 GHz to about 12 GHz will be
within the scope of the present invention. For example, the particles comprising
carbon can comprise carbon black. Carbon black may be described as a mixture of
incompletely-burned hydrocarbons, produced by the partial combustion of natural
gas or fossil fuels.
[0135]
Carbon blacks have chemisorbed oxygen complexes (e.g., carboxylic,
quinonic, lactonic, phenolic groups and others) on their surfaces to varying
degrees depending on the conditions of manufacture. These surface oxygen groups
are collectively referred to as the volatile content. In preferred embodiments,
the present invention uses carbon black having a moderate volatile content. The
volatile content of the preferred carbon black can be composed of hydrocarbons
having up to about 20 carbon atoms, or even up to about 30 carbon
atoms.
[0136]
The constituent parts of the electron activator preferably have
characteristic dimensions in the micrometer range, although other particle or
fragment sizes may also be used. Because carbon particles or particles
comprising another electron activator for use in the present invention can be
present in numerous configurations, and can be irregular in shape, the
term
56
"characteristic
dimensions" is used herein to describe the long axis in the case of
substantially cylindrical or otherwise oblong particles, and to describe
diameter in the case of substantially spherical particles, etc. In some
embodiments wherein the carbon particles comprise carbon black, the particles
can have characteristic dimensions of about 10 nm to about 250 gm. In other embodiments, the
particles can have characteristic dimensions of about 100 nm to about 100 gm, or
of about 200 nm to about 10 gm.
[0137] Preferred are electron
activators having characteristic dimensions that are conducive to ready
dispersion within hydrocarbon materials that are targeted for vaporization. The
electron activators can be contacted with the hydrocarbon materials by directly
introducing the electron activators into the hydrocarbon materials
environment.
[0138] In the present systems,
the electron activator particles can comprise any material that is capable of
absorbing at least a portion of the transmitted microwave radiation generated by
the microwave generator. In preferred embodiments the material comprises carbon.
The particles comprising carbon are preferably carbon substances that have a
resonating microwave frequency of from about 4 GHz to about 12 GHz. Many forms
of carbon are known by those skilled in the art, and, while not intending to
exclude other carbon types, it is contemplated that any form of carbon having a
resonating microwave frequency of from about 4 GHz to about 12 GHz will be
within the scope of the present invention. For example, the particles comprising
carbon can comprise carbon black. Carbon blacks have chemisorbed oxygen
complexes (e.g., carboxylic, quinonic, lactonic, phenolic groups and others) on
their surfaces to varying degrees depending on the conditions of manufacture.
These surface oxygen groups are collectively referred to as the volatile
content. In preferred embodiments, the present invention uses carbon black
having a moderate volatile content prepared by processing tire chips using
microwave radiation as described herein above.
[0139] The constituent parts
of the particles preferably have characteristic dimensions in the micrometer
range, although other particle or fragment sizes may also be used. Because
carbon particles or particles comprising another electron activator for use in
the present invention can be present in numerous configurations, and can be
irregular in shape, the term "characteristic dimensions" is used herein to
describe the long axis in the case of substantially cylindrical or otherwise
oblong particles, and to describe diameter in the case of substantially
spherical particles, etc. In some embodiments wherein the carbon particles
comprise carbon black, the particles can have characteristic dimensions of about
100 gm.
EXAMPLES
57
[0140]
The following examples are
provided to further describe the present invention. They are not to be construed to limit
the scope of the invention described in the claims. Many of the examples make use of the apparatus
substantially illustrated and described in FIG.
7.
Example
1
[0141]
A chamber capable of being subjected to between 4.0 to 12.0 GHz of microwave radiation
frequencies and rated to withstand reduced atmospheric pressure, was equipped
with a 700 W, 5.8 to 7.0 GHz VFM microwave tube (Lambda Technologies,
Morrisville, NC). The chamber was outfitted with a nitrogen gas inlet tube, a
vacuum inlet tube, and an outlet tube connected to a heat exchanger and
collection vessel. The chamber was also equipped with an infrared thermocouple
temperature probe.
Example
2
[0142]
A chamber capable of being subjected to between 4.0 to 12.0 GHz of
microwave radiation frequencies and rated to withstand reduced atmospheric
pressure, was equipped with a 1800 W, 7.3 to 8.7 GHz VFM microwave tube (Lambda
Technologies, Morrisville, NC). The chamber was outfitted with an nitrogen gas
inlet tube, a vacuum inlet tube, and an outlet tube connected to a heat
exchanger and collection vessel. The chamber was also equipped with an infrared
thermocouple temperature probe.
Example
3
[0143]
A 20 lb automobile tire was cut into approximately 4" x 4" pieces. These
pieces were washed and dried. The pieces were placed on a tray and loaded into
the chamber of Example 1. Twenty psi of N2 was introduced into the chamber. The
VFM microwave radiation was initiated (700 W, 5.8-7.0 GHz). When the temperature
of the tire pieces reached 465 °F, the microwave radiation was halted and the
tire pieces allowed to cool about 5-25 °F. Microwave radiation was resumed. This
process was repeated an additional three times. Total experiment run time was
approximately twelve minutes. The decomposition products were then
analyzed.
