WO2011078994A1

WO2011078994A1 - Increasing distillates yield in low temperature cracking process by using nanoparticles

Info

Publication number: WO2011078994A1
Application number: PCT/US2010/060476
Authority: WO
Inventors: Oleksander S. Tov; Petro E. Stryzhak
Original assignee: Consistent Llc
Priority date: 2009-12-24
Filing date: 2010-12-15
Publication date: 2011-06-30
Also published as: CN102812108A; RU2012131680A

Abstract

Metal or metal-oxide nanoparticles, such as iron or cobalt, are added to crude oil before initial distillation in order to increase the yield of light hydrocarbons obtained dunng initial distillation A solid acid micropowder, zeolites such as faujasite, mordenite, or HZSM, can be added with the metal or metal-oxide nanoparticles before initial distillation in order to increase yield of light hydrocarbons such as gasoline.

Description

INCREASING DISTILLATES YIELD IN LOW TEMPERATURE CRACKING PROCESS

BY USING NANOP ARTICLES

BACKGROUND OF THE INVENTION

1. Field of the Invention

[0001] 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.

2. State of the Art

[0002] 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.

[0003] 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.

[0004] 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. [0005] The alkanes are saturated hydrocarbons with straight or branched chains which contain only carbon and hydrogen and have the general formula C_nH_2n+2. The alkanes from pentane (C₅H₁₂) to octane (C₈H₁₈) are typically refined into gasoline (petrol). The alkanes from nonane (C₉H₂₀) to hexadecane (C₁₆H₃₄) 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.

[0006] 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_nH_2n. Cycloalkanes have similar properties to alkanes but have higher boiling points.

[0007] The aromatic hydrocarbons are unsaturated hydrocarbons which have one or more planar six-carbon (benzene) rings to which hydrogen atoms are attached.

[0008] 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.

[0009] 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.

[0010] 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.

[001 1 ] 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° - 750°C. With a catalyst, the temperatures and pressures may be lower, e.g. 480° - 530°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.

[0012] 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_nH_k = C_n-mH_k-1 + C_n-pH_k-q + C_m+pH_1+q

[0013] 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°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

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] According to a further aspect of the invention, nanoparticles of a solid acid are added to crude oil in a characteristic concentration before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation. [0021] According to another aspect of the invention, nanoparticles of a solid acid of a characteristic particle size are added to crude oil before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation.

[0022] According to an additional aspect of the invention, nanoparticles of two or more solid acids are mixed and added to crude oil before initial distillation in order to increase the yield of light hydrocarbons obtained during initial distillation.

[0023] According to yet another aspect of the invention, solid acid micropowder is added to a crude oil residue after a partial initial distillation to increase the yield of diesel oil resulting from the completed initial distillation.

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Fig. 1 is a flow diagram of a first method for implementing the invention.

[0025] Fig. 2 is a flow diagram of a second method for implementing the invention.

[0026] Fig. 3 is a flow diagram of a third method for implementing the invention.

[0027] Fig. 4 is a flow diagram of a fourth method for implementing the invention.

[0028] Fig. 5 is a flow diagram of a fifth method for implementing the invention.

[0029] Fig. 6 is a flow diagram of a sixth method for implementing the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] 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).

[0031] 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.

Examples for various nanoparticles and their compositions.

[0032] 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.

[0033] 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.

[0034] Example 1 -

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.

[0035] Example 2 -

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.

[0036] Example 3 -

A mixture of nanoparticles of iron (characteristic size 43nm) and zeolite Y micropowder (characteristic size of between 20nm and 10 micrometers (ΙΟ,ΟΟΟηηι) 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.

[0037] 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.

From Table 5, it is seen that iron nanoparticles of 43nm 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 450nm diameter (as seen by comparing Table 5 results above with the control of Table 8 below). Further, it is noted that nanoparticles of 1 lOnm diameter and of 17nm provided little improvement over the control.

[0038] 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., 90nm and larger) provided no ascertainable advantage. In addition, for iron-oxide, tests showed that the best results were obtained with 20nm particles.

[0039] 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., 140nm and larger) provided no ascertainable advantage. In addition, for cobalt-oxide nanoparticles, tests showed that the best results were obtained with 2nm

[0040] 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 43nm (±12nm).

From Table 8, various conclusions may be drawn. First, adding iron nanoparticles of 43nm 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 43nm 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 43nm 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).

[0041] A similar study on the effect of the nanoparticle concentration was conducted on 2nm cobalt-oxide nanoparticles. Table 9 provides the results of adding different amounts of 2nm 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.

From Table 9 it is seen that adding nanoparticles of cobalt-oxide having a diameter of 2nm 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 2nm nanoparticles (e.g., 0.05%>) did not increase yield. Further, it is noted that the percentage range that provided improved results for the 2nm cobalt- oxide nanoparticles (0.001 to 0.02) was not the same percentage range as provided improved results with 43nm 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.

[0042] 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, 2nm cobalt-oxide nanoparticles can be used in conjunction with 47nm cobalt-oxide nanoparticles in suitable concentrations to increase the light fraction yield.

Similarly, 7nm iron nanoparticles can be used in conjunction with 43nm iron nanoparticles in suitable concentrations to increase the light fraction yield.

[0043] 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% 43nm iron nanoparticles were added to a crude oil sample together with 0.001% 2nm 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%) 43nm 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% 2nm 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% 43nm iron nanoparticles.

[0044] As another example, 0.004% 43nm iron nanoparticles were added to a crude oil sample together with 0.001% 2nm 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% 43nm iron nanoparticles (21% petrol and naphtha, 36%> diesel, and 43% residue), and it was also better than the results obtained with 0.005%) 43nm 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% 2nm cobalt-oxide nanoparticles (14% petrol and naphtha, 24% diesel and 62% percent residue), and better than the results obtained with 0.005% 2nm 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.

