AU2007263525A1 - Method for releasing organics from shale and like materials to produce a liquid shale fuel - Google Patents

Description

WO 2008/001218 PCT/IB2007/002666 SPECIFICATION METHOD FOR RELEASING ORGANICS FROM SHALE AND LIKE MATERIALS TO PRODUCE A LIQUID SHALE FUEL 5 CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority to U.S. Provisional Application Ser. No. 60/816,857 filed on June 28, 2006. BACKGROUND OF THE INVENTION Field of the Invention 10 [0002] This invention resides in the field of an improved processes and equipment used in the treatment of materials in a liquid media by acoustic vortical streams using ultra sound waves. More specifically, this invention relates to an improved process using acoustic vortical streams to extract hydrocarbons into a liquid solvent medium from organic shale. 15 Description of the Prior Art [00031 The use of ultrasound for driving chemical reactions is known. Examples of publications that describe chemical uses of ultrasound are Suslick, K. S., Science, vol. 247, p. 1439 (1990), and Mason, T. J., Practical Sonochemistry, A User's Guide to Applications in Chemistry and Chemical Engineering, Ellis Norwood Publishers, West 20 Sussex, England (1991). Of the various sonicating systems that have been developed, those known as "probe"-type systems include an ultrasonic transducer that generates ultrasonic energy and transmits that energy to an ultrasonic horn for amplification. [0004] Disclosures of magnetostriction ultrasound transducers and their use in chemical reactions ppearinRuhmanetal.11S.Pat. No. 6,545,060-Blandits-PCT 25 counterpart WO 98/22277, as well as Yamazaki et al. U.S. Pat. No. 5,486,733; Kuhn et al. U.S. Pat. No. 4,556,467; Blomquist et al. U.S. Pat. No. 5,360,498; and Sawyer U.S. Pat. No. 4,168,295. The Ruhman et al. patent discloses a magnetostriction transducer that produces ultrasonic vibrations in a continuous-flow reactor in which the vibrations are oriented radially relative to the direction of flow and the frequency range is limited 30 to a maximum of 30 kHz. The Yamazaki et al. patent discloses a small-scale ultrasonic horn operating at relatively low power, in which magnetostriction is listed as one of a group of possible vibration-generating sources together with piezoelectric elements and electrostrictive strain elements. The Kuhn et al. patent discloses a continuous-flow 1 WO 2008/001218 PCT/IB2007/002666 processor that includes a multitude of ultrasonic horns and generators supplying frequencies less than 100 kHz. The Blomquist et al. patent discloses an ultrasonic generator utilizing a magnetostrictive powder composite operating at a resonance frequency of 23.5 kHz. The Sawyer et al. patent discloses a flow-through reaction tube 5 with three sets of ultrasonic transducers, each set containing four transducers and delivers ultrasound at a frequency of 20 to 40 kHz. [0005] SulphCo, Sparks, Nev., is promoting ultrasonics for upgrading heavy sour crude oils into lighter sweeter material. Its technology reportedly increases gravity and reduces sulfur and nitrogen levels and viscosity, thus providing more product per 10 barrel. A typical Middle East crude oil contains 40-45% residuum and 0-5% asphaltenes. The ultrasonic process converts a portion of these undesirable components to lighter, more desirable fractions. Sulfur and residuum content is claimed to be reduced by up to 80%. A test unit with a throughput of 2,000 bbl/d of petroleum products was recently installed at OIL-SC in South Korea. It has demonstrated a 5 15 degree rise in gravity on Arab Medium crude oil. [0006] The SonoCracking technology uses high-power ultrasonic energy on a mixture of crude oil and water in conjunction with inexpensive proprietary catalysts. The use of high-power ultrasound induces cavitations in the processed liquid, creating bubbles which grow, contract and eventually burst under the stress of the ultrasound 20 waves. The bursting generates excess heat and pressure in and around every micrometer and submicrometer-sized bubble. The entire process takes a few nanoseconds and each bubble behaves as a microreactor accelerating the physical reactions owing to the heat released. The high temperature (10,000 K) and pressure (10,000 psi) conditions cause disruption of molecular bonds. 25 [0007] Free radicals worm as a result ofthe breaking of molecular bonds in the water vapor at the thermolic center of the cavitation bubbles. While a large portion of these free radicals rapidly reform into water vapor, a few bring about the displacement of sulfur in the hydrocarbons. It also results in cracking the bonds of residuum elements, thereby enhancing the crude quality. 