U.S. patent application number 12/647202 was filed with the patent office on 2011-06-30 for increasing distillates yield in low temperature cracking process by using nanoparticles.
Invention is credited to Petro E. Stryzhak, Oleksander S. Tov.
Application Number | 20110155643 12/647202 |
Document ID | / |
Family ID | 44186166 |
Filed Date | 2011-06-30 |
United States Patent
Application |
20110155643 |
Kind Code |
A1 |
Tov; Oleksander S. ; et
al. |
June 30, 2011 |
Increasing Distillates Yield In Low Temperature Cracking Process By
Using Nanoparticles
Abstract
Metal or metal-oxide nanoparticles, or combinations of metal and
metal-oxide nanoparticles are added to crude oil before initial
distillation in order to increase the yield of light hydrocarbons
obtained during initial distillation. According to one aspect, a
solid acid micropowder can be added with the metal or metal-oxide
nanoparticles or combinations thereof before initial distillation
in order to increase yield. According to another aspect, the metal
or metal-oxide nanoparticles, or combinations thereof, or the
nanoparticles in conjunction with a solid acid micropowder can be
added after initial distillation of the gasoline fraction.
Inventors: |
Tov; Oleksander S.; (Kiev,
UA) ; Stryzhak; Petro E.; (Kiev, UA) |
Family ID: |
44186166 |
Appl. No.: |
12/647202 |
Filed: |
December 24, 2009 |
Current U.S.
Class: |
208/119 ;
208/121 |
Current CPC
Class: |
C10G 2300/1033 20130101;
C10G 2400/02 20130101; C10G 7/00 20130101; C10G 2400/04 20130101;
C10G 11/02 20130101; B01D 3/009 20130101 |
Class at
Publication: |
208/119 ;
208/121 |
International
Class: |
C10G 11/05 20060101
C10G011/05; C10G 11/04 20060101 C10G011/04 |
Claims
1. A method of increasing distillate yield in a crude oil
distillation, comprising: prior to distillation of the crude oil,
adding at least one of metal and metal-oxide nanoparticles of
diameter between 1 nm and 90 nm to the crude oil to create a crude
oil/nanoparticle mixture where the nanoparticles are present in
said mixture in a weight percentage of between 0.0004% and 0.02%;
and distilling said crude oil/nanoparticle mixture to generate at
least light fractions of hydrocarbons and a residue, where said
residue is smaller than a residue which would be generated from an
identical distillation of the crude oil without said
nanoparticles.
2. A method according to claim 1, wherein: said at least one of
metal and metal-oxide nanoparticles are chosen from iron,
iron-oxide, and cobalt-oxide nanoparticles.
3. A method according to claim 2, wherein: said at least one of
metal and metal-oxide nanoparticles are iron nanoparticles, and
said iron nanoparticles are between 2 nm and 76 nm in diameter.
4. A method according to claim 3, wherein: said iron nanoparticles
are 43 nm in diameter.
5. A method according to claim 4, wherein: said iron nanoparticles
constitute between 0.001% and 0.015% of said mixture.
6. A method according to claim 5, wherein: said iron nanoparticles
constitute between 0.002% and 0.01% of said mixture.
7. A method according to claim 6, wherein: said iron nanoparticles
constitute between 0.003% and 0.008% of said mixture.
8. A method according to claim 2, wherein: said at least one of
metal and metal-oxide nanoparticles are iron-oxide nanoparticles,
and said iron-oxide nanoparticles are between 20 nm and 62 nm in
diameter.
9. A method according to claim 8, wherein: said iron-oxide
nanoparticles are 20 nm in diameter.
10. A method according to claim 2, wherein: said at least one of
metal and metal-oxide nanoparticles are cobalt-oxide nanoparticles,
and said cobalt-oxide nanoparticles are between 2 nm and 84 nm in
diameter.
11. A method according to claim 10, wherein: said cobalt-oxide
nanoparticles constitute between 0.001% and 0.02% of said
mixture.
12. A method according to claim 11, wherein: said cobalt-oxide
nanoparticles constitute between 0.008% and 0.015% of said
mixture.
13. A method according to claim 1, wherein: said at least one of
metal and metal-oxide nanoparticles includes metal nanoparticles
and metal-oxide nanoparticles.
14. A method according to claim 13, wherein: said metal
nanoparticles are iron nanoparticles, and said metal-oxide
nanoparticles are cobalt-oxide nanoparticles.
15. A method of increasing distillate yield in a crude oil
distillation, comprising: prior to distillation of the crude oil,
adding at least one of metal and metal-oxide nanoparticles of
diameter between 1 nm and 90 nm to the crude oil and a solid acid
micropowder of diameter between 20 nm and 10 micrometers to create
a crude oil/nanoparticle/zeolite powder mixture where the
nanoparticles are present in said mixture in a weight percentage of
between 0.0004% and 0.02% and said solid acid micropowder is
present in said mixture in a weight percentage of between 0.001%
and 0.04%; and distilling said crude oil/nanoparticle/solid acid
micropowder mixture to generate at least light fractions of
hydrocarbons and a residue, where said residue is smaller than a
residue which would be generated from an identical distillation of
the crude oil without said nanoparticles and solid acid
micropowder.
16. A method according to claim 15, wherein: said solid acid
micropowder is chosen from Faujasite, Mordenite, and HZSM-5
micropowder.
17. A method according to claim 15, wherein: said solid acid
micropowder is present in said mixture in a weight percentage
between 0.01% and 0.04%.