[0045] As another example, 0.002% 43nm iron nonoparticles were added to a crude oil sample together with 0.001% 2nm 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% 43nm iron nanoparticles (16% petrol and naphtha, 34% diesel, and 50% residue), and it was also better than the results obtained with 0.003%) 43nm 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% 2nm cobalt-oxide nanoparticles (14% petrol and naphtha, 24% diesel and 62% percent residue).

[0046] According to another aspect of the invention, and based on Example 3 above, solid acid micropowders (20nm < 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.

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 (43nm) 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 (43nm) 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 (43nm) 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 (2nm) and 0.01 % Zeolite Y micropowder provides a better result than just the 0.005% cobalt-oxide 2nm 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 (2nm) and 0.01 % Zeolite Y micropowder provides a better result than just the 0.01% cobalt-oxide 2nm 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 (2nm) and 0.04 % HZSM-5 micropowder provides a better result than just the 0.005% cobalt-oxide 2nm nanoparticles (example i) or just the 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 (2nm) and 0.04 % HZSM-5 micropowder provides a better result than just the 0.01% cobalt-oxide 2nm 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 (2nm) and 0.02 % Mordenite micropowder provides a better result than just the 0.005% cobalt-oxide 2nm 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 (2nm) and 0.02% Mordenite micropowder provides a better result than just the 0.01% cobalt-oxide 2nm nanoparticles (example k) or just the Mordenite micropowder (example g).

[0047] 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.

[0048] 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.

[0049] 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, 0.1ml or colloidal solution may be added to 100ml 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).

[0050] 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°C or 360°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°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.

[0051] 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:

As seen in Table 11, by adding nanoparticles of a metal (e.g., 43nm iron), or a metal-oxide (e.g., 20nm iron-oxide), or a nanoparticles of a metal (e.g., 43nm 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°C, significant additional amount of diesel is obtained. Also, as shown in Table 12 below, when the temperature was raised even further to 420°C, the increase in the yield of the diesel from the residue was extremely large. Table 12. Yield of diesel at 420°C

At both temperatures (340°C and 420°C), the combination of 0.004% Fe, 43 nm, and 0.02% Mordenite micropowder provided the best results.

[0052] 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.

[0053] Turning now to Fig. 4, according to a fourth method for implementing the invention, at step 410, nanoparticles of a solid acid are added to and mixed into crude oil before the crude oil is subjected to distillation. At step 420, the crude oil with the

nanoparticles of solid acid 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 of solid acid had not been added to the crude oil. It is believed by the inventors that the nanoparticles of solid acid act to catalytically crack some of the larger molecule hydrocarbons at relatively low temperatures (i.e., the distillation temperatures of gasoline and diesel).

[0054] As described in more detail hereinafter, the nanoparticles of solid acid utilized at step 410 have a characteristic size of preferably between 3nm and 1100 nm, and more preferably between 30nm and 600nm and/or constitute a concentration weight percentage of preferably between 0.005%> and 0.2%>, and more preferably between 0.01% and 0.06%> of the crude oil/nanoparticle mixture. Also, as described in more detail hereinafter, the solid acid nanoparticles utilized at step 410 may be various types of solid acids (including micropowders) or combinations thereof. The preferred size and concentration of the nanoparticles which maximizes the percentage of light hydrocarbons yielded during initial distillation is believed to be at least partially dependent on the type of solid acid and/or the combination of solid acids utilized.

[0055] As previously described with reference to Table 1, three different samples of crude oil were initially obtained. To test the method set forth in Fig. 4, nanoparticles of solid acid were then added to additional portions of the samples according to the method set forth in Fig. 4 to form mixtures of crude oil/solid acid nanoparticles. The mixtures were then subjected to the same distillation procedure as the controls.

[0056] Example 4 -

Zeolite Y powder with an average particle size of 600 nanometers was added to second portions of the samples so that the Zeolite Y nanoparticles constituted 0.01% by weight of the nanoparticle/crude oil mixtures. As shown in Table 13 below, upon distillation using the same procedure as described above with respect to the controls, the yields of light hydrocarbons increased significantly over the yields of the controls (Table 12). The addition of Zeolite Y powder to all three crude oil samples in a concentration of 0.01% improved the yield of petrol and naptha by 3% and of diesel by 5-6%>.

[0057] Concentration tests were conducted with Zeolite Y powder (still with an average particle size of 600 nanometers). The Zeolite Y was added in concentrations varying from 0.0005%) to 0.3%) to additional portions of Sample 1 as shown in Table 14 below. Upon distillation using the same procedure as described above with respect to the controls, the yields of light hydrocarbons increased over the yields of the Sample 1 control. More particularly, the yields of light hydrocarbons remained the same with a Zeolite Y concentration of 0.0005%, increased slightly for diesel using a concentration of 0.001%, and markedly increased for both petrol/naphtha and diesel using a concentration of 0.01%. It is interesting to note that the yield of light hydrocarbons was the same using a Zeolite Y concentration of 0.1%, 0.2%, and 0.3% as it was using a concentration of 0.01%. Based on these results, it is expected that the preferred range of concentrations for Zeolite Y powder having an average particle size of 600 nanometers is between 0.001%> and 0.3%>, and most preferably between 0.01% and 0.3%>. It is anticipated based on this data that concentrations larger than 0.3% may also be used to improve the yield of light hydrocarbons relative to the yield of the control (e.g., since the residue yield did not increase between concentrations of 0.01% and 0.3%). At concentrations above 0.01%, the yield of light hydrocarbons does not depend on the concentration of solid acid. Therefore, the yield saturates at 0.01% of solid acid. This value gives the lower limit at which we obtain the best yield of light hydrocarbons

