CA1142879A - Method for enhancing chemical reactions - Google Patents
Method for enhancing chemical reactionsInfo
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- CA1142879A CA1142879A CA000357232A CA357232A CA1142879A CA 1142879 A CA1142879 A CA 1142879A CA 000357232 A CA000357232 A CA 000357232A CA 357232 A CA357232 A CA 357232A CA 1142879 A CA1142879 A CA 1142879A
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Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to enhancing chemical reactions and particularly reactions in a continuous system. The invention comprises circulating a fluid mass through the system at a selected rate of flow, introducing a chemical agent into the fluid mass, mounting two relatively straight tubes of different diameters in concentric radially spaced relationship to form an annular passage of substantially uniform thickness and isolating said tubes from each other to prevent direct transmission of sonic resonant energy from one tube to the other. The fluid mass is passed with said chemical agent introduced therein through the passage, setting up a cavitation condition throughout the length and circumference of at least one of said tubes in the ultrasonic range and transmitting said cavitation condition in a radial direction relative to the annular passage at a multiplicity of locations directly to the fluid mass and the chemical agent therein simultaneously and uniformly throughout the entire length and perimeter of the annular passage while said fluid mass and accompanying chemical agent are in transit through said annular passage. Then the resulting combination of said fluid mass and said chemical agent is collected at a discharge location. The improved method of this invention is useful in processing and recovery of metals and cuts down on the processing time over known methods and maximizes metal recovery.
The present invention relates to enhancing chemical reactions and particularly reactions in a continuous system. The invention comprises circulating a fluid mass through the system at a selected rate of flow, introducing a chemical agent into the fluid mass, mounting two relatively straight tubes of different diameters in concentric radially spaced relationship to form an annular passage of substantially uniform thickness and isolating said tubes from each other to prevent direct transmission of sonic resonant energy from one tube to the other. The fluid mass is passed with said chemical agent introduced therein through the passage, setting up a cavitation condition throughout the length and circumference of at least one of said tubes in the ultrasonic range and transmitting said cavitation condition in a radial direction relative to the annular passage at a multiplicity of locations directly to the fluid mass and the chemical agent therein simultaneously and uniformly throughout the entire length and perimeter of the annular passage while said fluid mass and accompanying chemical agent are in transit through said annular passage. Then the resulting combination of said fluid mass and said chemical agent is collected at a discharge location. The improved method of this invention is useful in processing and recovery of metals and cuts down on the processing time over known methods and maximizes metal recovery.
Description
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The present invention relates to enhancing chemical re-actions and particularly reactions in a continuous system.
Although ultrasonic cavitation of liquids has been re-sorted to in the past, as for example cleaning of metal objects, and also for processing purposes as evidenced by U.S. Patent No. 3,464,672, the objective has been to transmit sound energy directly to the liquid. In U.S.
Patent No. 3,464,672 material such as rubber normally used as sound insulation pads because of having vir-turally no modulus of elasticity, has been used intubular form as a support for transducers. Because of its sound deadening property, the rubber tube is in-capable of resonance in the ultrasonic range and merely holds the transducers in a position such that they can drive the sound energy through the rubber wall to the liquid. Since no ultrasonic resonance can be set up in the rubber wall, no ultrasonic energy will pass to the liquid except directly at the locations of the transducers, which must be placed virtually edge to edge in order to get maximum application of energy to the liquid.
In general, techniques and equipment used, for example, . .
in the processing and recovery oE such metals as gold, uranium, silver and copper have been improved through better utilization of instruments and controls. Over ~ the years there have obviously been improvements in ; process equipment and techniques used in the operation.
The introduction of new technology, equipment and methods such as ultrasonic hydrometallurgical treatment of the ~L14Zg37~
slurry or pulp during the leaching operation, for ex-ample, has not been applied.
Improving the effectiveness of existing plant opera-tions through the use of alternative process technology and the implementation of advances should lead to higher metal recovery and a reduction of metal lost to the tailing dumps~
In the case of gold recovery processing, for example, cyanide leaching is generally carried out in large tanks known as agitators or-leaching tanks where the slurry or pulp having a consistency of between 30 and 50 per-cent solids is agitated generally by a combination of propellers and airlift injection to minimize diffu-sional limitations and to provide the oxygen or other oxidizing agents necessary for oxidation and resultant cyanide reaction.
Oxygen is recognized as an indispensable oxidizing agent ~ in the dissolution of gold or ot.her metals. Pure : oxygen is generally too expensive to use. Therefore, atmospheric air is the customary source of the required oxygen gas used as an oxidizing agent. The degree of aeration of the cyanide pulp in gold processing is of significant importance and concern to the me-tallurgist since some ores, particularly silver ore, require more aeration than others. Agitation may be considered as stirring or mixing of the pulp with an excess of air in circular tanks of sufficient capacity to allow the bal-.ance of the gold to dissolve.
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The economic incentive ~or higher recovery efficiency of metals during the leaching process is substantial and suggests improvement through better use of new tech-nology. For example, it has been shown that a typical gold producing company with a recovery rate of 93 percent and with a sales of 50 million dollars annually could recover a significant amount of gold should the recovery efficiency be increased one percent to a value of 94 percent.
One of the current problems that occurs during the gold leaching process is to provide the proper rate of ox-ygen or air flow necessary -Eor oxidation within the cyanide concentration to recover the maximum amount of ~; gold from the ore. The atmospheric air which is intro-15 duced at the bottom of the agitator ranks causes an air lift in the form of bubbles which rise in part to the surface of the tanks. A portion of the agitation for mixing is provided by propeller mixing blades at the lower portion of the tanks.
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20 There is commonly a strong resistance to the mixing of air or other oxidizing chemical agents with the cyanide solution during this stirring ancl airlift operation.
The resistance is caused by the surface tension inter-face of the air bubbles and solution. As a result only - 25 a portion and an unpredictable amount of the air in the form of bubbles is dissolved in the cyanide pulp solu-tion to provide for oxidation. Furthermore, there is no certain or known controllable means of determining an accurate air flow rate utilizing conventional equip-30 ment to provide the ultimate desired amount of oxida- t tion and resultant reaction for maximum metal recovery.
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Another problem relates to the time required for dissolu-tion of metals in the agitation circuit. Although an important part of gold, for example, will dissolve in the grinding circuit if it is performed in a cyanide 5 solution, there still remains significant undissolved values that require complete oxidation to more fully com-plete the dissolution. The total retention time required in the agitation circuit will usually range from 6 hours to 4~ hours and sometimes somewhat longer on silver ores.
10 Part of the problem therefore is the exceptionally long time required for processing and final dissolution in the agitator circuit.
ii The present invention provides a method for enhancing 15 chemical reaction in a continuous system comprising circulating a fluid mass through the system at a selected rate of flow, introducing a chemical agent into the fluid mass, mounting two relatively straight tubes of different diameters in concentric radially spaced relationship to 20 form an annular passage of substantially uniform thick-ness and isolating said tubes from each other to prevent direct transmission of sonic resonant en~rgy from one tube to the other, and passing the fluid mass with said chemical agent introduced therein through the passage, ~i 25 setting up a cavitation condition throughout the length and circumference of at least one of said tubes in the ~' ultrasonic range and transmitting said cavitation con-dition in a radial direction relative to the annular passage at a multiplicity of locations directly to the 30 fluid mass and the chemical agent therein simultaneously L
and uniformly throughout the entire length and perimeter E
of the annular passage while said fluid mass and 1~2~B7~ -accompanying chemical agent are in transit through said annular passage, and than collecting the resulting com-bination of said fluid mass and said chemical agent at a discharge location.
The present invention consists of the construction~
arrangement, and combination of the various parts of the device, as hereinafter set forth, pointed out in the appended claims and illustrated in the accompanying drawings.
~ 10 FIG~RE l is a schematic view of the system adopted for - practice of the method applied to a slurry while in transit, showing the device in section.
FIGURE 2 is an end elevational view of the device taken 15 on the line 2--2 of Figure 1.
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FIGURE 3 is a cross-sectional view on the line 3--3 of Figure l.
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20 FIGURE 4 is a diagrammatic showing of the axial nodal pattern.
FIGURE 5 is a diagrammatic representation of the circum- ;
ferential nodal pattern.
25 FIGURE 6 is a longitudinal sectional view showing the location of both circumferential and axial nodes.
FIGURE 7 is a schematic representation of the system 4 including an agitator tank.
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30 FIGURE 8 is a side elevational view partially broken away of another form of the invention~
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FIGURE 9 is a cross sectional view on the line 9--9 of Figure 8. -' FIGURE 10 is a side elevational view partially broken 5 away of another form of the invention.
r FIGURE 11 is a cross sectional view on the one 11--11 of Figure 10.
10 FIGURE 12 is a side elevational view of still another form of the invention.
FIGURE 13 is a diagrammatic representation of the con-trol panel and related instrumentation.
15 FIGURE 14 is a schematic representation of a gravity system including a separator and solvent return system.
In an embodlment of the invention chosen for the pur-pose of illustration, there is shown in Figure 1 a D
20 supply conduit 10 for a stream of substantially liquid material, such as a pulp or slurry, which is passed through the system by action of a variable speed pump 11 and evacuated through a discharge conduit 13. A
chemical reactor assembly indicated generally by the 25 reference charactor 12 receives the stream from the supply conduit and ultimately passes it to the dis-charge conduit 13. The discharge conduit may, on some occasions be directed to recirculating the slurry back to the process through appropriate conventional means 30 or on occasions may pass the slurry to an agitator tank 14 as shown in Figure 7, from which it can be re-circulated back to the supply conduit 10.
