U.S. patent application number 14/004023 was filed with the patent office on 2014-01-23 for hydrocarbon viscosity reduction method.
This patent application is currently assigned to The University of Wyoming Research Corporation d/b/a Western Research Institute, The University of Wyoming Research Corporation d/b/a Western Research Institute. The applicant listed for this patent is Joseph F. Rovani, JR., John F. Schabron. Invention is credited to Joseph F. Rovani, JR., John F. Schabron.
Application Number | 20140021101 14/004023 |
Document ID | / |
Family ID | 46798509 |
Filed Date | 2014-01-23 |
United States Patent
Application |
20140021101 |
Kind Code |
A1 |
Schabron; John F. ; et
al. |
January 23, 2014 |
Hydrocarbon Viscosity Reduction Method
Abstract
In accordance with particular descriptions provided herein,
certain embodiments of the inventive technology may be described as
a hydrocarbon viscosity reduction method that comprises the steps
of: treating a hydrocarbon having asphaltenes therein to generate a
treated hydrocarbon, wherein said hydrocarbon has a first
viscosity; contacting said treated hydrocarbon with a sorbent
(whether as a result of pouring or other means); and adsorbing at
least a portion of said asphaltenes onto said sorbent, thereby
removing said at least a portion of said asphaltenes from said
hydrocarbon so as to generate a viscosity reduced hydrocarbon
having a second viscosity that is lower than said first
viscosity.
Inventors: |
Schabron; John F.; (Laramie,
WY) ; Rovani, JR.; Joseph F.; (Laramie, WY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Schabron; John F.
Rovani, JR.; Joseph F. |
Laramie
Laramie |
WY
WY |
US
US |
|
|
Assignee: |
The University of Wyoming Research
Corporation d/b/a Western Research Institute
Laramie
WY
|
Family ID: |
46798509 |
Appl. No.: |
14/004023 |
Filed: |
January 13, 2012 |
PCT Filed: |
January 13, 2012 |
PCT NO: |
PCT/US12/21317 |
371 Date: |
September 20, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61450515 |
Mar 8, 2011 |
|
|
|
Current U.S.
Class: |
208/309 |
Current CPC
Class: |
C10G 2300/302 20130101;
C10G 21/30 20130101; C10G 2300/206 20130101; C10G 2300/4043
20130101; C10G 25/003 20130101; C10G 2300/44 20130101; C10G
2300/802 20130101; C10G 25/12 20130101 |
Class at
Publication: |
208/309 |
International
Class: |
C10G 21/30 20060101
C10G021/30 |
Goverment Interests
STATEMENT OF GOVERNMENT RIGHTS
[0002] This invention was made with government support under DOE
Contract DE-FC26-08NT43293 awarded by the Department of Energy. The
government has certain rights in the invention.
Claims
1-98. (canceled)
99. A method of monitoring the efficiency of sorbent based
asphaltene removal, said method comprising the steps of: providing
a vessel having a substantially chemically inert stationary phase
established therein and having at least one vessel inlet, said
substantially chemically inert stationary phase forming a fixed bed
in said vessel; inputting a precipitant solvent into said vessel
through at least one vessel inlet; inputting a hydrocarbonaceous
material generated by said sorbent based asphaltene removal into
said vessel through at least one vessel inlet; intentionally
precipitating asphaltenes within said vessel and in the presence of
said substantially chemically inert stationary phase, wherein said
substantially chemically inert stationary phase is substantially
chemically inert relative to said asphaltenes such that
substantially all said precipitated asphaltenes do not adsorb onto
said substantially chemically inert stationary phase; generating a
remnant liquid upon performing said step of intentionally
precipitating said asphaltenes; inputting a material dissolving
solvent into said vessel through at least one vessel inlet; and
dissolving at least a portion of said asphaltenes with said
material dissolving solvent to generate a dissolved material
solution, monitoring and controlling said sorbent based asphaltene
removal.
100. A method as described in claim 99 wherein said step of
inputting a hydrocarbonaceous material into said vessel through at
least one vessel inlet comprises the step of inputting a
hydrocarbon sample into said vessel.
101-106. (canceled)
107. A method as described in claim 99 wherein said step of
inputting a precipitant solvent into said vessel through at least
one vessel inlet comprises the step of inputting into said vessel a
precipitant solvent selected from the group consisting of low
polarity solvents, low polarity solvent mixtures, aliphatic
solvents, heptane, pentane and isooctane.
108-109. (canceled)
110. A method as described in claim 109 wherein said step of
determining at least one characteristic of said sample comprises
the step of using a technique selected from the group consisting of
evaporative light scattering, mass spectrometry, optical
absorbance, x-ray, conductivity, oxidation/reduction, refractive
index, polarimetry, atomic spectroscopy, and fluorescence.
111-116. (canceled)
117. A method as described in claim 99 wherein said step of
inputting a material dissolving solvent comprises the step of
inputting a material dissolving solvent selected from the group
consisting of solvents having a higher polarity than that of said
precipitant solvent, solvent mixtures having a higher polarity than
that of said precipitant solvent, naphthenic oils, aromatic oils,
ketones, halogenated solvents, cyclohexane, toluene, cyclohexanone,
and methylene chloride.
118-122. (canceled)
123. A method as described in claim 99 wherein said step of
dissolving at least a portion of said asphaltenes with said
material dissolving solvent comprises the step of dissolving only a
first portion of said asphaltenes with said material dissolving
solvent.
124. A method as described in claim 123 further comprising the step
of inputting a second material dissolving solvent into said vessel
through at least one vessel inlet to dissolve at least a second
portion of said asphaltenes.
125. A method as described in claim 124 wherein said step of
inputting a second material dissolving solvent into said vessel
comprises the step of inputting a stronger material dissolving
solvent.
126. A method as described in claim 125 wherein said step of
inputting a stronger material dissolving solvent into said vessel
comprises the step of inputting into said vessel solvent that
gradually increases in strength.
127-142. (canceled)
143. A method as described in claim 99 wherein said step of
providing a vessel having a substantially chemically inert
stationary phase established therein comprises the step of
providing a vessel having established therein a stationary phase
selected from the group of: oligomers of PTFE, polymers of PTFE,
polyphenylene sulfide, fluorinated polymers, silicon polymer and
PEEK.
144-152. (canceled)
153. A method as described in claim 99 wherein said method is a
method selected from the group consisting of coking onset
estimation method, oil processing method; oil fractionating method,
oil production method, pipeline fouling related method,
hydrotreating, distillation method, vacuum distillation method,
atmospheric distillation method, visbreaking method, blending
method, asphalt formation method, asphalt extraction method, and
asphaltene content of oil measurement method.
154-247. (canceled)
248. A method comprising the steps of: (a) precipitating an amount
of asphaltenes from a liquid sample of a first
hydrocarbon-containing feedstock having solvated asphaltenes
therein with one or more first solvents in a column; (b)
determining one or more solubility characteristics of the
precipitated asphaltenes; (c) analyzing the one or more solubility
characteristics of the precipitated asphaltenes; and (d) monitoring
sorbent based asphaltene removal.
249. A method as described in claim 248 wherein said sorbent based
asphaltene removal effects an improved quality product oil.
250. (canceled)
251. A method as described in claim 248 wherein said sorbent based
asphaltene removal effects a product oil having a reduced fouling
tendency.
252-273. (canceled)
274. The method of claim 248, further comprising the step of
comparing a different sample of the same first
hydrocarbon-containing feedstock sample with the first
hydrocarbon-containing feedstock sample for quality control of the
first hydrocarbon-containing feedstock sample.
