Patent Application
20160236977
The present invention relates to a solid fuel with high thermal content which is called solid fuel. The main component of the solid fuel is the ash resulting from the process of oil shale treatment or oil shale dismantling process.
Rocks are the main components that make up the Earth.
Thermal energy is considered the backbone of any industry and its main engine, and the need for energy is increasing with development and civilization, so, to face this demand; large amounts of energy, clean energy resources, and sensible prices are required.
solid fuel is a solid fuel with high thermal content (heating capacity).
In the traditional oil shale dismantling processes under low temperatures; the residuals of this process cannot be completely free from the organic materials. The percentage of the organic materials that remains is in the range of 5% to 40%. This residual from the oil shale process is so-called spent shale.
The residue obtained by the oil shale dismantling processes under high temperatures tends to separate the organic and inorganic materials from the oil shale during the processing, resulting to what is called ash obtained by high temperature oil shale dismantling process.
Accordingly, the resulting ash from this process is claimed to be equivalent to the spent shale but with neglectable (negligible) percentage of the organic materials.
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.
Organic and inorganic additive materials are added. The amount of additives are determined related to the amount of energy required and the area of use such as production of clinker, cement etc.
Rocks are the main components that make up the Earth. Minerals are elements that make up the rock.
Chemical analysis, and empirical studies on the various types of rocks from the surface of the earth and in its interior at different depths, showed that a limited number of chemical elements are key components of the different types of rocks on the earth's surface and in the interior, these elements are:
These elements are key components of any type of rock, while the rest of the elements known and studied, do not exceed a total of 1.5% of the weight of the Earth's crust. Oxygen is the most important element and it displays electrical properties in the rocks of the Earth's crust.
Silicon comes first in the ability to combine with any element, such as Sio2, carbon is next, and then sulfur, phosphorus, and then nitrogen.
Silicates and oxides are the basic and main components of the rocks, rather than carbonates, sulfates, phosphates or nitrates.
The importance of oxygen as a key component in the rocks of the Earth's crust is presented in the crystal compounds found in rocks, the elements (K, Na, Mg, Ca, Fe, Al and Si) appear surrounded and connected to the oxygen atoms, but in fewer degrees.
Elements (Fe, Cl and S) play the role of oxygen:
Most of the rocks contain sufficient oxygen for bonding with elements of positive atomic weights, these compounds are called metal oxides and its percentages are summed up to 100% without specifying the percentage of oxygen directly, oxides of Silicate rocks are: SiO2, Al2O3, FeO, Fe2O3, CaO, MgO, Na2O, K2O, TiO2, P2O5, and H2O.
Carbonate rocks specifies the percentage of CO2 and sulfate rocks specifies the percentage of SO2.
Rocks that make up the Earth's crust have developed as a result of effective geological processes through a long geological time. These operations contributed to the construction of some types of rocks, and destruction of other types, but the rock cycle starts from molten rock to igneous rocks and then to deposits followed by sedimentary rocks followed or proceeded by a metamorphic phase that produced metamorphic rocks.
Rocks on the earth exposed to the impact of air, water and weather conditions of hot, cold and other weather effects, those operations are called rock weathering.
Chemical and mineral composition of the rocks:
The structure of the rocks starts from the underground melt stage, and then the weathering factor manipulated it to several kinds of rocks which are:
Igneous rocks: These rocks are structured from solidification process of the rock's magma that was emitted from the underground. The following table shows the rate of the major oxides in igneous rocks:
The igneous rocks consist of the main following elements: Si, Al, Fe, Mg, Ca, Na, K and O.
The main oxide is Silica with a percentage of (52.5-73.5)%.
Sedimentation: A geological process resulting from the overlap of the atmosphere and hydrosphere on the earth's crust.
Sedimentary rocks: representing 5% of the rocks of the Earth's crust, and is considered as a product resulting from the fragmentation of metamorphic or igneous rocks, its chemical composition varies and it can be in the form of shale, sand stone, or limestone with the following proportions 1%, 3% and 16% are for the shale, sandstone and limestone respectively.
The chemical composition rates of the sedimentary rocks are: Shale 82%, 12% and 6% for the shale, Sandstone, and Limestone respectively.
The mineral composition rates of the sedimentary rocks are:
Metamorphic rocks: Rocks of secondary origin that came from the mineral transformations that have occurred in the sedimentary and igneous rocks, so, its chemical composition is in between of both of them.
For example, the transformation of the shale rocks is illustrated by the following equation:
Shale→Slate→Phyllite→Micashist→Gneiss
Metals: elements formed by natural inorganic processes and are distinct from each other by their physical, chemical natural optical, electrical and magnetic characteristic, in addition to the chemical composition and crystal structure belonging to it.
Crystal chemistry science aims to clarify the relationship between the chemical composition, internal structure and natural characteristics in crystalline materials, in addition to the manufacture of crystalline materials.
Chemical bonds: Ions or atoms are bonded with each others in the crystal with electric powers and which makes them non-ionic bonds when appearing in salts.
Covalent bonds appear in diamond, Metallic bonds appear in the metals and the Vander Vals bonds which are responsible for the gases cohesion.
