U.S. patent application number 12/109812 was filed with the patent office on 2008-10-30 for production of lower molecular weight hydrocarbons.
Invention is credited to Jeffrey P. Newton.
Application Number | 20080269045 12/109812 |
Document ID | / |
Family ID | 30771182 |
Filed Date | 2008-10-30 |
United States Patent
Application |
20080269045 |
Kind Code |
A1 |
Newton; Jeffrey P. |
October 30, 2008 |
PRODUCTION OF LOWER MOLECULAR WEIGHT HYDROCARBONS
Abstract
A catalytic composition useful for cracking and reducing the
viscosity of heavy hydrocarbons. The catalytic composition
comprises Portland cement, a volcanic ash component, titanium
dioxide, and a transition metal salt. Optionally, a hydrogen source
is added to the catalytic composition.
Inventors: |
Newton; Jeffrey P.; (Ithaca,
NY) |
Correspondence
Address: |
DARBY & DARBY P.C.
P.O. BOX 770, Church Street Station
New York
NY
10008-0770
US
|
Family ID: |
30771182 |
Appl. No.: |
12/109812 |
Filed: |
April 25, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10627240 |
Jul 24, 2003 |
7371316 |
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12109812 |
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60398089 |
Jul 24, 2002 |
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Current U.S.
Class: |
502/66 ; 502/150;
502/207; 502/226; 502/250 |
Current CPC
Class: |
B01J 27/08 20130101;
C04B 24/36 20130101; B01J 2523/842 20130101; B01J 2523/842
20130101; B01J 2523/00 20130101; C04B 28/04 20130101; B01J 23/002
20130101; C04B 28/04 20130101; C04B 28/04 20130101; C09K 8/592
20130101; B01J 2523/00 20130101; C10G 11/04 20130101; C04B
2111/0081 20130101; C04B 28/04 20130101; B01J 35/023 20130101; B09C
1/08 20130101; B01J 2523/00 20130101; C09K 8/594 20130101; B01J
2523/31 20130101; B01J 2523/41 20130101; B01J 2523/22 20130101;
C04B 22/08 20130101; B01J 2523/31 20130101; C04B 22/12 20130101;
B01J 2523/41 20130101; C04B 14/305 20130101; B01J 2523/47 20130101;
C04B 14/30 20130101; C04B 14/14 20130101; B01J 2523/23 20130101;
C04B 22/0013 20130101; C04B 14/14 20130101; C04B 24/36 20130101;
C04B 22/12 20130101; C04B 14/14 20130101; B01J 2523/23 20130101;
C04B 24/36 20130101 |
Class at
Publication: |
502/66 ; 502/250;
502/207; 502/226; 502/150 |
International
Class: |
B01J 21/02 20060101
B01J021/02; B01J 29/072 20060101 B01J029/072; B01J 27/08 20060101
B01J027/08; B01J 31/02 20060101 B01J031/02 |
Claims
1.-51. (canceled)
52. A catalytic composition for upgrading high molecular weight
hydrocarbons comprising an admixture of water and the reaction
products of particles of the following components: silicon dioxide,
aluminum oxide, ferric oxide, calcium oxide, titanium dioxide or
boron oxide, and a transition metal salt, wherein the particles
have a Blaine surface area to weight ratio of at least 3000
cm.sup.2/gm.
53. A composition for the upgrading of a high molecular weight
hydrocarbon composition to form a lower molecular weight
hydrocarbon product, comprising the catalytic composition of claim
52 and a C.sub.5 to C.sub.25 alkane or cycloalkane.
54. The composition of claim 52, wherein the C.sub.5 to C.sub.25
alkane or cycloalkane is diesel fuel or naphtha.
55. The catalytic composition of claim 52, wherein the transition
metal salt is one or more of the compounds selected from ferric
halides, cupric halides, cobalt halides, and ferrous halides.
56. An admixture of a high molecular weight hydrocarbon and the
catalytic composition of claim 52 wherein the weight ratio of the
high molecular weight hydrocarbon to the catalytic composition is
from 2:1 to 4:1.
57. The admixture of claim 56 wherein the high molecular weight
hydrocarbon composition is one or more components selected from
bitumens, asphaltenes, oils, and tars.
58. A catalytic composition comprising an admixture of water and
the reaction products of particles of a cement component, a
volcanic ash component, a transition metal salt, and titanium
dioxide or boron oxide, wherein the particles have a Blaine surface
area to weight ratio of at least 3000 cm.sup.2/gm.
59. A composition for the upgrading of a high molecular weight
hydrocarbon composition to form a lower molecular weight
hydrocarbon product, comprising the catalytic composition of claim
58 and a C.sub.5 to C.sub.25 alkane or cycloalkane.
60. The composition of claim 59, wherein the C.sub.5 to C.sub.25
alkane or cycloalkane is diesel fuel or naphtha.
