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WO1993016572A1 - Method and means for changing characteristics of substances - Google Patents

Method and means for changing characteristics of substances Download PDF

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Publication number
WO1993016572A1
WO1993016572A1 PCT/US1993/001216 US9301216W WO9316572A1 WO 1993016572 A1 WO1993016572 A1 WO 1993016572A1 US 9301216 W US9301216 W US 9301216W WO 9316572 A1 WO9316572 A1 WO 9316572A1
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WO
WIPO (PCT)
Prior art keywords
solvent
field
substance
electric field
voltage
Prior art date
Application number
PCT/US1993/001216
Other languages
French (fr)
Inventor
John L. Remo
Original Assignee
Sgi International
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sgi International filed Critical Sgi International
Publication of WO1993016572A1 publication Critical patent/WO1993016572A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/11Electrochemical processes, e.g. electrodialysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G32/00Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
    • C10G32/02Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00168Controlling or regulating processes controlling the viscosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00171Controlling or regulating processes controlling the density
    • B01J2219/00175Optical density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824Details relating to the shape of the electrodes
    • B01J2219/0826Details relating to the shape of the electrodes essentially linear
    • B01J2219/083Details relating to the shape of the electrodes essentially linear cylindrical
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824Details relating to the shape of the electrodes
    • B01J2219/0832Details relating to the shape of the electrodes essentially toroidal
    • B01J2219/0833Details relating to the shape of the electrodes essentially toroidal forming part of a full circle
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824Details relating to the shape of the electrodes
    • B01J2219/0835Details relating to the shape of the electrodes substantially flat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873Materials to be treated
    • B01J2219/0877Liquid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2357/00Characterised by the use of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08J2357/02Copolymers of mineral oil hydrocarbons