2 WO 2008/001218 PCT/IB2007/002666 [0008] Oil shale is a general term applied to a group of rocks rich enough in organic material (called kerogen) to yield petroleum upon distillation. The kerogen in oil shale can be converted to oil through the chemical process of pyrolysis. The United States Energy Information Administration estimates the world supply of oil shale at 2.6 5 trillion barrels of recoverable oil, 1.0-1.2 trillion barrels of which are in the United States. [0009] There are two conventional approaches to oil shale processing. In one, the shale is fractured in-situ and heated to obtain gases and liquids by wells. The second (pyrolysis) is by mining, transporting, and heating the shale to about 450 0 C in the 10 absence of air, adding hydrogen to the resulting product, and disposing of and stabilizing the waste. Both processes use considerable water. The total energy and water requirements together with environmental and monetary costs (to produce shale oil in significant quantities) have so far made production uneconomic. [0010] These techniques are extremely expensive and require too much energy to 15 extract a relatively small amount of oil. They cause environmental damage like air and groundwater pollution, and result in waste disposal issues. [0011] A new process is reported to have been developed by Prof. M. Gvirtz and owned by A.F.S.K. According to the publications the shale is mixed and coated with bitumen, a remnant of normal oil refining, then put through a catalytic converter under 20 relatively low pressure. The output is synthetic oil that can be refined into gasoline and other products. The company also has developed a way to burn the leftover shale, which still contains residual fuel. [0012] Recently, the government awarded three companies the opportunity to develop the oil shale resources in Colorado. Shell, Chevron, and EGL resources have -2-5 received-leases on-160-acres to develop oil sha -They areexpyloring the-in-situ plan of heating the shale while in the ground, allowing the oil and gas to be pumped up to the surface. This on-site process alleviates some of the environmental concerns like carbon dioxide emissions. [0013] The Shell Oil Company has been testing this method with some success. 30 Their process involves creating a freeze wall around the targeted area to seal off groundwater. After removing the water, the company inserts electrical rods to heat the shale underneath to 700 0 F. But the heating process takes years to produce oil. Once the oil is produced, it is extracted using conventional drilling means. 3 WO 2008/001218 PCT/IB2007/002666 [0014] This technique has some major obstacles. A program producing 100,000 bbl/day of oil requires a lot of power. A plant is needed to consistently generate the 1.2 gigawatts necessary to heat the shale. The fact remains that the technology must improve before commercial production is possible. 5 [0015] Another technology is described in U.S. Patent No.4,304,656. The patent describes a method for extracting oil content from oil shale by compressing powdery grains of oil shale while applying ultrasonic waves to these powdery grains to separate the oil content from the powdery grains of oil shale. Also known is the treatment of crude oil fractions, fossil fuels, and products thereof with sonic energy described in 10 U.S. Patent No. 7,081,196. This process connected with contacting crude oil fraction exposed to sonic energy with hydrogen gas under conditions causing conversion of organic sulfur to hydrogen sulfide by hydrodesulfurization. Some of the disadvantages of these and other similar patents include: high temperature and high pressure processes; high water consumption; environmental damage; and high energy 15 consumption. Summary of the Invention [0016] None of the described processes have the desired characteristics of low temperature and pressure operation, low water consumption, small energy consumption, and low environmental impact when extracting hydrocarbons into a 20 liquid solvent medium from organic shale. The invention overcomes known problems by providing a process to treat shale in a liquid media by acoustic vertical streams using vibrations, including, ultrasound waves that is: (1) low cost; (2) does not consume water; (3) does not cause environmental damage; (4) requires no burning of shale or its' inorganic matter; (5) produces sulfur-free fuel; (6) does not employ chemical catalysts; 25 (7) has small energy consumption; (7) has negligible heat emission and hence no need for cooling; (8) the inorganic leftover can be used as feedstock for the cement production thus creating an overall non-waste technology; (9) enables modular deployment and upscaling; and (10) possibility to use lean and small shale deposits. [0017] The invention solves the problems of obtaining fuel from shale. While even 30 efficiently obtaining