Based on the nature of the bonds in the crystals, the crystals are classified into five categories which are:
Ionic Crystals, covalent crystals, molecular crystals and metallic crystals.
Polymorphism: An element or a compound that can have more than one atomic arrangement where a distinction is made between two types of interactions:
1) Reversible: occurs in specific temperature and pressure, such as the following transformation:
2) Irreversible: Does not require a degree of pressure and temperature
To achieve compatibility between the shale ashes resulting from the oil shale processing and the appropriate additives required to produce a solid fuel (solid fuel) and which can be used in various industrial fields, adequate thermal energy is needed. For example: Generation of electrical energy is performed under (450 to 650)° C. and the cement industry is performed under 1450° C., in addition to the thermal energy generation.
The remaining solid fuel and knowledge of its composition, its physical and chemical characteristics in order to introduce it to the right industrial field, for example the properties of materials used in cement must be known, as well as knowledge of finest composition of the cement to balance the ash and additives used for solid fuel production that achieves the required thermal energy and the remaining solid fuel is an important raw material for a wide range of basic industries.
The chemical composition of raw materials:
The temperatures for the reactions occurring in cement production furnaces are shown in the table below with its interactions:
To achieve solid fuel with exceptional high thermal content, and a model composition of typical cement, it is required to maintain the following criteria:
percentage=1.13C3A+1.35C4Af+MgO+Alkali (4)
The following table shows the cement composition model:
For the exact values of the criteria that show the typical composition of the cement, it is needed to go back to the previous equations that are associated with the typical composition of the cement to find:
The optimal Portland cement of class E, requires raw materials with percentages that assures the Silica Ratio (2.5-3.5), LSF (90-95), Percentage of liquid material (20-27), and BI (2.6-4.5).
The effect of chemical composition on BI to determine the BI for a certain mixture; two mixtures are chosen with the following percentages shown in the two tables below:
Percentage of the relative burning ability: The percentage of the burning ability is illustrated through the study of the data for the two mixtures which are shown in the table below:
By concluding the data in the two mixtures above; it can be observed that Mixture (1) is easier to be burnt than Mixture (2). If Gypsum was added to the mixture with the purpose of not allowing Alkalis to merge with the gases in the furnace, vision in the area of combustion significantly decreases.
Some of the Cement formation reactions are reversible, specifically in the area of combustion, the clinker produced in that area has to be immediately and quickly cooled to avoid obtaining such reversible reactions that result to a low quality product, as demonstrated in the following equation:
C3SC2S+free Ca
The thermal amount of a compound and decomposition are equal in the quantity and opposing in direction, in addition, this thermal amount depends on the status of the deteriorated compounds.
The slaw cooling leads to form C3S and C4AF in crystal form with taking into consideration that the thermal amount needed to form C3S is larger than the thermal amount needed to form C2S.
The oil shale is defined as fine crystals sedimentations that occur in different forms such as sedimentary limestone, sedimentary silicon rocks, sedimentary and clay rocks.
Microscopic study showed that basic mass of the Mastrecht and Eocene oil shale are similar and belong to the sedimentary lime rocks, silicon rocks and sedimentary clay rocks, of organic structure that look like unique or multiple moles/cells, big ones with Lime form and the small ones in the form of Dolomite and sometimes phosphate.
The moles/cells are filled with hydro carbonate material, where that Mortar is a microscopic crystals composed of Calcite and clay, that appears in yellow or brown color because of the absorption of the hydrocarbonate materials, it also sometimes appears in the form of Dolomite or phosphate crystals, Quartz fragments and phosphorous knots.
The components of the oil shale are restricted to the following basic ones:
Thermal energy is considered the backbone of any industry and its main engine, and the need for energy is increasing with the development and civilization, so, to face this increasing in the demand; large amounts of energy, clean energy resources, and sensible prices are required to be fulfilled. Oil shale can fulfill those demands and organizes the processes of the energy flow, in addition to conserving the balance and cleanliness of planet earth and protecting it from the disasters, as the structural units are balanced and aims for stability according to a precise system without exposing it to disasters that could lead to destruction and diminish, such as the nuclear plants.
By proposing and applying the following equation with the best available technologies:
Oil Shale=Natural gas+Crude oil+Coal
Ideas in which the solid fuel is built on:
2Al+Fe2O3→Fe+Al2O3+200 Kcal
2Zn+O2→2ZnO+170 kcal
All these ideas together dedicated enough drive to elevate the furnace temperature within (600 to 950)° C., within this range, reactions releasing energy take place.
If the organic analysis carried over oil shale samples is studied, then another analysis carried out over the inorganic samples, and within the temperature range mentioned, it is found out that all reactions based on those concepts do take place in addition to other reactions. These other reactions introduce the oil shale additives after extracting gas and oil from it to achieve a new type of solid fuel that we called solid fuel
Based on the obtained practical results; a relation between the chemical content of oil shale and oil shale ash is found. This relation leads to the idea of creating the solid fuel; accordingly, full analysis for the oil shale structure and its ash is performed and then joined to determine the additive materials to the ash in order to convert it to solid fuel.
