- - - x^uuiiυ U D /
Process for Cavitational-Wave Cracking of Hydrocarbons in a Turbulent Flow And Apparatus for Implementing the Process
BACKGROUND OF THE INVENTION
According to most forecasts, by 2020 the annual consumption of standard fuel by primary power sources globally will reach 16 to 18 billion tons. Mineral fuels such as coal will account for 90% of this amount, while hydrocarbons (oil, gas condensate, and gas distillate) will remain a marginal component.
The International Energy Agency estimates that about 55% of the bulk volume of oil consumed worldwide by 2020 will be used for transportation, and about 40% for energy production. As early as 2010, consumption of engine fuel in the United States and the Peoples Republic of China together will account for 2 billion tons of oil annually. Thus, demand will continue to grow for primary power resources generally and for hydrocarbons particularly.
Oil is expected to account for about 37% of total power resources, or about 120 million barrels per day, by 2030. The existing world reserves of primary power resources, including recoverable oil reserves, in principle are sufficient to meet this demand. Yet, the forms and especially the quality composition of these resources have changed over time. In the 1970s, for example, light oils represented more than 50% of the total amount of consumable oil, but the current figure is only 30%. In contrast, the share of heavy crude oils in the total amount of consumable oil will reach or exceed 70% by 2030. The anticipated increase in the use of heavy crudes and super-heavy crudes raises a number of problems in relation, on one hand, to the production, development, and transportation of oil and, on the other hand, to its processing and refining. The principal problems in this context are associated with high viscosity, high solidification temperature, high boiling point, high final boiling point in bulk, a low yield of light fractions, and the presence of undesirable heteroatomic elements, such as sulfur- and metal-containing constituents.
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SUMMARY OF THE INVENTION
To address these and other problems, the inventors have developed a comprehensive approach to transforming heavy crudes, natural oil asphalt, and substandard petroleum, particularly boiler oil and liquid asphalt, into light oil characterized by a high content of white fractions, while maintaining the mass of initial hydrocarbons and reducing the content of sulfur, mercaptans, and metals.
In accordance with one aspect of this approach, the methodology of the present invention provides for treating raw hydrocarbon material for transportation, where the material is comprised of one or plurality of fractions, differing one to the other at least by molecular mass. The inventive methodology further provides for processing such raw hydrocarbon material, thereby to obtain a higher value product.
Another aspect of the inventive approach is a cavitational-wave apparatus, which provides for conditions that ensure implementation of low-temperature cracking of hydrocarbons in a turbulent flow. The methodology and apparatus of the invention represent a revolutionary technical solution not only in the field of oil processing (refining) but also in other areas, due to the universal character of physicochemical processes that are central to this invention. Thus, the methodology and apparatus of the invention may be employed in a myriad of chemical-technological processes that require destruction of substance structures, followed by the synthesis of new substances and gravitational separation of those substances.
The inventive methodology and apparatus are applicable to processing of media that have single or multiple components and that are monophasic or polyphasic. More specifically, the invention is useful for carrying out the directed synthesis and/or the recovery of a monoproduct or individual substance.
In accordance with one aspect of invention, a method is provided for treating and processing raw hydrocarbon material that is comprised of one or a plurality of fractions, differing one to the other at least by molecular mass. For example, the raw material can comprise natural or associated gas, under a pressure from 4 • 105 to 16 •
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105 H/m2. In this aspect, the inventive method comprises: (A) declusterizing the raw material by creating regulated flows such that the flows acquire turbulent dynamics, leading to cavitation; (B) infusing the declusterized material with a heterogenizing substance to form a heterogeneous medium; and then (C) directing the heterogeneous medium into a wave energy field from an external source, such that homogeneous medium is formed, wherein the homogeneous medium is subjected to pulses of wave energy from the external source such that the homogenized medium undergoes cavitation and resultant cracking, to yield a hydrocarbon product that is lighter than the raw material. Following (C), the method optionally comprises (D) effecting directed synthesis of commercial hydrocarbons product a predetermined molecular structure and molecular mass. The wave energy thus employed can be selected from ultrasonic energy, electromagnetic energy, electrophysical energy, or a combination of these.
In a preferred embodiment, the aforementioned turbulence has an average velocity of at least 16 m/sec and a wave intensity not lower than 2 W/cm3. In another embodiment, the heterogenizing substance is a gas, including, inter alia, gaseous hydrocarbons, associated gas, air, and water vapor, that constitutes, in said heterogeneous medium, from 0.5 to 99% by mass. In addition, the heterogenizing substance comprise solid inclusions, possessing acoustic resistance of from about 4x 106 to about 1 Ox 106 kg/(m2 sec). These solid inclusions comprise, for instance, metal powder and/or metal alloy powder and/or non-metals that constitute from 0.001 to 0.01 % of the mass.
In another embodiment, (C) utilizes wave energy in a form of wave radiation, with a frequency from 1.0 Hz to 2.4 Hz, for example, such that the abovementioned cavitation includes both trans-sonic cavitation and vortex cavitation.
In yet another embodiment, (D) comprises formation of gasoline fractions and emission of hydrogen, which presents an independent product and/or which is employed for hydrogenation of unsaturated hydrocarbon compounds evolved in the process itself. More generally, (D) may include hydrogenation and/or isomerization
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and/or aromatization. After (D), furthermore, fractionating of product can be carried out by distillation, gravitational separation, ultrafiltration, or another technique.
In still another embodiment, a method according to the present invention is characterized by: heterogenizing substance that comprises hydrogen, constituting 0.001 to 3 percent of mass, for example, and metal solid inclusion; a mean turbulence velocity of between about 12 to about 105 m/sec; a wave intensity ranging between about 100 to about 109 Hz; and the formation of saturated hydrocarbons in (D), presenting commercial gasoline and/or kerosene and/or diesel fuel. In this regard, it is preferred that the mean turbulence velocity is between 3 and 105 m/sec, that wave intensity is between 100 to 109 Hz during (D), and that formation of isomers of a normal paraffin hydrocarbon molecule and/or a mixture of such isomers occurs during (D). Alternatively, an aromatic hydrocarbon compound or a mixture of aromatic compounds is formed during (D).
In a further embodiment, a method to the present invention entails a regulated chemical synthesis of organic substances, with prescribed structure and molecular mass, provided by means of structure regulation in the raw material and/or heterogenizing substances and/or solid inclusions.
In another embodiment, the process of the invention is carried out, at (C) and (D), under impact of wave energy pulses from an external source, under conditions of a stationary wave with (i) a number of half- waves ranging from five to hundreds, (ii) a wave amplitude resonance growth from four to several thousand times, and (iii) wave intensity of from units to hundreds of megawatt per m2. In this context, the frequency of stationary waves coincides with the generated frequency of an external source, and the wave pressure amplitude exceeds hydrostatic pressure in the medium by, for instance, about 2.2-fold.
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BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1 a, b, c, and d provide, in schematic perspective, variations on the theme of bringing into contact two turbulent (vortex) flows, each having an imparted centripetal or centrifugal acceleration. Such contact generates friction between the flows, contributing to the breaking of intermolecular linkages.
Figures 2 A and B provide schematic representations of the cavitation process: (A) There is a temporal relationship between sound pressure in a medium, the corresponding waves of compression and expansion that pass through the medium, and changes in the size of bubbles that form in the medium. As wave energy, such as ultrasound, propagates in the medium, associated expansion cycles exert negative pressure on the medium, pulling constituent molecules away from one another. If the wave energy is sufficiently intense, the negative pressure exceeds the local tensile strength of the medium; then the expansion cycles can create cavities (bubbles) in the medium. The small, gas-filled bubbles grow as they absorb energy by being irradiated with the wave energy. (B) Under appropriate conditions and wave-energy intensity, cavity growth can occur, by a process called "rectified diffusion," such that a bubble oscillates in size over many expansion-compression cycles. During these oscillations, the amount of gas or vapor that diffuses in or out of a bubble depends on the latter' s surface area, which is slightly larger during expansion than during compression. Thus, bubble growth during the expansion segment of the cycle is slightly greater than is the shrinkage during compression, and so the bubble grows over several cycles. The growing bubble eventually reaches a critical ("resonant") size, where it can absorb wave energy efficiently; hence, the bubble can grow rapidly during a single cycle. Once the bubble has overgrown, it cannot absorb energy as efficiently, which means that the bubble can no longer sustain itself. The surrounding medium rushes in, and the bubble implodes. The resultant compression is so rapid that little heat can escape from the bubble during collapse, and the surrounding medium quickly quenches the heated cavity. Thus, a short-lived, localized "hot spot" is generated in an otherwise "cold" medium.
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Figures 3 A, B, and C schematically depict the process of creating stretching (tensile) and compression tensions through the formation of: low pressure zone(s), up to fine vacuum (section S1 in Fig. 3C); high pressure zone(s), up to several dozen MPa (point H of section S in Fig. 3C); zones of depression, from single-digit Pa to single digit KPa (section S2 in Figure 3C ); and zones of compression, from fractions to several dozen MPa. The process allows for transformation of the developed turbulence mode (sections S1, S and S2) into a laminar flow mode At the moment of flow deceleration, namely, point H in Fig. 3C, which is a peak of pressure, temperature and density, the medium experiences the impact of a highly intensive shock wave, resulting in an instantaneous release of a considerable amount of energy. The process of the energy release proceeds with the frequency of the shock wave, and the released energy is employed both for declusterizing and homogenizing the medium. AU parameters specified in Figure 3A-C are adjustable, process-controlling parameters. Figure 4 depicts the process of forming Benar cells and Couette-type flows, respectively, in medium that is involved in the rotary movements of carrying surfaces. The carrying surfaces may rotate in opposite directions, with identical and/or different angular velocities, or they may rotate in the same direction but, necessarily, with different angular velocities. Accordingly, the streams undergo mutual friction and form cellular structures that are localized in the Couette and Taylor vortex flows. This process is overlapped by the process of stretching and compression tensions, effected by the shock wave described above. These overlapping processes provide developed turbulence, developed cavitation, active collapse of cavitation bubbles, fracture of Benar cells and Couette flow, and subsequent, instantaneous release of a significant amount of energy in small volumes. The released energy may be utilized for both declusterization and homogenization of the medium. As in the preceding figure, all parameters are both adjustable and process-controlling.
Figure 5 is a graph that depicts the process of heterogenization. For efficient homogenizing, it is necessary in some cases to decrease, and in other cases to increase, a wave propagation speed in the medium, which is in either turbulent
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pulsing or laminar flowing state. To decrease wave propagation speed, one can use a gas subjected to the aforementioned processes, taking place in the wave field from an external source. For increasing the wave propagation speed, one can use concentrators of wave-induced stresses, made of acoustically rigid materials , i.e., materials with an acoustic resistance that is higher than that of oil or natural gas.
Accordingly, one introduces a gas and/or an acoustically rigid material in the medium, via depression zone S2 and compression zone P1. This process of heterogenization increases the efficiency of the subsequent homogenizing process.
Figure 6 schematically illustrates a process of wave treatment using an ultrasound external source as an example. Standing waves are formed between the wave generator (irradiator) S 1 and the wave reflector, placed opposite one another. The process of wave treatment enables one to tune the waves in resonance with free oscillation of the medium. Further, wave treatment provides an ability to form a zone of medium deceleration and to make P, a pressure in the working zone, to be at least twice as high as P0, the input pressure. Wave treatment also allows exploiting of wave energy for molecular synthesis and for facilitating synthesis, by effecting the collision of molecular fragmentation products, such as radicals and ions. The process of wave treatment can be used for medium homogenization and/or for distillation, and/or for product rectification. The ultrasound external source can be replaced by generators of other types of energy.
Figure 7 schematically illustrates a process of turbulent- wave treatment of medium for deep homogenization and increasing the content of light fractions. Essential to this process is the fact that accelerated flows are tangentially delivered to parallel rotating bodies, such as wheels. Working under pressure against the forces of inertia from rotation and being compressed to the center, the resultant flows create vortex swirls, in the form of truncated cones, and vacuum in internal cavities of those cones. Both adjustable and process-controlling are all relevant parameters of this process, including the diameters and the heights of vacuum- vortex cones, the rates of local boiling and condensation of vapors of low-boiling fractions, and the force of the
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shock wave that tears the cones out from the wheels and removes them from the developed turbulence zone.
Figure 8 provides a schematic representation of a process that is like that described above, in relation to Fig. 7, but that involves oppositely rotating flows, the vortex cones of which collide and create the peak pressures. Further, these cones of collision are torn out by the flow emanating from wheel No 1, where the vapors of light petroproduct, low-boiling fractions are supplied under high pressure. In turn, these vapors create a field of supersonic cavitation ("trans-sound"). These phenomena also are adjustable and process-controlling. Figures 9 A, B and C provide a schematic process representation of producing the needed fraction by means of isomerization and hydrogenation. The depicted process takes place dynamically in the wave field from an external source.
Figure 10 provides a schematic representation of the process of vortex separation of light fractions from heavy fractions, as well as the following stage of vortex separation of motor fuel fractions separation. The parameters shown in the figure, as well as the pressure and velocity, are operating parameters and define a wide regulation range.