61. The catalytic composition of claim 58, wherein the cement
component is Portland cement.
62. The catalytic composition of claim 58, wherein the volcanic ash
component is one or more components selected from scoria, basalt,
pyroclastic rock, tuff, tuffstone, volcanic glass, pumice, mafic
rock, ultramafic rock, and silicate-based zeolites.
63. The catalytic composition of claim 58, wherein the transition
metal salt is one or more of the compounds selected from ferric
halides, cupric halides, cobalt halides, and ferrous halides.
64. A method of making a catalytic composition for the upgrading of
a high molecular weight hydrocarbon composition which comprises:
(a) admixing particles having a Blaine surface area to weight ratio
of at least 3000 cm.sup.2/gm of silicon dioxide, aluminum oxide,
ferric oxide, calcium oxide, titanium dioxide or boron oxide, and a
transition metal salt; and (b) blending the admixture with
water.
65. The method of claim 64, wherein the transition metal salt is
one or more of the compounds selected from ferric halides, cupric
halides, cobalt halides, and ferrous halides.
66. The method of claim 64, further including blending the
admixture with a C.sub.5 to C.sub.25 alkane or cycloalkane.
67. The method of claim 66, wherein the admixture is blended with
up to 50 weight percent C.sub.5 to C.sub.25 alkane or cycloalkane,
based on the total weight of the admixture and the C.sub.5 to
C.sub.25 alkane or cycloalkane.
68. The method of claim 66, wherein the C.sub.5 to C.sub.25 alkane
or cycloalkane is diesel fuel or naphtha.
69. A method of making a catalytic composition for the upgrading of
a high molecular weight hydrocarbon composition which comprises:
(a) admixing particles having a Blaine surface area to weight ratio
of at least 3000 cm.sup.2/gm of a cement component, a volcanic ash
component, a transition metal salt, and titanium dioxide or boron
oxide; and (b) blending the admixture with water.
70. The method of claim 69, wherein the cement component is
Portland cement.
71. The method of claim 69, wherein the volcanic ash component is
one or more components selected from scoria, basalt, pyroclastic
rock, tuff, tuffstone, volcanic glass, pumice, mafic rock,
ultramafic rock, and silicate-based zeolites.
72. The method of claim 69, wherein the transition metal salt is
one or more of the compounds selected from ferric halides, cupric
halides, cobalt halides, and ferrous halides.
73. The method of claim 69, further including blending the
admixture with a C.sub.5 to C.sub.25 alkane or cycloalkane.
74. The method of claim 73, wherein the C.sub.5 to C.sub.25 alkane
or cycloalkane is diesel fuel or naphtha.
75. The method of claim 69, wherein the admixture is blended with
up to 50 weight percent C.sub.5 to C.sub.25 alkane or cycloalkane,
based on the total weight of the admixture and the C.sub.5 to
C.sub.25 alkane or cycloalkane.
Description
PRIORITY DATA
[0001] This application claims priority from U.S. Provisional
Application Ser. No. 60/398,089 filed Jul. 24, 2002, which is
incorporated hereby by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to a process for catalytic
decomposition (cracking) followed by hydrogenation of high
molecular weight hydrocarbons to produce lower molecular weight
hydrocarbon products in both surface and subsurface applications at
ambient temperatures and pressure with no CO or CO.sub.2
emissions.
[0004] This invention further pertains to the separation of
inorganic solids, sands, clays, etc., from hydrocarbon compound
substrates and mixtures or sludge derived from an originating
petroleum source, subsurface or surface, or in the form of
petroleum contaminated waste.
[0005] This invention also pertains to the complete or partial
desulfurization by reduction of the sulfur-containing species.
[0006] This invention also pertains to the remediation of soils by
the removal of hydrocarbon contaminants.
[0007] 2. Description of Related Art/Prior Art
[0008] The generally accepted concept of the origination of oil and
gas is that it was generated from the thermal degradation of
kerogen, a fossilized material in shale and other sedimentary rock
that yields oil upon heating. It is the most common source of
carbon in the earth's crust. The major factors affecting the
concentration of petroleum are the chemical nature of the kerogen,
temperature, time, mineral composition, resident geological
structure, etc.
[0009] Traditional technology for cracking and hydrogenation, such
as catalytically cracking hydrocarbon, serve to form more valuable
lower molecular weight products. Hydrocracking reactions between
the initial hydrocarbon substrate and the catalytic agent may be
carried out in a series of bed reactors or in a distillation
column. Such reactions are endothermic and, as such, the reactors
must be heated. Additionally, hydrogen is recycled through the
system to ensure maximum hydrocarbon saturation to form the lower
molecular weight hydrocarbon products and to remove excess hydrogen
generated by the catalytic reaction. In these systems, polyaromatic
rings are also opened and the by-products hydrogenated.