The following tables show the results of the oil shale structure (Organic aspect) and its ash (inorganic aspect):
It is important to differentiate between materials that are able to be burnt to release thermal energy at low temperatures like Diesel, fuel oil and depleted oil, and the material that can be burnt but at high temperatures, like the ashes resulting from oil shale when extracting gas and oil from it.
The ability of the ash to be burnt is recognized from the reaction of CaCo3 with SiO2 and Al2O3 and Fe2O3, since without this reaction of those compounds; C2S and C3S will not be produced in addition to C4AF and C3A, which are also part of the thermal reactions used to produce the clinker. However, those chemical reactions wouldn't have occurred if appropriate conditions were not fulfilled with the specific additives.
The thermal energy released can be controlled and used, in order not to have a rapid reaction accompanied with high energy that significantly elevates the temperatures inside the furnace. However, good care should be taken to avoid the negative affect over the reaction medium as a result of the combustion in the furnace through the operations of the oil shale treatment. The additives are many and various. The main aim is to achieve solid fuel having high energy content and clean combustion energy that does not harm the essential life elements. The solid fuel residual can be greatly benefited as an entrance to several and basic industries.
The human contribute to destroy the nature without noticing this action; indeed, the cement industry uses Lime stone, clay, and silica sand in addition to Basalt, this is accompanied by transportation processes, crushing, grinding, blending and mixing with water to homogenize, use of fuel for machinery, use of electricity for these processes, the large amounts of water associated, wear and tear of the crushers, mills, conveyer belts and the lining of the furnaces, add to all this that production of 1 ton cement requires burning 160 kg of traditional liquid fuel oil. All these processes are not observed and are not counted in the environmental calculations, it is said that those projects are launched in the desert areas where the natural resources are available. However, when doing so, can it always been argued that it is maintained the motto “Petroleum is more precious to be burnt” as it should be directed to more important industries that have no effect on the environment and guarantees economic benefit and developmental qualities which is positively reflected on the progress of civilization, and familiar with scientific rules and making sure it is carefully applied regulates the use of energy and guarantees its flow in huge amounts with reasonable prices, and addition to the reservation of the beauty of nature even of it was a desert.
Work with these criteria in a scientific approach by relying on scientific rules as maintaining the energy and mass laws and taking into account the cleanliness of the energy and the reasonability of its price. In conclusion; the civilization criteria dictates that the energy sources should be safe and not accompanied with disasters when generating large amounts of clean energy for reasonable prices.
The proposed invention deals with the oil shale treatment technology which suggests a scientific and logical investment project for oil shale treatment, based on industrial experiments using an execution unit performed by a pilot plant that can have a commercial production line that gives important economic indicators on the return on investment, and with processes that finely affects the environment according to the following equation:
Oil Shale=Natural gas+Crude oil+Coal
Analyzing the previous equation with more details gives more general form shown in the following equation:
Oil Shale=Shale gas+Shale oil+Water+Hot air+solid fuel=Coal+Crude oil+Natural gas
The main components of the solid fuel is the ash which is a result of oil shale treatment, taking into consideration that the ash is comprised of flammable material when reacting with each other, and most of its reactions are regarded as energy releasing reactions.
The ash consists of TiOs, Na2O, K2O, SO3, MgO, Fe2O3, Al2O3, SiO2, CaO and negligible amount organic materials. Those oxides react with each other in an appropriate reaction medium, a proof of this is the reaction of Lime stone with the sand in the presence of clay and Basalt, the reaction medium is the furnace, where those reactions take place gradually and the results are the formation of: C2S and C3S in addition to C4AF (four carbonate Flouride aluminum) and C3A (third carbonate aluminum), then the combustion reactions begin that assures the reaction of those compounds with each other with adequate high temperatures, where clinker is produced, the clinker is then cooled, specific additives are added to it before being grinded to obtain shale cement.
From the studies of the chemical structure of the oil shale and oil shale ash, it is observed the presence of carbonates (Calcite, Dolomite, Silica Quartz, metal clay, Ellite, Vitmoriolonate, Pyrite, Magnazite, Apatite, and phosphorus fragments).
The lab analysis that was carried on the ash, indicates that the percentage of the ash resulting from oil shale treatment is between (56%-86%) and this ash contains a high a percent of CO2 (24%-38) %, where the percentage of CaO is (3-48)%, Al2O3(0.5-3.3)%, Fe2O3(0.4-2)%, MgO(0.5-3)%, and (K2O+Na2O=0.3)%.
The value indicating the melting temperature of the ash is (B=0.05-0.35), where B is the ability to burn the clinker and calculated from the following equation:
The inorganic Sulfur percent is (0.7-2.9)% in addition to the presence of other important metal elements, the percentages of their presence is represented by P.P.M. (Par Partitioning Million).
Use of Ash Obtained from Oil Shale Dismantling Process
Ash obtained from oil shale dismantling process can be used in grinded form as active carbon for; liquids and gases purification and filtering processing without any additives.
In the mixtures in this invention the percentages are given by weight of the ingredients of the mixture.
The most basic additive material is the air, which is added to the hot ash to keep it burnt continuously.