Figure 11 provides a schematic representation of a practical application of the inventive method to the task of oil pre-conditioning for transportation (I), oil processing (II), and heavy residue utilization (III).
Figure 12-15 depict instrumental embodiments of the present invention that allow for implementation of the above-described method. Thus, to organize the process of declusterization efficiently, a hydrodynamic radiator of different design is employed: Figure 12 Longitudinal section of a hydrodynamic radiator/emitter of acoustic oscillations
Figure 13 Scheme of a cantilever-like fixation of a plate in the hydrodynamic radiator of acoustic oscillations.
Figure 14 Scheme of a nozzle for a slit flow acceleration.
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Figure 15 Scheme of a nozzle for a low acceleration in the grooves.
Variations of the use of the units shown in Figs. 12-14, in accordance with the invention, are set out in tables 9-10.]
For implementing the heterogenization process of the present invention, an effective device is a vortex tube of different design (Figures 16-23):
Figure 16 Longitudinal section of the vortex tube. Figure 17 Longitudinal section of a multinozzle orifice. Figure 18 Two-level placement of multinozzle orifices. Figure 19 Disc body with two inlet pipes for tangential supply of medium(s). Figure 20 Double chamber collector design.
Figure 21 Longitudinal section of the vortex tube with a conical nozzle. Figure 22 Scheme of the vortex tube acting as a vacuum pump.
Figure 23 Longitudinal section of the vortex tube with an external wave radiator. For implementing deep homogenization, a jet-mechanical vortex tube (Figure
24) may be used instead of or in series with a unit for turbulent-wave treatment, as described above in relation to Fig. 7:
Figure 24 Longitudinal section of the j et-mechanical vortex tube. Figure 25 Longitudinal section of a collector-less variant of the jet device. Figure 26 Longitudinal section of the collector variant of the jet device, with multinozzle orifices.
For efficient organization of the turbulent flows and cavitation zones described above, the present invention comprehends the introduction of flow accelerators (Figures 27-37) into an inventive cavitational-wave cracking apparatus: Figure 27 Longitudinal section of a single chamber flow accelerator, with a single multinozzle annular orifice.
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Figure 28 Longitudinal section of a single chamber flow accelerator, with two multinozzle annular orifices.
Figure 29 Longitudinal section of a double chamber flow accelerator, with two multinozzle annular orifices. Figure 30 Longitudinal section of a flow accelerator subunit with an outer pipe in the form a confuser.
Figure 31 Longitudinal section of a flow accelerator subunit with a confuser annular multinozzle orifice.
Figure 32 Longitudinal section of the flow accelerator with sloping longitudinal grooves in the multinozzle orifice.
Figure 33 Longitudinal section of the flow accelerator with a threaded coupling of the multinozzle orifice.
Figure 34 Lateral section of the flow accelerator with a socket for active medium tangential supply. Figure 35 Longitudinal section of the flow accelerator with the socket for active medium tangential supply.
Figure 36 Longitudinal section of the flow accelerator with a flange coupling. Figure 37 Examples of joining the flow accelerator to the apparatus.
Figures 38-41 depicts certain variants of the inventive apparatus, integrated with separate elements related to end product-producing in accordance with this invention:
Figure 38 Longitudinal section of the apparatus with a mixer (stirrer).
Figure 39 Longitudinal section of the apparatus with an external radiation source. Figure 40 Longitudinal section of the apparatus with a conical nozzle.
Figure 41 Longitudinal section of the apparatus with a wave radiator at the edge.
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DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The inventors have formulated a comprehensive methodology for treating and processing a hydrocarbon medium. Their approach makes use of (A) high-speed turbulence and abrupt flow deceleration and redirection of movement of the medium, including but not limited to rotation of the medium. The inventive methodology combines these (A) phenomena with (B) cavitation in the medium, which is effected by internal hydrodynamic phenomena and by the external application of wave energy, which may be ultrasonic, electromagnetic, electrophysical, or a combination of these. More specifically, cavitation (B) is occasioned: (i) by lowering the speed of a spreading wave in one stream, relative to wave speed in the untreated (raw) medium, and increasing the speed of a spreading wave in another stream, such that the medium experiences the impact of internal hydrodynamic wave phenomena; and (ii) by applying wave-energy pulses from an external source.
The combination of (A) and (B), pursuant to the present invention, causes a breaking of intermolecular bonds, i. e. , a cracking without the supplying of heat from an external source. This "non-thermal" cracking generates electrically charged species or ions, that then undergo recombination and transformation. Unsaturated hydrocarbon molecules can be readily transformed into saturated molecules through hydrogenation by molecular hydrogen, produced when natural gas is processed into gasoline, pursuant the inventive approach. By the same token, the unsaturated hydrocarbons can undergo isomerization, cyclization, and aromatization.
In this manner the inventors harness non-thermal mechanisms for the chemical transformation of long-chain hydrocarbon molecules into shorter, saturated hydrocarbons of a predetermined constituency. Pursuant to the inventive approach, these non-thermal mechanisms are self-sustaining and, hence, autocatalytic.
Accordingly, the present invention dispenses with expensive catalysts, commonly used in conventional technologies, and still outperforms those technologies, including cat cracking, hydrocracking, and catalytic reforming, in terms of efficiency, output, and the balance of light fractions obtained.
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I. Force Factors Employed By The Invention
Heavy oil, boiler oil, and tar are comprised of long, saturated hydrocarbon molecules represented by the formula CnH2n+2, where n, the number of carbons, ranges from 30 to several hundred. For treating and processing such material, therefore, the principal challenge is (i) to break the long hydrocarbon molecules into shorter ones, forming two, three and more chains, and then (ii) to receive saturated hydrocarbon molecules with n < 22.
Conventional technology achieves purposes (i) and (ii) through stages of
• catalytic cracking,
• thermal heating of oils and evaporation,
• condensation of steams and receiving of compounds characterized by short- chain hydrocarbon molecules, including the unsaturated ones, and
• transformation of those compounds, by hydrogenation, hydrorefining, etc., into hydrocarbons of the required structure.
In contrast to such conventional technology, which is heavily dependent on external heating, the present invention realizes purposes (i) and (ii) by exploiting four energy factors. These factors are considered below:
A. Kinetic energy of turbulent flows
As noted, the present invention exploits turbulent flow of the medium (oil, boiler oil, tar, and even natural or associated oil gases); that is, flow in which, unlike a laminar flow, velocity at a given point varies erratically in magnitude and in direction. Friction between the turbulent flows brings about internal heating, which contributes to breaking up constitutive molecular and supramolecular structures, as described in Section II, below (Figure 1). B. Energy of wave pressure
Consider a wave of intensity J that propagates through the medium. More specifically, contemplate a length (J) of the medium through which the energy is
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spreading unidirectionally. The energy E crossing normally through an area A is given by the relationship total energy of each "oscillator" or particle x the number of particles (n), and
1
E = — mω2 a2 x nAl , (1),
2
where m is the mass, a is the amplitude of a particle oscillation, and ω is the angular frequency of each particle. Time taken for this energy to pass through the given area is:
t = - (2), v where v is the linear velocity of a particle oscillation movement. Thus, energy crossing the whole area A in time t is given by:
-L mω a x nAl
1 2 v
Intensity J of the energy crossing every unit area per unit time is given by: 1 1
J= - v ω2 a2x nm =— vpω2r2 (4),
2 2
since nm = p, which is the density of the medium. Accordingly, the intensity of a wave (J) propagating through the medium is proportional to the square of its amplitude of vibration, to wit:
2J = pVc*U0 2 (5)
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where Vc is the velocity of propagation of sound in the medium, and Uo is the oscillatory velocity of a particle subjected to sound activity. The wave exerts pressure (P) on a particle in the medium in accordance with the relationship:
P = pVc*U0, (6), and the particle undergoes oscillation with the velocity of:
U0 = s * H0, (7), where s is the frequency of sound.
From relationships (5) - (7), it is apparent that intensifying vibratory velocity increases pressure, thereby imparting energy to particles or molecules in the medium and contributing to the breakage of their linkages. To take advantage of this mechanical wave-energy factor, the present invention contemplates that the medium, along a given segment of its motion and during a given time, is made to develop turbulence, which creates considerable vibratory velocity and excites high-intensity, "mechanical" sound. In a medium of heavy crude, for example, sound with a frequency of 20 kHz and a vibration amplitude of 0.5 mm creates sound pressures of no less than 12 MPa.
In accordance with the present invention, the energy from this wave pressure in the medium aids in breaking down supramolecular structures and molecules in the medium. This effect can be enhanced by overlaying turbulent-flow pulsations, associated with the propagating waves, with a high-intensity wave field created in the medium from an external source, which can be ultrasonic, electromagnetic, electrophysical, or photonic. In other words, the impact of the external waves is to increase the wave intensity and pressure, pursuant to relationships (5), (6) and (7).
C. Energy from cavitation explosions At pressures of the order discussed above, e.g., at about 6 MPa or more, the large pressure differentials in the flowing medium generate hydrodynamic cavitation, a phenomenon discussed, for example, by F.R. Young, CAVITATION (McGraw-Hill, 1989), and by CE. Brennen, CAVITATION AND BUBBLE DYNAMICS (Oxford U. Press, 1995). More specifically, conditions conducive to hydrodynamic cavitation are
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described by Maris and Balibar, Physics Today (February, 2000), where it is noted at page 29 that hydrodynamic cavitation can occur in a liquid when the local pressure p(x) drops below the vapor pressure pv of the fluid.
Thus, one way to achieve cavitation is to increase the local flow velocity, U(x). To this end, one can reduce the cross section of a pipe (inside which the medium is moving) in a given region, making a so-called "diffuser" that produces large local flow velocities due to mass flux conservation. For steady potential flow, the corresponding local pressure p(x) can be estimated from Bernoulli's equation:
1 p(x)+ — pυ2 (x) ^constant, (8)
2 where u is the flow velocity.
At an ambient reference pressure of 1 • 105 H/m2 and at room temperature, a water velocity of about 14 m/s is' sufficient to nucleate bubbles. According to the present invention, the above-mentioned breaking of intermolecular bonds and the formation of shorter-chain hydrocarbons (see also section ILD, infra) yield low-boiling hydrocarbon compounds. These are present as vapors, which, along with steam, fill in bubbles that are forming in the medium.
Because the medium is subject to developed turbulence, the bubbles collapse when the oscillations reach a point of where vapor pressure is attained (or even exceeded) in the medium, resulting in transient cavitation ("boiling"). Strutt and Rayleigh mathematically described the dynamics of a collapsing void or bubble, assumed to be spherical with radius R(t), and laid the foundation of what is now called the Rayleigh-Plesset equation:
.. . R 2 a
where pg is the gas pressure inside the bubble (dependent on the radius), P(f) is the
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time-dependent external pressure, σ is the effective cross-section of a particle, and Po is the static pressure. See Strutt, Philos. Mag. 43: 94 (1917).
Rayleigh-Plesset dynamics can lead to energy focusing, as can be seen by neglecting all terms on the right-hand side of the foregoing equation, i.e., by considering only the inertial terms:
• • •
R - R +(3/2) R2 =0 (10)
Integration immediately gives the equation:
R(t) = RoKt* - t)/t*] (11) where t is the time.
In micro-volumes of the medium, therefore, the pressure reaches thousands of atmospheres, several thousands of times per second, and then drops substantially to zero, thereby effecting thousands of atmospheres of tension. This local cavitation boiling continues in an area of developed turbulence (i.e., during the period when the medium is turbulized) and then is supported, after the flow leaves the area of developed turbulence, by the action of ultrasonic or other waves, injected into the medium from an external source as described above.
Thus, the wave energy introduced from the external source brings about acoustic cavitation, in place of the hydrodynamic cavitation that occurred in the developed-turbulence zone. For instance, ultrasound spans the frequencies of roughly 15 kHz to 1 GHz, the propagation velocity in the medium is approximately 1500 m/s, and acoustic wavelengths range between about 10 and about 10"4 cm. If a moderately intense acoustic field (typically, greater that about 0.5 MPa) is applied to the liquid medium, then the medium can "fail" during the expansion or "negative-pressure" portion of the sound field, whereby weak sites ("cavitation nuclei") within the medium undergo rapid growth and produce vapor-and-gas-filled bubbles (see Figure 2A). These bubbles continue to grow during the negative-pressure portion of the field, until the latter turns positive. The dynamics leading to an inertial implosion of the bubbles (i.e., the transient cavitation) are shown in Figure 2B. Acoustic cavitation
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can be very violent and results in a concentration of energy within the small residual volume of the collapsed bubble, essentially in accordance with the Rayleigh-Plesset model. Gas-filled remnants from collapsed bubbles serve as cavitation nuclei for subsequent cycles of growth and collapse. D. Thermal energy from infra-medium processes
The phenomena discussed in the preceding subsections A - C effect a breaking of bonds in long-chain hydrocarbon molecules, yielding short-lived radicals and ions. As described in greater detail below, these electrically active fragments undergo restoration of linkages producing saturated, unsaturated, cyclic and aromatic compounds, to form stable, shorter-chain molecules possessing the smaller molecular mass. The reestablishment of bonds in this context releases internal thermal energy. Additionally, the internal heating occasioned by contact between flows (see LA, supra) is augmented by the kinetic energy generated by friction between the bulk medium and the fragments that, upon the breaking up of longer molecules, move away from each other rapidly.