275-279. (canceled)
280. A method for controlling sorbent based removal of asphaltenes
from a hydrocarbon-containing material having solvated asphaltenes
therein comprising the steps of: (a) precipitating an amount of the
asphaltenes from a liquid sample of the hydrocarbon-containing
material with an alkane mobile phase solvent in a column; (b)
dissolving a first amount and a second amount of the precipitated
asphaltenes by changing the alkane mobile phase solvent to a final
mobile phase solvent having a solubility parameter that is higher
than the alkane mobile phase solvent; (c) monitoring the amounts of
eluted fractions from the column; (d) creating a solubility profile
of the dissolved asphaltenes in the hydrocarbon-containing
material; (e) determining one or more asphaltene stability
parameters of the hydrocarbon-containing material; and (f)
monitoring sorbent based asphaltene removal.
281. The method of claim 280 wherein said step of monitoring the
amounts comprises the step of monitoring concentrations.
282. The method of claim 280 wherein said sorbent based asphaltene
removal effects an improved quality product oil.
283-292. (canceled)
293. The method of claim 280 wherein the hydrocarbon-containing
material comprises a substance selected from the group consisting
of oil, crude oil, asphalt and a coal-derived product.
294-311. (canceled)
312. A product produced by a process that is based on analysis
results generated, at least in part, upon performance of the method
of claim 280.
Description
[0001] This is an international, PCT application and claims
priority to U.S. Provisional Application No. 61/450,515, filed Mar.
8, 2011, the provisional application incorporated herein in its
entirety.
TECHNICAL FIELD
[0003] This invention relates generally to the field of processing
hydrocarbons for pipeline transportation, and more particularly to
treating hydrocarbons to reduce viscosity to meet pipeline
requirements.
BACKGROUND
[0004] By 2015 the amount of Alberta oil sands bitumen shipped to
U.S. refineries will be near 1.44 million barrels per day (Edmonton
Journal 2008). This is an energy security issue since U.S.
relations with Canada are cordial. Additional heavy oils will come
from U.S. enhanced oil recovery production and other imports. The
petroleum industry is currently undergoing a major paradigm shift
in converting refineries to be able to process the heavier feeds.
Alberta bitumens are solids or very viscous materials. To ship
these materials in pipelines, a significant decrease in viscosity
is required. About 25% by volume light oil diluent or 50% by volume
light synthetic crude oil is added to the bitumen to lower the
viscosity to meet pipeline specifications (Fan et al. 2009). The
mixture of the diluent and heavy bitumen is then shipped to the
U.S. to refineries that are capable of processing the Canadian
material. The solvent is removed by distillation at the refinery,
which is energy intensive. In some cases, diluent is pipelined back
to Canada for re-use since there is a limited supply, and the
amount of diluent available will limit Canadian bitumen
availability (Perry 2002). For example, Enbridge is constructing a
pipeline from Chicago to Edmonton to return 180,000 barrels per day
of diluent solvent back to Canada (Reuters 2009).
[0005] The pericondensed asphaltene component molecules cause
association effects in oil since they can be modeled as being
surrounded by other molecules of intermediate aromaticity and
polarity that act as peptizing agents. This results in associated
complexes which act as dispersed particles in the oil, resulting in
significant viscosity increases above the viscosity of the base
solvent oil. The associated complexes can be broken apart in a
reversible manner by heating the oil to temperatures below the
point where cracking reactions begin (Storm et al. 1995, 1996). If
the asphaltenic components such as highly pericondensed aromatic
core material can be freed from peptizing molecules which act as
solubilizing agents, they can be selectively adsorbed using
sorbents. Selective removal of the most pericondensed aromatic
molecules in heavy oil could significantly lower the oil viscosity
so that much less, if any diluent would be required for pipeline
shipment.
Asphaltene Component Adsorption and Deposition
[0006] Asphaltenes are defined as a solubility class of associated
chemical complexes which precipitate when petroleum is dissolved in
a low polarity solvent such as heptane. A wide variety of polar and
highly pericondensed aromatic molecules containing sulfur,
nitrogen, and oxygen as well as metal complexes containing nickel
and vanadium are concentrated in the asphaltenes. Asphaltenes act
as the major viscosity builders in oil. In catalytic upgrading
processes such as hydrotreating, the presence of these materials
can shorten catalyst life. The petroleum industry has developed
various deasphaltening processes that involve dissolving oil in an
excess of hydrocarbon solvent available in the refinery such as
compressed propane, or a liquid aliphatic solvent stream, resulting
in asphaltene precipitation. The disadvantage of such processes is
the high cost of operation resulting from gas compression or
solvent removal.
[0007] In prior work we have shown that asphaltene components of
petroleum residua can adsorb onto on metal surfaces when the oil is
heated to temperatures below the temperature at which pyrolysis
cracking reactions begin (<340.degree. C.). More deposits were
observed on aluminum metal surfaces as the temperature of residua
was increased from 100.degree. C. to 300.degree. C. (Schabron et
al. 2001). The resulting asphaltenic material enriched in Ni and V
was observed to deposit as dark spots on stainless steel and
aluminum surfaces, but not on a non-polar Teflon.RTM. surface. This
phenomenon appears to be due to the partitioning of the
intermediate polarity material surrounding the aromatic asphaltene
component molecules into the oil matrix solution, exposing the
highly pericondensed aromatic or polar material. The pericondensed
aromatic or polar material can flocculate and adhere to the polar
metal surface. This is a cause of heat-induced fouling of pipes and
heat exchangers in refineries. The concept of using this approach
to reduce the viscosity of the original oil was not considered at
that time.
[0008] A new analytical method called the Asphaltene
Determinator.TM. has been developed and is now in routine use at
WR1 (Schabron and Rovani 2008, Schabron et al. 2010, U.S. Pat. No.
7,875,464). The Asphaltene Determinator method involves analytical
scale precipitation of asphaltene components from a portion of oil
on a column packed with ground inert polytetrafluoroethylene (PTFE)
using a heptane mobile phase. The precipitated material is
re-dissolved in three steps using solvents of increasing solubility
parameter: cyclohexane, toluene, and methylene chloride:methanol
(98:2 v:v). The amount of asphaltenes (heptane insolubles) and the
Total Pericondensed Aromatic (TPA) content can be determined in
less than an hour. It was observed in the development work for the
method that glass wool or glass beads strongly adsorbed asphaltene
component molecules once they are separated from other peptizing
molecules in the oil. This observation of an undesired effect in
the analytical method reinforced the concept of the possibility of
asphaltene component molecule removal by adsorption onto a sorbent.
In addition, the Asphaltene Determinator method was ideally suited
to evaluate the efficiency of removal of pericondensed aromatic
molecules in solventless deasphaltening experiments conducted for
this patent application.
Pericondensed and Aromatic Components in Oil
[0009] An unexpected result occurred when preparative Asphaltene
Determinator separations were conducted on 3 g portions of heptane
asphaltenes from unpyrolyzed Lloydminster vacuum residuumn, and
Lloydminster vacuum residuum that had been mildly pyrolyzed at
400.degree. C. for 30 minutes (Schabron et al 2010). Although the
whole asphaltenes from pyrolyzed Lloydminster vacuum residuum were
99.7 wt. % soluble in methylene chloride, 10.3 wt. % methylene
chloride insolubles were isolated from this material in replicate
preparative Asphaltene Determinator separations. This material
resembles coke and it is highly electrostatic. It consists of
highly pericondensed aromatic molecules with few, if any alkyl side
chains. This is the most refractory component of oil.