The mechanism of adding the air and the burning process is shown below:
Making use of air is through multi use turbines of different types:
The organic additives are:
It is important to emphasize that through the experience, it is found that the main role of the solid fuel is not for the additives; it is rather for the Calcinations process that the ash need to be exposed to before adding the additives which is concluded in the release of CO2 from Lime stone to transform to live lime stone according to the following equation:
CaCO3→CaO+CO2
The calcinations process begins at the temperature of 900° C., the combustion gases inside the furnace carries CO2 with it, which resulted from the disintegration of the Lime stone, this process lays the ground for the reaction of CaO with SiO2 in the presence of Al2O3 and Fe2O3 and forms C2S and C3S in addition to C3A and C4AF as a step towards a combustion process that results in the formation of clinker where an appropriate additive is added then treatment processes are carried over that produces Cement that it is used in construction.
If it wasn't for the Calcinations process, the clinckerizing stage would not be reachable.
Not reaching the calcinations to its natural stage results in disruption of the functionality of the furnace, so the calcinations in general before entering the combustion area is very essential and cannot be discounted. This is necessary for burning the clinker well and in the right way to achieve high quality Cement.
If the goal was to achieve solid fuel with exceptional thermal content, and solid fuel remaining that is enough to cover the needs of Cement production then the additives fulfill the ideas that triggered the thought of solid fuel and the additives are then to make the remaining of the solid fuel is exactly the clinker.
To obtain solid fuel, ash is mixed with of various powdered metals such as Fe2O3 powder, Al powder, Zn powder, Sulfur powder, Ferrous powder, copper powder . . . etc. or any mixtures of them. The mixture is mixed very well to the point of complete blending:
The analysis on the samples exposed to treatment processes changes those percentages where the Cement standards require specific percentages of these materials, but a reaction between the oil shale and the blend releasing big amounts of energy that could elevate the temperature of the medium to 1500° C. without any external energy resource and under the condition of fulfilling the reaction medium.
When treating 1 ton of oil shale, the following products fulfills the law of conservation of mass and reflects the actual cost associated with this process, as for the additives, their percentages have already been highlighted, and it is originally available.
The additives are related to the amount of energy it is aimed to achieve and the area of use on the remaining of solid fuel.
As result of the reactions that are all energy releasing, the clinker is formed.
After the cooling process it is pulled and mixed with small percentages of gypsum, the resulting powder is Cement. The amount of the combustion loss during the extraction and production of cement, and the combustion loss is very low in the formation of the cement from the remnants of solid fuel. Following table can be used for comparison.
After the calcinations process thermal reactions take place that releases energy and thus forming: C4AF,C3A,C2S, and C3S, the percentage of each compound is determined by the following formulas:
C3S=4.07CaO−(7.6SiO2+6.72Al2O3+1.43Fe2O3+2.65SO3)
C2S=2.83SiO2−0.75C3S
C3A=2.65Al2O3−1.69Fe2O3
C4AF=3.04Fe2O3
Looking at these criteria, the indicators to the additives amounts of the ash in order to transform it to solid fuel is seen.
The solid fuel residual can produce such good quality of clinker by adjusting the additive materials to the solid fuel in a way that performs the previous relations.
As for the interpretations of those compounds:
C3S: responsible for the early growth of the mortar concrete, if the percentage of C3S is increased above 65% it gets difficult to be burnt.
C3A: Responsible for the ability of mortar formation by increasing its softness (the elastic cement is formed)
C4AF: Is responsible of the color of the cement, the more the percentage is, the darker the color becomes. A light cement color is preferred, iron is liquidated material and can help in the formation of the previous compounds in lower temperatures than the in the previously mentioned.
In the research it is aimed to improve combustion processes, fighting pollution resulting from combustion processes and the extraction of industrial raw materials processes in a random manner, the use of solid fuel in combustion processes, savings of amounts of air and water, decreasing costs (high chimneys, electrostatic precipitators, polluting gas separation, and smoke wash).
When the solid fuel 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 reactor and furnace; the particle size of the fuel is considered as key factor.
Reactions taking place inside the furnace:
There two main elements: Carbon and Silicon, which lay the base for the combustion in the solid fuel. Those two elements are characterized by the presence of four electrons on the last energy level, the Ionization energy is related to the atomic size, as it differs between two of them, those factors make the oxides of those elements to be oxides acidic.
Crystal Silicon has the shape of the tetrahedral diamond but the intensity of the thermal chemical bond between silicon atoms is less than that between carbon atoms
Si—Si=226 K·J/mol
C—C=356 K·J/mol
So the silicon does not possess the solidity of the diamond, and the noncrystallized silicon is a microcrystal powder.
Carbon and Silicon are not affected by diluted acids, the first reacts with bases, the second reacts with diluted bases.
If carbon in heated sufficiently in the presence of Oxygen, it gives CO2, small amounts of oxygen gives CO.
C+O2→CO2ΔH=−391 K·j·mol−1
C+½O→COΔH=−11 K·j·mol−1
Silicon is heated in the air till reaching the temperature that the silicon becomes red in color:
Si+O2SiO2→ΔH=−910 K·g·mol−1
It can be seen that the enthalpy for SiO2 is greater than that for CO2 because Si—O=452 K·j·mol−1 and C—O=358 Kj·mol−1.