II. Processes in the hydrocarbon medium in accordance with the Invention (Path of the medium)
Pursuant to the present invention, the energy factors detailed above are brought into play over the course of processes that together transform raw hydrocarbon material into light oil, with a high content of motor-fuel fractions. Because the basic energy factors are employed in lieu of external heating, a substantial improvement is realized in power efficiency. Improvement in both content and output of light fractions takes place relative to conventional technologies.
A. Declustering During the initial stage of the inventive approach, the starting material, raw hydrocarbon, is preconditioned so as to break up clusters of fluidized particles, formed from long-chain hydrocarbon molecules, that constitute a quasi-crystalline lattice in the bulk medium and that impart an extreme viscosity to high-tar crudes, boiler oils, and liquid asphalts, inter alia. Intermolecular connections in the long- chain hydrocarbons also are broken over the course of the initial stage.
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In the present description, "declustering" denotes this process of breaking up not only the quasi-crystalline lattice per se but also the constituent clusters, yielding colloidal aggregates of long-chain hydrocarbons, which likewise are broken up. Declustering can be effected, for example, by the combined means of inducing flow turbulence in the medium and irradiating the medium, in its total volume, with wave energy from an external source.
The design of a suitable turbulizer for this purpose is guided by standard principles of fluid mechanics. See, e.g., CT. Crowe, et al, ENGINEERING FLUID MECHANICS, 7th ed., John Wiley & Sons, Inc. (2002). For instance, one can employ the design motif shown in Figure 3, whereby the flow of medium is stalled, opened, and then disordered along the lower and upper surfaces, respectively, of two cone-shaped vortex generators of differing volumes. Heavy degassed hydrocarbon raw material in the presence of clusters does not withhold stretching, and in particular, the effects of negative pressure. These forces result in the fracture of clusters, a breach in the continuity of the medium flow, and formation of bubbles filled with gases and vapors of volatile hydrocarbon fractions and/or with gases and vapors additionally injected from outside. The phenomenon represented by the breach in the continuity of the medium and the formation of areas of underpressure, filled with steams of low-boiling fractions, is usually called "cavitation" of hydrocarbon medium. The initial stage of the cavitation process is ■ characterized by the formation of bubbles and by local boiling inside the bubbles, resulting from underpressure.
At standard conditions (pressure equal to IxIO5 N/m2 , temperature +2O0C), it is known that the pressure Pcav of oil is close to the pressure of saturated steams of low-boiling hydrocarbons, about 1.5 KPa, or equal to the mercury pressure =
200 mm. At the pressure of 1.5 Kpa, the boiling point of hydrocarbon C34H70 that is equal to +5000C (1 N/m2), decreases to +3000C. Similarly, the final boiling point of hydrocarbons that comprise benzine fractions decreases from +2050C to +6O0C. The boiling point of all basic benzine hydrocarbons, at the pressure of 1.5 KPa, decreases from +15O0C to +250C and lower.
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In view of these facts, the formula resulting from the Bernoulli equation and defining pressure Pj in the current point of the medium is:
Pi = Pg+ i/2 υ2 0i- 1/2 gυ2i , (12) where Pg is the statistical pressure in the system, particularly created with a pump; υOi is the known speed of the medium movement at a certain fixed point, taken for the account point, and υ; is the speed of the medium movement at the point where pressure Pj is determined.
According to Figure 3, if Pg = 0.3 MPa, then the movement speed of local volume of medium (υOi), with radius = 0.1 cm3 at points of a sphere with the radius = 0.1 cm, is 5 m/sec; at the radius r = 0.4, υi = 25 m/sec. There are several ways to achieve such velocity. In particular, if there is a rotating wheel (ω = 50 Vsec) with the radius of 0.4 m and a central receiving opening (inlet) of r = 0.1 m., then the resulting peripheral speed from rotation in the outlet at the external diameter will be 20 m/sec, and the absolute speed of medium, expressed by their sum, will be 25 m/sec. Then the pressure at r = 0.4 m will be equal to:
Pi = S lO5 + V2 103 • 25 - V2 103 • 625 = 103/2 (600 +25 - 625) = 0 (13)
That is, in the vicinity of points of a sphere with the radius r = 0.4 m, a significant decompression is created and active cavitation commences.
Further, assume that a stream moving at the velocity of 25 m/sec is abruptly decelerated. This could be achieved, for example, with the help of a wheel rotating in the direction opposite to the stream, with peripheral speed of the rim of no less than 25 m/sec, e.g., 100 m/sec.
In this case, the resulting speed will be equal to 25 + 100 = 125 m/sec, and the whole stream receives kinetic energy of V2 • 103 • 1252, while the breaking pressure in accordance with formula (12) will be equal to:
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P; = 3 • 105 + 1A ■ 103 • 15625 - V2 ■ 103 • O2 = 105/2 (6 + 156,25 - 0) =81,125 • 105 ~ 8 MPa (14) which considerably exceeds the critical pressure required for the collapse of cavitation bubbles.
Further, the rotating wheel carries the stream and accelerates it to the velocity of 105 m/sec = (100 + 5) m/sec. As a result, active pressure falls to zero; i.e., the process schematically depicted in Figure 3 takes place.
Alternatively, instead of the second rotating wheel, it is possible to utilize a countercurrent of the medium, as well as a co-current flow with lesser or higher speed. The pattern of the process, thus realized, will be identical to the process depicted in Figures 3.
The integration of a turbulizer/vortex tube , such as the unit depicted in Figures 3 AfB, Figure 4 and Figure 24, or, for instance, a hydrodynamic radiator (Figures 12-15) with an external source for wave energy, such as an ultrasound or microwave generator, also is accomplished in a conventional manner. One of the ways for organizing the developed turbulence and the medium active cavitation has been considered above. Thus, the set of processes described above effects an intensification of developed turbulence and active cavitation by an initial deceleration and the subsequent medium dynamics with the greater velocity. Figure 4 depicts the process of formation, growth, and collapse of cavitational bubbles involved in rotational movement in Benar cells and Quette flows.
Increasing the velocity of flow turbulence allows for a reduction in the intensity of the applied wave energy, and vice versa. That is, one may increase wave intensity from the external source, in order to accommodate a reduced turbulence velocity. Preferably, the average velocity of flow turbulence is not lower than 16 m/sec, and the wave intensity is not lower than 2 Watts/cm2.
A device of the invention that achieves these processes can be manufactured, for example, in the form of a wheel with tangential medium supply from periphery, and accelerators of the Laval nozzle-type. The accelerators are designed such that the flow accelerates towards the center of the wheel, whence it streams to the zone of
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wave treatment, as depicted in Figure 6. The medium is earlier heterogenized through the addition, for example, of natural gas.
In this context, the wave propagation speed will be determined pursuant to the formula:
where α is the gas content, mass share, and P is the gas pressure in the medium. For instance, if the gas concentration comprises 5% (α = 0.05) and its pressure reaches 0.45 MPa, then, with a medium of 948 kg/m
3 in density, the wave will propagate in the medium with the following velocity:
4.5 • 105 1A
Vc= ( 0.05 - 0.95 - 948 ) ~ 100 M/sec (16)
It is possible to accelerate the flow to the same and/or even higher speed. In this case, the wave perturbations will deviate and concentrate in a predetermined zone, such as in the area of treatment.
Figure 6 illustrates that a radiator with platform Z1, preferably is located in this zone. The radiator ensures the formation of standing waves, with the help of reflector Z2 and/or another radiator. The width of the work or treatment zone is selected to provide resonance of waves with natural oscillation of the medium. In this case, the efficiency of treatment will increase (a) through standing waves - 4 times, since the intensity of a wave depends on wave amplitude square and (b) through resonance — at least another 4 times. In addition, (c) the resonance mode will be boosted several dozen times through pressure corresponding to the mode of deceleration of the flow in the treatment zone, as discussed above, and (d) recombination of molecules frees heat will boost the waves several multiples. It is known that each one degree of heat increases the oscillation velocity no less than for 0.5 m/sec [I]. Thus, the calculations show that this will result in at least a 10- to 12-fold intensification of the wave field.
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To summarize, the intensity of wave treatment from an external source will increase at least 1600 times (4 x 4 x 10 x 10) through its superimposition with the action of turbulent fluctuation. The similar effect can be achieved by placing the emitters of external waves in rarefaction areas S1 and S2, in the compression area P1 of the turbulizer (see Figures 3 and 4).
Under the impact of declustering, the medium, which may begin as heavy crude, boiler oil, or liquid asphalt ("hydrocarbon raw material" or "initial raw"), becomes more uniform and more fluid, and bubbles appear in it. (As noted above, these bubbles contain low-boiling hydrocarbons, which have vaporized, and hydrocarbon gases.) Thus preconditioned, the medium can be transported much more easily, e.g., via pipeline or tanker, thereby realizing a significant savings over the energy- and labor-intensive procedures in current practice of crude oil transportation. Alternatively, the declustered medium can be taken directly into heterogenization, the next step of a processing series according to the present invention. B. Heterogenizittg
Hydrocarbon raw material and products derived from it are made up of hydrocarbon molecules, which possess characteristics both of a particle and of a wave. Thus, such molecules can be said to undergo high-velocity, oscillating motion in situ. The molecules of a heavy crude, for example, experience oscillation velocities of about 2200 to about 2700 m/sec, which translate to an angular velocity in the range of 109 to 1010 Hz.
From the perspective of particle-wave dualism, therefore, hydrocarbon molecules are typically characterized by a high oscillation intensity, and they provide a strong wave impedance to external influences, including thermal ones. By virtue of the latter impedance, thermal heating penetrates the medium only weakly.
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To control processing of the initial raw, the present invention entails infusing the declusterized medium with a substance that comprises a gas, thereby to produce a two-phase medium, vapor-liquid or gas-(vapor)-liquid. Illustrative of this "heterogenizing substance" are: • natural gas (methane, ethane) and a propane-butane mixture;
• natural gas and water steam;
• ambient air and water or water steam;
• any combination of the foregoing with activated metal powder; and
• water and metal powder, separately or combined. Natural gas and/or superheated vapors of low-boiling hydrocarbons undergo the processes in the wave field described in [0009] and [0010] with the radiator from an external source. Then, the intermolecular links breaking up takes place (CH4 → CH3 + H; H2O → OH + H; C6H14 → C3H8 + C3H6 ) with forming short-lived fragments. With that, their electron shells become excited so that the fragments themselves become additionally reaction-active.
The "heterogeneous medium" that results from introduction of the heterogenizing substance is compressible, whereas hydrocarbon raw material is essentially incompressible. By virtue of its compressibility, the heterogeneous medium can absorb the energy of a wave and reduce its velocity, allowing the wave to propagate a shorter distance, per time unit, than it would in a single-phase liquid.
The two-phase, heterogeneous medium preferably has solid inclusions, the V0 value of which (i.e., the characterizing speed of sound propagation) exceeds the corresponding parameter for oil, tar, and the like. The solid inclusions thus impart an additional wave impedance to the heterogeneous medium and, in a wave field, act as concentrators of wave-induced stresses. These stress concentrators facilitate the breaking of clusters and molecular linkages, as described above. In addition, they absorb nitrogen, sulfur, and other heteroatomic components from the oil, allowing for the reduction of such components.
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Like declustering, the heterogenizing process can be effected by a combination of induced flow turbulence and wave irradiation from an external source, along with the infusion of a heterogenizing substance under a low-pressure or a self- suction regimen. An illustrative design motif in this regard is shown in Figure 4. For increasing the degree of heterogeneity, that is, for the even gas distribution in the bulk of liquid and/or any other heterogenizing substance, it is necessary to run the heterogeneous mixture through the activator, disintegrator, turbulizer of the known type. After declusterizing, therefore, it is essential to conduct the processes similar to those described in the declusterizing section, above, but with injection the heterogenizing substances (gas, steam, metal, and/or their combinations) into the medium (see Fig. 5).
In this context, the volume of heterogenizing gas introduced into the medium varies by mass between about 1% and about 3% of the medium. When solid inclusions are present in the heterogenizing substance, their amount should comprise on the order of 0.001 % of the mass of the medium, while the volume of activated water (if employed) should make up from several to dozens of percent of the medium. Similarly, the amount of any molten metal introduced should vary, relative to the mass of the medium, between about 0.1% and about 10%.
During the heterogenizing process, supramolecular structures are formed as dispersion particles in the medium; these structures are characterized by a nucleus that is confined within a sphere of solvation. The nucleus incorporates any solid metal particles, liquid (water) and gaseous (natural gas or steam comprised of water and vaporized, low-boiling hydrocarbons) substances that are present (particularly but not exclusively) by introduction with the heterogenizing substance. Because the medium is subjected beforehand to declustering and then to dilution by the heterogenizing substance, as described, the medium pressure within the solvation sphere, as well as the surface tension of the sphere, is consistent with sustaining the integrity of the spheres, which appear as bubbles in the medium.