[0010] Substantial quantities of petroleum in the earth have proven
difficult or impossible to recover because they are in the form of
high molecular weight hydrocarbon mixtures which are distributed
and intermixed in tar sands, shale, and various rock formations.
Furthermore, hydrocarbon compounds cannot be economically extracted
from "depleted" oil wells because they are not sufficiently
concentrated to be extractable by drilling, have lost their
original gas pressure, and/or have relatively high density and
viscosity at the given location. The latter compounds will not flow
unless heat energy is applied to the petroleum deposit, as, for
example, by steam. Additionally, once extracted, these materials
still require heat energy to remain as liquids and may be
contaminated. Waste or contaminated materials (e.g., soil, rock,
sludge, oil tars) containing hydrocarbons, crude or refined, cannot
be economically extracted from naturally or man-made contaminated
materials.
[0011] There are well known enhanced production techniques to
obtain oil from depleted or under-producing wells. In situ
combustion is a technique used to heat crude petroleum materials
below the surface of the earth to reduce their viscosity. An
oxidizing agent, such as air, is injected into the subsurface
deposit at sufficiently high temperatures to initiate a combustion
process or a phosphorous bomb or gas burner is lowered into the
well. The lower molecular weight hydrocarbons generated then rise
to the surface of the deposit. There are drawbacks to this
procedure in that the high temperatures necessary for combustion,
combined with the presence of oxygen, lead to undesirable side
reactions of coking and the formation of phenols and ketones, which
are difficult to process through other refining techniques.
[0012] Thermal recovery techniques from under-producing, depleted,
and heavy oil wells and bitumen deposits may also comprise steam
injection. The purpose of the injected steam is to heat the heavy
hydrocarbon deposit, thereby significantly reducing the viscosity
and making an economically acceptable level of recovery of the
hydrocarbon deposit. In situ hydrovisbreaking and steam flooding
are alternatives to the combustive techniques. Sometimes, in this
process, a catalyst is suspended in the steam and circulated
throughout a subsurface deposit. This heat permits the endothermic
reaction to occur, causing lower molecular weight hydrocarbons rise
to the surface of the petroleum deposit. This process may only be
used in formations that have sufficient overburden thicknesses to
withstand the injection of high temperature, high pressure
materials.
[0013] Waterflooding techniques are also a frequently employed
method to improve oil recovery from depleted or nearly depleted oil
wells and can be expected to yield between 5% and 50% of the
remaining petroleum products. The water to be injected must first
be filtered to eliminate all potentially reactive particles. Then
it is pumped into the well under pressure either from a group of
strategically placed injection wells or from injection wells at the
edge of the oilfield. Water rarely circulates evenly through the
underground deposits. In most cases, the water permeates the
deposits until it causes a breakthrough, creating a path of least
resistance to the producing well along which the water will flow.
The oil has a lower specific gravity than water and floats on top
of the water. Such waterfloods are most effective in areas where
there is little primary production. Variants of this technique
include alkaline or caustic flooding, which involve the addition of
basic agents to the water, such as sodium hydroxide.
[0014] Miscible gas drive for enhanced oil recovery involves
injecting an inert gas, such as carbon dioxide, nitrogen, or
liquefied petroleum gas into the reservoir. The gas mixes with the
petroleum deposits, making the oil less viscous, and pressures the
fluid oil towards the producing well. Sometimes alternating between
pumping gas and water through the well is employed. Solvent or
chemical flooding comprises injecting a liquid with different
chemicals in batches (slugs) into a deposit. A micellar-polymer
flood will contain a polymeric surfactant to wash reservoir pore
spaces clean of the heavy oils present within the earth formation.
Other solvents can be used to mix with and reduce the viscosity of
the petroleum deposits. Frequently used solvents include aromatic
hydrocarbons, carbon disulfide, and carbon tetrafluoride, which are
all capable of dissolving bituminous petroleum deposits.
Water-based solvents have been used, with both heated and unheated
water, to carry active ingredients throughout subsurface
formations. Solvents or chemicals are frequently pumped through
pipelines along with the treated oil. These must be separated out,
e.g., by distillation to preserve both expensive solvents and the
treated oil. Elimination of this refining step would reduce
complications and cost.
[0015] It can be relatively difficult and economically unfeasible
to separate hydrocarbon compound mixtures from some of the
inorganic solid materials that are naturally intermixed.
BRIEF SUMMARY OF THE INVENTION
[0016] This invention relates to compositions and methods for
cracking and hydrogenating high molecular weight hydrocarbons to
produce lower molecular weight hydrocarbons from substrates
containing relatively higher molecular weight hydrocarbons.
Hydrogenation is facilitated by the presence of water and,
optionally, by the addition of refined and unrefined alkane and
cycloalkane hydrocarbons (C.sub.5-C.sub.25). The treatment with the
inventive composition results in the lower molecular weight
characteristics, as can be shown by both increased API value
(generally the API value is more than doubled) and lower viscosity.