Carbon Hydrates: there are two types of hydrates, a straight chain and closed chain; the two types are also consistent with two saturated hydrocarbon compound models, and unsaturated hydrocarbon compounds.
The numbers of carbon hydrates are many and various
Their model is: CHnH2n+2
The number of Silicon hydrates is limited and the volatile hydrate chain of the covalent bonds called “Silanes” that is similar to hydrocarbons, its general formula is: Sin H2n+2.
The self-adhesion phenomenon between the element's self-atoms is less important in the silicon compared to the carbon, and high silanes disintegrates slowly in high temperatures, and its sensitivity to oxygen becomes greater than its sensitivity to alkanes, additionally all silanes self-ignites in the air automatically as shown below:
CH4+2O2→CO2+2H2O
SiH4+2O2→SiO2+2H2O
When heating the silica to high temperatures and under fluctuating pressure SiO is formed in its metal form, by cooling a brownish powder is obtained that oxidizes and self-reduced according to the following equation:
2SiO→Si+SiO2
Si is a combustible element just like the carbon but its combustion reaction releases more energy than the carbon's.
When thinking of a mechanism of the silica existence in the nature and discussed ways of burning it to calculate the amount of the thermal energy released by burning it and compared it to carbon. The silica exists in nature in many crystal shapes mainly: kierelguhr, cristobalite, tridymite and quartz.
The solid crystallized aqua material had great ability of absorption and so its shapes are great particles where each silicon atom is linked to four oxygen atoms and appears in a tetrahedral shape, as follows:
Silicon can be obtained in pure form by decomposition tetrafluoride silicon or tetrachloride silicon, and then immediately have it burnt by adjuvant combustion material such as the hydrogen. The Silicon atoms can carry two sets of hydroxide which is unlike the carbon atom, so, by changing the compounds and the hydrolysis conditions; the straight chains, annular and the polymers are obtained to connect these Alsellkonat which have similar behavior of hydrocarbon. Moreover, the correlation and bond length enable the presence of silicon in term of oils form that are characterized by its stability under high temperatures, which enable it to be used as lubricants at low temperatures because the hydrocarbon lubricants' viscosity increases with the decrease of the temperature. Accordingly, the Silicon is regarded as water repellent material with High Isolation factor. It is noted when reviewing the information that the silicon is approaching a large degree of a carbon which is a combustible material in certain conditions.
Since the reaction medium is a high temperature furnace at the presence of strong airflow, and in addition to the presence of carbon as a catalyst; the combustible silicon ignites at a good degree, As a result, oxygen plays a key role in all components of the combustion of oil shale ash as well as additive materials which are inherently incombustible materials.
In the big industrial fields, relying on adding lime coal only even if it had low thermal content is possible.
An experiment was performed over the Turkish oil shale with the content of 1800 Kcal/kg, moisture of 8%, and Sulfur of 0.9%; the results of the analysis of this processing operations for the oil shale were as shown in the table below:
When the goals are to achieve solid fuel with high thermal content, clean combustion, large amounts of thermal energy and reasonable prices; then the mixture is linked to the importance of the solid fuel residual. If the main goal is to produce cement through the analysis which has been performed over the oil shale ash and the coal ash; the mixture consists of all the main materials for cement productions, which are resulting from the process of burning the mixture.
Accordingly it is confirmed that the oil shale treatment project is an energy production project, clinker and cement production project.
Coal: Combustible rock formed from the remnants of plants decomposition, its color is black or dark brown. The percent of carbon is 60% to 90% and this percentage depends on the degree of the coal roasting level.
The coal is considered as the most difficult for use among all kinds of fossil fuels due to the difficulty of the mining works and the environmental conditions related to its combustion.
The chemical composition of coal, carbon-hydrogen-oxygen, bonding with chemical reactions as main material resulting from photosynthesis in addition to additions form Nitrogen, chloride, sulfur and remaining of metallic elements.
The degree of coal/roasting is the standard for the percentages of the substances comprising the coal and CH4 are the associated gas for these reactions, they have to be rid of because of their harmful effects, resulting to obtaining the brown low quality coal, low in thermal content and low percentages of volatile matters.
The black coal(Antracite)-high quality-high thermal content, the volatile matter and impurities determines its uses.
The high thermal content of the coal encouraged the Chinese company (Foushon) to introduce coal to the oil shale during the treatment processes to make use of its thermal energy during the heating processes.
When the coal is used with suitable amounts to the combustion processes, many factors should be taken into account such as knowing the carbon which determines the amount of air required for combustion.
Moist contributes to decreasing the thermal value because of the capillary action coal absorbs moisture, the Sulfur's percent is 0.5%-5%, which is related to the pollution and erosion of the container.
Ash: the incombustible material and represents the debris that was found in the mud that the plant material was roasted in.
The oxygen: its percentage decreases with the increase of the roasting level, as the increases in its percentage results to the decrease of its use.
Aims at replacing petroleum derivatives with coal derivatives; this encourages the extraction of gas from coal, with less cost than extracting petroleum derivatives from coal.