[0058] Example 5 -

Sulphated zirconia dioxide (super acid) having a particle size of 3.1 nanometers was added in seven different concentrations to crude oil and the resulting mixtures were distilled as discussed above. The yields and residue resulting from these mixtures after initial distillation are shown in Table 15. As shown, increasing the acid concentration of the sulphated zirconia dioxide at a particle size of 3. Inm between 0.005% and 0.1% caused an increase in the yield of light hydrocarbons. Concentrations greater than zero but less than 0.001% did not result in any change in yield relative to the control (0.0% acid concentration), an acid concentration of 0.1% resulted in a slightly better yield for diesel than the yield for diesel at 0.06% concentration, and relatively large increases in acid concentrations above 0.1 %, namely, 0.2%> and 0.3%> produced negligible differences in yield relative to the yield at 0.1%. Thus, concentrations larger than 0.1% may be used to improve the yield of light hydrocarbons relative to the yield of the control, but not relative to the yield at 0.1%.

[0059] The effect of the particle size at a given concentration was tested. Table 16 shows the yields and residue resulting from eleven different particle sizes of sulphated zirconia dioxide at 0.03% concentration. The acid was added to crude oil at this concentration with varying particle sizes and the resulting mixtures were distilled as discussed above. As shown, increasing the particle size between 3.1nm and 7.6 nm did not significantly alter the yield of light hydrocarbons using 0.03% concentration of sulphated zirconia dioxide. Using an acid particle size between 15nm and 44nm slightly impaired the yield of diesel, but only caused the residue fraction to increase from 48% to 49%. Increasing the sulphated zirconia dioxide particle size between 150nm and 1100nm more significantly impaired the yield of light hydrocarbons, but the yield in this range was still better than that without use of the acid. Only particle sizes greater than 10,000nm resulted in light hydrocarbon yields which matched the hydrocarbon yields without use of the acid (e.g., 0%> acid - the control of Table 15).

[0060] Example 6 -

Alumosilicate (acid) having a composition of Si0₂-66%, A1₂0₃ - 16%, Fe₂0₃-4%, MgO-10%, CaO-3%, and other components 1%, and a particle size of 30nm was tested using the method of FIG. 4. As shown in Table 17 below, increasing the concentration of alumosilicate at this particle size from 0.001% to 0.05%> resulted in increased yield of light hydrocarbons, with the greatest increase relative to the control at and above 0.05% acid concentration. It is noted that the yields of light hydrocarbons at concentrations of 0.1% and 0.2% were identical to that at 0.05%. Thus, concentrations larger than 0.05% of alumosilicate at a particle size of 30nm may be used to improve the yield of light hydrocarbons relative to the yield of the control, but will cause little, if any, improvement over the yield at 0.05% .

[0061] Alumosilicates having a concentration of 0.03%> were also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 18 shows the yields and residue resulting from seven different particle sizes of alumosilicates having a concentration of 0.03%. As shown, a particle size of 30nm provided the biggest yield of light hydrocarbons relative to the control (0% alumosilicate - Table 17). Increasing the particle size from 30nm to 70nm caused a drop in yield of light hydrocarbons, though the yield remained greater than that of the control. Increasing the particle size between 70nm and 150nm caused a slight drop in Petrol and naphtha but a slight increase in diesel. Increasing the particle size between 150nm and 1200nm generally resulted in a relative decrease in yield of light hydrocarbons, but still provided a yield which was greater than that of the control. A particle size greater than 10,000nm did not provide a better yield of light hydrocarbons than the control.

Table 18. Effect of particle size, Alumosilicates, concentration

[0062] Example 7 -

Zeolite A (sodium aluminum silicate) with a particle size of 20nm was tested using the method of FIG. 4. As shown in Table 19, increasing the concentration of Zeolite A at this particle size from 0.001% to 0.2% resulted in an increased yield of light hydrocarbons, with the greatest increase relative to the control at and above 0.2%. It is noted that an increase in acid concentration from 0.2% to 0.3% did not produce any change in yield of light hydrocarbons. Thus, concentrations larger than 0.2% of alumosilicate at a particle size of 20nm may be used to improve the yield of light hydrocarbons relative to the control, but not relative to the yield at 0.2%.

[0063] Zeolite A having a concentration of 0.05%> was also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 20 below shows the yields and residue resulting from seven different particle sizes of Zeolite A at a concentration of 0.05%>. As shown, particle sizes of 20nm and 50 nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 50nm to 700nm generally resulted in a decreased yield of light hydrocarbons, but still provided increased yield relative to the yield of light hydrocarbons produced by the control (0% concentration of Zeolite A acid - Table 19), and a particle size of 1200nm and larger did not produce an increased yield of light hydrocarbons relative to the control.

[0064] Example 8 -

Keggin hetero polyacid (H₃PM0₁₃O₄₀) with a particle size of lnm was tested using the method of FIG. 4. As shown in Table 21, increasing the concentration of Keggin hetero polyacid at this particle size from 0.001% to 0.2% resulted in an increased yield of light hydrocarbons, with the greatest increase relative to the control at and above 0.2%. It is noted that an increase in acid concentration from 0.2% to 0.3% did not produce any change in yield. Thus, concentrations larger than 0.2% of Keggin hetero polyacid at a particle size of lnm may be used to improve the yield of light hydrocarbons relative to the control, but not relative to the yield at 0.2%. In addition, as the yield of light hydrocarbons at 0.001% acid concentration was greater than at 0% acid concentration, it is anticipated that concentrations less than 0.001% of Keggin hetero polyacid at a particle size of lnm may also be used to produce a yield of light hydrocarbons better than that of the control (no acid), but less than that at 0.001%.