18. A method according to claim 15, wherein: said at least one of
metal and metal-oxide nanoparticles are iron nanoparticles.
19. A method according to claim 15, wherein: said at least one of
metal and metal-oxide nanoparticles are cobalt-oxide
nanoparticles.
20. A method according to claim 18, wherein: said at least one of
metal and metal-oxide nanoparticles are iron nanoparticles, and
said solid acid micropowder is an HZSM-5 micropowder.
21. A method according to claim 20, wherein: said iron
nanoparticles are 43 nm diameter nanoparticles and constitute
0.004% of said mixture, and said HZSM-5 micropowder constitutes
0.04% of said mixture.
22. A method of increasing yield of diesel oil from a crude oil
fraction that does not contain gasoline after an initial partial
distillation of crude oil, said method comprising adding at least
one of metal and metal-oxide nanoparticles of diameter between 1 nm
and 90 nm to the crude oil fraction to create a crude oil
fraction/nanoparticle mixture where the nanoparticles are present
in said mixture in a weight percentage of between 0.0004% and
0.02%; and distilling said crude oil fraction/nanoparticle mixture
to generate at least light fractions of hydrocarbons and a residue,
where said residue is smaller than a residue which would be
generated from an identical distillation of the crude oil fraction
without said nanoparticles.
23. A method according to claim 22, wherein: said at least one of
metal and metal-oxide nanoparticles are chosen from iron,
iron-oxide, and cobalt-oxide nanoparticles.
24. A method according to claim 23, wherein: said at least one of
metal and metal-oxide nanoparticles are iron nanoparticles, and
said iron nanoparticles are between 2 nm and 76 nm in diameter.
25. A method according to claim 24, wherein: said iron
nanoparticles are 43 nm in diameter.
26. A method according to claim 25, wherein: said iron
nanoparticles constitute between 0.001% and 0.015% of said
mixture.
27. A method according to claim 26, wherein: said iron
nanoparticles constitute between 0.002% and 0.01% of said
mixture.
28. A method according to claim 27, wherein: said iron
nanoparticles constitute between 0.003% and 0.008% of said
mixture.
29. A method according to claim 23, wherein: said at least one of
metal and metal-oxide nanoparticles are iron-oxide nanoparticles,
and said iron-oxide nanoparticles are between 20 nm and 62 nm in
diameter.
30. A method according to claim 23, wherein: said at least one of
metal and metal-oxide nanoparticles are cobalt-oxide nanoparticles,
and said cobalt-oxide nanoparticles are between 2 nm and 84 nm in
diameter.
31. A method according to claim 30, wherein: said cobalt-oxide
nanoparticles constitute between 0.001% and 0.02% of said
mixture.
32. A method according to claim 21, wherein: said at least one of
metal and metal-oxide nanoparticles includes metal nanoparticles
and metal-oxide nanoparticles.
33. A method of increasing yield of diesel oil from a crude oil
fraction that does not contain gasoline after an initial partial
distillation of crude oil, said method comprising adding at least
one of metal and metal-oxide nanoparticles of diameter between 1 nm
and 90 nm and a solid acid micropowder of diameter between 20 nm
and 10 micrometers to the crude oil fraction to create a crude oil
fraction/nanoparticle mixture where the nanoparticles are present
in said mixture in a weight percentage of between 0.0004% and 0.02%
and said solid acid micropowder is present in said mixture in a
weight percentage of between 0.001% and 0.04%; and distilling said
crude oil fraction/nanoparticle/solid acid micropowder mixture to
generate at least light fractions of hydrocarbons and a residue,
where said residue is smaller than a residue which would be
generated from an identical distillation of the crude oil fraction
without said nanoparticles and solid acid micropowder.
34. A method according to claim 33, wherein: said solid acid
micropowder is chosen from Faujasite, Mordenite, and HZSM-5
micropowder.
35. A method according to claim 33, wherein: said solid acid
micropowder is present in said mixture in a weight percentage
between 0.01% and 0.04%.
36. A method according to claim 33, wherein: said at least one of
metal and metal-oxide nanoparticles are iron nanoparticles.
37. A method according to claim 33, wherein: said at least one of
metal and metal-oxide nanoparticles are cobalt-oxide
nanoparticles.
38. A method according to claim 33, wherein: said at least one of
metal and metal-oxide nanoparticles are iron nanoparticles, and
said solid acid micropowder is an HZSM-5 micropowder.
39. A method according to claim 38, wherein: said iron
nanoparticles are 43 nm diameter nanoparticles and constitute
0.004% of said mixture, and said HZSM-5 micropowder constitutes
0.04% of said mixture.
40. A mixture consisting essentially of crude oil in a weight
percentage of between 99.9996% and 99.98% and at least one of metal
and metal-oxide nanoparticles of diameter between 1 nm and 90 nm in
a weight percentage of between 0.0004% and 0.02%.
41. A mixture consisting essentially of crude oil in a weight
percentage of between 9.9986% and 99.94%, at least one of metal and
metal-oxide nanoparticles of diameter between 1 nm and 90 nm in a
weight percentage of between 0.0004% and 0.02%, and a solid acid
micropowder in a weight percentage of between 0.001% and 0.04%.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates broadly to the distillation of crude
oil (petroleum) or a fraction of crude oil distillation. More
particularly, this invention relates to methods of increasing the
distillates yield during distillation of an unprocessed (raw)
hydrocarbon composition by adding nanoparticles to the unprocessed
hydrocarbon composition.
