THERMAL DISMANTLING UNIT AND A HIGH TEMPERATURE FURNACE

Information

  • Patent Application
  • 20160251577
  • Publication Number
    20160251577
  • Date Filed
    May 13, 2014
    10 years ago
  • Date Published
    September 01, 2016
    8 years ago
Abstract
This invention is related to a thermal dismantling unit that; “Reaches high temperatures (up to 3500° C.),” Has been designed to be able to work with the three states (solid, liquid and gas) of fuel, “Works at low pressure by using a special vacuum circuit,” Bears a washing system in order to produce clean hot air suitable for domestic and industrial usage.
Description
FIELD OF INVENTION

This invention is related to a thermal dismantling unit that;

    • Reaches high temperatures (up to 3500° C.),
    • Has been designed to be able to work with the three states (solid, liquid and gas) of fuel,
    • Works at low pressure by using a special vacuum circuit,
    • Bears a washing system in order to produce clean hot air suitable for domestic and industrial usage.


The present invention can be used within any sector that requires very high temperature. These sectors could be stated as the iron and steel industry, cement industry, certain metal industries like aluminium, lead etc and the mining industry i.e. thermal mineral processing.


In this invention, reactor and furnace for the thermal dismantling unit and a high temperature furnace for burning solid fuel have been developed.


The solid fuel can be produced from the ash which is spent shale, ash obtained by high temperature oil shale dismantling process, treated spent shale, ash obtained from direct burning of oil shale, ash obtained from indirect burning of oil shale or any mix of them.


PRIOR ART

There are different types of ovens or furnaces used to deal with the solid fuel such as the old furnaces which were used to burn the coal; these furnaces are no longer used in these days, because the extraction of coal has become difficult and expensive and the amount of the generated heat is not big when compared to the liquid and gas fuels generated thermal energy.


In addition to the negative environmental impacts those results from the burning processes. These furnaces are nowadays used mainly in generating electric energy. Liquid-fuelled furnaces are widely spread and depend on the types of burners that consume large amounts of fuel to get large amounts of heat, resulting to the high economic cost mainly in the application areas that need continuous burning processes; this makes the processes even more difficult and expensive. This is in addition to the emissions associated with the combustion processes, which have a very significant negative impact on the environment.


The best types of fuel burners is the gas burners in term of the speed of combustion, cleanness and the resulting amount of heat, however, using the gas burners in the areas that need continuous burning operations is not economically feasible.


On the other hand, using the electric furnaces is limited and is not possible because of the significant shortfall in the amount of electricity emerged recently. In addition, the electricity that heats the ovens is isolated from the air resulting to a big problem because it does not allow any reactions during the burning that may be required in the used applications.


This invention has a remarkable point in the proposed ovens; which is the ability of working with gaseous or liquid fuel till the temperature reaches above 300° Celsius, and then the liquid or gaseous fuel feeding is stopped to be replaced directly with the solid fuel, this can be performed without the existence of any special equipment to burn the solid fuel. Accordingly, this furnace can reach to any required temperature as long as the furnace lining can stand it, in addition to any amount of heat required to be generated.


Complex equipment in burning oil shale as a strong recommended field to use this furnace; does not exist in a scientific experiment with commercial production in which achieves economic and environmental standards to be applied on the ground.


Solid Fuel

The solid fuel is a type of solid fuel that burns according to environmental criteria, and causes high temperature that can reach up to 3500° C., and does not burn at a low temperature. It requires an appropriate burning media and the furnace whose temperature is above 300° C. The additives that are being mixed with the oil shale ashes depend on what the solid fuel is planned to be used for. For example, burning this fuel to generate electrical energy requires a range of 450° C. to 650° C., therefore; specific additive should be chosen. If this fuel is to be used in the glass manufacturing industry for example; this requires a temperature of about 1850° C., accordingly, the appropriate amount of air is chosen to achieve this high temperature.


The ash to be used in production of solid fuel can be spent shale, ash obtained by high temperature oil shale dismantling process, treated spent shale or any mix of them.


Consequently, the residue of the burning process also differs. In order to maintain the chain of reactions going on inside the furnace/oven, so, the difference in the quality and quantity of the additives should be taken into account as for the system itself, it is one and the same.


A furnace/oven with a temperature of above 300° C.+solid fuel (ash+additives) which is pumped into the oven by a high-pressure turbine, a turbine to withdraw the air from outside and to pump it inside the furnace, a turbine to withdraw the gases resulting from the burning process in order to guarantee the continuation of the reaction during the burning process.


Background to Thermal Mineral Processing

The thermal mineral processing depends on the use of high temperature during the oil shale extraction process. The basic procedure employed during the treatment of oil shale is thermal dismantling. Whereby raw materials are treated using high temperatures until they dissolute. At the beginning; the volatile materials are separated, the extraction process ends when the whole organic materials become gas, e.g., the end of the volatile process is regarded as the end of the extraction process. New quantities of the oil shale are inserted to be treated and so on. The thermal dismantling unit has a homogeneous environment that keeps the temperature steady while it is working nonstop. All the reactions taking place are taken into consideration in order to make sure that they neither collapse nor alienation occurs to the lining of the oven.


BACKGROUND ART

Mineral extraction is a model of separation methods of metals from the ores that are containing them, disassembly chemical heat is the principle adopted for the dismantling of different compounds and blended with each other. The oil shale is a model of rocks that blend the organic part with prong limited to the wide contrast inorganic metallic.


The physical and chemical process that allows obtaining separated products from raw materials that are mixed together are called mineral processes.


Thermal Mineral Processing: are processes that occur in the presence of extreme heat, and cause chemical changes in the raw materials.


Preparation of the raw materials: are the operations that start from receiving the raw materials from the mines, and the preparation for the mineral processes, provided all the condition relevant to the extraction of the products are met; and provided that the chemical composition or chemical status of the raw materials remains unchanged. The Mineral process involved primary grinding (crushing), secondary grinding (crushing) to separate the granules, loading and weighing, and lifting, making the material ready to be used as a raw material for the extraction mineral process.


Thermal Mineral Processing: a process that involves very high temperatures to extract the gaseous and liquid products from the raw material being thermally mined. The process on which this procedure is undertaken depends on the process of thermal dismantling.


Thermal Dismantling: A chemical procedure during which the state of the matter changes due to the high temperature, without pressure, and without the presence of a solvent, and results in the separation of the nonvolatile matter and its isolation from the remaining solid matter. The nonvolatile matter is the organic matter and the moisture, while the remaining solid matter is the ash resulting from the dismantling.


The Importance of the thermal mineral processing: The left-over ash;

    • Is totally free from moisture,
    • Does not contain any organic matter,
    • Is volatile and there will be no loss incurred during the forthcoming burning processes since it has already been exposed to very high temperature,
    • Contains a large quantity of non-organic carbon and fossilized carbon which was exposed to high temperature prior to the point of separation, which is the point whereby there is a separation between the organic and the non-organic matter in the oil shale, and
    • Is based on the Gibbs-Helmhoh equation which links the free energy and the temperature at which dismantling of certain materials occur.


For example, the point of dismantling of CaCO3 is calculated as per the following equation:





CaCO3→CaO+CO2





ΔG=42,300−37.7T


When the pressure of the CO2=1 atmospheric pressure





ΔG=the free energy=O






T=42300/37.7→T=1223° F.

    • T=850° C.


The speed of the dismantling is determined by the speed at which the thermal energy is transferred to the CaCO3. Raising the temperature above the temperature of dismantling is very important, and the burning gases must move in the opposite direction of the CaCO3, whereby CO2 gas is emitted from the moving gases, provided that the pressure within the oven does not exceed 1 Atmospheric Pressure. Accordingly, the CO2 must be withdrawn so that the dismantling of CaCO3 can continue.


The quantity in the reactor plays a major role, and must be higher than the level of equality in order to guarantee the transformation of raw materials into oxides, and thus form the solid fuel residue.


PRIOR ART

US 2010/0187161 A1 describes a thermal dismantling method in processing oil sand comprising a distillation reactor operated at a temperature of 800° C. wherein shale gas, shale oil, water are extracted and separated in a distillation column. In US 2010/0187161 A1, the heating processes go under three separate stages starting from 110 and ending up with 800 C to extract the shale oil, shale gas and water, the oil shale ash is then heated till 1050 degree, where the reactor and the furnace are separated, while in the present invention, reactor is inside the furnace and the oil shale heating is being performed in one stage inside the reactor which is exchanging the heat with the furnace in an indirect way. Moreover in the present invention the heating point inside the furnace in is starting from 550 C by using external igniter and then at the temperature of 550 C; the oil shale is inserted inside the reactor furnace to be treated at the temperature at between 850 to 950 degrees. Where, at this temperature, the oil shale is being treated to extract 100% of organic materials.


The oil shale ash is then taken out of the reactor to be cooled and treated and then fed into the furnace to be used as solid fuel to heat new oil shale. Moreover, the present invention's products are shale oil, shale gas, water, solid fuel and purified hot air.


Regarding the hot air, the present invention provides full system to clean and purify the hot air and practically tested it to be environmental friendly and usable outside the treatment unit because of the washing and cleaning unit which is followed by the four stage combustion waste precipitator unit. The precipitator stages consist of three stages to precipitate the combustion waste where in each stage different size of the combustion waste is precipitated and the fourth stage is used to exchange the heat.


