WO2015053721A1 - High range temperature thermal dismantling method in processing oil shale - Google Patents

High range temperature thermal dismantling method in processing oil shale Download PDF

Info

Publication number
WO2015053721A1
WO2015053721A1 PCT/TR2013/000319 TR2013000319W WO2015053721A1 WO 2015053721 A1 WO2015053721 A1 WO 2015053721A1 TR 2013000319 W TR2013000319 W TR 2013000319W WO 2015053721 A1 WO2015053721 A1 WO 2015053721A1
Authority
WO
WIPO (PCT)
Prior art keywords
shale
oil
gas
oil shale
water
Prior art date
Application number
PCT/TR2013/000319
Other languages
French (fr)
Inventor
Trad AL AHMAD
Original Assignee
Al Ahmad Trad
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Al Ahmad Trad filed Critical Al Ahmad Trad
Priority to PCT/TR2013/000319 priority Critical patent/WO2015053721A1/en
Priority to EP14742607.6A priority patent/EP3055384A1/en
Priority to EA201690566A priority patent/EA201690566A1/en
Priority to EA201690568A priority patent/EA201690568A1/en
Priority to CN201480058816.8A priority patent/CN105765051A/en
Priority to EA201690569A priority patent/EA201690569A1/en
Priority to PCT/TR2014/000163 priority patent/WO2015053723A1/en
Priority to US15/028,027 priority patent/US20160251577A1/en
Priority to CN201480058561.5A priority patent/CN105745308A/en
Priority to CN201480060382.5A priority patent/CN105722952A/en
Priority to EP14742608.4A priority patent/EP3055404A1/en
Priority to CA2926952A priority patent/CA2926952A1/en
Priority to US15/028,030 priority patent/US20160251578A1/en
Priority to PCT/TR2014/000162 priority patent/WO2015053722A1/en
Priority to AU2014332590A priority patent/AU2014332590A1/en
Priority to CA2926956A priority patent/CA2926956A1/en
Priority to PCT/TR2014/000164 priority patent/WO2015053724A1/en
Priority to CA2926955A priority patent/CA2926955A1/en
Priority to EP14741996.4A priority patent/EP3055383A1/en
Priority to US15/028,029 priority patent/US20160236977A1/en
Priority to AU2014332589A priority patent/AU2014332589A1/en
Publication of WO2015053721A1 publication Critical patent/WO2015053721A1/en
Priority to IL244994A priority patent/IL244994A0/en
Priority to IL244996A priority patent/IL244996A0/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks

Definitions

  • This invention consists of a new thermal dismantling method that enables reaching very high temperatures of 950°C in order to transform any quality oil shale into directly 5 refmeable shale oil and to shale gas equal to natural gas, without using liquid oil for temperature rise and without using water as a cooling system, resulting in ash production where the ash could be transformed into high fuel and high fuel into other industrial products like insulation materials, clinker etc and as a byproduct producing water and clean hot air. 10
  • This mixture contains a broad spectrum ofmineral elements and it has the ability to generate all traditional sources of energywhen treated by the thermal dismantling method.
  • the thermal dismantling method is based on separating the volatile section which consists of the shalegas, the shale oil and the water, the remaining section (the nonvolatile section) is called the ash.
  • the ash is taken, and then appropriate additives materials in specific quantities are added to it to produce the solid fuel. In such way, it can be claimed that the following equation is maintained in an economical criteria and 20 environmental standards:
  • Oil shale Coal + Crude oil + Natural Gas
  • This invention is intended to be used to process the oil shale by using a new high range temperature thermal dismantling method,and then to produce more products other than the shale oil and shale gas oil such as the high fuel, the residual, water and hot air. 25
  • the technical field usage for the invention is then related to the field where these products are proposed to be used.
  • the shale gas extracted from the oil shale through the thermal disassembly processing well matches to the natural gas, accordingly, it is used in all fields where the natural gas is and could be used, and moreover, the shale gas can be in dry or wet situations.
  • the dry shale gas is used as source to produce the thermal energy, while the wet gas is used for many petrochemical industries.
  • the produced shale oil matches in the chemical composition with the oil of the Middle East, and can be immediately directed to the refineries for refining and separating its distillates to be used as a fuel for the internal combustion engines.
  • the lubricating oils and lubricants for cars and various industrial vehicles can be extracted as one of the distillates' products.
  • the distillates can be separated and treated to obtain the raw materials which are used for the production of plastic materials, fertilizers, medicines, dyes and pesticides.
  • the proportion of the aromatic materials; which exist in the oil shale construction, is considered; if the percentage of this proportion is high; the product is regarded as a high economic value product, and then preferred to be an important input for the medical petrochemical industries.
  • the food (potatoes - corn - wheat - rice - fat) is used for the production of several basic industrial materials such as, synthetic fatty acids, the production of synthetic alcohols, olefins production, the production of synthetic rubber, and synthetic fiber production; however, the shale oil can be used to produce the exact same products which means saving the food sources.
  • the technical field for using the oil shale ash is different in its structure and quality from the various types of global oil shale ash.
  • the reason why this ash is different is basically because the global technologies depend on heating the oil shale at the temperature limit of (450 to 550) ° C, while the ash resulting from the treatment process technology adapted by this invention is subjected to tackle the oil shale in a much wider range of temperature which 5 is (750 to 950) 0 C. In this regard of temperature, a large change in the chemical composition of the ash is occurred.
  • this ash is mixed with suitable additives rate (10 to 30)% from the ash weight; the resulting mixture is the high fuel with the minimum heat 10 content of 8000 kcal per kg, which needs an appropriate burning system to take advantage of the full thermal energy stored in it.
  • the high fuel is regarded as solid fuel with high heat content and the burning efficiency, this is within the acceptable environmental effects. 15
  • the high fuel which is produced by the invention'smethod when processing the oil shale can be used with its burning system for:
  • the high fuel with the existence of appropriate combustion system can generate the required heat quantities and temperatures which can reach the excess of 3500 degrees Celsius;and thus opens the wide door to the establishment of mining industries which has not been possible to reach without using the high fuel.
  • the usage field of the high fuel residual is determined by the chemical changes in the basic composition during use, such as the cement industry - road-paving materials industry - thermal insulation industry, building materials - soil stabilization and any industries in which the high fuel 15 residual would be a basic or essential raw material.
  • the resulting high fuel residual can reach a final product; which is the ready clinker for cement industry.
  • the high fuel residual provides raw materials used in the cement industry and all the operations related to it. If so, it can be confirmed that using the shale ash saves in the 20 fuel consumption which used in drying and burning of the clinker raw materials, also saves in the necessary amounts of electricity consumption for the overall operations associated with the cement industry.
  • This invention is regarded as a technology to produce water when processing the oil 25 shale rather than consuming it as it is in the technologies used in the whole world.
  • the produced water can be purified and used in the field of agriculture.
  • the technical field for using the hot air is the technical field for using the hot air:
  • This new technology produces such huge amount of hot air with temperature that can reach 400 degrees.
  • the amount of the hot air is unmeasured and can be used in the domestic heating system.
  • the oil shale is considered as bounded and compacted layers of rocks with a sedimentary origin that contain organic matters.
  • the organic matters were formed as a result of gathering all of the Alchenyat, algae and micro animals that used to live in 10 the shallow water, which exposed to the impact of active bacteria in the sludge and mud, and then undergone through physical effects resulting to several transformations in the structure.
  • the oil shale consists of Inorganic matters metallic mixed with different matters and metal items as shown in table 1 below:
  • the oil shale can be considered as sedimentary rocks consist of wet soft kernels, where the moisture can be separated in term of water.
  • the oil shale consists of organic matters that can be extracted in term of oil and gas simultaneously.
  • the remainders of the oil shale consist of inorganic matters metallic that can be transformed to solid fuel (high fuel) by performing the proper processes that suit the purposes of use.
  • the general atmosphere for the oil shale shows that it is consisted of sediments located in shallow ponds or seas that are rich with Alchenyat (Albumin + hydrocarbons).
  • the oil shale contains a wide range from the organic and inorganic matters where the organic matters are derived from Alchenyat, algae, and organic detritus such as aquatic and terrestrial plants and aquatic and terrestrial animals, on the other hand, the inorganic matters contain Vhmauah metallic matters such as carbonates (Calcite and Dolomite), in addition to debris materials such as Quarts and Wlosbat related to clays (Aallili and Chlorite).
  • Vhmauah metallic matters such as carbonates (Calcite and Dolomite)
  • debris materials such as Quarts and Wlosbat related to clays (Aallili and Chlorite).
  • the main source for the organic matters in the oil shale is the Alchenyat (Hydrocarbons and Albumen) in addition to the plant residues, spores and the pollens that form Alashinah fat.
  • the Bacteria plays important rule to transform the organic matters to kerogen.
  • the decomposition of the organic matter generates the warm climate Bacteria which helps in the growth of floating and benthic Alachenyat.
  • the alive creatures are then affected by the Bacteria and the process of oxidative stress under the affect of the biochemical processes, with the absence of free oxygen and the present of the active Bacteria, resulting to changing in the structure of the raw organic matters which transform it to the kerogen.
  • the partial disintegration for the organic matters creates the metallic matters such as Quarts and clays, and the plant residues.
  • the Bacteria rule starts to be activated in the benthic alluvial silt with the absence of the oxygen, resulting to acquired medium (accepting electrons) which forms the organic matters and the Berit in alkaline conditions and highly acquired medium
  • acquired medium accepting electrons
  • the Phosphate centers and part from the Alcalat are formed, while in the mild oxidative stress and mild acquired medium, the Filadgoonit is formed.
  • the sea water is rich with Calcium ions Ca +2 in term of bi-calcium carbonate that precipitates under the effect of AlmtafeeatandAlgdraminger.
  • the effect of the 5 Bacteria participates in forming the aggregate kerogen stone which is poor in organic matters.
  • the Alcheny silt is incompact and remain suspended between the water and the silt, however, in later stages, it turns to become compacted and solid because of the effect of the formed sediment and the increase in the sedimentation ponds' depth.
  • the resulting solid Alcheny silt gathers in saturated sediment layers with the time, and the rare materials in the accumulated sediment layers overlap under the effect of the physical conditions such as time, temperature, pressure and motion, and with the presents of chemical effects, that led to establishing an atmosphere that achieves the principle of succession of life, which led to form the oil shale that produces the gas 15 and oil.
  • the Vocabulary petroleum means the oil of rocks, so, this leads to the relation between these Vocabularies and how these Vocabularies were formed. More importantly is to know the structure of the raw organic matters in the petroleum and the oil shale which is the main motivation to do more researches over the ray organic 20 matters in the petroleum.
  • the terrestrial plants contain on the Alljuginin while the aquatic plants do not contain it and it is rarely found in the structure of the benthic plants.
  • Metallization ⁇ H 2 o + Co 2 ioes not occur in an atmosphere that has Oxygen, while it partially disintegrated in the present of the Oxygen and in an atmosphere that is poor in term of having Oxygen resulting to aldepal acids.
  • the Idjanindepal materials are transmitted by rivers to seas which is a source to 5 generate the petroleum.
  • the acid depal is able to form such complicated compounds from the Alkanes that contain large molecules, and with the present of the progressed Bernoadah hydrocarbons that plays the inter-mediator role which transmit the compounds from 15 the land surface to the seas.
  • the cellulose (C6Hio05) n is the most depal poly sugars stable that can be mineralized at the upper layer of the sediment located at the bottom and in airy medium to launch H 2 , CH 4 , Co 2 , and H 2 o.
  • the micro 20 creatures that feed on carbohydrates can make other components such as the Lipids which could be a source for the petroleum hydrocarbon.
  • the Bacteria digest the proteins that starts the interacting with the water after the organisms atrophy in the absent of air medium resulting to full mineralization that gives H 2 o, Co 2 , N3 ⁇ 4, H 2 S, H 2 , and C3 ⁇ 4. 25
  • the Lipid components belong to living matters that converge in their chemical composition and molecular building with some petroleum hydrocarbons. 10
  • Fats are the glycerin esters and the fatty acids chain of all kinds that are saturated and unsaturated, in addition to the Hydroxylated and Ketonah of the carbon chain C 12
  • the Lipid in herbs and zooplankton are rich in unsaturated acids, which is characterized by containing 35% from the materials that are not capable of 20 saponification , this percentage increases whenever the object is more primitive.
  • the waxy materials are mixture of the uni-atoms esters alcohol materials and the uni- base organic acids. Moreover, the primary uni-atoms alcohols participate in the formation of the waxy materials C -> C 34 that have ordinary structure with an even number of carbon atoms in the molecule. 25
  • the higher fatty acids are considered as uni-base saturated compounds with non- branched chain.
  • the steroids are considered as annular compounds with carbon structure that is composed of totally or partially hydrogenated derivatives for 1 -2 Cyclo-penta- venantryn which are component of micro-living materials.
  • the steroids are considered as the most common micro-living materials which contain saturated or unsaturated alcohols with annular structure such as Alchollsterolat Alargeosterol (C2 8 H44O).
  • the resin acids are involved in consisting of the Biomechanical outcomes of the land plants.
  • amber resins, resin acids and the hydrocarbons which is existed in the micro- living materials represent a significant proportion in the filtered material from the seawater, which consists of micro -plankton, fossilized dung and organic residues. These components are considered as a source for carotenoids of micro-organisms in the zooplankton which move to organic silt and sediment.
  • Severe transformations occur over the organic matters of the vestigial organisms, the zooplankton and the phytoplankton in water and silt mediums that located in the bottom Microbiological activity is accompanied by the disintegration of raw material and form bacterial biomass resulting to:
  • the polymer structure for kerogen is exposed to small changes where the temperature is 50° to 60°.
  • the changes can be summed up to deduce the carboxyl, water and the external functional groups as a result of the separation of CH 4 , H 2 s, NH 2 , Co 2 , and H 2 o.
  • the temperature reaches 80° 15 tol 70°, which is the point that the effective disintegration begins for the basic structure of the kerogen associated with increasing the proportion of liquid bitumen to reach 30% to 40% of the original mass of the kerogen.
  • the carbohydrates consists more quickly than their displacement to the reduction layers, when the depth increases, which leads to enrich 30 the organic matter with the Bituminous components, and the process of formatting the hydrocarbon subsides with increasing the rocks depth, which is justified by consumption of the main part of the kerogen.
  • the speed of the displacement of hydrocarbon constantly increases, as well as the speed of exhausting the bituminous materials and hydrocarbons from organic matter, with increasing the depth of the rocks that generates the petroleum.
  • the main stage of 5 forming the petroleum comes to the end accompanied with further changes on the kerogen as the sediment depth increases from 4 km to 6km under the temperature of 200° to 250°.
  • Alkokih stage starts, which is the higher stage of carbonization, where the kerogen losses big amount from its hydrogen resulting to activate the process of forming the hydrocarbon gas to achieve the end of 10 forming gas main stage.
  • the koregen contains on 85% to 90% of the carbon and 1.5% to 3% of the hydrogen.
  • the scattered organic materials such as the carbon, inters the intra Sitish stage from its transforming processes.
  • the bitumen is an essential element of organic matters in the sediment rocks, so, the bitumen cannot leave the organic matters unless through a solvent that can influence rocks to merge with the most movable bitumen materials, and then carry the mixture 25 to a low pressure zone via the water and or gas, as the displacement can only be performed through dissolved water or soluble gas.
  • the rock fusion is considered as of the ways to help performing the process of displacement, in addition to other well- known ways such as re-crystallizing the carbonate material, the phenomenon of the spreading, capillary forces, surface tension forces, and seismic phenomena 30
  • the displacement is accompanied with a change in the nature of the displaced material, such as simplifying, contiguity, reducing the proportion of compounds with non-homogeneous atoms, and weakening the annularity.
  • the sedimentary rocks are considered as a suitable medium, where the petroleum has the process of forming.
  • the petroleum contains optically active substances of biological origin which are existed in the bituminoides.
  • the petroleum contains compounds of biological origin which are found in the bitumen that is located in the sedimentary rocks, such as Alborverinat, 30 alkanes, Alasubrtwedih hydrocarbons, hydrocarbons with Alasteroada construction.
  • oil shale which is called carbonates shale in former stages that contains rich organic matters during the antiquity with period from the Cambrian era to the Cretaceous era; it is the result of sedimentation processes in a variety of 10 different environments such as sea basins, lakes and swamps, regardless of whether the water is salty or sweet.
  • the oil shale is younger than geological formations of the oil-bearing and gas -bearing rocks.
  • the petroleum contains a large number of the hydrogen coal such as the paraffin, Alinvtinih and fungal coal where each kind of the petroleum has different ratios from these elements.
  • the same principle can be applied over the shale sediments characteristics, i. e., different types of sediment shale has different properties because each kind of the 25 sediment shale has different location (depth and medium), however, there are common characteristics among all model of the oil shale, the reason for the similarity in the characteristics is referred to the similarity between all kinds of the oil shale in the conditions of forming the shale sediment, these conditions can be listed below: 1- The synchronization between the organic matters disintegration and the position of the soft grains of the debris metallic, which leads to mixing the organic components with the non-organic components.
  • Multiplicity kinds of petroleum match with the existence of multiple models of oil shale such as:
  • oil shale consist of a silesia template with poor organic matters.
  • Other kinds of the oil shale consist of calcareous template, which is richer in the organic matters than the previous kind.
  • the Bituminous facies need to be in a stable acquired medium (accepts electrons) for long period of time, in addition to organisms and microorganisms, moreover, it is a must to have a large proportion of floating Alachenyat near the surface of the water in the sedimentary medium, because it is the source of the accumulation of organisms at the bottom of the sedimentation basin.
  • the shale is younger than the biological formations of the petroleum bearer.
  • the nature factors, pressure, temperature, time and rotational motion of the earth's seismic helped not turning those sediments to crude oil. So, the sediments were formed in 15 swamps or shallow mere that are related to the formation of coal in coastal environments, which justify the reason the shale contains a wide range of metal compounds and organic materials, which makes the shale able to produce the shale gas, and shale oil, and this is what justifies using the shale as fuel for direct combustion processes for thermal power generation.
  • the most important characteristics of the oil shale are the heat content and the content of the oil in the shale, and they both are directly proportional to the ratio of the organic matters in the shale.
  • the first one is the Mineleiet which is one and half folder poorer in term of the amount of oil in the shale than the second type which is the Alcolmasi.
  • the content of the oil in the shale is more related to the organic matters than the content of the heat in the shale in the same ratio (one and half folder) as shown in the following examples:
  • Alcolmasi organic matter type yields 70% oil from its original matters.
  • Vulva organic matters type yields 51% oil from its original matters.
