Increasing Distillates Yield in Low Temperature Cracking Process by Using Nanoparticles of Solid Acids

Solid acid 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, 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. According to another aspect, 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. According to another aspect, 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.

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Description
BACKGROUND OF THE INVENTION

1. Field of the Invention

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 of various solid acids to the unprocessed hydrocarbon composition.

2. State of the Art

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.

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.

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.

The alkanes are saturated hydrocarbons with straight or branched chains which contain only carbon and hydrogen and have the general formula CnH2n+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.

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 CnH2n. Cycloalkanes have similar properties to alkanes but have higher boiling points.

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

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.

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.

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.

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.

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:


CnHk=Cn-mHk-1+Cn-pHk-q+Cm+pHl+q

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

According to one 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.

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.

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.

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

FIG. 1 is a flow diagram of a first method for implementing the invention.

FIG. 2 is a flow diagram of a second method for implementing the invention.

FIG. 3 is a flow diagram of a third method for implementing the invention.

 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Turning now to FIG. 1, according to a first method for implementing the invention, at step 10, nanoparticles of a solid acid 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 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).

As described in more detail hereinafter, the nanoparticles of solid acid utilized at step 10 have a characteristic size of preferably between 3 nm and 1100 nm, and more preferably between 30 nm and 600 nm 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 10 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.

As shown in Table 1, three different samples of crude oil were initially obtained. To avoid the common problem of 1% gas being present in the crude oil, the crude oil was first heated at 70° C. for two hours. 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)) as presented below.

TABLE 1 Yield of distillation fractions for three different samples of crude oil. Boiling range % w/w Fraction (° 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

To test the method set forth in FIG. 1, nanoparticles of solid acid were then added to additional portions of the samples according to the method set forth in FIG. 1 to form mixtures of crude oil/solid acid nanoparticles. The mixtures were then subjected to the same distillation procedure as the controls.

Example 1

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 2 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 1). 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%.

TABLE 2 Changes of the light fractions yield after adding 0.01% of zeolite Y powder. Boiling range Change of yield, % w/w Fraction (° C.) Sample 1 Sample 2 Sample 3 Petrol and naphtha  40-180 +3 +3 +3 Diesel 180-360 +6 +5 +5

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 3 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

TABLE 3 Effect of the Zeolite Y concentration on the yield of distillation fractions for crude oil Sample 1. Concentration, % w/w Fraction 0 0.0005 0.001 0.01 0.1 0.2 0.3 Petrol and naphtha 13 13 13 16 16 16 16 Diesel 22 22 24 29 29 29 29 Residue 64 64 62 54 54 54 54

Example 2

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 4. As shown, increasing the acid concentration of the sulphated zirconia dioxide at a particle size of 3.1 nm 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%.

TABLE 4 Effect of concentration, Sulphated zirconia dioxide, particle size = 3.1 nm Concentration Fraction w/w % Petrol and sulphated zirconia naphtha Diesel Residue 0 16 27 57 0.001 16 27 57 0.005 18 29 53 0.01 20 29 51 0.03 22 30 48 0.05 22 32 46 0.06 24 34 42 0.1 24 35 41 0.2 23 34 42 0.3 24 35 41

The effect of the particle size at a given concentration was tested. Table 5 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 3.1 nm 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 15 nm and 44 nm 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 150 nm and 1100 nm 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 10,000 nm resulted in light hydrocarbon yields which matched the hydrocarbon yields without use of the acid (e.g., 0% acid—the control of Table 4).

TABLE 5 Effect of particle size, Sulphated zirconia dioxide, concentration = 0.03 w/w % Fraction Petrol Particles size, nm and Sulphated zirconia naphtha Diesel Residue 3.1 22 30 48 4.0 22 29 49 4.7 22 30 48 7.3 23 29 48 7.6 22 30 48 15 22 29 49 44 22 29 49 150 20 28 52 600 17 29 54 1100 17 29 54 >10000 16 27 57

Example 3

Alumosilicate (acid) having a composition of SiO2—66%, Al2O3—16%, Fe2O3—4%, MgO—10%, CaO—3%, and other components 1%, and a particle size of 30 nm was tested using the method of FIG. 1. As shown in Table 6 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 30 nm 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%.

TABLE 6 Effect of concentration, alumosilicate, particle size = 30 nm Fraction Concentration w/w % Petrol and alumosilicate naphtha Diesel Residue 0 16 27 57 0.001 16 28 56 0.005 17 28 55 0.007 19 28 53 0.01 19 32 49 0.03 20 32 48 0.05 21 33 46 0.1 21 33 46 0.2 21 33 46

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 7 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 30 nm provided the biggest yield of light hydrocarbons relative to the control (0% alumosilicate—Table 6). Increasing the particle size from 30 nm to 70 nm caused a drop in yield of light hydrocarbons, though the yield remained greater than that of the control. Increasing the particle size between 70 nm and 150 nm caused a slight drop in Petrol and naphtha but a slight increase in diesel. Increasing the particle size between 150 nm and 1200 nm 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 10,000 nm did not provide a better yield of light hydrocarbons than the control.