Definitions

  • This invention relates to changing the characteristics of substances, and particularly to untangling, stretching or otherwise unraveling very large molecular assemblages, and especially to methods and means for converting waste substances such as crude oil residues to usable substances.
  • An object of the invention is to change the characteristics of substances.
  • Another object is to untangle, stretch, or otherwise unravel large molecular assemblages.
  • Another object of the invention is to overcome these difficulties.
  • Another object of the invention is to reconstitute waste materials.
  • these objects are attained in whole or in part by passing the substance along a path, passing a solvent for that substance along the path, and subjecting the substance and the solvent to a pulsating electric field.
  • the field is pulsed at a frequency to create resonances in polar moments, e.g. dipoles, of large molecular assemblages in the substances so as to untangle the assemblages.
  • Fig. 1 is a schematic diagram of a recycling arrangement embodying features of the invention.
  • Fig. 2 is a cross-section 2-2 of a portion of Fig. 1.
  • Fig. 3 is another embodiment of the cross- section in Fig. 2.
  • Fig. 4 is a cross-section 4-4 of Fig. 3
  • Figs. 5 to 9 are graphs of waveforms usable in the circuit of Fig. 1.
  • Figs. 10 is schematic diagram of another arrangement embodying features of the invention.
  • Fig. 11 is cross-section 11-11 of a portion of Fig. 10.
  • Fig. 12. is schematic diagram of yet another system embodying features of the invention.
  • SUBSTITUTESHEET Fig. 13 is a schematic diagram of another arrangement embodying the invention.
  • Fig. 14 is a schematic diagram of a precipitator for use in Fig. 13.
  • Figs. 15, 16, and 17 illustrate various waveforms with duty cycles of approximately 20% each.
  • the invention is described with respect to the reconstitution of waste crude oil residues, although the invention may be applicable to any changes in the characteristics of substances, and particularly to untangling, stretching or otherwise unraveling very large molecular assemblages.
  • a non-conductive cylinder 10 of glass, ceramic, or other material receives crude oil residue (COR) 12 which an impeller 20 injects through a first input port 24.
  • a second impeller 26 injects a solvent 28, such as diesel range gas oil, to the cylinder 10 through a second input port 30.
  • the solvent is heptane, kerosene, isooctane, methylcyclohexane, ethylcyclohexane, or combinations of these.
  • SUBSTITUTESHEET pulsating high voltage from a high voltage (HV) source 40 and impose a pulsating high voltage electric field 42 across the COR and solvent.
  • HV high voltage
  • a signal generator 46 connected to the source 40 controls the waveform and polarity of the field which the HV source imposes on the COR 12 and solvent 28. Hence the signal generator 46 and the source 40 determine the nature of the electric field 42.
  • the COR 12 and solvent 28 are processed by allowing the pulsed electric field 42 to promote interactions between those materials. After sufficient processing to complete the desired interaction between the COR 12 and solvent 28, the processed material 18 is expelled from the cylinder 10 by the ejector 16. The processed material 18 is then passed by the sensor 68 which detects properties of the processed material 18. For example, the sensor 68 may measure the viscosity and opacity of the processed material 18 to determine the effectiveness of the previous processing cycle. Data on the measurements then go to a microprocessor 80 which controls the signal generator 46 to adjust the pulse amplitude and frequency during the subsequent processing cycle. The microprocessor 80 could also control the quantities of COR 12 and solvent 28 admitted to the cylinder 10 by sending appropriate signals to the impellers 20 and 26.
  • the field 42 is pulsed unidirectionally and according to one embodiment of the invention.
  • the pulse rate may vary from 0.1 Hz to 100 Hz.
  • the pulse rate varies from 0.3 Hz to 20 Hz, and most preferably from .5 Hz to 4 Hz.
  • the voltage of the field is 3,000 to 10,000 volts and preferably 4,500 to 6,000 volts and most preferably 5,000 volts across a distance from 5 to 50 cm, preferably 7 to 30 cm, an most preferably 10 cm.
  • the pulsing rate may be optimized by varying the frequency of the signal generator 46 and observing the production rate of the treated material 18.
  • the voltage may be selected by varying the voltage setting of the HV supply 40 and observing the production rate of the processed material 18. Pulsation rate, rise time, and shape variation permit higher applied voltages and allow greater effective (internal to material) voltage for a given discharge.
  • Fig. 2 illustrates one shape of the electrodes 34 and 36, while Fig. 3 illustrates another shape.
  • the longitudinal section in Fig. 4 illustrates converging electrodes which form a homogeneous field.
  • Figs. 5 to 8 illustrate various types of pulsed signals S generated by the signal generator 46 to control the high voltage source 40
  • the solvent 28 loosens the interaction of large polymers and polar asphaltenes are squeezed out of the COR and stabilized by the pulsating high voltage field.
  • the solvent dilutes the COR and creates a critical level of mobility in which the asphaltenes can become free and interact with their dipoles.
  • the high voltage pulsed field creates a high specific impulse, generates torques to break down the COR asphaltene mixture and also some H bonds.