[0065] Example 9 -

Aluminum trichloride (AICI3) with a particle size of lOOnm was tested using the method of FIG. 4. As shown in Table 22, increasing the concentration of Aluminum trichloride at this particle size from 0.001% to 0.2% resulted in an increased yield of light hydrocarbons, with the greatest increase relative to the control at and above 0.2%. It is noted that increasing the concentration of acid from 0.2% to 0.3% did not produce any change in yield relative to the yield at 0.2%. Thus, concentrations larger than 0.2% of Aluminum trichloride at a particle size of lOOnm may also be used to improve the yield of light hydrocarbons relative to the control but not relative to the yield at 0.2%. In addition, as the yield of light hydrocarbons at 0.001% concentration was slightly greater than at 0% concentration, is anticipated that concentrations of Aluminum trichloride less than 0.001% may produce a yield marginally better than that of the control.

[0066] Aluminum trichloride having a concentration of 0.05% was also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 23 below shows the yields and residue resulting from five different particle sizes of Aluminum trichloride at a concentration of 0.05%. As shown, a particle size of lOOnm provided the biggest yield of light hydrocarbons. Increasing the particle size from lOOnm to 700nm generally resulted in a decreased yield of light hydrocarbons (mostly for Diesel), but still provided increased yield relative to the yield of light hydrocarbons produced without any acid - the control (0% concentration of Aluminum trichloride - Table 22), and particle sizes at 1200nm and greater than ΙΟ,ΟΟΟηηι did not produce a yield of light hydrocarbons in excess of the control.

Table 23. Effect of particle size, A1C1₃, concentration

[0067] Example 10 -

Faujasite with a particle size of 30nm was tested using the method of FIG. 4. As shown in Table 24, increasing the concentration of Faujasite at this particle size from 0.005% to 0.2% resulted in an increased yield of light hydrocarbons, with the greatest increase relative to the control at and above 0.2%. It is noted that increasing the concentration of acid from 0.2% to 0.3% and to 0.4% did not produce any change in the yield of light hydrocarbons relative to the yield at 0.2%. Thus, acid concentrations larger than 0.2% of Faujasite at a particle size of 30nm may also be used to improve the yield of light hydrocarbons relative to that of the control but not relative to that at 0.2%. In addition, as the yield of light hydrocarbons at 0.005% concentration was slightly greater than at 0% concentration (for Diesel), it is anticipated that concentrations of Faujasite less than 0.005% may produce a yield better than that of the control and less than that at 0.005% (for Diesel). It is further noted that different results were obtained using Faujasite and Zeolite Y. Comparison of the results for Faujasite and Zeolite Y shows a higher yield of petrol and naphta, as well as diesel, for Zeolite Y. This difference may be associated with differences in the acidic properties of these solid acids. In particular, the surface concentration of acid sites of Faujasite and Zeolite Y responsible for conversion of heavy hydrocarbons to light hydrocarbons, as well as their respective accessibility or strength, are different for Faujasite and Zeolite Y. Increasing the surface concentration of acid cites, strength or accessibility increases the yield of light hydrocarbons.

[0068] Faujasite having a concentration of 0.05% was also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 25 below shows the yields and residue resulting from six different particle sizes of Faujasite at a concentration of 0.05%>. As shown, a particle size of 30nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 30nm to 700nm generally resulted in a decreased yield of light hydrocarbons (mostly of Diesel), but still provided increased yield relative to the yield of light hydrocarbons produced without any acid - the control (0% concentration of Faujasite - Table 24). Increasing the particle size from 700nm to 1200nm caused a slight drop in petrol and naphtha but a slight increase in diesel, and thus no significant overall change to the residue fraction. Particle sizes greater than ΙΟ,ΟΟΟηηι did not produce a yield of light hydrocarbons in excess of the control.

Table 25. Effect of particle size, Faujasite, concentration

[0069] Example 11 -

HZSM-5 with a particle size of 50nm was tested using the method of FIG. 4. As shown in Table 26, increasing the concentration of HZSM-5 at this particle size from 0.005% to 0.2% resulted in an increased yield of light hydrocarbons, with the greatest increase relative to the control at and above 0.2%. It is noted that increasing the concentration of acid from 0.2% to 0.3% did not produce any change in the yield of light hydrocarbons relative to the yield at 0.2%. Thus, acid concentrations larger than 0.2% of HZSM-5 at a particle size of 50nm may also be used to improve the yield of light hydrocarbons relative to that of the control but not relative to that at 0.2%. In addition, as the yield of light hydrocarbons at 0.005% concentration was slightly greater than at 0% concentration (for Diesel), it is anticipated that concentrations of HZSM-5 less than 0.005% may produce a yield better than that of the control and less than that at 0.005% (for Diesel).

[0070] HZSM-5 having a concentration of 0.05%> was also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 27 below shows the yields and residue resulting from six different particle sizes of HZSM-5 at a concentration of 0.05%. As shown, a particle size between 50nm and 400nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 400nm to 1200nm resulted in a decreased yield of light hydrocarbons, but still provided increased yield relative to the yield of light hydrocarbons produced without any acid - the control (0% concentration of HZSM-5 - Table 26). It is also noted that the yield of light hydrocarbons at 50nm is greater than that of the control (no acid). Thus, particle sizes less than 50nm are likely also to improve the yield of light hydrocarbons at this acid concentration of HZSM-5. Particle sizes than ΙΟ,ΟΟΟηηι did not vary the yield of light hydrocarbons relative to the control.