TABLE 7 Effect of particle size, Alumosilicates, concentration = 0.03 w/w % Fraction Particles size, nm Petrol and alumosilicate naphtha Diesel Residue 30 20 32 48 70 20 30 50 150 19 31 50 400 19 27 54 700 17 27 56 1200 17 27 56 >10000 16 27 57

Example 4

Zeolite A (sodium aluminum silicate) with a particle size of 20 nm was tested using the method of FIG. 1. As shown in Table 8, 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 20 nm may be used to improve the yield of light hydrocarbons relative to the control, but not relative to the yield at 0.2%.

TABLE 8 Effect of concentration, Zeolite A, particle size = 20 nm Fraction Concentration w/w % Petrol and Zeolite A naphtha Diesel Residue 0 16 27 57 0.001 16 28 56 0.005 19 29 52 0.01 20 30 50 0.05 21 31 48 0.1 22 31 47 0.2 22 32 46 0.3 22 32 46

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 9 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 20 nm and 50 nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 50 nm to 700 nm 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 8), and a particle size of 1200 nm and larger did not produce an increased yield of light hydrocarbons relative to the control.

TABLE 9 Effect of particle size, Zeolite A, concentration = 0.05 w/w % Fraction Particles size, nm Petrol and Zeolite A naphtha Diesel Residue 20 21 31 48 50 21 31 48 150 18 30 52 400 18 27 55 700 17 27 56 1200 16 27 57 >10000 16 27 57

Example 5

Keggin hetero polyacid (H3PMo13O40) with a particle size of 1 nm was tested using the method of FIG. 1. As shown in Table 10, 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 1 nm 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 1 nm 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%.

TABLE 10 Effect of concentration, H3PMo13O40, particle size = 1 nm Fraction Concentration w/w % Petrol and H3PMo13O40 naphtha Diesel Residue 0 18 31 51 0.001 18 33 49 0.005 20 37 43 0.01 21 40 39 0.05 21 41 38 0.1 22 41 37 0.2 23 41 36 0.3 23 41 36

Example 6

Aluminum trichloride (AlCl3) with a particle size of 100 nm was tested using the method of FIG. 1. As shown in Table 11, 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 100 nm 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.

TABLE 11 Effect of concentration, AlCl3, particle size = 100 nm Fraction Concentration w/w % Petrol and AlCl3 naphtha Diesel Residue 0 16 27 57 0.001 17 27 56 0.005 20 29 51 0.01 22 31 47 0.05 23 30 47 0.1 24 31 45 0.2 24 32 44 0.3 24 32 44

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 12 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 100 nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 100 nm to 700 nm 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 11), and particle sizes at 1200 nm and greater than 10,000 nm did not produce a yield of light hydrocarbons in excess of the control.

TABLE 12 Effect of particle size, AlCl3, concentration = 0.05 w/w % Fraction Particles size, nm Petrol and AlCl3 naphtha Diesel Residue 100 21 31 48 400 20 30 50 700 20 25 55 1200 16 27 57 >10000 16 27 57

Example 7

Faujasite with a particle size of 30 nm was tested using the method of FIG. 1. As shown in Table 13, 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 30 nm 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.

TABLE 13 Effect of concentration, Faujasite, particle size = 30 nm Fraction Concentration w/w % Petrol and Faujasite naphtha Diesel Residue 0 16 27 57 0.005 16 29 55 0.01 17 30 53 0.03 19 29 52 0.05 19 31 50 0.1 20 31 49 0.2 20 32 48 0.3 20 32 48 0.4 20 32 48

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 14 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 30 nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 30 nm to 700 nm 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 13). Increasing the particle size from 700 nm to 1200 nm 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 10,000 nm did not produce a yield of light hydrocarbons in excess of the control.

TABLE 14 Effect of particle size, Faujasite, concentration = 0.05 w/w % Fraction Particles size, nm Petrol and Faujasite naphtha Diesel Residue 30 19 31 50 150 19 29 52 400 17 29 54 700 19 25 56 1200 18 26 56 >10000 16 27 57

Example 8

HZSM-5 with a particle size of 50 nm was tested using the method of FIG. 1. As shown in Table 15, 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 50 nm 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).