crude oil from shale remains a problem, the present invention solves the problem to obtain directly a more advanced light fraction rich fuel, which could be used after slight refining as a motor fuel, jet fuel, or the like. 4 WO 2008/001218 PCT/IB2007/002666 [0018] The invention uses ultrasonic waves produced by either piezoelectric, magnetostrictive transducers, or hydrodynamic radiators to obtain the above light fraction rich fuel. A magnetostrictive material is one that undergoes a physical change in size or shape as the result of the application of a magnetic field. Magnetostrictive 5 transducers are made of a piece of iron or nickel surrounded by an electric coil; current passed through the coil generates a magnetic field, causing the metal to expand and contract at ultrasonic frequencies. [0019] The ultrasonic waves impose an oscillation pressure on the liquid media. The invention can also use vibrations to impart wave energy on the liquid media. At 10 low intensity, the wave will induce a mixing motion, a process called acoustic streaming. At higher intensities, ultrasonics propagate by oscillating pressure waves that alternately stretch and compress the liquid. Microbubbles form when the local pressure during the expansion phase falls below the vapor pressure of the liquid. During this step, gases dissolved in the bulk liquid can enter the microbubbles and then 15 react during collapse. This compression stage leads to the release of energy that is both short lived and concentrated on the order of microvolumes. The result can be extremely high shear forces for micromixing and the appearance of reactive species such as free radicals within the bubbles. [0020] The sound waves alter naturally occurring molecular structures in 20 hydrocarbons and water. The high temperature created during cavitation breaks the hydrogen - oxygen bond in water, forming hydrogen and hydroxyl radicals. The cavitation also breaks up bonds in the complex hydrocarbons. [0021] In one embodiment; insoluble organic shale has been turned soluble by following the disclosed inventive process. During the process, a sample of ground 25 Israel shale-oil-has beenputinto a liquidT whichunder normal condition is unable to dissolve it. In the first stage, a water mixture of shale oil is subject to vortical movements, wave movements, acoustical streams, or combinations thereof, until a foam appears due to cavitation. The foam, which contains organic particles of shale oil, is placed in an organic solvent (e.g. ethanol) causing separation of the organic shale 30 matter from the non-organic matter. This results in a brownish solution, consisting of both the liquid and the extracted organic matter of the shale. In the second stage, the brownish solution is subject to vortical movements, wave movements, acoustical streams, or combinations thereof to separate the organic substances from the inorganic solids. This stage also converts the organic substances into liquid form, which readily 5 WO 2008/001218 PCT/IB2007/002666 mixes with the solvent to form a brownish shale fuel. The inorganic solids are removed and can be used in the cement manufacturing process. [0022] In another embodiment, a sample of a finely ground shale is submerged in a solvent (e.g. ethanol) and subject to ultrasound excitation (sonication). The sonication 5 causes cavitation and the emergence of (vortical) turbulent streams. The cavitation produces free radicals, where the free radicals extract hydrocarbons from the shale (primarily benzene derivatives) and mix with the solvent, thus creating a solution with new features. These features include high flammability and high caloric value, meaning that the obtained solution can be used (possibly after slight reforming, 10 alteration) as an efficient fuel. The leftover of the shale (primarily inorganic matter) precipitates and can be used in the cement manufacturing process. [0023] The yielded brownish solution is far closer to fuels, then ordinary oil, and it requires less refining, if any, to be used as a fuel. The obtained brownish solution did not change its color for three months and no additional precipitates were observed. The 15 obtained shale fuel is highly combustible, with a combustion temperature more then 10000C. [0024] The inventive process is also effective when butanol is used in place of ethonal. Further, the inventive process is also effective at extracting hydrocarbons from butanol, tar sands, bitumen and coal. 20 [0025] Another object of the invention is to provide a process that can be used to produce non-organic matter of shale, consisting primarily of clay, calcite and minerals. The non-organic matter can be used, for example, in cement manufacturing. [0026] A further object of the invention is to provide a