  • Figures 1 and 2 show the relation between the organic matter percentage and the density for the Almstrich and Eocene eras respectively:
  • Fig.1 shows the relation between the organic matter percentage and the density for the Alsmstrich era
  • Fig.2 showsthe relation between the organic matter and the density for the Eocene era.
  • Figures 3 and 4 show the relation between the organic matters and the thermal content kcal/kg for the Almstrich and the Eocene eras respectively:
  • Fig.3 shows the relation between the organic matters and the thermal content (kcal/kg) for the Almstrich era.
  • Fig.4 shows the relation between the organic matter and the thermal content (kcal/kg) for the Eocene era.
  • Figures 5 and 6 show the relation between the thermal content (kcal/kg) and the shale oil percentage for the Almstrich and Eocene eras respectively:
  • Fig.5 showsthe relation between the shale oil and the thermal content (kcal kg) for the 5 Almstrich era
  • Fig. 6 shows the relation between the shale oil percentage and the thermal content (kcal/kg) for the Eocene era.
  • Figures 7 and 8 show the relation between the organic sulfur percentage with the shale oil quality represented by C/H for the Almstrich and the Eocene eras respectively: 10
  • Fig.7 shows the relation between the organic matter percentage and the shale oil quality for the Almstrich era.
  • Fig.8 showsthe relation between the organic matter percentage and the shale oil quality for the Eocene era.
  • Figures 9 ad 10 show the relation between the organic sulfur percentage and the shale 15 oil quality represented by C/H for the Almstrich and the Eocene eras respectively:
  • Fig.9 shows the relation between the organic sulfur percentage and the organic matters percentage for the Almstrich era.
  • Fig. lO shows the relation between the organic sulfur percentage and the organic matters percentage for the Eocene era. 20
  • the minimum heat content of the oil shale rock used in the direct combustion processes for electric power generation should be at least 1000 kcal/kg and the organic matters percentage of at least 16%, and then leading this type of shale to undergo enrichment processes.
  • the enrichment process the process to raise 25 the heat content by physicist solution.
  • the minimum heat content of the processed shale to extract the oil shale must be 900 kilo Cal per kg (kcal/kg).
  • the treatment processes of the oil shale, with or without the enrichment are: extracting, smashing, milling, physical process and then pumped into special furnaces.
  • the invention's industrial unit can handle all kinds of oil shale; in fact, it can handle the oil shale with as small heat content as 750 Cal/kg.
  • water is not needed to deal with the inorganic matters, which stood as an obstacle that 10 had not been overcome yet or even disposed. This method not only overcomes this issue but also holds it as strength.
  • the first one is the solid fuel at the presence of suitable additives which are available and consistent with the use of this fuel.
  • This solid fuel 15 can be used in various applications, starting from water desalination and power generation until the use in the mining operations that require high temperatures that exceed 2000°.
  • the second utility can be used strongly in the building materials industry, cement industry and in wide range industrial areas.
  • the implemented analyzes show the industrial fields that can use the remnants of the 20 raw materials in these industry applications.
  • the first stage is to know the compositional structure of the oil shale and how they are located in details over all layers.
  • the second stage is related to the ability of concentration the oil shale, and the optimal concentration method to be able to obtain such distinctive quality of the oil shale that can be used in the direct combustion processes. 5
  • Oil shale industry is considered as successful when the cost of extracting the shale oil and gas are not linked to the prices of traditional energy sources (coal, petroleum and natural gas). Moreover, choosing the perfect treatment unit that reaches production capacity of 1,000 barrels per day, accordingly, the total production capacity of the 30 commercial companies is determined by the number of the optimal processes units which should meet the needs of a particular area.
  • the rock processing techniques need to be done outside the work place (surface treatment), in addition to the wide range mining operations, however, commercially, the surface treatment is quite limited as most of the mining operations are being performed in the same project's location (spatial treatment) but for limited mining 10 operations that depends on developing the heating methods of the oil shale rocks.
  • thermal disassembly for the oil shale, performing a tough hydrogenation process over the 15 extracted oil before being sent to the refinery to distillation process (separate its components into final products), taking into consideration that the thermal disassembly can be performed by using either the direct combustion or the indirect combustion methods.
  • the spatial treatment processes include precise and integrated studies, very limited mining operation, thermal processes for the oil shale inside the work location and injecting hot contusive materials inside the oil shale.
  • the heading is made either thermally or electrically, and then the liquefied oil gathers in internal drilled wells and 10 then pumped to the surface to be treated in the same treatment processes used in surface treatment.
  • Shell initiated to protect groundwater from contamination, as it has created an ice wall that serves as a cooling wall around the place of the treatment to prevent oil leakage and mixing with the groundwater.
  • ExxonMobil also leads the research which relies on heating the rocks in place by hydraulic cracking where electrically connected materials fill the cracks to heat the kerogen and turns it into oil.
  • Raaxion technology purchased by Schlumberger, which relies on the use of Radio Frequencies (RF) microwave and critical gas (SCF) such as carbon dioxide (Co 2 ) in 25 order to heat the kerogen in the oil shale and convert it into shale gas and shale oil.
  • RF Radio Frequencies
  • SCF critical gas
  • CO 2 carbon dioxide
  • the retorting process is used to extract the kerogen from the oil shale, and then the resulting kerogen undergoes to heating processes to reach 450° to 550° in the absent of air heating conditions. After certain physical processing steps, the shale oil will be extracted.
  • the maximum extracted oil amount reaches 10% of the shale weight, and this ratio 10 can be practically obtained with proper treatment steps for such good quality of the oil shale rocks, such as the used oil shale in the research work (oil shale in Sultani area in Jordan).
  • the extracted unsaturated hydrocarbon oil faces several problems which are considered as the main obstacles that face the extracted oil before the distillation 15 process; the main problem is the low heat content which does not exceed 4000 kcal/kg, moreover, the high content of sulfur and nitrogen beside the high rate of heavy metals.
  • the extracted oil undergoes to harsh hydrogenation process, separating the pervasive water molecules between the oil molecules. Moreover, the 20 sulfur and nitrogen must be separated as well beside to removing the heavy metals. After these modification processes, the extracted oil is then ready to be pumped to the refinery. The way the invention performs the previous processes is directly reflected over the economic cost for the production of shale oil in addition to the negative environmental effects associated with those operations. 25
  • This method is performed in two ways: 1 - Following operations are made in the same order: extraction, crushing, milling to the level of 100 to 200 microns and then puffed to private furnaces combined with liquid fuel and air or gas.
  • This method is not practically implemented yet as all the oil shale treatment is applied over the oil shale with heat content of 2400 kcafkg. However, it is important to fully study this method as it deals with the oil shale with heat content below 1000 kcal/kg, which is most of the oil shale in the world. So, this treatment method has a good 10 future to deal with a very wide range of oil shale.
  • the resulting mixture is physically treated by Physicist mix (Majnti + water) to raise the heat content.
  • the resulting mixture is then pumped to various types of furnaces and then the air is compressed to mix the fuel molecules, the coal molecules and the ash molecules in addition to the steam which is impelled from 15 the bottom.
  • This method is applied over the medium and poor quality of the shale, where the shale is considered as poor if it has heat content of 1000 kcal/kg or less.
  • coal liquefaction is the conversion of the coal to liquid that is in this case hydrocarbon fuels.
  • This method depends on the 25 reduction of the weight ratio of the carbon to the hydrogen by either hydrogenation or removing some carbon atoms by producing of the coal Cole or carbon monoxide.
  • These treatment processes are accompanied by secondary fuel products such as, gas, gasoline light, heavy oils and wax.
  • secondary fuel products such as, gas, gasoline light, heavy oils and wax.
  • Organic matter is composed of kerogen (complex hydrocarbons) and Batonin (mixed hydrocarbon); the first part is exclusively extracted by the thermal smashing, while the second part is extracted by using the proper solvents.
  • This technique is based on the principle of reducing the cost of the extracted barrel of shale oil when located in the ground under the lid and to mitigate the negative impacts over the environment.
  • the purpose of this action is to get rid of the cost of mining operations, as well as to get rid of the remnants of heating after extracting the shale oil.
  • the principle depends on digging a range of holes in the oil shale reservoir location, and then pumping the heat or heating materials into these holes resulting to heat the earth layers that contain the oil shale.
  • the heating process is either thermally or electrically which is accompanied with moving the shale oil that resulted from the thermal smashing of organic matters. So, the method is basically based on heating the oil shale container layers, by either injecting thermal materials or applying high voltage over conductors which are inserted inside the oil shale reservoir to heat the earth surrounding layers.
  • Shell International as one of the leader in the use of this technique, should be asked whether the rid of the high cost of mining and mitigation of environmental impact are equivalent. Especially with regard to what is happening on earth! If the answer is 10 'necessities permit prohibitions', it can be confirmed that the quality of the resulting shale oil from the treatment process of this method faces the same problems that were faced by the obtained shale oil by the former methods, such as, being pumped from the assembly holes, directed to the process of hydrogenation, and then being subjected to the same treatment to get rid of the harmful substances such as sulfur, nitrogen, 15 heavy metals, separating the unsaturated hydrocarbon, Etc.
  • the first one is the amount of ash resulting from the combustion processes which is estimated in the 30 range of 56% to 85% of the original amount of the oil shale rocks.
  • the second challenge is the amount of ash that results from extracting the shale oil and gas oil. These two types of ashes are regarded as a solid waste and non-symmetric waste; first waste is treated in the field of 450°C to 550°C and the second waste is caused by the burning at 1200°.
  • the amount of ash that has heat content of 800 or less is unable to be treated by the available processing units, in addition to the 5 quantities of water, air and the pumping gas required for the treatment and transportation.
  • the global oil shale technologies launched from the petroleum simulation of the petroleum formation processes, i., e., the slow changing that happened under the earth 10 over millions of years, where the temperature range is from 60 o to 110° which is accompanied with the pressure of the vibratory ground motion.
  • Kinetic chemistry explains that it is possible to convert the kerogen into oil over a period of time that takes anywhere from minutes to hours, providing the availability of suitable reactors and treatment temperature of 450° to 50°. 15
  • Shale oil is considered as a sedimentary rock with soft granules of different origin, consisting of inorganic metallic materials (carbonate, silicate, clays) that mixed with organic materials (Bitomino and kerogen) which then overlapped with different metal elements.
  • Heat content , from 850 Kcal per kg to 1585 kcal/kg.
  • Oil percentage from 6% to 12%.
  • Oil percentage in the organic matters from 40% to 50%.
  • Table 2 The three kids of shale oil quality according to the three quality grade factors. Shale oil quality
  • the Alpetrograveh study shows that, the basic block (basic rock) of oil shale rock is a microscopic organic structured and are mostly contented of a single cabin or multiple cabins.
  • the large cabin has Kelsey template and the mall cabin has Dolomiti template, were both types of cabins are full with organic matters (hydrocarbons).
  • Energy source is a material that provides light, heat or power and they are classified as:
  • a- Fossil fuel such as the nuclear fuel (uranium), oil shale and the asphaltic sands.
  • Non fossil fuel such as the potential energy of water, solar energy, wind energy, kinetic energy of the tides, waves energy, energy results from the 15 variation in temperature between the surface and depth in the ocean, geothermal energy in the ground, bio-energy, biomass energy and waste energy.
  • C, H, O, and S are the percentage of the materials that are contented in the burned amount, taking into consideration that the components of the equation are determined by chemical analyzes that are performed over the combustion material.
  • the factor W is the percentage of moisture in the oil shale.
  • Oil Shale coal + crude oil + natural gas
  • Shale gas + Shale oil + water + solid fuel + remnants of solid fuel + hot air coal + crude oil + natural gas.
  • the oil shale is a sedimentary rock in the composition that contains organic matters located in precise placements. 15
  • the rocks containing kerogen is a type of sedimentary rocks such as limestone, clay, silica sand, phosphate, or any mixture of these substances.
  • Table 3 Historical view over the use of shale oil in several countries from 1838 to 1957.
  • Shell has implementation of slow heating test of oil shale rock by using electric heating poles at the site, but faced with the problem of groundwater contamination, and therefore has created the ice wall idea to solve this problem.
  • This method could be called a luxury treatment method.
  • Company Este Energy uses Djilatorr method to extract the oil together with the backed allies Aanavi to develop a commercial method to deal with the oil shale.
  • Figure 11 shows the oil shale processing methods
  • Table 3 The produced products from one tone of the oil shale.
  • Shale ores are characterized by high content of metallic materials (content of ash + carbonate content from 80% to 90%), and contain of Co x which is estimated by 10 27% to 31%.
  • the sulfur proportion increases with the increase of the organic matters percentage which reaches up to 2.8% while the value of the moisture it is variable and not fixed.
  • the layer modification method (Fluidized bed): Method of extraction, crushing, milling, blending, push to the surface of the perforated layer, 5 pushing air through the perforated surface, pay heavily vapor of the bottom of the layer, mixed with fuel and ash particles and coal.
  • Differentiation between the minimum temperature is a must, which is the degree to which the molecule begins boiling, and then the temperature continues to rise until reaching the maximum temperature, which is the degree to which the molecule 10 reaches the maximum speed, which is the speed that the molecule starts leaving the modification layer then out of the furnace, while the non-complete-burnt molecules can be returned to the furnace.
  • Oil shale is extracted, subjected to mining operations, packaged, entered into 20 treatment heat units, increase the temperature to reach about 550° degree, between the range of 450° and 550° the kerogen material starts the disintegrating to give oil and gas simultaneously. Because of the mechanism of blending between the organic materials and inorganic remains, from 15% to 20% of the organic matter origin contented in the oil shale remains untreated. 25
  • This method combines the direct combustion and the indirect combustion (retorting ) methods.
  • the shale oil and the shale gas can be extracted.
  • the remainders organic matters undergo to direct combustion process to obtain extra heat used to rise the heating gas temperature and to generate the electric power.
  • Specific surface area is determined, a group of wells dug geometrically (pumping wells and production wells), heat or heating materials is pumped into those wells to 20 heat the container layers of oil shale in the studied area. This is performed either thermally or electrically, upon arrival to the desired temperature, shale oil and shale gas move from the organic matters consisted in oil shale.
  • the essence of the process is injecting hot liquid materials and electric conductors to control the temperature. 25
  • ICP oil shale layers by heating poles.
  • the idea ice wall was invented to prevent oil leakage into the groundwater.
  • Exxon Mobil leads the experience that depends on the hydraulic cracking, the cracks are filled with electrically conductor materials and then, high voltage is applied to heats the materials that contribute to exchange the heat between the conductor materials and the oil shale to reach the degree of the dismantling of the organic matters contained in the oil shale. 5
  • Schlumberger used a technique based on a combination of using radio frequencies (RF) in microwaves principle (Microwave idea) and critical gas (SCF) such as carbon dioxide, to heat the organic matters in the oil shale.
  • RF radio frequencies
  • SCF critical gas
  • the Kerogen is dealt with by the thermal decomposition only, which is the basis of dealing with all previous techniques that has been mentioned.
  • the heating materials are injected into the first group of wells and then connected to high voltage to heat the oil shale layer electrically; the heating process progresses gradually, and the temperature rises to the level that the kerogen starts disintegrating and transformed into shale gas and shale oil.
  • the produced shale gas and shale oil are gathered in production wells, and then pumped into the earth surface to be treated before being redirected to the refinery for refining and separating the components.
  • This method is classified according to the position of heating materials and devices and according to the flow of oil:
  • the oil shale is fed into two devices with 40 tones capacity each from the top, where the hot gas is fed as well to heat the oil shale continually till reaching to the temperature of kerogen dismantles, resulting to shale gas and the shale oil productions.
  • the amount of air and the retuned gas are adjusted, while the thermal decomposition continues toward the bottom.
  • the gas is condensed and turns to a liquid, the remaining gaseous section is directed to heat the oil shale producing more shale oil and shale gas.
  • the shale gas is again redirected to heat new oil shale and these processes continuous periodically.
  • the oil shale is crashed to pieces with dimensions of 0.5 inch to 2 inches.
  • the heater height is up to 45 meters above earth surface.
  • the shale oil is fed from the heater's exist and then inserted to the oil shale feeder.
  • a compressor with diameter of 3 meters pushes the oil shale to the top of the heater.
  • the gas is heated by an opposite stream of rotor gas that is inserted 25 from the top of the heater. This process continues till reaching the temperature of the kerogen disintegration, resulting to condensed oil that is gathered at the bottom of the heater.
  • the consumed oil shale is then pushed out via a tunnel at the bottom of the heater.
  • the shale enters continuously from the top to downward under the influence of gravity, the combustion area is near to air and gas distribution area, and then the steam rises towards the top to heat oil shale which falls toward the bottom
  • the steam is directed to Sapklon then to a removal device and then to 5 electric precipitator.
  • the oil shale fells from the top downward towards the bottom contributes to heat the interred air and gas, and finally, the gas is recycled continuously to take advantage of it.
  • the disadvantage of this method is the accumulation of forming the clinker.
  • the oil shale is crashed to pieces of dimensions of 0.25 inch to 3 inches to be fed from the top of the heater and distributed evenly by a rotor distributor.
  • a mixture of gas and air enters to the heater from several places distributed over the entire heater walls; the gas inside the heater is then heated from bottom by the falling oil shale from the top.
  • the combination of the fog and steam-hydrocarbon move to an electric precipitator and then, the heat exchange between the hot steam and the cold oil shale is performed at the top to reduce the use of water.
  • the oil shale is heated inside a silo by a specific fluid, and then it is 20 moved to a horizontal heater to be heated by a hot ceramic. The consumed oil shale is then pushed over a sieve to get cooled and stored.
  • Jetting quantity is large when compared to other methods.
  • the heating process does not depend on the gas molecules as a 30 heat-bearer inside the device. • The heating process is performed from the outside, and the resulting gas has high heating content, which does not contain 2 or Co x . .3 The Combined Method:
  • This method is similar to NTU method but it is implemented under the ground 5 using multiple distillation processes which are performed in a huge silo using a horizontal cliff to rise from 15% to 20% of the oil shale that is somehow handled.
  • the extracted shale oil contains a high percentage of the chemical compositions of olefins (unsaturated hydrocarbon compounds) sometimes by up to 40% of the shale oil origin. 25
  • the oil shale has sedimentary origin, when undergoes to thermal cracking processes, the extracted oil shale contains a high proportion of metals, that have a negative impact by eroding the mediators that used in the refining process.
  • the boiling range of the oil shale is narrower, which is unlike the crude oil, when the shale oil subjected to the separation process, it is noted that it produces limited number of products, such as, naphtha and fuel oil, with limited quantity in shale oil.