  • the HV field pulsed or steady state, keeps polar and non-polar components separate.
  • the electric field 42 may perturb the solvation reaction in such a way that new chemical species are formed.
  • the combined effect of the solvent 28 and the electric field 42 may enable loosely bound molecular fragments attached to the asphaltenes to be released. Such molecular fragments may then form new solvent material or other valuable molecular products, which may then be recovered.
  • the outflow from the cylinder 10 of disentangled COR is in the form of a low viscosity fluid usable as a fuel but containing solid asphaltenes.
  • a portion of the fluid may be utilized a solvent.
  • the liquid outflow viscosity may be as light as kerosene and even lighter.
  • an outflow passes to a sensor 68.
  • a distiller 72 receives the outflow that has passed through the sensor 68 and separates it into various components 74 and 76.
  • a pipe 78 passes some of the components back to the solvent
  • SUBSTITUTESHEET impeller 26 for use as a solvent in the process.
  • the sensor 68 senses the viscosity and other characteristics of the outflow 60 and applies the sensed data to a microprocessor 80.
  • the latter analyzes the characteristics of the outflow and controls the signals of the signal generator 46 so as to vary the output to obtain a fluid with desired characteristics.
  • the system can customize the characteristics of the outflow 60.
  • a display 82 exhibits the voltage signal from the signal generator 46.
  • the display 82 could show any of the data processed by the data processor 80 including characteristics of the processed material 18 measured by the sensor 68.
  • each parameter favors a different phase structure.
  • the combination of the pulsed high voltage field 42 and the solvent 28 serve to break down the COR into a thin low-viscosity fluid.
  • the fluid is a very low viscosity petroleum product.
  • SUBSTITUTESHEET is believed to occur most effectively at the boundaries between the COR 12 and the solvent 28.
  • the COR changes from a dark viscous substance to a clear solution in the form of a translucent amber liquid.
  • cellulose, coal ash or another adsorbent adsorb the liquid to form a product that can be recycled into a solvent or used as a fuel.
  • FIGs. 10, 11, and 12 where parts corresponding to parts in the remaining figures have like reference characters.
  • a concentric inner conductive cylinder 96 spaced 1 cm to 10 cm from the outer cylinder 90 by spacers (not shown) retains the COR 12 in an annular space 98 which the cylinders 90 and 96 form between them.
  • a source 100 of solvent 28 injects the solvent at an entry end 104 of the annular space 98.
  • a suitable impeller arrangement not shown, drives the solvent 28 and COR 12 from the entry and 104 toward an exit end 112 of the annular space 98 to create a continuous flow of COR 12 and solvent 28 from the entry end 104 to the exit end 112.
  • the high voltage (HV) source 40 connected across the space 98 to the inner and outer conductive cylinders 90 and 96 establishes an inhomogeneous divergent electric field 122 of shifting value.
  • the signal generator 46 connected to the source 40 controls
  • the arrangements of Figs. 1, 10, 11, and 12 include a precipitator 144 in the line 60 to the sensor 68. Such an arrangement appears in Fig. 13 and is intended to represent this variation of the embodiments of Figs. 1, 10, 11, and 12.
  • the precipitator 144 removes the asphaltenes in the outflow.
  • Fig. 14 illustrates details of the precipitator 144.
  • the flow passes through the precipitator 144 which includes collector plates 154, baffles 158, and electrodes 160.
  • the asphaltene particles 168 are electrostatically attracted to the electrodes 160 and are caught by the collector plates 154.
  • the baffles 158 reduce asphaltene particle re-entrainment.
  • SUBSTITUTESHEET waveforms with duty cycles of approximately 20% each. Different materials respond to different duty cycles.
  • the source 40 varies the duty cycle the basis of the sensed output of the system to achieve an optimum output.
  • the invention involves pulsing, and hence torquing, polar moments, e.g. dipoles, at microscopic levels to get macroscopic effects in an ordered manner.
  • the source 40 pulses at the range of frequencies mentioned to create the torquing upon the molecules which are loosely associated, weakly bonded, in a liquid lattice and exhibit large inertia.
  • the frequency ranges of the source 40 is significant for creating resonances which enhance the torques in the high inertia environment. This makes it unnecessary to shock the substance and break down the molecules by establishing disorder. Rather the molecules are untangled, stretched, and unraveled.
  • Smaller particles having diameters less than 0.2 p are subject to diffusion charging in which ions meet the particles on account of their thermal motion.
  • n b (pE 0 d 2 / 4e) (t/ [t+ (l/ ⁇ Nek) ] ⁇
  • d particle size
  • e permittivity of particle
  • E Q field strength to which the particle is exposed.
  • the self-field of the particles as they charge will act in opposition to E 0 so that the charging rate falls with time.
  • the invention may be used in other fields to promote changing the characteristics of various substances.
  • it may be employed to accelerate or control interactions between two or more substances.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