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The chemical reactor assembly 12 consists of an outer resonant tube 15 having flanges 16 at respective oppc- !
site ends bolted in sealed condition by means of bolts 17 to respective flanges 18 supporting in part an inner 5 resonant tube 19.
For a tube like the tube 19 to be resonant it should be of resilient stiff material with a modulus of elasticity in the range of from about 30,000,000 to about 21,500,000 10 or slightly lower. This is recognizably the range for metallic materials such as steel, stainless steel, nickel, alloys of copper and perhaps some of the harder alloys of aluminium with the possible inclusion of some specially constituted non-metallic materials. The 15 stability inherent in the metallic materials is a highly desireable characteristic. Materials such as soft rubber or fiber reinforced rubber, or comparable pliable synthetic materials of which various hoses have been made and even phenolics with a modulus of 500,000 are 20 clearly outside the required range and could not resonate in the ultrasonic range.
,, The outer flanges 19 have feet 24, which rest on resili-ent isolation supports 20. These in turn are carried 25 on a pad 21 on a stationary bed 25 thereby to mount the chemical reactor in position~
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As shown, the inner resonant tube has an outside diameter substantially smaller than the inside diameter of the L
30 outer resonant tube providing an annular passageway 22 L
therebetween. As shown, it is the passageway 22 which the supply conduit 10 is directed into and from which the discharge conduit 13 flows.
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An annular isolation ring 26 at each end serves to isolate and seal the inner resonant tube from the outer resonant tube 15 and to permit the tubes to be isolated in resonance.
5 In designating the ring 2~ as an isolation ring con-; sideration must be given to the intensity and wave length of the ultra sonic character of the device. The isola-tion material should normally be much denser than that r acceptable to sonic energy in the audible range and mayJ
; 10 on occasions, be omitted entirely.
Mounted on the exterior of the outer resonant tube 15 are three sets of ultrasonic magnetrostrictive trans- 3 ducers 30. In the chosen embodiment there are four such 15 transducers in each set and all are mounted at an appropriate wave length antinodal point~ In practice one or more transducers may be used depending on the power requirement of the system or a multiple number as shown. The ultrasonic heavy duty magnetostrictive trans-20 ducers 30 are substantially conventional in their mechanical makeup, and adapted to be supplied with electric current from their power supply generator and ~,rthrough appropriate leads 31.
25 Piezoelectric transducers are customarily made with a resonant diaphragm at which point the high frequency {
sound energy is accummulated and from which the sound wave energy is projected. In the device herein dis-closed the resonant tube is itself a diaphragm for the 30 magnetostructive transducers and irrespective of whether one or a multiple number of transducers are employed the entire tube is set in resonance at the Z~79 same ultrasonic frequency. The transducers and the en-tire length and circumference being in that way activated produces a source of sound wave energy applied completely throughout the entire surface of contact of the liquid with the resonant tube. A high power transfer of sound energy is in that way made possible.
' In the present disclosure, the structure itself, namely the entire length and circumference of the resonant tube or tubes, as the case may be, provides a disphragm for sound emission in the ultrasonic range which generates the desired cavitation in liquid flowing adjacent to it.
By providing dual resonant tubes the liquid passage 22 is kept narrow and substantially all liquid passes in contact with the resonant tube exposed surfaces. When both tubes are set in resonance by transducer action, cavitation is produced over an area encompassing the entire length and circumference of the liquid media to be treated.
' For greater conveniehce the transducers are shown mounted on the exterior of the outer tube. For generating resonance directly in the inner tube the transducers could be mounted on the interior of the inner tube.
The inner surface of outer resonant tube 15 and the outer surface of inner resonant tube 19 are plasma sprayed for corrosion and abrasion resistance. ;~
~, To integrate the transducers with the wall of the resonant tube, and employ the tube as the transducer 30 --diaphragm, the transducers are silver brazed directly to the resonant tube. Flats 32 may be milled on the ~1 4ZE~75~
surface of the tube itself at the transducer locations where the brazing is to take place. , ;.
In the system as shown in Figure l an orifice flange 40 is provided in the discharge conduit 13 which is serviced 5 by a flow transmitter-indicator 41 through leads 42, - From the flow transmitter a lead 43 leads to a flow.ratio controller 44. The same flow ratio controller also services a second flow transmitter-indicator 45 and r : orifice flange 46 through leads 47 and 48. As noted, 10 the orifice flange 46 is in a line 50 for the introduc-tion of oxygen or other appropriate oxidizing agent to the system. In the'line 50 is an automatic control valve~51, the operation of which is dependent upon operation of the flow ratio controller 44 acting on a 15 diaphragm valve actuator 52 through appropriate con-nection 53.
A pressure reducing control valve 55 and companion pressure gauge 57 are located in the line 50 upstream 20 with respect to the orifice flange 46. At the down-stream discharge end of the line 50 and located within the annular passageway 22 is an aspirator nozzle 56.
A check flow valve 54 is shown near the discharge of line 50, Oxygen or other appropriate chemical oxid~izing 25 agent flows,from the line.50 through the slurry within the annular passageway 22, ~he slurry is forced through the annular passageway 22 by means of the pump 11 which is located at the inlet end of the annular passageway.
A manual valve 69 may be mounted in the supply conduit t 30 ,.10 as shown, .
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Figuxe 7 represents a recirculation system added to the disclosure of Figure l and shows the chemical reactor 12 and its associated e~uipment interconnected to, ~or example, commercial type of propeller agitator 5 or leaching tank 14 for continuous recirculation of the ' contents of the agitator tank for processing by the chemical reactor 12.
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A process inflow line 66 passes pulp or slurry to the 10 tank reservoir chamber 62, and an outflow line 67 re-turns the processed material to the main process system circuit. A propeller 60 within the tank driven by motor - 61 provides stirring, lift and agitation for the tank's contents. In addition, the tank is provided with a 15 series of air jets 63 located on a spreader 64 at the bottom of the tank and supplied by an auxiliary air line 65. The purpose o~ the jets is to provide oxida-tion of the tank's material and to also induce an addi-tional air lift for agitation. ~' 20 The recirculation is provided by a conduit lO' located r near the bottom of the tank and a conduit 13' located near the top portion of the tank. The pump 11 passes the material through the chemical reactor and returns the contents to the agitator tank through conduit 13'.
25 To illustrate graphically the activity of the resonant tubes 15 and l9 there is shown in Figure 4 a rèsonant pattern which contains four axial wave length nodal points 70. There are also circumferentially disposed ,wave length nodal points as shown advantageously in Figure 5, namely, the nodal points 73, 74, 75, 76, 77, and 78.
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The chemical reactor as shown in the drawings is a device to provide a controlled rate of oxidation and reaction of the pulp and cyanide solution and in proportion to the pulp flow rate, and also subject tha pulp mixture solution passing through the reactor chamber to intense dispersion, mixing, cleaning, and to a chemical reaction within the confined annuIar passageway 22. In the passageway the mixture is processed under precisely con-trolled conditions by.very intense ultrasonic energy which in turn produces a high energy field of cavitation energy directed in spherical and perpendicular fashion across and through the slurry solution within the annular passageway 22 as shown in Figure 3 and as it flows through the reactor chamber.
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Since the reactor is a self-contained device which can be designed to a wide range of flow rates, it lends it-self to choice of locations in the cyanide leach.ing circuit. As desired by the meta:Llurgist, for example, an effective installation would be to utilize the ; 20 chemical reactor as a recirculation device for one or more of the holding tanks, whereby flow capacities rang-ing from 40,000 gallons.per hour or higher could be withdrawn continuously from a tank, circulated throu~h the reactor for processing and returned to the agitator tank. In this manner, the contents of the tank would be recirculated and processed for controlled oxidation and reaction many times during processing. For larger tanks where larger rates of recirculation may be re-quired, multiple use of the chemical reactors can be utilized.
Figure 7 shows the conduit lO' flowing ~rom the agitator ~4~7~
Figure 7 shows the conduit 10' flowing from the agitator tank 14 which transports the slurry and cyanide solu-tion to the reactor, the flow rate of which is measured by either a segmental orifice or a flow nozzle and its transmitter. The pump 11 is shown in the line to cir-culate the pulp solution through the agitator assembly 12 to the tank 14. The compressed gas flow rate is measured in turn by the orifice 46 and its transmitter ~5. The two flow transmitters 41 and 45 in turn transmit their individual flow rate results to the flow ratio controller 44 which automatically regulates control valve 51 in the compressed air line to proportion and maintain a fixed ratio of airflow to pulp solution flow.
The flow ratio controller 44 is equipped with a manual ratio setting to enable the metallurgist to adjust the desired value or ratio from time to time as may be re-quired to maintain optimum oxidation and reaction tak-ing place in the agitator holding tank closed system in order to increase the efficiency of metal recovery.
The compressed air may be passed to the reactor assembly 12 through a shutoff valve 59 shown in solid lines or through a line 50' and shutoff valve 59' to a point up steam of the pump 11 as shown by broken lines.
The resonant tube 15, which is a cylindrical shell, is specifically designed to one of the desired axial and circumferential ultrasonic resonant frequencies that have been selected for the structure. An example of the wave '~
length frequency patterns showing nodes and antinodes referred to for the cylindrical shell is illustrated in Figures 4, 5 and 6. The same description applies also ~-to the tube 19. "
Employment of the chemical reactor in ore and metal chemical processing dictates that the cylindrical shell be designed for the ultrasonic frequency range chosen preferably at a value between 20,000 and 40,000 cycles 5 per second. The cavitation implosions therefore in microns would permit the cavitation energy to penetrate, attack and implode the ore surfaces, pores, fissures and grain boundries and to also implode the molecules of the metals themselves. Ultrasonic heavy duty industrial r 10 magnetostrictive transducers are commercially available to supply the ultrasonic frequencies required for in-stallation on the resonant tubesO
Modern ultrasonic magnetostrictive transducers are 15 furnished commercially with solid state power supplies that are provided with adjustable output power and ad-justable frequency. These features are ideally suited for application to the chemical reactor, and also offer engineered reliability represented by 10 year guarantees.