[0003] 2. State of the Art
[0004] For much of the last century, crude oil (petroleum) has been
one of the primary sources of energy world-wide. Crude oil contains
primarily hydrocarbons. One of the major uses of crude oil is in
the production of motor fuels such as gasoline and diesel. These
motor fuels are obtained through the refining of crude oil into its
various component parts. Refining results in the production of not
only gasoline and diesel, but kerosene and heavy residues.
[0005] Refining of crude oil is typically accomplished by boiling
at different temperatures (distillation) and using advanced methods
to further process the products which have boiled off at those
different temperatures. The chemistry of hydrocarbons underlying
the distillation process is that the longer the carbon chain of the
hydrocarbon component of the crude oil, the higher the temperature
at which that component boils. As a result, a large part of
refining involves boiling at different temperatures in order to
separate the different fractions of crude oil and other
intermediate streams.
[0006] As previously mentioned, crude oil or petroleum contains a
mixture of a very large number of different hydrocarbons, most of
which have between 5 and 40 carbon atoms per molecule. The most
common molecules found in the crude oil are alkanes (linear or
branched), cycloalkanes, aromatic hydrocarbons and more complicated
chemicals like asphaltenes. Each petroleum variety has a unique mix
of molecules which define its physical and chemical properties.
[0007] The alkanes are saturated hydrocarbons with straight or
branched chains which contain only carbon and hydrogen and have the
general formula C.sub.nH.sub.2n+2. The alkanes from pentane
(C.sub.5H.sub.12) to octane (C.sub.8H.sub.18) are typically refined
into gasoline (petrol). The alkanes from nonane (C.sub.9H.sub.20)
to hexadecane (C.sub.16H.sub.34) are typically refined into diesel
fuel and kerosene which is the primary component of many types of
jet fuel. The alkanes from hexadecane upwards (i.e., alkanes having
more than sixteen carbon atoms) are typically refined into fuel oil
and lubricating oil. The heavier end of the alkanes includes
paraffin wax (having approximately 25 carbon atoms) and asphalt
(having approximately 35 carbon atoms and more), although these are
usually processed by modern refineries into more valuable products
as discussed below. The lighter molecules with four or fewer carbon
atoms (e.g., methane), are typically found in the gaseous state at
room temperature.
[0008] The cycloalkanes are also known as naphthenes and are
saturated hydrocarbons which have one or more carbon rings to which
hydrogen atoms are attached according to the formula
C.sub.nH.sub.2n. Cycloalkanes have similar properties to alkanes
but have higher boiling points.
[0009] The aromatic hydrocarbons are unsaturated hydrocarbons which
have one or more planar six-carbon (benzene) rings to which
hydrogen atoms are attached.
[0010] Although just about all fractions of petroleum find uses,
the greatest demand is for gasoline and diesel. While the amount
(weight percentage) of hydrocarbons in the crude oil samples which
through a simple distillation ends up in gasoline and diesel varies
widely depending upon the geographical source of the crude oil,
typically, crude oil contains only 10-40% gasoline and 20-40% of
diesel. Increasing gasoline and diesel yield from a particular
crude oil sample may be done by cracking, i.e., breaking down large
molecules of heavy heating oil and residues; reforming, i.e.,
changing molecular structures of low quality gasoline molecules;
and isomerization, i.e., rearranging the atoms in a molecule so
that the product has the same chemical formula but has a different
structure, such as converting normal heptane to isoheptane.
[0011] Generally, the simplest refineries undertake first-run
distillation that separates the crude oil into light (gas, naphtha
and gasoline), middle (kerosene and diesel) and heavy (residual
fuel oil) distillates. These simple refineries may include some
hydrotreating capacity in order to remove sulfur, nitrogen, and
unsaturated hydrocarbons (aromatics) from the distillates, and may
also include some reforming capabilities. The next level of
refinery complexity typically incorporates cracking capabilities
and some additional hydrotreating in order to improve distillates
quality; i.e., increasing the octane number for gasoline fractions
and decreasing the sulfur content for gasoline and diesel. The most
complex refineries add coking, and more hydrotreating and
hydrocracking.
[0012] The catalytic cracking process utilizes elevated heat and
pressure and optionally a catalyst to break or "crack" large
hydrocarbon molecules into a range of smaller ones, specifically
those used in gasoline and diesel components. In other words, the
cracking produces light hydrocarbons from heavy hydrocarbons, for
example, gasoline and kerosene from heavy residues. Typically, a
mixture of gases (hydrogen, methane, ethane, ethylene) is also
produced in cracking of heavy distillates. Likewise, a residual oil
may be produced by the conventional cracking process.
[0013] Cracking of heavy hydrocarbons without a catalyst requires
the use of high pressures and temperatures, e.g. pressures of
600-7000 kPa and temperatures of 500.degree.-750.degree. C. With a
catalyst, the temperatures and pressures may be lower, e.g.
480.degree.-530.degree. C. and moderate pressure of about 60-200
kPa. However, even at these relatively lower temperatures and
pressures, a separate unit must be built to accommodate the
process.
[0014] During cracking the hydrocarbon molecules are broken up in a
fairly random manner to produce mixtures of smaller hydrocarbons,
some of which have carbon-carbon double bonds. A typical reaction
involving the hydrocarbon might be:
C.sub.nH.sub.k=C.sub.n-mH.sub.k-1+C.sub.n-pH.sub.k-q+C.sub.m+pH.sub.l+q
[0015] Catalytic cracking generally uses solid acids as the
catalyst, particularly zeolites. Zeolites are complex
aluminosilicates which are large lattices of aluminium, silicon and
oxygen atoms carrying a negative charge which are typically
associated with positive ions such as sodium ions. The heavy
hydrocarbon (i.e., large molecule alkane) is brought into contact
with the catalyst at a temperature of about 500.degree. C. and
moderately low pressures (e.g., 60-200 kPa). The zeolites used in
catalytic cracking (e.g., ZSM-5, Y, and E) are chosen to yield high
percentages of hydrocarbons with between 5 and 10 carbon atoms
which are particularly useful for generating petrol (gasoline).