A method and means for changing the characteristics of a substance (12), particularly a viscous substance, involves passing the substance into a path (10), passing a solvent (28) for that substance into the path, and subjecting the substance and the solvent to a pulsating electric field (42) in the frequency range of 0.1 Hz to 100 Hz.

Description

TITLE
METHOD AND MEANS FOR CHANGING CHARACTERISTICS OF
SUBSTANCES
BACKGROUND OF THE INVENTION
This is a continuation-in-part of U.S. Patent
Application No. 07/832,285 filed 10 February 1992, of John L. Remo.
This invention relates to changing the characteristics of substances, and particularly to untangling, stretching or otherwise unraveling very large molecular assemblages, and especially to methods and means for converting waste substances such as crude oil residues to usable substances.
It is often desirable to change the characteristics of substances to make them serviceable. Many industrial processes accomplish this end chemically or physically through mixing or interaction with other materials. However some materials are viscous or solid, so that mixing or normal interaction may demand too much time or energy to make the process worthwhile. For example, such a problem arises with waste products such as crude oil residues. These serve few useful purposes and pose environmental hazards. Most efforts have been expended in disposing of these residues such as by burning or burial. However, no simple way has been found to employ or discard such
SUBSTITUTESHEET material safely. Attempts to recycle or reconstitute them, by such means as dissolving them, so they can serve a useful purpose have been largely unsuccessful.
OBJECTS AND SUMMARY OF THE INVENTION
An object of the invention is to change the characteristics of substances.
Another object is to untangle, stretch, or otherwise unravel large molecular assemblages.
Another object of the invention is to overcome these difficulties.
Another object of the invention is to reconstitute waste materials.
According to a feature of the invention, these objects are attained in whole or in part by passing the substance along a path, passing a solvent for that substance along the path, and subjecting the substance and the solvent to a pulsating electric field.
According to another feature of the invention, the field is pulsed at a frequency to create resonances in polar moments, e.g. dipoles, of large molecular assemblages in the substances so as to untangle the assemblages.
SUBSTITUTESHEET These and other features of the invention are pointed out in the claims. Other objects and advantages of the invention will become evident from the following description when read in light of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic diagram of a recycling arrangement embodying features of the invention.
Fig. 2 is a cross-section 2-2 of a portion of Fig. 1.
Fig. 3 is another embodiment of the cross- section in Fig. 2.
Fig. 4 is a cross-section 4-4 of Fig. 3
Figs. 5 to 9 are graphs of waveforms usable in the circuit of Fig. 1.
Figs. 10 is schematic diagram of another arrangement embodying features of the invention.
Fig. 11 is cross-section 11-11 of a portion of Fig. 10.
Fig. 12. is schematic diagram of yet another system embodying features of the invention
SUBSTITUTESHEET Fig. 13 is a schematic diagram of another arrangement embodying the invention.
Fig. 14 is a schematic diagram of a precipitator for use in Fig. 13.
Figs. 15, 16, and 17 illustrate various waveforms with duty cycles of approximately 20% each.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is described with respect to the reconstitution of waste crude oil residues, although the invention may be applicable to any changes in the characteristics of substances, and particularly to untangling, stretching or otherwise unraveling very large molecular assemblages.
In the embodiment of the invention shown in Figs. 1 and 2, a non-conductive cylinder 10 of glass, ceramic, or other material receives crude oil residue (COR) 12 which an impeller 20 injects through a first input port 24. A second impeller 26 injects a solvent 28, such as diesel range gas oil, to the cylinder 10 through a second input port 30. According to other embodiments of the invention, the solvent is heptane, kerosene, isooctane, methylcyclohexane, ethylcyclohexane, or combinations of these.
As the COR 12 encounters and mixes with the solvent 28, opposing electrodes 34 and 36 receive a
SUBSTITUTESHEET pulsating high voltage from a high voltage (HV) source 40 and impose a pulsating high voltage electric field 42 across the COR and solvent.
A signal generator 46 connected to the source 40 controls the waveform and polarity of the field which the HV source imposes on the COR 12 and solvent 28. Hence the signal generator 46 and the source 40 determine the nature of the electric field 42.