[0071] Example 10 -

Mordenite with a particle size of 150nm was tested using the method of FIG. 4. As shown in Table 28, increasing the concentration of Mordenite at this particle size from 0.005% to 0.05% resulted in an increased yield of light hydrocarbons (mostly of Diesel), with the greatest increase relative to the control at and above 0.05%. It should be noted that increasing the acid concentration from 0.05% to 0.1%, and 0.2% did not produce any change in the yield of light hydrocarbons relative to the yield at 0.05%. Thus, acid concentrations larger than 0.05% of Mordenite at a particle size of 150nm may also be used to improve the yield of light hydrocarbons relative to that of the control but not relative to that at 0.05%. In addition, as the yield of light hydrocarbons at 0.005% concentration was slightly greater than at 0%

concentration (for Diesel), it is anticipated that concentrations of Mordenite less than 0.005% may produce a yield better than that of the control and less than that at 0.005% (for Diesel). Table 28. Effect of concentration, Mordenite, particle size = 150 nm

[0072] Mordenite having a concentration of 0.05% was also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 29 below shows the yields and residue resulting from five different particle sizes of Mordenite at a concentration of 0.05%. As shown, increasing the particle size from lOOnm to 1200nm at this concentration resulted in a decreased yield of light hydrocarbons (mostly Diesel), but still produced a yield of light hydrocarbons in excess of the control (0% concentration of Mordenite - Table 28). In addition, it is noted that the yield of light hydrocarbons was greater at a particle size of lOOnm and at a particle size of greater than 10,000 than it was for the control. Thus, it is anticipated that particle sizes smaller than lOOnm and larger than 10,000 may also be used at this concentration of Mordenite acid to improve the yield of light hydrocarbons relative to the control.

[0073] Example 13 -

MCM-41 with a particle size of 50nm was tested using the method of FIG. 4. As shown in Table 30, increasing the concentration of MCM-41 at this particle size from 0.005% to 0.05% resulted in an increased yield of light hydrocarbons with the maximum yield at an acid concentration at and above 0.04%. It is noted that the yield of light hydrocarbons using a concentration of 0.005% was identical to that of the control (0% concentration of MCM-41). In addition, increasing the acid concentration from 0.04% to 0.1% and 0.2% did not have any effect on the yield of light hydrocarbons at this particle size - the yield of light hydrocarbons simply remained at its highest level. Thus, acid concentrations larger than 0.05% of MCM-41 at a particle size of 50nm may also be used to improve the yield of light hydrocarbons relative to that of the control but not relative to that at 0.05%.

[0074] MCM-41 having a concentration of 0.05% was also added to crude oil with varying particle sizes and the resulting mixtures were distilled as discussed above. Table 31 below shows the yields and residue resulting from six different particle sizes of MCM-41 at a concentration of 0.05%. As shown, increasing the particle size from 50nm to 700nm at this acid concentration resulted in a generally constant yield of light hydrocarbons which was higher than the yield of the control (0% MCM-41 - Table 30). It is noted that the fraction of light hydrocarbons yielded at a particle size of 50nm and at a particle size of 1200 was greater than it was for the control. At particle sizes greater than 10,000nm, the yield was the same as it was for the control. Thus, it is anticipated that particle sizes less than 50nm and particle sizes greater than 1200nm may also be used at this concentration of acid to improve the yield of light hydrocarbons relative to the control.

[0075] The above tables clearly show a general trend in which increasing the

concentration of the nanoparticles of a given solid acid between 0.005% and 0.2% causes a general increase in yield of light hydrocarbons with the biggest increases occurring toward, and likely above, the upper end of this range. The above tables also reveal a general trend in which using a characteristic acid particle size ranging from 3nm to 1200nm with acid concentration values of 0.03% to 0.05% maintained the yield of light hydrocarbons above that of the control, the biggest yields relative to the control occurring with use of the smallest particle sizes.

Based on this data, it is believed that the best way to maximize yield of light hydrocarbons is to use the smallest nanometer particle size available for a given acid and the highest concentration within the range outlined above for the given acid. It will be appreciated that acid particle size and acid concentration are offsetting factors, and thus that different combinations of acid particle size and acid concentration may produce the same yield of light hydrocarbons provided that the acid particle size is not too large and/or the acid concentration is not too small. [0076] According to another aspect of the invention, when nanoparticles of different acids are mixed with crude oil prior to initial distillation, the increased yield of light hydrocarbons after distillation is generally additive. For example, as shown below in Table 32, HZSM-5 at 0.02% concentration with a particle size of 43nm was mixed with MCM-41 at 0.02% concentration with a particle size of 50nm (which is close to 43nm) in crude oil prior to initial distillation. After initial distillation, the fractional yield was 16% petrol/naphtha; 30% diesel; and 54% residue. HZSM-5 at 0.04%> concentration (e.g. twice as much) with a particle size of 50nm was then mixed by itself in crude oil prior to initial distillation - this produced a fractional yield of 17% petrol/naphtha (a slight increase); 29% diesel (a slight decrease); and 54%) residue (identical). In addition, MCM-41 at 0.04%> concentration (e.g., twice as much) with a particle size of 50nm was then mixed by itself in crude oil prior to intitial distillation - this produced a fractional yield of 16%> petrol/naphtha (identical); 30%> diesel (identical); and 54% residue (identical). Thus, it may be inferred that the combination of HZSM-5 and MCM- 41 mixed with the crude oil prior to initial distillation had an additive effect.