Heat-Induced Deposition and Asphaltene Removal Using Sorbents
[0010] The above results suggest that the highly pericondensed
material in oils are solubilized by intermediate polarity peptizing
molecules present in the oils, however when these are separated,
the highly pericondensed molecules self-associate to form large
insoluble pre-coke and coke complexes. The surface energy of the
pericondensed material is the highest of any component in oil
(Pauli et al. 2005). This and other observations related to
heat-induced deposition have led us to consider the possibility
that the most pericondensed, viscosity building aromatic structures
could be selectively removed from oil by heating or pre-treating
the oil and exposing it to high surface energy polar or highly
aromatic sorbent material. The resulting oil would be deficient in
the most refractory viscosity-building pericondensed aromatic
structures and the product oil would be much less viscous than the
original oil. The pericondensed material adsorbed to the sorbent
possibly could later be desorbed by solvent rinsing, or the whole
material could be combusted as a fuel to provide heat for the
process. Relatively inexpensive yet highly aromatic materials which
might be utilized as sorbent include ground petroleum coke or coal
based sorbents.
Asphaltenes and Viscosity
[0011] Asphaltenes can be modeled mathematically to be related to
the dispersed phase of suspended particles in a base oil, or
solvent phase. The effective size of the suspended particles is due
to the presence of peptizing molecules that surround the more
aromatic or refractory asphaltene "core" molecules. The effective
size of these peptized complexes can be decreased by heating the
oil. The relative viscosity of a residuum is affected significantly
by the effective volume fraction of suspended particles (Schabron
et al. 2001). The heat of interaction of the peptizing molecules
with the asphaltene core materials was observed to range from
470-1,600 cal/mol for five residua. A similar value of 1,800
cal/mol was observed for Ratawi vacuum residuum by Storm et al.
(1995). These heats of interaction indicate that the peptizing
molecules can be reversibly separated from the asphaltene core
material by heating a heavy oil or residuum to temperatures below
the temperature at which pyrolysis begins (<340.degree. C.).
Below pyrolysis temperature, the removal of the peptizing molecules
by heating is reversible upon cooling.
[0012] Partial removal of asphaltenes can result in a significant
decrease in viscosity. For example, up to 98% viscosity reduction
of Canadian heavy oils has been observed when different asphaltene
components were selectively removed in stages in laboratory
asphaltene precipitation experiments using a series of solvent with
decreasing solvent strength (Kharrat 2009). Decreasing the
effective relative volume of the dispersed phase results in
significant viscosity reduction (Storm et al. 1995, 1996).
[0013] Results from our prior heat-induced deposition experiments
suggest the possibility that the most aromatic and refractory
asphaltene component molecules can be removed selectively from a
heavy oil by heating the oil to a temperature between
150-300.degree. C. and exposing the heated oil to high surface
energy sorbent material. The sorbent surface could then be rinsed
with an aromatic solvent and used again to repeat the process.
Alternatively, carbon based sorbents could be burned as fuel for
the process rather than being rinsed with solvent.
[0014] It might be easier to remove the most pericondensed
components of asphaltenes from a heavy oil or residuum using a
solventless adsorptive process if the oil has been subjected to
mild pyrolysis first. Aliphatic side chains that can hinder
adsorption will decrease, and the Ni and V content of the
asphaltenes will increase relative to the maltenes. Thus, part of
the invention includes sorbent-based asphaltene removal from oil
that has been subjected to mild pyrolysis. Even if only a portion
of the asphaltenes can be removed, if these represent the most
pericondensed, aromatic and refractory components, both the
viscosity of the oil can be decreased dramatically and the quality
of the oil can be increased significantly. If the pyrolysis
conditions are kept at a mild level, the formation of double bonds
and unstable liquids requiring subsequent hydrogen addition can be
minimized.
[0015] Another possibility for exposing the asphaltene core
materials to allow them to adsorb onto a sorbent is by adding a
solvent or chemical additives including acids or bases which
partially destabilize the oil to deplete the peptizing molecules
surrounding the cores. Maqbool et al. (2011) evaluated the
destabilization of the asphaltene microstructure which occurs in
crude oil with the addition of relatively small amounts of heptane.
Material treated in this or similar manners could subsequently be
exposed to a sorbent for selective adsorption of the asphaltene
component molecules.
[0016] Since asphaltenes are the main viscosity builders, partial
removal at the production site could lower the viscosity and
decrease the amount of diluent required for pipeline shipment. A
cost effective alternative to solvent dilution that provides
stable, low viscosity oil would provide a significant energy
savings. Viscosity can be reduced by removing relatively small
portions of the asphaltenes. This invention describes as novel
method for viscosity reduction by selective removal of portions of
the most refractory pericondensed aromatic or other types of
asphaltene components that act as viscosity builders in the oil.
Removal of the components is accomplished by an adsorptive process
in which the oil is initially heated or treated by various means
and then contacted with sorbent to adsorb portions of the
asphaltenic material. The sorbent can be but is not limited to a
solid in a fixed bed, a fluidized bed, a surfaced, or a porous
membrane. One means of initial treatment is to heat the oil to
disrupt the ordered structure and to separate the most aromatic and
refractory molecules from peptizing molecules that associate with
them to keep them in solution. Another possible treatment is mild
pyrolysis. Another possible treatment is to add an amount chemical
additive or low polarity or other solvent (polar, aromatic, acid or
base) to destabilize the ordered structure but not sufficient to
completely precipitate asphaltenes from solution. Combinations of
these treatments are also possible. The asphaltenic components are
then adsorbed onto a stationary phase material. After treatment,
the total amount of diluent required to lower the viscosity would
be less that that used without the treatment.
[0017] The sorbent can be one with high surface energy that is
selective to adsorption of asphaltene component molecules such as
highly pericondensed aromatic molecules. Examples of the sorbents
which may be particularly useful include but not limited to metals,
ceramics, zeolites, clays, silica, limestone, glass, quartz, sand,
alumina, or high surface energy carbonaceous materials such as
petroleum coke, coal, charcoal, activated carbon, or similar
materials. Other stationary phases such as salts or acids or bases
might be useful also.
DISCLOSURE OF INVENTION
[0018] By 2015 the amount of Alberta oil sands bitumen shipped to
U.S. refineries will be near 1.44 million barrels per day. This is
an energy security issue since U.S. relations with Canada are
cordial. Additional heavy oils will come from U.S. enhanced oil
recovery production and other imports. The petroleum industry is
currently undergoing a major paradigm shift in converting
refineries to be able to process the heavier feeds. Alberta
bitumens are solids or very viscous materials. To ship these
materials in pipelines, a significant decrease in viscosity is
required. About 25% by volume light oil diluent or 50% by volume
light synthetic crude oil is added to the bitumen to lower the
viscosity to meet pipeline specifications. The mixture of the
diluent and heavy bitumen is then shipped to the U.S. to refineries
that are capable of processing the Canadian material. The solvent
is removed by distillation at the refinery, which is energy
intensive. In some cases, diluent is pipelined back to Canada for
re-use since there is a limited supply.