The COR 12 and solvent 28 are processed by allowing the pulsed electric field 42 to promote interactions between those materials. After sufficient processing to complete the desired interaction between the COR 12 and solvent 28, the processed material 18 is expelled from the cylinder 10 by the ejector 16. The processed material 18 is then passed by the sensor 68 which detects properties of the processed material 18. For example, the sensor 68 may measure the viscosity and opacity of the processed material 18 to determine the effectiveness of the previous processing cycle. Data on the measurements then go to a microprocessor 80 which controls the signal generator 46 to adjust the pulse amplitude and frequency during the subsequent processing cycle. The microprocessor 80 could also control the quantities of COR 12 and solvent 28 admitted to the cylinder 10 by sending appropriate signals to the impellers 20 and 26.
According to one embodiment of the invention, the field 42 is pulsed unidirectionally and according
SUBSTITUTESHEET to another it is pulsed bidirectionally. According to the invention, the pulse rate may vary from 0.1 Hz to 100 Hz. Preferably the pulse rate varies from 0.3 Hz to 20 Hz, and most preferably from .5 Hz to 4 Hz. The voltage of the field is 3,000 to 10,000 volts and preferably 4,500 to 6,000 volts and most preferably 5,000 volts across a distance from 5 to 50 cm, preferably 7 to 30 cm, an most preferably 10 cm. However, even higher voltages and a larger range of distances are contemplated. The pulsing rate may be optimized by varying the frequency of the signal generator 46 and observing the production rate of the treated material 18.
For different applications, the voltage may be selected by varying the voltage setting of the HV supply 40 and observing the production rate of the processed material 18. Pulsation rate, rise time, and shape variation permit higher applied voltages and allow greater effective (internal to material) voltage for a given discharge.
The cross-sectional view in Fig. 2 illustrates one shape of the electrodes 34 and 36, while Fig. 3 illustrates another shape. The longitudinal section in Fig. 4 illustrates converging electrodes which form a homogeneous field. Figs. 5 to 8 illustrate various types of pulsed signals S generated by the signal generator 46 to control the high voltage source 40
SUBSTITUTESHEET Within the cylinder 10, the solvent 28 loosens the interaction of large polymers and polar asphaltenes are squeezed out of the COR and stabilized by the pulsating high voltage field. The solvent dilutes the COR and creates a critical level of mobility in which the asphaltenes can become free and interact with their dipoles. The high voltage pulsed field creates a high specific impulse, generates torques to break down the COR asphaltene mixture and also some H bonds. The HV field, pulsed or steady state, keeps polar and non-polar components separate.
The electric field 42 may perturb the solvation reaction in such a way that new chemical species are formed. For example, the combined effect of the solvent 28 and the electric field 42 may enable loosely bound molecular fragments attached to the asphaltenes to be released. Such molecular fragments may then form new solvent material or other valuable molecular products, which may then be recovered.
The outflow from the cylinder 10 of disentangled COR is in the form of a low viscosity fluid usable as a fuel but containing solid asphaltenes. A portion of the fluid may be utilized a solvent. The liquid outflow viscosity may be as light as kerosene and even lighter. As shown in Fig. 1, an outflow passes to a sensor 68. A distiller 72 receives the outflow that has passed through the sensor 68 and separates it into various components 74 and 76. A pipe 78 passes some of the components back to the solvent
SUBSTITUTESHEET impeller 26 for use as a solvent in the process.
The sensor 68 senses the viscosity and other characteristics of the outflow 60 and applies the sensed data to a microprocessor 80. the latter analyzes the characteristics of the outflow and controls the signals of the signal generator 46 so as to vary the output to obtain a fluid with desired characteristics. By varying the pulse shape, the pulse rise time, the pulse frequency, and the magnitude of the high voltage which the signal generator 46 imposes on the HV generator 40 on the basis of the analysis of the microprocessor 80, the system can customize the characteristics of the outflow 60. A display 82 exhibits the voltage signal from the signal generator 46. Alternatively, the display 82 could show any of the data processed by the data processor 80 including characteristics of the processed material 18 measured by the sensor 68.
Further controlling the characteristics of the interaction between the COR 12 and the solvent 28 are the mixture of polar and non-polar components and the interface parameter between the polar and non-polar components. At 100 A, 500 A, and 2500 A, each parameter favors a different phase structure.
The combination of the pulsed high voltage field 42 and the solvent 28 serve to break down the COR into a thin low-viscosity fluid. Essentially the fluid is a very low viscosity petroleum product. The result