These substrates may be treated on the earth's surface or in
subsurface deposits at ambient temperatures and pressures.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The catalytic composition of the present invention is a
reactive inorganic composition capable of homogeneous cracking and
hydrogenation of high molecular weight hydrocarbon compounds in the
presence of water at ambient temperature and pressure. The
catalytic composition is an admixture of organic compounds in
water.
[0018] The exact proportions of said catalytic composition are
varied depending on the high molecular weight hydrocarbon to be
treated and the desired lower molecular weight hydrocarbon
products. The essential particulate components of the catalytic
composition are SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, and
CaO. Typical ranges are shown in Table 1 below. All weight percents
are based on the total weight of these components combined in a
particulate blend.
TABLE-US-00001 TABLE 1 Particulate Broad Range Preferred Component
(wt. %) Range (wt. %) SiO.sub.2 20-60 5-35 Al.sub.2O.sub.3 1-10
1.5-5 Fe.sub.2O.sub.3 0.5-15 1-10 CaO 20-40 25-35
TiO.sub.2/B.sub.2O.sub.3 2-4 2 FeCl.sub.3/FeCl.sub.2 8-12 8
[0019] To form the catalytic composition, all of the particulate
components must initially be ground to about 3000 Blaine or finer.
Blaine is a measurement of grain fineness consisting of the ratio
of a particle's surface area (in square centimeters) to weight (in
grams). Then, these particles are blended with about one to five,
preferably two to three times their weight water. An essential
first reaction occurs when the solid particles are added to the
water. This reaction forms reactive colloidal particles based on
the connected surfaces of clays, metal oxides, zeolitic entities,
and molecular sieves. The mixture is blended until the particles
are completely suspended in the water.
[0020] Alternatively, the catalytic composition may use composite
materials to provide the essential components. For example a cement
component and a volcanic ash component may provide the SiO.sub.2,
Al.sub.2O.sub.3, Fe.sub.2O.sub.3, and CaO components. Table 2 below
illustrates the broad and preferred ranges of these compounds.
TABLE-US-00002 TABLE 2 Particulate Broad Range Preferred Component
(wt. %) Range (wt. %) Portland 30-50 45 Cement Volcanic Ash 30-50
45 TiO.sub.2 2-4 2 FeCl.sub.3/FeCl.sub.2 8-12 8
[0021] The cement component is most preferably a Portland cement.
Portland cements are mixtures of limestone and clay that have been
ground and treated in a kiln from 1400 to 1600.degree. C. About 24%
of Portland cement by weight is calcium silicate and about 66% by
weight is CaO. Impurities may include up to about 3% by weight of
alumina, ferric oxide, and magnesia.
[0022] The volcanic ash component may consist of scoria, pumice,
tuff, tuffstone, mafic volcanic rock, ultramafic volcanic rock,
pyroclastic rock, volcanic glasses, basalt or silica-based
zeolites. Scoria is the most preferred volcanic ash component. The
most preferred embodiment contains British Columbia scoria. Scoria
is the most common material in volcanic cones and is formed of
small particles (about 1 cm across) of hardened volcanic lava.
British Columbia scoria consists of about 46% SiO.sub.2, about 18%
Fe.sub.2O.sub.3, about 8% CaO, and about 2.4% TiO.sub.2. Scoria
from southern Mexico consists of about 79% SiO.sub.2 and about 6.6%
F.sub.2O.sub.3. Pumice is a light pyroclastic rock that is hardened
from a lava foam into a porous glass. Tuffstone is created from
pieces of volcanic ash welded together by lithification upon
eruption. Tuff consists of non-welded pieces of volcanic ash. Mafic
rock is defined as igneous rock which contains substantial
quantities of silicates, such as pyroxene, amphibole, olivine, and
mica. Ultramafic rock a volcanic rock with an ultrabasic
composition and over 90% composed of Fe--Mg minerals, predominantly
olivine, orthopyroxene, and clinopyroxene. Pyroclastic rock is rock
which is formed by either a volcanic explosion or an aerial
expulsion from a volcanic vent. Volcanic glasses are called
obsidian and consist of silica particles fused by the intense heat
of a volcano. Basalt is a mafic, igneous rock composed of
plagioclase. Different varieties of basalt differ in their degree
of silica saturation. Zeolites are a family of aluminum silicate
minerals that may occur naturally or be produced synthetically.
Zeolites from British Columbia typically consist of about 89%
SiO.sub.2, 0.8% Fe.sub.2O.sub.3, and about 1% CaO.
[0023] Any transition metal salt with a +2 or +3 oxidation state
will function in the catalytic composition. Preferred compounds
include ferric chloride, ferrous chloride, cupric chloride, and
cobalt chloride. Ferric chloride is the most preferred.