SUMMARY OF THE INVENTION
[0016] According to one aspect of the invention, metal or
metal-oxide nanoparticles, or combinations of metal and metal-oxide
nanoparticles are added to crude oil before initial distillation in
order to increase the yield of light hydrocarbons obtained during
initial distillation.
[0017] According to another aspect of the invention, metal or
metal-oxide nanoparticles or combinations of metal and metal-oxide
nanoparticles of characteristic size less than 90 nm are added to
crude oil before initial distillation in order to increase the
yield of light hydrocarbons obtained during initial
distillation.
[0018] According to a further aspect of the invention, metal or
metal-oxide nanoparticles or combinations of metal and metal-oxide
nanoparticles are added to crude oil before initial distillation in
a weight percentage of between 0.0004 and 0.02%, and more
preferably in a weight percentage of between 0.001 and 0.01% in
order to increase the yield of light hydrocarbons obtained during
initial distillation.
[0019] According to an additional aspect of the invention
nanoparticles of metals or metal-oxides, are mixed with zeolite
micropowders and added to crude oil before initial distillation in
order to increase the yield of light hydrocarbons obtained during
initial distillation.
[0020] According to another aspect of the invention, nanoparticles
of metals or metal-oxides, are mixed with nanoparticles of solid
acids (e.g., zeolites or or halides) and added to crude oil before
initial distillation in order to increase the yield of light
hydrocarbons obtained during initial distillation.
[0021] According to yet another aspect of the invention, metal or
metal-oxide nanoparticles are added to a crude oil residue after an
initial to increase the yield of diesel oil in a second or later
stage processing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a flow diagram of a first method for implementing
the invention.
[0023] FIG. 2 is a flow diagram of a second method for implementing
the invention.
[0024] FIG. 3 is a flow diagram of a third method for implementing
the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] Turning now to FIG. 1, according to a first method for
implementing the invention, at step 10, nanoparticles are added to
and mixed into crude oil before the crude oil is subjected to
distillation. At step 20, the crude oil with the nanoparticles is
subjected to a first stage distillation. The result of the first
stage distillation, as described in more detail below, is that an
increased yield of gasoline and diesel (light hydrocarbons) is
obtained than would otherwise be obtained if the nanoparticles had
not been added to the crude oil. It is believed by the inventors
that the nanoparticles act to catalytically crack some of the
larger molecule hydrocarbons at relatively low temperatures (i.e.,
the distillation temperatures of gasoline and diesel).
[0026] As described in more detail hereinafter, the nanoparticles
utilized at step 10 have a characteristic size of less than 90 nm
and are added in an amount such that they constitute a weight
percentage of between 0.0004 and 0.02%, and more preferably in a
weight percentage of between 0.001 and 0.01% of the crude
oil/nanoparticle mixture. Also, as described in more detail
hereinafter, the nanoparticles utilized at step 10 may be
nanoparticles of metals, metal-oxides, a combination of metals and
metal-oxides, or a combination of metals or metal-oxide
nanoparticles and micropowders of solid acids such as zeolites or
halides. The preferred size and preferred concentration of the
nanoparticles utilized is believed to be at least partially
dependent on the type or combinations of nanoparticles
utilized.
[0027] Examples for Various Nanoparticles and Their
Compositions.
[0028] Three different samples of crude oil were obtained. First
portions of each sample were distilled as a control using a
standard test method for distillation of petroleum products at
atmospheric pressure (i.e., European Standard EN 228 and ASTM
D2892-05 Standard Test Method for Distillation of Crude Petroleum
(15-Theoretical Plate Column). The results of their distillation
are presented in Table 1 below.
TABLE-US-00001 TABLE 1 Yield of distillation fractions for three
different samples of crude oil. Boiling % w/w Fraction range
(.degree. C.) Sample 1 Sample 2 Sample 3 Gases up to 40 1 -- --
Petrol and naphtha 40-180 13 18 22 Diesel 180-360 22 31 27 Residue
above 360 64 51 51
[0029] To test the method set forth in FIG. 1, nanoparticles were
then added to additional portions of the samples according to the
method set forth in FIG. 1 to form mixtures. The mixtures were then
subjected to the same distillation procedure as the controls.
Example 1
[0030] Iron (Fe) nanoparticles (characteristic size of 43
nanometers) were added to second portions of the samples so that
the iron nanoparticles constituted 0.004% by weight of the mixture.
Upon distillation using the same procedure as the control, the
yields of light hydrocarbons increased significantly over the
yields of Table 1 (the controls) as set forth in Table 2 below.
TABLE-US-00002 TABLE 2 Changes of the light fractions yield after
adding 0.004% of Fe nanoparticles. Boiling Change of yield, % w/w
Fraction range (.degree. C.) Sample 1 Sample 2 Sample 3 Petrol and
naphtha 40-180 +8 +3 +3 Diesel 180-360 +14 +8 +12
Example 2
[0031] Iron oxide nanoparticles (characteristic size of 20
nanometers) were added to third portions of the samples so that the
iron oxide nanoparticles constituted 0.01% by weight of the
mixture. Upon distillation using the same procedure as the control,
the yields of light hydrocarbons increased significantly over the
yields of Table 1 (the controls) as set forth in Table 3 below.