SUBSTITUTESHEET is believed to occur most effectively at the boundaries between the COR 12 and the solvent 28. The COR changes from a dark viscous substance to a clear solution in the form of a translucent amber liquid. According to one embodiment cellulose, coal ash or another adsorbent adsorb the liquid to form a product that can be recycled into a solvent or used as a fuel.
Other embodiments of the invention appear in Figs. 10, 11, and 12 where parts corresponding to parts in the remaining figures have like reference characters. In Figs. 10 and 11, an outer conductive cylinder 90 rece;./es crude oil residue 12 through injection ports shown as holes 94 along its length and periphery. A concentric inner conductive cylinder 96 spaced 1 cm to 10 cm from the outer cylinder 90 by spacers (not shown) retains the COR 12 in an annular space 98 which the cylinders 90 and 96 form between them. A source 100 of solvent 28 injects the solvent at an entry end 104 of the annular space 98. A suitable impeller arrangement, not shown, drives the solvent 28 and COR 12 from the entry and 104 toward an exit end 112 of the annular space 98 to create a continuous flow of COR 12 and solvent 28 from the entry end 104 to the exit end 112.
The high voltage (HV) source 40 connected across the space 98 to the inner and outer conductive cylinders 90 and 96 establishes an inhomogeneous divergent electric field 122 of shifting value. The signal generator 46 connected to the source 40 controls
SUBSTITUTESHEET the waveform and polarity of the voltage which high voltage source 40 applies to the cylinders 90 and 96. Hence, the signal generator 46 and HV source 40 determine the nature of the electric field 122 in the space 98. The COR 12 and solvent 28 passing longitudinally through the annular space 98 respond to the pulsing electric field 122 as described with respect to Fig. 1.
In Fig. 12, the application of the COR 12 and the solvent 28 differ from that of Fig. 10. Here, the solvent 28 enters the openings 94 and the COR enters the entry end 104 of the space 98. The system works otherwise like that of Figs. 1 and 10.
According to an embodiment of the invention, the arrangements of Figs. 1, 10, 11, and 12 include a precipitator 144 in the line 60 to the sensor 68. Such an arrangement appears in Fig. 13 and is intended to represent this variation of the embodiments of Figs. 1, 10, 11, and 12. The precipitator 144 removes the asphaltenes in the outflow. Fig. 14 illustrates details of the precipitator 144. In Fig. 14, the flow passes through the precipitator 144 which includes collector plates 154, baffles 158, and electrodes 160. The asphaltene particles 168 are electrostatically attracted to the electrodes 160 and are caught by the collector plates 154. The baffles 158 reduce asphaltene particle re-entrainment.
Figs. 15, 16, and 17 illustrate various
SUBSTITUTESHEET waveforms with duty cycles of approximately 20% each. Different materials respond to different duty cycles. According to an embodiment of the invention, the source 40 varies the duty cycle the basis of the sensed output of the system to achieve an optimum output.
The invention involves pulsing, and hence torquing, polar moments, e.g. dipoles, at microscopic levels to get macroscopic effects in an ordered manner. The source 40 pulses at the range of frequencies mentioned to create the torquing upon the molecules which are loosely associated, weakly bonded, in a liquid lattice and exhibit large inertia. The frequency ranges of the source 40 is significant for creating resonances which enhance the torques in the high inertia environment. This makes it unnecessary to shock the substance and break down the molecules by establishing disorder. Rather the molecules are untangled, stretched, and unraveled.
Smaller particles having diameters less than 0.2 p are subject to diffusion charging in which ions meet the particles on account of their thermal motion.
The number of basic electronic charges varies with time t according to nb = (pE0d2 / 4e) (t/ [t+ (l/πNek) ] } where t = time p = 3 e/ ( e + 2 ) , d = particle size, e = permittivity of particle
SUBSTITUTE SHEET p = 3 when particles conduct,
EQ ≡ field strength to which the particle is exposed. The self-field of the particles as they charge will act in opposition to E0 so that the charging rate falls with time.
The diffusion charging rate dnj/dt = (πd2sN/4) exp (-2nde2 /dKT) where nd = (dKT/2e2) log (1 + πdsNe2t/2KT) where K = Boltzman's constant. Particle migration velocity ω = neE0/37rμd.
The invention may be used in other fields to promote changing the characteristics of various substances. For example, it may be employed to accelerate or control interactions between two or more substances.
While embodiments of the invention have been described in detail, it will be evident to one skilled in the art that the invention may be embodied otherwise without departing from its spirit and scope.
SUBSTITUTESHEET