[0024] Not including the specific metal oxides listed above, the
most preferred metal oxide is titanium dioxide (TiO.sub.2). In the
most preferred embodiment, titanium dioxide accounts for about 2%
by weight of the total weight of the catalytic composition. Boron
oxide (B.sub.2O.sub.3) can also be substituted and used in place of
and in concert with TiO.sub.2.
[0025] The components other than Portland cement are varied
depending on the specific high molecular weight substrate being
treated. Such customization can be readily carried out by testing
small samples of the substrate with different catalytic
compositions to determine the most effective components and
relative component ratios. Particular examples are set forth below.
Solid components may account for 2-10% by weight of the catalytic
composition, and preferably comprise 5-10% by weight.
[0026] Though specific materials are recited herein by their common
names, it will be understood that other composites formed of
various minerals and compounds may also be used.
[0027] Optionally, refined and unrefined alkanes and cycloalkanes,
such as naphtha or diesel fuel, of the C.sub.5 to C.sub.25 range
are frequently employed to facilitate and intensify the
hydrogenation process. This refined or unrefined hydrocarbon
component is incorporated to serve as a hydrogen donor. The
included water will also function as a hydrogen source. Typically,
diesel fuel or naphtha is mixed with the high molecular weight
hydrocarbon substrate prior to the addition of the aqueous colloid
suspension. The refined or unrefined hydrocarbon component may
consist of any C.sub.5 to C.sub.25 alkane or cycloalkane or mixture
thereof and may range from 0 to 50% by weight of the total
catalytic composition added. Naphtha or condensate is the most
preferred refined hydrocarbon.
[0028] Catalytic composition to crude oil loading may vary from a
ratio of 2:1 to 4:1. The preferable loading ratio is 3:1.
[0029] After vigorously admixing the catalytic composition in water
with the high molecular weight hydrocarbon compounds and,
optionally, with a refined hydrocarbon at ambient temperatures and
pressures, a rapid, almost instantaneous, reaction of cracking and
hydrogenation occurs to produce a product composed of lower
molecular weight hydrocarbons. The lower molecular weight
hydrocarbons float on top of the water-based colloid in a separate
layer. Sulfur-based and metallic impurities form solid, inert
precipitates upon reaction with the catalytic composition after
mixing. The process proceeds to completion very rapidly, often
within minutes from the time of complete addition of the catalytic
composition with no CO.sub.2 or CO emissions.
[0030] The terms high molecular weight hydrocarbon and low
molecular weight hydrocarbon as used herein are relative terms to
one another. The term high molecular weight hydrocarbon signifies a
mixture of hydrocarbons and their entrained impurities with an
average molecular weight of the hydrocarbons higher than the
average molecular weight of the hydrocarbons in a low molecular
weight hydrocarbon. Thus, the use of the terms "high molecular
weight hydrocarbon" and "low molecular weight hydrocarbon" does not
signify any particular molecular weight ranges.
[0031] High molecular weight hydrocarbons are typically materials
such as crude oils, asphaltenes, tars, heavy oils, and the like
which have limited or no practical use, but which can be converted
to more valuable and useful lower molecular weight hydrocarbons via
chemical means. Medium oils have resins or polar fractions less
than about 25% of the weight of the total oil and have API gravity
of 20 to 30 with viscosities in the range of about 100 to 1000
centipoise; heavy oils have resins or polar fractions between about
25 and 40% of the total weight of the oil and have API gravity of
10 to 20 with a viscosities in the range of about 100 to 10000
centipoise; tars have resins or polar fractions greater than about
40% of the total weight of the oil and have API gravity less than
about 8 to 10 and a viscosity greater than about 8000
centipoise.
[0032] The lowest molecular weight hydrocarbons may include C.sub.1
to C.sub.4 gases, e.g., methane, propane, natural gas. The
inventive process also results in a reduction of density and
viscosity and an increased API gravity value in the treated
hydrocarbon mixture.
[0033] In the inventive process, any solid fraction in the starting
high molecular weight hydrocarbon (soils, sediments, rock mixtures,
sands, etc.) will precipitate to the bottom of the aqueous mixture.
A significant percentage of heavy metal ion impurities in the
starting high molecular weight hydrocarbon will attach or bind to
the solid fraction in the precipitate. The low molecular weight
hydrocarbon product will float to the surface of the water allowing
for easy retrieval of the products.
1. Subsurface Application
[0034] For treatment of a high molecular weight hydrocarbon below
the earth's surface, the solids in the inventive catalytic
composition are initially slurried with water or with a
water/refined hydrocarbon mixture. This mixture is then injected
into a reservoir or source rock formation of an oil or gas well.