TABLE-US-00003 TABLE 3 Changes of the light fractions yield after
adding 0.01% of iron oxide nanoparticles. Boiling Change of yield,
% w/w Fraction range (.degree. C.) Sample 1 Sample 2 Sample 3
Petrol and naphtha 40-180 +2 +2 +1 Diesel 180-360 +7 +7 +5
Example 3
[0032] A mixture of nanoparticles of iron (characteristic size 43
nm) and zeolite Y micropowder (characteristic size of between 20 nm
and 10 micrometers (10,000 nm) were added to seventh portions of
the samples so that the iron nanoparticles constituted 0.001% by
weight of the mixture and the zeolite Y constituted 0.01% of the
mixture. Upon distillation using the same procedure as the control,
the yields of light hydrocarbons increased significantly over the
yields of Table 1 (the controls) as set forth in Table 4 below.
TABLE-US-00004 TABLE 4 Changes of the light fractions yield after
adding 0.001% of Fe-nanoparticles and 0.01% of zeolite Y
nanoparticles. Boiling Change of yield, % w/w Fraction range
(.degree. C.) Sample 1 Sample 2 Sample 3 Petrol and naphtha 40-180
+5 +4 +5 Diesel 180-360 +8 +9 +6
[0033] Based on the above examples, studies were conducted on
different size nanoparticles. Thus, iron nanoparticles of different
sizes were added in the amount 0.004% to various samples in order
to determine yield and residue. Table 5 shows yields and residue
resulting from adding seven different diameters of iron
nanoparticles to crude oil and distilling as discussed above.
TABLE-US-00005 TABLE 5 Light fraction and residues after adding
0.004% of Fe-nanoparticles of differing sizes Diameter, nm Fraction
2 7 17 43 76 110 450 Petrol and naphtha 15 17 14 21 15 13 13 Diesel
27 24 22 36 26 23 22 Residue 58 59 64 43 59 64 65
From Table 5, it is seen that iron nanoparticles of 43 nm provided
the best result when added at an amount by weight of 0.004%. It is
also interesting to note that when a control with no nanoparticles
added to the sample was subjected to the distillation procedure,
the yield of petrol and naphtha and diesel and the residue were
exactly the same as when adding nanoparticles of 450 nm diameter
(as seen by comparing Table 5 results above with the control of
Table 8 below). Further, it is noted that nanoparticles of 110 nm
diameter and of 17 nm provided little improvement over the
control.
[0034] A similar size study was carried out with iron-oxide
nanoparticles which were added to samples in the amount of 0.01%.
As seen in Table 6, the use of larger size nanoparticles (i.e., 90
nm and larger) provided no ascertainable advantage. In addition,
for iron-oxide, tests showed that the best results were obtained
with 20 nm particles.
TABLE-US-00006 TABLE 6 Light fraction and residues after adding
0.01% of Fe-oxide nanoparticles of differing sizes Diameter, nm
Fraction 20 37 45 62 90 >500 Petrol and naphtha 15 17 15 16 13
13 Diesel 29 25 22 24 22 22 Residue 56 58 63 60 65 65
[0035] Yet another similar size study was carried out with
cobalt-oxide nanoparticles which were added to samples in the
amount of 0.01%. As seen in Table 7, the use of larger size
nanoparticles (i.e., 140 nm and larger) provided no ascertainable
advantage. In addition, for cobalt-oxide nanoparticles, tests
showed that the best results were obtained with 2 nm particles.
TABLE-US-00007 TABLE 7 Light fraction and residues after adding
0.01% of cobalt-oxide nanoparticles of differing sizes. Diameter,
nm Fraction 2 5 13 47 84 140 >1000 Petrol and naphtha 18 18 15
17 13 13 13 Diesel 32 30 30 31 25 22 22 Residue 50 52 55 52 62 65
65
[0036] Based on Examples 1-3 discussed above, and according to
another aspect of the invention, additional studies were conducted
where the concentration of a particularly-sized nanoparticle was
varied and added to samples which were subjected to the
distillation procedure, in order to determine the yield of petrol
and naphtha and diesel and the residue. Table 8 provides results
from a study conducted with different concentrations of iron
nanoparticles of diameter 43 nm (.+-.12 nm).
TABLE-US-00008 TABLE 8 Light fractions and residues after adding
iron nanoparticles of diameter 43 nm in different concentrations 43
nm Fe Concentration, Fraction % w/w Petrol and naphtha Diesel
Residue 0 (control) 13 22 65 0.0004 13 24 63 0.001 15 27 58 0.002
16 34 50 0.003 17 34 49 0.004 21 36 43 0.005 21 35 44 0.008 19 36
45 0.01 16 33 51 0.015 15 28 57 0.02 12 23 65 0.025 10 21 69 0.03 9
17 74 0.035 8 15 77 0.04 9 14 77
From Table 8, various conclusions may be drawn. First, adding iron
nanoparticles of 43 nm size in as small an amount by weight
fraction of 0.0004% provided an increase in light fraction yield,
and adding the nanoparticles in an amount by weight fraction as
small as 0.001% provided a significant increase in light fraction
yield. Second, adding too many iron nanoparticles of 43 nm size
does not increase yield at all and may actually decrease yield.