  • the acids, alkalis, sulphates, nitrates and hydrocarbon have fixed rates in the temperature range from 370° to 400°, but these rates change in a large scale in the temperature range of 475° to 525°, which is a clear indicator for the disintegration of these compounds.
  • Oil shale in its chemical composition contains high percentages of sulfur and nitrogen, so, when using the direct combustion to obtain the thermal energy stored in the oil shale; both of So x and No x are formed. 25
  • So x Has a toxic effect on humans and animals, air and soil. For example; if this gas is emitted into the atmosphere under the rain, it forms H2S04, which affects the soil and on plant.
  • N02 affects the plants causing paleness and defoliation.
  • it 30 affects the respiratory system and mucous membranes of the organisms. No, affects to humans because it reacts with blood hemoglobin.
  • Oil shale processing may be accompanied with emissions of different kinds of Co x .
  • Groundwater contamination problem is one of the biggest challenges facing 15 modern techniques that are based on processing of oil shale in place (in-situ).
  • the oil shale is a renewable energy source which can meet a simple equation that 20 gives positive signals indicated in the circulation News of shale gas, and its entry as an equivalent energy alternative to bridge the strong lack of the needed energy. This equation is:
  • Oil Shale coal + crude oil + natural gas
  • the present invention seeks to achieve and implement this equation in a commercial 25 production scale, according to economical and environmental standards which have been achieved.
  • the practical research emphasizes the successes that have been achieved in the extraction of shale gas, which will be the right solution to the puzzle mentioned in the shale gas extraction.
  • the Estonian oil shale kind is regarded as superior quality of the shale with heat content of 2800 kcal/kg and contains a very high organic material up to 40% of the 10 rock weight and with a large proportion of the oil can be extracted out of the organic material (up 26% of the rock weight).
  • the extracted shale oil contains a very high percentage of olefins, in addition to high percentage of the sulfur, nitrogen, oxygen and heavy metals therefore, cannot be directed to the refinery in order to separate the products, so, it is only used for direct combustion (ships fuel).
  • the extracted oil at that time was marketed at a lower rate than the fuel oil, since the fuel oil did not have a commercial market at that time.
  • the present invention implemented experiment over the oil shale with heat content of 850 kcal/kg to 1585 kcal/kg shows such interesting results that emphasize that, it is 30 now the time for the Estonian wrong experiment to come to an end.
  • this method requires limited mining operations that depend on injecting electrical conductor heating materials designed to heat the oil shale through the heat exchange process to extract the shale oil.
  • This method achieves three main goals which are, reducing the economic cost of extracting barrels of oil, reducing the environmental impact 5 accompanied with the process of extraction, and the salvation of the problem of ash which results from the operation of extracting the shale oil from the oil shale.
  • Fig.12 Thermal Dismantling Unit (the unit for oil shale processing to obtain final 5 product which are shale oil, shale gas, hot air, water, ash to produce high fuel and ash to produce high fuel residual)
  • Fig.13 Pulling, condensing and vacuum unit (the unit for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure)
  • Fig.14 Gas pulling and liquidizing unit (the unit for extracting the shale gas in its 10 liquid form by pulling and liquidizing operations).
  • Thermal Dismantling Unit for oil shale processing to obtain final product 25 which are shale oil, shale gas, hot air, water, ash to produce high fuel and ash to produce high fuel residual comprises the following elements.
  • Reactor (12.1.1) and furnace (12.1.2) unit (12.1) To heat the oil shale using the heating exchange methodto reach any temperature in between 600°C to 3500°C degrees. Butit works in between 600 °C to 950°C for processing the oil shale 30
  • Purification and combustion products ua hiii g unit ( 12 2) To purify th combustion gags and deposing the planktons.
  • Multi-stage heat exchanger and plankton precipitator (12.4) To spread the hot air over the usage fields, beside the help in precipitating the planktons.
  • Roasting, moisture pulling and oil shale drying unit (12.5) To dry the oil shale before inserting it to the oven.
  • Cooling and condensation unit which is related to the oil shale moisture (12.5): To condense the moisture gases to convert it into water.
  • Condensate water collection tank (12.6) To collect the condensed water inside it.
  • Nutrition unit entrance (roasting and drying unit) (12.7): To provide the oil shale to the roaster.
  • Centrifugation and pulling the washing outputs unit (12.8) To pull the water from the washing unit.
  • Centrifuge unit Pull, process, pushing of the purified water (12.9): To purify the water and washing the gases planktons.
  • Treatment water collectiontank (12.10) To collect the washed water.
  • Pulling, condensing and vacuum unit ( Figure 14) for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure comprises the following elements.
  • the distillatescollectiontank2 (13.6): To collect the distillated liquids that condensed in
  • Gas gathering tank (13.10): To collect the uncondensed gases.
  • Centrifuge pump (3.13): To pull the shale oil from the glasses Tower and then pumping it to the oil collection tank.
  • Gas pulling and liquidizing unit ( Figure 14) for extracting the shale gas in its liquid form by pulling and liquidizing operations comprises the following elements.
  • Heat Exchanger (14.3): To cool gas under liquidizing process.
  • Surveyor device (14.4): To purify the gases from the joined liquids.
  • Kettle (14.5): To initially heat the gas.
  • Cooler -intensive (14.6): To cool the gas.
  • First direction is the extraction the organic materials from the oil shale by using the 10 chemical solvents.
  • the resulting ash from this technique is huge in quantity and cannot be used in the industrial field.
  • TheFisher scale was adopted in the scientific research work to determine the shale oil and the shale gas percentage contented in the oil shale. Moreover, it is realized that 5 the utilization of the oil shale with the proportion of organic matter of (25) % or below cannot be transformed into an investment project, as long as the cost of a barrel of shale oil extraction linked to the price of oil barrel.
  • a device was developed handling (3) kg of the oil shale during (22) minutes to process the oil shale without using the direct combustion method to avoid using the oil as a source of the 10 thermal energy, and by auditing most of the data and analysis the results; building an industrial unit that can process (50 tons ⁇ day) in a way totally unlinked to the oil was carried out.
  • severeal technical challenges were faced to set (800 to 900) kg of the oil shale to be processed within (27 - 32) minutes.
  • the organic materials burnt temperature is 950 °C, which means that it is impossible to obtain any shale gas or shale oil at any temperature higher than 20 this.
  • the present invention's technology can process the averagequality kinds of oil shale with average thermal content to yield profit that exceeds the profit 30 when processing the high quality oil shale based on the principle of direct combustion treatment such as the Estonian oil shale process method.
  • the present invention'sraw material is the oil shale; the oil shale processing products are shale gas, oil shale, high fuel, high fuel residua, water and hot air.
  • the present invention In parallel to producing the fuel as the primary products; the present inventionbeholds a promising future to meet the requirements of other industries' materials such as manufacturing (plastics, medicines, dyes, fertilizers, pesticides), in addition to well perform the famous slogan which says: 'the oil is more precious than to be burnt'.
  • Chemical reactions get processes of (abandon - share - displacement - transmission - provide - forming) of an electron or more from the surface electrons of atoms among the combined materials. Accordingly, we distinguish between the two types of chemical reactions which are quickunidirectionalreactions and slawunidirectionalreactions.
  • the chemistry depends on the inorganic and organic industries, accordingly, the processes of treatment, extraction, separation and purification start from the science of chemistry, so, the oil shale with its raw compound materialsis regarded as an essential corner stone for these industries (organic and inorganic industries).
  • the present invention performs the heating process which does not depend on pressure (which makes the possibilit of explosions to be nil), moreover, no solvents or catalysts materialsare used (which makes the possibility of dangerous reactions to be nil) during the components separation processes of the oil shale, finally, no enrichment operations are used and concentration of the shale before subjected to treatment which makes the technique 5 fully aware with the materials under treatment with no unexpected bad surprises.
  • Table 1 the results of organic chemistry lab tests carried out on a sample of oil shale.
  • Table 2 The results of non-organic chemistry lab tests carried out on a sample of oil shale.
  • the lid of the reactor (Fig.12.1) is opened to insert full trays of more oil shale by a crane, to be treatedinside the reactor (Fig.12.1), then the lid is closedagain and the process of mining extractionbegins.
  • the quantity which is subjected to the treatment process is (820 - 890) kg of oil shale.
  • Oil shale under treatment lasts for (27-31) minutes inside the reactor (Fig.12.1 ) to be fully treated.
  • the start operation point is recorded with the temperature of the furnace at that moment, keep monitoring and recording the temperature data that serve the experiment till the furnace temperature reaches to 600°C; when the temperature inside the 15 furnace is 600 °C, the high fuel is then provided to the furnace where the burner is completely stopped from the work.
  • the high-pressure turbine works with a small frequency,whenever the temperature stops rising in the furnace; the air stream is then changed, and then continue refueling the furnace with the high fuel till reaching the 20 temperature of (800 to 850) Celsius degrees.
  • Cooling cycle is early run to secure the amount of cold water which is estimated at 5 m 3 and the temperature of cooling water is (2 to 6) ° C to be used in the cooling processes through the mineral extraction processes.
  • the reactor lid is opened and the oil shale bearer trays are then inserted into the reactor by the crane, the reactor lid is then closed, observing the reactor temperature which will decrease till it reaches a stable and fixed temperature.
  • the reactor temperature starts to raise again, the 30 high value of the pressure on the pressure meters is noted; accordingly, the pressure vacuum pumps are then run.
  • the cold water pumps are then run and the heat exchange processes are observed between the volatile fumes and cold water.
  • the reactor lid is then closed, and the new readings are taken for (electricity - water - liquid fuel (1)), and then the products are withdrawn, where the shale gas is gathered in the tank outside the unit, so the process of calculating the shale gas quantity is available and easy.
  • the shale oil is measured while mixed 10 with the water, and then the mixture injected into glass towers of which the oil is separated from the water.
  • the trays are then withdrawn from the isolation rooms and then weighed before being discharged.
  • the weight before and after the treatment is matched; to make sure that the law of mass conservation and functioning of the energy 15 flow are maintained.
  • This experiment is based on the direct combustion process, extracting 700 tons per day of oil shale from the mine; the extracted quantity is transformed to the cement plan by tracks to pass through the fallow treatment processes: cracking till obtaining 10 grains with dimensions of 10 mm, then pushed to the homogeneous mixing unit, and then the direct combustion at equal degrees.
  • the obtained products from the direct combustion possess fixed specifications as it is used as one of the fundamental components of the cement.
  • the units of mixing and homogenization are fed with the oil shale through the cracker and preparation unit.
  • This heterogeneous mixture is then fed into the furnace from the top with the necessary air to complete the burning.
  • the air is processed by being pressed through jets distributors located on the perimeter of the furnace, to distribute the combustion on a regular basis in the entire furnace; even at the bottom.
  • the combustion of the oil shale operations are performed at temperatures of 800° to 20 850°, the surface of the combustion increases at the upper part of the oven, till the fully combustion process is performed.
  • the high rates of heat transfer and turbulent movements inside the furnace lead to increase the oil shale temperature very quickly, leading to the ignition of oil shale and this requires feeding the furnace with additional quantities of combustion materials to maintain a constant temperature inside the furnace.
  • the heat in contact with the combustion gases coming out of the furnace is used in the production of steam through the boiler, which is connected with a generator and turbine.
  • Products of the combustion are withdrawn from the bottom of the furnace, cooled and mixed with the soft parts that are associated to the combustion gases process, and then stored in silos attached to the manufacturer of cement, the result compounds are then milled and mixed with the clinker that is produced from the rotary furnace in the traditional way, as a result of these operations, shale cement is manufactured, which is equivalent to the well-known Portland cement.
  • Combustion products is characterized by the property of using the water as interaction intimidator due to the thermal conditions of the furnace, so an electrostatic deposition unit is needed for purifying the combustion gases before directing it to the chimney.
  • Oil shale cement it is contented of 70% of clinker and 30% of the oil shale combustion products.
  • the property of using the water as an interaction intimidator, of this type of cement are perfectly matched to the properties ofPortland cement at low amount of heat.
  • the annual output of the plant is 300,000 tons.
  • Road-paving materials it is contented of 30% of clinker and 70% of the oil shale combustion products.
  • the ratio of the cement rock that is produced to the road paving material is (1 :1) which is equal to 200,000 tons each.
  • 2- The heat content of the oil shale used in the combustion process is 950 kcal/kg.
  • the amount of the required oil shale is (200,000 ⁇ 1.45) tons per year and combustion products of 308,000 tons per year.
  • the power station plan consumes 10% of the generated power, so, the remaining amount of energy is 75600 MW/h, accordingly, the total generated 15 power is 11,7 MW when assuming that one working year is equal to 7200 working hours.
  • the shale oil used in this factory has two utilities; generating the necessary power for the operation of the plant, and raising the production capacity of cement plant.
  • the station is the largest station ever that exploits the oil shale using the direct combustion processes method to generate the electric power.
  • the electric capacity is 10 1600 Mw.
  • the station includes eight groups; the generation capacity is 200 MW for each.
  • the only source of energy available in the Republic of Estonia is the oil shale, which is extracted from surface mines with cover thickness of 2 meters and shale layer thickness of 2.75 meters. There are interface layers placed between oil shale layers.
  • the oil shale is prepared in the mine in the form of blocks with dimensions of 15 (l x l x l) m.
  • the block is then fed into a crasher; the dimensions of exited pieces is (25 x25x25) mm, which then fed to mills with hammers to leave as beads of dimensions 100 Micro meter to 200 Micro meter.
  • the resulting power is then dried to get rid of the moisture before it is sent to the furnace, where the shale powder puffed into the furnace through eight distributors around the furnace.
  • the temperature in the 20 furnace reaches 1400°, so, we need amounts of hot air (primary and secondary), water and steam to complete the combustion operation.
  • the temperature of the steam when leaving the furnace is 450° and the pressure of 105 bars.
  • Organic matter percentage in the oil shale 32% to 36% of the oil shale weight.
  • the station consumption 10 Million tons to 12 Million tons per year.
  • the station capacity 9 billion kilowatt hours per year.
  • Ash storage space size 1000 hectares. 10
  • the resulted shale oil ash from the direct combustion per year is estimated by 6 million tons, which are removed from the station using pumped water as means of transportation, and then deposited in specific locations.
  • the resulted ash from the direct combustion process is used in several areas such as:
  • Block cements industry 10%.
  • Sand for construction work 15%.
  • Paving roads 10%.
  • Electrostatic precipitators used to purify the smoke produced by combustion 20 processes.
  • This experiment is based on the direct combustion process, extracting 700 tons per day of oil shale from the mine; the extracted quantity is transformed to the cement plan by tracks to pass through the fallow treatment processes: cracking till obtaining grains with dimensions of 10 mm, then pushed to the homogeneous mixing unit, and then the direct combustion at equal degrees.
  • the obtained products from the direct 10 combustion possess fixed specifications as it is used as one of the fundamental components of the cement.
  • the units of mixing and homogenization are fed with the oil shale through the cracker and preparation unit.
  • This heterogeneous mixture is then fed into the furnace from the top with the necessary air to complete the burning.
  • the air is processed by being pressed through 15 jets distributors located on the perimeter of the furnace, to distribute the combustion on a regular basis in the entire furnace; even at the bottom.
  • the combustion of the oil shale operations are performed at temperatures of 800° to 850°, the surface of the combustion increases at the upper part of the oven, till the fully combustion process is performed.
  • the heat in contact with the combustion gases coming out of the furnace is used in the 25 production of steam through the boiler, which is connected with a generator and turbine. Based on this construction to generate the electricity; we need 30 tons/h of water steam, steam temperature of 450° and steam pressure of 42 bar, to generate 3 Megawatt.
  • Products of the combustion are withdrawn from the bottom of the furnace, cooled and mixed with the soft parts that are associated to the combustion gases process, and then 5 stored in silos attached to the manufacturer of cement, the result compounds are then milled and mixed with the clinker that is produced from the rotary furnace in the traditional way, as a result of these operations, shale cement is manufactured, which is equivalent to the well-known Portland cement.
  • Combustion products is characterized by the property of using the water as interaction 10 intimidator due to the thermal conditions of the furnace, so an electrostatic deposition unit is needed for purifying the combustion gases before directing it to the chimney.
  • Oil shale cement it is contented of 70% of clinker and 30% of the oil shale combustion products.
  • the property of using the water as an interaction intimidator, of 15 this type of cement are perfectly matched to the properties ofPortland cement at low amount of heat.
  • the annual output of the plant is 300,000 tons.
  • Road-paving materials it is contented of 30% of clinker and 70% of the oil shale combustion products.
  • the ratio of the cement rock that is produced to the road paving material is (1 : 1) which is equal to 200,000 tons each.
  • the heat content of the oil shale used in the combustion process is 950 kcal/kg.
  • the amount of the required oil shale is (200,000 ⁇ 1.45) tons per year and 5 combustion products of 308,000 tons per year.
  • the power station plan consumes 10% of the generated power, so, the remaining amount of energy is 75600 MW h, accordingly, the total generated power is 11 ,7 MW when assuming that one working year is equal to 7200 10 working hours.
  • the shale oil used in this factory has two utilities; generating the necessary power for 15 the operation of the plant, and raising the production capacity of cement plant.
  • Volumetric weight 1.3 to 2.5 ton/m 3 .
  • Humidity 6% to 10% of the oil shale weight.
  • Processes that are needed for the treatment process extraction, transport, initial cracking, secondary cracking, packaging so that the dimensions of the grains is from 1.5 cm to 3 cm and preferably with equal dimensional, and then enter the unit of the thermal dismantling.
  • the quantity of the treatment amount of the oil shale is 1 ton, 25 and the treatment period is from 22 minutes to 27minutes. We do not use any amount of water during the treatment process.
  • the wet gas shale can be directed to the areas of petrochemicals, shale oil is directly subjected to the refinery, and then its products are separated and directed to the industries of: Plastic, Fertilizers, Pharmaceuticals, dyes, and pesticides in addition to its use as a 15 fuel.
  • high oil residual which 25 is an important raw material for the manufacturing of cement and other building materials, if fact; settable additives can be added to the high oil at the first place to end up with ready clinker after burning the high fuel.
  • the extracted shale oil by using different methods; whether it involves on-site or out-site extraction methods, is not sent to the refineries, is not used in the 15 petro-chemical industries, and is not fit for burning. In fact, it needs to be treated and stabilized;it's thermal standard is low, it is saturated with unstable active components, and it contains nitrogen elements, sulphur, and oxygen, in addition to various heavy minerals. Therefore, it must be put through a treatment unit prior to being refined to eliminate these components. Only then 20 can this be considered for a refining process.
  • These problems have been successfully modified in the shale oil quality and type resulting to extracting such good quality of shale oil and shale gas which are very similar to the natural gas and petroleum in the Middle East.