[0019] The pericondensed asphaltene component molecules present in
bitumen cause association effects in the oil since they can be
modeled as being surrounded by other molecules of intermediate
aromaticity and polarity that act as peptizing agents. This results
in associated complexes which act as particles in the oil,
resulting in significant viscosity increases above the viscosity of
the base solvent oil. The associated complexes can be broken apart
in a reversible manner by heating the oil to temperatures below the
point where cracking reactions begin. Heating exposes the highly
pericondensed aromatic core materials by freeing them from
peptizing molecules which act as solubilizing agents. The
associated complexes can also be destabilized by mild pyrolysis or
by adding materials to the oil such as solvents or other chemical
additives.
[0020] Since asphaltenes are the main viscosity builders, partial
removal at the production site could lower the viscosity and
decrease the amount of diluent required for pipeline shipment. A
cost effective alternative to solvent dilution that provides
stable, low viscosity oil would provide a significant energy
savings. Viscosity can be reduced by removing relatively small
portions of the asphaltenes. This invention describes a novel
method for viscosity reduction by selective removal of portions of
the most refractory pericondensed aromatic or other types of
asphaltene components that act as viscosity builders in the oil.
Removal of the components is accomplished by an adsorptive process
in which the oil is initially heated or treated by various means
and then contacted with sorbent to adsorb portions of the
asphaltenic material. The sorbent can be a solid in a fixed bed, a
fluidized bed, a surface, or a porous membrane. One means of
initial treatment is to heat the oil to disrupt the ordered
structure and to separate the most aromatic and refractory
molecules from peptizing molecules that associate with them to keep
them in solution. Another possible treatment is mild pyrolysis.
Another possible treatment is to add an amount of chemical additive
or low polarity or other solvent to destabilize the ordered
structure but not sufficient to completely precipitate asphaltenes
from solution. Combinations of these treatments are also possible.
The asphaltenic components are then adsorbed onto a stationary
phase material. After treatment, the total amount of diluent
required would be less that that used without the treatment.
[0021] The sorbent can be one with high surface energy that is
selective to adsorption of asphaltene component molecules such as
highly pericondensed aromatic molecules. Examples of the sorbents
which may be particularly useful include but not limited to metals,
ceramics, zeolites, clays, silica, limestone, glass, quartz, sand,
alumina, or high surface energy carbonaceous materials such as
petroleum coke, coal, charcoal, activated carbon, or similar
materials. Other sorbents such as salts or acids or bases might be
useful also.
[0022] This invention describes a new process for lowering the
viscosity of heavy oil by the selective removal of the most
pericondensed aromatic or other asphaltenic components from oil
using an adsorptive process. This is accomplished by initially
treating the oil to destabilize the solvent phase/dispersed phase
ordered structure to separate the peptizing molecules from the
polar asphaltenic and pericondensed aromatic molecules in the oil.
Initial treatment can include heating, mild pyrolysis, and/or
addition of a solvent or chemical additive. Once the pericondensed
aromatic and polar materials are less peptized, portions of these
materials can be selectively adsorbed onto high surface energy
solid sorbents such as metals, ceramics, zeolites, clays, silica,
limestone, glass, quartz, sand, alumina, or high surface energy
carbonaceous materials such as petroleum coke, coal, charcoal,
activated carbon, acids, bases, salts, or similar materials. In
some cases sorbents can be regenerated using small portions of
strong solvent formulations. The potential use of carbon based
sorbents is attractive since they can be used as part of the fuel
for the process and would not need to be rinsed with solvent to
desorb the aromatic material.
[0023] Selective asphaltene removal using sorbents as an
alternative to solvent precipitation, which is the conventional
method, could provide a means by which the required amount of
diluent could be significantly decreased for lowering viscosity of
heavy oils for shipping them from Canada to U.S. refineries in
pipelines. Canadian bitumen shipment to the U.S. in pipelines of
1.44 million barrels per day of containing about 25% (v:v) diluent
represents 360,000 barrels per day of diluent that will need to be
removed by distillation, requiring about 114,000 BTU per barrel, or
total energy consumption of 41 billion BTU per day with
corresponding CO.sub.2 release of 3,570 tons per day (USDOE 1998).
This does not include the costs or manufacturing the diluent or
shipping it to the production site. A decrease in the amount of
diluent used by implementing a solventless deasphaltening process
could result in a significant increase in energy efficiency and
decrease in CO.sub.2 emissions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 shows an Apparatus Used for Heated Sorbent Filtration
Experiments
[0025] FIG. 2 shows Table 1--Sorbent Asphaltene Removal Results for
Lloydminster Vacuum
Residuum
[0026] FIG. 3 shows Table 2--Sorbent Asphaltene Removal Results for
Cold Lake Vacuum Residuum
[0027] FIG. 4 shows Table 3--Viscosity Reduction for Diluted Cold
Lake Residuum Processed by Sorbent Treatment at 250.degree. C.
[0028] FIG. 5 shows Table 4--Elevated Temperature Pouring Sorbent
Experiment Viscosities with Athabasca Bitumen
[0029] FIG. 6 shows Table 5--Asphaltene Determinator Results for
Original Athabasca Bitumen
[0030] FIG. 7 shows Table 6--Asphaltene Determinator Results for
Athabasca Bitumen Poured at 150.degree. C.
MODES FOR CARRYING OUT THE INVENTION
[0031] As mentioned earlier, the present invention includes a
variety of aspects, which may be combined in different ways. The
following descriptions are provided to list elements and describe
some of the embodiments of the present invention. These elements
are listed with initial embodiments, however it should be
understood that they may be combined in any manner and in any
number to create additional embodiments. The variously described
examples and preferred embodiments should not be construed to limit
the present invention to only the explicitly described systems,
techniques, and applications. Further, this description should be
understood to support and encompass descriptions and claims of all
the various embodiments, systems, techniques, methods, devices, and
applications with any number of the disclosed elements, with each
element alone, and also with any and all various permutations and
combinations of all elements in this or any subsequent
application.
Laboratory Results
Vacuum Residua Elevated Temperature Sorbent Pouring Experiments
[0032] Initial work was conducted to define elevated temperature
asphaltene adsorption for developing a sorbent-based asphaltene
removal process for heavy oils and residua that does not involve
asphaltene precipitation from the oil. Experiments were performed
in an apparatus designed and assembled to perform the sorbent tests
at an elevated temperature of 250.degree. C. in an inert gas
atmosphere. The apparatus was constructed in a 0.65 cu. Ft. (18.4
L) Thermo Scientific Lindberg/Blue M vacuum oven with a maximum
temperature capacity of 260.degree. C. The oven has a sealed
chamber equipped with inert gas purge vents. It was purged with
ultrapure dry nitrogen at 5 L/min during each experiment, from the
heating cycle through the overnight cooling cycle. Vacuum was not
used.
[0033] An apparatus to conduct two experiments at a time was
constructed in the oven chamber (FIG. 1). Access to the chamber was
through a standard one-inch pipe fitting at the back of the oven. A
length of 7/8 inch od (24 mm) conduit pipe was inserted into the
oven and it protruded out the back of the oven. Two jars containing
25 g oil each were attached to the pipe. Below the pipe was a glass
sintered-glass medium-frit filter funnel with 70 mm od containing
25 mL of sorbent. This was constructed from a 250-mL glass filter
funnel which was cut down to a total height of 84 mm to fit in the
oven. Below each filter was a glass Petri dish 80 mm od.times.27 mm
high cut from a 400 mL beaker to collect the filtered oil. For the
control runs, there was no sorbent in the filter funnel.