TABLE 15 Effect of concentration, HZSM-5, particle size = 50 nm Fraction Concentration w/w % Petrol and HZSM-5 naphtha Diesel Residue 0 16 27 57 0.005 16 28 56 0.01 17 29 54 0.04 17 29 54 0.05 17 31 52 0.1 18 30 52 0.2 18 31 51 0.3 18 31 51

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 16 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 50 nm and 400 nm provided the biggest yield of light hydrocarbons. Increasing the particle size from 400 nm to 1200 nm 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 15). It is also noted that the yield of light hydrocarbons at 50 nm is greater than that of the control (no acid). Thus, particle sizes less than 50 nm are likely also to improve the yield of light hydrocarbons at this acid concentration of HZSM-5. Particle sizes greater than 10,000 nm did not vary the yield of light hydrocarbons relative to the control.

TABLE 16 Effect of particle size, HZSM-5, concentration = 0.05 w/w % Fraction Particles size, nm Petrol and HZSM-5 naphtha Diesel Residue 50 17 31 52 150 17 30 53 400 17 31 52 700 16 30 54 1200 16 29 55 >10000 16 27 57

Example 9

Mordenite with a particle size of 150 nm was tested using the method of FIG. 1. As shown in Table 17, 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 150 nm 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 17 Effect of concentration, Mordenite, particle size = 150 nm Fraction Concentration w/w % Petrol and Mordenite naphtha Diesel Residue 0 16 27 57 0.005 16 28 56 0.01 17 29 54 0.04 17 32 51 0.05 17 33 50 0.1 17 33 50 0.2 17 33 50

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 18 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 100 nm to 1200 nm 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 17). In addition, it is noted that the yield of light hydrocarbons was greater at a particle size of 100 nm 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 100 nm 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.

TABLE 18 Effect of particle size, Mordenite, concentration = 0.05 w/w % Fraction Particles size, nm Petrol and Mordenite naphtha Diesel Residue 100 17 33 50 400 17 31 52 800 17 29 54 1200 16 29 55 >10000 16 28 56

Example 10

MCM-41 with a particle size of 50 nm was tested using the method of FIG. 1. As shown in Table 19, 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 50 nm 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%.

TABLE 19 Effect of concentration, MCM-41, particle size = 50 nm Fraction Concentration w/w % Petrol and MCM-41 naphtha Diesel Residue 0 16 27 57 0.005 16 27 57 0.01 16 29 55 0.04 16 30 54 0.05 17 29 54 0.1 17 29 54 0.2 17 29 54

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 20 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 50 nm to 700 nm 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 19). It is noted that the fraction of light hydrocarbons yielded at a particle size of 50 nm and at a particle size of 1200 was greater than it was for the control. At particle sizes greater than 10,000 nm, the yield was the same as it was for the control. Thus, it is anticipated that particle sizes less than 50 nm and particle sizes greater than 1200 nm may also be used at this concentration of acid to improve the yield of light hydrocarbons relative to the control.

TABLE 20 Effect of particle size, MCM-41, concentration = 0.05 w/w % Fraction Particles size, nm Petrol and MCM-41 naphtha Diesel Residue 50 17 29 54 150 16 29 55 400 17 29 54 700 16 30 54 1200 16 28 56 >10000 16 27 57

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 3 nm to 1200 nm 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.

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 21, HZSM-5 at 0.02% concentration with a particle size of 43 nm was mixed with MCM-41 at 0.02% concentration with a particle size of 50 nm (which is close to 43 nm) 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 50 nm 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 50 nm was then mixed by itself in crude oil prior to initial 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.

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 21, when sulphated zirconia of 0.025% concentration with a particle size of 3.1 nm was mixed with Mordenite of 0.025% concentration with a particle size of 100 nm 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 3.1 nm 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 100 nm 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.

On the other hand, as seen below in Table 21, when sulphated zirconia of 0.015% concentration with a particle size of 3.1 nm was mixed with alumosilicate of 0.015% having a particle size of 700 nm 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 3.1 nm 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 700 nm, which gave a yield 17% petrol/naphtha (much lower), 27% diesel (much lower), and 56% residue (much higher). Effectively then, the combination of 3.1 nm sulphated zirconia with the 700 nm 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.

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 21, 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 800 nm 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.