  • the present invention's shale oil can be immediately directed to the refinery in the same way the Middle East 25 oil is directed.
  • the present invention has met the international criteria for scientific research, beginning with the Fisher Apparatus using lOOg of oil shale, and has identified a wide range of data about oil shale which has been proven. This was followed with an experimental apparatus that can treat up to 3kg, which participated in increasing the data base and proved vital values that can be depended on for the treatment process. This was an introduction to the building of a semi- industrial unit with the ability to treat one ton every 30 minutes. The treatment 5 processes were based on a scientific methodology that is also economically, as well as environmentally, feasible.
  • the present invention does not undertake any enrichment processes, and does not use solvents in the treatment process, moreover, does not consume any water or 10 any gases such as (H20(9) - - C02 - CO) to separate the organic from the non-organic elements.
  • the invention basesits technology from the method of the formation of the oil itself, and its migration to the final base.
  • the ideal time for the extraction of oil and gas from shale is 18-22 minutes for the quantity that is needed to treat it, irrespective of how much, and this is 15 relevant to the thermal dissolution unit which depends on the time of thermal energy exchange between the quantity of oil being treated and the dissolution unit.
  • the invention then has a state of thermal stability after which it starts the extraction process, which ends with the production of (shale gas - shale oil - high fuel - high fuel residue - water and hot air).
  • 201 - The techniques that are currently being used have failed to achieve the economic and environmental feasibility standards, and have therefore focused on developing heating methods, failing to segregate the process of extracting a barrel of shale oil, from the process of extracting a barrel of crude oil (petroleum). Additionally, these techniques have failed to prove the values 25 they have included in the economic feasibility studies that they presented. The reality of extracting a barrel of oil shale rises with the on-going cultural progress that people live.
  • the present invention is accurately able to prove and set the temperature at which organic elements separate from non-organic ones, and 30 has created the appropriate environment for the formation of the chemicals bonds between the weak radicals, which has made oil shale highly similar to crude oil, and shale gas similar to natural gas.
  • the way petroleum is formed is based on the presence of large amounts of organic matter, and the transformation methods (heat - pressure - the rotation of the earth), which are all elements that the present invention has benefitted from, with the major advantage of having the ability to distinguish between distillation under pressures, and distillation in a vacuum.
  • 5- The treatment of oil shale, whether on-site or off-site,is undertaken using various heating methods to achieve a temperature of 400-500°C.
  • Thistechnology can be used on all kinds of oil shale with a thermal energy of 750kcal/kg without having to make any amendments to the 30 treatment unit, because the metallic compounds carrying the organic matter have almost the same structural units, with the latter having the same metallic elements, which can have either a negative or a positive effect on the high fuel, and the high fuel residue, and limits the scopes in which high fuel can be used.
  • Oil shale is impermeable and is an isolator that prevents the exchange of thermal energy. It must be broken in a certain manner and placed in a treatment unit in a specific way. Also the distance between the particles must 5 be equal and there should be smooth particles among these equal-sized particles. These factors helped in the transfer of thermal energy. All the particles of oil shale are equal until the oil and gas are extracted at the same time from all the particles. This data reflects on the mechanical extraction of the shale oil, and indicates the presence of a large quantity of organic matter 10 stored in the oil shale.
  • the quantity and type of organic material extracted from oil shale depends on the temperature of extraction, and the time it takes to do so, in addition to the chemical and physical composition of the oil shale. There are no elements whose quantity or quality will change by changing the temperature or the 15 duration of the treatment, because at the degree of fixation, a complete separation between the organic and non-organic components will occur.
  • the purpose of increasing the temperature will change the compound kerosene and the bitumen mixed in with it, to gaseous and liquid hydrocarbon, and thus there will no longer be between any difference in the chemical structure of the 20 kerosene and the bitumen.
  • the present invention does not agree with the German experiment, but base this work on present experience which has proved that the treatment of oil shale can fulfill the requirements for energy and the shortage in cement, as well.
  • Saving water and energy means that the treatment of the oil shale should involve the same process of manufacturing cement, since high fuel changes into cement, without the need to have a separate cement-manufacturing entity, and the experience and 30 relevant analysis have proved this.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

This invention consists of a new thermal dismantling method that enables reaching very high temperatures of 950oC in order to transform any quality oil shale into directly refineable shale oil and to shale gas equal to natural gas, without using liquid oil for temperature rise and without using water as a cooling system, resulting in ash production where the ash could be transformed into high fuel and high fuel into other industrial products like insulation materials, clinker etc and as a byproduct producing water and clean hot air. The oil shale is one of the rocks in which organic prong is mixed with widely variant of non-organic metal prong. This mixture contains a broad spectrum of mineral elements and it has the ability to generate all traditional sources of energy when treated by the thermal dismantling method. The thermal dismantling method is based on separating the volatile section which consists of the shalegas, the shale oil and the water, the remaining section (the nonvolatile section) is called the ash. The ash is taken, and then appropriate additives materials in specific quantities are added to it to produce the solid fuel. In such way, it can be claimed that the following equation is maintained in an economical criteria and environmental standards: Oil shale = Coal + Crude oil + Natural Gas

Description

HIGH RANGE TEMPERATURE THERMAL DISMANTLING METHOD IN
PROCESSING OIL SHALE
TECHNICAL FIELD OF INVENTION:
This invention consists of a new thermal dismantling method that enables reaching very high temperatures of 950°C in order to transform any quality oil shale into directly 5 refmeable shale oil and to shale gas equal to natural gas, without using liquid oil for temperature rise and without using water as a cooling system, resulting in ash production where the ash could be transformed into high fuel and high fuel into other industrial products like insulation materials, clinker etc and as a byproduct producing water and clean hot air. 10
The oil shale isoneoftherocksinwhich organic prong is mixed with widely variant of non-organic metal prong.
This mixture contains a broad spectrum ofmineral elements and it has the ability to generate all traditional sources of energywhen treated by the thermal dismantling method. 15
The thermal dismantling method is based on separating the volatile section which consists of the shalegas, the shale oil and the water, the remaining section (the nonvolatile section) is called the ash. The ash is taken, and then appropriate additives materials in specific quantities are added to it to produce the solid fuel. In such way, it can be claimed that the following equation is maintained in an economical criteria and 20 environmental standards:
Oil shale = Coal + Crude oil + Natural Gas
This invention is intended to be used to process the oil shale by using a new high range temperature thermal dismantling method,and then to produce more products other than the shale oil and shale gas oil such as the high fuel, the residual, water and hot air. 25 The technical field usage for the invention is then related to the field where these products are proposed to be used.
The technical field for using the shale gas:
The shale gas extracted from the oil shale through the thermal disassembly processing well matches to the natural gas, accordingly, it is used in all fields where the natural gas is and could be used, and moreover, the shale gas can be in dry or wet situations. The dry shale gas is used as source to produce the thermal energy, while the wet gas is used for many petrochemical industries.
The technical field for using the shale oil:
The produced shale oil matches in the chemical composition with the oil of the Middle East, and can be immediately directed to the refineries for refining and separating its distillates to be used as a fuel for the internal combustion engines. Moreover, the lubricating oils and lubricants for cars and various industrial vehicles; can be extracted as one of the distillates' products. On the other hand, the distillates can be separated and treated to obtain the raw materials which are used for the production of plastic materials, fertilizers, medicines, dyes and pesticides.
The proportion of the aromatic materials; which exist in the oil shale construction, is considered; if the percentage of this proportion is high; the product is regarded as a high economic value product, and then preferred to be an important input for the medical petrochemical industries.
Moreover, the food (potatoes - corn - wheat - rice - fat) is used for the production of several basic industrial materials such as, synthetic fatty acids, the production of synthetic alcohols, olefins production, the production of synthetic rubber, and synthetic fiber production; however, the shale oil can be used to produce the exact same products which means saving the food sources.
The technical field for using the oil shale ash: The invention's shale oil ash is different in its structure and quality from the various types of global oil shale ash. The reason why this ash is different is basically because the global technologies depend on heating the oil shale at the temperature limit of (450 to 550) ° C, while the ash resulting from the treatment process technology adapted by this invention is subjected to tackle the oil shale in a much wider range of temperature which 5 is (750 to 950) 0 C. In this regard of temperature, a large change in the chemical composition of the ash is occurred.
The ash resulting from the processing of oil shale, per calling for optimism cases, ranges from (56 to 86%). In this technique; this ash is mixed with suitable additives rate (10 to 30)% from the ash weight; the resulting mixture is the high fuel with the minimum heat 10 content of 8000 kcal per kg, which needs an appropriate burning system to take advantage of the full thermal energy stored in it.
The technical field for using the high fuel:
The high fuel is regarded as solid fuel with high heat content and the burning efficiency, this is within the acceptable environmental effects. 15
The high fuel which is produced by the invention'smethod when processing the oil shale can be used with its burning system for:
• Desalination of sea water, which requires temperatures approaching 350 0 C in
order to be vaporized.
• Textile industries that require temperatures approaching 450 ° C for steam 20 generation.
• Electric power generation, which requires temperatures of (450 to 650) ° C for steam generation and steam roasting in order to rotate the steam turbine.
• The cement industry needs a wider range of temperatures ranging from (100 to
1450) 0 C for steaming, drying and combustion processes. 25
• Glass industry needs greater amounts of heat and high temperatures that could
reach up to 1850 Celsius degree in order to get high-quality glass products. • Mining industries that consume very large amounts of heat, which is accompanied by disastrous environmental effects on the climate. This industry is not available in the Middle East because the furnaces that can meet this industry must be at least at temperature of about 2000 Celsius degree, which is achievable only under special conditions, and will always depend on the electric furnaces 5 that achieve specific goals.
The high fuel with the existence of appropriate combustion system can generate the required heat quantities and temperatures which can reach the excess of 3500 degrees Celsius;and thus opens the wide door to the establishment of mining industries which has not been possible to reach without using the high fuel. 10
The technical field for using the residual high fuel:
After using the high fuel as a thermal energy source; the usage field of the high fuel residual is determined by the chemical changes in the basic composition during use, such as the cement industry - road-paving materials industry - thermal insulation industry, building materials - soil stabilization and any industries in which the high fuel 15 residual would be a basic or essential raw material.
In fact, after burning the high fuel; the resulting high fuel residual can reach a final product; which is the ready clinker for cement industry. When using the high fuel residual as clinker; it provides raw materials used in the cement industry and all the operations related to it. If so, it can be confirmed that using the shale ash saves in the 20 fuel consumption which used in drying and burning of the clinker raw materials, also saves in the necessary amounts of electricity consumption for the overall operations associated with the cement industry.
The technical field for using the water:
This inventionis regarded as a technology to produce water when processing the oil 25 shale rather than consuming it as it is in the technologies used in the whole world.
The produced water can be purified and used in the field of agriculture. The technical field for using the hot air:
This new technology produces such huge amount of hot air with temperature that can reach 400 degrees. The amount of the hot air is unmeasured and can be used in the domestic heating system.
Figure imgf000007_0001
Oil shale background
1.1 Introduction
After giving clear and generalinformation about the oil shale field for example the technical methods that are frequently used of the oil shale treatment, the invention would be introduced to show the advantages and the solutions for the widely known problems of the field.
1.2 The Mechanism of the Oil Shale
The oil shale is considered as bounded and compacted layers of rocks with a sedimentary origin that contain organic matters. The organic matters were formed as a result of gathering all of the Alchenyat, algae and micro animals that used to live in 10 the shallow water, which exposed to the impact of active bacteria in the sludge and mud, and then undergone through physical effects resulting to several transformations in the structure.
These transformations can be expressed as:
1.2.1 Degradation 15
Gases Organic
Mass of Heating Multiple Polycyclic
CH,-CO: acidsAlcohol alivecreatur compounds (Aromatic - + Carbons +
Physical CO H2- water es Niftheneya)
effects C2H4
1.2.2 Crackin
20
Hydrocarbon gases Organic compounds+ Heating
+ Aqueous phase CO-CO2- H2-C2H4 + Water Physical effects
Solubility (melting) and Formatting
Mass of Heating
CO + H
alivecreaturesCzHxOy 20 CHmO„ + C02 + H20 + C
Intermediates 1.2.4 Oil Shale Components
The oil shale consists of Inorganic matters metallic mixed with different matters and metal items as shown in table 1 below:
Table 1 : Oil shale components
Figure imgf000008_0001
1.3 Oil Shale
The oil shale can be considered as sedimentary rocks consist of wet soft kernels, where the moisture can be separated in term of water. In addition, the oil shale consists of organic matters that can be extracted in term of oil and gas simultaneously. The remainders of the oil shale consist of inorganic matters metallic that can be transformed to solid fuel (high fuel) by performing the proper processes that suit the purposes of use. The general atmosphere for the oil shale shows that it is consisted of sediments located in shallow ponds or seas that are rich with Alchenyat (Albumin + hydrocarbons).
Accordingly, the oil shale contains a wide range from the organic and inorganic matters where the organic matters are derived from Alchenyat, algae, and organic detritus such as aquatic and terrestrial plants and aquatic and terrestrial animals, on the other hand, the inorganic matters contain Vhmauah metallic matters such as carbonates (Calcite and Dolomite), in addition to debris materials such as Quarts and Wlosbat related to clays (Aallili and Chlorite).
1.3.1 Oil Shale Formation:
The main source for the organic matters in the oil shale is the Alchenyat (Hydrocarbons and Albumen) in addition to the plant residues, spores and the pollens that form Alashinah fat.
The Bacteria plays important rule to transform the organic matters to kerogen. The decomposition of the organic matter generates the warm climate Bacteria which helps in the growth of floating and benthic Alachenyat.
When the floating and benthic Alachenyat die, it is then exposed to oxidation and disintegration because of the dissolved oxygen in water.
The alive creatures (alive materials, Hydrocarbons, and fat) are then affected by the Bacteria and the process of oxidative stress under the affect of the biochemical processes, with the absence of free oxygen and the present of the active Bacteria, resulting to changing in the structure of the raw organic matters which transform it to the kerogen.
The partial disintegration for the organic matters creates the metallic matters such as Quarts and clays, and the plant residues.
The Bacteria rule starts to be activated in the benthic alluvial silt with the absence of the oxygen, resulting to acquired medium (accepting electrons) which forms the organic matters and the Berit in alkaline conditions and highly acquired medium In the oxidized medium, the Phosphate centers and part from the Alcalat are formed, while in the mild oxidative stress and mild acquired medium, the Filadgoonit is formed.
The sea water is rich with Calcium ions Ca+2 in term of bi-calcium carbonate that precipitates under the effect of AlmtafeeatandAlgdraminger. The effect of the 5 Bacteria participates in forming the aggregate kerogen stone which is poor in organic matters.
The Alcheny silt is incompact and remain suspended between the water and the silt, however, in later stages, it turns to become compacted and solid because of the effect of the formed sediment and the increase in the sedimentation ponds' depth. 10
The resulting solid Alcheny silt gathers in saturated sediment layers with the time, and the rare materials in the accumulated sediment layers overlap under the effect of the physical conditions such as time, temperature, pressure and motion, and with the presents of chemical effects, that led to establishing an atmosphere that achieves the principle of succession of life, which led to form the oil shale that produces the gas 15 and oil.
The Vocabulary petroleum means the oil of rocks, so, this leads to the relation between these Vocabularies and how these Vocabularies were formed. More importantly is to know the structure of the raw organic matters in the petroleum and the oil shale which is the main motivation to do more researches over the ray organic 20 matters in the petroleum.
1.3.2 Raw Organic Matters in the Petroleum
The plants and animal's organic detritus (plankton and benthic materials) and Bacteria (germs) play important role in collecting the organic matters and precipitating them under the water, and in the disintegration of the vestigial creatures which is an 25 inevitable stage to form the petroleum.
The terrestrial plants contain on the Alljuginin while the aquatic plants do not contain it and it is rarely found in the structure of the benthic plants. Metallization ► H2o + Co2 ioes not occur in an atmosphere that has Oxygen, while it partially disintegrated in the present of the Oxygen and in an atmosphere that is poor in term of having Oxygen resulting to aldepal acids.
1.3.3 Scientific Belief:
The Idjanindepal materials are transmitted by rivers to seas which is a source to 5 generate the petroleum.
1.4 The Scientific Research
It is a matter of fact that the organic matters which reach to the seas in the shape crumbs and colloidal turbid are sufficiently oxidized, and they are consisting of acid depal and pieces of oxidized plant tissues. These organic matters cannot be a suitable 10 source for the hydrocarbons; however, it does play indirect way in the process of forming the petroleum, i.e., forming CH4, and Co2.
The acid depal is able to form such complicated compounds from the Alkanes that contain large molecules, and with the present of the progressed Bernoadah hydrocarbons that plays the inter-mediator role which transmit the compounds from 15 the land surface to the seas.
The cellulose (C6Hio05)n is the most depal poly sugars stable that can be mineralized at the upper layer of the sediment located at the bottom and in airy medium to launch H2, CH4, Co2, and H2o.
At the absent of the air medium when various fermentation processes occur; the micro 20 creatures that feed on carbohydrates can make other components such as the Lipids which could be a source for the petroleum hydrocarbon.
The Bacteria digest the proteins that starts the interacting with the water after the organisms atrophy in the absent of air medium resulting to full mineralization that gives H2o, Co2, N¾, H2S, H2, and C¾. 25
In the absence of air medium that arises from the silt which is located in the bottom, the disintegration becomes incomplete for the proteins and their compounds with other materials. The resulting materials which appear during the condensation of amino acids with the carbohydrates, transform to depal materials that differ in the chemical structure from the acid depal that is existed in the perjury (raw coal) and the coal.
The process of removing the amino from the amino acid leads to generate small molecules fatty acids. After removing the Carboxyl from these fatty acids, gaseous 5 hydrocarbons are yielded.
Since sulfur and nitrogen compounds are encountered in the petroleum, this confirms the presence of proteins between the components of the petroleum.
The Lipid components belong to living matters that converge in their chemical composition and molecular building with some petroleum hydrocarbons. 10
Fats are the glycerin esters and the fatty acids chain of all kinds that are saturated and unsaturated, in addition to the Hydroxylated and Ketonah of the carbon chain C12
C2o with degree of saturation of various fatty acids in animal fats and vegetable fats of non- branched Aolivatih chain. Small amounts of branched fatty acids from the G,
C28 carbon chain were deduced from the bacteria and fatty tissues. Moreover, the 15 large molecules jS-Hydroxy acids with long substring in the situation a were deduced from the micro organisms and fungi.