The thermal dismantling method of WO 2010/034621 A1 produces product vapours which are separated by distillation, yielding shale gas, shale oil, water. Thermal treatment procedures of WO 2010/034621 A1 are strictly controlled to obtain residual depleted shale containing coke, which is used as a solid fuel. In WO 2010/034621 A1, there are reactor and oven in vertical position and both are working under the direct combustion; while in the present invention, the vertical the reactor is placed inside the furnace and the oil shale inside is being heated in indirect way.


In WO 2010/034621 A1, multiple stage heat exchanger is used, however, the used multiple stage heat exchanger in the present invention is the inventor's own design and it has a precipitator stages where the hot air from the second precipitating stage is sent back to the oven to help in combustion processes and the rest of it is sent to the third stage. In conclusion, the inventor has an invented multiple stage heat exchanger and precipitator.


EP 0107477 A1 describes a method and apparatus for the recovery of oil from oil shale by retorting fresh feed shale and heat medium particles using a fluidized bed. The apparatus produces product vapours which are separated in a separation tower by distillation, yielding liquid and gaseous products. After removing said vapours said vapours the residual depleted shale contains carbon residue remaining on the shale. The residual depleted shale is considered to be a solid fuel, which is burned in a vertical transport combustor used for producing steam and heating fresh oil shale.


All comments for WO 2010/034621 A1 is valid for EP 0107477 A1. In addition, the fuel which is used to heat the oil shale is the produced solid fuel in the present invention, which is unlike EP 0107477 A1 which uses the produced gas.


U.S. Pat. No. 3,817,192 A comprises a furnace, especially for combustion of garbage and sewage sludge which has a cylindrical combustion chamber and an ignition device such as an oil burner. In U.S. Pat. No. 3,817,192 A, the designed system is for garbage and sewage sludge, accordingly, it does not have any ability to extract any gas or oil fuel. Moreover, the maximum temperature for the furnace is 300 C in D4, while it is the starting temperature in the present invention which could reach up to 1500 C at the final processing stops.


Based on above, neither the furnace in the present invention can be used to combust the garbage nor can the garbage combusting furnace treat the oil shale


Example of U.S. Pat. No. 4,054,492 A includes a thermal dismantling method in processing oil sand comprising vertical reactors operated at temperatures of 520 and 750° C., and obtained shale gas, shale oil, hot air are extracted and separated.


U.S. Pat. No. 4,431,483 A relates to a shale oil distilling furnace with shale descending between slotted partitions and hot gases passing through it horizontally.


U.S. Pat. No. 4,502,942 A describes a retort process and the product therefrom relating to the recovering of oil from Western-type U.S. shale utilizing carbon dioxide as a sweep gas.


In U.S. Pat. No. 4,502,942 A, an electric device is used, while in the present invention, no electric device is used because of the huge amount of treated oil shale which makes using the electric device is both of expensive and impractical.


Moreover, the present invention reaches such high temperature to treat the oil shale at temperature of 850 to 950 C and then to heat the oil shale ash to the degree of 1500 C which cannot be reached by using the electric device.


Regarding the produced water, the present invention can obtain till 60 L per ton of water and then purify it to be used in the agriculture field which is not obtained by D8.


In the present invention, the oil shale is being treated at the temperature of 850 to 950, so, almost all the organic materials are extracted and a very good quality of shale gas and shale oil are extracted, then the remaining oil shale ash is extracted to out of the treatment unit to be treated by adding the proper additives and then re-inserted inside the oven to be used as solid fuel. This is different than the disclosure in the document DE2646451 as the system mentioned in it treats the oil shale at the temperature at the temperature of 500 to 550 C to extract the shale gas and the shale oil (low quality) and then push the oil shale ash inside the furnace directly without any treatment.


In conclusion, the present invention is different from DE2646451, in term of the shale oil and shale gas qualities and quantities besides to the fact that the present invention produces hot air and good amount of water.


In U.S. Pat. No. 3,475,319, oil shale is retorted serially downwardly through a preheating zone, a retorting zone, and a combustion zone. Hue gas generated from burning carbonaceous material on the spent oil shale is withdrawn from the combustion zone and introduced into said preheating zone. All comments in DE2646451 are valid for U.S. Pat. No. 3,475,319 besides that the present invention has its invented multiple stages heat exchange and precipitating unit to obtain clean hot air, and finally, the present invention has completely different design to perform more operations as treating the oil shale and to keep the oven in regular temperature.


The furnace in the present invention has the following properties;

    • It is used to burn any of the three types of fuel which are gas fuel, liquid fuel and solid fuel.
    • The way the flame is distributed over the oven and heading the oil shale in indirect way.
    • The way the oven exposes the combustion waste after under gone it to the washing, cleaning and precipitating processes to obtain hot and clean air.
    • The oven has a novel mechanism to extract the oil shale ash residual to out of the treatment unit.





DEFINITION OF FIGURES

In order to better describe the high temperature thermal dismantling unit developed in this invention, figures have been prepared. Definitions of the figures are below.



FIG. 1—Schematic view of thermal dismantling unit



FIG. 2—Roasting, moisture pulling and oil shale drying unit



FIG. 3—Schematic view of the reactor and furnace of the thermal dismantling unit



FIG. 4—Schematic view of the high temperature furnace for burning solid fuel





DEFINITION OF PARTS/FEATURES REFERRED IN THE FIGURES

In order to better describe the high temperature thermal dismantling unit developed in this invention, the features in the figures have been numbered. Definitions of the features are below.

    • 1—Reactor and furnace unit
    • 1.1 Combustion products transferring pipe—1
    • 1.2 Combustion products transferring pipe—2
    • 2.1 Purification and combustion products washing unit—1
    • 2.2 Purification and combustion products washing unit—2
    • 3.1 Air turbine for combustion gases
    • 3.2 Air turbine to regulate the furnace temperature
    • 3.3 Air turbine to distribute the hot air
    • 4—Multi-stage heat exchanger and combustion waste precipitator
    • 5—Roasting, moisture pulling and oil shale drying unit
    • 6—cooling and condensation unit which is related to the oil shale moisture
    • 7—Condensate water collection tank
    • 8—Nutrition unit entrance (roasting and drying unit)
    • 9—Centrifugation and pulling the washing outputs unit
    • 10—Centrifuge unit (pull, process, pushing) of the purified water
    • 11—Treatment water collection tank
    • 12—Combustion products exit after purification
    • 13—Reactor
    • 13.1—Reactor
    • 13.2—Compiling and condensing vapours of heavy components tower.
    • 13.3—Intensification of Tower 1
    • 13.4—Intensification of Tower 2
    • 13.5—The distillates collection tank1
    • 13.6—The distillates collection tank2
    • 13.7—viscosity breaking tower
    • 13.8—Vacuum tower
    • 13.9—Vacuum pump
    • 13.10—Gas gathering tank
    • 13.11—Glass distillates showing tower 1
    • 13.12—Glass distillates showing tower2
    • 13.13—Centrifuge pump
    • 13.14—Distillate liquid collection tank
    • 14—Furnace
    • 15—Reactor lid
    • 16—solid fuel entrance of reactor and furnace unit
    • 17—Spiral for feeding solid fuel
    • 18—Gas collector for vacuuming
    • 19—Temperature sensor of reactor and furnace unit
    • 20—Gas collection pipe for vacuuming
    • 21—Diesel flow holes of flame distributor
    • 22—Flame distributor
    • 23—Air turbine of reactor and furnace unit
    • 24—Spiral for taking the ash of reactor and furnace unit
    • 25—Tray bearer
    • 26—Oil shale plate/tray/carrier
    • 27—Pipe for transfer of collected gas
    • 28—High temperature Furnace for burning solid fuel
    • 29—Temperature sensor of solid fuel burning furnace
    • 30—Chimney
    • 31—solid fuel entrance
    • 32—Air turbine of solid fuel burning furnace
    • 33-1—Burner working by liquid fuel
    • 33-2—Cylinder for distributing the flame inside the furnace
    • 34—Spiral for taking the ash of solid fuel burning furnace
    • 35—High temperature furnace for burning solid fuel
    • 36—Hydrogene turbine


Thermal dismantling unit comprises;

    • Reactor and furnace unit (1),
    • Purification and combustion products washing units (2-1 and 2-2)
    • Air turbine for combustion gases (3.1)
    • Air turbine to regulate the furnace temperature (3.2)
    • Air turbine to distribute the hot air (3.3)
    • Multi-stage heat exchanger and combustion waste precipitator (4)
    • Roasting, moisture pulling and oil shale drying unit (5) (this unit is also defined as pulling, condensing and vacuum unit (it is the unit for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure)
    • Cooling and condensation unit which is related to the oil shale moisture (6)
    • Condensate water collection tank (7)
    • Entrance of roasting, moisture pulling and oil shale drying unit (8)
    • Centrifugation and pulling the washing outputs unit (9)
    • Centrifuge unit (pull, process, pushing) of the purified water (10)
    • Treated water collection tank (11)
    • Exit of combustion products after purification (chimney) (12)
    • The isolation chamber to extinguish the processed oil shale (not shown in the figure):


Reactor and furnace unit (1) is the unit where burning process occurs. It has two parts; one is furnace (14 and 28) and the other is reactor (13). The dismantling process takes place in the reactor (13). It is placed inside the furnace (14 and 28).


Purification and combustion products washing units (2-1 and 2-2) is the unit in which combustion products occurred in the furnace are washed and purified.


Air turbine for combustion gases (3.1) is the air turbine which sucks the combustion product gases from the furnace (14 and 28).


Air turbine to regulate the furnace temperature (3.2) is the air turbine which is used to maintain the desired temperature inside the furnace (14 and 28).