This petroleum-containing geologic formation associated with a
given oil and/or gas well may be considered "dead" or
under-producing and still be a candidate for the inventive
treatment. The catalytic composition will reduce oil density,
increase API gravity, and reduce the viscosity of any contacted oil
deposits. This will increase the value of the oil per barrel.
Typical barrel price of heavy oil, with an API below 16, is about
$8 to about $10. With the addition of about $1.50 to $2.00 of
chemistry per barrel, the value of the same oil will increase to
about $15 to about $18 per barrel.
[0035] In the context of a fracture and/or stimulation project on
the given well, the composition may be injected under pressure. The
chosen catalytic composition is directed to the reservoir formation
associated with the oil or gas producing formation which has been
deemed to have the greatest amount of oil and gas. The catalytic
composition reacts with the silicates in the geologic formation as
well as high molecular weight hydrocarbons present in the region of
fracture/stimulation. The chemical reactions between the catalytic
composition and the hydrocarbons generate C.sub.1 to C.sub.4 gases,
most notably methane and butane, and these relatively lower
viscosity hydrocarbon gases then diffuse into the surrounding
hydrocarbon mass. This pervasive in-situ chemical reaction
stimulates the formation of desirable lower molecular weight
hydrocarbon liquid and gases with the lower density and
viscosity.
[0036] Another subsurface application of the present invention can
occur at shallow depths in heavy oil producing environments where
the method of hydrocarbon recovery uses water flooding and a
pressure circulation system through the oil-bearing formation. The
catalytic composition can be added to the circulating water to
cause cracking and hydrogenation reactions in the heavy oils,
thereby reducing the viscosity by the generation of C.sub.1 to
C.sub.4 gases and lower molecular weight hydrocarbons with lower
density and viscosity. This causes and increased rate of recovery
of desirable hydrocarbons from the treated well. Also, the quality
of the recovered oil is improved. The addition of the catalytic
composition to steam being injected into the treated hydrocarbons
is also possible.
[0037] The present invention will allow the oil to be recovered
more rapidly than conventional technology, thereby using less
steam, energy, and time for the upgrading and recovery process. The
overall petroleum quality in terms of a reduction in viscosity and
API value would be improved by the application of these enhanced
production technologies. Treated oils with lower viscosities and
densities may increase the value and efficiency of heavy oils that
need to be transported by pipelines.
2. Surface Application
[0038] The inventive procedure may be used to upgrade high
molecular weight hydrocarbon material or substrates on the earth's
surface. For example, it may be used in the treatment or
"upgrading" of tar sands or heavy oil. The hydrocarbon is treated
in a storage and mixing facility. The catalytic composition is
admixed with the substrate of high molecular weight hydrocarbon
material. Diesel fuel or condensate or a like refined or unrefined
hydrocarbon is added to the admixture as a supplemental hydrogen
source for the cracking reactions. Upgrading consists of chemically
treating or fractionating bitumen or heavy oils to increase its
value by reducing the density and viscosity, thereby generating a
higher quality crude oil substitute. The specific objectives of
upgrading are to increase the percentage of the saturate and
aromatic fractions, reduce the polar and pentane insolvable
fractions, reduce viscosity, increase API gravity, and reduce
overall hydrocarbon molecular weight. API gravity is a term to
relate the relative specific densities of oil products developed by
the American Petroleum Institute. To convert between API gravity
and specific gravity, the following formula should be followed: API
to specific gravity: SG=141.5/(131.5+.degree.API).
[0039] By reducing the density, increasing the API gravity, and
reducing the viscosity heavy oil or tar sands bitumen would need no
or reduced addition of condensate to allow the oil to be pumped
through pipes. For example, there exists a pipeline that moves
778,000 barrels of heavy oil per day from Alberta to U.S. In
addition to the oil, 300,000 barrels of condensate are added so it
can be pumped. The value of the oil is currently $12 per barrel. If
the API gravity were 20 to 23, then there would be no need of
condensate. The value of the treated oil would now be $16-$18 per
barrel and the operator could then pump 1,000,000 barrels of oil
per day. Condensate is in such short supply that the condensate is
currently distilled out of the oil in the U.S. and pumped back to
Alberta daily.
[0040] For surface applications of the present invention, the
inventive reaction may be carried out at ambient temperatures and
pressure, i.e., at about room temperature, which is defined as
about 20 to 25.degree. C. (about 68 to 77.degree. F.). Ambient
pressure is about 1 atmosphere (about 760 Torr).
3. Desulfurization and the Elimination of Hydrogen Sulfide
[0041] Hydrogen sulfide may be generated in large amounts by
thermal cracking from kerogen and from liquid sulfur-containing
compounds present in crude oils. Sulfur content of crude oil
generally decreases with depth, possibly due to cracking and
elimination of sulfur as H.sub.2S. The total sulfur content in
crude oil, heavy oil, bitumens, and tars varies from 0.04% to 8%.