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C. Homogenizing
From the previous section, it is apparent that the heterogeneous medium is compositionally and structurally complex. Converting that medium to a homogeneous mixture (i.e., providing a "homogeneous medium") in part is accomplished, pursuant to the present invention, by overlaying pulsations of turbulent flow with pulses of wave energy from an external source, in a manner described above. A design motif that is suitable to this end is shown in Figure 6.
Homogenization is the creation of short-molecular compounds, thereby increasing the content of light fractions in hydrocarbons while maintaining basic mass, as well as decreasing or completely eliminating heteroatomic compounds, via their coagulation. The first part of the problem — breaking the clusters, shortening the length of hydrocarbon molecules, and creating saturated, short-molecular hydrocarbons ~ is resolved, employing the methodology that is illustrated in Figures 3-7 and that is described in the foregoing paragraphs concerning these figures, by controlling parameters of the processes. Therefore, special attention is warranted to the following aspects of the inventive process: the formation of an area of developed turbulence with high-intensity, high-quality pulsation; the formation of a zone of tensile stresses and a zone of intense compression, thereby to achieve deceleration pressure, where active cavitation occurs and is influenced by, in addition the energy of turbulent pulsation, the impact of high-intensity wave energy from an external source; the formation of Benar cells, involving Couette flows, that are displaced by the turbulent flow and that, under decelerating pressure, undergo tensile stress and compression; the formation of a high-pressure area (deceleration) with a nucleus in the form of vortex cones, in the inner cavities of which a vacuum is formed, where there occur low-temperature boiling of the medium, destruction of the nucleus through shock wave pressure, and inclusion of the treated medium in general laminar flow.
As a consequence of homogenizing, the oscillatory amplitude and frequency of molecules in the medium increase, with a corresponding increase in wave intensity and pressure. By the same token, there is an intensification of the processes of
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breaking intermolecular bonds and of restoring bonds between fragments (see below), with a concomitant, localized heating of the medium due to internal heat emission.
The homogenizing process also is advanced by disrupting the above- mentioned supramolecular structures and bringing about the collapse or microexplosion of bubbles that have formed in the medium, which releases substantial amounts of additional energy, pursuant to cavitation mechanisms describe above. In other words, this enhanced or "deep" homogenization is a function of repeated, microexplosion-generated shock waves that spread through the medium, which consequently undergoes local (microscopic) heating to temperatures in the range, for example, of 2000° to 26000C.
The breaking of molecular bonds in the homogenized medium should provide fragments ~ shorter hydrocarbon radicals and ions — at a level that is sufficient for molecular assembly, as described in the next section. Achieving this goal is facilitated (as an aspect of deep homogenization) by separating the medium into two streams, one of which is accelerated to a velocity that is below the speed of sound in the raw starting material (the "subsonic stream"). The other stream is accelerated to a velocity above that speed of sound (the "supersonic stream").
The subsonic and the supersonic streams thereafter are redirected into mutual contact, which, due to the velocity difference between the streams, causes an intensified molecular oscillation and, hence, an elevation of acoustic pressure in the medium. This increased pressure and concomitant local heating is enhanced further by supplying wave energy, upon mutual contact of the two streams after the mutual contact of two streams has taken place), from an external source that has a frequency substantially matching that of the aforementioned, internal oscillation. Figures 6 and 16-24 depict an illustrative design motif, based on a vortex tube, for effecting deep homogenization.
When the pressure is oscillating periodically, bubbles also oscillate periodically, due to the gas compressibility, around the ambient radius i?0 that the bubble would have under static, ambient conditions. If instead the bubble is kicked
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with a single pressure pulse, then the bubble's resonance frequency /0 survives longest; all other frequencies damp out earlier.
To calculate the resonance frequency, one needs the restoring force, which results from the pressure in the gas bubble. For large enough bubbles, i?0 » sAP0 » 1 mm, the force depends on the ambient pressure Pc and the actual radius R(t), and the resonance frequency (f0) is given by:
Here γ is the adiabatic exponent, the ratio of the constant-pressure and constant- volume heat capacities of the gas. For air bubbles (for which γ = 1.4) in water under standard conditions, for foregoing equation reduces to/oi?o » 3 kHz mm. See C. E. Brennen (1995), supra.
D. Restoring Intermolecular Connections The foregoing processes effect a mix of macroscopic turbulent chaos with microscopic thermal chaos in the homogenized medium. These interpenetrative and mutually amplifying phenomena create the requisite chemical instability for avalanche cracking of the medium to occur.
As noted, cracking of the medium, pursuant to the present invention, creates electrically charged species. Overall, the breaking of molecular links occurs such that generalized electrons (A) are divided equally between the fragments, creating shortlived radicals, or (B) are transferred fully to one fragment, which thereby becomes a negative carbanion, and a second fragment, without a generalized electron, becomes a positive carbocation. The resultant hydrocarbon radicals and ions, which appear during the breaking of molecular connections, move from their initial positions a considerable distance (in the scale of molecular dimensions), and thereby create a triboeffect.
Due to their charged character, the hydrocarbon radicals and ions subsequently interact, in accordance with the present invention, to restore intermolecular connections, yielding hydrocarbon molecules of desirably shorter length. To
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appreciate how this happens, it is useful to review what happens during the cracking of hydrocarbon gases and heavy hydrocarbons.
During the cracking, the energy released from collapsing of cavitational bubbles and related energy of bubble formation, are used for breaking chemical bonds in large hydrocarbon molecules. The bond energies vary in hydrocarbons within a wide range, from about 40 kJ/mole to about 400 kJ/mole. The strength of Csec-H bond, the bond between carbon in the middle part of the hydrocarbon molecule and hydrogen, is weaker than the Cend-H bond, the bond between carbon at the end of the hydrocarbon molecule and hydrogen, thus, it is easier to strip hydrogen from the molecule in the middle part than at the end. The C-C binding energy also is also getting somewhat weaker towards the middle part of the hydrocarbon molecule, therefore, long hydrocarbon molecules usually split in their middle part, i.e., far from the end.
The active particles formed in the cavitational process - radicals - cause the chemical process of isomerization and aromatization:
1) chain initiation
C2H6 -> CH3 +CH3 (18)
C2H6 +C2H4 → 2C2H5 (i9)
2) substitution
CH3 + C2H6 → CH4 + C2H5 (20)
3) radical fission (disintegration) with formation of unsaturated molecules:
CH3 CH2 CHCH3 -> CH2 = CHCH3 + CH3 (21)
4) radical addition to multiple bond of unsaturated molecule (the reaction is reverse to the radical fission) CH3 + C2H4 → C3H1 (22)
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5) rearrangement (isomerization) of free radicals. It is assumed that the rearrangement proceeds via cyclic transitional state, thus making the formation of 6-member rings easier:
cH? CH0 cH, CH7 CH7 CH9 CH. <→
<-→- CH
3CH
2CH
2CH
2CH
2CHCH
3 (23)
CH2
The chain reactions can be terminated via the following reactions: 6) radical recombination (dimerization)
CH3 + CH → C2H6 (24)
7) disproportionation:
CH3 + C2H5 → CH4 + C2H4 (25)
Stable to radical fission but extremely reactive, methyl and ethyl radicals and hydrogen atoms react with the initial hydrocarbon molecules, stripping them of a hydrogen atom:
H + C4Hx, → H2 + C4H9 W
CH3 + C4H10 -> CH4 + C4H9 (27)
CH3CH2 + C4H10 -» CH3CH3 + C4H9
(ZX)
As to transformation of cycloalkanes, the initial decomposition occurs via breaking the weakest C-C-bond , with formation of a biradical:
CH
2 CH
2 CH
2 CH
2 CH
2 CH
2 (29)
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3C,
CH2 CH2 CH 2 CH 2 CH 2 CHj 2H-" 4 (30)
The above cycloalkane reaction proceeds via a non-chain mechanism.
Alkenes are usually not found in oil fractions but are formed under thermal decomposition of alkanes and cycloalkanes. Alkenes decompose mainly via a chain mechanism.
CH2 = cH2 → cH2 = cH + H (31)
CH2 = CHCH = CH2 + H
CH2 = CHCH2CH3 + CH2 = CH
The lower the temperature and the higher the pressure, the greater is the role of butylenes accumulating reaction (b), and the less significant is the role of butadiene-forming reaction (a).
With regard to transformation of alkadienes and alkynes, the main direction of reactions is toward diene synthesis, according to a molecular mechanism:
CH2=CH-CH=CH2 + CH2=CH2
The thermal stability of arenes strongly depends on their structure. Unsubstituted and methyl-substituted benzene and naphtalenes are much more stable than alkanes. Meanwhile, alkyl-substituted arenes with alkyl substituent other than methyl decompose more readily than alkanes.
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The benzene condensation proceeds according to the following scheme:
When a cracking extent is small, toluene decomposes according to the following scheme:
Reactions of carbocations:
Carbocations are extremely reactive compounds. Rate constants of ionic reactions are typically several orders of magnitude higher than rate constants of corresponding radical reactions. The relative stability of an individual carbocation can be assessed based its enthalpy of formation, in kJ/mole
These data demonstrate that the stability of carbocations grows in the following sequence: primary < secondary < tertiary.
As for radicals, the main reactions for carbocations are a monomolecular fission by /?-rule and bimolecular reactions of substitution and addition. The key
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distinction between carbocations and radicals is the isomerization ability of the former.
Isomerization of carbocations can occur via migration of either hydride-ion or methylanion:
O CH
3 C HCHCH
2CH
3 <-> CH
2CH
2 C HCH
2CH
3
CH3 CH3
I I I i
+ + (37Ϊ
CH3 c HcH3 : CH3 o CH3 CH CH2 o CH3 c CH3 + 76 kj/moie v '
Fission by the β-rule: Fission of carbocations usually occurs via the weakest bond β-C-C. The reaction is endothermic:
CH2CH2CH2CH2CH2CH2CH2CH3 →CH2 = CH2 +CH2CH2CH2CH2CH2CH3 -
- 92 kJ/mole (38) The stability of carbocations to fission grows in sequence: primary < secondary < tertiary.
A comparison of fission and isomerization energies suggests that isomerization will precede fission in most cases.
Another reaction involves the loss of a proton by an adjoining carbon atom and the transfer of the proton to an alkene molecule, for example:
CH3CH2 C HCH3 → CH3CH = CHCH3 + H+ (39)
This reaction is most favorable energetically, when the proton is depleted from a primary carbocation, forming a tertiary carbocation as the result.
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Abstracting a hydride ion from alkane can proceed as illustrated below:
CH3 C HCH2CH3 + CH3CH(CH3 )CH3 → CH3CH2CH2CH3 + CH3 C(CH3 )CH3 + (40)
+ 67 kJ/mole Reaction of cycloalkanes:
The decomposition of the cyclohexyl ion can undergo via ring fission.
Alkenyl ion formed as the result of breaking C-C bond can readily isomerize into allyl ion.
H2C=C(R)CH2CH2CH2CH2- H2C=CRCHCH2CH2CH3
(42)
The allyl ion can undergo fission by β-rule, abstract hydride-ion from initial hydrocarbon or transfer a proton to alkene molecule.
Reactions of arenes:
The reaction rate grows with the increasing chain length of alkyl substituent.
Ultrasonic phase compression acts as an impact activating a reaction when a difference Δ V between active volumes of reagents Vp and the molar volume of the transition complex Vn is significant.
A V = Vp- Vn, (44)
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InK=In Ko-[I /RT ] JAVdp (45)
Δ V = Δ V0(l+βp)-2 (46) where K is the rate constant and p is pressure.
The alternating sign of pressure changes under impact of high-frequency oscillations provides for activating of decay/fission reactions, usually resulting in the volume increase (Δ VO), as well as for activating of synthesis reactions.
Thus, the impact of produced cavitation- wave treatment on a chemical reaction, such as cracking, comes down to three factors that determine the rate and direction of the ongoing process: (1) initiating radical and ion reactions during the phase break-up and bubbles collapse (cavitation);
(2) changing reaction rate constant during compression/decompression of the phase; and
(3) shifting the equilibrium in the output of reaction products in the heterogenic system "liquid-gas" under pressure.
E. Managing the balance of hydrogen in the cracking-process
The balance of hydrogen and managing the saturation degree of post-cracking products is extremely important. This is so because these processes ultimately determine the quality of the obtained product, including such characteristics as the calorific value, detonation stability, and phase-transition temperature.
In the present invention, the ion-radical mechanism described above facilitates the process without strongly pronounced limiting stages. In general, cracking necessarily results in an increase of the aromaticity and hydrogen deficiency because preservation of n-limit, i.e., preservation of post-cracking hydrocarbon in alkane state, requires adding 1 mole H2 per each mole of decomposing hydrocarbon:
CnH2n+2 + H2 → 2Cn72Hn+2 (44)
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Otherwise, cycloalkane or alkane is formed:
CnH2n+2 → 2CnZ2Hn (45)
The alternative could be in the process of coking, i.e., hydrogen saturation due to carbon withdrawal
5 CnH2n+2 + 2/m CmHm → Cn/2Hn+2 + 2C (46)
This process, however, is characteristic of high-temperature cracking.