Research on Germany succeeded some accomplishments, other research in USA and UK in the area of transforming coal to gas and even coal liquidation, large credits were dedicated to these researches.
Coal gasification: Process of transforming coal to gas fuel, and so the idea of Synthetic natural gas aroused, but this idea will not be successful with the evolution of a new culture that depends on coal as an additive rather than a combustion material.
Coal liquidation: Process of transforming coal to liquid hydrocarbon fuel, and depends on decreasing the percent of carbon and increasing the percent of hydrogen, either by hydrogenation, or elimination of some carbon atoms, by producing coal or CO gas, all these ideas remained not applicable due to its high cost and large energy requirements.
The scientific efforts are focusing on supporting the research of the following cases:
These efforts were not successful because it did not prove its self in the discovery stages, and here it is mentioned that the research and development is only applied over successful ideas, for example when it is desired to stop the random use of energy; and to stop the chaotic production of cement; why large amounts of energy is used without previously studying it.
So when the oil shale treatment project is considered; it is confirmed that the needs for gas and oil are linked to the needs to the cement. All this is apparent in a comprehensive project that provides raw materials, energy, and water.
Accordingly, separate cement factories are not needed which is reflected on the economical aspect of the project and fulfills suitable conditions for earth stability.
In WO 2010/034621 a thermal dismantling method which produces product vapours which are separated by distillation, yielding shale gas, shale oil, water is disclosed. In our present invention; all the organic materials are vapored at the degree of 950 C, so, the remaining ash is totally free from any organic materials, and accordingly, it could not be coke. Moreover, our solid fuel is mixed up with different external additives.
Regarding adding the Oxygen to the combustion process, we agree that it is well known for the skilled person, but we managed to find the relation between the amount of the added Oxygen and the desired temperature with and without the external additives.
Regarding claim 2 of the present invention, the additives used in WO 2010/034621 A1 are just the petrol, water and coke gas which are all organic materials where in the present invention there are more added materials in term of organic and/or non-organic.
As a results to the added organic or/and non-organic materials, the present invention controls the desired temperature and the use of the residual ash resulted from burning the solid fuel.
Regarding to Claim 3 of the present invention, WO 2010/034621 A1 added organic materials which are all resulting from the dismantling processes, while in the present invention; the added organic materials could be any organic materials from outside the dismantling unit such as the poultry residuals, peat . . . etc. Accordingly the solid fuel that includes 0% of organic materials is being taken out of the reactor to be cooled and then treated to be used again in the furnace to treat the new oil shale.
Regarding Claims 4 and 5 of the present invention; WO 2010/034621 A1 does not mention adding any extra additives other than water and coke gas and petrol, whereas in the present invention many organic and/or non-organic additives are added with the specific percentage for each added material.
Regarding the ignition temperature of 150° C. to 720° C. in WO 2010/034621 A1, WO 2010/034621 A1 mentioned the temperature related to the added Oxygen rate. In the present invention the method of using temporary igniter works with liquid or gas fuel till reaching the temperature of 550° C. or above.
In U.S. Pat. No. 4,886,521, the added Fe2O3 is mixed with the oil shale in a gaseous atmosphere. In the present invention; the added Fe2O3 is mixed with the oil shale ASH, which is totally organic free due to heating the oil shale to the temperature of up to 1000° C. and then Fe2O3 is used with other elements that their reactions release the heat energy as illustrated in the chemical reaction equations in the description and claims. Moreover an igniter is used to reach the temperature of above 550° C. for starting the burning process without the need of the gaseous atmosphere. Accordingly, the present invention does not need gaseous atmosphere and it works with the oil shale ash after extracting the whole organic material rather than burning it in the heating processes.
In IL 102275 A, adding rubbers to the oil shale to extract shale oil, shale gas and solid fuel is performed over the oil shale while in the present invention; the additives are added to the oil shale ash which is %100 free of organic materials. Moreover, in the present invention; many other additives are added so, all other comments for WO 2010/034621 A1 are valid for IL 102275 A.
In CN 1453344 A, a combustion method of solid fossil fuel is disclosed. According to the disclosure, oil shale carbocoal waste in 60-100 weight % and oil shale screenings in 0-40 wt % are mixed, crushed and burnt in circular fluidized bed boiler at low temperature of 850-950° C.
In the present invention; oil shale ash which is %100 organic free is mixed with different additives to be used as solid fuel. So, all the comments for WO 2010/034621 A1 are valid for CN 1453344 A.
Finally, the temperature range obtained in CN 1453344 after burning it in fluidized bed boiler is in between 850 to 950° C. while in the present invention, the temperature after burning can reach up to 3500° C.
In EP 0107477 A1, the residual depleted shale is regarded as solid fuel and then get bunt to produce steam and heating fresh oil shale, in the present invention; oil shale ash which is %100 organic free is mixed with different additives and then burned. So, all the comments for WO 2010/034621 A1 are valid for EP 0107477 A1, in addition, in the present invention the solid fuel can be used as heat source for outside of the dismantling unit which is unlike EP 0107477 A1 where the heat is just being used to heat the new fresh oil shale and to produce the steam.