20 With reference to Figure 1, the pulp solution containing atmospheric air as an oxidizing agent enters the ultra-sonic chamber, namely, the passageway 22, for processing ,~
where it is exposed to an intense field of cavitation ~, where the energy thus released within the pulp and ~-25 solution causes the interfaces and surface tensions of '' the materials to be broken and also to provide an energy means for oxidizing a good portion of the oxygen into reaction. In addition, the high energy kinetic reaction that takes place within the pulp solution causes dis-30 ,persion, agitation, mixing and surface cleaning of the materials and intense implosion on the sur~aces of the exposed metal to more fully release the metallic mol-ecules into solution.
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The combined resonant system consists of the resonant cylindrical tubes 15 and 19, one or more transducers, or T
a multiple number of transducers, and its ultrasonic generator power supply. The resonant cylindrical tubes 5 are excited sinusoidally into one of their wave length modes of natural frequency in the ultrasonic range at a chosen value between 20,000 and 50,000 cyeles per second.
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The longitudinal and circumferential elastic wave 10 energy at resonance and thus released from the cylin-drical tube, causes very intense acoustic compressional sinusoidal wave energy to be transmitted in per~endi-cular fashion from the outer resonant tube surface thrGugh the pulp solution or slurry as shown in Figure 3.
15 The speed of the transmitted compressional wave energy within the unpure pulp solution is estimated at 5500 feet per second. The shearing forces of the compression wave energy traveling through the pulp solution cause a very high degree of kinetic energy reaetion to take 20 place within the pulp mixture which in turn fractures and ruptures the solution into a known form of energy namely vapouous cavitation whieh is a eommonly accepted term for such a condition.
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25 The vaporous cavitation energy field within the solu- I`
tion is continuously subjected to alternating positive and negative pressure cyeles whieh eause mieroscropic bubbles to be formed during the pressure cyeles and to be eollapsed during the negative eycles thus eausing a s 30 very intense vacuuming or implosion action on all the surfaces of materials in solution, for oxidation and implosion of ore surfaces and crevices which contain molecules of metal.
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Such energy life cycle transformations in three force planes take place each 10 9 of a second and form ellipsoid energy patterns in three planes which are continuously in a state of formation and collapse.
It is during the negative pressure or collapse phase of the energy cycle that voids are produced, as are also vapor cavities in solution. This in turn produces very intense vacuuming action on the surfaces and crevices of the ore material in solution, sometimes referred to as an implosion effect. The implosions which take place on the surfaces of the ore even to minute sur-face diameters of a few microns cause the surface tensions to be broken and permit the chemical solution to produce additional dissolution of the metal by penetration into the ore crevices and to also provide for a higher degree of oxidation to take place.
Basically, there are four mechanisms involved in re-moving additional metal from ore while undergoing pro-20 cessing in a chemical reactor: (1) solvation, ~2) in- i terface exchange, t3) chemical reactivn, and (4) dis-solution.
In the case of gold recovery, for example, a cyanide solution serves as a chemical solvent agent for dis-solving the gold from the ore. Any mechanical agitation speeds up the solvation process. The forces of cavi- ~ '`
tation will provide a direct and effective mechanical agitation.
Civitation can also serve to break down the molecular force or interface that exists between the solution and .
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the ore particles containing gold. The breaking of these forces can be accomplished by the direct shock or impact imparted by acoustical vaporous cavitation or can be the result of a fatiguing action caused by repeated bombard-ment and resulting explosions. Once the molecularattraction of the solution to the ore and metal is ; broken, the surface metal is imploded and cleaned and thus exposed for further dissolution.
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Chemical mechanisms can also be in the form of chemical conversioans or of the addition of chemical energy to the dissolution pxocess. Among the latter the addition of air or other chemical oxidation agents are most widely used. Cavitation serves to accelerate this energy reaction. When the mechanism is a chemical conversion, the usual action is to convert the metal to a soluable form.
Cavitation aids also in these reactions by means of the great pressure differentials that are set up by the implosions in the microscopic pores, cracks and grain boundries of the ore and metal and by the heat dissipated at the moment of implosion. The cavities or voids left by these implosions are instantaneously filled with the chemical fluid solution that surrounds the ore particles and are driven by very high transitory pres-sures. The resulting pressures generated at the loci of these implosions have been measured up to 1000 atmo-spheres. Furthermore, the heat dissipated at the moment of implosion has been determined to be in excess of 1000 degrees centigrade. Chemical processes can also be aided in a vaporous cavitation field by the direct mechanical agitation of cavitation, since they maintaln ~3~4~
a maximum concentration gradient of the chemical solu-tion at the surfaces of the ore particles.
One unique feature of cavitation is tha-t it can be generated anywhere that a compressional sound wave of sufficient intensity can penetrate, and reaction will occur deep within the interstices of an ore particle with complicated geometric configuration. Ore particle surfaces which are seemingly smooth to the naked eye have microscopic pores r crevices, cracks and grain boundries. The specific action of cavitation penetrates these minute areas with very intense transitory energy and results in implosions and resultant ruptures and fissures of the ore material at the microscopic level which can be equaled by no other known method. The implosions occurring on and within the ore particles create tremendous transitory pressures within the material. The alternative vacuum and pressure energy action reaching 10Q0 atmospheres o pressure occur many thousands of times per second and at resonance, which causes fatigue within the pores, cracks, grain bound-ries and fissures of the ore particles which forces the ore particles to be fractured to a large extent and thus to expose more fully the molecules and surfaces of metal for further recovery by means of chemical reaction and dissolution.
The solid state ultrasonic system is an efficient means to provide the energy necessary for operation of the chemical reactor. The individual power requirements, ; ,for example, for multiple transducer units is relatively low and may be supplied commerically as desired in power increments up to 12,000 watts. In special cases where very high capacities are required for a single chemical reactor, a multitude of transducers 30 representing a !
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multiple system may be used as shown in Figure 1. In this case the multiple transducers would be driven in phase from a single power source. An alternate installa-tion for higher rates of circulation could be made by utilizing muItiple chemical reactors.
In the form of invention of Figures 8 and 9 there are provided dual resonant tubes 80 and 81 the outer tube , 80 being of substantially the same thickness and res-onant character as the inner tube 81 which is spaced therefrom providing an annular passageway 82. `
, The tubes 80 and 81 are isolated from each other by the same structure described in connection with Figure 1 and are carried by appropriate supports 20 in the same fashion.
Because of the resonant character of the outer tube 80 ~ there is provided at the end of the supply conduit 10 ; 20 a flexible isolation ioint 83 of an appropriate vibra-tion damping material through which the fluid flows to a stub conduit 84, directly connected to the outer res-onant tube 80 by a regid weldment 85. A similar flexi-ble isolation joint 86 at the end of the line 50 carry-25 ing the oxydizing agent connects to a stub 87 ~y which the agent is conducted into the passageway 82 through the wall of the outer resonant tube 80.
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Similarly also a discharge stub 88 connects to the dis-30 charge conduit 13 through an isolating joint 89.
The joints as described taken together with the mountings at the end of the resonant tube assembly isolate the r ~'12~379 entire reactor structure from any rigid attachment or connection which would otherwise impair the effective-ness of the ultrasonic wave action which is generated.
5 By way of example there are shown three transducers 90, 91, and 92, on this occasion all connected to the ex-terior of the outer resonant tube 80. ~he transducers e are axially spaced one ~rom another in such fashion that they apply their force to the outer resonant tube 10 80 at wave length antinodal points.
As indicated in Figure 9 ultrasonic eneryy set up in the outer resonant tube 80 is transmitted by fluid material 93 to the inner resonant tube 81 causing the 15 inner resonant tube to be excited at resonance thereby to set up a resonant wave pattern in the fluid material in an opposite direction also as indicated by the arrows in Figure 9.
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20 A chamber 94 through the inner tube is clear.
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The embodiment of Figures 10 and 11 differs in that an inner tube 95 is thick walled and stationary whereas an outer tube 96 is relatively thinner walled and resonant.
25 The tubes are concentric and radially spaced from one another providing an annular passageway 97 for the fluid material which is subject to the reac*ion. Here again transducers 98. 99. amd 100 are mounted on the exterior of the outer tube 96 at respective wave length anti-30 nodal points to generate an ultrasonic frequency res-onant wave condition such as that illustrated by the arrows of Figure 11. In the device of Figures 10 and 11 there is an open chamber 101 extending through the inner tube 95.
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~n augmented transducer pattern is illustrated in Figure g 12 where, by way of example, an inner tube 105 and an oute~ tube 106 are illustrated as resonant tubes com-parable to the arrangement of Figures 8 and 9. The tubes 105 and 106 following the arrangement of the other forms of the device provide an annular passageway 107 for the fluid material which is to be reacted, there being a clear chamber 108 through the inner tube 105.
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For this arrangement transducers 108, 109, and 110 are applied to the exterior of the outer tube 106 at longi-tudinally spaced intervals so that they are located at antinodal points for the vibration condition which is set up. On this occasion additional transducers 112, 15 and 113 extend circumferentially around the outer tube 106 at the longitudinal midline.