Thus, when iron nanoparticles were added to the crude oil to
constitute 0.02% by weight and then the crude oil was distilled, no
improvement was seen, and when more iron nanoparticles were added,
the resulting light fractions decreased. Thus, for iron
nanoparticles of 43 nm size, a concentration range of 0.0004% to
0.015% by weight percentage provided an advantage, and the
advantage was greatest between 0.002% and 0.01% (0.004% providing
the best result).
[0037] A similar study on the effect of the nanoparticle
concentration was conducted on 2 nm cobalt-oxide nanoparticles.
Table 9 provides the results of adding different amounts of 2 nm
cobalt-oxide nanoparticles to samples which were then subjected to
the distillation procedure in order to determine the yield of
petrol and naphtha and diesel and the residue.
TABLE-US-00009 TABLE 9 Light fractions and residues after adding
cobalt-oxide nanoparticles of diameter 2 nm in different
concentrations 2 nm Cobalt-oxide Fraction concentration % w/w
Petrol and naphtha Diesel Residue 0 (control) 13 22 65 0.0005 13 22
65 0.001 14 24 62 0.005 16 27 57 0.008 18 30 52 0.01 18 32 50 0.015
19 29 52 0.02 16 26 58 0.05 15 20 65
From Table 9 it is seen that adding nanoparticles of cobalt-oxide
having a diameter of 2 nm to crude oil such that the nanoparticles
constitute a weight concentration in the range of 0.001% to 0.02%
provided an advantage. The largest advantage was obtained with
concentrations between 0.005% and 0.015% (with 0.01% providing the
best result). In addition, it is noted that adding too much
cobalt-oxide 2 nm nanoparticles (e.g., 0.05%) did not increase
yield. Further, it is noted that the percentage range that provided
improved results for the 2 nm cobalt-oxide nanoparticles (0.001 to
0.02) was not the same percentage range as provided improved
results with 43 nm iron nanoparticles (0.0004 to 0.015). Thus, for
a particular nanoparticle being utilized (e.g., iron, or
iron-oxide, or cobalt-oxide or another metal or metal-oxide),
desirable results depend not only on the size of the nanoparticles,
but on the concentrations for that type of nanoparticle.
[0038] According to another aspect of the invention, it is believed
that nanoparticles of the same composition but different sizes can
be effectively utilized to increase light fraction yield. Thus, for
example, 2 nm cobalt-oxide nanoparticles can be used in conjunction
with 47 nm cobalt-oxide nanoparticles in suitable concentrations to
increase the light fraction yield. Similarly, 7 nm iron
nanoparticles can be used in conjunction with 43 nm iron
nanoparticles in suitable concentrations to increase the light
fraction yield.
[0039] According to another aspect of the invention, nanoparticles
of two or more different compositions (e.g., different metals or
different metal-oxides, or one or more metals and one or more
metal-oxides) may be utilized together to increase light fraction
yield. For example, 0.003% 43 nm iron nanoparticles were added to a
crude oil sample together with 0.001% 2 nm cobalt-oxide
nanoparticles, and the resulting fractions were 21% petrol and
naphtha, 35% diesel and 44% residue. Comparing this result to Table
8, this result was better than the results obtained with just
0.003% 43 nm iron nanoparticles (17% petrol and naphtha, 34%
diesel, and 49% residue), and comparing this result to Table 9,
this result was better than the results obtained with just 0.001% 2
nm cobalt-oxide nanoparticles (14% petrol and naphtha, 24% diesel
and 62% percent residue). However, this result was not better than
the results obtained with 0.004% 43 nm iron nanoparticles.
[0040] As another example, 0.004% 43 nm iron nanoparticles were
added to a crude oil sample together with 0.001% 2 nm cobalt-oxide,
and the resulting fractions were 22% petrol and naphtha, 38%
diesel, and 40% residue. Comparing this result to Table 8, this
result was better than the results obtained with just 0.004% 43 nm
iron nanoparticles (21% petrol and naphtha, 36% diesel, and 43%
residue), and it was also better than the results obtained with
0.005% 43 nm iron nanoparticles (21% petrol and naphtha, 35%
diesel, and 44% residue). Likewise, comparing this result to Table
9, this result was better than the results obtained with 0.001% 2
nm cobalt-oxide nanoparticles (14% petrol and naphtha, 24% diesel
and 62% percent residue), and better than the results obtained with
0.005% 2 nm cobalt-oxide nanoparticles (16% petrol and naphtha, 27%
diesel and 57% percent residue). Thus, adding cobalt-oxide
nanoparticles to the "best" percentage of iron nanoparticles
provided yet better results.
[0041] As another example, 0.002% 43 nm iron nonoparticles were
added to a crude oil sample together with 0.001% 2 nm cobalt-oxide,
and the resulting fractions were 19% petrol and naphtha, 40%
diesel, and 41% residue. Comparing this result to Table 8, this
result was better than the results obtained with just 0.002% 43 nm
iron nanoparticles (16% petrol and naphtha, 34% diesel, and 50%
residue), and it was also better than the results obtained with
0.003% 43 nm iron nanoparticles (17% petrol and naphtha, 34%
diesel, and 49% residue). Likewise, comparing this result to Table
9, this result was better than the results obtained with 0.001% 2
nm cobalt-oxide nanoparticles (14% petrol and naphtha, 24% diesel
and 62% percent residue).
[0042] According to another aspect of the invention, and based on
Example 3 above, solid acid micropowders (20 nm<particle
size<10 micrometers) were added with metal or metal-oxide
nanoparticles. As seen in Table 10 below, use of the zeolites such
as Faujasite (also known as Zeolite Y), Mordenite, and HZSM-5
(based on a zeolite synethic available from the Mobil Oil Company
(ZSM)) significantly enhanced the yield of the light fractions.