In DE 3916597, residues from processing of cattle or pig manure are eliminated by mixing the residues with lignite dust and/or coal dust, to render the material inert and reduce NOX due to the NH3 content, with production of a non-polluting coal product. At the same time, components binding SO2, HCl and HF may be added, e.g. lime (CaO, Ca(OH)2, CaCO3) or waste lime from sugar beet production. USE/ADVANTAGE—The product is used as fuel in heating and power stations. Addition of the residue to the dust renders it inert and reduces the risk of explosion.
In the document WO 2010/066316 A1, a process for producing cement or cement substitutes on the basis of carbon-containing compounds, wherein the carbon-containing compounds are burnt in a furnace at a temperature of 600 to 900° C. is disclosed. In the present invention the non-carbon compounded materials are obtained from the oil shale by burning it at a temperature between 850-1000° C. where no any organic materials remains in the oil shale ash which carbon free oil shale ash. The oil shale ash that does not contain any carbon is then mixed up with the proposed additives by excluding the coke.
Document CN 102875184 A provides an aerated brick made from oil shale residue. The compound of making it comprises, besides inorganic and organic additives, Al-powder. In D9, the method of producing the bricks using the oil shale and oil shale ash is disclosed. In the present invention the non-carbon compounded materials are obtained from the oil shale by burning it at a temperature between 850-1000° C. where no any organic materials remains in the oil shale ash which carbon free oil shale ash.
In EP 0727398 A2, a composite cement, which hardens and develops full strength rapidly, which contains calcined oil shale, cement clinker, calcium sulpho-aluminate, anhydrous calcium sulphate and water-reducing agent is disclosed. Comments mentioned in WO 2010/066316 A1 are valid for EP 0727398 A2.
The document U.S. Pat. No. 3,972,724 relates to burning fuel shale to produce cement clinker and energy at the same time Comments mentioned in WO 2010/066316 A1 and D9 are valid for US 3972724 A.
CN 101143766 discloses an oil shale based porous adiabatic construction material for construction of wall and roof, which comprises a preset amount of oil shale as basic component, burnable additive, oxide and intensifier. Comments mentioned in WO 2010/066316 A1 and D9 are valid for CN 101143766 A.
JP 588538 describes that spent oil shale is supplied to an absorbing tower and contacted with the exhaust gas from a conduit to carry out wet desulfurization. In JP 588538 A, the tower is used to desulfurization, however, in the present invention, the produced active carbon is capable to be used in gas and liquid purification, filtering, adsorption and absorption. Moreover, the produced active carbon is obtained from the oil shale treatment at a temperature of 850-1000° C. where the organic materials are zero.
In U.S. Pat. No. 5,571,490 high sulphur content fuel is combusted in the presence of oil shale containing significant amounts of calcium carbonate so that the sulphur and calcium carbonate oxidize and react to form calcium sulphate particulate which captures the sulphur and in the fuel and prevents its release to the atmosphere.
In the document WO 2009/010157 a process and a plant for refining solids containing oil and/or bitumen, in particular oil sand or oil shale is disclosed.
In the document U.S. Pat. No. 4,054,482, “a dry distillation process for treating bituminous or oil-containing fine-grained material, particularly tar sand, with a heat carrier comprising fine-grained dry distillation residue which is heated in a pneumatic conveyor line by hot combustion gases and then fed to a collecting vessel and mixed in a dry distillation zone with the fine-grained material to be subjected to dry distillation” is disclosed.
In the document U.S. Pat. No. 3,972,724; a method of processing fuel shale to produce energy and cement clinker at the same time, oil shale and/or coal shale are disintegrated, homogenized and activated in a pin beater mill or vibrating mill. The effect of the treatment is monitored by X-ray microanalysis and the treatment is automatically controlled. The admixtures required for the production of a cement having the desired quality are added simultaneously at controlled rates. The thus treated material is then burnt in a boiler plant, preferably at combustion temperatures up to 1400° C. and with simultaneous sintering, whereby ash and/or slag is formed which contains at least 60% cement clinker. Said cement clinker is separated from the residual ash and slag and in an impact-type mill is disintegrated in such a manner that each clinker particle is subjected to 3-8 impacts within a time of preferably less than 0.01 second by beating elements which are moved at a velocity of at least 15 meters per second, preferably at a velocity between 50 meters and 250 meters per second.
in the present invention, ash is defined as 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. It is used as the main component of solid fuel.
In order to burn this ash which is the main component of the solid fuel with or without additives, at least 5 m/s of air flow is needed. Oxygen may be added to improve burning. Additionally the temperature needed to ignite the burning is more than 300° C. After the ignition; the burning starts and the furnace temperature gradually increases. The furnace temperature can reach up to 3500° C. by control of air and/or flow and the additives. Oxygen may be added to improve burning.
In the mixtures in this invention the percentages are given by weight of the ingredients of the mixture.
The calorific values for presently used energy sources and ash to be used in production of solid fuel are in the below Table.
Types of additives to ash, their percentages and calorific values and the calorific value of the produced solid fuel are in the below Table.
In the present invention, spent shale means the ash obtained after the presently used oil shale dismantling methods and has organic materials inside.