1.4.1 For Confirmation:
The Lipid in herbs and zooplankton are rich in unsaturated acids, which is characterized by containing 35% from the materials that are not capable of 20 saponification , this percentage increases whenever the object is more primitive.
The waxy materials are mixture of the uni-atoms esters alcohol materials and the uni- base organic acids. Moreover, the primary uni-atoms alcohols participate in the formation of the waxy materials C -> C34 that have ordinary structure with an even number of carbon atoms in the molecule. 25
The higher fatty acids are considered as uni-base saturated compounds with non- branched chain.
The steroids are considered as annular compounds with carbon structure that is composed of totally or partially hydrogenated derivatives for 1 -2 Cyclo-penta- venantryn which are component of micro-living materials. The steroids are considered as the most common micro-living materials which contain saturated or unsaturated alcohols with annular structure such as Alchollsterolat Alargeosterol (C28H44O).
The resin acids are involved in consisting of the Biomechanical outcomes of the land plants.
The amber resins, resin acids and the hydrocarbons which is existed in the micro- living materials represent a significant proportion in the filtered material from the seawater, which consists of micro -plankton, fossilized dung and organic residues. These components are considered as a source for carotenoids of micro-organisms in the zooplankton which move to organic silt and sediment.
1.5 Transformations of the Organic Detritus:
Severe transformations occur over the organic matters of the vestigial organisms, the zooplankton and the phytoplankton in water and silt mediums that located in the bottom Microbiological activity is accompanied by the disintegration of raw material and form bacterial biomass resulting to:
1 - The percentage of the protein compounds decreases by 100 to 200 times.
2- The percentage of the free amino acids decreases by 10 to 20 times.
3- The percentage of the carbohydrates decreases by 12 to 20 times.
4- The percentage of the lipids decreases by 4 to 8 times.
Simultaneously, multiple condensation processes occur which are accompanied with polymerization process for the unsaturated compounds, which is the basic of the organic part of any kerogen. Moreover, polymerization process for fatty acid, hydroxylated acids and the unsaturated compounds, which leads to transform the condensation products into forms of non-soluble kerogen in both annular and non- annular form, in addition to materials consist a rotten floating part of the kerogen.
The process of polymerization of the most stable part from the lipids and the hydrocarbons form the soluble kerogen, which can be seen in the formed asphalt materials and resins.
1.6 Scientific Fact: If the intensity of oxidative processes increase, the proportion of hydrogen in the kerogen will be decreased from 8% to 10% to 3% to 4% and a small percentage of it turns to adsorbed form with rocks that consisting a complicated organic metal compounds. The oxidative process is associated with interaction with sulfur operations process of up to 8% to 10%. When the depth of the sedimentation area 5 increases for up to 100 m to 200 m, the microbial processes with the absence of air subside, and the oxidation of organic matter stops and the organic matters transformation ends, which is the stage that the kerogen inters the physical and chemical transformations stage that is determined by the temperature and pressure in the ground. 10
In the first stage, where the depth of the sediment is from 1.5 km to 2 km, the polymer structure for kerogen is exposed to small changes where the temperature is 50° to 60°.
The changes can be summed up to deduce the carboxyl, water and the external functional groups as a result of the separation of CH4, H2s, NH2, Co2, and H2o.
When the depth of the sediment is from 2 km to 3.5 km, the temperature reaches 80° 15 tol 70°, which is the point that the effective disintegration begins for the basic structure of the kerogen associated with increasing the proportion of liquid bitumen to reach 30% to 40% of the original mass of the kerogen. The Bitumen containing of annular alkanes, alkanes and small and large Alarnjat, in addition to complicated compounds with annular heterogeneous asphalt materials and resin, on the other hand, 20 the percentage of bituminous ingredients in the organic matters increases by several times.
Disintegration of the greatest part of the kerogen and forming the main mass of the Petroleum Hydro carbonate, name the main stage for forming the oil.
When petroleum hydrocarbon formed, the process of desorption begins, and then their 25 displacement process with gas and water from the clay sediment compacted carbonate to permeable layers of sand reductase as a result for the sudden changes in the pressure.
At the beginning of the main stage, the carbohydrates consists more quickly than their displacement to the reduction layers, when the depth increases, which leads to enrich 30 the organic matter with the Bituminous components, and the process of formatting the hydrocarbon subsides with increasing the rocks depth, which is justified by consumption of the main part of the kerogen. On the other hand, the speed of the displacement of hydrocarbon constantly increases, as well as the speed of exhausting the bituminous materials and hydrocarbons from organic matter, with increasing the depth of the rocks that generates the petroleum. At this point, the main stage of 5 forming the petroleum comes to the end accompanied with further changes on the kerogen as the sediment depth increases from 4 km to 6km under the temperature of 200° to 250°. Under this temperature and depth, Alkokih stage starts, which is the higher stage of carbonization, where the kerogen losses big amount from its hydrogen resulting to activate the process of forming the hydrocarbon gas to achieve the end of 10 forming gas main stage. After this stage, the koregen contains on 85% to 90% of the carbon and 1.5% to 3% of the hydrogen. When the rocks depth increases more and more than this stage, slight changes occur with temperature rise in the ground over the koregen, as it gradually becomes more and more carbon and releases small amounts of the gas products. 15
Under high temperature and high pressure, the scattered organic materials such as the carbon, inters the intra Sitish stage from its transforming processes.
1.7 Missing Link:
The issue of petroleum displacement has not been adequately studied, and yet basic principles have not been justified. For example, the percentage of the organic matters 20 in the carbonate rocks is 1.5% to 2% while the Bitumen percentage does not exceed the decimal fractions (below 1%).
The bitumen is an essential element of organic matters in the sediment rocks, so, the bitumen cannot leave the organic matters unless through a solvent that can influence rocks to merge with the most movable bitumen materials, and then carry the mixture 25 to a low pressure zone via the water and or gas, as the displacement can only be performed through dissolved water or soluble gas. The rock fusion is considered as of the ways to help performing the process of displacement, in addition to other well- known ways such as re-crystallizing the carbonate material, the phenomenon of the spreading, capillary forces, surface tension forces, and seismic phenomena 30 The displacement is accompanied with a change in the nature of the displaced material, such as simplifying, contiguity, reducing the proportion of compounds with non-homogeneous atoms, and weakening the annularity.
1.8 The Organic Origin for Petroleum
Assumptions regarding the petroleum organic origin based on the following factors 5 are:
1 - Organic nature of the original materials in the petroleum.
2- The relation between the organic matters and the sedimentary rocks.
3- The suitable conditions for the transformation of the buried materials (kerogen) to Petroleum 10
1.8.1 Geological Foundations
1 - Industrial petroleum reservoirs are chronically correlated with the sedimentary rocks.
2- Crystalline volcanic reservoirs are existed and linked with the sedimentary rocks.
3- The sedimentary rocks are considered as a suitable medium, where the petroleum has the process of forming.
4- There are operations of a direct relationship between the petroleum and the coal formation, and the process of accumulation types of tars.
5- The contracture of the petroleum and asphalt types in it is similar in the 20 structure for the raw fuel that has organic origin such as the coal and the oil shale.
6- The processes of forming the petroleum occurred in various geological eras, where the age of the rocks is around 500 million years, and the minimum age of the rocks is 20 million years to 30 million years.
1.8.2 Geochemical Foundations
1- The petroleum contains optically active substances of biological origin which are existed in the bituminoides.
2- The petroleum contains compounds of biological origin which are found in the bitumen that is located in the sedimentary rocks, such as Alborverinat, 30 alkanes, Alasubrtwedih hydrocarbons, hydrocarbons with Alasteroada construction.
3- The hydrocarbon structure of the bitumen that found in the organic matter (kerogen) which produces the petroleum. Using mass spectrometry analysis, gas chromatography and liquid chromatography, show that the quantitative 5 ratios and chemical composition of the bitumen found in sedimentary rocks and in sand tar are completely and exactly matched.
Regarding to the oil shale which is called carbonates shale in former stages that contains rich organic matters during the antiquity with period from the Cambrian era to the Cretaceous era; it is the result of sedimentation processes in a variety of 10 different environments such as sea basins, lakes and swamps, regardless of whether the water is salty or sweet.
In conclusion, the oil shale is younger than geological formations of the oil-bearing and gas -bearing rocks.
Further researches are needed to determine widely and precisely, the age of the oil 15 shale and the petroleum.
1.9 The Origin of Oil Shale Sediments
Different types of petroleum have different properties; however, the elemental analysis or atomic analysis shows similarity between them with small different in the ratios of the consisting elements that distinguishes each type from the other. 20
The petroleum contains a large number of the hydrogen coal such as the paraffin, Alinvtinih and fungal coal where each kind of the petroleum has different ratios from these elements.
The same principle can be applied over the shale sediments characteristics, i. e., different types of sediment shale has different properties because each kind of the 25 sediment shale has different location (depth and medium), however, there are common characteristics among all model of the oil shale, the reason for the similarity in the characteristics is referred to the similarity between all kinds of the oil shale in the conditions of forming the shale sediment, these conditions can be listed below: 1- The synchronization between the organic matters disintegration and the position of the soft grains of the debris metallic, which leads to mixing the organic components with the non-organic components.
2- The presence of large amounts of organisms that decomposed in the absence of oxygen condition in the middle of a medium that is rich with sulfide hydrogen.
3- Quiet sedimentation in order not to make any change in the quality of the dissolved gases in the water. This atmosphere is existed in fresh water lakes, enclosed seas and deltas, over a warm tropical climate.
4- The organic matters in the sediments that generate the kerogen and the bitumen, have organic origin, which requires the availability of organic matters, especially river Alachenyat and marine Alachenyat, in addition to the benthic foraminifera and floating foraminifera
1.10 Shale Models
Multiplicity kinds of petroleum match with the existence of multiple models of oil shale such as:
1- Alturbanat: The richest oil shale, which is characterized by low rate of the metallic compounds and high rate of the organic matters. This kind of shale is existed in the form of associated blocks with locations for the charcoal that are located in disintegrated mediums. It is located mainly in Australia and Pennsylvania.
2- Altasmanic: Distinct model of shale that formed in shallow seas close to beaches. Its organic components are linked to the Alachenyat kinds, widely speed and located in Tasmania and Alaska.
3- Silt ryger: The most important kind of shale (in term of the good quality, big quantity, the amount of the organic matters), with marine origin and its sediments from rash and Seltston. It is spread in Alallosa and located in Colorado and Ottawa.
4- Alkourkasi: widely spread in the republic of Estonia and dates back to the era of Udoveza.
1.11 Geological Conditions to the Shale Formation: The multiplicity of patterns and different shale characteristics that are related to its origin are the results for the variety in the petroleum kinds.
The shale sediments strutagravealy spread from the Cambrian era to modern era. Its best marine kind is the black oil shale which is extended over large areas but in low thicknesses. 5
Some kinds of the oil shale consist of a silesia template with poor organic matters. Other kinds of the oil shale consist of calcareous template, which is richer in the organic matters than the previous kind.
When the oil shale consists of inorganic matters metallic that contains the flint, in this case, the oil shale is combined with the phosphate rocks. 10
The continental thresholds and modern geological corridors are considered as appropriate to investigate these types of rocks.
As for oil shale with mere origin which was formed during the movements that generated the mountains in the modern world, there are more than 165 mere basins that its sediments date backed to the Triple era and they contain oil shale. The movements that generated the mountains in Asia and Europe yielded the oil shale sediments.
1.12 Geological and Tectonic State for the Shale Sediments
The formation of the oil shale requires suitable tectonic, geological, geochemical and vitality conditions in the sedimentary basins.
The Bituminous facies need to be in a stable acquired medium (accepts electrons) for long period of time, in addition to organisms and microorganisms, moreover, it is a must to have a large proportion of floating Alachenyat near the surface of the water in the sedimentary medium, because it is the source of the accumulation of organisms at the bottom of the sedimentation basin.
So, the suitable conditions in sedimentation basins and within certain tectonic activities, which restricted these eras in the upper Alsenoni layers era, lower Baliusan and Eocene eras where the bituminous rocks and oil shale are existed. These facies were formed in marine basins that are adjacent to advancement areas during the Almakrat geological era. In the period of the GeologicanAltitusAlmakrat era, Marginal basins were formed with extensions linked to the tectonic activities that are related to that period.
Within sedimentary basins, carbonaceous sediments had developed such as marl limestone, the marl and the lime Apostle, in addition to minor levels of debris. All that 5 happened as a result of the decrease in oxygen, the increase the gas hydrogen sulfide and other gases resulting from the activity of bacteria and the accumulation of a large section of the floating fossils descending to the depths, with the transformation of the medium to become stronger returner of electrons (strong acquired medium), and with forming the bituminous that associated with sediments of carbonate. These ID developments and conditions occurred during the upper Cretaceous layer era and the lower Albaleugen era, resulting to forming the bituminous rocks and oil shale.
So, the shale is younger than the biological formations of the petroleum bearer. The nature factors, pressure, temperature, time and rotational motion of the earth's seismic helped not turning those sediments to crude oil. So, the sediments were formed in 15 swamps or shallow mere that are related to the formation of coal in coastal environments, which justify the reason the shale contains a wide range of metal compounds and organic materials, which makes the shale able to produce the shale gas, and shale oil, and this is what justifies using the shale as fuel for direct combustion processes for thermal power generation. 20
The experiences and analyzes that carried out on the gas and the oil shale emphasize the big match in its chemical structure with crude oil and natural gas.
1.13 Evaluation of Shale Ores
Traditional energy sources such as coal, natural gas, and oil, in addition to some problems that are yet unsolved properly are the reasons which make the shale to be 25 less important energy source. The most well known problems that need more considerations are the high proportion of ash resulting from the processing of oil shale and the waist which consists the rate of 55% to 85% from the shale weight, beside the fact that the resulting oil shale compounds are most of the sect's compounds of the unsaturated hydrocarbon which needs hard hydrogenation process to convert the 30 hydrocarbons to a saturated compound, and then at later stages, to be transported to the refinery, all these operation processes with ignoring the heavy metals in the oil, in addition, a huge amount of water is needed for the operation processes, which leads to the penetration of water small molecules between the oil molecules, which requires further operations to separated them before heading to the refinery.
The high cost of mining to extract the rocks, crashing it and preparing it for the 5 treatment made the Estonians use the direct combustion of oil shale rock to generate electric power, which could not have succeeded without large amounts of water.
Estonians lead the direct combustion experience which succeeded at that time, however, nowadays, the direct combustion is admitted to be wrong because of using the expensive oil to do so, that is why shell company uses the thermal injection 10 method using columns of thermal and electric heating inside the mine. This process continues till dismantling the kerogen into liquid that can be collected via collection columns. The collection columns must use the idea of the ice wall at the processing area to prevent the contamination of the ground water which is another mistake (besides the mistake of heating the ground) that should be avoided. 15
To face all these challenges in a scientific manner, you must know and adjust the following things:
1- Studying the structure and knowledge of the components of the rock and the knowledge of the full specification of the rock.
2- Studying the shale units and its layers distribution. 20
3- Studying the general situation for a variety of oil shale in the entire sedimentation basin which the shale was formed in.
4- Determine the environmental and economic problems associated with oil shale investment.
1.14 Turning Point: 25
As long as the price of a barrel of oil controls the cost of extracting a barrel of oil from oil shale, there will not be a real investment process with acceptable environmental standards and profitable economic criteria in the shale field.
To be able to open a new gate in the shale investment field, we need to release the cost of extracting the oil shale via using the petroleum to do so, i., e., to extract the oil 30 shale without using the petroleum for the direct combustion. In such way, it can be claimed that the oil shale can become an unlimited source of energy.
The most important characteristics of the oil shale are the heat content and the content of the oil in the shale, and they both are directly proportional to the ratio of the organic matters in the shale.
Two types of the organic matters are referred to; the first one is the Mineleiet which is one and half folder poorer in term of the amount of oil in the shale than the second type which is the Alcolmasi. Moreover, the content of the oil in the shale is more related to the organic matters than the content of the heat in the shale in the same ratio (one and half folder) as shown in the following examples:
1- The Alcolmasi organic matter type yields 70% oil from its original matters.
2- The Greinerfr organic matters type yields 66% oil from its original matters.
3- The Vulva organic matters type yields 51% oil from its original matters.
4- The Mineleiet organic matters type yields 21% less oil ratio from its original matters than what Alcolmasi organic matters type yields.
Implementing the experiment on the shale that extracted from the Sultani area in Jordan shows its point of view which is related to the following characteristics as shown in the attached figures:
Figures 1 and 2 show the relation between the organic matter percentage and the density for the Almstrich and Eocene eras respectively:
Fig.1 shows the relation between the organic matter percentage and the density for the Alsmstrich era
Fig.2 showsthe relation between the organic matter and the density for the Eocene era.
Figures 3 and 4 show the relation between the organic matters and the thermal content kcal/kg for the Almstrich and the Eocene eras respectively:
Fig.3shows the relation between the organic matters and the thermal content (kcal/kg) for the Almstrich era. Fig.4shows the relation between the organic matter and the thermal content (kcal/kg) for the Eocene era.
Figures 5 and 6 show the relation between the thermal content (kcal/kg) and the shale oil percentage for the Almstrich and Eocene eras respectively:
Fig.5showsthe relation between the shale oil and the thermal content (kcal kg) for the 5 Almstrich era
Fig. 6shows the relation between the shale oil percentage and the thermal content (kcal/kg) for the Eocene era.
Figures 7 and 8 show the relation between the organic sulfur percentage with the shale oil quality represented by C/H for the Almstrich and the Eocene eras respectively: 10
Fig.7shows the relation between the organic matter percentage and the shale oil quality for the Almstrich era.
Fig.8showsthe relation between the organic matter percentage and the shale oil quality for the Eocene era.
Figures 9 ad 10 show the relation between the organic sulfur percentage and the shale 15 oil quality represented by C/H for the Almstrich and the Eocene eras respectively:
Fig.9shows the relation between the organic sulfur percentage and the organic matters percentage for the Almstrich era.
Fig. lOshows the relation between the organic sulfur percentage and the organic matters percentage for the Eocene era. 20
As results for these relations, several indicators could be given regarding the oil shale and the extracted oil such as, the minimum heat content of the oil shale rock used in the direct combustion processes for electric power generation should be at least 1000 kcal/kg and the organic matters percentage of at least 16%, and then leading this type of shale to undergo enrichment processes. The enrichment process the process to raise 25 the heat content by physicist solution. On the other hand, the minimum heat content of the processed shale to extract the oil shale must be 900 kilo Cal per kg (kcal/kg). The treatment processes of the oil shale, with or without the enrichment are: extracting, smashing, milling, physical process and then pumped into special furnaces.