Generally, oils with high densities and low API gravities will have
higher sulfur contents.
[0042] Some of the hydrogen generated from surface catalytic
reactions between the catalytic composition and water and with the
refined or unrefined hydrogen source will convert sulfur
heteroatoms in the polar (resin) and asphaltene fractions to
H.sub.2S. Through a series of oxidation reactions, the catalytic
composition converts the H.sub.2S to CaSO.sub.4. Free sulfur, if
present, may also react with the hydrocarbons to produce H.sub.2S.
Sulfate reduction, if present in the sediments, and the related
oxidation of hydrocarbons may also occur beyond 150.degree. C.,
resulting in the generation of H.sub.2S and CO.sub.2.
4. Soil Decontamination
[0043] The inventive catalytic compound may be mixed with
contaminated soil in a tank containing water and mechanically
agitated with the injection of air. The contaminated soil will be
remediated through the cracking and hydrogenating the impurities.
The treated soil will precipitate to the bottom of the reaction
vessel and the organic waste products will float on the surface of
the water. The hydrocarbon layer can be decanted off and reused as
a secondary fuel. Also, the catalytic compound may be injected and
mixed into the soil on the ground, achieving the same end state
results.
[0044] The following examples illustrate embodiments of the
invention, but are not intended to be limiting:
EXAMPLE 1
[0045] Crude oil samples (about 200 to 250 grams each) were taken
straight from the well at the Lloydminister oil fields,
Lloydminister, Alberta, Canada (API gravity 16 to 18) and Peace
River oil fields, Peace River, Alberta, Canada (API gravity 8 to
10). The samples were each placed in two-liter jars and an equal
weight of water heated to 100.degree. C. was added to facilitate
mixing with the catalytic composition. The samples were allowed to
cool to ambient temperature (16.degree. C.) after treatment. The
jars had screw-on gas tight lids with rubber diaphragms in place of
a hole that had been drilled in the covers to allow withdrawal of
headspace gas samples for analysis. The inventive composition, in
powder form, was added to each of the samples in amounts of 5 and
10% by weight to weight of oil. The composition contained 48%
Portland cement, 42% volcanic glasses-red scoria, 8% ferric
chloride and 2% titanium dioxide, all percentages being based on
the total weight of the composition.
[0046] The following table shows the weight percent of Portland
cement and volcanic ash components in the catalytic
composition.
TABLE-US-00003 TABLE 3 Catalytic Composition SiO.sub.2
Al.sub.2O.sub.3 Fe.sub.2O.sub.3 CaO Portland 8.65% 2.10% 1.30%
27.03% Cement Volcanic Ash 34.65% 3.97% 1.03% 0.12%
[0047] The samples were then stirred with a metal rod for 1.5 to 2
minutes and the lids were then screwed on tightly. A separate set
of control samples of each crude oil without the added catalytic
composition were allowed to stand for four days at ambient
temperatures and pressure. Thereafter, the headspace gases were
analyzed by gas chromatography for each sample.
[0048] Significant amounts of hydrocarbon gases were found in the
headspace gas of the Lloydminister samples, except for the control,
in which there was only a water and oil mixture present.
Specifically, compared to the control sample, the treated headspace
gas contained 41 times more methane, 23 times more ethane, 14 times
more propane, 10 times more isobutene, and 71 times more butane.
The speed of the reaction is very fast and that for the Peace River
samples, hydrocarbon gases were generated very rapidly and lost
before the lid could be placed on the jar, or not generated for
some reason. The composition of the headspace gases was determined
by gas chromatography.
[0049] Additional tests with crude oil from Lloydminister field
showed that hydrocarbon gases were rapidly generated and the
analysis indicated that 2 to 3% of the total initial carbon was
converted to C.sub.1 to C.sub.4 hydrocarbon gases, with methane
being the most prominent in quantity. No hydrocarbon gases were
found in the headspace gases of the treated Peace River
samples.
[0050] Saturate, aromatic, polar, and pentane insoluble fractions
(SAPA) analysis of the treated and untreated heavy oil showed
significant changes in the Lloydminister heavy crude oil samples.
The 9% and 8% increases in the saturates and aromatic fractions,
respectively, and the 19% and 1% decreases in the polar and pentane
insoluble fractions, respectively, represent significant
improvements in the quality of that heavy oil sample.
[0051] There was a consistent 2% lower distillation temperature
across the mass spectrum of the saturates fraction for the
untreated Lloydminister heavy oil relative to the saturates
fraction of the untreated oil. This means the treated saturates
fraction was a relatively lighter molecular weight fraction than
the untreated saturates fraction.
EXAMPLE 2
[0052] Samples of Syncrude bitumen were prepared to demonstrate the
effectiveness of different embodiments of the present invention.