With the proposed arrangement ultrasonic vibrations of two different kinds are generated in the outer resonant 20 tube 106 thereby emphasizing the pattern of both radial and longitudinal wave action, the elements of which have already been described in connection with Figures 4 and 5. It should be observed further that the circumfer-entially disposed transducers should also be applied 25 at antinodal points. Moreover, additional circum~ ~
ferentially disposed transducers are contemplated at S
other antinodal points corresponding, for example, to the locations of transducers 108 and 110.
30 Further still, although for the embodiment of Figure 12 several resonant tubes are shown, it may be found pre-ferable to provide only one resonant tube as for example, ~14Z~
making the inner tube 105 thicker walled and stationary.
Further still by following the pattern of mounting of Figures 1 and 2, transducers of appropriate size and capacity can be mounted not only at axially spaced locations but also at circumferentially spaced loca-tions around the inner circumference of the inner tube, where that tube is made a resonant tube.
Since the resonant character of the tube in which the b 10 transducers are mounted is appreciably significant, as well as the location of the transducers at wave length antinodal points a typical installation can be calculated.
Assuming the resonant tube to be of steel, the speed of 15 sound in the tube can be assume to be 14,610 feet per second. The frequency imparted to ordinary steel by the transducer may be designed for 22,000 cycles per second.
Therefore in the equation:
22,00o = .6641 feet 20 8 inches - .6666 feet. As a consequency, the transducers, P
where more than one are mounted on the resonant tube, will need to be at intervals of which would be multiples o~ approximately 8 inches. Because of known properties of the materials and related standard mathematical con-stants the entire structure can be designed to have the resonant characteristics desired. ~`
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The control panel of Figure 13 is illustrative only and shows a control, for example, the flow ratio controller or selector valve 44, the flow transmitter 41 for the oxidizing agent, a proportioning control valve 115 and s a fluid flow measuring device 116.
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Ultrasonic power supply generators are indicated on the panel by reference characters 118 and ll9. Flow re-:5 cording meters are indicated by the characters 120 and 121 and flow ratio controller by the reference character 122. A remote manual selector valve for control of the total flow leaving the reactor is shown at 123 and a manual automatic flow leaving the reactor is shown at 123 and a manual automatic flow ratio selector valveat 124. Because of the nature of the apparatus~and process made possible by the arrangement of equipment shown, careful control and regulation is a requisite and for adequate effectiveness all controls and indi-cators need to be concentrated at a single location.
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. Although the application of the chemical reactor for themine processing industry has been detailed in this dis-~ closure~ there are other significant uses for the chemi-: 20 cal reactor in the chemical processing industry generally where such methods and technology may be utilized in other forms of processing namely, dispersion, cleaning, : chemical washing, mechanical agitation, mixing and com-: pletion of chemical reactions by the introduction of 25 various forms of oxidizing agents in a control.led manner. .~
; ~.
An example of a system capable of accommodating, for example, a method or process directed to solvent extrac-`tion of oil from tar sands or oil sands is shown in a : 30 pilot extraction plant system as illustrated in Figure 14.
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As there shown, the system is one set up for operation !
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principally as a gravity system in the interest of economizing further power requirements.
An acceptable apparatus as shown would involve several processing steps. The first step in the process is the reduction oE the oil sand agglomerate. Deagglomeration to a maximum one-quarter inch size is sufficient, since i the high frequency energy action quickly reduces the tar sand to individual granules. The tar sands would be processed continuously by a single-toothed crusher since the material is easily reduced. The tar sands thus supplied by the mass 130 are continuously fed to a hopper 132.
The material is then funneled into an automatic contin-uous weighing gravimetric feeder 133 and weighed in terms of LBS/HR and from there into a mixing tank 134 which has an impeller agitator 135. In this instance solvent 136 from a solvent tank 137 is fed by gravity to the mixing tank 134. The flow is metered by a meter 138 in terms of LBS/HR in a solvent line 139. The flow through a line 140 is manually set to a metered amount on a weight basis by means of a manual valve 143 so that the solvent flow weight to the mixing tank 134 and the - 25 tar sand weight to the tank 134 are at a ratio of one to - one, or less, by weight. A heater 144 in the solvent tank 137 maintains a low temperature of 150F. A -float control merchanism in tank 134 will automatica~ly close a normally open valve 142 by means of a pneumatic line 141 when the tank level of 134 exceeds its desired le~el ~or safety purposes.
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~3L'lZ~ ~9 From the tank 134 the slurry mixture flows continuously through a discharge line 146 in which there is a hand-operated valve 1~7 and a metering device 148 to the upper end of a chem.ical reactur assembly 150 of the type here-tofore made reference to.
A by-pass line 170 is provided to pass a small amount of fresh solvent 136 as a chemical reagent to the chemi-cal reactor assembly and is metered by a meter 171 through a valve 172. This relati.vely small by-pass chemi.cal reagen-t f].ow provides a process corrective means to ; produce highest extraction efficiency within the chemical reactor.
The mixing tank 134 also serves a significant function as a detention device since the tank volume is designed to be many times the annular processing chamber volume of the chemical reactor. A flow detention time of 15 to 30 minutes has been found sufficient to soften the tar or the crushed tar sand before final extraction takes place in the chemical reactor 150.
The pre-mixed slurry enters the annular high frequency ener~y chamber of the chemical reactor 150 where cavi- ,~
tation at 22,000 cycles/sec., which is created by the transducers, quickly reduces the tar sand by implosions to individual grains. As the action continues, cavita-tion also blends the solvent with the bitumen and the energy implosions separate it from the sand. The unique advantage of using sonic energy is that it acts on each individual grain of sand. Cavitation, the minute vacuous bubbles that constantly form and collapse, causes an !
~26-intense energy release that implodes the materiall caus-ing the softened bitumen to be puIled away from the hard surface of the sand much the same as it pulls soil or contamination away from hard surfaces in cleaning opera-5 tions. In this instance, however, the purpose is not to clean the sand, but to remove the bitumen.
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The next step in the process is to pass the slurry mixture of bitumen, sand and solvent by gravity flow through a P
line 153 to a clarifier 154.
The clarifier provides à standard means for liquid-solids separation. The solid in this case is sand and the liquid represents the oil-solvent solution. Water within 15 the clarifier acts as a separation medium since the specific gravity of the oil-solvent is considerably lower than water. The oil-solvent mixture rises to the top of the water solution and is skimmed off the top through a line 160 for further processing. The clarifier mech-20 anism also provides a high rate of circulation and agita-tion which causes further dissolution of the bitumen i-n the solvent solution. The clean sand slowly falls to g the bottom of the clarifier and is removed through a line 156 by a screw auger. A slight amount of detergent 25 added to the water solution will enhance the removal of t-solvent from the sand surfaces.
t Waste water from the clarifier is removed through a line 157 and processed in a water filtration unit 158, 30 clean water being removed through a line 159 and returned to the clarifier. Make-up water is supplied to the clari-fier by means of line 152 in order to maintain a con-stant water level in the clarifier 154. b i~L42~37~
The next step in the process is to pass the oilsolvent solution to a fractionating tower 163 by means of a line 160 and pump 162 as metered by a meter 161. The solvent is taken off, decanted and returned to thé
solvent tank 137 by means of a line 165 for further use.
The oil at approximately 18 API is removed through a line 164 and subjected to the usual processes, such as cracking, reforming and alkylation, to produce motor fuel, fuel oil and similar products. Solvent loss 10 experimentally is less than 1%. Oil extraction from tar sands has been shown experiemntally to be 96% to 98~.
The continuous flow solvent extration process, as shown in the schematic pilo-t plant illustrated in Figure 14, ~ 15 may be implemented to a large oil extraction production ; plant of 10r000 Bbls/day to 20,000 Bbls/day or higher and within the framework of sound engineering practice.
This, for example, may be accomplished by enlarging the 20 outside deameter of the chemical reactor 150 to six feet or larger whereby the annular processing chamber is de-signed to desired volumetric considerations while at the same time maintaining the proper and most efficient energy transmission dis-tance within the annular chamber r 25 for efficient extraction purposesO
Individual high capacity chemical reactor units may be added in the form of modules to obtain any total desired plant capacity. These modules would operate in a parallel 30 configuration and be supplied by one or several slurry feeders.
The present invention relates to enhancing chemical re-actions and particularly reactions in a continuous system.
Although ultrasonic cavitation of liquids has been re-sorted to in the past, as for example cleaning of metal objects, and also for processing purposes as evidenced by U.S. Patent No. 3,464,672, the objective has been to transmit sound energy directly to the liquid. In U.S.
Patent No. 3,464,672 material such as rubber normally used as sound insulation pads because of having vir-turally no modulus of elasticity, has been used intubular form as a support for transducers. Because of its sound deadening property, the rubber tube is in-capable of resonance in the ultrasonic range and merely holds the transducers in a position such that they can drive the sound energy through the rubber wall to the liquid. Since no ultrasonic resonance can be set up in the rubber wall, no ultrasonic energy will pass to the liquid except directly at the locations of the transducers, which must be placed virtually edge to edge in order to get maximum application of energy to the liquid.
In general, techniques and equipment used, for example, . .
in the processing and recovery oE such metals as gold, uranium, silver and copper have been improved through better utilization of instruments and controls. Over ~ the years there have obviously been improvements in ; process equipment and techniques used in the operation.
The introduction of new technology, equipment and methods such as ultrasonic hydrometallurgical treatment of the ~L14Zg37~
slurry or pulp during the leaching operation, for ex-ample, has not been applied.