[0144]
This experiment produced 1.2 gallons of #4 oil (see Tables 1 and 2), 7.5
lbs of carbon black, 50 cu. ft. of combustible gases (including methane, ethane,
propane, butane, and isobutene), and 2 lbs of steel. FIGS.
9A-9C depict electron microscope photographs of samples of carbon black
produced using this method. FIG.
9C demonstrates that the carbon black produced by this method is
comparable to commercial-grade rubber black.
Table 1: Analysis of Oil
Produced by Example 3.
TEST
|
RESULT
|
Gross
Heat of Combustion
|
18308
BTU/xx
|
Xxxxx
Heat of Combustion
|
144688
BTU/gal
|
58
Sulfur
|
0.931
wt. %
|
Kinematic
Viscosity @ 122 °F
|
9.773
cSt
|
Saybolt
Furol Viscosity @ 122 °F
|
78.9
sus
|
Sediment
by Extraction
|
0.02
wt. %
|
Ash
@ 775 °C
|
0.024
wt. %
|
Nitrogen
|
0.43
wt. %
|
Samples
were tested by ITS
Xxxxx Xxxxx, Deer Park, TX Samples were filtered through a 100 mesh
filter prior to testing.
Table 2: Analysis of Oil
Produced by Example 3
TEST
|
RESULT
|
Corrected
Flash Point
|
92
°C
|
Corrected
Flash Point
|
198
°F
|
API
Gravity 15.56 °C, 60 °F
|
13.7
°API
|
Samples
were tested by ITS Xxxxx Xxxxx, Deer Park, TX
Example
4
[0145] A sample of oil
cuttings, oil shale, tar sands, oil sands, slurry oil, and/or a material
contaminated with petroleum-based materials, is placed in the apparatus of
Example 2. The pressure is reduced to 20 Torr. Microwave radiation is applied to
the sample for a time sufficient to vaporize all the petroleum-based material in
the sample. At 20 Torr, the petroleum- based materials vaporize between about
400 and 520 °F. The vaporized petroleum-based materials are cooled and collected
in a collection vessel. The material remaining in the chamber is substantially
free of petroleum-based material.
Example
5
[0146] A plastic bottle was
placed in the apparatus of Example 1 and exposed to microwave radiation. The
exposure to microwave radiation resulted in complete vaporization of the bottle
and recovery of petroleum-based materials.
[0147] When ranges are used
herein for physical properties, such as molecular weight, or chemical
properties, such as chemical formulae, all combinations, and subcombinations of
ranges for specific embodiments therein are intended to be
included.
[0148] The disclosures of each
patent, patent application, and publication cited or described in this document
are hereby incorporated herein by reference, in its entirety.
[0149] Those skilled in the
art will appreciate that numerous changes and modifications can be made to the
preferred embodiments of the invention and that such changes and modifications
can be made without departing from the spirit of the invention. It is,
therefore,
59
intended
that the appended claims cover all such equivalent variations as fall within the
true spirit and scope of the invention.
60
What
is Claimed:
1. A method for
obtaining oil or a combustible gas from oil shale, comprising:
subjecting
oil shale comprising shale rock and kerogen to microwave radiation for a time
sufficient to at least partially decompose said kerogen,
wherein
said microwave radiation comprises at least one frequency component in the range
of from about 4 GHz to about 18 GHz; and
recovering
oil or a combustible gas from the decomposed kerogen.
2. The method of
claim 1, wherein the oil shale is subjected to microwave radiation at a pressure
of less than one atmosphere.
3. The method of
claim 2, wherein the oil or a combustible gas is recovered from the decomposed
kerogen at a pressure of less than one atmosphere.
4. A method for
obtaining a carbon-based material from coal, comprising:
subjecting
coal to microwave radiation for a time sufficient to at least partially
decompose said coal,
wherein
the temperature of said coal does not exceed about 700 °F, wherein said
microwave radiation comprises at least one frequency component in
the range of from about 4 GHz to about 18
GHz; and
recovering
a carbon-based material from the decomposed coal.
5. The method of
claim 4, wherein the coal is subjected to microwave radiation at a pressure of
less than one atmosphere.
6. The method of
claim 4, wherein the carbon-based material is recovered from the decomposed
coal at a pressure of less than one atmosphere.
7. The method of
claim 4, wherein the carbon-based material is a hydrocarbon.
8. The method of
claim 7, wherein the hydrocarbon is oil or a combustible gas.