1.15 Indication:
The wider oil shale layer in the thermal reservoir capacity ranging from 700 to 800 Cal/Kg, and each type of the oil shale needs to be undergone through amendments to 5 the processing unit being able to deal with any kind of oil shale rocks.
1.16 Uniqueness:
The invention's industrial unit can handle all kinds of oil shale; in fact, it can handle the oil shale with as small heat content as 750 Cal/kg. During the treatment processes, water is not needed to deal with the inorganic matters, which stood as an obstacle that 10 had not been overcome yet or even disposed. This method not only overcomes this issue but also holds it as strength.
In fact, in the industrial processes,these inorganic matters are exploited to be used in two different utilities; the first one is the solid fuel at the presence of suitable additives which are available and consistent with the use of this fuel. This solid fuel 15 can be used in various applications, starting from water desalination and power generation until the use in the mining operations that require high temperatures that exceed 2000°. The second utility can be used strongly in the building materials industry, cement industry and in wide range industrial areas.
The implemented analyzes show the industrial fields that can use the remnants of the 20 raw materials in these industry applications.
1.17 Studying the Shale Units:
There are different forms of the way the oil shale located in the sediment basin; the best form is when the oil shale exists in consecutive layers, without the presence of interference from other types of rocks. This kind of layers structure contains a good 25 quality oil shale.
An idea of concentrating the oil shale by heavy fluids was launched to increase the oil shale heat content which redirected the way of studying the type of the oil shale to be in two stages: 1- The first stage is to know the compositional structure of the oil shale and how they are located in details over all layers.
2- The second stage is related to the ability of concentration the oil shale, and the optimal concentration method to be able to obtain such distinctive quality of the oil shale that can be used in the direct combustion processes. 5
1.17.1 Studying the Location of the Oil Shale in Sedimentary Basins:
The following key points must be considered when implementing the study:
1 - The amount of the location positions, the knowledge of nature and the knowledge of its Physical, chemical and mechanical specifications for each layer located in the basin. 10
2- The number of units and oil shale levels in the sedimentation basin, to determine if there is one composition or more and study its homogeneity, which affects the mining work that can be performed over the studied units.
3- The entire structure is fully studied, and then the specifications to choose the optimal unit investment method in the sedimentation basin are defined. 15
4- In the studied area, the oil shale structure backed dated to the era of Almasturnjta which is characterized by large thickness, which enables to perform the mining work over small and limited spaces.
5- The knowledge of the structural situation of the oil shale and determining the direction of the slope in the layer(s), to facilitate the convergence process 20 between the different types of the oil shale layers.
6- Ensure that there is ground movements that affected the sedimentation basin, and if it remained symmetric. This can be known through comparing the drilled wells during the implementation of the operational studies.
1.18 Economic and Environmental Standards for the Investment Processes 25 over the Oil Shale Field:
Oil shale industry is considered as successful when the cost of extracting the shale oil and gas are not linked to the prices of traditional energy sources (coal, petroleum and natural gas). Moreover, choosing the perfect treatment unit that reaches production capacity of 1,000 barrels per day, accordingly, the total production capacity of the 30 commercial companies is determined by the number of the optimal processes units which should meet the needs of a particular area. These facts are directly reflected in the cost of capital and the cost of the investment which is necessary to set up a business to invest in shale.
The social status of the areas that contain oil shale is reflected on the need for oil shale development projects, in addition to the ability for these areas to the 5 development and to take advantage of the geographical location.
The existing shale zones are often desert areas and are almost free from farms strategy, so, the geotechnical and hydrogeological conditions are suitable for the mining work rather than the agribusiness.
Since the techniques used in the work, it is depended on the execution of the surface 10 treatment for the extraction of oil shale which is related to the wide mining work accompanied environmental impacts which are entirety under the complete control. However, extracting the oil shale in large quantities can cause biological damage to the ecosystem of the land, in addition to the released carbon dioxide which results from the shale thermal dissociation, however, this issue is totally under total control. 15
It is worth mentioning that, thetechniques used, neither affect the groundwater nor consume any amount of water during the treatment processes, in fact, this invention produces 40 liters to 60 liters of water per 1 ton oil shale.
All the rest of environmental factors associated with the various stages of the project achieve the permitted environmental regulations for the water, soil, air, organisms and 20 humans, so, it can comfortably be claimed that the invention and the technologies to be applied fit the economy under the permitted environmental affect.
25
Figure imgf000027_0001
Oil Shale Treatment method Background
2.1 Introduction
In this section, the most applicable methods which deal with oil shale are introduced.
At first the type of the oil shale treatment and the background about the former used methods to extract the shale oil and shale gas from the oil shale are mentioned. 5
2.2 Oil Shale Processing Methods:
The rock processing techniques need to be done outside the work place (surface treatment), in addition to the wide range mining operations, however, commercially, the surface treatment is quite limited as most of the mining operations are being performed in the same project's location (spatial treatment) but for limited mining 10 operations that depends on developing the heating methods of the oil shale rocks.
2.2.1 Surface Treatment Processes:
It includes implementing integrated studies; extracting the oil shale, primary smashing operations, mining operations and preparing the oil shale for the treatment, thermal disassembly for the oil shale, performing a tough hydrogenation process over the 15 extracted oil before being sent to the refinery to distillation process (separate its components into final products), taking into consideration that the thermal disassembly can be performed by using either the direct combustion or the indirect combustion methods.
Examples for the surface treatment processes: 20
• The Alberta Taciuk Process (ATP) technology derived from the processing of the asphalt sands in Canada.
• The technology of Baraho had been applied and then stopped in Queensland in Australia.
• The technology of petro-6 which is performed by the Brazil's Petrobras (linked 25 to the alliance of Total). • The technology of Aanavi which is implemented by the Estonian Aistieinerjna with the new allies for doing developmental work derived from oil extraction methods.
• The technology of Fushun which is implemented by a Chinese mining group that mixes the coal into the treatment processing. 5
2.2.2 Spatial Treatment Processes
The spatial treatment processes include precise and integrated studies, very limited mining operation, thermal processes for the oil shale inside the work location and injecting hot contusive materials inside the oil shale. The heading is made either thermally or electrically, and then the liquefied oil gathers in internal drilled wells and 10 then pumped to the surface to be treated in the same treatment processes used in surface treatment.
For commercial application, several companies supervise the research and implementation work, such as Shell, Hevrdn, and the U.S. Company for oil shale rock. These companies rent a land containing oil shale and implement empirical 15 research to reach a new generation of technologies to achieve the implementation of, the technical economic feasibility, environmental and commercial studies.
Shell initiated to protect groundwater from contamination, as it has created an ice wall that serves as a cooling wall around the place of the treatment to prevent oil leakage and mixing with the groundwater. 20
ExxonMobil also leads the research which relies on heating the rocks in place by hydraulic cracking where electrically connected materials fill the cracks to heat the kerogen and turns it into oil.
Raaxion technology purchased by Schlumberger, which relies on the use of Radio Frequencies (RF) microwave and critical gas (SCF) such as carbon dioxide (Co2) in 25 order to heat the kerogen in the oil shale and convert it into shale gas and shale oil.
2.3 Worldview of OilShale as an Energy Source
Nowadays, the researchers and those interested in investment stand on the threshold of the oil shale investment, which can provide us with the energy over the next decade, if they were reasonably able to draw the stored energy in the oil shale and support this source by the other renewable sources of energy in its various forms.
Below the global aspirations and forms of investment to exploit the energy stored in the oil shale are shown:
2.3.1 First: Thermal Decomposition (Retorting): 5
The retorting process is used to extract the kerogen from the oil shale, and then the resulting kerogen undergoes to heating processes to reach 450° to 550° in the absent of air heating conditions. After certain physical processing steps, the shale oil will be extracted.
The maximum extracted oil amount reaches 10% of the shale weight, and this ratio 10 can be practically obtained with proper treatment steps for such good quality of the oil shale rocks, such as the used oil shale in the research work (oil shale in Sultani area in Jordan).
The extracted unsaturated hydrocarbon oil faces several problems which are considered as the main obstacles that face the extracted oil before the distillation 15 process; the main problem is the low heat content which does not exceed 4000 kcal/kg, moreover, the high content of sulfur and nitrogen beside the high rate of heavy metals.
To solve these problems, the extracted oil undergoes to harsh hydrogenation process, separating the pervasive water molecules between the oil molecules. Moreover, the 20 sulfur and nitrogen must be separated as well beside to removing the heavy metals. After these modification processes, the extracted oil is then ready to be pumped to the refinery. The way the invention performs the previous processes is directly reflected over the economic cost for the production of shale oil in addition to the negative environmental effects associated with those operations. 25
2.3.2 Second: Direct combustion:
This method is performed in two ways: 1 - Following operations are made in the same order: extraction, crushing, milling to the level of 100 to 200 microns and then puffed to private furnaces combined with liquid fuel and air or gas.
This method is applied to the good quality kinds of shale with heat content of 1800 kcal/kg and above. This is the exact method which is being applied in Estonia. 5
2- The layer modification method (Fluidized bed):
This method is not practically implemented yet as all the oil shale treatment is applied over the oil shale with heat content of 2400 kcafkg. However, it is important to fully study this method as it deals with the oil shale with heat content below 1000 kcal/kg, which is most of the oil shale in the world. So, this treatment method has a good 10 future to deal with a very wide range of oil shale.
After the milling process, the resulting mixture is physically treated by Physicist mix (Majnti + water) to raise the heat content. The resulting mixture is then pumped to various types of furnaces and then the air is compressed to mix the fuel molecules, the coal molecules and the ash molecules in addition to the steam which is impelled from 15 the bottom.
This method is applied over the medium and poor quality of the shale, where the shale is considered as poor if it has heat content of 1000 kcal/kg or less.
2.3.3 Third: Gaseous Smashing (Gas Ifcarion):
It is a research idea that has not been implemented yet, this idea based on conversion 20 of the solid fuels (coal and oil shale) into gaseous fuel with high heat content. This gaseous fuel is then directed to power stations which are operated either by gas turbines or by combined cycles to produce the electrical energy.
This idea is linked to another idea named coal liquefaction, which is the conversion of the coal to liquid that is in this case hydrocarbon fuels. This method depends on the 25 reduction of the weight ratio of the carbon to the hydrogen by either hydrogenation or removing some carbon atoms by producing of the coal Cole or carbon monoxide. These treatment processes are accompanied by secondary fuel products such as, gas, gasoline light, heavy oils and wax. In conclusion, this method is well known but it is far beyond being able to be implemented.
United States raised the efficiency of the liquefaction and is working to achieve economic feasibility of this method, which focused on:
1- Hydrogenation of coal or oil shale under high pressure conditions.
2- High heat decomposition (pyrolysis).
3- Resolving the coal or the oil shale with suitable solution.
4- Improving the resulted synthetic gases by using Lurgi method.
2.3.4 Fourth: Extraction of Organic Matter from the Oil Shale:
Organic matter is composed of kerogen (complex hydrocarbons) and Batonin (mixed hydrocarbon); the first part is exclusively extracted by the thermal smashing, while the second part is extracted by using the proper solvents.
The possibility of extracting these two parts together is extremely complicated besides the high economical cost which is the main obstacle in implementing this method, moreover, to implement this method; high temperature and high pressure need to be obtained with the presence of other technologies that require the presence of steam, hydrogen, carbon monoxide and/or carbon dioxide. All these conditions do increase the cost of producing a barrel of shale oil, taking into consideration the quality of the extracted shale oil and the ability to be sent to the refineries.
2.3.5 Fifth: In-Situ Conversion Process Method:
This technique is based on the principle of reducing the cost of the extracted barrel of shale oil when located in the ground under the lid and to mitigate the negative impacts over the environment. The purpose of this action is to get rid of the cost of mining operations, as well as to get rid of the remnants of heating after extracting the shale oil.
The principle depends on digging a range of holes in the oil shale reservoir location, and then pumping the heat or heating materials into these holes resulting to heat the earth layers that contain the oil shale. The heating process is either thermally or electrically which is accompanied with moving the shale oil that resulted from the thermal smashing of organic matters. So, the method is basically based on heating the oil shale container layers, by either injecting thermal materials or applying high voltage over conductors which are inserted inside the oil shale reservoir to heat the earth surrounding layers.
One can ask, does this method take into account the impact of heating over the earth's gaseous envelope? Does that have been linked to the phenomenon of global warming? 5 These questions should be asked and answered before wondering about the reasons of the accelerated climate changes for the earth!
Shell International, as one of the leader in the use of this technique, should be asked whether the rid of the high cost of mining and mitigation of environmental impact are equivalent. Especially with regard to what is happening on earth! If the answer is 10 'necessities permit prohibitions', it can be confirmed that the quality of the resulting shale oil from the treatment process of this method faces the same problems that were faced by the obtained shale oil by the former methods, such as, being pumped from the assembly holes, directed to the process of hydrogenation, and then being subjected to the same treatment to get rid of the harmful substances such as sulfur, nitrogen, 15 heavy metals, separating the unsaturated hydrocarbon, Etc.
2.4 The Wastes of the Oil Shale
If the method that is implemented by Shell International is excluded, and an amount of oil shale which is estimated by 20,000 tons as an example are intended to be invested, a two-way investment is being faced: 20
1- Extracting the shale oil and gas from the oil shale, and then performing the treatment and purification of shale oil before directing it to the refinery, which produces different types of fuel or performs the process of separating the oil compounds which are regarded as the basis of petrochemical industries.
2- Direct combustion after performing the following processes: smashing, 25 milling, injecting particular materials to improve the combustion processes, pumping to special furnaces mixed with air or liquidized or gaseous fuel in order to generate the steam and the electricity.
Two challenges which should be properly treated are being faced. The first one is the amount of ash resulting from the combustion processes which is estimated in the 30 range of 56% to 85% of the original amount of the oil shale rocks. The second challenge is the amount of ash that results from extracting the shale oil and gas oil. These two types of ashes are regarded as a solid waste and non-symmetric waste; first waste is treated in the field of 450°C to 550°C and the second waste is caused by the burning at 1200°. In the second challenge, the amount of ash that has heat content of 800 or less is unable to be treated by the available processing units, in addition to the 5 quantities of water, air and the pumping gas required for the treatment and transportation.
2.5 Where from the Global Technology Launched for the Oil Shale
The global oil shale technologies launched from the petroleum simulation of the petroleum formation processes, i., e., the slow changing that happened under the earth 10 over millions of years, where the temperature range is from 60 o to 110° which is accompanied with the pressure of the vibratory ground motion.
Kinetic chemistry explains that it is possible to convert the kerogen into oil over a period of time that takes anywhere from minutes to hours, providing the availability of suitable reactors and treatment temperature of 450° to 50°. 15
Shale oil is considered as a sedimentary rock with soft granules of different origin, consisting of inorganic metallic materials (carbonate, silicate, clays) that mixed with organic materials (Bitomino and kerogen) which then overlapped with different metal elements.
2.6 Shale OH Classification: 20
Shale classification based on the rates of the major components:
First of all, the shale oil components are listed below: Organic materials: Bitumen and Kerogen. Metallurgy Alvhmaiiah: Calcite and Dolomite.
Debris materials. Quartz, Wlosbat, and Clay metals. 25 According to the above listed components, there are two types of shale oil:
1 - Oil shale with a high content of Calcium dates back to the era of Almastranga. 2- Oil shale with high content of Calcium kerogen dates back to the era of Alallosa.
2.6.1 Shale Classification Based on the Percentage of Phosphate:
In such type of classification, there are three types of the shale oil:
1 - Shale oil with low phosphate content P2O5 by 1 % to 5%.
2- Shale oil with medium phosphate content P2O5 by 5% to 15%.
3- Shale oil with high phosphate content P2O5 by above 15%.
2.6.2 Oil Shale Specification Used inThe Present Invention
The specifications of oil shale that has been studied in the present invention are:
Content of organic material: from 14% to 25%.
Heat content:, from 850 Kcal per kg to 1585 kcal/kg.
Oil percentage: from 6% to 12%.
Oil percentage in the organic matters: from 40% to 50%.
Sulfur percentage: From 0.8% to 1.8%
Humidity rate: 6% to 10%
Proportion of gas losses: 8% to 12%
2.6.3 Shale Oil Quality Grade
Three factors to determine the shale oil quality grade could be relied on:
1 - The intensity of combustion processes.
2- The flame color and shape.
3- The possibility of the presence of the external black flame (Sohar) at the top of the flame.
According to these three factors, three kinds of shale oil quality as shown in the table 2 below could be counted:
Table 2: The three kids of shale oil quality according to the three quality grade factors. Shale oil quality
Factor 1 Factor 2 Factor 3 grade kind
Good quality of Clear and continues flame after Gives strong and
Kind 1
flame removing the heating source powerful smell
Less good quality Flame disappears when Gives good
Kind 2
of flame than 1 removing the source of heating smell
Bad quality of the Gives just
Kind 3 Flameless
flame normal smell
The Alpetrograveh study shows that, the basic block (basic rock) of oil shale rock is a microscopic organic structured and are mostly contented of a single cabin or multiple cabins. The large cabin has Kelsey template and the mall cabin has Dolomiti template, were both types of cabins are full with organic matters (hydrocarbons).
2.7 Energy Sources: 5
Energy source is a material that provides light, heat or power and they are classified as:
1 - Traditional sources: These sources have emerged with the advent of the human to life, and they are being used since then. These materials are: wood, coal, crude oil and natural gas. 10
2- New and renewable sources are divided into.
a- Fossil fuel: such as the nuclear fuel (uranium), oil shale and the asphaltic sands.
b- Non fossil fuel: such as the potential energy of water, solar energy, wind energy, kinetic energy of the tides, waves energy, energy results from the 15 variation in temperature between the surface and depth in the ocean, geothermal energy in the ground, bio-energy, biomass energy and waste energy.
When the Industrial Revolution in Europe launched, it relied on coal, where the quantity was large and the cost to exploit this source was cheap, but the 20 environmental impact of this source was not satisfactory. However, with the progress of civilization and the role of energy in securing amenities and transport for human, the discovery of oil appeared and had been followed by the discovery of natural gas to increase the availability of energy sources and secure its continuity.
Human beings started consuming the energy sources randomly, and without controls, 5 which led to the emergence of environmental problems affected the basic necessities of life (air, the atmosphere, soil, surface water and groundwater), which makes it necessary to control the energy sources and their consumptions.
Example: To calculate the heat of combustion of oil shale rock, proceeding from the basic data for the results of tests that carried out on the studied samples; the following lo equation is applied:
Q= 81C + 246H -26(0-S) - 97 - K(02m) - 6W
Where C, H, O, and S are the percentage of the materials that are contented in the burned amount, taking into consideration that the components of the equation are determined by chemical analyzes that are performed over the combustion material. 15 The factor K is coefficient of carbon decomposition; when K=0; this means that there is no any decomposition, and when K=l; this means that the material is completely decomposed. And finally, the factor W is the percentage of moisture in the oil shale.