[0034] Tests were conducted to percolate heated residuum through
the various sorbents. The two oils used were Lloydminster and Cold
Lake vacuum residua. The residua and sorbents were heated to
250.degree. C. Once the oven was turned on, it took 100 minutes to
reach 250.degree. C. The oven was maintained at this temperature
for 60 minutes, and then the conduit pipe was rotated and the
heated oil was poured into the heated sorbent. The oil was
separated from the sorbent through the medium glass frit filter
below the bed of sorbent. Oil that percolated through the sorbent
was collected in the glass Petri dish.
[0035] The oil was analyzed before and after the sorbent tests
using the Asphaltene Determinator to determine if pericondensed
asphaltene material was removed by the sorbent. Complex viscosities
were measured at 10 rad/sec with a Malvern Kinexus dynamic shear
rheometer. Complex viscosity measurements were made at a frequency
of 10 Hz at 50.degree. C., which is a pipeline specification
temperature, and at 60.degree. C., which is a temperature used for
paving asphalt viscosity measurements.
[0036] The sorbents tested were 20-4 mesh Caballo lignite coal, 6
mesh glass beads, 70-100 mesh glass beads, 20-40 mesh petroleum
coke from a Canadian oil, and size C 316 stainless steel
Helipak.TM. material (small wire coils).
[0037] Results from the sorbent tests for Lloydminster vacuum
residuum are presented in Table 1 (see FIG. 2). This includes
viscosities data and Asphaltene Determinator data for wt. % heptane
insolubles and total pericondensed aromatic (TPA) content (Schabron
et al. 2010). This residuum released a small amount of thick
viscous amber oil at 250.degree. C. that coated the inner walls of
the oven. This affected results of the tests since the loss of mass
offset some asphaltene component molecule removal. In addition, the
coal contained volatile components, which is common for coal. The
asphaltene and TPA content of the oil actually increased for the
coal sorbent experiment relative to the control. The viscosity
increased also. However, the asphaltene content remained about the
same or decreased slightly for the other sorbents. For the glass
beads and the stainless steel, viscosity decreases at 60.degree. C.
of up to 43.7% were noted in the product oil relative to the
control.
[0038] Results from the sorbent tests with Cold Lake residuum are
presented in Table 2 (see FIG. 3). The Cold Lake residuum did not
release significant volatiles, so the asphaltene removal results
are more dramatic. The asphaltenes and TPA contents decreased for
all the sorbent experiments relative to the control. The percent
decreases in viscosity were significant. By passing Cold Lake
residuum through a stainless steel sorbent at 250.degree. C., the
heptane insolubles (asphaltene) content as measured by the
Asphaltene Determinator dropped from 16.87 (16.67, 17.03, 16.90)
for the control filtered in similar manner without sorbent, to
14.32 (14.61, 14.03) wt. %. This is a 15.1% decrease in asphaltene
content, or 1.77% of the whole oil.
[0039] The complex viscosity was 1.71 E+7 mPa s for the control
that was filtered at 250.degree. C. but without a sorbent. Passing
the heated residuum through the stainless steel Helipak sorbent
resulted in a complex viscosity of 7.73 E+6 mPa s. This is 54.8%
decrease from the original residuum viscosity. By removing 15% of
the asphaltenes by a sorbent-based process (representing only 2.5%
of the whole residuum), the viscosity was cut by more than half. A
similar effect was observed using petroleum coke as sorbent, where
the asphaltene content decreased from 16.78% to 14.97%, which
represents removal of 10.8% of the asphaltenes, or 1.81% of the
whole oil. The complex viscosity at 60.degree. C. decreased from
1.71 E+7 mPa s for the control to 8.86 E+6 mPa s which represents a
48.2% decrease in viscosity. Similar results were noted for both
sizes of glass beads, and to a lesser extent with the coal
sorbent.
[0040] Mass balances are good for all experiments except for the
Lloydminster coal sorbent experiment, in which volatiles loss from
the coal were significant. The amount of oil remaining on the
sorbent is a function of the gravimetric pouring experiment. The
amount retained could be minimized by pumping heated oil through a
bed of heated sorbent. Once the sorbent is no longer active, it can
be regenerated by rinsing with a small portion of a strong
chromatographic extraction solvent such as toluene:ethanol (85:5
v:v) and then re-used. For the carbon-based sorbents, the spent
sorbent with adsorbed material could be burned as fuel for the
process.
[0041] Residua solutions consisting of 22 wt. % heptane and
cyclohexane respectively were made for the control Cold Lake poured
material and the Cold Lake material that was poured through 70-100
mesh glass bead and Helipak stainless steel sorbents, respectively.
Complex viscosities were measured for these solutions at 19.degree.
C. The results are shown in Table 3 (see FIG. 4). When compared to
the heptane solutions of the control material, the data show a
22.6% decrease in viscosity for a solution of the material poured
through glass beads. A similar effect was observed for cyclohexane
solutions of the control and material poured through the stainless
steel sorbent, where a 56.0% decrease in viscosity was noted.
[0042] These results are significant since one goal of the current
invention is to develop a process to decrease the amount of diluent
required to transport Canadian bitumen to U.S. refineries by
pipeline. The effect of the removal of a small portion of the most
refractory asphaltene materials is to allow less diluent to be used
relative to untreated material to achieve a desired lower
viscosity. The experiments described above were conducted with
vacuum residua. These are significantly more viscous than the
actual Canadian bitumens, which are atmospheric 350.degree.
C.+residua materials.
Atmospheric Bitumen Elevated Temperature Sorbent Pouring
Experiments
[0043] Viscosity and Asphaltene Determinator data were evaluated
from Canadian Athabasca bitumen sorbent pouring experiments
conducted at 150, 200, and 250.degree. C. using three sorbents:
glass beads, petroleum coke, and stainless steel Helipak wire.
Since the bitumen is an atmospheric residuum, unlike a vacuum
residuum, it contains volatile components that can be lost in open
vessel elevated temperature experiments.
[0044] The viscosity of the whole bitumen is 18.2 Pa s and 9.11 Pa
S at 50 and 60.degree. C., respectively. The corresponding dynamic
viscosities of the heptane maltenes following gravimetric removal
of the 11.8 wt. % gravimetric heptane asphaltenes are 1.43 and
0.697 Pa s at 50 and 60.degree. C., respectively. This reflects a
92% decrease in viscosity at 60.degree. C. by removing the
asphaltenes, which is similar in magnitude to the results reported
by Kharrat (2009) using asphaltene removal by solvent
precipitation. The effect of asphaltene removal from this material
on viscosity is significant. Dynamic viscosities at 50 and
60.degree. C. of the original bitumen and the bitumen poured
through the sorbents at 150, 200, and 250.degree. C. are provided
in Table 4 (see FIG. 5). Percent viscosity decrease values relative
to the original unpoured bitumen are tabulated. The viscosities at
60.degree. C. showed significant decreases relative to the unpoured
material for bitumen poured at 150.degree. C. The poured control
material with no sorbent also showed a viscosity decrease. This is
possibly due to adsorption of components onto the 3 mm thick coarse
sintered glass filter which likely acted as a sorbent. Volatiles
loss ranged from 2.2-2.9 wt. % at 150.degree. C. At 200 and
250.degree. C. there was significantly more volatiles loss and the
viscosities of the poured material show an increase relative to the
unpoured control sample. This increase is likely due to the loss of
significant amounts of volatile material. For practical use, the
volatiles loss must be controlled, or the volatiles will need to be
added back to the system for viscosity reduction to occur.