Air turbine to distribute the hot air (3.3) is the air turbine which is used to direct the clean hot air towards the roaster unit (5).


Multi-stage heat exchanger and combustion waste precipitator (4) is used to precipitate the combustion contaminant material released in the furnace during burning of the solid fuel and to distribute the remaining clean hot air.


Roasting, moisture pulling and oil shale drying unit (5) is used to roast the oil shale to remove the moisture and dry it.


Cooling and condensation unit which is related to the oil shale moisture (6) is used to cool and condense the vapour that has been sucked from the roasting unit.


Condensate water collection tank (7) is used to store the condensed water.


Entrance of roasting, moisture pulling and oil shale drying unit (8) is used to feed the oil shale into roasting, moisture pulling and oil shale drying unit (5).


Centrifugation and pulling the washing outputs unit (9) is used to suck the contaminated water from the purification and combustion products washing unit (2)


Centrifuge unit (pull, process, pushing) of the purified water (10) is used to purify the contaminated water, and then to push it toward the treated water collection tank (11)


Treated water collection tank (11) is used to store the treated water and direct to purification and combustion products washing unit (2).


Exit of combustion products after purification (chimney) (12) is used to direct the exhausted gas to outside the unit.


Roasting, moisture pulling and oil shale drying unit (5) comprises;

    • Compiling and condensing vapours of heavy components tower (13.2).
    • Intensification of Tower 1 (13.3)
    • Intensification of Tower 2 (13.4)
    • The distillates collection tank 1 (13.5)
    • The distillates collection tank 2 (13.6)
    • viscosity breaking tower (13.7)
    • Vacuum tower (13.8)
    • Vacuum pump (13.9)
    • Gas gathering tank (13.10)
    • Glass distillates showing tower 1 (13.11)
    • Glass distillates showing tower 2 (13.12)
    • Centrifuge pump (13.13)
    • Distillate liquid collection tank (13.14)


Purpose and duty of each element are below;

    • Reactor (13 and 13.1): is used to heat the oil shale in indirect way to reach any temperature in between 600 to 950° C.
    • Compiling and condensing vapors of heavy components tower (13.2): To pull and condense the heavy materials.
    • Intensification of Tower1 (13.3): To condense initial produced gages.
    • Intensification of Tower2 (13.4): To condense the light gases.
    • The distillates collection tank1 (13.5): To collect the distillated liquids that condensed in Tower 1.
    • The distillates collection tank2 (13.6): To collect the distillated liquids that condensed in Tower 2.
    • Viscosity breaking tower (13.7): To condense the maximum possible amount of gases.
    • Vacuum tower (13.8): To collect the gases which are coming from the reactor.
    • Vacuum pump (13.9): To pull the volatile gases through the processing.
    • Gas gathering tank (13.10): To collect the uncondensed gases.
    • Glass distillates showing tower 1 (13.11): To view the products and to separate the water from the shale oil which are coming from Tower 1.
    • Glass distillates showing tower 2 (13.12): To view the products and to separate the water from the shale oil which are coming from Tower 2.
    • Centrifuge pump (3.13): To pull the shale oil from the glasses Tower and then pumping it to the oil collection tank.
    • Distillate liquid collection tank (13.14): To collect the liquids.
    • Reactor (13) is inside of the furnace (14 and 28).
    • Reactor (13) is the place in which the dismantling process takes place.
    • Furnace (14 and 28) is the place in which the solid fuel is burned.
    • Reactor and furnace unit (1) comprises;
    • Reactor lid (15)
    • solid fuel entrance of reactor and furnace unit (16)
    • Spiral for feeding solid fuel (17)
    • Gas collector for vacuuming (18)
    • Temperature sensor of reactor and furnace unit (19)
    • Gas collection pipe for vacuuming (20)
    • Diesel flow holes of flame distributor (21)
    • Flame distributor (22)
    • Air turbine of reactor and furnace unit (23)
    • Spiral for taking the ash of reactor and furnace unit (24)
    • Tray bearer (25)
    • Oil shale tray/carrier (26)
    • Pipe for transfer of collected gas (27)


Description of the Thermal Dismantling Unit:

The iron structure is insulated from inside with materials like bricks, which need to be heat resistant. The furnace (14 and 28) is between 3 m to 15 m high and its inner diameter is between 1 m to 10 m.


If a cross-section of the furnace (14 and 28) is examined, it can be seen that it is made of two cylinders attached to the base. The diameter of the upper circle is around 1.7 m, and the diameter of the lower circle is estimated around 2 m, in which the reactor (13) is placed, and there is a cylinder to distribute the heat at the bottom of which there is the source of the flames, and which in turn, is formed of 4 cylinders attached to one another. The first is a large cylinder with a large base facing up, in which in there is the cylinder that distributes the flame and extinguishes it and ends with an opening for the observation, and a unit for providing hot air in some cases. Additionally the burner and the fuel tank are placed on it. As for the second cylinder, this carries the unit that injects the solid fuel, in addition to a unit to feed the liquid fuel (2) with a tank ending in the distribution unit, and a high-pressure turbine, which pushes the solid fuel coming in from the feeding unit through a spiral structure, operated by an adapter. There are observation points for each process. The third cylinder has an observation platform at the very top, which can be reached by a safety ladder which also has a sensor on it to monitor the temperature of the furnace (14 and 28). The fourth cylinder is a conical trunk with its small base facing up, carrying the neck which has 4 external carriers for the reactor. It also has exits for the gases resulting from the burning process to be eliminated, the first of which sucks out the gases, and the second regulated the temperature inside the furnace (14 and 28). The cover has the continuation of the furnace's (4) external carrier, penetrated by a tube to withdraw droplets from the reactor. As for the base, which is at the bottom of the furnace (14 and 28) as well, this is a metal structure insulated with bricks which can withstand high temperature, and is a conical trunk with its small base facing down, standing on the ground on 6 legs carrying the previously-mentioned structure with all its parts. The small base has a perforation to eliminate the solid fuel reside, and ends with a spiral operated by a suction engine to withdraw the solid fuel reside, and another spiral structure to expel the solid fuel reside, on this there is a sensor to measure the temperature at the bottom of the furnace (14 and 28) and which is the center of the heat being distributed to all parts of the furnace (14 and 28). It also carries two turbines to withdraw air from outside and inject it inside the furnace (14 and 28), in order to complete the burning process inside the furnace (14 and 28). This plays a vital role in the burning process. There are three carriers on the outside body in order to carry the upper part of the furnace (14 and 28), whereby the upper part is totally separated from the base.


The Reactor (13): The closed thermodynamic unit, where the major part of thermal dismantling of oil shale takes part. The reactor (13) is completely sealed in order for the thermal dismantling process to occur in a vacuum. This, of course, distinguishes this technology from others that depend on storing, putting pressure, and adding various gases like H2O, CO and CO2. Sometimes, individual gases are used to break up the non-organic matter and separate it from the organic matter, and to saturate the organic compounds. Technologies that depend on heat and pressure require large machinery/equipment, but the errors and malfunction play a major role in leading to painful accidents. But the idea of thermal dismantling in a vacuum involves heating without pressure, and so there are no dangers involved in the thermal dismantling process of the extraction operation.


The reactor (13) has a moving cover that can be sealed, and thus ensure that the gases do not leak out during the thermal dismantling process. It could be made of a hard iron vent, a neck made of pliable iron that also helps to seal it, a cylinder with a diameter of 80 cm and a height of 275 cm, with upper and lower exist point to release the steam of the organic matter which is being extracted from the oil shale, and which is mixed in with it. These exit points collect and exit at one point outside the reactor, then outside the furnace (14 and 28). The reactor and all the parts attached to it are made up of materials such as chrome (NTK310) which can withstand high temperature and does not chemically react. At the bottom of the reactor, there is a round frame carrying the base of the plates' carrier (26) that does not block the steam exits located at the bottom of the reactor.


The Oil Shale Plates/Trays/Carriers (26): are basically plates (26) made of perforated iron and alike which is heat-resistant. They are cylindrical in shape, approximately 18 cm high and for each plate (26) there are three carriers 2.5 cm high. In the center there is a cylinder (diameter=6 inches). 8 slits were added to the lower base in order to allow for the thermal exchange process to occur to all the quantity of the oil shale in the reactor. There are 10 plates with an individual capacity of 80 to 95 kg.


The apparatus carrying the plates which is tray bearer (25) is an iron base and could be designed in the shape of a plus sign (+), and a heat-resistant iron tube 5 inches in diameter, ending with 2 opening opposite each other to hold the plates. They are raised with a lever and arranged on top of one another and arranged in terms of mass, ensuring that all the granules of the oil shale in the same plate are homogenous in size, which is very vital for this process. Each plate can contain a certain type of shale, making it possible to study several different samples during the same experiment, which is another advantage. For example, plate (A) can carry oil shale of a sandy origin, which is broken up, loaded into the plate, and weighted, while plate (B) can carry oil shale of a calcium origin which will also be broken up, loaded, and weighed, and so on. Studies can also be conducted on different sizes (big and small) provided the granules in one plate are of the same size, which are also weighed and placed on the lower plates with the upper plates carrying the larger granules, in order to facilitate the movement of the steam. It is best to avoid the soft granules which could block up the exit points, and should be avoided in order to achieve the ideal time of extraction, which should not exceed 30 minutes.