They also made the composition more stable. In addition, it is
expected that other solid acids can be utilized.
TABLE-US-00010 TABLE 10 Light fractions and residues after adding
zeolite micropowders and metal or metal-oxide nanoparticles to
crude oil prior to distillation Concentration Fraction
Concentration w/w % w/w % Petrol and Additive 1 Additive 2 naphtha
Diesel Residue a. Fe 43 nm 0.004 Faujasite 0.01 24 37 39 b. Fe 43
nm 0.004 -- 21 36 43 c. -- Faujasite 0.01 16 29 55 d. Fe 43 nm
0.004 HZSM-5 0.04 27 40 33 e. -- HZSM-5 0.04 15 26 59 f. Fe 43 nm
0.004 Mordenite 0.02 28 42 30 g. -- Mordenite 0.02 16 29 55 h.
Co.sub.2O.sub.3 2 nm 0.005 Faujasite 0.01 19 31 50 i.
Co.sub.2O.sub.3 2 nm 0.005 -- 16 27 57 j. Co.sub.2O.sub.3 2 nm 0.01
Faujasite 0.01 22 35 43 k. Co.sub.2O.sub.3 2 nm 0.01 -- 18 32 50 l.
Co.sub.2O.sub.3 2 nm 0.005 HZSM-5 0.04 20 27 53 m. Co.sub.2O.sub.3
2 nm 0.01 HZSM-5 0.04 22 37 41 n. Co.sub.2O.sub.3 2 nm 0.005
Mordenite 0.02 19 35 46 o. Co.sub.2O.sub.3 2 nm 0.01 Mordenite 0.02
20 37 43
Examples b, c, e, g, i and k of Table 10 are provided for
comparative purposes. Thus comparing example a with examples b and
c, it will be appreciated that the combination of 0.004% iron (43
nm) and 0.01% Zeolite Y provides a better result than just the iron
nanoparticles or just the Zeolite Y micropowder. Similarly,
comparing example d with examples b and e, it will be appreciated
that the combination of 0.004% iron (43 nm) and 0.04% HZSM-5
zeolite provides a better result than just the iron nanoparticles
(example b) or just the HZSM-5 zeolite micropowder (example e).
Likewise, comparing example f with examples b and g, it will be
appreciated that the combination of 0.004% iron (43 nm) and 0.02%
Mordenite zeolite provides a better result than just the iron
nanoparticles (example b) or just the Mordenite micropowder
(example g). It is noted that example f provided the best yield of
all of the examples. Also, comparing example h with examples c and
i, it will be appreciated that the combination of 0.005%
cobalt-oxide nanoparticles (2 nm) and 0.01% Zeolite Y micropowder
provides a better result than just the 0.005% cobalt-oxide 2 nm
nanoparticles (example i) or just the Zeolite Y micropowder
(example c). Comparing example j with examples k and c, it will be
appreciated that the combination of 0.01% cobalt-oxide
nanoparticles (2 nm) and 0.01% Zeolite Y micropowder provides a
better result than just the 0.01% cobalt-oxide 2 nm nanoparticles
(example k) or just the 0.01 Zeolite Y micropowder (example c).
Further, comparing example 1 to examples i and e, it will be
appreciated that the combination of 0.005% cobalt-oxide
nanoparticles (2 nm) and 0.04% HZSM-5 micropowder provides a better
result than just the 0.005% cobalt-oxide 2 nm nanoparticles
(example i) or just the 0.04% HZSM-5 micropowder (example e). In
addition, comparing example m to examples k and e, it will be
appreciated that the combination of 0.01% cobalt-oxide
nanoparticles (2 nm) and 0.04% HZSM-5 micropowder provides a better
result than just the 0.01% cobalt-oxide 2 nm nanoparticles (example
k) or just the 0.04% HZSM-5 micropowder (example c). Comparing
example n with examples i and g, it will be appreciated that the
combination of 0.005% cobalt-oxide nanoparticles (2 nm) and 0.02%
Mordenite micropowder provides a better result than just the 0.005%
cobalt-oxide 2 nm nanoparticles (example i) or just the Mordenite
micropowder (example g). Finally, comparing example o with examples
k and g, it will be appreciated that the combination of 0.01%
cobalt-oxide nanoparticles (2 nm) and 0.02% Mordenite micropowder
provides a better result than just the 0.01% cobalt-oxide 2 nm
nanoparticles (example k) or just the Mordenite micropowder
(example g).
[0043] It will be appreciated by those skilled in the art that
Table 10 is representative of just a few of the combinations that
can be made, and that many other combinations of nanoparticles
(metal, metal-oxide or combinations thereof) can be made with the
same or different sizes and with the same or different zeolites,
and that the percentages utilized of each can be changed.
It has been shown that the addition of metal or metal-oxide
nanoparticles into the crude oil increases a resulting yield of
light hydrocarbons (gasoline and diesel) during distillation. It is
believed that the increased yield is due to catalytic low
temperature cracking. It is believed that the addition of the metal
or metal-oxide nanoparticles is environmentally benign. In
addition, according to one aspect of the invention, the addition of
the metal or metal-oxide nanoparticles into the crude oil helps
prevent a corrosion of the distillation. It is noted that the
addition of the metal or metal-oxide nanoparticles does effect the
fractional composition of gasoline as it results in decreasing the
benzene concentration in gasoline. The appears that benzene
concentration is decreased due to the benzene alkylation reactions
by low chain hydrocarbons catalyzed by Luis acid cites which are
naturally present in the metal or metal-oxide nanoparticles. The
addition of the metal or metal oxide nanoparticles also results in
decreasing the sulfur contamination in the diesel fraction. The
decrease in the sulfur contamination is believed caused by
preferable catalytic breaks of the C--S bonds during catalytic
cracking resulting in increasing the sulfur contamination in the
residue.