[0045] The Asphaltene Determinator separation results for the
original bitumen are provided in Table 5 (see FIG. 6). The data for
the material poured at 150.degree. C. are provided in Table 6 (see
FIG. 7). The Coking Index ratio is the ratio of the peak area of
the cyclohexane soluble material to the peak area for the methylene
chloride:methanol (98:2 v:v) peak area. Values above 1 indicate a
material that has not been subjected to severe pyrolysis (severe
cracking). Pyrolysis decreases the amount of cyclohexane soluble
peak material and increases the amount of pre-coke pericondensed
aromatics that are represented by the methylene chloride:methanol
peak (Schabron et al. 2010). The AD Asphalt Aging Index is an
indicator of oxidation severity. It is the ratio of the
pericondensed aromatic toluene soluble material to the ratio of the
pericondensed aromatic heptane soluble material that absorbs light
at 500 nm. Values near 1 or below indicate little oxidation, and
values increase with oxidation to values of 3 or higher. The data
for the evaporative light scattering detector (ELSD) were corrected
for the volatiles loss that occurred from the heptane soluble
material in the ELSD evaporator. The data show very little apparent
difference between the poured bitumen materials and the original
unpoured control. However, there is a small decrease in relative
peak areas observed with the 500 nm and 700 nm absorbance detector
for the methylene chloride:methanol (98:2 v:v) material in the
heated, poured samples at 150.degree. C. except for the petroleum
coke sorbent experiment, where this material increased slightly,
probably from extraction of highly pericondensed aromatic material
from the coke. This material represents the most pericondensed
aromatic pre-coke material in the bitumen. The 500 nm and 700 nm
Coking Index ratios of cyclohexane soluble to methylene
chloride:methanol soluble peak areas increased slightly with
pouring relative to the unpoured control. Peaks from the ELSD
detector for the methylene chloride:methanol fraction are too small
to make a similar observation reliably. The results indicate that
the sorbents including the glass filter frit appear to be adsorbing
some of the most pericondensed and highest surface energy pre-coke
asphaltene material from the bitumen.
[0046] In accordance with particular descriptions provided herein,
certain embodiments of the inventive technology may be described as
a hydrocarbon viscosity reduction method that comprises the steps
of: treating a hydrocarbon having asphaltenes therein (as a
component of the hydrocarbon) to generate a treated hydrocarbon,
wherein the hydrocarbon has a first viscosity; contacting the
treated hydrocarbon with a sorbent (whether as a result of pouring
or other means); and adsorbing at least a portion of the
asphaltenes onto the sorbent, thereby removing the at least a
portion of the asphaltenes from the hydrocarbon so as to generate a
viscosity reduced hydrocarbon having a second viscosity that is
lower than the first viscosity.
[0047] The term hydrocarbon may include, but is not necessarily
limited to, bitumen, shale oil, coal oil, coal tar, biological oil,
heavy oil or residuum. It may be or include atmospheric bitumen or
vacuum bitumen. It is note that the sorbent is preferably a solid
sorbent, and may be either a stationary phase or fluidized sorbent.
Solid sorbents include but are not limited to: fixed bed sorbent,
fluidized bed sorbent, surfaced sorbent, porous membrane sorbent,
high surface energy sorbent, highly aromatic sorbent, sorbent that
is selective to adsorption of asphaltenes, metal sorbent, steel
sorbent, steel wire sorbent, steel wire coil sorbent, metal wire
sorbent, metal wire coil sorbent, ceramic sorbent, zeolite sorbent,
clay sorbent, silica sorbent, limestone sorbent, glass sorbent,
mesh glass sorbent, glass bead sorbent, mesh glass bead sorbent,
quartz sorbent, sand sorbent, alumina sorbent, and high surface
energy carbonaceous material sorbent, salt sorbent, acid sorbent,
base sorbent, carbon based sorbent, and high surface energy
carbonaceous materials (e.g., petroleum coke, ground petroleum
coke, coal-based sorbents, charcoal, activated carbon). It is of
note that in the case of carbon based sorbents, such sorbents,
after being expended as sorbents, can conveniently be burned as
fuel for any heating process or step (including those specifically
mentioned herein).
[0048] The step of treating a hydrocarbon may involve heating the
hydrocarbon to above or below a cracking temperature (any
temperature that effects cracking of the hydrocarbon; typically at
or above 340 C). Heating of the hydrocarbon may be accomplished, in
part or whole, via heating from a heat source that is upstream of
the sorbent. Such heating step may be, but need not be,
supplemented with heating from the sorbent itself (in such case,
the method further includes the step of heating the sorbent to
generate a heated sorbent). It is of note that in particular
embodiments, the heating of the hydrocarbon may be achieved
exclusively by heat transfer from the sorbent. In other words, in
practice, regardless of the temperature to which the hydrocarbon is
to be raised (i.e., regardless if it is to be cracked, even only
partially, or not cracked at all), heating of the hydrocarbon may
be accomplished strictly via heating from a source other than the
sorbent (e.g., upstream of the sorbent, in a heated vessel, for
example), strictly via heating from a heated sorbent, or via
combination of the two. In those embodiments where the treated
hydrocarbon, upon contact with the sorbent, has been heated via
both heat transfer occurring upstream of the sorbent (e.g., in a
heating vessel) and heat transfer from the sorbent (via a heated
sorbent), the respective temperatures to which the two heating
operations raise the hydrocarbon need not be the same. Indeed, the
temperature to which a heating vessel upstream of the heated
sorbent raises the hydrocarbon may be less than, or greater than,
or even equal to, the temperature to which the heated sorbent
raises (or lowers) the hydrocarbon. As such, in particular
embodiments, the heated sorbent (where heated implies heating to
some temperature that is above ambient temperature) may actually
cool the hydrocarbon heated upstream of the sorbent (i.e., reduce
the temperature it achieved from heating upstream of the sorbent).
It is of note that, as mentioned, the steps of treating the
hydrocarbon (or at least part of the step of treating the
hydrocarbon) may involve contacting the untreated hydrocarbon with
the sorbent, particularly in those cracking heat embodiments where
the sorbent is at a cracking temperature. The step of contacting
the treated hydrocarbon with the sorbent may occur later (perhaps
immediately later, such as even fractions of a second later,
particularly where the required heating (whether to a cracking
temperature or not) is to be supplied entirely by the sorbent),
after the sorbent heating effectively treats the hydrocarbon.
Further, in those embodiments involving cooling of the hydrocarbon,
the hydrocarbon that contacts the sorbent, whether heated or not,
is still a treated hydrocarbon. It is of further note that heating,
regardless of whether the heat source is "upstream" of the sorbent
or is the sorbent itself, can utilize any of the well known manners
of heating a substance--convection, radiation, conduction, heating
element, oven, flame, heated gas, heated liquid, solar, hot
solvent, electric, fuel, microwave oven, geothermal, nuclear,
external or internal fuel combustion, heating coil, burning
deposited material from the sorbent, chemical reaction, and
friction, etc.