Improving the effectiveness of existing plant opera-tions through the use of alternative process technology and the implementation of advances should lead to higher metal recovery and a reduction of metal lost to the tailing dumps~
In the case of gold recovery processing, for example, cyanide leaching is generally carried out in large tanks known as agitators or-leaching tanks where the slurry or pulp having a consistency of between 30 and 50 per-cent solids is agitated generally by a combination of propellers and airlift injection to minimize diffu-sional limitations and to provide the oxygen or other oxidizing agents necessary for oxidation and resultant cyanide reaction.
Oxygen is recognized as an indispensable oxidizing agent ~ in the dissolution of gold or ot.her metals. Pure : oxygen is generally too expensive to use. Therefore, atmospheric air is the customary source of the required oxygen gas used as an oxidizing agent. The degree of aeration of the cyanide pulp in gold processing is of significant importance and concern to the me-tallurgist since some ores, particularly silver ore, require more aeration than others. Agitation may be considered as stirring or mixing of the pulp with an excess of air in circular tanks of sufficient capacity to allow the bal-.ance of the gold to dissolve.
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The economic incentive ~or higher recovery efficiency of metals during the leaching process is substantial and suggests improvement through better use of new tech-nology. For example, it has been shown that a typical gold producing company with a recovery rate of 93 percent and with a sales of 50 million dollars annually could recover a significant amount of gold should the recovery efficiency be increased one percent to a value of 94 percent.
One of the current problems that occurs during the gold leaching process is to provide the proper rate of ox-ygen or air flow necessary -Eor oxidation within the cyanide concentration to recover the maximum amount of ~; gold from the ore. The atmospheric air which is intro-15 duced at the bottom of the agitator ranks causes an air lift in the form of bubbles which rise in part to the surface of the tanks. A portion of the agitation for mixing is provided by propeller mixing blades at the lower portion of the tanks.
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20 There is commonly a strong resistance to the mixing of air or other oxidizing chemical agents with the cyanide solution during this stirring ancl airlift operation.
The resistance is caused by the surface tension inter-face of the air bubbles and solution. As a result only - 25 a portion and an unpredictable amount of the air in the form of bubbles is dissolved in the cyanide pulp solu-tion to provide for oxidation. Furthermore, there is no certain or known controllable means of determining an accurate air flow rate utilizing conventional equip-30 ment to provide the ultimate desired amount of oxida- t tion and resultant reaction for maximum metal recovery.
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Another problem relates to the time required for dissolu-tion of metals in the agitation circuit. Although an important part of gold, for example, will dissolve in the grinding circuit if it is performed in a cyanide 5 solution, there still remains significant undissolved values that require complete oxidation to more fully com-plete the dissolution. The total retention time required in the agitation circuit will usually range from 6 hours to 4~ hours and sometimes somewhat longer on silver ores.
10 Part of the problem therefore is the exceptionally long time required for processing and final dissolution in the agitator circuit.
ii The present invention provides a method for enhancing 15 chemical reaction in a continuous system comprising circulating a fluid mass through the system at a selected rate of flow, introducing a chemical agent into the fluid mass, mounting two relatively straight tubes of different diameters in concentric radially spaced relationship to 20 form an annular passage of substantially uniform thick-ness and isolating said tubes from each other to prevent direct transmission of sonic resonant en~rgy from one tube to the other, and passing the fluid mass with said chemical agent introduced therein through the passage, ~i 25 setting up a cavitation condition throughout the length and circumference of at least one of said tubes in the ~' ultrasonic range and transmitting said cavitation con-dition in a radial direction relative to the annular passage at a multiplicity of locations directly to the 30 fluid mass and the chemical agent therein simultaneously L
and uniformly throughout the entire length and perimeter E
of the annular passage while said fluid mass and 1~2~B7~ -accompanying chemical agent are in transit through said annular passage, and than collecting the resulting com-bination of said fluid mass and said chemical agent at a discharge location.
The present invention consists of the construction~
arrangement, and combination of the various parts of the device, as hereinafter set forth, pointed out in the appended claims and illustrated in the accompanying drawings.
~ 10 FIG~RE l is a schematic view of the system adopted for - practice of the method applied to a slurry while in transit, showing the device in section.
FIGURE 2 is an end elevational view of the device taken 15 on the line 2--2 of Figure 1.
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FIGURE 3 is a cross-sectional view on the line 3--3 of Figure l.
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20 FIGURE 4 is a diagrammatic showing of the axial nodal pattern.
FIGURE 5 is a diagrammatic representation of the circum- ;
ferential nodal pattern.
25 FIGURE 6 is a longitudinal sectional view showing the location of both circumferential and axial nodes.
FIGURE 7 is a schematic representation of the system 4 including an agitator tank.
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30 FIGURE 8 is a side elevational view partially broken away of another form of the invention~
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FIGURE 9 is a cross sectional view on the line 9--9 of Figure 8. -' FIGURE 10 is a side elevational view partially broken 5 away of another form of the invention.
r FIGURE 11 is a cross sectional view on the one 11--11 of Figure 10.
10 FIGURE 12 is a side elevational view of still another form of the invention.
FIGURE 13 is a diagrammatic representation of the con-trol panel and related instrumentation.
15 FIGURE 14 is a schematic representation of a gravity system including a separator and solvent return system.
In an embodlment of the invention chosen for the pur-pose of illustration, there is shown in Figure 1 a D
20 supply conduit 10 for a stream of substantially liquid material, such as a pulp or slurry, which is passed through the system by action of a variable speed pump 11 and evacuated through a discharge conduit 13. A
chemical reactor assembly indicated generally by the 25 reference charactor 12 receives the stream from the supply conduit and ultimately passes it to the dis-charge conduit 13. The discharge conduit may, on some occasions be directed to recirculating the slurry back to the process through appropriate conventional means 30 or on occasions may pass the slurry to an agitator tank 14 as shown in Figure 7, from which it can be re-circulated back to the supply conduit 10.
~L4287~
The chemical reactor assembly 12 consists of an outer resonant tube 15 having flanges 16 at respective oppc- !
site ends bolted in sealed condition by means of bolts 17 to respective flanges 18 supporting in part an inner 5 resonant tube 19.
For a tube like the tube 19 to be resonant it should be of resilient stiff material with a modulus of elasticity in the range of from about 30,000,000 to about 21,500,000 10 or slightly lower. This is recognizably the range for metallic materials such as steel, stainless steel, nickel, alloys of copper and perhaps some of the harder alloys of aluminium with the possible inclusion of some specially constituted non-metallic materials. The 15 stability inherent in the metallic materials is a highly desireable characteristic. Materials such as soft rubber or fiber reinforced rubber, or comparable pliable synthetic materials of which various hoses have been made and even phenolics with a modulus of 500,000 are 20 clearly outside the required range and could not resonate in the ultrasonic range.
,, The outer flanges 19 have feet 24, which rest on resili-ent isolation supports 20. These in turn are carried 25 on a pad 21 on a stationary bed 25 thereby to mount the chemical reactor in position~
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As shown, the inner resonant tube has an outside diameter substantially smaller than the inside diameter of the L
30 outer resonant tube providing an annular passageway 22 L
therebetween. As shown, it is the passageway 22 which the supply conduit 10 is directed into and from which the discharge conduit 13 flows.
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An annular isolation ring 26 at each end serves to isolate and seal the inner resonant tube from the outer resonant tube 15 and to permit the tubes to be isolated in resonance.
5 In designating the ring 2~ as an isolation ring con-; sideration must be given to the intensity and wave length of the ultra sonic character of the device. The isola-tion material should normally be much denser than that r acceptable to sonic energy in the audible range and mayJ
; 10 on occasions, be omitted entirely.
Mounted on the exterior of the outer resonant tube 15 are three sets of ultrasonic magnetrostrictive trans- 3 ducers 30. In the chosen embodiment there are four such 15 transducers in each set and all are mounted at an appropriate wave length antinodal point~ In practice one or more transducers may be used depending on the power requirement of the system or a multiple number as shown. The ultrasonic heavy duty magnetostrictive trans-20 ducers 30 are substantially conventional in their mechanical makeup, and adapted to be supplied with electric current from their power supply generator and ~,rthrough appropriate leads 31.
25 Piezoelectric transducers are customarily made with a resonant diaphragm at which point the high frequency {
sound energy is accummulated and from which the sound wave energy is projected. In the device herein dis-closed the resonant tube is itself a diaphragm for the 30 magnetostructive transducers and irrespective of whether one or a multiple number of transducers are employed the entire tube is set in resonance at the Z~79 same ultrasonic frequency. The transducers and the en-tire length and circumference being in that way activated produces a source of sound wave energy applied completely throughout the entire surface of contact of the liquid with the resonant tube. A high power transfer of sound energy is in that way made possible.
' In the present disclosure, the structure itself, namely the entire length and circumference of the resonant tube or tubes, as the case may be, provides a disphragm for sound emission in the ultrasonic range which generates the desired cavitation in liquid flowing adjacent to it.
By providing dual resonant tubes the liquid passage 22 is kept narrow and substantially all liquid passes in contact with the resonant tube exposed surfaces. When both tubes are set in resonance by transducer action, cavitation is produced over an area encompassing the entire length and circumference of the liquid media to be treated.
' For greater conveniehce the transducers are shown mounted on the exterior of the outer tube. For generating resonance directly in the inner tube the transducers could be mounted on the interior of the inner tube.
The inner surface of outer resonant tube 15 and the outer surface of inner resonant tube 19 are plasma sprayed for corrosion and abrasion resistance. ;~
~, To integrate the transducers with the wall of the resonant tube, and employ the tube as the transducer 30 --diaphragm, the transducers are silver brazed directly to the resonant tube. Flats 32 may be milled on the ~1 4ZE~75~
surface of the tube itself at the transducer locations where the brazing is to take place. , ;.