Solid Fuel Feeding Unit (16): This is made up of a cylinder and a conical trunk, with the small base facing down. The height of the cylinder from the top is 1 mm high and has a diameter of 90 cm, perforated by a spiral fuel-feeding tube coming in from the solid-fuel mixer. The small base of the conical trunk, which also ends in a spiral shape transfer the solid fuel from the cylinder to the solid fuel-feeding tube. The high pressure turbine pushes the fuel inside the hot furnace (14 and 28) in preparation for the burning process, and in order to benefit from the thermal energy stored in it. The unit feeding in the solid fuel is placed on the floor with two Loshatuli carriers.


The unit that washes the gases resulting from the burning, and separates the debris accompanying these gases is made up of a cylinder with a diameter of 90 cm and is 2.2.5 m high, placed on the ground on three legs. Inside are the separator and sedimenter to separate and sediment the debris, and this is porous insoluble sedimentation sand, which has a high surface area and is mixed with water. This is attached to a circuit to determine the amount of the water and a buoy in order to replace the water that is lost. This is attached to a large turbine linking this unit with a thermal exchange unit, thus allowing us to benefit from the hot air that is coming out of the furnace (14 and 28) anyway.


These lead to a chimney from the furnace (14 and 28) to the washing unit, with the aid of two turbines to withdraw and expel, and the thermal exchange unit at the top of the cylinder. Also on the upper part there is an opening to pour in the matter for washing and sedimenting the debris. When the black smoke begins to rise from the upper chimney, the centrifugal force unit is operated. This withdraws the water carrying the debris and pushes it into the treatment unit whereby the debris is removed, and the water is purified and then sent to a new storage tank to be sent to the washing unit again.


Furnace Temperature Regulating Unit:

When the furnace (14 and 28) is full of gases resulting from the burning process, the temperature could stop rising and sometimes could even begin to fall. Then the two turbines of the furnace (14 and 28) temperature regulating circuit have to be operated through the following path: tube—chimney from the furnace (14 and 28) to the suction/expulsion turbine. When the turbine withdraws the gases resulting from the burning process inside the furnace (14 and 28), and expels them to the thermal exchange unit, whose sole purpose is to rid it of the debris, and small flakes, and prevent them from reaching the external environment. These are sedimented in the base of the exchanger and are then removed from there.


The thermal exchanger is made up of a cylinder 5 m high with a diameter of 80 cm, standing on the ground on three legs between the washing and purification unit, and the temperature-regulating unit inside the furnace (14 and 28). It has an opening (a small door that can be manually opened and closed) from/to the 2 previously mentioned units, whereby when one door is opened the other is closed. Inside the exchanger, there are a large number of tubes (1.5 inches in diameter) for thermal compensation. The exchanger also has opening through which hot air can be taken at different temperature. The exchanger ends with a chimney 9 m high, which is actually an iron cylinder with a diameter of 30 cm that ends in a secondary chimney (1.5 m high and with a diameter of 5 inches). At the bottom of the exchanger, there is an opening for cleaning, this is opened and all the debris that was sedimented from the tubes is cleaned out. This is made up of 4 connections, each of which is supplied with a thermometer in order to be able to determine the temperature of each one, and consequently the temperature in each section of the exchanger.


A turbine is mounted on the first suction/expulsion opening that returns the hot air into the furnace (14 and 28). The second opening also has a suction/expulsion opening that feeds the roaster with hot air in order to increase the temperature in the rotating roaster in which the oil shale is found, prior to withdrawing the moisture stored inside it, and transform it into water via the cooling and condensation unit attached to the roaster.


The third opening is for the sucking out of the excess air resulting from the previous operations and expelling it away from the treatment process.


The Loshatuli tubes inside the exchanger allow us to make use of the largest amount of the heat carried by the gases resulting from the burning process, to be used for the operation of the said opening. They also play a major role in sedimentating the small matter sticking to the gas which managed to escape the washing unit and the heat-regulating unit inside the furnace (14 and 28).


As for the two chimneys attached to the thermal exchanger, their main role is to expel the gases resulting from the burning, outside the treatment unit. The last part of the chimney has a diameter of 5 inches and is 1.5 m high, and its role is to achieve complete burning of the solid fuel, and ensure that the maximum amount of the thermal energy stored in the solid fuel is made use of, and is not expelled to the air outside.


The Importance of Liquid Fuel:

Burning could cease, and in order to ensure that the furnace (14 and 28) does not stop working, and in order to raise the temperature to the degree that allows it to feed in the solid fuel, the liquid fuel is used. Its circuit is made up of a mixer (used oil and diesel) at a ratio of (2:1) using a pump that is lowered into the tank and then withdrawn by another pump. A small circular trough is placed at the bottom and on top of it is the flame blazer. When the fuel is alight, the amount of fuel (like in a fireplace) is increased. This helps in operating the high-pressure turbine. When the temperature adequate to burn the solid fuel is arrived, introducing fuel is stopped. Fuel is used) as well when the temperature of the furnace (14 and 28) drops as a result of an in-pour of solid fuel and the burning process stops, which helps burn it and return it to the normal set-up.


The unit that mixes the solid fuel: which is made up of a unit to feed in the ashes and the solid fuel residue, resulting from the treatment recess, consists of a cylinder that is fixed by its lower third section. Its movement is controlled by a hydraulic jack that empties out the cylinder by moving its base in the shape of a semi-circle to empty it out. The feeding of solid fuel occurs through a mechanically-operated blowing cylinder and a mixer, whose engine circumference is Loshatuli that also empties out the additives and the ashes from the mixer. The mixture is blended together well and the components are well distributed. The engine is run which is operated by a spiral structure located at the bottom of the mixer, that moves the solid fuel from the mixer to the solid fuel-feeding unit, since the solid fuel cannot be stored in the feeding unit or it would burn before it is sent to the furnace (14 and 28) because the tube that sends the solid fuel into the furnace (14 and 28) is in close contact with the spiral structure that sucks out the solid fuel from the feeding unit.


The Isolation Chamber to Extinguish the Processed Oil Shale:

When the plates/trays/carriers (26) carrying the treated oil shale are taken out, their temperature is more than 900° C. When it comes in contact with air, it lights up (blazes) with the height of the flame depending on the speed of outside wind. The faster the wind is, the higher the flame height becomes. If the plates (26) remain exposed to air, and the speed of air is appropriate, it will continue to burn until all the charred carbon that could not escape from the reactor, burns, as well as all the non-organic carbon stored in the oil shale ash. These products must be examined, and if they are important in the various industries as “filling materials” there is no need to continue burning them to reach the post-calcification stage, when the ash changes from black to white. It is suggested that the solubility of the ash in water be studied, in order to be able to use it in industries other than building materials and the manufacturing of cement. The plates (26) are lifted by a crane by their hooks, and removed from the heart of the reactor, and transferred into the isolation chamber in order to keep them away from the outside environment.


The Way the Thermal Dismantling Unit Works:

The operation of the Thermal Dismantling Unit is considered a major process in the experiment. After receiving the oil shale from the mines, and after checking on the tests conducted on the trial wells, and making sure to compare the thermal content of the like, the percentage of the organic material, and the percentage of moisture, the raw materials are prepared to proceed with the mineral process. This is followed with the loading and weighing processes, and then the laying out of the plates (26) on the relevant holders. The high temperature thermal dismantling unit bears the potential of being used with other sources of unconventional energy other than oil shale, such as bituminous sand and immature oil that are usually considered not so easy to deal with (especially immature oil) resulting in high quality oil and gas and other by products that could be used in other industries as raw material when treated with this invention.


Bituminous sand (silica sand mixed with bitumen) is another, unconventional source of energy. While bituminous sand has been used widely in order to produce oil, the effects of the traditional production on the environment are serious. When the usage of fresh water and CO2 emission are taken into consideration the oil and gas produced from the high temperature thermal dismantling unit would definitely be described as environmentally friendly. Bituminous sand could be used with the high temperature dismantling unit that is used for oil shale treatment as well, so that the bitumen, which constitutes 12-22% of total weight of the bituminous sand, transforms into gas and oil which leaves silica sand as remnant where the gas and oil are considered to be of high quality.


Afterwards the silica sand goes through a washing process and then directed for suitable industrial purposes to be used as raw material in that industry. (Silica sand is used in the making of glass and creating molds and castings in industrial processing. This sand is also used in sand blasting, adding texture to slick roads and as a raw material in production of ceramics and equestrian surfaces).


In other words, the concept of high temperature thermal dismantling treatment could be applied to bituminous sand very effectively and successfully.


The main origin of unconventional energy resources is carbon and hydrogen. However the main origin of immature oil is kerogen (carbon, hydrogen and oxygen) and if it properly undergoes the following physical factors (pressure, temperature, vibrating motion and time) it transforms into conventional oil. With the high temperature thermal dismantling unit, used for oil shale, all of the physical factors could be accomplished by using the solid fuel as a prime tool in this process. Therefore, the principle of high temperature thermal dismantling unit can surely be applied on immature oil to transform it with very high efficiency into conventional oil which can be further refined in any existing or available refinery.


Regulating all the Processes Relevant to the Treatment Process

Read the electricity meter, note the capacity of the liquid fuel tank, note the capacity of the liquid fuel tank, operate the cooling circuit in order to maintain a temperature of 2-8, ensure that the expulsion pumps are working properly, ensure that the non-return valves are working properly, ensure that the pressure gauges are placed on all the towers and tanks, and that they are all working properly, check all the faucets, some of which are open and other closed, make sure all the heat sensors are operational and functioning normally, prepare the right quantity and size of the fuel (ash+additives).


The burner which runs on diesel is operated and monitoring the temperature inside the furnace (14 and 28) starts, based on the following table:
















Time of clock
Temperature









4:05
 14° C.