process that can also be used to treat oil shale to form compounds used as a substitution for crude oil. 25 [0027]- Another objec oftheinventionis toprovide process to enrich ethanol and increase its energy content by way of extracting into it organic shale matter. BRIEF DESCRIPTION OF THE DRAWINGS [0028] The method of the present invention is explained in detail by the accompanying drawings: 30 [0029] FIG. 1 is a constructional view of the device used in the embodiments of the inventive process. [0030] FIG.2 is constructional view of a buster used in the embodiments of the inventive process. Page 6 of 15 6 WO 2008/001218 PCT/IB2007/002666 DETAILED DESCRIPTION OF THE EMBODIMENTS [0031] The organic release method according to the invention comprises a process for pulverizing shale oil into powdery grains by, for example, a mechanical means; mixing grains in a liquid and treatment of the mixture by vortical movements, wave 5 movements, acoustical streams, or combinations thereof; foaming; removing the foam ,which contains the organic materials of shale oil, from the mixture; mixing the foam containing organic materials with the liquid solvent, for example ethanol; and processing this mixture by vortical movements, wave movements, acoustical streams, or combinations thereof. The processing forms a liquid, which contains derivates of 10 benzene (see Table 1) and light fractions of hydrocarbons, for example, Toluene, Xylene and others (see Table 2) that are released from organic materials of shale oil. The non-organic solids from the shale oil consist of, for example, Calcite, Clay, and minerals (see Table 3). The whole process takes place under ambient temperature and atmospheric pressure without the presence of catalysts. No water is consumed and no 15 gases are released. [0032] The obtained liquid is a brownish solution, which is a true (real) solution, since it did not change its color for more then three months and no additional precipitates were observed following termination of the process. The yielded brownish solution is closer to fuel, than ordinary shale oil, and it requires far less refining if any 20 to be used as a fuel. Therefore, one may justify calling it a shale fuel rather than a shale oil. [0033] By way of example and in no means limiting, the following explains the device used to carry out the method according to the present invention with reference to Figure 1 and Figure 2. 25 [0034] The technique for separation of organic substances out of solid agents such as, shale, is proposed as well as conversion of separated solid organic substances into liquid state characterized as a true solution with combustion temperature of above 1000 0 C, a density of 0.7 g per cubic cm, and a heat combustion substantially equal to diesel fuel. 30 [0035] According to the invention, said process consists of the following steps: a) preparing a liquid suspension or aqueous mixture made of ground shale; 7 WO 2008/001218 PCT/IB2007/002666 b) processing the mixture by a wave process comprising vibrational energy or vortical movements, wave movements, acoustic turbulent streams, or combinations thereof that promote separation and release of oil shale organic fractions; c) causing cavitation of the mixture and a resultant foam; 5 d) removing the foam from the aqueous mixture surface; e) mixing the foam into a liquid solvent, for instance, ethanol; f) processing the mixture by using vibrational energy vortical movements, wave movements, acoustic turbulent streams, or combinations thereof that promote the dissolution of solid organic substances found in the foam, and their conversion into the 10 liquid state; and g) isolating the inorganic solid particles from the liquid; [0036] The liquid obtained is eliminated from the separated insoluble particles and can be used as a fuel that can fully or partially replace gasoline. The bulk of insoluble particles consisting of calcite, clay, and such minerals as quartz, pyrite, apatite can be 15 used as construction material, which altogether ensures the wasteless technology of inventive process. [0037] Figure 1 shows the device called a turbulizer, which clarifies the inventive process. The turbulizer comprises waveguide 1 placed into cylinder 2. Aqueous mixture of shale particles 3 is poured into cylinder 1 up to the level 4 coinciding with 20 nodular plane 5 of waveguide 1 immersed into the waveguide down to the depth equal to AA, where X, is the length of the wave propagating in the waveguide. The height of the liquid 6 is defined as H, where H = 0.4 k. Said conditions ensure acoustic turbulent flows during the waveguide performance in the cylinder. [0038] Figure 2 further describes the inventive process. Vertical motions 7 of 25 mixture-3enemergein he turbuizer -cylinder-as-a-result