When, during heterogenization, the processed medium is infused with low- molecular hydrocarbon and/or water, condensation of hydrocarbons or water vapor conversion can occur, providing a source of hydrogen:
10 nCH4 → CnH2n+2 + (n-l)H2 (47)
CH4 + 2H2O → CO2 + 4H2
As shown above, this reaction represents the transformation, providing a hydrogen supply, only in formal terms. In reality, the mechanism of interaction is more complicated. Due to the absence of the apparent limiting stages in the process, 15 accumulation of intermediates is absent as well, which substantiates that the system is in kinetic equilibrium.
Thus, reactions of hydrogen consumption (44) and hydrogen accumulation (47) should be considered jointly:
oπ CnH2n+2 + H2 → 2C172Hn+2 (48)
ZΌ nCH4 → CnH2n+2 + Cn-I)H2
(n-2) CnH2n+2 + nCH4 → 2(n-l)Cn/2Hn+2
In addition, one should remember that the cavitation process itself can alternately shift the equilibrium towards the formation of a gas phase or towards formation of end 25 product.
Even if a local increase of partial pressure is possible, doing so immediately causes acceleration of reaction (48). This can be confirmed as well by differential temperature-distillation curves, which in effect characterize distribution of fractions
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by boiling temperatures. After several processings of raw material in this manner, the distribution becomes Gaussian and is gradually reduced to a straight line, which characterizes a homologous series of hydrocarbons.
The above-described processes take place in parallel at all stages in the implementation of the inventive method, using apparatus as described above.
Depending on what composition is desired for end product, the invention makes it possible to manage the processes of cracking and molecular assembling, by infusing the required components in the initial processed medium, by altering flow velocity, by changing external wave impact intensity, by removing solid and gaseous products, and by adjusting the constructional design of the apparatus.
F. Further Processing - Refining, Stabilization, Fractionizing
The light, clear oil thus obtained is readily subjected to distillation by means of gravitation separation of lighter from heavier fractions. For this purpose, one can employ a well-known principle of vortex tubes and vortex cyclones. The difference is in using the flow accelerators for improving the efficiency of the separation process on molecular mass. The wave effect from an external source is applied for this purpose, as well for intensifying the process of gravitational fractionizing.
Within the apparatus designed in accordance with Figure 7, as well as Figures 16-20, at a speed of around 12,000 rotations per minute (RPM), one can separate the medium into layers, as a function of layer density. The speed can be increased or decreased, to contribute to an efficient implementation of the processes performed in the laminar-flow wave accelerators. Inertial forces, such as Coriolis and centrifugal forces, which direct particles to the periphery and upwards, depend on the angular velocity and the square of the radius and curvature of a cyclone or vortex tube, as well as on particle mass. Moreover, the separation process is influenced by the periodic wave pressure, i.e., by successive compression and expansion.
The wall of the vortex chamber or tube thus serves as the external wave reflector. Accordingly, one needs to select the form and size of the vortex chamber that are optimal for both whirls and waves.
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The product of separation, typically a mixture of benzene, ligroin, kerosene and diesel fuel fractions, is readily separated from the remaining heavy residue, which can include tars, condensed heteroatomic compounds, and other admixtures. That is, the distillate can be fractionated into motor-fuel components by means of high-speed rectification, when speeds can reach 200,000 to 240,000 RPM. This can be accomplished using, for example, a standard multi-chamber vortex turbulizer.
In a separation process performed with the use of metal powder, the post separation heavy residue contains a mixture of sulfur, insoluble asphaltenes, mechanical suspensions, and metal sulphides. The residue also can contain potentially valuable components, such as compounds of different metals found in oil, and condensed heteroatomic compounds. In addition, the heavy residue can contain a solid component, such as tar substances. The solid component of the heavy residue makes possible a viscous flow of the residue in the course of gravitational separation. Thus, the solid residue can be similar to bitumen with sulfur content of 30-50%. The unrefined, unsaturated motor-fuel fractions, which are part of the distillate mixture obtained from this stage, can be stabilized by hydrogenation, which results in hydration of unsaturated molecules and hydrorefining. This improves hydrocarbon quality and decreases the medium's congelation temperature. According to the present invention, a source of hydrogen for these purposes is natural gas from reactions of isomerization and aromatization (ring formation). In addition to hydrogenation, the unsaturated hydrocarbons in the fuel product can be isomerized and/or cyclized to produce, among others, aromatic hydrocarbons, such as toluene and xylene produced in the course of the inventive methodology.
Refining of the motor fuels includes a boosting of the gasoline octane number and the diesel fuel cetane number, which results, respectively, in a lowering of the temperature of fuel turbidity and congelation to about -4O0C or lower, and in reducing or even eliminating of sulfur content, without employing additives or other agents. The processes of isomerization and cyclization, boost the gasoline octane number by yielding aromatic hydrocarbons, particularly toluene and xylene. By the same token, these processes increase the content of cetane hydrocarbons by forming such
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molecules, thereby boosting the diesel fuel cetane number. Moreover, the hydrocarbons that appear during isomerization lower the turbidity and congelation temperatures.
The aforementioned methods for processing and treating hydrocarbon raw employ turbulent-wave medium treatment in depression zones (up to vacuum) and compression zones, utilizing both centrifugal and centripetal forces. The centrifugal forces are created using the device illustrated in Figures 3 and 4. The centripetal forces are created using the devices illustrated in Figures 3-10. The practical realization of both centrifugal and centripetal forces is accomplished in a unit presented as a block-diagram in Figure 11. Separate components of the unit are depicted in Figures 12-41.
The unit organizes the centrifugal acceleration of flows and the zone of underpressure, down to zero pressure, where low-temperature boiling of the medium and forming of cavitation bubbles take place. At that point, the process proceeds in the manner described above, in accordance with changes in dynamic pressure P in the medium, as presented in Figure 3 C and Figure 5.
The unit also organizes centripetal flow acceleration and vortex swirls with internal- vacuum cavities, inside of which low-temperature boiling and medium volume condensation take place. The nozzle accelerators of the unit have jet ejectors, located along the rims of the operating elements, which create the dynamic shock waves. The shock waves pull out the vortex cones from the developed turbulent flow zone and move them into the zones of the medium laminar flows. At the moment of a dynamic shock, the medium experiences instant deceleration; hence, it is effected by maximal pressure, damping, and maximal heat. The medium volume condensation leads to formation of low-boiling fractions, i. e. , to medium enrichment with light fractions. Overall, the inventive process proceeds as described above and as represented in Figures 6-10.
G. Other areas of the in vention application
Principles of flow organization for raw materials and additional components "of the above methods for processing and treatment of raw materials and namely, a wave
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treatment on a medium, cavitation, centripetal and centrifugal acceleration of the flows, allow one to utilize the present invention for other applications. Such applications include effective separation of solid particles and their removal from a technological process, purification of water from hydrocarbons, and concentrating of medium components.
III. Illustrative Implementation Of Inventive Approach
Set forth in Figure 11 are general schemes of applying the inventive approach in the field, for preconditioning of oil for transportation and for processing at refineries, respectively. A system of reactive vessels and equipment, as listed in tables 9 and 10, was employed to convert a base oil into "homogenizate," the product obtained when the inventive approach is implemented through the stage of deep homogenization (cracking).
AU processes described above are illustrated by Figures 1-11, where the inventive approach is applied for improving the oil quality by means of: decreasing its viscosity (better fluidity), lowering its congelation temperature, increasing its barrelization rate, and removing gases, mechanical impurities etc. The inventive methodology also can be applied at a crude oil-preconditioning shop at a refinery. The output of light fractions at the level of atmospheric-vacuum towers will increase, as has been noted, and the residue should be returned for recycling, thereby eliminating the costly- process of thermo-catalytic cracking of the tailings (heavy residues) of atmospheric- vacuum towers.
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Table 9 - Classification of technological processes
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Table 10 - List of equipment for inventive process
IV. Separate elements of the apparatus for implementation of the inventive approach A. Hydrodynamic radiator of acoustic oscillations
By its design, a hydrodynamic radiator of the invention (Fig. 12), for producing acoustic oscillations, can have improved operational efficiency. As elaborated below, the hydrodynamic radiator comprises a hollow cylinder sealed at each end by a spherical cover. These covers act as wave reflector, forming together with the hollow cylinder a closed resonator volume. Each of the covers has a pipe on it. Each of the pipes is placed coaxially to its respective cover, i.e., the axis of the pipe is the same as the axis of the cover. One of the pipes, the initial medium supply pipe, has a narrowing orifice mounted on it. This narrowing orifice comprises a focusing piece ("confuser) and a rectangular slit nozzle, placed inside the closed resonator volume.
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Figures 12-15 illustrate the hydrodynamic radiator. In particular, Figure 12 represents the longitudinal section of this unit, Figure 13 illustrates cantilever (console) attachment of the plate; Figure 14 demonstrates a cross section of the nozzle with the slit flow acceleration, and Figure 15 shows a cross section of the nozzle with the flow acceleration in grooves.
The inventive hydrodynamic radiator of oscillations (Fig. 12) contains a hollow cylinder 1 sealed at both ends by spherical covers 2, and 3, which also are acoustic oscillation reflectors. Upon assembly, these components form a closed resonator volume 4. Covers 2 and 3 contain pipes 5 and 6, respectively. Pipe 5 serves for letting initial medium in, while pipe 6 serves for letting jet-disintegrated medium out. Each of the pipes is coaxial with its respective cover. Pipe 5, the initial medium inlet pipe, has a narrowing orifice 7 mounted on it. This orifice is comprised of a confuser 8 and a rectangular slit nozzle 9. Slit nozzle 9 has on its edge a plurality of cogs 10 for slicing the rectangular flow of the initial medium directly in the slit nozzle. Orifice 7 is within the closed resonator volume 4. Plate 11, with its sharpened edge 12 directed towards the incoming flow of the processed medium, is placed some adjustable distance away from the edge of nozzle 9. Plate 11 is coaxial to nozzle 9.
The hydrodynamic radiator of acoustic oscillations has two flow accelerators, one on the rectangular slit nozzle 9 and the other on the outlet pipe 6. Each of the flow accelerators is formed by two or more pipes or tubes, tightly fitted on each other. Annular collectors 13, 14 are placed on the narrowing orifice 7 and slit nozzle 9.
Following the collector 14, slit clearance 15 is placed in the immediate vicinity of the effective cross-section of the slit nozzle 9. The slit clearance allows for production of an accelerating medium flow, supplied from an external source (not shown in the drawing). The accelerating medium flow creates a depression, immediately after rectangular nozzle 9, when the accelerating flow section has the form of a narrow slot along the perimeter of nozzle 9. The accelerating flow can be produced only if the cross-section of accelerating flow has a thin slit shape, defined by the perimeter of nozzle 9.
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To increase the velocity of the jet-creating depression for the initial medium flow, its effective cross-section includes a plurality of grooves 17, made on the inner surface of the side wall 16 of the rectangular slit nozzle 9 (Fig. 15). Grooves 17 are machined into the thickness of the sidewall 16, such that they can match the flow profile as much as possible.
The depression is created by the accelerating initial medium supplied from an external source (not shown) through pipe 18, annular collector 13, reach-through holes 19 in the body, narrowing orifice 7, and annular collector 14, wherein the annular collector is positioned in the immediate vicinity from the edge of the slit nozzle 9. Grooves 17 extend along the entire width of the annular collector 14.
Accelerating medium outflow is carried out through the clearance 15 or grooves 17, depending on the version of effective section organized by the cover 20, which seals the edge of the narrowing orifice 7.
Pipe 6 for letting out jet-disintegrated (i.e., declusterized) medium contains a flow accelerator, comprising round tube segments 21 and 22, which are tightly fitted on each other. The inner tube 21 has a plurality of grooves starting one tube end and extending along the combined width of annular collector 23 and inlet pipe 27 tangential to the tube segments 24 and 21. The outlet pipe 6 has a step in the zone of its attachment to the spherical cover 3. The outlet pipe 6 comprises tube segments 24 and 21 tightly fit on each other. The edge of the inner tube 24 contains a plurality of cogs 25. The outer surface of the inner tube 24 has longitudinal grooves 26. The inner tube 24 is partially inserted inside the resonator volume 4, thus, forming with the spherical cover 3 an annular confuser. The bottleneck of the confuser is an effective cross section formed by the longitudinal grooves 26 formed on the outer surface of the inner tube 24. Pressure provided in the pipes 18 and 27 has to be higher than the initial medium pressure and declusterized medium pressure in the resonator volume 4. The inner tube 24 can have a diffuser profile, i.e., a diffuser-like longitudinal section.
Fixation of the plate 11 is performed by use of cantilever/console ledges/spans 28 and 29 (Fig. 13), placed diametrically opposite to each other on the body of the
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narrowing orifice 7. The cantilever ledges 28 and 29 are fixed using screws or bolt joints, which can be used for adjusting the position of the sharpened edge 12 relative to the end of narrowing orifice 7.