Claims

What is claimed is:
1. The method of changing the characteristics of a substance, which comprises: passing the substance along a path; passing a solvent for that substance along the path; and subjecting the substance and the solvent to a pulsating electric field.
2. The method as in claim 1, wherein the electric field exceeds 1,000 volts.
3. The method as in claim 1, wherein the electric field is pulsed at a frequency from 0.1 Hz to 100 Hz.
4. The method as in claim 1, wherein the electric field is pulsed from 0.3 Hz to 20 Hz.
5. The method as in claim 1, wherein the electric field is pulsed from .5 Hz to 4 Hz.
6. The method as in claim 1, wherein the voltage of the field is 3,000 to 10,000 volts.
7. The method as in claim 1, wherein the voltage of the field is 4,500 to 6,000 volts.
8. The method as in claim 1, wherein the voltage of the field is 5,000 volts.
SUBSTITUTESHEET
9. The method as in claim 2, wherein the voltage of the field is 3,000 to 10,000 volts.
10. The method as in claim 2, wherein the voltage of the field is 4,500 to 6,000 volts.
11. The method as in claim 2, wherein the voltage of the field is 5,000 volts
12. An apparatus for changing the characteristics of a substance, comprising: means forming a path; means for passing the substance along the path; means for passing a solvent for that substance along the path; and means for subjecting the substance and the solvent to a pulsating electric field.
13. The apparatus as in claim 1, wherein the electric field exceeds 1,000 volts.
14. The apparatus as in claim 1, wherein the electric field is pulsed at a frequency from 0.1 Hz to 100 Hz.
15. The apparatus as in claim 1, wherein the electric field is pulsed from 0.3 Hz to 20 Hz.
16. The apparatus as in claim 1, wherein
SUBSTITUTESHEET the electric field is pulsed from .5 Hz to 4 Hz.
17. The apparatus as in claim 1, wherein the voltage of the field is 3,000 to 10,000 volts.
18. The apparatus as in claim 1, wherein the voltage of the field is 4,500 to 6,000 volts.
19. The apparatus as in claim 1, wherein the voltage of the field is 5,000 volts.
20. The apparatus as in claim 2, wherein the voltage of the field is 3,000 to 10,000 volts.
SUBSTITUTESHEET
PCT/US1993/001216 1992-02-10 1993-02-10 Method and means for changing characteristics of substances WO1993016572A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2337946A (en) * 1998-02-24 1999-12-08 Thames Water Utilities Activating polymers or polymer solutions using electrical pulses
CN102220157A (en) * 2010-04-13 2011-10-19 中国石油化工集团公司 Crude oil pulse desalination and dehydration method

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3676181A (en) * 1969-09-16 1972-07-11 Du Pont Electrical discharge treatment of tetrafluoroethylene/hexafluoropropylene copolymer in acetone
US4208263A (en) * 1979-02-15 1980-06-17 Mobil Oil Corporation Solvent extraction production of lube oil fractions
US4957606A (en) * 1987-07-28 1990-09-18 Juvan Christian H A Separation of dissolved and undissolved substances from liquids using high energy discharge initiated shock waves

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676181A (en) * 1969-09-16 1972-07-11 Du Pont Electrical discharge treatment of tetrafluoroethylene/hexafluoropropylene copolymer in acetone
US4208263A (en) * 1979-02-15 1980-06-17 Mobil Oil Corporation Solvent extraction production of lube oil fractions
US4957606A (en) * 1987-07-28 1990-09-18 Juvan Christian H A Separation of dissolved and undissolved substances from liquids using high energy discharge initiated shock waves

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2337946A (en) * 1998-02-24 1999-12-08 Thames Water Utilities Activating polymers or polymer solutions using electrical pulses
US6294057B1 (en) 1998-02-24 2001-09-25 Thames Water Utilities Enhanced polymer activation system and apparatus
GB2337946B (en) * 1998-02-24 2002-08-21 Thames Water Utilities Enhanced polyelectrolyte activation system and apparatus
CN102220157A (en) * 2010-04-13 2011-10-19 中国石油化工集团公司 Crude oil pulse desalination and dehydration method

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