4:10
125° C.



4:25
300° C.



4:35
275° C.



5:00
339° C.



5:30
400° C.



6:15
627° C.










At the temperature of above 300° C., then the solid fuel is introduced and the burning process completely stops.


Then the spiral that leads from the mixer to the solid fuel feeding unit is started, and then the spiral that sucks the solid fuel from the feeding unit is stared. Then it is pushed into the furnace (14 and 28) by a high-pressure turbine. At the base of the furnace (14 and 28) there is a turbine that sucks in the air from outside and into the furnace (14 and 28). Pumping in a certain amount of oxygen at the beginning is preferred because the oxygen in the air may not be enough to ensure the continuation of the burning process. When the temperature inside the furnace (14 and 28) reaches 800° C.-850° C., pumping in oxygen is stopped.


The mixer must continuously be fed with solid fuel which is transferred to the feeding unit all the time so that it is not stored, and to make sure that the additives do not burn before entering the furnace (14 and 28). The burning process begins at a temperature of 800° C.-850° C. which leads to an increase in the burning surface and so the burning process is complete. Both the speed the heat is transferred and the motion of the furnace, cause a rapid increase in the temperature of the solid fuel, causing it to burst into flames. This requires continuous feeding with additional quantities in order to maintain a certain temperature inside the furnace without the need for an external burner.


The heat inside the furnace (14 and 28) is radiant, meaning that the center of the furnace (14 and 28) is the hottest, cooling off towards the outside surface. When the temperature is high enough CaCO3 begins dismantling (breaking apart), and CO2 is released. Then the gas washing and purification turbine which sucks out the CO2 are operated and according to Loshaluti; a large part of the CaCO3 breaks up. In the burning region, the percentage of CaO increases, and there is a mixture of Silica (SiO2), Aluminum (Al2O3), and Ferrous Oxide (Fe2O). By operating the heat regulator inside the furnace (14 and 28) the Sintering Temperature (flocculation) is reached whereby the mixture becomes sticky and this process is characteristically liquefying.


At this point the cover of the reactor is opened, and the plates (26) are lifted up by the hooks on these plates (26), and placed inside the reactor, then the reactor is covered again.


Consequently the thermal exchange process within the reactor begins. The reactor (13) is surrounded by bricks, and its temperature is around 900° C. Underneath it is a solid fuel burner and a turbine to suck out the gases resulting from the burning, to wash and purify them, which plays a major role in transferring the heat to all parts, particularly since the turbine feeding in the air from the outside environment ensure the continuation of the burning process. This goes on until the temperature stops decreasing and stabilizes at a certain degree; say 800° C. for example.


It then starts to rise again, and by doing so it is understood that the dispersion point is reached, and the organic matter and non-organic matter begin to break-up. The organic matter appears as volatile matter. The pressure gauge working on the towers attached to the reactor will show an increase in pressure. By turning the vacuum circuit, preceded by the pumping of cold water, these fumes pass through a number of towers and are subjected to extreme cold. A large percentage of these fumes, under certain adequate conditions, start to condense and turn into liquids. The remaining fumes remain gaseous and are sucked out by the expulsion pump circuit via the towers, and are washed and filtered before they go through the vacuum pump. These moist gases pass through the non-return valves and the vacuum pump and to the gas collection chamber by a pressure pump and through a safety valve that opens up when the pressure exceeds a certain point, in addition to a faucet to withdraw the liquids that gather in the gas tank, and another faucet to take samples. There is also another exit point that allows for the use in any of the burning operation in the industrial unit. By changing the value of the pressure gauge, and the temperature of the chrome pipes that link the reactor to the elimination tower, so that it is possible to touch it by hand, when the extraction process has ended, whereby the cover of the reactor could be opened and raised, and then the plates (26) lifted out from inside the reactor, and then these plates (26) are transferred to the isolation chamber, where they are completely isolated from the outside environment. The vacuum pump and the water-cooling circuit are also stopped. As for what happens at the bottom of the furnace (14 and 28), it could be explained in some details: the solid fuel (ashes+additives); the additives ignite as soon as they enter the furnace (14 and 28) because they do not need any lighting fuel; the ashes contain a certain percentage of fossilized carbon when oil shale is treated and the shale oil, shale gas, and water are extracted from it, in addition to inorganic carbon. The temperature of the furnace (14 and 28), the ignition of the additives, and the oxygen introduced into the furnace (14 and 28) is enough to burn the ashes and turn it from black in color to white. This is what is concluded from the calcification process, whereby CO2 is expelled from the calcium rock which becomes Limestone in accordance to the following equation





CACO3------->CaO+CO2


The gases resulting from the burning contain CO2 due to the dismantling process.


The burning process reactions inside the furnace (14 and 28) cannot occur until the CaCO3 has dissoluted, since this is the major dismantling process and it cannot be avoided. If a transformation of the byproducts of the burning process into clinker is desired, in the presence of high temperature and the on-going addition of the solid fuel, the major component of Clinker is formed (C3S). By increasing the temperature even more C3S forms indicating that CaO is uniting with SiO2, until the calcium disappears completely. Additionally and increase in temperature will cause the Clinker to burn and the C3S and C2S begin to react with the C3A and C4AF, which leads to the production of high quality Clinker. The spiral located at the bottom of the furnace (14 and 28) which sucks out all the matter that has been collected in the furnace (14 and 28), which is alight, is operated. At which temperature it could be removed from the furnace (14 and 28) could also be controlled depending on how and where the solid fuel residue in the relevant industry is planned to be used. First the gauge is read and the amount of electricity used during the experiment is calculated. The quantity of the liquid fuel used to raise the temperature of the furnace (14 and 28) is also measured; the amount of solid fuel used (ashes and additives) is also noted; the gases emitted during the burning process is monitored; the duration of the extraction process starting from the sealing of the reactor's cover is measured, (irrespective of the quantity); the amount of the gas in relation to the pressure inside the reactor is measured; the amount of shale gas extracted during the treatment process is calculated. In the experiment, there are 4 towers consecutively connected to the reactor, therefore four kinds of extracted shale oil from the treatment of oil shale are obtained. The plates (26) are then emptied out and then separately measured to be compared to its weight before the treatment in order to find out what kind of oil is best, and which granule size is better. Two plates (26) are used for each kind of shale, then; the leftovers of the oil shale after the treatment are gathered. The Law of Conservation of Matter needs to be abided, made sure that the transfer of energy is correct, and finally all these inputs with the outputs are linked in order to assess the economic cost accurately. Most of the experiments that were undertaken during the trial period gave results relevant to the treatment of between 800 and 850 kilograms of the Jordanian oil shale which is extracted from the old Sultani Mines whose specifications were as follows:















Density
2.1-2.6  









Volumetric weight
1.3-2.5
ton/m3


Thermal energy
950-1,585
Kcal/Kg








Percentage of organic matter
10-22%


Overall sulphur content
05.-2.8%


Percentage of moisture
 6-10%


Rigidity coefficient
6-9 as per Brokodiakonov









Rigidity coefficient at displacement
(17-78) × 105
Pascal


Rigidity coefficient under pressure
(170-920) × 105
Pascal


Rigidity coefficient when withdrawn
(21-110) × 105
Pascal









The following approximate results apply to the treatment of 800 to 850 kg of oil shale with the above-mentioned specifications.



















Estimated ther-
Total ther-





mal energy
mal energy


Name of


per unit
per unit


Product
Unit
Quantity
(Kcal)
(Kcal)



















Shale gas
m3
 92-110
14,800
1,494,800


Shale oil
Liters
 80-100
10,500
945,000


solid fuel
Kilogram

8,000
4,920,000


solid fuel
Kilogram
420-580
Artificial use


residue


Water
Liter
40-60
Subject to





purification


Hot air

Immeasurable




quantity



Kilo-
Total temperature

7,359,800



calorie
that can be ob-




tained if the




products are burnt









Based on the fact that the percentage of the organic materials is 22%, accordingly, the expected flame when burning the oil shale is alight in color, which is an indicator of the good quality of the flame. When a good amount of flammable matter is added (between 5 and 30)%; the oil shale can be completely burnt, however, in addition, when the components of the cement are ground very well; it will be easy to have it burnt, resulting to allow the major components (CaO, SiO, Al2O3, Fe2O3) of cement to be mixed well. In such way, it could be claimed that using the oil shale ash in making the cement could be one of the best ways to have the highest homogeneous cement components.


The Advantages of Burning Solid Fuel





    • 1. It is possible to control the temperature at which the burning occurs in the required environment, starting at 750° C. whereby the chemical reaction in the furnace (14 and 28) begins.

    • 2. The thermal exchange between the granules of the solid fuel is fierce and massive, which, in turn, doesn't require a thermal copper surface since the brick does this, and achieves the desired results.

    • 3. The poisonous gas emissions (Sulphuric and nitrogenous) are practically non-existent, because a percentage of these accompany the shale gas and shale oil which has been extracted from the oil shale, and the remaining percentage form bonds with the left over CaO and form CaSO4, which does not dissolve easily. All these operations contributed to the environment feasibility of the process, since the CaSO4 is considered a component of the ashes.

    • 4. It is possible to contribute to the dismantling of CaCO3, whose dismantling plays a major role in enabling the oxides to react together, and consequently several reactions, that generate heat, take place at the same time, and thus achieve self-burning.

    • 5. Moisture contributes to the loss of a lot of heat and hinders the burning process of the solid fuel. There is no moisture here because the treated oil shale lost all its moisture during the treatment, and the additives, with the exception of the rock coal, do not have any moisture.