The hydrodynamic radiator of acoustic oscillations functions the following way. The initial medium, for example, oil or boiler oil, enters the resonator volume 4, formed by the hollow cylinder 1 and the covers 2 and 3, through the inlet pipe 5. This medium, a subject of jet disintegration, enters to the narrowing orifice 7, where subsequently it goes through confuser 8 and rectangular slit nozzle 9, from which it flows out. Since the slit nozzle 9 has a plurality of cogs 10 over the perimeter of its edge profile, the initial medium flow is split and separated already in nozzle 9. The initial medium flow is further split in the vertical direction by plate 11, which has its sharpened edge 12 directed towards the flow. Plate 11 starts oscillating intensely with a high frequency, thereby jet-disintegrating the incoming initial medium flow, already split and separated by the cogs of nozzle 9. The nozzle 9 is provided with the annular collectors 13 and 14 and the slit clearance 15 of the same rectangular shape as the perimeter of the side wall 16 of the slit nozzle. Therefore, in the version of the hydrodynamic radiator where slit 15 is placed after the annular collectors 13 and 14, the high- velocity accelerating flow of the medium from an external source produces a depression immediately after the edge of nozzle 9, thereby increasing a pressure drop in the nozzle. This pressure drop causes an increase in the velocity of the initial medium flow at the exit from the nozzle 9.
In the version of the hydrodynamic radiator, where the accelerating flow of the medium proceeds through the grooves 17, the jet velocity grows as the jet streams through the grooves 17, embedded in the thickness of side wall 16. In this version, the accelerating flow is discrete and is in the immediate proximity of the initial medium flow that is undergoing acceleration, hi both versions, the accelerating flow of the medium captures the initial medium flow being accelerated.
The above effects lead to a composite velocity growth of two flows, surging on plate 11 and, more precisely, on its sharpened edge 12. These effects also intensify
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the jet disintegration impact on initial medium compounds. An increase in the outflow velocity from nozzle 9 of the aggregate flow of the processed medium causes an increase in the medium volume in the resonator 4.
The accelerating medium from an external source enters through the inlet pipe 18, the annular collector 13, and reach-through holes 19 on the body of orifice 7. From there the accelerating medium goes to the annular collector 14, formed by the cover 20 sealing the edge of the nozzle 9 to the slit clearance 15, or through the grooves 17, depending on the version of the radiator.
The pressure accumulated in the resonator volume 4 needs a release through pipe 6. This release is effected in two steps.
In the first step, the pressure is released by creating a depression in the accelerating system (flow accelerator), formed by tube segments 21 and 24, through the groove 26 on the tube 24. The diffuser profile (longitudinal section) of the inner tube 24 results in an increase in the efficiency of the flow splitting by cogs 25 and in a decrease in hydraulic resistance of the treated medium flow running through the outlet pipe 6. The accelerating medium for this step is supplied from an external source through the circular collector 23 and the pipe 27.
In the second step, when decompression already is created by the external accelerating medium, the pressure release is carried using the internal pressure potential in the resonator volume 4. The pressure release is achieved by the inner tube 24 which has cogs 25 and longitudinal grooves 26. Due to its partial cantilever-like insertion into the volume of the resonator 4, tube 24 captures the flow in a manner similar to confuser, and the captured flow creates additional decompression at the edge of the pipe 6. This allows producing such an acceleration that the flow of the processed medium outflowing from the nozzle 9 will rush immediately into the outlet pipe 6. Meanwhile, the resonator volume 4 acts as an effective resonator, reflecting waves on the boundary metal- walls-liquid, and an adjustment of position of the plate 11 with respect to the edge of the nozzle 9 is performed with screws/bolts 28 and 29.
The efficiency of the inventive hydrodynamic radiator of acoustic oscillations can be characterized by:
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(1) an increased efficiency of jet-disintegrated processing of the initial medium, by virtue of using an accelerator capturing the flow by jets at the outlet of the nozzle 9; and/or
(2) an increased resonance capability for the resonator body 4, which is implemented by ensuring flow movement without a hold-up or delay in the resonator volume 4.
These factors increase the efficiency and enhance the quality of the initial medium jet- disintegrating processing.
B. Vortex Tube One of the most important aspects of a cavitational reactor of the present invention is the organization of the medium flow according to the "tornado" principle in the vortex tube, which is one of the constituent components of the reactor.
The inventive vortex tube (Fig. 16) contains a disc body 1 with pipes for letting in initial medium (pipe 2), for letting out heated medium (pipe 3), and cooled down medium (pipe 4). The vortex tube has an annular cartridge 5 placed inside the disc body 1. Around the perimeter of the cartridge 5, a plurality of windows 6 are placed in steps. The axes of the windows 6 are directed tangentially to the outer surface of the cartridge 5. Multinozzle orifices 7 are mounted coaxially in the windows 6. The cartridge 5 and the peripheral zone of the disc body 1 form an annular collector 8. Limited by the cartridge 5, the central part of the disc body 1 has a variable cross section profile comprising a "confuser" 9, a bottleneck 10 and a diffuser 11, all three of which have annular cross sections. The bottleneck 10 and the diffuser 11 have around their perimeters longitudinal grooves 12 placed with a certain step with respect to each other. The longitudinal grooves 12 are tangential to the perimeters of the pipes 3 and 4 for letting out the heated and cooled down mediums respectively.
Heated medium outlet pipe 3 contains a regulating needle 13 and a plurality of variable cross section channels 14. The cross section of the multinozzle orifice 7 comprises a plurality of individual nozzles 15, as illustrated in Figure 17. A standard wrench knob head 16, 17, regulating positions of the needle 13 and the channels 14, is
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protected from an external impact by a sealed cover 18. The multinozzle orifice 7 comprising a plurality of individual nozzles 15 further comprises longitudinal grooves 19 along the perimeter of the outer surface of the mouthpiece as illustrated on Figure 17. These longitudinal grooves increase the intensity of the medium processing in each of the multinozzle orifices 7.
Increased output and high efficiency of the vortex tube are ensured by its design. Particularly, the vortex tube contains inside the body a guiding accelerating channel. This accelerating channel has a nozzle-like inlet and a variable cross-section profile surface, which turns into a cylindrical chamber with diffusers and a needle regulating medium flow. This needle is itself a channel of variable cross section.
The vortex tube has an annular cartridge inside the disc body. Along the perimeter of the cartridge, a plurality of windows are placed with a certain step with respect to each other. The axes of the windows are directed tangentially to the outer surface of the cartridge. The multinozzle orifices, each containing a plurality of individual nozzles, are mounted on the windows. The cartridge and the body of the vortex tube in the peripheral zone form an annular collector. In the central zone, the cartridge and the body form a profile of a variable cross section formed by a confuser, a bottleneck and a diffuser, all three of which have a shape of a ring. The diffuser and the bottleneck have longitudinal grooves around their perimeters. The longitudinal grooves are placed tangentially with respect to the perimeters of the pipes for letting out the heated and cooled down mediums (the heated medium pipe and cooled medium pipe, respectively). The heated medium pipe contains a regulating needle and windows of adjustable cross section for medium transport.
The disc body of the vortex tube can have two or more pipes for letting medium(s) in. On one hand, multiple inlet pipes provide conditions for increasing the output of the tube and, on the other hand, they allow supplying mediums of different composition in the tube. The multinozzle orifices can be mounted in the cartridge on two levels. The multilevel arrangement allows increasing of the intensity of the hydrodynamic processing of the medium by the jet, i.e., it increases the medium processing rate.
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In some embodiments, the collector of the vortex tube can have two chambers, with each chamber having its own tangentially placed inlet pipes, i.e., pipes for medium supply. The multi-chamber arrangement allows one to introduce and process mediums of different compositions. The double chamber design can be implemented by installing in the collector a hermetically sealing wall that defines the individual chambers.
The outer surface of each of the cylindrical multinozzle orifices can have longitudinal grooves, placed around the perimeter of the outer surface with a certain step with respect to each other and directed along the axis of the individual mouthpiece. This arrangement allows one to increase the quantity of individual nozzles for each of the multinozzle orifice.
Figures 16-20 further illustrate the vortex tube and its separate elements. Particularly, Fig. 17 represents a longitudinal section of the multi-nozzle orifice 7 which contains, in addition to individual nozzles 15, individual nozzles 19. Figure 18 is a longitudinal cross-section of two level (levels 20 and 21) placement of multinozzle orifices 7, which allows one to increase the output capacity of the initial medium spinneret hydrodynamic treatment without changing the dimension of the vortex tube body 1. Figure 19 shows two-collector design of the disc body containing two inlet pipes 2. The two-collector design allows one to increase the volume of the medium supplied to collector 8, to implement vortex swirling of the medium in the collector, and to supply several distinct mediums into a single body 1. Figure 20 represents a double chamber design of the collector with cross-sections of individual inlet pipes. For this purpose, a separating wall 22 is placed inside collector 8. The double chamber design allows supplying two different mediums for processing, for instance, hydrocarbons and other heterogenizing mediums or hydrogen source.
Figure 21 is a longitudinal cross-section of the vortex tube with a conical nozzle. In this embodiment, the vortex tube acts as a vortex jet pump/stirrer. Figure 22 shows a longitudinal cross-section of the vortex tube in the embodiment, wherein the vortex tube acts as a vacuum pump. Figure 23 represents a longitudinal cross- section of the vortex tube in the embodiment utilizing an external radiator.
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The vortex tube of the present invention functions in the following manner. The initial medium enters the disc body 1 of the vortex tube through inlet pipe 2. The processed medium is removed from the disc body through outlet pipes 3 (heated medium) and 4 (cooled down medium). After entering the disc body 1, the medium goes into the annular zone up to the cartridge 5. The cartridge 5 has a plurality of windows 6 with multinozzle orifices 7. Jet/spinneret streaming of the flow leaving the annular collector 8 takes place in the multinozzle orifices 7. The medium formed in the jet streaming undergoes a jet-fragmentation, due to high velocities of the jet streaming processes.
The jet-fragmented medium proceeds in two flows. The first flow goes through the confuser 9, the bottleneck 10 and in the diffuser 11. The first flow passes through the circular bottleneck 10 with a high angular velocity in a vortex-like way and enters into the asymmetric diffuser 11 where the flow has both high angular and linear velocities.
The second flow is formed in the longitudinal grooves 12. This flow runs tangentially with respect to pipes 3 and 4 and, therefore, creates a tornado like flow with a high vacuum in the center. Due to a high pressure of the medium in the confuser and a deep vacuum in the vortex tube's center, the first and the second flows interact with each other at very high disintegration velocities, thereby weakening the linkage between each other. This weakening facilitates thermo-density separation of the flow into a flow of the heated medium and a flow of the cooled down medium. The heavier flow of the cooled down medium runs down, while the lighter flow of the heated medium goes up.
The vortex process is facilitated by a process of tangential swirling of the medium flow in the annular confuser 9 by a virtue of creating by the multinozzle orifices 7 a tangential swirling flow along the surface of the cartridge 5. Due to its high flow rate and due to a decompression in center of the disc body 1, this tangential swirling flow increases a lifetime of the vortex flow in the disc body 1.
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The adjustment of medium flow movement parameters, such as medium consumption and flow rate, can be carried out by the regulating needle 13 and the variable cross section channels 14. The medium consumption can also adjusted by changing the number of individual nozzles 15 on the multinozzle orifice 7. A position of the regulating needle 13 and cross section of the channels 14 can be adjusted by adjusting the positions of knobs 16 and 17 respectively. To access knobs 16 and 17, one has to take off a protective sealing cover 18.
Jet/spinneret outflow process through the multinozzle orifices 7 can be increased by running the medium through the longitudinal grooves 19 placed along the outer surface of the individual multinozzle orifice in some embodiments of the invention.
To increase medium consumption in the collector 8, the disc body 1 can be provided with two or more inlet pipes 2. One can also use multiple inlet pipes 2 when it is necessary to introduce two or more different mediums inside the collector 8. The introduction of two different mediums, such as hydrocarbons and/or other heterogenizing mediums and/or hydrogen sources, which can be necessary for producing hydrocarbon fuels, also can be carried out by using a double chamber collector, comprising chambers 20 and 21 and a separating wall 22.
The vortex tube of the invention allows for increasing the output and reliability of the inventive apparatus to industrial device level. The output of the inventive apparatus is facilitated by the design of the multinozzle orifices 7 and by the potential for increasing processing intensity by the longitudinal grooves 19 on the outer surface of each of the orifices 7. Additionally, the vortex tube provides an option for placing two or more pipes 2 for introducing initial medium(s) on the vortex tube body 1. The vortex tube of the invention also allows for increasing the processing rate and output without changing the physical dimensions of the apparatus, which is accomplished using the multilevel design for placing the multinozzle orifices 7.
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The vortex tube of the invention has a high reliability of operation, as it does not include any rotating parts.
Utilization of the vortex tube in the cavitation-wave reactor of the present invention allows one not only to process of two and more mediums simultaneously, but also to produce from the mediums new hydrocarbon structures and other classes of chemical compounds.
A high pressure in the collector increases the time that medium spends in the vortex tube. The cross section profile of the disc body 1 together with the longitudinal grooves 12 in the bottleneck 10 and in the diffuser 11 produce a stable vacuum in the central part of the vortex tube. The high pressure in the collector 8 and a vacuum in the central part of the vortex tube, combined with the long time the the flow spends in the "tornado" mode, substantially increase the intensity of the gravitational and thermal separations.