[0077] Similarly, when acids of small particle size are mixed with acids of large particle size, the results can be additive in the sense that the acid of smaller particle size tends to improve the yield of light hydrocarbons more than the acid of larger particle size, and the combination provides a result which is in between what is obtained with using either the small particle size additive alone or the large particle size additive alone. For example, as shown in Table 32, when sulphated zirconia of 0.025% concentration with a particle size of 3.1nm was mixed with Mordenite of .025% concentration with a particle size of lOOnm in crude oil prior to initial distillation, the fractional yield after initial distillation was 19% petrol/naphtha; 33% diesel; and 48% residue. Sulphated zirconia of 0.05% concentration (e.g., twice as much) with a particle size of 3. lnm was then mixed with crude oil by itself prior to initial distillation, and the fractional yield after initial distillation was 22% petrol/naphtha (higher); 32% diesel (slightly lower); and 46% residue (lower). Mordenite of 0.05% concentration (e.g., twice as much) with a particle size of lOOnm was then mixed with crude oil by itself prior to initial distillation, and the fractional yield after initial distillation was 17% petrol/naphtha (lower); 33%) diesel (the same); and 50% residue (higher). Thus, using an acid with a larger particle size in combination with an equal amount of a different acid of smaller particle size produced a smaller yield of light hydrocarbons than that produced by simply using twice as much of the acid with the smaller particle size. This is expected since, as discussed above, improved yield is inversely related to the acid particle size within the relevant range. [0078] On the other hand, as seen below in Table 32, when sulphated zirconia of 0.015% concentration with a particle size of 3. Inm was mixed with alumosilicate of 0.015% having a particle size of 700nm in crude oil prior to initial distillation, the fractional yield after initial distillation was 22% petrol/naphtha, 32% diesel, and 46% residue. This compared favorably with respect to the addition of sulphated zirconia of particle size 3. Inm in an amount of 0.03% (e.g., twice as much) which gave a yield of 22% petrol/naphtha (same), 30% diesel (slightly lower) , and 48% residue (slightly higher). Likewise, it compared favorably with respect to the addition of 0.03% alumosilicate 700nm, which gave a yield 17% petrol/naphtha (much lower), 27%) diesel (much lower), and 56% residue (much higher). Effectively then, the combination of 3. Inm sulphated zirconia with the 700nm alumosilicate was synergistic and provided even better results than the unexpected results obtained when adding nanoparticles of a single acid to the crude oil prior to initial distillation.

[0079] Synergistic results were also found when aluminum trichloride 100 nm nanoparticles were mixed with 800 nm Mordenite nanoparticles with each constituting 0.025% by weight in the crude oil prior to initial distillation (both of the nanoparticles being relatively large). As seen in Table 32, the fractional yield after initial distillation was 23%

petrol/naphtha, 31% diesel, and 46% residue. This compared favorably with respect to the addition of aluminum trichloride of particle size 100 nm in an amount of 0.05% (e.g., twice as much) which gave a yield of 23% petrol/naphtha (same), 30% diesel (slightly lower), and 47% residue (slightly higher). Likewise, it compared favorably with respect to the addition of 0.05%) Mordenite 800nm which gave a yield 17% petrol/naphtha (much lower), 29% diesel (lower), and 54% residue (much higher). The inventors believe that nonadditive increases in the yield of light hydrocarbons for some mixtures may be caused by strong interaction of the mixing components. For mixture of sulphated zirconia and alumosilicate or for mixture of aluminum trichloride and mordenite, it is believed that interaction of nanophased components leads to a formation of nanophased interfacial structure where strong acid sites are located. These acid sites are characterized by the highest of catalytic activity with regard to cracking of heavy hydrocarbons. As a result, it is believed that the yield of light hydrocarbons increases nonadditively. [0080]

[0081] It will be appreciated by those skilled in the art that Table 21 is representative of just a few of the combinations that can be made, and that many other combinations of nanoparticles of different acids can be made with the same or different sizes, and that the concentrations and particle sizes utilized for each can be modified.

[0082] It has been shown that the addition of solid acid nanoparticles into crude oil prior to initial distillation increases the resulting yield of light hydrocarbons (e.g., gasoline and diesel) during initial distillation. It is believed that the increased yield is due to catalytic low temperature cracking. It is also believed that the addition of the solid acid nanoparticles is environmentally benign.

[0083] Turning now to Fig. 5, according to a second method for implementing the invention, at step 510, solid acid nanoparticles (e.g., sulphated zirconia dioxide) are added to and mixed into hexane. At step 515, ultrasound is used to distribute the solid acid

nanoparticles in the hexane and generate a colloidal solution. The hexane-nanoparticle colloidal solution is then added at step 518 to crude oil and mixed. By way of example only, 0.1ml or colloidal solution may be added to 100ml of crude oil. At step 520, 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 a larger yield of gasoline and diesel (light hydrocarbons) is obtained than would otherwise be obtained if the solid acid 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).

[0084] According to another aspect of the invention, solid acid micropowders are added to a crude oil fraction that remains after a partial initial distillation of the crude oil to remove gas, gasoline and optionally crude oil. The 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. 6, at step 605, crude oil is subject to partial first stage distillation up to approximately 350°C or 360°C to obtain gases, gasoline (petrol) and diesel, and a residue crude oil fraction. Then, at step 610, the nanoparticles/micropowder is added to and mixed into the residue crude oil fraction and at 620 the mixture of the

nanoparticles/micropowder/residue fraction are subjected to completion of the first stage distillation (typically by boiling up to 420°C). The result of the first stage distillation, as described in more detail below, is that an increased yield of light hydrocarbons are obtained than would otherwise be obtained if the nanoparticles/micropowder had not been added.

[0085] Using the method of Fig. 6, samples of crude oil residue fractions (e.g., the crude oil already having had the gasoline and diesel distilled out in a standard manner by subjecting the crude oil to temperatures between 350°C and 360°C) were tested with different nanoparticles/micropowders or additive combinations. After the partial initial distillation, the addition to the residue of nanoparticles/micropowders of solid acids and combinations thereof, with different sized particles and different concentrations, such as discussed above with reference to Tables 12-32 (but not limited thereto), yielded additional yields of light hydrocarbons.