[0049] It is of note that in particular dual heating embodiments
where the treated hydrocarbon that contacts the heated sorbent is
to have been cracked, even if only mildly, one of such temperatures
must be a cracking temperature. It is of note that in embodiments
where the treated hydrocarbon is a cracked hydrocarbon, the
temperature of the treated hydrocarbon (i.e., when it contacts the
sorbent), need not be at a cracking temperature (however, in such
case, at some point therebefore the hydrocarbon must have been
raised to a cracking temperature). Cracking heat treatment
embodiments (i.e., irreversible heating embodiments) may, but need
not, involve the step of cooling the cracked hydrocarbon to a
temperature below a cracking temperature (such that the treated
hydrocarbon (i.e., the hydrocarbon as it is when it contacts the
sorbent) might not even be at a cracking temperature). This is
because the intent of the cracking is to create an irreversibly
modified hydrocarbon; even if a cracked hydrocarbon is cooled it
will have properties that enhance asphaltene adsorption (in this
invention). As mentioned, such cooling can take place, in
embodiments where the heat is applied upstream of the sorbent, even
where the sorbent is heated (although certainly it could also take
in the case where the sorbent is not heated). However, it is of
note that in embodiments wherein the treatment of the hydrocarbon
before sorbent contact does not involve cracking (i.e., reversible
heating embodiments), the temperature of the treated hydrocarbon
(in such case, merely a heated (and not cracked) hydrocarbon)
should never have reached a cracking temperature, and upon contact
with the sorbent, should be elevated sufficiently above ambient but
below a minimum cracking temperature.
[0050] Any embodiments, whether involving heating of the
hydrocarbon or not, may further comprise the step of rinsing the
sorbent with an aromatic solvent after asphaltene adsorption, in
order to cleanse the sorbent and prepare it for additional runs. In
particular embodiments, the aromatic solvent may be a strong
chromatographic extraction solvent such as a halogenated solvent,
an aromatic solvent, an alcohol, or a mixture thereof.
[0051] In embodiments where treatment involves heating (whether
with or without a supplemental solvent/chemical additive addition
step further described below), the step of heating the hydrocarbon
occurs for a heating time, and such time may be optimized (perhaps
minimized). In such manner, energy efficient/environmental
pollutant emissions reduction benefits may be realized. Another
additional benefit attendant the inventive methods is a reduction
of the amount of subsequent hydrogen addition required due to the
formation of double bonds and unstable liquids; this benefit may be
most pronounced in the case of mild pyrolysis. Further, sorbent
contact times may be optimized (lowered to a minimum amount
necessary to achieve a desired amount of asphaltene adsorption), to
enhance process efficiency.
[0052] It is of note that while certain hydrocarbon treatment
embodiments that involve heating may be solventless, some may be
supplemented with addition of a solvent or chemical additive.
Indeed, treatment of the hydrocarbon may, in some embodiments, may
be entirely heat free, and be accomplished exclusively with solvent
and/or chemical additive addition to an untreated hydrocarbon to
generate a treated hydrocarbon that, upon contact with an
appropriate sorbent, will have at least some asphaltenes adsorbed
thereto. In particular embodiments, the solvent may be a low
polarity solvent; whether it be conventionally referred to as a
solvent or a chemical additive, it may be a polar material, an
aromatic material, or and an acid or base (as but a few
characterizations). Preferably, addition of the substance does not
effect asphaltene precipitation.
[0053] The step of adsorbing at least a portion of the asphaltenes
onto the sorbent may comprise the step of adsorbing at least a
portion of the most pericondensed aromatic structures of the
hydrocarbon, the most pericondensed, aromatic and refractory
structures of the hydrocarbon, and/or the most pericondensed and
highest surface energy pre-coke asphaltene materials.
[0054] The method may further comprise the step of adding a diluent
amount to the viscosity reduced hydrocarbon so as to generate a
diluted hydrocarbon having a diluted hydrocarbon viscosity that is
no greater than a certain viscosity (e.g., a viscosity governed by
pipeline specifications, such as a maximum viscosity allowable for
hydrocarbons to be pumped through the pipeline). The diluent amount
is preferably less than that untreated hydrocarbon diluent amount
required to reduce viscosity of an untreated hydrocarbon to the
diluted hydrocarbon viscosity.
[0055] In particular embodiments, another aspect of the inventive
technology may be described as a new method for transporting a
hydrocarbon, comprising the steps of: treating an untreated
hydrocarbon to generate a treated hydrocarbon, and thereby lowering
viscosity of the untreated hydrocarbon to a treated hydrocarbon
viscosity; adding an amount of diluent to the treated hydrocarbon
to generate a diluted hydrocarbon, thereby further lowering the
treated hydrocarbon viscosity to a pipeline specification
viscosity, wherein the amount of diluent is less than a
conventional amount of diluent required to reduce the viscosity of
the untreated hydrocarbon to the pipeline specification viscosity;
and pumping the diluted hydrocarbon. The step of treating an
untreated hydrocarbon may comprise the step of removing at least a
portion of asphaltenes from the untreated hydrocarbon. This may be
done via any of the methods specifically described herein. The
amount of diluent may be a weight percentage of diluent for a given
weight of treated hydrocarbon, while the conventional amount of
diluent may be a weight percentage of diluent for a given weight of
untreated hydrocarbon. It is of note that the pipeline
specification viscosity may be the maximum viscosity allowable for
hydrocarbons to be pumped through the pipeline. The method may
further comprise the step of removing the diluent from the diluted
hydrocarbon (after transport via pumping). It is of note that
required diluent reduction may effect a reduction in greenhouse gas
emissions (if only because less energy is required to eliminate the
reduced amount of diluent from the post-transit hydrocarbon).
Reduced diluent requirements may also result in reduced hydrocarbon
piping costs, and increased hydrocarbon transportation operation
efficiencies.
[0056] As can be easily understood from the foregoing, the basic
concepts of the present invention may be embodied in a variety of
ways. It involves both heating techniques as well as devices to
accomplish the appropriate heating. In this application, the
heating techniques are disclosed as part of the results shown to be
achieved by the various devices described and as steps which are
inherent to utilization. They are simply the natural result of
utilizing the devices as intended and described. In addition, while
some devices are disclosed, it should be understood that these not
only accomplish certain methods but also can be varied in a number
of ways. Importantly, as to all of the foregoing, all of these
facets should be understood to be encompassed by this
disclosure.
[0057] The discussion included in this application is intended to
serve as a basic description. The reader should be aware that the
specific discussion may not explicitly describe all embodiments
possible; many alternatives are implicit. It also may not fully
explain the generic nature of the invention and may not explicitly
show how each feature or element can actually be representative of
a broader function or of a great variety of alternative or
equivalent elements. Again, these are implicitly included in this
disclosure. Where the invention is described in device-oriented
terminology, each element of the device implicitly performs a
function. Apparatus claims may not only be included for the device
described, but also method or process claims may be included to
address the functions the invention and each element performs.
Neither the description nor the terminology is intended to limit
the scope of the claims that will be included in any subsequent
patent application.
[0058] It should also be understood that a variety of changes may
be made without departing from the essence of the invention. Such
changes are also implicitly included in the description. They still
fall within the scope of this invention. A broad disclosure
encompassing both the explicit embodiment(s) shown, the great
variety of implicit alternative embodiments, and the broad methods
or processes and the like are encompassed by this disclosure and
may be relied upon when drafting the claims for any subsequent
patent application. It should be understood that such language
changes and broader or more detailed claiming may be accomplished
at a later date (such as by any required deadline) or in the event
the applicant subsequently seeks a patent filing based on this
filing. With this understanding, the reader should be aware that
this disclosure is to be understood to support any subsequently
filed patent application that may seek examination of as broad a
base of claims as deemed within the applicant's right and may be
designed to yield a patent covering numerous aspects of the
invention both independently and as an overall system.
[0059] Further, each of the various elements of the invention and
claims may also be achieved in a variety of manners. Additionally,
when used or implied, an element is to be understood as
encompassing individual as well as plural structures that may or
may not be physically connected. This disclosure should be
understood to encompass each such variation, be it a variation of
an embodiment of any apparatus embodiment, a method or process
embodiment, or even merely a variation of any element of these.