C. Jet-Mechanical Vortex Tube Another embodiment of the present invention relates to the j et-mechanical vortex tube (Fig. 24) for deep homogenization. The jet-mechanical vortex tube includes two rotors 1 and 2, rotating in opposing directions. Rotors 1 and 2 are rigidly attached to baskets 3 and 4, respectively. Baskets 3 and 4 have annular edges 5 and 7 (basket 3) and 6 (basket 4). Edges 5, 6, and 7 form a slicing instrument, comprising a plurality of slit openings 8 that are located, on the edges 5, 6 and 7, with a certain step with respect to each other.
The baskets 3 and 4 are placed inside a common body 9. Openings 8 form channels for a liquid flow. The rest of the side edges 5, 6 and 7 form a plurality of cogs 10 that slice the liquid flow. In the basket 3, a slicing side edge has two levels 5 and 7 separated by an annular recess 11, whereto the annular edge 6 of the opposite basket 4 is embedded. A certain clearance is provided between the edge 6 and the edges 5 and 7. This clearance makes possible a free rotation the baskets 3 and 4 in the opposite directions, which in turn allows using ordinary electric motors with rotating frequencies of 50-60 Hz for producing high wave frequencies.
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The wave frequency also depends on the number of the openings 8 and on the number of the cogs on each of the baskets 3 and 4. Accordingly, the openings can alternate with a high frequency necessary for a structural decomposition of liquid media molecular structures. The j et-mechanical vortex tube performs a j et-mechanical structural decomposition of the medium in two stages: first, between slicing edges 5 and 6 and then between the slicing edges 6 and 7. The initial medium is supplied through inlet pipe 12, while the processed medium is removed through outlet pipe 13.
The openings 8 can have a variety of forms. For example, the openings can be round, square, rectangular, etc. holes. The rotation of the rotors 1 and 2 is provided by electric motors 14 and 15 which are connected to the baskets 3 and 4 via clutch couplings 16 and 17. The basket 3 is rigidly fixed on the rotor 1 using ribs 18 separated from each other by side-to-side windows 19.
The jet-mechanical vortex tub operates as follows. Rotation of rotors 1 and 2 in the opposite directions translates into rotation of the baskets 3 and 4. The initial medium located in the baskets 3 and 4 is pushed by centrifugal forces from the center to the peripheral zone where the slicing edges 5, 6 and 7 are located. Under the influence of centrifugal forces, medium streams go through openings 8 first on the level 5-6 and then on the level 6-7. All these processes occur inside the body 9. When the treated medium enters a peripheral circular zone of the body 9, the streams passing through the openings 8 collide with the cogs 10 which causes dynamical decomposition of liquid/fluidic media. The initial medium for processing can be any hydrocarbon fuel or other appropriate medium.
On the first level 5-6, the liquid is decomposed in the recess 11 by the slicing edge 6 of the basket 4. The initial medium for processing is introduced inside the body 9 through inlet pipe 12 tangentially in the center of the basket 3, the processed medium is removed through tangential outlet pipe 13.
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D. Jet Device
The present invention provides two versions of the jet device: with collector (Fig. 25) and without collector (Fig. 26). One can use the "collector-less" version of the jet device for producing external wave treatment on the medium. The distinctive feature of the "collector-equipped" version is an annular confuser/cartridge in the discs of the s wirier. In its center, the confuser/cartridge becomes an annular nozzle. The rest of "collector-equipped" version design is the same as the "collector-less" version.
The jet collector-less device (Fig. 25) includes a body 1 and a main nozzle 2. The main nozzle comprises a confuser 3, a diffuser 4, a bottleneck 5 placed between them and a mixing chamber 6 for mixing an active medium and a passive medium. The active medium such as a vaporous medium comprising light hydrocarbon fractions enters the mixing chamber flowing out of the nozzle 2, while the passive medium enters the mixing chamber from flow swirlers 7. The active vaporous medium is supplied in the body 1 of the apparatus through tangential inlet pipe 8, while the passive liquid medium is supplied through tangential inlet pipes 9 and 10.
The jet device contains an additional nozzle 11 placed coaxially and in series with the main nozzle 2. The disc swirlers 7 end with annular nozzles 12, 13 and 14. Nozzle 12 for outflow of the vaporous/active medium is placed at the inlet of the confuser 3 of the main nozzle 2. Nozzle 13 for removal of the liquid medium supplied to the s wirier 7 from pipe 9 is located at the outlet of the diffuser 4 of the main nozzle 2. Nozzle 14 for vortex removal of the passive/liquid medium entering the swirler 7 from tangential inlet pipe 10 is placed at a bottleneck 15 of the additional nozzle 11. A conical annular insert 16 is placed inside an outlet diffuser of the additional nozzle 11. A plurality of side to side longitudinal grooves 17 are provided along the outer surface of the insert 16.
Inside the mixing chamber 6 of the main nozzle 2, a regulating hollow needle 18 having a plurality of windows 19 on its outer surface is placed coaxially with the body 1. One side of the chamber 6 has a head of the needle 18, with a standard
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wrench knob and a removable cover 20, while the other side has windows 19 and a multinozzle orifice 21 comprising a set of individual nozzles 22.
The jet device functions in the following manner. The active and passive mediums enter the body 1. Particularly, the vaporous active medium comprising light hydrocarbon fractions enters through the main nozzle 2 into the confuser 3, then passes through the bottleneck 5 and exits through diffuser 4. Then, the vaporous medium enters the mixing chamber 6.
The vaporous active medium is supplied to the disc swirler 7 through tangential inlet pipe 8 from an external source (not shown on the drawings). Simultaneously, the liquid/passive medium is supplied to swirlers 7 via tangential inlet pipes 9 and 10.
The interaction of the liquid medium whirled flow with a high linear velocity flow of vaporous active medium takes place in the discs of the swirlers 7. Mixing of the two flows occurs when they flow out from their respective nozzles 12 (active medium) and 13 and 14 (passive medium). The liquid medium is processed in the nozzles 13 and 14 with the vaporous flow flowing out from the nozzle 12. The processed flow is removed after its treatment in the bottleneck 15 and passing, on one side, through the conical circular insert 16 and, on the other side, through the longitudinal grooves 17 provided on the outer surface of the insert 16 which is a diffuser of the j et apparatus.
The nozzle 2 in the mixing chamber 6 has a cross section which can be varied by adjusting the position of the hollow needle 18. Even when the bottleneck 5 of the nozzle 2 is completely blocked by the needle 18, the vaporous medium can still get from the mixing chamber 6 through the windows 19 to the multinozzle mouthpiece 21 comprising a set of individual nozzles 22. On the opposite side, the needle 18 is sealed with the cover 20. Inside the cover 20, the needle 18 is provided with a head knob that is compatible with a standard wrench.
Figure 26 depicts a collector-equipped version of the jet device. As mentioned above, the distinct feature of the collector equipped version is a built-in annular cartridge 23. On the perimeter of the cartridge, windows 24 are placed with a step
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relative to each other. The axes of windows 24 are directed tangentially to the lateral surface of the cartridge 23. Multinozzle orifices 25 are mounted on the windows 24. Each of the orifices 25 comprises a set of individual nozzles 26. In the peripheral part of the swirler 7, cartridge 23 forms annular collector 27. Active and passive mediums are supplied to collector 27 via tangential inlet pipes 8 (active medium) and 9 and 10 (passive medium).
The collector equipped version (Fig. 26) of the jet device, operate in the following way. Active and passive mediums are supplied to collector 27 via tangential inlet pipes 8 (active medium) and 9 and 10 (passive medium). From collector 27, the respective medium enters swirler 7 through the nozzles 26 of the multinozzle orifice 25. The outflow of the vaporous medium from the nozzles proceeds with a supersonic velocity and is accompanied by compression shock, which produces sound/acoustic waves. Accordingly, individual nozzles 26 of the multinozzle orifice 25 are designed in the form of supersonic nozzles. The further operation of the unit is similar to the work of the collector-less jet device (Fig. 25). The collector-equipped version of the jet device design allows performing additional mechanochemical treatment (cracking) in a cavitational wave interaction mode with formation compression and decompression shocks inside the body 1.
In both versions of the jet device, the annular nozzle in each of the swirler s can have, for example, a plurality of helically placed ribs to whirl the jet stream.
E. Flow accelerator
Figures 27-36 illustrate longitudinal sections of the different designs of inventive flow accelerators.
Figure 27 relates the longitudinal section of a single chamber flow accelerator with a single multinozzle orifice. This flow accelerator comprises an inner pipe segment 1, an outer pipe segment 2, an inlet socket 3 for a medium to be accelerated and an outlet socket 4 for an accelerated medium. Chamber 6 is placed coaxially to the pipe segments 1 and 2 with a clearance 5. The chamber 6 has an inlet pipe 7 for an accelerating medium. In the zone of tight fitting of pipes 1 and 2 (conjugation zone), longitudinal grooves 8 are provided. The longitudinal grooves 8 are connected
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with cannelure (annular step) 9. The outer pipe 2 has a annular facet 10 on its end placed inside the chamber 6. The annular facet 10 serves as an annular collector for medium introduction inside the longitudinal grooves 8. The step 9 and the annular facet 10 are connected to the longitudinal grooves 8 that form as a whole a multinozzle annular orifice 11, which produces a outflow front of streams active in a near- wall layer of the outer pipe 2. The multinozzle orifice 11 is located in a zone of step-like expansion 12. This zone is responsible for producing inside the outer pipe segment 2 a mobile channel formed by a high velocity layer, so that the flow of a passive medium, i.e., the medium to be accelerated, slides through this mobile channel. Step-like expansion 12 acts as an inverted valve that lets the flow run in the straight-forward direction.
Figure 28 shows a longitudinal section of a single chamber flow accelerator with two annular multinozzle orifice. This flow accelerator comprises three tube sections: internal 1, intermediate 13 and external 2, and two annular multinozzle orifices 11.
Figure 29 presents a longitudinal section of a single chamber flow accelerator with two independent sealed chambers 6 formed by the wall 14. Each chamber has its individual inlet socket for medium supply. This flow accelerator modification can serve as a regulating feeder for individual mediums and/or compounds, each supplied from its own separate source. This flow accelerator can accelerates and regulate the medium flow.
Figure 30 shows a longitudinal section of a flow accelerator subunit, which has an outer pipe segment as a confuser focusing the outgoing flow of the medium
Figure 31 represents a longitudinal section of the flow accelerator subunit, which has the annular multinozzle orifice 11 with a confuser profile. This confuser focuses the accelerated flow on the axis of the accelerator.
Figure 32 represents the longitudinal section of the flow accelerator subunit, which has longitudinal grooves 8 made, for example, oblique relative to the accelerator axis. This feature allows swirling accelerated flow in a helical fashion.
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Figure 33 shows a threaded joint in the area of longitudinal grooves of multinozzle orifice.
Figure 34 represents a cross section, and Fig. 35 represents a longitudinal section of the flow accelerator with a tangential inlet socket. The latter creates swirling of the active medium flow in the annular chamber 6, prior to the active medium outflow from the multinozzle orifice 12.
Figure 36 represents a longitudinal section of the flow accelerator having a visible clearance formed by sliding orifices in the inner 1 and outer 2 tubes. This clearance compensates for temperature expansions of the pipeline. Figures 37 A, B, C, D schematically show longitudinal sections of different options of flow accelerator inclusion in the trunk pipeline system (technological chain). The flow accelerators can be included in the pipeline system not only for the trunk main medium flow acceleration, but also for simultaneous release of overpressure in the trunk pipeline system, as well as for dosing mediums of different chemical composition and for flow acceleration in the main pipeline. More specifically, Fig. 37 A represents a flow accelerator inclusion in the technological chain using a single pump; Fig. 37B represents a flow accelerator inclusion in the technological chain using the second pump separate from the first pump; Fig. 37C represents an inclusion in the technological chain of the single chamber flow accelerator with two multinozzle orifices; and Fig. 37D represents an inclusion in the technological chain of the double chamber flow accelerator with two multinozzle orifices.
F. Embodiments of in ventive apparatus that include components related to end-product processing The invention also comprehends apparatus versions, illustrated in Figs. 38-41, that incorporate an external energy source . For example, the variant of Fig. 38 has an external radiation source 7 in the form of (i) an induction coil or (ii) an electric engine stator, cooled by water or air, and the rotor. The apparatus of Fig. 38 contains three parts:
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- The first part of the apparatus, the vaporizing section 1, is formed by a vortex evaporator-steam generator 4 with a adjoining area 1. The vortex evaporator-steam generator is represented by the vortex tube described above.
- The second part of the apparatus, the condensing section 2, is formed by a cooler 5 of the increased cooling capacity. The cooler 5 provides a double-sided cooling for the vaporous flow in annular openings/slits 6, through cooling water pipes connected to the cooler. Needle 11 contains longitudinal grooves 12. Needle 11 is fixed to the cover 14 on the condensing section edge by the bar with screwed connection 13. Outlet pipe 15, for removing gases and creating vacuum inside the column, also is located in the cover 14.