[0086] As illustrated above in Table 23, solid acid micropowders of all of the solid-acids discussed above with respect to Tables 12-32 (except for Zeolite Y and Faujasite) were each added to a respective sample residue fraction of crude oil which had been subjected to crude oil temperatures between 350°C and 360°C. Each micropowder/residue mixture was then boiled up to 420°C. Without exception, these trials produced significant yields of light hydrocarbons (naphta/petrol and diesel) from their respective residue fractions, even when relatively small concentrations were utilized. For example, H₃PM0₁₃O₄₀ at a concentration of just 0.001 produced a yield of 22% light hydrocarbons from a residue fraction, and sulphated zirconia with a particle size of 3.1nm and a concentration of just 0.001 produced a yield of 17% light hydrocarbons from a residue fraction. Mordenite at a concentration of just 0.01 produced a yield of 17% light hydrocarbons from a residue fraction in a first trial using a particle size of lOOnm, and a yield of 41% light hydrocarbons from a residue fraction in a second trial using a particle size of 800nm in conjunction with AICI₃ having a particle size of lOOnm and also present in a concentration of 0.01. MCM-41 with a particle size of 400nm at a concentration of 0.01 produced a yield of 21% light hydrocarbons from a residue fraction. HZSM-5 with a particle size of 50nm at a concentration of 0.01 produced a yield of 24% light hydrocarbons from a residue fraction. Thus, relatively small concentrations and relatively larger particle sizes still produced significant yields of light hydrocarbons from a residue fraction of crude oil. Larger concentrations of solid acids also produced significant yields of light hydrocarbons from a residue fraction of crude oil. AICI₃ with a particle size of lOOnm at a concentration of 0.05 produced a yield of 27% light hydrocarbons from a residue fraction. Alumosilicate at a concentration of 0.025 produced a yield of 22% light hydrocarbons from a residue fraction. Zeolite A with a particle size of 400nm at a concentration of 0.025 produced a yield of 26% light hydrocarbons from a residue fraction. [0087] It will be appreciated that as the yields of light hydrocarbons listed in Table 33 were produced from residue fractions following a partial standard distillation at temperatures between 350°C and 360°C, such yields were additional to those produced from the original samples of crude oil during the partial initial distillation without the solid acids, which accounted for roughly 16% petrol/naphta, 27% Diesel, and 57% Residue (43% light hydrocarbons, 57% Residue) of the original crude oil samples as discussed above. For example, since Sulphanated zirconia at 3.1 nm in a concentration of 0.001 produced a yield of 17% light hydrocarbons from the residue fraction, the total percentage of light hydrocarbons produced from the original crude oil sample corresponding to this particular test was roughly 53%: (43% light hydrocarbons from partial initial distillation) + (0.17)* (57%)) = 53% total light hydrocarbons.

[0088] Similarly, since Zeolite A at 400nm in a concentration of 0.025 produced a yield of 26% light hydrocarbons from the residue fraction, the total percentage of light hydrocarbons produced from the original crude oil sample corresponding to this particular test was roughly 57%: (43% light hydrocarbons from partial initial distillation) + (0.26)*(57%)) = 57% total light hydrocarbons.

[0089] By contrast, the inventors have found that simply heating the original crude oil to 420°C without adding any solid acids produced a yield of 45%, slightly higher than the 43% produced by heating the original crude oil to between 350°C and 360°C, but far less than the total light hydrocarbons produced by adding solid acids to the residue fractions after the partial initial standard distillations.

[0090] 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, or nanoparticles of solid acids, or solid acid micropowder, and combinations thereof to the crude oil. 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 particular solid acids, micropowders, and combinations thereof have been disclosed, it will be appreciated that other acids, solid acids, micropowders, and combinations thereof could be used as well. 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. Similarly, while certain ranges of concentrations of solid acids have been described, it will be recognized that other concentrations and weight percentages could be utilized. Furthermore, while specific sizes of nanoparticles of solid acid have been described, it will be understood that other sized nanoparticles can be similarly utilized. 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.

Claims

We claim:

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 lnm and 90nm 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 2nm and 76nm in diameter.

4. A method according to claim 3, wherein: said iron nanoparticles are 43nm in diameter.

5. A method according to claim 4, wherein: said iron nanoparticles constitute between .001% and .015% of said mixture.

6. A method according to claim 5, wherein: said iron nanoparticles constitute between .002% and .01% of said mixture.

7. A method according to claim 6, wherein: said iron nanoparticles constitute between .003% and .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 20nm and 62nm in diameter.

9. A method according to claim 8, wherein: said iron-oxide nanoparticles are 20nm 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 2nm and 84nm in diameter.

1 1. A method according to claim 10, wherein: said cobalt-oxide nanoparticles constitute between .001% and .02% of said mixture.

12. A method according to claim 1 1 , wherein: said cobalt-oxide nanoparticles constitute between .008%) and .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 lnm and 90nm to the crude oil and a solid acid

micropowder of diameter between 20nm 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 .01% and .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 43nm 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 lnm and 90nm 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 2nm and 76nm in diameter.

25. A method according to claim 24, wherein: said iron nanoparticles are 43nm in diameter.

26. A method according to claim 25, wherein: said iron nanoparticles constitute between .001% and .015% of said mixture.

27. A method according to claim 26, wherein: said iron nanoparticles constitute between .002% and .01% of said mixture.

28. A method according to claim 27, wherein: said iron nanoparticles constitute between .003% and .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 20nm and 62nm 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 2nm and 84nm in diameter.

31. A method according to claim 30, wherein: said cobalt-oxide nanoparticles constitute between .001% and .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 lnm and 90nm and a solid acid micropowder of diameter between 20nm 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 .01% and .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 43nm 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 lnm and 90nm 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 lnm and 90nm 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%>.