If the goal of the investment in oil shale is to reduce the dependence on the crude oil or the natural gas, that is used as a process of the power generation; the high cost of 20 the these two sources and the possibility of depletion, were behind the fact that supports the idea of investing in oil shale instead, and redirect the use of oil and natural gas to the other various industries, rather than to be used as fuel for combustion processes when used to generate the power.
Experience proves that plastics and fertilizer industries, as well as pharmaceuticals 25 and dyes, in addition to the pesticide industry are all industries that can be accessed by petroleum;it could be assured that the extracted shale oil can be an easier gateway and closer to those industries than petroleum. Shale is a model of the rock, which shows the blending of organic metallic part with organic part, so, when the oil shale is put under scientific experiment and researches and according to precise criteria mode, the following equation comes up:
Oil Shale = coal + crude oil + natural gas
And to get into the above equation in detailed form, the equation could be rewritten 5 as:
Shale gas + Shale oil + water + solid fuel + remnants of solid fuel + hot air = coal + crude oil + natural gas.
It could be noted that the detailed equation shows that, when oil shale are treated in scientific and realistic ways; the oil shale is higher and richer than all other traditional 10 energy sources when they are combined, and this is different from the scientific reality that states that oil is the top source for power generation.
2.8 The History of Oil Shale Treatment
The oil shale is a sedimentary rock in the composition that contains organic matters located in precise placements. 15
When the rock undergoes a thermal dismantling process; the organic matter that is basis ofkerogen (a Greek word meaning oil generator) can be separated from the rock to give shale oil and shale gas.
The rocks containing kerogen is a type of sedimentary rocks such as limestone, clay, silica sand, phosphate, or any mixture of these substances. 20
To handle the rock, it is necessary to perform assessment tests to determine the proportion of organic matter, analysis of the quality of combustion and the flame shape, analyzes included the type and quantity of minerals and determine the amount of oil in the rock. These tests are made using Fischer device which represents a scale model to determine the most important values, it gives the proportion of oil, water 25 ratio, the specific weight of the oil, the proportion of gas and ash content.
Economically treatment method to convert the project to a commercial production requires the study of metallic components and the organic side to determine the degree of benefit. The project is considered as a pioneer when it achieves the law of conservation of mass and energy flow law.
Through the history, the use of oil shale as a source of energy and its benefits put it under the attention. Table 3 below shows the old use of the oil shale by several countries. 5
Table 3: Historical view over the use of shale oil in several countries from 1838 to 1957.
Figure imgf000038_0001
The most famous and biggest examples for using the oil shale which have been performed newly are listed below:
1 - Estonia's experience in direct combustion of oil shale rock which has not been repeated in any other country possesses huge reserves of oil shale though it is such giant experience.
2- The experience of Germany, which is based on direct combustion processes first to generate steam and electricity, and then cooling the combustion products to be used in the cement production.
3- China's experience in oil extraction with the implementation of mining operations and processing of oil shale rock where the coal is involved in the treatment processes. Research and development are directed to develop the combustion ways, taking into account the economic costs and environmental impacts, but ignoring the development of treatment methods itself, which is what the present invention aims to.
Shell has implementation of slow heating test of oil shale rock by using electric heating poles at the site, but faced with the problem of groundwater contamination, and therefore has created the ice wall idea to solve this problem.
The economical impact from using the ice wall idea should be questioned.
Schlumberger uses dual technology, by radio frequency (RF) microwave idea, in addition to the use of the critical gas (SCF) such as carbon dioxide for heating processes.
This method could be called a luxury treatment method.
Company Este Energy uses Djilatorr method to extract the oil together with the backed allies Aanavi to develop a commercial method to deal with the oil shale.
In conclusion, the oil shale processing methods in the Figure 11 below could be listed asattached.
Figure 11 shows the oil shale processing methods
Having started from the standard device Fisher to handle 100 grams, and then a Pilot that can handle 4 Kg every 20 minutes, and then a half industrial unit that can almost handle one full ton every 27 minutes were developed. The result of treatment on a mixture of oil shale with the lowest heat content from 850 kcal/kg to 1585 kcal/kg, the percentage of organic matter from 10% to 22% and the moisture content of 6% to 10%. The detailed results of this experiment are shown in table 3 below (products per one tone of oil shale):
Table 3: The produced products from one tone of the oil shale.
Figure imgf000039_0001
Shale oil Liter (L) 80 to 100 10500 kcal
High fuel Kilo gram (Kg) 530 to 700 8000 kcal
Remnant of High
Kilo gram (kg) 420 to 580 Industrial use fuel
40 to 60 in need for
Water Liter (L) - purification
Hot air - Unmeasured -
2.9 The Investment Ways of the Oil Shale
There are no effective experiences in the field of investment in this very important energy source, which scattered the researches efforts and makes their way unclear. So, all ways of investments are facing very difficult challenges because the price of a 5 barrel of oil does not leave a space for overcoming these challenges.
2.9.1 First: Direct Combustion:
Shale oil used as fuel for burning and are relied upon to generate steam and electric power. Shale ores are characterized by high content of metallic materials (content of ash + carbonate content from 80% to 90%), and contain of Cox which is estimated by 10 27% to 31%. The sulfur proportion increases with the increase of the organic matters percentage which reaches up to 2.8% while the value of the moisture it is variable and not fixed.
Burning good quality fuels (solid, liquid and gas) that content little ash is well thought out and has regulations and standards. The medium and bad qualities of oil shale with 15 a high content of ash and gas emissions caused us problems, mainly, the high rate of burning materials that contribute to the decrease in heat transfer from the center of the furnace to the walls, due to the accumulation of ash, which made efforts tend to distinguish between the two types of oil shale and the presence of two methods for direct burning of oil shale rock which are: 20 1 - The method of extraction, crushing, milling in the form of powder, pumping to the furnaces via a special path. This method is applied over good kinds of oil shale (Estonian experiment).
2- The layer modification method (Fluidized bed): Method of extraction, crushing, milling, blending, push to the surface of the perforated layer, 5 pushing air through the perforated surface, pay heavily vapor of the bottom of the layer, mixed with fuel and ash particles and coal.
Differentiation between the minimum temperature is a must, which is the degree to which the molecule begins boiling, and then the temperature continues to rise until reaching the maximum temperature, which is the degree to which the molecule 10 reaches the maximum speed, which is the speed that the molecule starts leaving the modification layer then out of the furnace, while the non-complete-burnt molecules can be returned to the furnace.
In both ways of the direct combustion, it has to be taken into account that the percentage of moisture in the rock has a negative role; it is harmful and contributes to 15 increase the loss of the combustion heat and thus, decreasing the resulting of the thermal energy .
2.9.2 Second: Shale Oil Extract by Thermal Decomposition (Retorting Processes):
Oil shale is extracted, subjected to mining operations, packaged, entered into 20 treatment heat units, increase the temperature to reach about 550° degree, between the range of 450° and 550° the kerogen material starts the disintegrating to give oil and gas simultaneously. Because of the mechanism of blending between the organic materials and inorganic remains, from 15% to 20% of the organic matter origin contented in the oil shale remains untreated. 25
The retorting processes depend on the direct combustion and the indirect combustion:
1 - Direct combustion: The treatment oil shale furnaces are fed with raw material from the top with ranging sizes from 6 to 100 mM, and then combustion gas + combustion air are blown from the bottom of the furnace (the retorting remainders area), the coal in the retorting remainders get burnt, resulting to 30 increase the temperature of the air emitted from the bottom, up to the temperature that is sufficient to dismantle the kerogen that is existed in the oil shale into shale oil and shale gas. The collected shale oil and shale gas are located at the top of the heating furnace to maintain the oil fumes from the combustion.
2- Indirect combustion: The combustion gases do not touch the used oil shale to extract the shale oil and shale gas from it. Material that touches the oil shale is 5 heated solids (heat-resistant balls, retorted oil shale and heated gas), the heat exchange between these heating materials and oil shale that wanted to be treated. When oil shale reaches the degree of 550°, the organic matters disintegrated onto shale oil and shale gas.
2.9.3 Third: The Combined Method: 10
This method combines the direct combustion and the indirect combustion (retorting ) methods. When the oil shale undergoes to the retorting processes, the shale oil and the shale gas can be extracted. The remainders organic matters undergo to direct combustion process to obtain extra heat used to rise the heating gas temperature and to generate the electric power. 15
2.9.4 Fourth: In-Site Retorting:
Wide mining operations are not needed; moreover, it is not required to extract the oil shale as the treatment operation is performed in the same location of the oil shale.
Specific surface area is determined, a group of wells dug geometrically (pumping wells and production wells), heat or heating materials is pumped into those wells to 20 heat the container layers of oil shale in the studied area. This is performed either thermally or electrically, upon arrival to the desired temperature, shale oil and shale gas move from the organic matters consisted in oil shale.
The essence of the process is injecting hot liquid materials and electric conductors to control the temperature. 25
Shell International conducted tests on three techniques from (ICP) that relies on the slow heating of the oil shale layers by heating poles. To prevent contamination of groundwater, the idea ice wall was invented to prevent oil leakage into the groundwater. Exxon Mobil leads the experience that depends on the hydraulic cracking, the cracks are filled with electrically conductor materials and then, high voltage is applied to heats the materials that contribute to exchange the heat between the conductor materials and the oil shale to reach the degree of the dismantling of the organic matters contained in the oil shale. 5
Schlumberger used a technique based on a combination of using radio frequencies (RF) in microwaves principle (Microwave idea) and critical gas (SCF) such as carbon dioxide, to heat the organic matters in the oil shale.
2.9.5 Fifth: Gaseous Smashing (Gas Ifcation):
The idea has not been applied, and still under discussion. It starts from converting the 10 solid fuels (coal and oil shale) into gas fuel with a high thermal content, and then this gas fuel is directed to electric power plants that work by the gas turbine or the combined cycle in order to produce the electric power.
2.9.6 Sixth: Extraction of the Organic Matters from the Oil Shale:
The organic matters contented from the kerogen (complex hydrocarbon) that does not 15 dissolve in solvents and the bitumen (mixed hydrocarbon) that dissolves in solvents.
The Kerogen is dealt with by the thermal decomposition only, which is the basis of dealing with all previous techniques that has been mentioned.
The bitumen is dealt with through the use of organic solvents, The possibility of reconciling of extracting the two materials is difficult, expensive and not possible to 20 be implemented mainly, when we think to supply the extracted fuel for the whole country, the problem lies in the fact that the boiling degrees of the solvents are different, in addition to that the kerogen dismantle needs to high temperature and high pressure and reconciling them is not possible. However, this technique succeeds when used for limited quantities (dissolve the carbon, then dissolve the silicates and 25 silica, and then separate the organic matters), but the cost is high-priced and even if achieved, it does not rise to meet the needs of a country of shale oil or shale gas.
Technological Methods to Extract Shale Oil from Oil Shale 2.10.1 First: In-Site Thermal Decomposition (In-Situ):
Similar to the gasification of coal method for the coal that is located in the ground, where we initially choose a specific area and drilling multiple wells, a group of these wells used to inject the hot material in and to apply high-voltage and the second group of wells are used to collect the produced shale oil and called the production wells.
The heating materials are injected into the first group of wells and then connected to high voltage to heat the oil shale layer electrically; the heating process progresses gradually, and the temperature rises to the level that the kerogen starts disintegrating and transformed into shale gas and shale oil. The produced shale gas and shale oil are gathered in production wells, and then pumped into the earth surface to be treated before being redirected to the refinery for refining and separating the components.
Advantages and disadvantages for in-situ method:
The advantages are listed below:
1- There are no negative impacts on the environment.
2- This technology can be applied in agricultural and residential areas.
3- The cost of extraction and transportation of oil shale rocks is not existed.
4- There are no ashes must be get rid of. and,
5- The ability of applying this technique to the oil shale that is located at abyssal depths.
And the disadvantages are listed below:
1 - The extraction technology is complicated.
2- The obtained oil must undergo to all processing steps that are performed over the extracted oil by other methods.
3- Shale impermeability and impenetrability, which makes the possibility of the removal of the oil through to be a difficult process.
4- The control of the heating process and increasing it gradually is difficult and complicated.
5- The possibility of oil and gas leakage through the cracks into groundwater basins, which contaminate it. 2.10.2 Second: Out-site thermal decomposition (Ex-situ):
This method is classified according to the position of heating materials and devices and according to the flow of oil:
2.10.2.1 Vertical Format (Oil Falls):
2.10.2.1.1 Nevada, Texas and Utah (NTV) method: 5
The oil shale is fed into two devices with 40 tones capacity each from the top, where the hot gas is fed as well to heat the oil shale continually till reaching to the temperature of kerogen dismantles, resulting to shale gas and the shale oil productions. The amount of air and the retuned gas are adjusted, while the thermal decomposition continues toward the bottom. At the bottom, the gas is condensed and turns to a liquid, the remaining gaseous section is directed to heat the oil shale producing more shale oil and shale gas. The shale gas is again redirected to heat new oil shale and these processes continuous periodically.
The disadvantages for this technique are listed below:
• The soft oil shale impedes the periodic movement of the gas.
• The formed coal gathers in the rewind oil equipments.
• This operation discontinuous.
• The production capacity is small.
2.10.2.1.2 UNION Oil Method: 20
The oil shale is crashed to pieces with dimensions of 0.5 inch to 2 inches. The heater height is up to 45 meters above earth surface. The shale oil is fed from the heater's exist and then inserted to the oil shale feeder. A compressor with diameter of 3 meters pushes the oil shale to the top of the heater. The gas is heated by an opposite stream of rotor gas that is inserted 25 from the top of the heater. This process continues till reaching the temperature of the kerogen disintegration, resulting to condensed oil that is gathered at the bottom of the heater. The consumed oil shale is then pushed out via a tunnel at the bottom of the heater. 2.10.2.2 Vertical Format (Oil Rises to the Top):
The shale enters continuously from the top to downward under the influence of gravity, the combustion area is near to air and gas distribution area, and then the steam rises towards the top to heat oil shale which falls toward the bottom The steam is directed to Sapklon then to a removal device and then to 5 electric precipitator. The oil shale fells from the top downward towards the bottom contributes to heat the interred air and gas, and finally, the gas is recycled continuously to take advantage of it.
The disadvantage of this method is the accumulation of forming the clinker.
2.10.2.2.1 Paraho Method: 10
The oil shale is crashed to pieces of dimensions of 0.25 inch to 3 inches to be fed from the top of the heater and distributed evenly by a rotor distributor. A mixture of gas and air enters to the heater from several places distributed over the entire heater walls; the gas inside the heater is then heated from bottom by the falling oil shale from the top. 15 The combination of the fog and steam-hydrocarbon move to an electric precipitator and then, the heat exchange between the hot steam and the cold oil shale is performed at the top to reduce the use of water.
210.2.3 Horizontal Position TOSCO 11:
The oil shale is heated inside a silo by a specific fluid, and then it is 20 moved to a horizontal heater to be heated by a hot ceramic. The consumed oil shale is then pushed over a sieve to get cooled and stored.
The cold ceramic passes over the sieve and be brought back to the heater by a crane, and finally the gas is condensed and then distilled; non-condensed gas used as fuel. 25 The advantages of this method are:
• Jetting quantity is large when compared to other methods.
• Good thermal efficiency.
• The production capacity is high.
• The heating process does not depend on the gas molecules as a 30 heat-bearer inside the device. • The heating process is performed from the outside, and the resulting gas has high heating content, which does not contain 2 or Cox. .3 The Combined Method:
This method is similar to NTU method but it is implemented under the ground 5 using multiple distillation processes which are performed in a huge silo using a horizontal cliff to rise from 15% to 20% of the oil shale that is somehow handled.
Several holes are drilled in the ground and then explosives are placed in these wholes; then detonated every periods of time, the device becomes full with rocks and in a shape of a narrow chimney. The empty volume of this chimney is equal 10 to the volume of the removed rocks. The broken rocks are supporting the walls and ceiling, but allows the flow of gas. Then the oil shale is burned from the top and the shale oil and shale gas ran in parallel towards the bottom where the cooling and condensation are performed in the lower areas, then the oil is pumped from the whole at the bottom. The remainder carbon from the cracking at the 15 combustion zone is burnt.
Finally, the section of the gas with low heat content value is returned to the top and burn to increase the heat needed for the cracking process. it can be noticed that this method is called combined method, because the oil shale which is near to the earth surface is processed using the out-situ method, while the 20 oil shale which is far from the earth surface is processed using the in-situ method. 1 Industrial Challenges:
• The extracted shale oil contains a high percentage of the chemical compositions of olefins (unsaturated hydrocarbon compounds) sometimes by up to 40% of the shale oil origin. 25
• The existing of a nitrogen ratio accounted about 2%, either in the free form or in the compound form, which plays a very negative role in the elimination of the role of the mediator, which is used in refining operations. • The sulfur exists in organic and inorganic forms which has a significant negative impact on the refining methods.
• The oil shale has sedimentary origin, when undergoes to thermal cracking processes, the extracted oil shale contains a high proportion of metals, that have a negative impact by eroding the mediators that used in the refining process.
• The boiling range of the oil shale is narrower, which is unlike the crude oil, when the shale oil subjected to the separation process, it is noted that it produces limited number of products, such as, naphtha and fuel oil, with limited quantity in shale oil.
• The density and viscosity of the oil shale are high, when compared with the density and viscosity of crude oil, resulting to different styles of shale oil refining processes to get the same final products of oil.
• During the process of thermal decomposition of the oil shale, the temperature of the oil shale rises in an atmosphere of Co, ¾o and ¾, however, sometimes just water is used to crack the inorganic matters to release the kerogen according to the temperature and pressure, which leads to the penetration of the water micro-molecules between the gas molecules and thus the possibility of separation becomes more difficult even when using the most precise methods.
• The acids, alkalis, sulphates, nitrates and hydrocarbon have fixed rates in the temperature range from 370° to 400°, but these rates change in a large scale in the temperature range of 475° to 525°, which is a clear indicator for the disintegration of these compounds.
• Regarding to the hydrocarbon, it has a fixed concentration when using the water to extract the organic matters at low temperature range. However, at the high temperature range; the situation is different, for example C28- C34 have higher concentration ratios t) Ci2-^C20 , which confirms the existence of thermal disintegration. • The constant of oxygen is content at the temperatures below 250°, when the temperature increases, content of oxygen starts decreasing due to the disintegration of the oxygenic compounds. At the temperature range above 350°; we notice that the rate of the disintegration increases. This can be seen through the decrease of the resin amount of and the increase in the amount of 5 the hydrocarbon in the shale oil, but this is associated with a significant increase in the quantities of the olefins.