- The third part of the apparatus, the activation section 3, comprises a transfer body containing an external wave radiation source 7, rotor 8, nozzle 9 and an outlet pipe 22 for liquid fractions.
Figure 39 exemplifies another practical implementation of this invention. More specifically, Fig. 39 shows a cross-section of the apparatus with a stirrer. This version of the apparatus, while including the above-described components, has its own characteristic features. Specifically,
- The first part of the apparatus, the vaporizing section 1, now is formed by a vortex evaporator-steam generator 4, which is a stirrer. The stirrer includes multinozzle orifice 19, which comprises individual nozzles 18 and which is fixed on the cover 17.
- The second part of the apparatus, the condensing section 2, is formed by a cooler 5 of the increased cooling capacity. The cooler 5 provides a double-sided cooling of the vaporous flow in annular openings/slits 6, through cooling water pipes connected to the cooler. Needle 11 contains longitudinal grooves 12. Needle 11 is fixed to the cover 14 on the condensing section edge by the bar with screwed connection 13. Outlet pipe 15, for removing gases and creating vacuum inside the column, also is located in the cover 14.
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- The third part of the apparatus is represented by the activation section 3, which comprises a transfer body that contains nozzle 9 and an outlet pipe 22 for liquid fractions.
Figures 40 and 41 present versions of the activation section, with an external wave radiation source, created by the block 20, installed inside the apparatus (Figure 40), or by a magnetostrictor with membrane 21 (Figure 41), located in the first part of the apparatus formed by the vortex evaporator-steam generator 4. The second and third parts are similar to those shown in Fig. 39.
V. Advantages of the Proposed Technology The inventive approach for oil processing concentrates the latest scientific and technological advances in the field of petrochemical processing. The essence of the inventive technology is performing the main stages of low-temperature cracking processes under high-energy cavitational/ acoustic wave treatment. The combination of low-temperature cracking and cavitational/ acoustic wave treatment apparatus, pursuant to the present invention, allows for processing of raw materials differing in properties and composition, and for obtaining a variety of final products as a function of demand. The final product output can depend on the raw material type, on additives/inclusions used, and on particular requirements for final product quality.
The approach of the present invention significantly exceeds known oil- refining/processing technologies in energy saving and in potential for managing raw material physicochemical and chemical transformations. Moreover, the inventive technology allows one to maximize yield of distillate fractions, by adjusting technological parameters, such as the composition of additives/inclusions and the energy of cavitational acoustic wave treatment on the heterophasic process in the reactor apparatus.
In the processing of oil and other petroleum products, such as boiler oil, one typically regards as optimal the process conditions that result in a yield of the distillate fractions that reaches 95%. Studies performed on various raw types by the inventors demonstrate that distillate products produced with the inventive technology are close in physicochemical properties to commercial products. The inventive
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technology also allows for production of heating oils or bunker fuels. Depending on the particular process running mode, one can achieve a different assortment of output products, with controllable quality. For the inventive technology, as the optimal product assortment and the respective balanced yield, one can regard distillate fractions that can meet gasoline, kerosene, or diesel distillate standards or heating oil (tar-bitumen residue up to 5-10% by mass) standards, for major physicochemical properties, and that have a distillate yield up to 50-95% by mass. The inventive technology can process oil or boiler oil, as a raw material, almost completely into light petroleum products. Thus, one can state that the inventive technology has 95- 96% yield of light petroleum products, and 5-10% yield of solid residue.
The invented technology, the efficiency of which has been tested and proved, provides solutions for a wide range of technological problems. In particular, the present invention unifies oil processing and petrochemistry into a single technological approach, based on a unified physicochemical foundation and apparatus design concept. By controlling polycondensation reactions of heavy hydrocarbons, one can minimize the heavy residue yield and maximize the distillate yield. In addition, the inventive technology does not use oxidizing and vacuum columns.
A particularly important innovation in instrumental design, according to the present invention, is a cavitational-acoustic wave treatment apparatus. The use of such apparatus significantly decreases both cracking temperature (from 500 to 80- HO0C) and process pressure (from 2.5 to 0.5 MPa). The five-fold pressure decrease in turn allows one to reduce the amount of metal used in the equipment. Moreover, due to the lowered cracking temperature and pressure, one can run the process with lower power input and suppress undesired processes occurring during cracking. For petroproduct processing, the inventive technology utilizes high energy methodology that maximizes the yield of distillate (light) fractions. In the cavitational-wave treatment process of the invention, one can achieve the yield of 96% for oil processing and converting boiler oil completely into motor fuels. The inventive combination of cracking process and cavitation-acoustic wave treatment
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apparatus allows for processing hydrocarbon raw of variable composition and properties, to obtain a range of commercial products.
Oil and petroleum residue refining processes often are based on phase transitions typical for oil dispersion systems. One can affect phase transition kinetics by introducing chemical compounds such as surface-active agents, additives, etc. and/or by applying physical fields such as thermal, cavitational, electromagnetic, etc. These effects change both the nuclei radius and the adsorption-solvation shell thickness of the complex structural unit of the oil dispersion system. Cavitational treatment accelerates oil diffusion in the paraffin cavities and intensifies the process of paraffin destruction. Acceleration of paraffin dissolution occurs due to intensification of oil mixing on the oil-paraffin boundary and due to the pressure pulses, which splash paraffin particles out. The viscosity of oil does not obey the laws of Newton, Poiseuille and Stokes, because long, disorderly placed molecules of paraffin and tars form some sort of flexible grid, within which the solution of liquid hydrocarbons is located. As a system, therefore, oil shows significant resistance to shift forces. Cavitation destroys continuous chains by breaking bonds between separate parts of molecules. Because these bonds are relatively weak, only a relatively insignificant acoustic wave impact is necessary to break them.
Cavitational-wave cracking of oil, according to the present invention, is a tool for fine tuning of the petrochemical production process. A distinctive feature of cavitational-wave cracking is an ability to adjust the activation degree of chemical reactions, by changing cavitation intensity and treating the medium with ultrasound.
A principal reason for acceleration of a cracking process of the invention is the initiation of homolytic and heterolytic decomposition of large molecules, during medium continuity violation and the collapse of cavitation bubbles. Temperature is an extremely important parameter for the cracking process. In conventional cracking, temperature activates the hydrocarbon chain breaking but also leads to carbonization of the significant part of oil, thus reducing the yield of light fractions. The inventive technology favorably differs from conventional technology in this aspect, since the former can ensure a high degree of oil conversion into light fractions of high
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aromaticity, without the use of an additional source of hydrogen. Infusing the reactive mixture with additional components allows one to make up for the hydrogen deficit in oil, thereby improving motor-fuel quality significantly.
Another advantage of the proposed technology is realized in the centrifugal fractioning of the final product, as described above. This substantially reduces the cost of producing commercial motor fuel fractions.
The following examples are provided only to illustrate the inventive approach, without limiting it, by relating the mode of cavitation- wave cracking and molecular assembly of hydrocarbons in the turbulent flow, and the hardware implementation of the process. ,
A. Oil from KARAZHANBAS FIELD, the Republic of Kazakhstan
In this example, the base oil has characteristics listed below.
- Density: 941.6 kg./M3
- Flow point: solid at +2O0C - Initial boiling point: +1670C;
Final boiling point of 18% of mass: +3000C.
The base oil contains mercaptans, sulfides, salts, and metals such as nickel and vanadium, among others. The oil is very heavy, viscous, resinous, and paraffinic, with a low yield of white fractions, which boil away at 30O0C. All fractions of distillation contain sulfurous impurities at levels exceeding the Maximum Permissible Content ("MPC"), set by the international standards. Accordingly, benzines, kerosenes, and diesel fuels produced with existing technology must be desulfurized. In conventional usage, moreover, there is an oil residue, which is refined into bitumen. By contrast, 90% of the product obtained via the inventive approach was comprised of white fractions, with the following parameters:
- Density: 850.3 kg./M3;
- Viscosity: 18 centistokes;
- Solidification point: -250C. The gases present were primarily hydrogen (48%) and methane (40%).
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In addition, gas-chromatographic analysis and fractional distillation confirmed the transformation of the base oil, itself of low- value, hardly transportable, and practically unsuitable for processing without liquefaction by preliminary heating and demetallization of highly resinous oil into a homogenizate comprised of paraffinic, isoparaffinic, and aromatic hydrocarbons. Pursuant to the present invention, the latter product is readily separated into benzene fraction (about 30%), with the octane value of 102, and diesel fraction (more than 60%).
According to other indicators of the gas-chromatographic analysis, the obtained product contained a considerably lower quantity of unsaturated hydrocarbons. Metals, sulfur components, and other chemical impurities were removed by the inventive approach, and the content of mercaptan sulfur likewise decreased a dozen fold, relative to the base oil. It is meant that mechanical impurities precipitate and stream down to special pockets in cyclones named collectors-entraps.
More specifically, the nature of the base oil from the Karazhanbas Field is evidenced in Table 1, which lists the results of an analysis conducted by the Saibolt Laboratory (Moscow), at the request of the "Munai Gas" Kazakh Research and Development Institute.
Table 1
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For comparison with Table 1 , Tables 2-5 provide data on the fractional composition of the oils and distillates manufactured pursuant to the present invention depending on multiplicity (cycles) of passing the processed raw through the unit.
Table 2. Refined Product from Karazhanbas Field Oil. Declusterization, one cycle
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Distillation of the product Temperature
Initial boiling point (IBP): 60°C
10% 230°C
50% 340°C
90% 500°C
Final boiling point (FBP) 550°C
Table 3. Oil refining product distillate from Karazhanbas Field. Homogenization, two cycles
Distillation: Temperature
IBP: 380C
10% 95°C
50% 25O0C
90% 3300C
FBP: 3700C
Table 4. Oil refining product distillate from Karazhanbas Field. Homogenization, three cycles.
Distillation: Temperature
IBP: 45°C
10% 1000C
50% 1950C
90% 26O0C
96% 28O0C
Table 5. Oil refining product distillate from Karazhanbas Field.
Homogenization, four cycles. Fractionating - separation of gasoline fractions
Distillation: Temperature:
IBP: 560C
50% 115°C
90% 156°C
FBP: 180°C
B. Oil from the Saigak Field, the Republic of Kazakhstan
In a second illustration of the present invention, the product was produced from oil of the Saigak Field. The base-oil parameters were as follows:
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Density: 847.7 kg./M3
Kinematic viscosity: 14.78 centistokes
Solidification point: -130C
Cloud point: -30C
Final boiling point of 50% of mass: higher than +36O0C.
By virtue of breaking up of longer-chain molecules, pursuant to the invention, the base oil was transformed into the product, in the form of very light oil, that was characterized as follows:
Density: 764.3 kg./M3
Viscosity: close to the viscosity of water
Cloud point: below -4O0C
Final boiling point of 90% of mass: 2540C.
Gas-chromatographic analysis and fractional distillation confirmed the transformation of a hard-to-process, high-tar oil into homogenizate of paraffmic and isoparaffinic hydrocarbons with a wide range of boiling points under the inventive approach. This homogenizate was easily separated into a straight-run petrol fraction (about 30%), with an octane number of 78.6, and a diesel fraction (more than 60%), with a cetane number 49.
According to other parameters revealed by the gas-chromatographic analysis, the content of mercaptan sulfur in the product had decreased several dozen fold, and the amount of unsaturated hydrocarbons also had decreased significantly.
Table 6 sets forth the fractional composition Qf oil from the Saigak Field. Table 6. Fractional Composition of Oil from Saigak Field
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Table 7 sets out a comparison of parameters for the base oil and the product received after one cycle from the said oil, respectively.
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Thus, the product obtained according to the inventive approach is commercial-grade. C. Oils from the Kumkol Fields, the Republic of Kazakhstan
The oils from the Kumkol Fields are representative of medium-density (830 kg./M3), high-viscosity, high-tar (19%) oils that also are high-paraffin (up to 15%) and high-solidifying (at more than +2O0C). Accordingly, examples oils from the Kumkol Fields group were selected to demonstrate the capabilities of the inventive approach, with respect to processing under the benzine option (the "Kor" company oil, volumetric share of petrol fractions 76%), under the benzine-kerosene option (Lukoil company oil, volumetric share of benzine-kerosene fractions 94%), and under the fuel option (the "Aidan" company oil; volumetric share of benzine-kerosene-diesel fuel fractions 96%), respectively (see Table 8).
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Table 8. Molecular Composition of Light Oils Produced from Crude from the Kumkol Field Group after One Cycle
D. Product from Boiler Oil of the M-100 Grade
In this example, the starting parameters of the base boiler oil, M-100 Grade (GOST 10585 - 75), were as follows:
Density: 965 kg./M3;
Viscosity at +5O0C: 43.8 centistokes; Solidification point: +1O0C; Water content: 1.5%.
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Pursuant to the present invention approach and the unit, the boiler oil was reworked into the product with parameters corresponding to those of an enriched oil white fraction:
Content of white fractions: 85%;
- Average density: 830 kg./M3;
- Viscosity at +2O0C: 2.8 centistokes; Solidification point: not higher than -250C;
- Final boiling point: not higher than 35O0C.
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