Particularly, it should be understood that as the disclosure
relates to elements of the invention, the words for each element
may be expressed by equivalent apparatus terms or method
terms--even if only the function or result is the same. Such
equivalent, broader, or even more generic terms should be
considered to be encompassed in the description of each element or
action. Such terms can be substituted where desired to make
explicit the implicitly broad coverage to which this invention is
entitled. As but one example, it should be understood that all
actions may be expressed as a means for taking that action or as an
element which causes that action. Similarly, each physical element
disclosed should be understood to encompass a disclosure of the
action which that physical element facilitates. Regarding this last
aspect, as but one example, the disclosure of a "heater" should be
understood to encompass disclosure of the act of "heating"--whether
explicitly discussed or not--and, conversely, were there
effectively disclosure of the act of "heating", such a disclosure
should be understood to encompass disclosure of a "heater" and even
a "means for heating" Such changes and alternative terms are to be
understood to be explicitly included in the description. Further,
each such means (whether explicitly so described or not) should be
understood as encompassing all elements that can perform the given
function, and all descriptions of elements that perform a described
function should be understood as a non-limiting example of means
for performing that function.
[0060] Any patents, publications, or other references mentioned in
this application for patent are hereby incorporated by reference.
Any priority case(s) claimed by this application is hereby appended
and hereby incorporated by reference. In addition, as to each term
used it should be understood that unless its utilization in this
application is inconsistent with a broadly supporting
interpretation, common dictionary definitions should be understood
as incorporated for each term and all definitions, alternative
terms, and synonyms such as contained in the Random House Webster's
Unabridged Dictionary, second edition are hereby incorporated by
reference. Finally, all references listed in the list of references
below or other information statement filed with the application are
hereby appended and hereby incorporated by reference, however, as
to each of the above, to the extent that such information or
statements incorporated by reference might be considered
inconsistent with the patenting of this/these invention(s) such
statements are expressly not to be considered as made by the
applicant(s).
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Provisional Application Number 60/711,599, filed Aug. 25, 2005,
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Provisional Applicstion Number 61/450,515 filed 08 Mar. 2011
entitled Reduction of Heavy Oil Viscosity Using Solid Sorbents
[0061] Thus, the applicant(s) should be understood to have support
to claim and make a statement of invention to at least: i) each of
the viscosity reduction devices as herein disclosed and described,
ii) the related methods disclosed and described, iii) similar,
equivalent, and even implicit variations of each of these devices
and methods, iv) those alternative designs which accomplish each of
the functions shown as are disclosed and described, v) those
alternative designs and methods which accomplish each of the
functions shown as are implicit to accomplish that which is
disclosed and described, vi) each feature, component, and step
shown as separate and independent inventions, vii) the applications
enhanced by the various systems or components disclosed, viii) the
resulting products produced by such systems or components, ix) each
system, method, and element shown or described as now applied to
any specific field or devices mentioned, x) methods and apparatuses
substantially as described hereinbefore and with reference to any
of the accompanying examples, xi) an apparatus for performing the
methods described herein comprising means for performing the steps,
xii) the various combinations and permutations of each of the
elements disclosed, xiii) each potentially dependent claim or
concept as a dependency on each and every one of the independent
claims or concepts presented, and xiv) all inventions described
herein.
[0062] With regard to claims whether now or later presented for
examination, it should be understood that for practical reasons and
so as to avoid great expansion of the examination burden, the
applicant may at any time present only initial claims or perhaps
only initial claims with only initial dependencies. The office and
any third persons interested in potential scope of this or
subsequent applications should understand that broader claims may
be presented at a later date in this case, in a case claiming the
benefit of this case, or in any continuation in spite of any
preliminary amendments, other amendments, claim language, or
arguments presented, thus throughout the pendency of any case there
is no intention to disclaim or surrender any potential subject
matter. It should be understood that if or when broader claims are
presented, such may require that any relevant prior art that may
have been considered at any prior time may need to be re-visited
since it is possible that to the extent any amendments, claim
language, or arguments presented in this or any subsequent
application are considered as made to avoid such prior art, such
reasons may be eliminated by later presented claims or the like.
Both the examiner and any person otherwise interested in existing
or later potential coverage, or considering if there has at any
time been any possibility of an indication of disclaimer or
surrender of potential coverage, should be aware that no such
surrender or disclaimer is ever intended or ever exists in this or
any subsequent application. Limitations such as arose in Hakim v.
Cannon Avent Group, PLC, 479 F.3d 1313 (Fed. Cir 2007), or the like
are expressly not intended in this or any subsequent related
matter. In addition, support should be understood to exist to the
degree required under new matter laws--including but not limited to
European Patent Convention Article 123(2) and United States Patent
Law 35 USC 132 or other such laws--to permit the addition of any of
the various dependencies or other elements presented under one
independent claim or concept as dependencies or elements under any
other independent claim or concept. In drafting any claims at any
time whether in this application or in any subsequent application,
it should also be understood that the applicant has intended to
capture as full and broad a scope of coverage as legally available.
To the extent that insubstantial substitutes are made, to the
extent that the applicant did not in fact draft any claim so as to
literally encompass any particular embodiment, and to the extent
otherwise applicable, the applicant should not be understood to
have in any way intended to or actually relinquished such coverage
as the applicant simply may not have been able to anticipate all
eventualities; one skilled in the art, should not be reasonably
expected to have drafted a claim that would have literally
encompassed such alternative embodiments.
[0063] Further, if or when used, the use of the transitional phrase
"comprising" is used to maintain the "open-end" claims herein,
according to traditional claim interpretation. Thus, unless the
context requires otherwise, it should be understood that the term
"comprise" or variations such as "comprises" or "comprising", are
intended to imply the inclusion of a stated element or step or
group of elements or steps but not the exclusion of any other
element or step or group of elements or steps. Such terms should be
interpreted in their most expansive form so as to afford the
applicant the broadest coverage legally permissible. The use of the
phrase, "or any other claim" is used to provide support for any
claim to be dependent on any other claim, such as another dependent
claim, another independent claim, a previously listed claim, a
subsequently listed claim, and the like. As one clarifying example,
if a claim were dependent "on claim 20 or any other claim" or the
like, it could be re-drafted as dependent on claim 1, claim 15, or
even claim 25 (if such were to exist) if desired and still fall
with the disclosure. It should be understood that this phrase also
provides support for any combination of elements in the claims and
even incorporates any desired proper antecedent basis for certain
claim combinations such as with combinations of method, apparatus,
process, and the like claims.
[0064] Finally, any claims set forth at any time are hereby
incorporated by reference as part of this description of the
invention, and the applicant expressly reserves the right to use
all of or a portion of such incorporated content of such claims as
additional description to support any of or all of the claims or
any element or component thereof, and the applicant further
expressly reserves the right to move any portion of or all of the
incorporated content of such claims or any element or component
thereof from the description into the claims or vice-versa as
necessary to define the matter for which protection is sought by
this application or by any subsequent continuation, division, or
continuation-in-part application thereof, or to obtain any benefit
of, reduction in fees pursuant to, or to comply with the patent
laws, rules, or regulations of any country or treaty, and such
content incorporated by reference shall survive during the entire
pendency of this application including any subsequent continuation,
division, or continuation-in-part application thereof or any
reissue or extension thereon.
* * * * *
References