9. A microwave
system for processing coal, oil shale, or both, comprising:
an infeed airlock configured to receive
coal, oil shale, or both, said infeed airlock being sealable at a pressure less than
one atmosphere, wherein said infeed airlock is
61
configured
to gravity feed coal, oil shale, or both into a microwave reactor coupled to
said infeed airlock;
said
microwave reactor being oriented to permit gravity-driven transport therethrough
of coal, oil shale, or both;
said
microwave reactor further comprising a microwave antenna orientable towards said
coal, oil shale, or both, to irradiate said coal, oil shale, or both while being
transported through the microwave reactor;
said
microwave reactor further comprising a vacuum port to receive carbon- containing
fluid generated from coal, oil shale, or both being irradiated with microwave
radiation characterized as having at least one frequency component in the range
of from about 4 GHz to about 18 GHz;
a
microwave radiation generator operatively coupled to said microwave antenna via
a microwave waveguide, wherein said microwave radiation generator is capable of
generating microwave radiation characterized as having at least one frequency
component in the range of from about 4 GHz to about 18 GHz;
a vacuum
generator operatively coupled to said vacuum port, wherein said vacuum generator
is capable of generating pressure within said microwave reactor below one
atmosphere;
a vessel
or conduit operatively coupled to said vacuum port to receive the carbon-
containing fluid; and
a
discharge airlock operatively coupled to the microwave reactor to receive
microwave-processed coal, microwave-processed oil shale, or both from the
microwave reactor, wherein said discharge airlock is capable of discharging the
microwave- processed coal, the microwave-processed oil shale, or both, from the
microwave system while maintaining pressure within the microwave reactor at less
than one atmosphere.
10. Oil
produced by the method of claim 1.
11. Oil
produced by the method of claim 4.
12. A
combustible gas produced by the method of claim 1.
13. A
combustible gas produced by the method of claim 4.
62
ABSTRACT
The
present invention provides methods and systems for obtaining oil or a
combustible gas from oil shale or coal, by subjecting oil shale or coal to
microwave radiation for a time sufficient to at least partially decompose or
extract oil, gas, or other carbon-containing materials from the oil shale and
coal. The disclosed processes and systems use microwave radiation comprising at
least one frequency component in the range of from about 4 GHz to about 18
GHz.
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This
Acknowledgement Receipt evidences receipt on the noted date by the USPTO
of the indicated documents, characterized by the applicant, and including
page counts, where applicable. It serves as evidence of receipt similar to
a Post Card, as described in MPEP 503.
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35 U.S.C. 111
If
a new application is being filed and the application includes the
necessary components for a filing date (see 37 CFR 1.53(b)-(d) and MPEP
506), a Filing Receipt (37 CFR 1.54) will be issued in due course and the
date shown on this Acknowledgement Receipt will establish the filing date
of the application.
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International Application under 35 U.S.C. 371
If
a timely submission to enter the national stage of an international
application is compliant with the conditions of 35 U.S.C. 371 and other
applicable requirements a Form PCT/DO/E0/903 indicating acceptance of the
application as a national stage submission under 35 U.S.C. 371 will be
issued in addition to the Filing Receipt, in due course.
New International
Application Filed with the USPTO as a Receiving Office
If
a new international application is being filed and the international
application includes the necessary components for an international filing
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International Application Number and of the International Filing Date
(Form PCT/RO/105) will be issued in due course, subject to prescriptions
concerning national security, and the date shown on this Acknowledgement
Receipt will establish the international filing date of the
application.
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103
SCHEDULE
B - EXISTING PROTOTYPE MACHINE
Microwave
equipment including:
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Five
Hydrocarbon specific microwave tubes located within individual power
supply units.
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·
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Waveguide
assemblies including splitters, isolators, couplers, chokes, and windows,
and antennas
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Double
gate airlock feed systems located on the load and unload ends of the external
housing.
The
processor external housing is a fabricated mild steel housing that includes
removable covers on each end for maintenance. The housing also includes
microwave antenna mountings, vacuum port, temperature and pressure transmitters,
and a rupture disk, The processor housing is supported by a structural steel
frame.
A 3
tiered belt conveyor driven by an externally mounted variable speed electric
motor drive package. There is also an external drive utilized for belt
vibration.
An
out-feed screw assembly comprising a steel frame supporting a schedule 40 carbon
steel pipe housing with a hardened helical screw driven by a direct coupled
electric motor to transfer product out of the microwave processor.
NEMA 4
water resistant electrical motor control panel, 480v/3ph/60Hz - 24 volt
control circuits to control all sensors, drives, motor controls, including a PLC
control with touch screen HMI diagnostics. I/O racks.
Two
liquid-ring vacuum pumps for 20in.hg vacuum continuous duty
operation
Temperature
and pressure transmitters located at the microwave processor housing and in the
vacuum. A pressure switch is provided in the processor housing as a back-up to
the pressure transmitter. A second temperature transmitter is provided to
measure the temperature of the out-feed processed material.
The
system also includes external piping, condensing loops, oil collections tanks
with sight glasses and (4) gas storage tanks.
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