42. A method of increasing distillate yield in a crude oil distillation, comprising:

prior to distillation of crude oil, adding a plurality of solid acid nanoparticles of diameter between 3nm and 1200nm to the crude oil to create a crude oil/nanoparticle mixture, the solid acid nanoparticles comprising a weight percentage of the crude oil/nanoparticle mixture between 0.001%> and 0.2%>; and distilling said crude oil/nanoparticle mixture to generate at least one light hydrocarbon and a residue, whereby said residue generated from distilling said crude oil/nanoparticle mixture is smaller than a residue which would be generated from an identical distillation of the crude oil without said solid acid nanoparticles added thereto.

43. A method according to claim 42, wherein:

said plurality of solid acid nanoparticles are chosen from at least one of sulphated zirconia, alumosilicate, Zeolite A, Zeolite Y, keggin acid, aluminum trichloride, Faujasite, HZSM-5, Mordenite, and mcm-41.

44. A method according to claim 43, wherein:

said plurality of solid acid nanoparticles which comprise said weight percentage are no more than 150nm in diameter.

45. A method according to claim 44, wherein:

said solid acid nanoparticles which comprise said weight percentage are no more than lOOnm in diameter.

46. A method according to claim 45, wherein:

said solid acid nanoparticles which comprise said weight percentage are no more than 50nm in diameter.

47. A method according to claim 46, wherein:

said solid acid nanoparticles which comprise said weight percentage are no more than 20nm in diameter.

48. A method according to claim 42, wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is at least 0.005%.

49. A method according to claim 48, wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is at least 0.01%.

50. A method according to claim 49, wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is at least 0.03%.

51. A method according to claim 50, wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is at least 0.05%.

52. A method according to claim 51 , wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is at least 0.1%.

53. A method according to claim 42, wherein:

said plurality of solid acid nanoparticles are sulphated zirconia, have a diameter of between 3nm and 4nm, and comprise a weight percentage of the crude oil/nanoparticle mixture of at least 0.1%.

54. A method according to claim 42, wherein:

said plurality of solid acid nanoparticles are H₃PM0₁₃O₄₀, have a diameter of substantially lnm, and comprise a weight percentage of the crude oil/nanoparticle mixture of at least 0.1%.

55. A method of increasing yield of hydrocarbons from a crude oil, said method comprising: subjecting the crude oil to a partial initial distillation by heating the crude oil to a temperature between 350°C and 360°C to generate an initial quantity of light hydrocarbons and a residue from the crude oil;

adding nanoparticles of a solid acid micropowder to the residue of the partially distilled crude oil to create a partially distilled crude oil residue/solid acid micropowder mixture; and completing the initial distillation of the crude oil by heating said mixture to a temperature above 360°C and below 450°C and distilling said mixture to generate additional light hydrocarbons therefrom, whereby the total light hydrocarbons generated from the initial partial distillation and the completing of the initial distillation is larger than the total light hydrocarbons which would be generated from an identical initial distillation of the crude oil without said solid acid micropowder.

56. A method according to claim 55, wherein:

said solid acid micropowder is chosen from Zeolite A, Alumosilicate, Mordenite, Sulphated zirconia, aluminum trichloride, MCM-41, H₃PM0₁₃O₄₀, and HZSM-5 micropowder.

57. A mixture consisting essentially of:

crude oil in a weight percentage between 99.999% and 99.8%; and

a plurality of solid acid nanoparticles having a weight percentage between 0.001% and 0.2% and having respective diameters between 3nm and 1200nm.

58. A mixture according to claim 57, wherein:

said nanoparticles have respective diameters of no more than 150nm.

59. A mixture according to claim 58, wherein:

said nanoparticles have respective diameters of no more than 50nm.

60. A mixture according to claim 57, wherein:

said plurality of solid acid nanoparticles comprise a weight percentage of said mixture of at least 0.005%.

61. A method according to claim 60, wherein:

said plurality of solid acid nanoparticles comprise a weight percentage of said mixture of at least 0.01%.

62. A method according to claim 61, wherein:

said plurality of solid acid nanoparticles comprise a weight percentage of said mixture of at least 0.03%.

63. A method according to claim 62, wherein:

said plurality of solid acid nanoparticles comprise a weight percentage of said mixture of at least 0.05%.

64. A method according to claim 63, wherein:

said plurality of solid acid nanoparticles comprise a weight percentage of said mixture of at least 0.1%.

65. A method of increasing distillate yield in a crude oil distillation, comprising:

prior to distillation of crude oil, adding hexane and a plurality of solid acid

nanoparticles of diameter between 3nm and 1200nm to the crude oil to create a crude oil/hexane/nanoparticle mixture; and

distilling the crude oil/hexane/nanoparticle mixture to generate at least one light hydrocarbon and a residue, whereby said residue generated from distilling said crude oil/hexane/nanoparticle mixture is smaller than a residue which would be generated from an identical distillation of the crude oil without said hexane and said solid acid nanoparticles added thereto.

66. A method of increasing distillate yield in a crude oil distillation, comprising:

prior to distillation of crude oil, adding a plurality of solid acid nanoparticles of diameter between 3nm and 1200nm to the crude oil to create a crude oil/nanoparticle mixture, the solid acid nanoparticles comprising a weight percentage of the crude oil/nanoparticle mixture greater than 0.001% and

distilling said crude oil/nanoparticle mixture to generate a fractional amount of hydrocarbons and a fractional amount of residue, whereby said fractional amount of hydrocarbons generated from distilling said crude oil/nanoparticle mixture is larger than a fractional amount of hydrocarbons which would be generated from an identical distillation of the crude oil without said solid acid nanoparticles added thereto.

67. A method according to claim 66, wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is no more than 0.2%.