Three liquid samples of Syncrude bitumen were blended with 35-50%
by weight of naphtha. For two samples, the catalytic composition
was prepared by adding the inorganic composition to hot tap water
and mixing with a metal stirring rod the resulting colloid into the
crude oil sample. The third sample received no addition of the
catalytic composition and serves as the control. The catalytic
composition called "Mix 1" consisted of 45% by weight Portland
cement, 45% by weight volcanic scoria from British Columbia, 2% by
weight titanium dioxide, and 8% by weight ferric chloride. "Mix 2"
consisted of 45% Portland cement, 45% clinoptilolite zeolite from
British Columbia, 2% titanium dioxide, and 8% ferric chloride.
[0053] The following table shows the weight percent of the Portland
cement and volcanic ash components in the Mix 1 and Mix 2 catalyst
compositions.
TABLE-US-00004 TABLE 4 Catalytic Composition SiO.sub.2
Al.sub.2O.sub.3 Fe.sub.2O.sub.3 CaO Mix 1 Portland 8.65% 2.10%
1.30% 27.03% Cement Volcanic Ash 20.70% 0% 8.10% 0% Mix 2 Portland
8.65% 2.10% 1.30% 27.03% Cement Zeolite 40.05% 0% 0.36% 0.45%
[0054] 100 grams of naphtha were added to 300 grams of hot tap
water and 10 grams of the catalytic compositions described above,
for those samples receiving the composition.
[0055] The inventive treatment for each oil sample was added and
mixed vigorously for about 30 seconds. The reaction was completed
almost instantaneously. The liquid in the jar separated into three
layers; the treated oil at the top, a water layer in the middle,
and a precipitate of inorganic material at the bottom. The gas
generation occurred slowly through low bubbling and was even
evidenced briefly in the sample without the catalytic
composition.
[0056] When the reaction vessels were opened, measurements were
conducted to determine the change in the viscosity of each sample
and SAPA (Saturate, Aromatic, Polars or resins, and Pentane
insolubles or asphaltenes) analyses were performed. Table 5 below
uses these characteristics to demonstrate the properties of each
sample.
TABLE-US-00005 TABLE 5 Polars Pentane or Insolubles - Viscosity Oil
Sample Saturates Aromatics Resins Asphaltenes API (centipoises)
Syncrude Bitumen & 12 26.4 40.7 20.9 27.3 91.88 Naphtha -
Untreated Syncrude Bitumen, 13.8 23.9 37.4 24.9 91.88 Naphtha,
& Mix 1 % Change +15.0% -9.5% -8.1% +19.1% Syncrude Bitumen,
13.1 22.4 41.8 22.7 380.8 Naphtha & Mix 2 % Change +9.2% -15.2%
+2.7% +8.6%
[0057] After 24 hours, headspace gases generated in each sample
were analyzed. The gas analyses of the Mix 1 and Mix 2 samples
showed the same compounds and relative concentrations as was found
in the untreated control sample. However, the CO.sub.2 level was
91% less in the treated samples than it was in the untreated
sample. It is possible that the hydrocarbon gases generated by the
inventive process were reabsorbed into the treated hydrocarbon
mass.
EXAMPLE 3
[0058] Samples of heavy oil from the Lloydminister oil fields were
prepared to demonstrate the effectiveness of different embodiments
of the present invention. This sample had an initially high polar
fraction, 38.7%. Polar fractions have a dramatic effect on the
viscosity and density of an oil sample. Two 200-gram liquid samples
of oil bitumen with an initial API gravity of 9.9 were tested. The
process for addition and composition of the catalytic composition
used in this example is the same as that described in mix 1 of
example 2 above. The specific catalytic composition consisted of
45% by weight Portland cement, 45% by weight volcanic scoria from
British Columbia, 2% by weight titanium dioxide, and 8% by weight
ferric chloride. Diesel fuel and the catalytic composition were
added to Sample 1. After 1 hour, the API gravity of Sample 1 had
reached 22.1 and, after 24 hours, was 27.3. Sample 2 had no diesel
fuel added, and reached an API gravity of 14.9 one hour after the
addition of the catalytic composition, and an API gravity of 17.5
24 hours later.
[0059] After 24 hours of reacting, the reaction vessels were opened
and measurements were conducted to determine the change in the
viscosity of each sample and SAPA (Saturate, Aromatic, Polars or
resins, and Pentane insolubles or asphaltenes) analyses were
performed. Table 6 below uses these characteristics to demonstrate
the properties of each sample.
TABLE-US-00006 TABLE 6 Polars Pentane Oil or Insolubles - Sample
Saturates Aromatics Resins Asphaltenes API Untreated 17 25 22.0 19
9.9 Oil Sample 1 21 25 22.0 14 27.3 % Change +24% 0 0 -26% 176%
Sample 2 20 26 18 17 17.5 % Change +18% +4% -18% -11% 77%
* * * * *