ofthe waveguide operation, which can lead to foaming 8, and in this process light organic particles 9 appear at the surface of mixture 3 and are trapped by foam 8. The nonlinear shape of the waveguide concentrator of ultrasound energy can be described, for example, by a catenoid, ensures gradient grad = (V - Vo) \ (X\4) of vibration rate between waveguide 1, nodular plane 30 5, and waveguide 1 end 11, where Vo is the nodular plane vibrational rate equal to zero, and V is vibrational rate of waveguide 1 end 11, equal to the maximal meaning of V = n, and that results in the combination of vertical and wave motions in the mixture (i.e. turbulent acoustic flows). Increased foaming intensity is achieved after surfactant introduction into the mixture. 8 WO 2008/001218 PCT/IB2007/002666 [0039] The organic-particle-enriched foam 8 (supported by the chemical analysis data tabulated in Tables 1, 2) is eliminated from the mixture surface and moved to the other similar turbulizer (not shown in the Figures), where it is mixed with liquid organic solvent, for example, ethanol, and is exposed to turbulent acoustic flows. The 5 exposure to turbulent acoustic flows results in the dissolution of solid organic particles and emergence of liquid with dissolved gasoline components that represent such light fractions of benzene derivatives as Toluene, p-Xylene,, Benzene, 1-ethyl-2-methyl, Benzyne, 1,2,3-trimethyl- and others (See chemical analysis data in Table 2). [0040] The mixture is then segregated into liquid and solid sedimented fractions. 10 The segregation can be either spontaneous or forced. The liquid fraction is a flammable fluid enriched with benzene derivates and its characteristics are given in the Table 2. [0041] The liquid fraction is removed from the second turbulizer to the reservoir (not shown in the figures). Its solid sedimented portion includes insoluble solid 15 particles and essentially represents the shale inorganic portion. The inorganic portion is made primarily of calcite and clay that can be used as a construction material, which thus ensures wasteless, ecologically pure production (shale composition is given in Table 3). [0042] The fuel obtained differs critically by its brownish color, which does not 20 alter with time, and is a true solution of shale organic fraction. The fuel combusts totally and does not contain sulfur. (See chemical analysis results in the Table 2 and combustion results in Table 4). Table 1: Increase of yield of organic material from suspension of shale oil in foam after wave activation (i.e. turbulent acoustic stream) on suspension in water Duration of Total yield of Experiment wave movement Benzene Yield (%) organic material number conditional derivations from slate solid units part (%) 1 (control) 0 Benzene, (1- 4.0 35.44 butylheptyl) 2 1 Benzene, (1- 7.42 86.44 butyheptyl) 3 1.5 Benzene, (1- 10.28 96.82 butylheptyl) 25 9 WO 2008/001218 PCT/IB2007/002666 Table 2: Chemical analysis of Liquid Fuel from the Inventive Process Pk # Real Time Area (%) Components 1 2.11 2.73 Propane, 2-ethoxy 2 2.52 28.60 Toluene 3 2.97 3.88 Triethyl borate 4 4.40 4.31 Ethylbenzene 5 4.64 12.84 p-Xylene 6 5.38 5.29 p-Xylene 7 7.05 6.30 Benzene, 1-ethyl-2-methyl 8 7.19 1.99 Benzene, 1, 2, 3-trimethyl 9 7.40 1.62 4-Ethylphenethylamine Table 3: Shale Oil Composition as solid substance (% wt. dry basis) Organic Material 10-27 Calcite 45-65 Clay 10-30 Moisture 2.2% Quartz, Apatite, Gypsum, Pyrite Balance 5 [0043] The organic materials obtained from the inventive process contain benzene derivates, for example, benzene (1-butyheptyl) and others, which is dissolved in the organic liquid solvent. After wave treatment (turbulent acoustic streaming) with frequency in diapason 10kHz - 100kHz, the organic materials separate from the inorganic solids. The result is the extraction of the organic materials into the organic 10 liquid solvent, which can be used as a fuel since its burning temperature is 1010 0 C and its calorific value is 10.3 Mcal/kg, which is higher than pure ethanol (see Table 4). Table 4: Heat of combustion for common fuels Fuel MJ/kg Meal/kg BTU/lb Hydrogen 141.9 33.9 61,000 Gasoline 47- 1.3 -20400 Diesel 45 10.7 19,300 Ethanol 29.8 7.1 12,800 Propane 49.9 11.9 21,500 Butane 49.2 11.8 21,200 Wood 15 3.6 6,500 Coal 15-27 4.4-7.8 8,000-14,000 Natural Gas 54 13 23,000 [0044] The energy content of the shale fuel obtained from the above example is 15 higher than that of ethanol and is close to that of diesel and is slightly lower than gasoline. The burning takes place with a reddish-yellow flame. 10 WO 2008/001218 PCT/IB2007/002666 [0045] The inorganic matter of shale, precipitated in the course of the process, consists primarily of clay, calcite, and minerals. This can be used in cement manufacturing. 11