    • 6. The direct burning methods of oil shale are accompanied by a large quantity of CO2, resulting from the dismantling of CaCO3 when treating the oil shale at a high temperature of almost 900° C., whereby a change in the chemical structure of the shale's non-organic matter occurs. Consequently, when burning solid fuel, these amounts are not noticed, since the gases resulting from the burning process carry most of them, in addition to the presence of a washing and purification process which plays a major role in limiting this quantity.

    • 7. All the burning processes used to occur in electrical ovens, without any oxygen. Therefore the results of the burning processes were not accurate. However, burning in the presence of the adequate amount of oxygen helps the burning and the formation of CO2. If the quantity of oxygen is too little, the burning is not good and leads to the formation of highly poisonous CO gas, which is also an environmental pollutant.

    • 8. This process succeeded in solving two of the most complex problems which have hindered the oil shale industry; the first one, transforming the ash, which is about 86% of the weight of the shale, to solid fuel with a good thermal content, and solid fuel residue which is a very important material used in many industries, and the second one is the ability to release the process of extracting a barrel of shale oil from the fluctuating cost of traditional fuel (shale coal, crude petroleum and natural gas) since extracting the shale oil and shale gas is performed by heating them using the solid fuel; this means that the oil and the coal are no more used to produce the shale oil and the shale gas.

    • 9. Reducing the destruction of nature, provision of industrial raw materials, to provide different amounts of energy, and focus on linking the cement industry with the oil shale processing projects.





The Employed Experiment Methodology

The selection process is subject to physical criteria, including the fact that the oil shale to be treated should have a thermal content between 850 and 1585 kcal/kg, in order to be transferred to and used near to the quarry.

    • 1. The breaking process starts with feeding the quantity needed to treat into a crusher. A sieve is attached to it to eliminate the granules that are less than 5 mm in diameter, whereby the quantity of the rock which will be broken will pass through the sieve and can be collected. However, since it is still not homogenous, it will be put through another sieve to eliminate all the granules whose diameter is less than 1 cm.
    • 2. Plate (26), with a diameter of 77 cm and a height of 18 cm, with hinges 12.5 cm high are fixed. These have a hole in the center measuring 15 cm in diameter. Each empty plate (26) is then weighed, and filled with the granules that are almost homogenous in size. Then the plate (26) is weighed again and given a number. The plates (26) are then placed on a pole (220 cm high) on a base measuring 13 cm in diameter. The pole carries 10 bases, one for each plate (26), which are arranged in a way to allow the observation of the changes that occur within them.
    • 3. At the bottom of the reactor, there are perforations (5 cm in diameter); while on the top there are perforations (1 cm in diameter). There are also 5 rows of perforations, evenly distributed along the circumference of the reactor, which merge into 2 washing structures, (diameter 84 cm) and a spiral cylinder of 12 cm high, ending in one point of exit where the two perforations at the bottom of the reactor meet through a tube 4 cm in diameter.
    • 4. The furnace (14 and 28) is located on the exterior and runs on diesel, which is used at the rate of 30 L per hour, aided by liquid fuel (diesel+used oil). The burning process takes place in the furnace (14 and 28), which operates when necessary: when the temperature of the furnace (14 and 28) rises to 450° C. There is also the option of using the cuttable oil which is initialized when the temperature of the furnace (14 and 28) rises to 550° C. When the temperature rises to 650° C., the burning of liquid fuel ceases completely, and the burning involves solid fuel exclusively.
    • 5. A small turbine is located at the bottom of the furnace (14 and 28) to help burn the solid fuel. Sensitive sensors on the top and bottom of the furnace (14 and 28) allow reading the temperature on the control panel.
    • 6. The burning process begins with the burning of the diesel, and the temperature rises every 3 seconds, until it reaches 350° C. whereby it rises every 10 seconds. Once it has reached 500° C., pumping in the liquid fuel begins (used oil+diesel) until the temperature reaches 750° C., whereby the solid fuel is introduced and the introduction of diesel is ceased completely. The solid fuel is fed in until the temperature reaches 1000° C. whereby adding fuel is stopped to allow the temperature to decrease, though the time needed for the temperature to fall to 750° C. is about 75-80 minutes.
    • 7. The temperature inside the furnace (14 and 28) is regulated by a series of turbines, the first of which is attached to the circuit for cleaning and depositing the by-products of the burning process which are pushed out to an exchanger and out through the chimney. The second turbine withdraws from the furnace (14 and 28) and pours into the exchanger directly. The third withdraws from the exchanger and returns the hot air to the furnace (14 and 28). There is also a turbine that pushes the solid fuel inside the furnace (14 and 28), aided by another turbine which plays a major role in burning the solid fuel, and most importantly increasing the temperature of the furnace (14 and 28) quickly (approximately 1 degree every second).
    • 8. When the temperature has risen to the temperature necessary for dismantling (separating the organic from the non-organic elements) depending on the various and different components of the oil shale. If the oil shale that is being treated is taken from one location, then the temperature remains standard and limited to a certain degree, about 650-850° C., depending on the reaction environment and the environment surrounding the reactor. At this point, the cover of the reactor is removed by a moving lever, and every 10 plates (26) are raised by a special crane and placed into the reactor, whereby the bases of the plates (26) placed are based in a circular fashion at the bottom of the reactor leaving spaces between the base of the reactor and the base of the plates (26), and the reactor is once again covered. Uncovering and then re-covering the reactor takes up about 5 minutes. When this is done, the thermal exchange process begins in a thermodynamic manner that can be noted from a tower lined directly to the reactor. This goes on until the break-even point when the temperature of the reactor stabilizes for a period of 1.5 minutes, and then begins to rise. At this point, all indicators of a rise in pressure are evident, and all the resulting steam, must be removed by means of an evacuation pump. The temperature continues to rise, resulting in more steam being formed from the organic compounds of the oil shale, with each type of oil shale having a different fixation temperature, though the degree by which the pressure rises is what indicates the amount of steam produced.
    • 9. The cooling circuit, which provides a quantity of cold water, about 5 m3 with a temperature between 3° C. and 6° C., of the lowest entry value, and the second value returning to the storage tank, this circuit feeds into five condensation towers, each tower ending in a steam-condensation collection tank. The sequence from the reactor to the evacuation tank then to the dual condensation tower, to a regular condensation tower, to a gas collection tank, through a filter to purify the gas before it enters into the purification pump which compresses the gas into a gas-collection tank which is fully equipped with valves to ensure the gas does not go back, in addition to safety valves, points to withdraw samples, and points to eliminate any liquid that may form in the tank.
    • 10. If the gas needs to be purified from the compounds that contain sulfur, this is done by the afore-mentioned towers. It is always recommended that the installation of two purification pumps on the purification tank, in case of emergency, since all the plates (26) need to undergo thermal dismantling, irrespective of the circumstances.
    • 11. The fixation temperature is maintained, and any increase will result in the increase of coal that is formed inside and outside the purification tower, but inside the reactor, which causes an increase in the formation of steam that can decrease the time that the plates can be left inside the reactor.
    • 12. Maintaining a steady temperature inside the furnace (14 and 28), ensuring that the temperature of the reactor is set at a specific degree are 5 turbines alternating to work in 4 stages, 2 chimneys, and a unit that washes, purifies and sediments debris.
    • 13. At the bottom of the furnace (14 and 28) there is a spiral tube operated by an engine. Following the burning of cuttable oil, it is collected at the bottom, and should it turn into a paste, then motion is necessary to fragment it and facilitate drawing it out of the furnace (14 and 28).
    • 14. The important indicators that the unit is working properly are; the cooling circuit, the thermometer which shows when the cooling is insufficient and that the elimination circuit must be increased, a two-way air-pressure indicator with a zero indicator, and an indicator to show increasing pressure showing that the elimination process is inadequate. When it falls below zero, and shows a decrease then it should be understood that the elimination circuit is working properly.
    • 15. A change in temperature of the tubes linking the reactor to the elimination tower indicates the end of the extraction process, whereby the cover of the reactor must be removed, and new un-treated plates (26) inserted in their place.
    • 16. In order to withdraw the plates (26) that have under-gone thermal dismantling, and having studied the previously mentioned data that indicate the end of the extraction process, whereby the temperature of the furnace (14 and 28)=the temperature of the reactor=the temperature of the plates=850° C., the cover of the reactor is opened. As soon as the air comes in contact with the rocks, at the same temperature the rock blazes and the hooks of the crane are lowered to lift the plates (26) which are placed in an air-free room which is then shut off. The cover of the reactor is then closed, and so the process of commercially producing about one ton of treated products is finished: shale oil, shale gas, water, the raw materials of solid fuel, and hot air. This is followed by stopping the operation of the elimination unit, and the cooling unit, and the process is repeated if it is wished to continue.
    • 17. The first step includes maintaining the preservation of mass theory: the mass of the matter entered=the mass of the matter produced (i.e. the mass of the oil shale which underwent treatment=the mass of the shale oil+shale gas+water+the raw materials of solid fuel) (1 m3 of shale gas is equal to ±1 Kg.).
    • 18. As for the cost of extracting the products of the treatment process, this reflects on the first experience only, since diesel is relied on for the burning process in order to raise the temperature of the furnace (14 and 28) to 900° C., after which the solid fuel is depended on which is one of the by-products, using about 50 kg every 10 minutes. Burning as much of this as possible is favored in order to obtain the solid fuel residue which is a raw material with numerous industrial uses.
    • 19. Electricity is also used for the operation (the elimination circuit, the cooling circuits, the turbine, and the mobile crane). As for the quantity of water that evaporates is lost because the range of is (3-10)° C. (entering and returning), bearing in mind that the perished elements, the oils used in the elimination circuit, and the changing of gas filters.
    • 20. Register all the data used in the said experiment including—input, output, consumed products (water-oil-electricity and air), and the items that perish and their weight; all of which are linked to the economic feasibility mentioned in the assessment, along with the environmental impact of implementing this experiment, following the measurements relevant to the air, soil, water and sound pollution. Once performed; the extraction and mineral processing aspect can be studied, and the cost of treatment can be added in order to obtain the cost of extracting 1 ton of shale oil, then the value of the products of a ton of shale oil can be calculated, and thus determine its economic value, and connect it to the thermal value resulting from the treatment of 1 ton of oil shale.
    • 21. This way, the first step of the industrial operation process resulting in commercial production is over. Random samples are then taken and sent to the laboratories to ensure the stability of the properties of the production, in addition to checking the environmental aspect of the operation involved in the extraction process, and then determining the economic feasibility of the process based on inputs and outputs.
    • 22. Research and studies all indicate that the oil stored in oil shale is close to 3.4 trillion barrels. This figure is somewhat modest. However, this means that there at least 392 trillion cubic meters of shale gas, exceeding the total reserve of crude oil. And at a time when there is a severe shortage of energy, this is motivating to introduce a technology that realizes the economic and environmental challenges, and can fulfill the need for clean energy at reasonable prices, resulting in an equation that is stable and reliable:





Oil shale=Shale gas+Shale oil+High energy solid fuel+Water+Hot air=Coal+Crude oil+Natural gas.

    • 23. The reality of it, supported by the experiment, indicates that oil shale gives even more, and all those interested to work on developing methods to treat oil shale need to be urged, and not just heating methods, and all the successful relevant initiatives support, since the development of heating methods is a notion that is now “dead, and gone”, and does not require any research nor development.


Leading Improvement Techniques in the Oil Shale





    • 1—Conventional burning systems that rely on liquid or gas fuel to produce thermal energy cannot burn the solid fuel in an acceptable burning efficiency to take the full advantage of the high heat content stored in the solid fuel; accordingly, the present invention of burning system has been designed to be able to work with the burning fuel in its three states (solid, liquid and gas).

    • 2—The burning system used in the proposed invention works on traditional fuel (diesel) until it reaches the temperature of above 300 degrees Celsius inside the furnace (14 and 28), then the burner that works with the liquid fuel (diesel) is stopped and then the temperature inside the furnace (14 and 28) through feeding it with the solid fuel is maintained. Accordingly, the furnace (14 and 28) works non-stop and without the need for any amount of conventional fuel as using the solid fuel is totally enough to carry on the burning system.

    • 3—Conventional burning systems used in the oil shale processing can achieve high temperatures but this requires the consumption of large quantities of fuel which may exceed the extracted amount of fuel during the oil shale processing operations. In the present invention, the consumed liquid and gas fuel can be replaced by the created solid fuel to achieve the desirable high temperatures to process the oil shale; in such way, the extracted shale oil and shale gas is much more than the consumption oil which is needed in the treatment processes.

    • 4—When using the solid fuel in the burning system, the burner can achieve any desirable temperature, ‘even though 3500 C.° is possible to be achieved’, in addition, at such high temperature; the oil shale ash can be treated to be usable as raw materials in different industry fields, such as cement industry, thermal isolation raw materials, and others.

    • 5—The conventional fuel burning systems rely on the use of water vapour in order to complete the process of burning the solid fuels; however, the burning system uses just the normal air to perform full and efficient burning process to fully use the stored energy in the solid fuel.

    • 6—The conventional burning systems require such huge amount of fuel to achieve the very high temperature such as 2000 C.°, however, when using this burning system; cheap solid fuel with such high thermal content is needed to achieve this temperature easily and smoothly with the acceptable environmental standards, so, the present invention can save in the used fuel and the fuel cost.

    • 7—The burner temperature in the proposed burning system depends on the amount of the air used and its rate, in addition to the additive materials to the oil shale ash (which is used as the solid fuel) rather than the amount of the solid fuel itself.

    • Reactor (13) and furnace (14 and 28) unit (1) which is the basic unit of the high temperature thermal dismantling unit comprises;
      • Reactor lid (15)
      • solid fuel entrance of reactor and furnace unit (16)
      • Spiral for feeding solid fuel (17)
      • Gas collector for vacuuming (18)
      • Temperature sensor of reactor and furnace unit (19)
      • Gas collection pipe for vacuuming (20)
      • Diesel flow holes of flame distributor (21)
      • Flame distributor (22)
      • Air turbine of reactor and furnace unit (23)
      • Spiral for taking the ash of reactor and furnace unit (24)
      • Tray bearer (25)
      • Oil shale plate/tray/carrier (26)
      • Pipe for transfer of collected gas (27)

    • Reactor lid (15) is the lid placed at the top of the reactor to load or unload the tray bearer (25) and oil shale plate/tray/carriers (26).

    • solid fuel entrance of reactor and furnace unit (16) is the entrance of solid fuel.

    • Spiral for feeding solid fuel (17) feeds solid fuel into the furnace (14 and 28).

    • Gas collector for vacuuming (18) is used for collecting the gases, oil and water in vapor form.

    • Temperature sensor of reactor and furnace unit (19) measures the furnace temperature.

    • Gas collection pipe for vacuuming (20) is used for collecting the gases, oil and water in vapor form.

    • Diesel fuel flow holes of flame distributor (21) are the holes of the flame distributor for fuel passage.

    • Flame distributor (22) is used to initiate the burning of solid fuel. It burns diesel. When the temperature of the furnace is above 300° C. then it is taken out from the furnace.

    • Air turbine of reactor and furnace unit (23) is used to provide the proper air into the furnace (14 and 28) for better burning of the solid fuel.

    • Spiral for taking the ash of reactor and furnace unit (24) is used to take the ash from the furnace (14 and 28)

    • Tray bearer (25) holds the oil shale plate/tray/carrier (26)

    • Oil shale plate/tray/carrier (26) carries the oil shale.

    • Pipe for transfer of collected gas (27) is used to transfer the gases, oil and water in vapor form by gas collector for vacuuming (18) and gas collection pipe for vacuuming (20).

    • High temperature achievement mechanism is explained below.

    • The idea behind burning the advanced solid fuel system is derived from the knowledge of the series of the successive thermal interactions that occur on the surface of the stars and its mass limitation and the stages of its life cycle. Adequate knowledge of these concepts leads to understanding the difference between chemical energy and nuclear energy.

    • The chemical energy is often stored inside the material and contributes to the process of binding the atoms in the molecule, as well as binding the material's molecules together. Chemical energy often turns into thermal energy through chemical reactions.

    • The nuclear energy is initiated from the atom of the nucleus as a result of the nuclear particles' rearrangement and assembling. This is accompanied with a transfer of parts of the mass of these particles into energy.

    • The temperature raising mechanism from nuclear energy is explained below.

    • The amount of transformed amount of mass into energy is a key factor in the process of temperature control that can be achieved within the reaction medium.

    • The atom is the essence of the material's structure, and energy is considered as the engine of this essence which indicates a complementary relationship between the material and energy. From here, it can be concluded that the mass of the nucleus is the main criteria for the material's energy content.

    • As the mass of the nucleus is less than the sum of its components' masses; the shortfall in the nucleus mass is regarded as an indicator to the correlation energy between the components of the nucleus. The correlation energy between the nucleus components can be calculated with the Lahnstein Law bellow:








ΔE=ΔMC2

    • Where ΔE is the change in the amount of the correlation energy, ΔM is the change in the nucleus mass and C is the speed of light.
    • The temperature raising mechanism from the chemical interaction energy is explained below.
    • In this field; the advantage of the chemical interactions must be taken to obtain the thermal energy.
    • The chemical reactions take place between the reactants in large amounts and it needs so-called activation energy to occur. Activation energy can be obtained from various sources such as heat to speed up the movement of the atoms and molecules. Chemical interactions release thermal energy by means of heat. The resulting heat is calculated based on the amounts of the reactants.
    • Nuclear reactions: in which a nucleus interacts with other nucleus or nucleolus (proton or neutron). The interaction occurs in a very short period of time in order to produce a new nucleus or more. The resulting interaction is associated with releasing small particles and energy.
    • When the interaction energy is calculated on the basis of grams rather than the interaction of the nucleus; the amount of the released energy would be enormous.
    • These facts make the interaction approach nuclear reactions that make the thermal reaction medium achieve high temperatures. The resulting high temperatures contribute to the occurrence of new series of successive thermal interactions, as a result; the reaction medium temperatures could achieve the temperatures of up to a level that is similar to the surface temperature of the stars, and this medium is suitable for the continuation of the thermal nuclear reactions.
    • In conclusion; energy can be obtained either from the nuclear energy stored in the nucleus mass according to Lahnstein Law in terms of correlation energy, or from the chemical interactions energy which is stored in the bonds.
    • To process oil shale; it is enough to reach the temperature of 1600° C. at the center of the combustion reaction medium and 1000° C. at the reactor's wall.
    • If the propose from using the combustion system (combustion medium) is to access high temperatures that meet the requirements of the mining industry (starts from temperatures of 2000° C. and above); it is enough to change the reaction medium (reactor liner material) and to increase the amount of the material that is used to be changed into energy (achieving what is happening on the surface of the stars). Accordingly; the more the amount of material transformed into energy is increased; the higher the temperature of the reaction medium is achieved.
    • In conclusion; the high temperatures are obtained by taking advantage of the nature of chemical reactions at first, as well as the nature of the interactions of thermal nuclear secondly. This underlines the amount of benefit achieved from the potential energy stored in the advanced solid fuel to reach such high temperatures.
    • Since all types of rocks consist of eight key elements in addition to no more than 2% of different secondary elements; all of these elements are considered as combustible in presence of oxygen or the presence of a sufficient amount of air.
    • The existence of the above mentioned scientific facts and the implementation of the well-studied calculations; temperatures that contribute in melting and evaporating metals can be obtained, taking into consideration that reaching the desired high temperature relies on the combustion medium that can bear that temperature without reaching the state of collapse. Thus, any high temperature can be accessed provided that the combustion medium that can stand this temperature exists.
    • The combustion media (furnace) releases dirty smoke filled with the combustion products (remains waste). The dirty smoke is then led to the Purification and combustion products washing unit (2-1) through a specific path/pipe (1-1 and 1-2). The purification and combustion products washing unit (2-1) is connected to the air turbine for combustion gases (3-1) which pumps the purified and washed air to the Multi-stage heat exchanger and combustion products precipitator (4). The Multi-stage heat exchanger and combustion products precipitator unit (4) performs the function of precipitating the combustion products through the four stages of the heat exchanging with equal four quarters as follows:
    • The first quarter of the heat exchanger contains a large number of pipes with small and equal diameters to precipitate the small-sized combustion products.
    • The second quarter of the heat exchanger contains a smaller number of pipes than the number used in the first quarter with equal larger diameters than the diameters of the pipes implemented in the first stage, to precipitate bigger-sized combustion products which have not been precipitated in the first quarter.
    • The third quarter of the heat exchanger contains a smaller number of pipes than the number in the second quarter with equal larger diameters than the diameters of the pipes implemented in the second stage, to precipitate bigger-sized combustion products which have not been precipitated in the first and the second quarters.
    • The fourth quarter of the heat exchanger contains no any pipes and it is used just to exchange the heat from ‘ideally’ the pure and clear hot air that is resulted from the previous three precipitating stages.
    • The heat exchanger fourth quarter is followed by a long and wide chimney (12) which is the exit of the combustion products after being purified, washed, and precipitated. To increase the emitted hot air's pressure; a second chimney with a smaller diameter than the diameter of chimney (12) can be implemented, in fact, even a cascaded of chimneys with smaller and smaller diameters can be implemented to reach the desired pressure.
    • As a result, the output hot air of the first quarter is neither used inside the treatment unit nor outside because the combustion products are yet not precipitated in a satisfactory level, while the part of the smoke produced from the second quarters is brought back to the furnace to help in the combustion process because it is clean enough for this propose. Hence the pure hot air (treated combustion smoke) produced from the third and the fourth quarter is the one which is being taken advantage of in outside the treatment unit.
    • Based on above, the emitted combustion product smoke is practically tested and can be confirmed that it has no any (minimum) negative impact over the environment, and this is justified by the rigorous washing, cleaning, purifying, and precipitating processes adapted in our treatment technology.
    • In the case when the air turbine for combustion gases (3-1) cannot alone manage pulling all the smoke from the combustion unit; the combustion medium′ (furnace) temperature stop rising as a result of a suffocation occurs inside the furnace, in this particular case; a second and separate path (2) is opened to increase the amount of smoke drawn from the furnace. This additional dirty smoke is then led to the Purification and combustion products washing unit (2-2) through the specific path (2). The purification and combustion products washing unit (2-2) is connected to the air turbine for combustion gases (3-2) which pumps the purified and washed air to the Multi-stage heat exchanger and combustion products precipitator (4), then the extra combustion products go through the same process the normal combustion products go through in the normal scenario (no suffocation) i.e., precipitating stages and then exiting through the chimney (12). Accordingly, we have two different combustion products paths, turbines, and purification and combustion products washing units. The two purification and combustion products washing units (2-1 and 2-2) are connected to the same Multi-stage heat exchanger and combustion products precipitator (4).
    • Worth mentioning that both air turbine for combustion gases (3-1 and 3-2) work together just for short period of time to tackle the suffocating problem, and soon the temperature start rising again; path (2) is closed, and both of purification and combustion products washing unit (2-2) and the air turbine for combustion gases (3-2) are switched off. In our practical experience; the suffocating case lasts for few minutes.
    • Again, we notice that even in the suffocating scenario; the exited hot air through the chimney (12) to the outside environmental is as clear as the exited hot air in the normal scenario as it goes through the same processes.
    • The solid fuel can be produced from the ash which is spent shale, ash obtained by high temperature oil shale dismantling process, treated spent shale, ash obtained from direct burning of oil shale, ash obtained from indirect burning of oil shale or any mix of them.
    • The solid fuel can be burned in a specially designed high temperature furnace. High temperature furnace for burning solid fuel (35) comprises,
      • Temperature sensor of solid fuel burning furnace (29)
      • Chimney (30)
      • solid fuel entrance (31)
      • Air turbine of solid fuel burning furnace (32)
      • Flame distributor of solid fuel burning furnace (33)
      • Burner working by liquid fuel (33-1) and cylinder for distributing the flame inside the furnace (33-2)
      • Spiral for taking the ash of solid fuel burning furnace (34)
    • Temperature sensor of solid fuel burning furnace (29) measures the temperature in the furnace.
    • Chimney (30) is used to deliver the combusted gases.
    • Solid fuel entrance (31) is the entrance of the furnace to take the solid fuel for burning.
    • Air turbine of solid fuel burning furnace (32) is used to feed the required air into the furnace.
    • Cylinder for distributing the flame inside the furnace (33-2) is used to initiate the burning of solid fuel. It burns diesel. When the temperature of the furnace reaches to 300° C. then it is taken out from the furnace.
    • Spiral for taking the ash of solid fuel burning furnace (34) is used to take the ash from the furnace.


When the fuel to be burned in the high temperature furnace for burning solid fuel (35) is dried and then powdered as the particle size less than 200 μm; then its ignition temperature can be as low as 100° C. Accordingly when designing the high temperature furnace for burning solid fuel (35); the particle size of the fuel is considered as key factor.

Claims
  • 1- Thermal dismantling unit for processing the oil shale or bituminous sand or immature oil, comprising; Reactor (13) and furnace (14 and 28) unit (1), wherein reactor is inside of the furnace,Purification and combustion products washing unit (2),Multi-stage heat exchanger and combustion waste precipitator (4),Roasting, moisture pulling and oil shale drying unit (5),Centrifugation and pulling the washing outputs unit (9),The Isolation Chamber to extinguish the processed oil shale.
  • 2- Thermal dismantling unit as claimed in claim 1 and characterized in that the roasting, moisture pulling and oil shale drying unit (5) to be used for processing oil shale to obtain shale oil, shale gas, water, hot air, ash and residual comprises; Compiling and condensing vapors of heavy components tower (13.2).Intensification of Tower 1 (13.3)Intensification of Tower 2 (13.4)The distillates collection tank 1 (13.5)The distillates collection tank 2 (13.6)viscosity breaking tower (13.7)Vacuum tower (13.8)Vacuum pump (13.9)Gas gathering tank (13.10)Glass distillates showing tower 1 (13.11)Glass distillates showing tower 2 (13.12)Centrifuge pump (13.13)Distillate liquid collection tank (13.14)
  • 3- Reactor (13) and furnace (14 and 28) unit for the thermal dismantling unit as claimed in any of the preceding claims comprises; Reactor lid (15)solid fuel entrance of reactor and furnace unit (16)Spiral for feeding solid fuel (17)Gas collector for vacuuming (18)Temperature sensor of reactor (13) and furnace (14 and 28) unit (19)Gas collection pipe for vacuuming (20)Diesel flow holes of flame distributor (21)Flame distributor (22)Air turbine of reactor and furnace unit (23 and 3.1)Spiral for taking the ash of reactor and furnace unit (24)Tray bearer (25)Oil shale plate/tray/carrier (26)Pipe for transfer of collected gas (27)
  • 4- Reactor (13) and furnace (14 and 28) unit for the thermal dismantling unit as claimed in claim 3 and characterized that the speed of the air blown by the air turbine of reactor and furnace unit (23 and 3.1) is above 5 m/s.
  • 5- High temperature furnace for burning solid fuel (35) and obtaining temperature up to 3500° C., comprises; Air turbine of solid fuel burning furnace (32)Burner working by liquid fuel (33-1) and cylinder for distributing the flame inside the furnace (33-2)Spiral for taking the ash of solid fuel burning furnace (34)
  • 6- High temperature furnace for burning solid fuel (35) as claimed in claim 5 and characterized in that the speed of the air blown by the air turbine of solid fuel burning furnace (32) is above 5 m/s.
  • 7- High temperature furnace for burning solid fuel (35) as claimed in claim 5 or 6 and characterized in that the ignition temperature is above 300° C.
  • 8- High temperature furnace for burning solid fuel (35) as claimed in claim 5 or 6 and characterized in that the ignition temperature is above 100° C. if the particle size of the fuel is less than 200 μm.
Priority Claims (3)
Number Date Country Kind
PCT/TR2013/000319 Oct 2013 TR national
2013/14919 Dec 2013 TR national
2013/14922 Dec 2013 TR national
PCT Information
Filing Document Filing Date Country Kind
PCT/TR2014/000162 5/13/2014 WO 00