In the present invention, ash means the ash obtained by the high temperature oil shale dismantling method and has no organic material inside.
The present invention claims; use of spent shale obtained after the presently used oil shale dismantling methods or ash obtained by the high temperature oil shale dismantling method as solid fuel.
In the present invention, the solid fuel may also be the mixture of 1% to 100% of 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, with 0% to 99% of organic and/or inorganic additives or any mixture of organic and inorganic additives.
The ash without any additives can be used as solid fuel. Solid fuel can also be produced by mixing 30% to 90% of ash with 10% to 70% of organic or inorganic additives or any mixture of them.
In order to produce solid fuel, 30% to 90% of ash is mixed with 10% to 70% of organic additives. These organic additives are organic creatures. The residuals of slaughter houses or organic remnants from poultry houses peat, cellulose, viscose, acrylic, plastic or peat of olives residue can be used as organic additives or any mix of them.
As an alternative, in order to produce solid fuel, 30% to 90% of ash is mixed with 10% to 70% of inorganic additives. These inorganic additives are one or more various powdered metals. Any combination of two or more of Fe2O3 powder, Al powder, Zn powder, sulfur powder, ferrous powder or cupper powder can be used as inorganic additives.
In order to produce solid fuel, 1% to 5% of Sulfur is mixed to 95% to 99% of solid fuel which is produced by any one of the abovementioned processes.
Clinker which is the main component of cement can also be produced by the present invention. In order to produce clinker, 50% to 100% of ash is mixed with 0% to 50% of low quality coal and/or inorganic additives and/or organic or inorganic additives or any mix of them and then the mixture is burned again in the furnace at the temperature of 650° C. to 3500° C. by feeding air with the speed of above 5 m/s. Oxygen may be added to improve the burning. The ash (residue) of this burning is clinker. It can be used in producing cement. However, the best quality of clinker can be produced after burning the mixture of 75% ash with 25% of low quality coal.
Another product, raw material for manufacturing thermal isolation (insulation) materials that can be used in construction of furnaces or isolation materials in construction industry can also be produced by the present invention. In order to obtain raw material for manufacturing thermal isolation (insulation) materials, 40% to 100% of ash is mixed with 0% to 60% of various powdered metal and/or coal or any mix of them, and then the mixture is burned in the furnace at the temperature of 650° C. to 3500° C. by feeding air with the speed of above 5 m/s and raw material for manufacturing thermal isolation (insulation) materials are obtained. In order to use this ash as raw material for manufacturing thermal insulation materials, the ash is grinded and used as the main element of manufacturing the thermal insulation materials. Oxygen may be added to improve the burning. However, the best quality of raw material for manufacturing thermal isolation (insulation) materials can be produced by mixing 85% of ash with 15% of various powdered metal.
Method for producing raw material for manufacturing thermal isolation (insulation) materials that can be used in construction of furnaces or isolation materials in construction industry, Fe2O3 powder, Al powder, Zn powder, sulfur powder, Ferrous powder or copper powder can be used as powdered metals.
Another product, raw material for manufacturing brick blocks as construction materials can also be produced by this invention. In order to obtain construction materials to produce brick blocks 30% to 100% of ash is mixed with 0% to 70% of organic and/or inorganic and/or coal or any mix of them, and then the mixture is burned in the furnace at the temperature of 650° C. to 3500° C. by feeding air with the speed of above of 5 m/s, the ash from the furnace is grinded to be used raw material for manufacturing brick blocks by the presently used methods. Oxygen may be added to improve the burning. However, the best quality of raw material for manufacturing brick blocks can be produced by mixing 85% of ash with 15% of various powdered metals.
The organic materials are the organic creatures such as peat of olives residue or the residuals of slaughter houses or organic remnants from poultry houses peat, cellulose, viscose, acrylic or plastic . . . etc.
Another product, raw material for manufacturing pavement blocks can also be produced by this invention. In order to obtain pavement blocks, 30% to 100% of ash is mixed with 0% to 70% of organic creatures and/or various powdered metals and/or coal or any mix of them and then the mixture is burned in the furnace at the temperature of 650° C. to 3500° C. by feeding air with the speed of above of 5 m/s, the ash from the furnace is grinded to be used raw material for manufacturing pavement blocks by the presently used methods. Oxygen may be added to improve the burning. However, the best quality of raw material for manufacturing pavement blocks can be produced by mixing 95% of ash with 5% of various powdered metal
In order to obtain pavement blocks Fe2O3 powder, Al powder, Zn powder, sulfur powder, ferrous powder or copper powder can be used as powdered metals.
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 can be treated to be 100% free from organic materials; that can be used in grinded form as active carbon for the purpose of purification, filtering and adsorption and absorption of liquids and gases. The particle size of the ash after grinding for liquid purification is in between 8 to 40 μm. The particle size of the ash after grinding for gas purification is in between 4 to 10 μm.
ΔE=ΔMC2
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/TR2013/000319 | Oct 2013 | TR | national |
| 2013/14919 | Dec 2013 | TR | national |
| 2013/14922 | Dec 2013 | TR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/TR2014/000163 | 5/13/2014 | WO | 00 |