Claims (20)

1. A process for releasing organic materials from a solid substance into a liquid product medium, said process comprising the steps of: (a) placing the solid substance into a first liquid medium; (b) subjecting said first liquid medium to vibrations; (c) causing cavitations in said first liquid medium, whereby said first liquid medium forms a foam; (d) removing said foam from said first liquid medium; (e) introducing said foam into a second liquid medium; (f) subjecting said second liquid medium to turbulent acoustic streams, whereby the non-organics of the solid substance precipitate; and (g) separating said precipitated non-organic matter of the solid substance from the second liquid medium;

2. The process of according to claim 1, wherein said vibrations are caused by vortical movements, wave movements, or vortical acoustic streams, or combinations of vortical movements, wave movements, or vortical acoustic streams.

3. The-process-according to-claim-2, whereinsaidturbulent-aeoustical-streams are caused by hydrodynamic radiators operating in a frequency range from about 0.1 Hz to 100 MHz.

4. The process according to claim 2, wherein said turbulent acoustical streams are caused by ultrasound waves in diapason of 10-100 kHz.

5. The process according to claim 2 wherein said second liquid medium is an organic solvent. 12 WO 2008/001218 PCT/IB2007/002666

6. The process according to claim 5, wherein said organic solvent is selected from the group consisting of methanol, ethanol, and butanol.

7. The process according to claim 2 wherein said first liquid medium is water, whereby the application of turbulent streams causes cavitations and the emergence of foam.

8. The process according to claims 2, wherein said foam facilitates the concentration of substantially organic matter of the solid substance.

9. The process according to claim 7, wherein said foam facilitates the concentration of substantially organic matter of the solid substance.

10. The process according to any one of claims 1-7, wherein said solid substance is selected from the group consisting of shale, shale oil, tar sands, bitumen, and coal.

11. The process according to claim 2 wherein said solid substance is shale oil powder and said second liquid medium is an organic solvent selected from the group consisting of methanol, ethanol, and butanol.

12. The process according to claim 2 wherein said solid substance is shale oil powder mixed with one of the following: powder of dry tree leaves, tar sand, coal, sawdust or similar materials.

13. The-process accordingto-claimn Zor 1, whereinsaid non-organic matterarb used as a feed stock for cement production or building materials.

14. A product made by the process according to any one of claims 1-9, wherein said liquid product medium is a liquid fuel, having substantially inter gasoline components, through the release of lights fractions of hydrocarbons from the solid substance. 13 WO 2008/001218 PCT/IB2007/002666

15. A product made by the process according to claim 11, wherein said liquid product medium is a liquid fuel, having substantially inter gasoline components, through the release of light fractions of hydrocarbons from the shale oil powder.

16. A product made by the process according to claim 2, wherein said solid substance is shale and said liquid product medium is a liquid fuel, having substantially inter gasoline components, through the release of light fractions of hydrocarbons from the shale.

17. A product made by the process according to claim 1, wherein said solid substance is shale and said liquid product medium is a liquid fuel having substantially inter gasoline components, through the release of light fractions of hydrocarbons from the shale.

18. A product made by the process according to claim 11, wherein said liquid product medium contains about 28% Toluene.

19. A product made by the process according to claim 11, wherein said liquid product medium contains about 10-27% weight on a dry basis of organic material.

20. A product made by the process according to claim 11, wherein said liquid product medium has a heat of combustion of about 11 Mcal/kg. 14