In the system as shown in Figure l an orifice flange 40 is provided in the discharge conduit 13 which is serviced 5 by a flow transmitter-indicator 41 through leads 42, - From the flow transmitter a lead 43 leads to a flow.ratio controller 44. The same flow ratio controller also services a second flow transmitter-indicator 45 and r : orifice flange 46 through leads 47 and 48. As noted, 10 the orifice flange 46 is in a line 50 for the introduc-tion of oxygen or other appropriate oxidizing agent to the system. In the'line 50 is an automatic control valve~51, the operation of which is dependent upon operation of the flow ratio controller 44 acting on a 15 diaphragm valve actuator 52 through appropriate con-nection 53.
A pressure reducing control valve 55 and companion pressure gauge 57 are located in the line 50 upstream 20 with respect to the orifice flange 46. At the down-stream discharge end of the line 50 and located within the annular passageway 22 is an aspirator nozzle 56.
A check flow valve 54 is shown near the discharge of line 50, Oxygen or other appropriate chemical oxid~izing 25 agent flows,from the line.50 through the slurry within the annular passageway 22, ~he slurry is forced through the annular passageway 22 by means of the pump 11 which is located at the inlet end of the annular passageway.
A manual valve 69 may be mounted in the supply conduit t 30 ,.10 as shown, .
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Figuxe 7 represents a recirculation system added to the disclosure of Figure l and shows the chemical reactor 12 and its associated e~uipment interconnected to, ~or example, commercial type of propeller agitator 5 or leaching tank 14 for continuous recirculation of the ' contents of the agitator tank for processing by the chemical reactor 12.
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A process inflow line 66 passes pulp or slurry to the 10 tank reservoir chamber 62, and an outflow line 67 re-turns the processed material to the main process system circuit. A propeller 60 within the tank driven by motor - 61 provides stirring, lift and agitation for the tank's contents. In addition, the tank is provided with a 15 series of air jets 63 located on a spreader 64 at the bottom of the tank and supplied by an auxiliary air line 65. The purpose o~ the jets is to provide oxida-tion of the tank's material and to also induce an addi-tional air lift for agitation. ~' 20 The recirculation is provided by a conduit lO' located r near the bottom of the tank and a conduit 13' located near the top portion of the tank. The pump 11 passes the material through the chemical reactor and returns the contents to the agitator tank through conduit 13'.
25 To illustrate graphically the activity of the resonant tubes 15 and l9 there is shown in Figure 4 a rèsonant pattern which contains four axial wave length nodal points 70. There are also circumferentially disposed ,wave length nodal points as shown advantageously in Figure 5, namely, the nodal points 73, 74, 75, 76, 77, and 78.
~ ~2137~
The chemical reactor as shown in the drawings is a device to provide a controlled rate of oxidation and reaction of the pulp and cyanide solution and in proportion to the pulp flow rate, and also subject tha pulp mixture solution passing through the reactor chamber to intense dispersion, mixing, cleaning, and to a chemical reaction within the confined annuIar passageway 22. In the passageway the mixture is processed under precisely con-trolled conditions by.very intense ultrasonic energy which in turn produces a high energy field of cavitation energy directed in spherical and perpendicular fashion across and through the slurry solution within the annular passageway 22 as shown in Figure 3 and as it flows through the reactor chamber.
F
Since the reactor is a self-contained device which can be designed to a wide range of flow rates, it lends it-self to choice of locations in the cyanide leach.ing circuit. As desired by the meta:Llurgist, for example, an effective installation would be to utilize the ; 20 chemical reactor as a recirculation device for one or more of the holding tanks, whereby flow capacities rang-ing from 40,000 gallons.per hour or higher could be withdrawn continuously from a tank, circulated throu~h the reactor for processing and returned to the agitator tank. In this manner, the contents of the tank would be recirculated and processed for controlled oxidation and reaction many times during processing. For larger tanks where larger rates of recirculation may be re-quired, multiple use of the chemical reactors can be utilized.
Figure 7 shows the conduit lO' flowing ~rom the agitator ~4~7~
Figure 7 shows the conduit 10' flowing from the agitator tank 14 which transports the slurry and cyanide solu-tion to the reactor, the flow rate of which is measured by either a segmental orifice or a flow nozzle and its transmitter. The pump 11 is shown in the line to cir-culate the pulp solution through the agitator assembly 12 to the tank 14. The compressed gas flow rate is measured in turn by the orifice 46 and its transmitter ~5. The two flow transmitters 41 and 45 in turn transmit their individual flow rate results to the flow ratio controller 44 which automatically regulates control valve 51 in the compressed air line to proportion and maintain a fixed ratio of airflow to pulp solution flow.
The flow ratio controller 44 is equipped with a manual ratio setting to enable the metallurgist to adjust the desired value or ratio from time to time as may be re-quired to maintain optimum oxidation and reaction tak-ing place in the agitator holding tank closed system in order to increase the efficiency of metal recovery.
The compressed air may be passed to the reactor assembly 12 through a shutoff valve 59 shown in solid lines or through a line 50' and shutoff valve 59' to a point up steam of the pump 11 as shown by broken lines.
The resonant tube 15, which is a cylindrical shell, is specifically designed to one of the desired axial and circumferential ultrasonic resonant frequencies that have been selected for the structure. An example of the wave '~
length frequency patterns showing nodes and antinodes referred to for the cylindrical shell is illustrated in Figures 4, 5 and 6. The same description applies also ~-to the tube 19. "
Employment of the chemical reactor in ore and metal chemical processing dictates that the cylindrical shell be designed for the ultrasonic frequency range chosen preferably at a value between 20,000 and 40,000 cycles 5 per second. The cavitation implosions therefore in microns would permit the cavitation energy to penetrate, attack and implode the ore surfaces, pores, fissures and grain boundries and to also implode the molecules of the metals themselves. Ultrasonic heavy duty industrial r 10 magnetostrictive transducers are commercially available to supply the ultrasonic frequencies required for in-stallation on the resonant tubesO
Modern ultrasonic magnetostrictive transducers are 15 furnished commercially with solid state power supplies that are provided with adjustable output power and ad-justable frequency. These features are ideally suited for application to the chemical reactor, and also offer engineered reliability represented by 10 year guarantees.
20 With reference to Figure 1, the pulp solution containing atmospheric air as an oxidizing agent enters the ultra-sonic chamber, namely, the passageway 22, for processing ,~
where it is exposed to an intense field of cavitation ~, where the energy thus released within the pulp and ~-25 solution causes the interfaces and surface tensions of '' the materials to be broken and also to provide an energy means for oxidizing a good portion of the oxygen into reaction. In addition, the high energy kinetic reaction that takes place within the pulp solution causes dis-30 ,persion, agitation, mixing and surface cleaning of the materials and intense implosion on the sur~aces of the exposed metal to more fully release the metallic mol-ecules into solution.
~4Z~71~
The combined resonant system consists of the resonant cylindrical tubes 15 and 19, one or more transducers, or T
a multiple number of transducers, and its ultrasonic generator power supply. The resonant cylindrical tubes 5 are excited sinusoidally into one of their wave length modes of natural frequency in the ultrasonic range at a chosen value between 20,000 and 50,000 cyeles per second.
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The longitudinal and circumferential elastic wave 10 energy at resonance and thus released from the cylin-drical tube, causes very intense acoustic compressional sinusoidal wave energy to be transmitted in per~endi-cular fashion from the outer resonant tube surface thrGugh the pulp solution or slurry as shown in Figure 3.
15 The speed of the transmitted compressional wave energy within the unpure pulp solution is estimated at 5500 feet per second. The shearing forces of the compression wave energy traveling through the pulp solution cause a very high degree of kinetic energy reaetion to take 20 place within the pulp mixture which in turn fractures and ruptures the solution into a known form of energy namely vapouous cavitation whieh is a eommonly accepted term for such a condition.
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25 The vaporous cavitation energy field within the solu- I`
tion is continuously subjected to alternating positive and negative pressure cyeles whieh eause mieroscropic bubbles to be formed during the pressure cyeles and to be eollapsed during the negative eycles thus eausing a s 30 very intense vacuuming or implosion action on all the surfaces of materials in solution, for oxidation and implosion of ore surfaces and crevices which contain molecules of metal.
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Such energy life cycle transformations in three force planes take place each 10 9 of a second and form ellipsoid energy patterns in three planes which are continuously in a state of formation and collapse.
It is during the negative pressure or collapse phase of the energy cycle that voids are produced, as are also vapor cavities in solution. This in turn produces very intense vacuuming action on the surfaces and crevices of the ore material in solution, sometimes referred to as an implosion effect. The implosions which take place on the surfaces of the ore even to minute sur-face diameters of a few microns cause the surface tensions to be broken and permit the chemical solution to produce additional dissolution of the metal by penetration into the ore crevices and to also provide for a higher degree of oxidation to take place.
Basically, there are four mechanisms involved in re-moving additional metal from ore while undergoing pro-20 cessing in a chemical reactor: (1) solvation, ~2) in- i terface exchange, t3) chemical reactivn, and (4) dis-solution.
In the case of gold recovery, for example, a cyanide solution serves as a chemical solvent agent for dis-solving the gold from the ore. Any mechanical agitation speeds up the solvation process. The forces of cavi- ~ '`
tation will provide a direct and effective mechanical agitation.
Civitation can also serve to break down the molecular force or interface that exists between the solution and .
Z'8,~
the ore particles containing gold. The breaking of these forces can be accomplished by the direct shock or impact imparted by acoustical vaporous cavitation or can be the result of a fatiguing action caused by repeated bombard-ment and resulting explosions. Once the molecularattraction of the solution to the ore and metal is ; broken, the surface metal is imploded and cleaned and thus exposed for further dissolution.