TABLE 21 Additive effect of different solid acids Fraction Petrol Concentration Concentration w/w % and w/w % Additive 1 Additive 2 naphtha Diesel Residue Mixture works additively HZSM-5 50 nm MCM-41 50 nm 0.02 16 30 54 0.02 HZSM-5 50 nm — 17 29 54 0.04 — MCM-41 50 nm 0.04 16 30 54 Sulphated zirconia Mordenite 100 nm 19 33 48 3.1 nm 0.025 0.025 Sulphated zirconia 22 32 46 3.1 nm 0.05 Mordenite 100 nm 17 33 50 0.05 Mixture works synergistically Sulphated zirconia Alumosilicate 22 32 46 3.1 nm 0.015 700 nm 0.015 Sulphated zirconia 22 30 48 3.1 nm 0.03 Alumosilicate 17 27 56 700 nm 0.03 AlCl3 100 nm 0.025 Mordenite 800 nm 23 31 46 0.025 AlCl3 100 nm 0.05 23 30 47 Mordenite 800 nm 17 29 54 0.05

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.

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.

Turning now to FIG. 2, according to a second method for implementing the invention, at step 110, solid acid nanoparticles (e.g., sulphated zirconia dioxide) are added to and mixed into hexane. At step 115, 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 118 to crude oil and mixed. By way of example only, 0.1 ml or colloidal solution may be added to 100 ml of 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 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).

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. 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, the nanoparticles/micropowder is added to and mixed into the residue crude oil fraction and at 220 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.

Using the method of FIG. 3, 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 1-21 (but not limited thereto), yielded additional yields of light hydrocarbons.

TABLE 22 Yield of light hydrocarbons by heating the residue at 420° C. in the presence of nanoparticles/micropowders. nanoparticles/micropowder concentration Yield, % — — 3 Zeolite A 400 nm 0.025 26 Alumosilicate 0.025 22 Mordenite 100 nm 0.01 17 HZSM-5 50 nm 0.01 24 Sulphated zirconia 3.1 nm 0.001 17 AlCl3 100 nm 0.05 27 MCM-41 400 nm 0.01 21 H3PMo13O40 0.001 22 Mordenite 800 nm 0.01 41 AlCl3 100 nm 0.01

As illustrated above in Table 22, solid acid micropowders of all of the solid-acids discussed above with respect to Tables 1-21 (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, H3PMo13O40 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 3.1 nm 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 100 nm, and a yield of 41% light hydrocarbons from a residue fraction in a second trial using a particle size of 800 nm in conjunction with AlCl3 having a particle size of 100 nm and also present in a concentration of 0.01. MCM-41 with a particle size of 400 nm at a concentration of 0.01 produced a yield of 21% light hydrocarbons from a residue fraction. HZSM-5 with a particle size of 50 nm 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. AlCl3 with a particle size of 100 nm 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 400 nm at a concentration of 0.025 produced a yield of 26% light hydrocarbons from a residue fraction.

It will be appreciated that as the yields of light hydrocarbons listed in Table 22 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.

Similarly, since Zeolite A at 400 nm 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.

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.

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 solid acids, 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 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 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

1. 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 3 nm and 1200 nm 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.

2. A method according to claim 1, 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.

3. A method according to claim 1, wherein:

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

4. A method according to claim 3, wherein:

said solid acid nanoparticles which comprise said weight percentage are no more than 100 nm in diameter.

5. A method according to claim 4, wherein:

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

6. A method according to claim 5, wherein:

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

7. A method according to claim 1, wherein:

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

8. A method according to claim 7, wherein:

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

9. A method according to claim 8, wherein:

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

10. A method according to claim 9, wherein:

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

11. A method according to claim 10, wherein:

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

12. A method according to claim 1, wherein:

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

13. A method according to claim 1, wherein:

said plurality of solid acid nanoparticles are H3PMo13O40, have a diameter of substantially 1 nm, and comprise a weight percentage of the crude oil/nanoparticle mixture of at least 0.1%.

14. 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.

15. A method according to claim 14, wherein:

said solid acid micropowder is chosen from Zeolite A, Alumosilicate, Mordenite, Sulphated zirconia, aluminum trichloride, MCM-41, H3PMo13O40, and HZSM-5 micropowder.

16. 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 3 nm and 1200 nm.

17. A mixture according to claim 16, wherein:

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

18. A mixture according to claim 17, wherein:

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

19. A mixture according to claim 16, wherein:

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

20. A method according to claim 19, wherein:

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

21. A method according to claim 20, wherein:

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

22. A method according to claim 21, wherein:

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

23. A method according to claim 22, wherein:

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

24. 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 3 nm and 1200 nm 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.

25. 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 3 nm and 1200 nm 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.

26. A method according to claim 25, wherein:

said weight percentage of said solid acid nanoparticles in said crude oil/nanoparticle mixture is no more than 0.2%.
Patent History
Publication number: 20120132563
Type: Application
Filed: Nov 29, 2010
Publication Date: May 31, 2012
Inventors: Oleksander S. Tov (Kiev), Petro E. Stryzhak (Kiev)
Application Number: 12/955,215