[0044] Turning now to FIG. 2, according to a second method for
implementing the invention, at step 110, metal or metal-oxide
nanoparticles (e.g., iron), are added to and mixed into hexane. At
step 115, ultrasound is used to distribute the nanoparticles in the
hexane and generate a colloidal solution. The hexane-nanoparticle
colloidal solution is then added at step 118 to crude oil and
mixed. By way of example only, 0.1 ml or colloidal solution may be
added to 100 ml or crude oil. At step 120, the crude oil with the
colloidal solution is subjected to a first stage distillation. The
result of the first stage distillation, as described above, is that
an increased yield of gasoline and diesel (light hydrocarbons) is
obtained than would otherwise be obtained if the nanoparticles had
not been added to the crude oil. As previously stated, it is
believed that the nanoparticles act to catalytically crack some of
the larger molecule hydrocarbons at relatively low temperatures
(i.e., the distillation temperatures of gasoline and diesel).
[0045] According to another aspect of the invention, metal and/or
metal-oxide nanoparticles, or metal and/or metal-oxide
nanoparticles plus solid acid micropowders are added to a crude oil
fraction that remains after initial distillation of the crude oil
to remove gas, gasoline and optionally crude oil. The nanoparticles
and solid acid micropowders are mixed into the remaining crude oil
fraction before the crude oil fraction is subjected to additional
distillation. Thus, as seen in FIG. 3, at step 205, crude oil is
subject to partial first stage distillation up to approximately
350.degree. C. or 360.degree. C. to obtain gases, gasoline (petrol)
and diesel, and a residue crude oil fraction. Then, at step 210,
nanoparticles are added to and mixed into the residue crude oil
fraction and at 220 the mixture of the nanoparticles and residue
fraction are subjected to completion of the first stage
distillation (typically by boiling up to 420.degree. C.). The
result of the first stage distillation, as described in more detail
below, is that an increased yield of diesel is obtained than would
otherwise be obtained if the nanoparticles had not been added.
[0046] Using the method of FIG. 3, samples of crude oil residue
fractions (already having had the gasoline and diesel distilled
out) were tested with different nanoparticles or additive
combinations:
TABLE-US-00011 TABLE 11 Yield of diesel from residue at 340.degree.
C. Additive Yield of diesel, % w/w Control (no additive) 0 0.004%
Fe, 43 nm 10 0.01% Fe-oxide, 20 nm 5 0.004% Fe, 43 nm and 0.02%
Mordenite 12
As seen in Table 11, by adding nanoparticles of a metal (e.g., 43
nm iron), or a metal-oxide (e.g., 20 nm iron-oxide), or a
nanoparticles of a metal (e.g., 43 nm iron) plus a micropowder of
solid acid (Mordenite) to a crude oil residue which had already had
gasoline and diesel distilled out, and then subjecting the crude
oil residue/nanoparticle or residue/nanoparticle/solid acid
micropowder mixture to a distillation up to 340.degree. C.,
significant additional amount of diesel is obtained. Also, as shown
in Table 12 below, when the temperature was raised even further to
420.degree. C., the increase in the yield of the diesel from the
residue was extremely large.
TABLE-US-00012 TABLE 12 Yield of diesel at 420.degree. C. Additive
Yield of diesel, % w/w Control (no additive) 5 0.004% Fe, 43 nm 45
0.01% Fe-oxide, 20 nm 30 0.004% Fe, 43 nm and 0.02% Mordenite
75
At both temperatures (340.degree. C. and 420.degree. C.), the
combination of 0.004% Fe, 43 nm, and 0.02% Mordenite micropowder
provided the best results.
[0047] Based on the improved results shown in Tables 11 and 12, it
is believed that even after a partial initial distillation, the
addition to the residue of nanoparticles of different metals or
metal-oxides, or combinations thereof, in different sizes and
different amounts such as discussed above with reference to Tables
5-9 (but not limited thereto), will yield improved results.
Likewise, it is believed that the additional of nanoparticles of
different metals or metal-oxides, or combinations thereof, in
further combination with micropowders of different solid acids such
as discussed above with reference to Table 10 (but not limited
thereto), will likewise yield improved results.
[0048] There have been described and illustrated herein several
embodiments of methods for increasing the light fraction output of
a crude oil distillation by adding nanoparticles of metals,
metal-oxides, combinations thereof, or any of the same with solid
acid micropowders. While particular embodiments of the invention
have been described, it is not intended that the invention be
limited thereto, as it is intended that the invention be as broad
in scope as the art will allow and that the specification be read
likewise. Thus, while particular metals and metal-oxides have been
disclosed, it will be appreciated that other metals and
metal-oxides could be used as well. In addition, while particular
types of solid acids have been disclosed, it will be understood
that other solid acids can be used. Also, while certain ranges of
concentrations of the metals and metal-oxides were described
preferred, it will be recognized that other amounts could be
utilized. Furthermore, while certain diameter nanoparticles were
described, it will be understood that other diameter nanoparticles
can be similarly used. It will therefore be appreciated by those
skilled in the art that yet other modifications could be made to
the provided invention without deviating from its spirit and scope
as claimed.
* * * * *