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Chemical mechanisms can also be in the form of chemical conversioans or of the addition of chemical energy to the dissolution pxocess. Among the latter the addition of air or other chemical oxidation agents are most widely used. Cavitation serves to accelerate this energy reaction. When the mechanism is a chemical conversion, the usual action is to convert the metal to a soluable form.
Cavitation aids also in these reactions by means of the great pressure differentials that are set up by the implosions in the microscopic pores, cracks and grain boundries of the ore and metal and by the heat dissipated at the moment of implosion. The cavities or voids left by these implosions are instantaneously filled with the chemical fluid solution that surrounds the ore particles and are driven by very high transitory pres-sures. The resulting pressures generated at the loci of these implosions have been measured up to 1000 atmo-spheres. Furthermore, the heat dissipated at the moment of implosion has been determined to be in excess of 1000 degrees centigrade. Chemical processes can also be aided in a vaporous cavitation field by the direct mechanical agitation of cavitation, since they maintaln ~3~4~
a maximum concentration gradient of the chemical solu-tion at the surfaces of the ore particles.
One unique feature of cavitation is tha-t it can be generated anywhere that a compressional sound wave of sufficient intensity can penetrate, and reaction will occur deep within the interstices of an ore particle with complicated geometric configuration. Ore particle surfaces which are seemingly smooth to the naked eye have microscopic pores r crevices, cracks and grain boundries. The specific action of cavitation penetrates these minute areas with very intense transitory energy and results in implosions and resultant ruptures and fissures of the ore material at the microscopic level which can be equaled by no other known method. The implosions occurring on and within the ore particles create tremendous transitory pressures within the material. The alternative vacuum and pressure energy action reaching 10Q0 atmospheres o pressure occur many thousands of times per second and at resonance, which causes fatigue within the pores, cracks, grain bound-ries and fissures of the ore particles which forces the ore particles to be fractured to a large extent and thus to expose more fully the molecules and surfaces of metal for further recovery by means of chemical reaction and dissolution.
The solid state ultrasonic system is an efficient means to provide the energy necessary for operation of the chemical reactor. The individual power requirements, ; ,for example, for multiple transducer units is relatively low and may be supplied commerically as desired in power increments up to 12,000 watts. In special cases where very high capacities are required for a single chemical reactor, a multitude of transducers 30 representing a !
Z8 ~
multiple system may be used as shown in Figure 1. In this case the multiple transducers would be driven in phase from a single power source. An alternate installa-tion for higher rates of circulation could be made by utilizing muItiple chemical reactors.
In the form of invention of Figures 8 and 9 there are provided dual resonant tubes 80 and 81 the outer tube , 80 being of substantially the same thickness and res-onant character as the inner tube 81 which is spaced therefrom providing an annular passageway 82. `
, The tubes 80 and 81 are isolated from each other by the same structure described in connection with Figure 1 and are carried by appropriate supports 20 in the same fashion.
Because of the resonant character of the outer tube 80 ~ there is provided at the end of the supply conduit 10 ; 20 a flexible isolation ioint 83 of an appropriate vibra-tion damping material through which the fluid flows to a stub conduit 84, directly connected to the outer res-onant tube 80 by a regid weldment 85. A similar flexi-ble isolation joint 86 at the end of the line 50 carry-25 ing the oxydizing agent connects to a stub 87 ~y which the agent is conducted into the passageway 82 through the wall of the outer resonant tube 80.
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Similarly also a discharge stub 88 connects to the dis-30 charge conduit 13 through an isolating joint 89.
The joints as described taken together with the mountings at the end of the resonant tube assembly isolate the r ~'12~379 entire reactor structure from any rigid attachment or connection which would otherwise impair the effective-ness of the ultrasonic wave action which is generated.
5 By way of example there are shown three transducers 90, 91, and 92, on this occasion all connected to the ex-terior of the outer resonant tube 80. ~he transducers e are axially spaced one ~rom another in such fashion that they apply their force to the outer resonant tube 10 80 at wave length antinodal points.
As indicated in Figure 9 ultrasonic eneryy set up in the outer resonant tube 80 is transmitted by fluid material 93 to the inner resonant tube 81 causing the 15 inner resonant tube to be excited at resonance thereby to set up a resonant wave pattern in the fluid material in an opposite direction also as indicated by the arrows in Figure 9.
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20 A chamber 94 through the inner tube is clear.
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The embodiment of Figures 10 and 11 differs in that an inner tube 95 is thick walled and stationary whereas an outer tube 96 is relatively thinner walled and resonant.
25 The tubes are concentric and radially spaced from one another providing an annular passageway 97 for the fluid material which is subject to the reac*ion. Here again transducers 98. 99. amd 100 are mounted on the exterior of the outer tube 96 at respective wave length anti-30 nodal points to generate an ultrasonic frequency res-onant wave condition such as that illustrated by the arrows of Figure 11. In the device of Figures 10 and 11 there is an open chamber 101 extending through the inner tube 95.
137~
~n augmented transducer pattern is illustrated in Figure g 12 where, by way of example, an inner tube 105 and an oute~ tube 106 are illustrated as resonant tubes com-parable to the arrangement of Figures 8 and 9. The tubes 105 and 106 following the arrangement of the other forms of the device provide an annular passageway 107 for the fluid material which is to be reacted, there being a clear chamber 108 through the inner tube 105.
,.
For this arrangement transducers 108, 109, and 110 are applied to the exterior of the outer tube 106 at longi-tudinally spaced intervals so that they are located at antinodal points for the vibration condition which is set up. On this occasion additional transducers 112, 15 and 113 extend circumferentially around the outer tube 106 at the longitudinal midline.
With the proposed arrangement ultrasonic vibrations of two different kinds are generated in the outer resonant 20 tube 106 thereby emphasizing the pattern of both radial and longitudinal wave action, the elements of which have already been described in connection with Figures 4 and 5. It should be observed further that the circumfer-entially disposed transducers should also be applied 25 at antinodal points. Moreover, additional circum~ ~
ferentially disposed transducers are contemplated at S
other antinodal points corresponding, for example, to the locations of transducers 108 and 110.
30 Further still, although for the embodiment of Figure 12 several resonant tubes are shown, it may be found pre-ferable to provide only one resonant tube as for example, ~14Z~
making the inner tube 105 thicker walled and stationary.
Further still by following the pattern of mounting of Figures 1 and 2, transducers of appropriate size and capacity can be mounted not only at axially spaced locations but also at circumferentially spaced loca-tions around the inner circumference of the inner tube, where that tube is made a resonant tube.
Since the resonant character of the tube in which the b 10 transducers are mounted is appreciably significant, as well as the location of the transducers at wave length antinodal points a typical installation can be calculated.
Assuming the resonant tube to be of steel, the speed of 15 sound in the tube can be assume to be 14,610 feet per second. The frequency imparted to ordinary steel by the transducer may be designed for 22,000 cycles per second.
Therefore in the equation:
22,00o = .6641 feet 20 8 inches - .6666 feet. As a consequency, the transducers, P
where more than one are mounted on the resonant tube, will need to be at intervals of which would be multiples o~ approximately 8 inches. Because of known properties of the materials and related standard mathematical con-stants the entire structure can be designed to have the resonant characteristics desired. ~`
~
The control panel of Figure 13 is illustrative only and shows a control, for example, the flow ratio controller or selector valve 44, the flow transmitter 41 for the oxidizing agent, a proportioning control valve 115 and s a fluid flow measuring device 116.
~ .
Ultrasonic power supply generators are indicated on the panel by reference characters 118 and ll9. Flow re-:5 cording meters are indicated by the characters 120 and 121 and flow ratio controller by the reference character 122. A remote manual selector valve for control of the total flow leaving the reactor is shown at 123 and a manual automatic flow leaving the reactor is shown at 123 and a manual automatic flow ratio selector valveat 124. Because of the nature of the apparatus~and process made possible by the arrangement of equipment shown, careful control and regulation is a requisite and for adequate effectiveness all controls and indi-cators need to be concentrated at a single location.
~.
. Although the application of the chemical reactor for themine processing industry has been detailed in this dis-~ closure~ there are other significant uses for the chemi-: 20 cal reactor in the chemical processing industry generally where such methods and technology may be utilized in other forms of processing namely, dispersion, cleaning, : chemical washing, mechanical agitation, mixing and com-: pletion of chemical reactions by the introduction of 25 various forms of oxidizing agents in a control.led manner. .~
; ~.
An example of a system capable of accommodating, for example, a method or process directed to solvent extrac-`tion of oil from tar sands or oil sands is shown in a : 30 pilot extraction plant system as illustrated in Figure 14.
,.
As there shown, the system is one set up for operation !
~ 4~
principally as a gravity system in the interest of economizing further power requirements.
An acceptable apparatus as shown would involve several processing steps. The first step in the process is the reduction oE the oil sand agglomerate. Deagglomeration to a maximum one-quarter inch size is sufficient, since i the high frequency energy action quickly reduces the tar sand to individual granules. The tar sands would be processed continuously by a single-toothed crusher since the material is easily reduced. The tar sands thus supplied by the mass 130 are continuously fed to a hopper 132.
The material is then funneled into an automatic contin-uous weighing gravimetric feeder 133 and weighed in terms of LBS/HR and from there into a mixing tank 134 which has an impeller agitator 135. In this instance solvent 136 from a solvent tank 137 is fed by gravity to the mixing tank 134. The flow is metered by a meter 138 in terms of LBS/HR in a solvent line 139. The flow through a line 140 is manually set to a metered amount on a weight basis by means of a manual valve 143 so that the solvent flow weight to the mixing tank 134 and the - 25 tar sand weight to the tank 134 are at a ratio of one to - one, or less, by weight. A heater 144 in the solvent tank 137 maintains a low temperature of 150F. A -float control merchanism in tank 134 will automatica~ly close a normally open valve 142 by means of a pneumatic line 141 when the tank level of 134 exceeds its desired le~el ~or safety purposes.
. ;
.
~3L'lZ~ ~9 From the tank 134 the slurry mixture flows continuously through a discharge line 146 in which there is a hand-operated valve 1~7 and a metering device 148 to the upper end of a chem.ical reactur assembly 150 of the type here-tofore made reference to.
A by-pass line 170 is provided to pass a small amount of fresh solvent 136 as a chemical reagent to the chemi-cal reactor assembly and is metered by a meter 171 through a valve 172. This relati.vely small by-pass chemi.cal reagen-t f].ow provides a process corrective means to ; produce highest extraction efficiency within the chemical reactor.
The mixing tank 134 also serves a significant function as a detention device since the tank volume is designed to be many times the annular processing chamber volume of the chemical reactor. A flow detention time of 15 to 30 minutes has been found sufficient to soften the tar or the crushed tar sand before final extraction takes place in the chemical reactor 150.
The pre-mixed slurry enters the annular high frequency ener~y chamber of the chemical reactor 150 where cavi- ,~
tation at 22,000 cycles/sec., which is created by the transducers, quickly reduces the tar sand by implosions to individual grains. As the action continues, cavita-tion also blends the solvent with the bitumen and the energy implosions separate it from the sand. The unique advantage of using sonic energy is that it acts on each individual grain of sand. Cavitation, the minute vacuous bubbles that constantly form and collapse, causes an !
~26-intense energy release that implodes the materiall caus-ing the softened bitumen to be puIled away from the hard surface of the sand much the same as it pulls soil or contamination away from hard surfaces in cleaning opera-5 tions. In this instance, however, the purpose is not to clean the sand, but to remove the bitumen.
j.
The next step in the process is to pass the slurry mixture of bitumen, sand and solvent by gravity flow through a P
line 153 to a clarifier 154.
The clarifier provides à standard means for liquid-solids separation. The solid in this case is sand and the liquid represents the oil-solvent solution. Water within 15 the clarifier acts as a separation medium since the specific gravity of the oil-solvent is considerably lower than water. The oil-solvent mixture rises to the top of the water solution and is skimmed off the top through a line 160 for further processing. The clarifier mech-20 anism also provides a high rate of circulation and agita-tion which causes further dissolution of the bitumen i-n the solvent solution. The clean sand slowly falls to g the bottom of the clarifier and is removed through a line 156 by a screw auger. A slight amount of detergent 25 added to the water solution will enhance the removal of t-solvent from the sand surfaces.
t Waste water from the clarifier is removed through a line 157 and processed in a water filtration unit 158, 30 clean water being removed through a line 159 and returned to the clarifier. Make-up water is supplied to the clari-fier by means of line 152 in order to maintain a con-stant water level in the clarifier 154. b i~L42~37~
The next step in the process is to pass the oilsolvent solution to a fractionating tower 163 by means of a line 160 and pump 162 as metered by a meter 161. The solvent is taken off, decanted and returned to thé
solvent tank 137 by means of a line 165 for further use.
The oil at approximately 18 API is removed through a line 164 and subjected to the usual processes, such as cracking, reforming and alkylation, to produce motor fuel, fuel oil and similar products. Solvent loss 10 experimentally is less than 1%. Oil extraction from tar sands has been shown experiemntally to be 96% to 98~.
The continuous flow solvent extration process, as shown in the schematic pilo-t plant illustrated in Figure 14, ~ 15 may be implemented to a large oil extraction production ; plant of 10r000 Bbls/day to 20,000 Bbls/day or higher and within the framework of sound engineering practice.
This, for example, may be accomplished by enlarging the 20 outside deameter of the chemical reactor 150 to six feet or larger whereby the annular processing chamber is de-signed to desired volumetric considerations while at the same time maintaining the proper and most efficient energy transmission dis-tance within the annular chamber r 25 for efficient extraction purposesO
Individual high capacity chemical reactor units may be added in the form of modules to obtain any total desired plant capacity. These modules would operate in a parallel 30 configuration and be supplied by one or several slurry feeders.
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for enhancing chemical activity in a contin-uous system comprising continuously circulating a liquid-like mass through the system at a selected rate of flow, con-tinuously introducing a chemical agent into the liquid-like mass to form a liquid-like composite mass, confining the flow of said composite mass to a stream of annular cross-sec-tional shape having an inflow at one end and an outflow at the other end, moving the composite mass in a freely flowing stream and a substantially continuous rate from said inflow end to said outflow end, setting up a multiplicity of ultrasonic sources of resonance through the length and circumference of said stream and transmitting said resonance in radially inwardly converging directions toward and into the free flowing stream of said composite mass simultaneously and uniformly throughout the entire length and perimeter thereof, whereby to develop a condition of cavitation in the ultrasonic range while said composite mass is in transit, and then collecting the resulting combination of said composite mass at discharge location.
2. A method for enhancing chemical activity in a continuous system comprising preparing a source of supply of a first liquid-like mass and placing said first liquid-like mass under a first selected rate of flow, preparing a source of supply of a second mass comprising a chemical agent and placing said second mass under a second rate of flow, adding the second mass to the first liquid-like mass to form a liquid-like composite mass, confining the composite mass to a passage of annular cross-sectional shape having hard and resilient outer and inner surfaces and providing an inlet adjacent one end an outlet adjacent the other end, injecting said first liquid-like mass through said inlet into the passage at said first selected rate of flow, introducing said second mass into said first liquid-like mass at a location upstream of said inlet, thereby forming a free flowing stream of said composite mass through said passage, constantly sensing the total rate of flow of the composite mass in said passage, constantly sensing the rate of flow of the second mass downstream of said source of supply, bringing both said rates of flow into a counter-balancing relationship whereby to establish a supply flow rate for the second mass in proportion to the total rate of flow of the composite mass, maintaining the flow of said second mass into said first liquid-like mass at said supply flow rate, setting up a multiplicity of ultrasonic sources of resonant energy throughout the length and circumference of said hard outer surface of the passage, projecting said resonant energy from said sources in radially converting directions relative to the composite mass while in said annular passage and trans-mitting said resonant energy condition to and into said com-posite mass throughout the entire space provided by the annu-lar passage, continuing the transmitting of said energy to all portions of the composite mass as it progresses the length of the passage thereby creating a statge of cavita-tation in the ultrasonic range within the composite mass for the duration of transit of said composite mass through said passage and then collecting the product of said composite mass.
3. A method as in Claim 1 including collecting the resul-ting combination of said composite mass in a reservoir, intro-ducing a second chemical agent in said reservoir to form second composite mass, agitating the second composite mass while in said reservoir and then discharging said second composite mass from the reservoir.
4. A method as in Claim 3 including continuously passing a first portion of the second composite mass from the reser-voir to the system and continuously discharging a second portion of the second composite mass from the reservoir while the first portion is being passed to the system.
5. A method as in Claim 3 including returning the product of said second composite mass to said supply of the first liquid-like mass whereby to form a mixture, and drawing off quantities of said mixture.
6. A method as in Claim 1 including passing the liquid-like mass through the system by gravity flow, introducing the chem-ical agent by gravity into the liquid-like mass and metering the flow of said chemical agent in proportion to the flow of said liquid-like mass to form the composite mass, passing the composite mass by gravity and in said condition in the ultra-sonic range to said discharge location.
7. A method as in Claim 6 including adding to the liquid-like mass a mixture of finely divided solids and a soluble ingredient of finely divided solids and a soluble ingre-dient and including the step of combining the chemical agent with the souble ingredient, and subjecting the compos-ite mass to said resonant condition while the combining is taking place, whereby the solids are separated from the composite mass, removing the soluble ingredient with the chemical agent in combined condition from the finely divided solids and then separating the chemical agent from the sol-uble material.
8. A method as in Claim 7 including returning the chemical agent to the place of introduction after separating the chemical agent from the soluble material.
9. A method as in Claim 6 including making up said com-posite mass from a finely divided mass of solid material and and water wherein the resulting composite mass is in the form of a slurry, collecting said slurry in a reservoir for introduction of said chemical agent and metering the flow of the chemical agent into the reservoir in proportion to the flow of said composite mass with the chemical agent present from said reservoir.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000357232A CA1142879A (en) | 1980-07-29 | 1980-07-29 | Method for enhancing chemical reactions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000357232A CA1142879A (en) | 1980-07-29 | 1980-07-29 | Method for enhancing chemical reactions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142879A true CA1142879A (en) | 1983-03-15 |
Family
ID=4117534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000357232A Expired CA1142879A (en) | 1980-07-29 | 1980-07-29 | Method for enhancing chemical reactions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1142879A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112553268A (en) * | 2020-11-10 | 2021-03-26 | 南宁汉和生物科技股份有限公司 | Method and device for synthesizing trehalose by using ultrasonic-assisted enzyme |
-
1980
- 1980-07-29 CA CA000357232A patent/CA1142879A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112553268A (en) * | 2020-11-10 | 2021-03-26 | 南宁汉和生物科技股份有限公司 | Method and device for synthesizing trehalose by using ultrasonic-assisted enzyme |
| CN112553268B (en) * | 2020-11-10 | 2023-10-03 | 南宁汉和生物科技股份有限公司 | Method and device for synthesizing trehalose by ultrasound-assisted enzyme |
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