• In the studied areas, it is noted that, there are two types of organic matters, bitumen and kerogen which shows the difference in the chemical composition of each of them. 10
• Different quantitative and chemical composition of organic matters as well as the inorganic section difference in the chemical composition, are the reason for the difference between the different types of oil shale and this is what prompted specialists to say that, each type of oil shale is in need for a particular pattern of treatment, and the extraction unit that is used to deal with 15 the Estonian oil shale, as an example, is not suitable to be used in processing the American oil shale, and that is justified by the previously mentioned factors.
• The distribution of organic matters and inorganic materials in the oil shale is non-regular and non-homogeneous which underlines the difficulty of 20 separating them. 2 Environmental Problems:
• Oil shale in its chemical composition contains high percentages of sulfur and nitrogen, so, when using the direct combustion to obtain the thermal energy stored in the oil shale; both of Sox and Nox are formed. 25
• Sox: Has a toxic effect on humans and animals, air and soil. For example; if this gas is emitted into the atmosphere under the rain, it forms H2S04, which affects the soil and on plant.
• Nox: If emitted in the atmosphere, it has several biological effects, for example, N02 affects the plants causing paleness and defoliation. Moreover, it 30 affects the respiratory system and mucous membranes of the organisms. No, affects to humans because it reacts with blood hemoglobin.
• Dust and high vibrations that are associated with the mining operation and extraction of the oil shale, in addition to the dust resulting from the treatment which cannot be controlled by using the electrostatic precipitators. 5
• Acids resulting from the process of oxidative stress when the extracted oil shale exposed to the sun and air; these compounds affect the human lives.
• Extracting large amounts of oil shale from one place may cause changing in the earth's layered structure, which could be associated with ground movements. 10
• Oil shale processing may be accompanied with emissions of different kinds of Cox.
• Massive amounts of water used during extracting the shale oil and shale gas treatment operations, which is considered as 4 m3 per 1 oil tone).
• Groundwater contamination problem is one of the biggest challenges facing 15 modern techniques that are based on processing of oil shale in place (in-situ).
• The destruction of the nature if the thickness of the oil shale layer is small, this factor decreases when the thickness of the oil shale layer increases.
2.13 Unjustified Challenges:
The oil shale is a renewable energy source which can meet a simple equation that 20 gives positive signals indicated in the circulation News of shale gas, and its entry as an equivalent energy alternative to bridge the strong lack of the needed energy. This equation is:
Oil Shale = coal + crude oil + natural gas
The present invention seeks to achieve and implement this equation in a commercial 25 production scale, according to economical and environmental standards which have been achieved. The practical research emphasizes the successes that have been achieved in the extraction of shale gas, which will be the right solution to the puzzle mentioned in the shale gas extraction.
At some point while ago, the price of a barrel of crude oil was equal to 180 U.S. cents, 30 and the cost of the refining was equal to 25 U.S. dollars. At a later stage, the price of a barrel of crude oil became equal 180 U.S. dollars and the cost of the refining was equal to 5 U.S. dollars.
Despite the high cost of oil barrel and fast acceleration in increasing the oil barrel's price, and the heavy daily bill and its impact on national income. When, however, we present the idea of investing over oil shale, this idea is faced by large magnitude of 5 disapproval because of the high initial investment in this area, which is estimated at about 2 billion U.S. dollars, the suffering story which begins with legislation difficulties, environmental considerations are complex, criticizing the use of huge amounts of water (4 m3 of water per 1 ton oil). For those criticizers, it should be asked: Are you forgetting or ignoring the fact that India, as an example of an average 10 consumer pays a bill of S 8 billion annually for the petroleum imported from SA in addition to the $ 4 billion U. S. dollar annually for the petroleum imported from Iran?
However, though 2 billion is not recognized as a big amount of money when compared with the cost of the used petrol; the investment in oil shale can cost no more than tens of Millions when it is directed to support one full city instead of the whole 15 country, which is the most suitable investment in the oil shale.
Yes the investment in oil shale costs far less than one month bill for the consumed petroleum in U.S. or China!
Regarding the use of huge amount of water; present invention experiment shows that there is no need for any amount of water in the processes of the oil shale treatment. In 20 fact, our method does produce the water as 40 liters to 60 liters per ltone of oil shale, and this amount of water is able to be treated to be used in agriculture feels.
Regarding the environmental impact, it is enough just to mention that the present invention method does not use the direct combustion in the treatment processes, and it is totally under the environmental stander limit. 25
And finally, it can be confirmed that the resulting ash is highly suitable to be used in cement industry as shale cement which is equivalent to the well-know Portland cement.
In the top of the above challenges, there is a challenge in the research pat; the research and development need to be in harmony of various disciplines which may be difficult 30 to reconcile with each other, the beginning is with Geology, accompanied by survey, followed by mining and oil followed by chemistry and environment linked to economy but another question needs to be asked: If the experience of direct combustion of oil shale (experiment Estonia - Station Narva) is leading, why do not we apply and generalize this experience over various places of the world, taking into 5 consideration the difference in quality between them and Estonian oil shale?
2.14 The wrong Idea
The direct combustion to this good quality kind of oil shale:
The Estonian oil shale kind is regarded as superior quality of the shale with heat content of 2800 kcal/kg and contains a very high organic material up to 40% of the 10 rock weight and with a large proportion of the oil can be extracted out of the organic material (up 26% of the rock weight). The oil shale with very low density compared to other rocks (an indicator of low proportion of inorganic materials).
2.14.1 Justifications for Resorting to the Direct Combustion Method:
Several practical problems appeared when extracting the shale oil in the Estonian 15 experiment, and these reasons were behind appearing the need of using the direct combustion method. One of the most important problems is that, the extracted shale oil contains a very high percentage of olefins, in addition to high percentage of the sulfur, nitrogen, oxygen and heavy metals therefore, cannot be directed to the refinery in order to separate the products, so, it is only used for direct combustion (ships fuel). 20 Moreover, the extracted oil at that time was marketed at a lower rate than the fuel oil, since the fuel oil did not have a commercial market at that time. There were other factors, such as, the small size of the heaters at that time, the very large number of labors, the absence of energy sources in the work area, the cost of a barrel of extracted shale oil which has no market at that time was very high when compared with the 25 price of a barrel of oil, the high economic cost of treatment operations at that time, and the environmental impact accompanied with the extraction, mining and treatment processing operations.
The present invention implemented experiment over the oil shale with heat content of 850 kcal/kg to 1585 kcal/kg shows such interesting results that emphasize that, it is 30 now the time for the Estonian wrong experiment to come to an end. With regarding to the in-situ shale oil treatment processes; this method requires limited mining operations that depend on injecting electrical conductor heating materials designed to heat the oil shale through the heat exchange process to extract the shale oil. This method achieves three main goals which are, reducing the economic cost of extracting barrels of oil, reducing the environmental impact 5 accompanied with the process of extraction, and the salvation of the problem of ash which results from the operation of extracting the shale oil from the oil shale.
2.15 The Raised Difficulties :
In the in-site treatment method, we face several problems, such as the following:
1 - The problem of groundwater contamination, and the associated ideas such as, 10 creating an ice wall around the place of the treatment process.
2- The extracted shale oil quality and its chemical compounds and if it is possible to send the extracted shale oil to the refinery for the refining and the separation of its components or just use if for direct combustion usage.
3- The proportion of the organic matters stored in the oil shale roughly 15 approaches 30% of the oil shale, which is the maximum amount of the oil shale that we can benefit form; so, is the process of exploitation of 30% of the oil shale covers the economic cost incurred with acceptable margin of profits?
4- When heating the earth layers that contain the oil shale and the associated heat exchange processes with the surrounding medium, it must be taken into 20 account the phenomena of global warming and climate change situations associated with the change of the earth temperature.
5- Cement industry depends on the following raw materials: limestone, containing calcium carbonate cac03, clay containing the aluminum oxide AL2O3, sand Silica containing silicon oxide containing Sio2, basalt containing 25 iron oxideFe203 and gypsum containing CaSo42H2o. Taking into account that 47% of the cement industry cost is the cost of the thermal energy for heating, wewhich are not taken into account. But when using the oil shale ash in the shale cement industry, this huge percentage and huge amount of the consumed heating energy are taken into account. 30 6- To understand the difference between the use of oil shale ash or not in the cement industry, we carefully examine the following example of a practical experiment:
The result of treatment on a mixture of oil shale that was extracted from Alsultani area in Jordan, with the lowest heat content from 850 kcal/kg to 5 1585 kcal/kg, the percentage of organic matter from 10% to 22% and the moisture content of 6% to 10%, the sulfur percentage range is from 0.5% to 2.8%.
The detailed results of this experiment are shown in table 4 below (products per one tone of oil shale): 10 Table4: The produced products from one ton of the oil shale.
Figure imgf000054_0001
The solid fuel that can be used to generate heat sufficient for the following industries: water desalination plants, textile industries, power generation, cement industry, glass industry and mining industries. Thus we confirm that we have achieved this slogan: 'The oil is more precious than to be burnt'. 15 The Present Invention's oil shale process technique:
In order to explain the present invention the following figures have been prepared. Explanation of the figures is below.
Fig.12: Thermal Dismantling Unit (the unit for oil shale processing to obtain final 5 product which are shale oil, shale gas, hot air, water, ash to produce high fuel and ash to produce high fuel residual)
Fig.13: Pulling, condensing and vacuum unit (the unit for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure)
Fig.14 : Gas pulling and liquidizing unit (the unit for extracting the shale gas in its 10 liquid form by pulling and liquidizing operations).
In order to explain the present invention better the features in the drawings have been numbered. Explanation of them is below.
Figure imgf000055_0001
13.1- Reactor
13.2- Compilingandcondensingvaporsofheavy components tower. 30 13.3- Intensification of Towerl
13.4- Intensification of To wer2
13.5- The distillatescollectiontankl
13.6- The distillates collection ank2
13.7- viscosity breaking tower
13.8- Vacuum tower
13.9- Vacuum pump
13.10- Gas gathering tank
13.11- Glassdisti Hates showing tower 1
13.12- Glassdistillates showing tower2
13.13- Centrifuge pump
13.14- Distillate liquidcollectiontank
14.1- Gas absorber device fromthereservoir
14.2- Pump fittedwithatwin-engines (pull andpush) 15
14.3- Heat Exchanger
14.4- Surveyor device
14.5- Kettle
14.6- Cooler -intensive
14.7- Accumulator of spraying: 20
14.8- Richgas entrance to be liquidized
14.9- Poor gasoutlet
14.10- LNG as a major product
Explanation of each item (element) shown in the Figures are
Thermal Dismantling Unit (Figure 12) for oil shale processing to obtain final product 25 which are shale oil, shale gas, hot air, water, ash to produce high fuel and ash to produce high fuel residual comprises the following elements.
Reactor (12.1.1) and furnace (12.1.2) unit (12.1): To heat the oil shale using the heating exchange methodto reach any temperature in between 600°C to 3500°C degrees. Butit works in between 600 °C to 950°C for processing the oil shale 30
Purification and combustion products ua hiii g unit ( 12 2) To purify th combustion gags and deposing the planktons. Turbine (pull - push combustion products) (12.3): To pull the combustion gases from inside the oven and then push it to the washing and purification unit.
Multi-stage heat exchanger and plankton precipitator (12.4): To spread the hot air over the usage fields, beside the help in precipitating the planktons.
Roasting, moisture pulling and oil shale drying unit (12.5): To dry the oil shale before inserting it to the oven.
Cooling and condensation unit which is related to the oil shale moisture (12.5): To condense the moisture gases to convert it into water.
Condensate water collection tank (12.6): To collect the condensed water inside it.
Nutrition unit entrance (roasting and drying unit) (12.7): To provide the oil shale to the roaster.
Centrifugation and pulling the washing outputs unit (12.8): To pull the water from the washing unit.
Centrifuge unit (pull, process, pushing) of the purified water (12.9): To purify the water and washing the gases planktons.
Treatment water collectiontank (12.10): To collect the washed water.
Combustionproducts exit afterpurification (12.11): The exit path of the treated combustion gases.
In reactor (12.1.2) and furnace (12.1.1) unit (12.1), oil shale placed in the reactor (12.1.1) are heated indirectly.Because the temperature in the reactor must not exceed 950 °C. Because the organic materials are burnt above 950 °Ctemperature and it is impossible to obtain any shale gas or shale oil at any temperature higher than 950 °C.
Pulling, condensing and vacuum unit (Figure 14) for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure comprises the following elements.
Reactor (13.1): To heat the oil shale in indirect way to reach any temperature in between600 to 950°C.
Compilingandcondensingvaporsof heavy components tower (13.2): To pull and condense the heavy materials.
Intensification of Towerl (13.3): To condense initial produced gages. Intensification of Tower2 (13.4): To condense the light gases. The distillatescollectiontankl (13.5): To collect the distillated liquids that condensed in
Tower 1.
The distillatescollectiontank2 (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. 5
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. 10
GlassdistiUates showing tower2 (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 liquidcollectiontank (13.14): To collect the liquids. 15
Gas pulling and liquidizing unit (Figure 14) for extracting the shale gas in its liquid form by pulling and liquidizing operations comprises the following elements.
Gas absorber device from the reservoir (14.1): To absorb the gas from the gas tank to prepare it to be liquefied.
Pump fitted with twin-engines (pull and push) (14.2): To pull the liquidized gas.
Heat Exchanger (14.3): To cool gas under liquidizing process. Surveyor device (14.4): To purify the gases from the joined liquids. Kettle (14.5): To initially heat the gas. Cooler -intensive (14.6): To cool the gas.
Accumulator of spraying (14.7): To wash the gases and to separate the liquids. Richgas entrance to be liquidized (14.8): The entrance of the gas that is under liquidizing process.
Poor gasoutlet (14.9): The outer of the poor gas. LNG as a major product (14.10): The liquidized gas.
5
Introduction:
Everything started with treating the oil shale as an expected rentable source of energy, so, after studying the available technologies for processing the oil shale, it was found that there are two main directions to deal with the oil shale:
First direction is the extraction the organic materials from the oil shale by using the 10 chemical solvents.
It was realized that the extracted organic materials when using this technique is not usable to extract the fuel as it is just complicated carbohydrate materials. Moreover, the price of the solvent is really high besides the difficulty of providing large quantities of this material enough to extract organic material for hundreds of 15 thousands of tons of oil shale per day.
The resulting ash from this technique is huge in quantity and cannot be used in the industrial field.
Then the second main direction of treating the oil shalewas taken, which is the direct combustion method. 20
It was found that this technique requires large and expensive mining operations, moreover, this technique needs such expensive burning system equipments. In summary, it can be added that; the resulting ash is huge in quantity and it is unusable in the industrial fields, the huge amount of water which is needed forthe combustion and the transfer operations, the huge evaporating operations that result in losing large 25 amounts of water during the process of power generation and the environment effect associated to the extraction operation is unacceptable. Based on above, the final conclusion was; to be able to deal with the oil shale in an investable miner; a new technique must be used to modify the old technique's problems and to be profitable in term of the expected capital that is needed to do so.
TheFisher scale was adopted in the scientific research work to determine the shale oil and the shale gas percentage contented in the oil shale. Moreover, it is realized that 5 the utilization of the oil shale with the proportion of organic matter of (25) % or below cannot be transformed into an investment project, as long as the cost of a barrel of shale oil extraction linked to the price of oil barrel. Accordingly, a device was developed handling (3) kg of the oil shale during (22) minutes to process the oil shale without using the direct combustion method to avoid using the oil as a source of the 10 thermal energy, and by auditing most of the data and analysis the results; building an industrial unit that can process (50 tons \ day) in a way totally unlinked to the oil was carried out. Through the standard operating;several technical challenges were faced to set (800 to 900) kg of the oil shale to be processed within (27 - 32) minutes.
It is important to emphasize that the chosen treatment temperature in our reactor is 15 between 600 °Cto 950°C; the reason we use only this range is the fact that the resulting shale oil at a temperature less than 600 °Cneeds to be directed to Hydrogenation process as its quality is poor and its quantity is small.
On the other hand, the organic materials burnt temperature is 950 °C, which means that it is impossible to obtain any shale gas or shale oil at any temperature higher than 20 this.
(3420) practical experiments were performed and then, all the results have been recorded and well investigated, and after all that work and results, the unique method to process the oil shale was confirmed. This technique runs from the mining extraction, based to mining warming and applied the principle of thermal dissociation. 25 Most importantly; this technique does not use the oil as the source of the thermal energy of the direct combustion; instead, the present invention uses the produced high fuel to continue the oil shale process without the need for the oil.
This means that the present invention's technology can process the averagequality kinds of oil shale with average thermal content to yield profit that exceeds the profit 30 when processing the high quality oil shale based on the principle of direct combustion treatment such as the Estonian oil shale process method.
The present invention'sraw material is the oil shale; the oil shale processing products are shale gas, oil shale, high fuel, high fuel residua, water and hot air.
The world's need to enormous amounts of clean energy, cheap and permanently available is the main gate to for the oil shale industry.
In parallel to producing the fuel as the primary products; the present inventionbeholds a promising future to meet the requirements of other industries' materials such as manufacturing (plastics, medicines, dyes, fertilizers, pesticides), in addition to well perform the famous slogan which says: 'the oil is more precious than to be burnt'.
This research is based on solid scientific facts which are:
• Chemical reactions get processes of (abandon - share - displacement - transmission - provide - forming) of an electron or more from the surface electrons of atoms among the combined materials. Accordingly, we distinguish between the two types of chemical reactions which are quickunidirectionalreactions and slawunidirectionalreactions.
• Starting from the oil extraction method by mining and rely on the thermal dismantling process to separate the biochemprong from the organic prong.
• Ensuring appropriate conditions for the forming of liquid and gaseous compounds of volatile vapors during the extraction process.
• The chemistry depends on the inorganic and organic industries, accordingly, the processes of treatment, extraction, separation and purification start from the science of chemistry, so, the oil shale with its raw compound materialsis regarded as an essential corner stone for these industries (organic and inorganic industries).
Research was carried out on the following stages:
To the Natural Resources Authoritywere applied to extract the amount of (10,000) tones of oil shale to be our experiment raw material. This requestwas approved by the authority, but that approval was conditioned with several requirements which are:
• Providing a plan to extract the requested (10,000) tones of the oil shale. • Submitting a plan to rehabilitate the site.
• Paying fees per (1 ) extracted ton.
• Submit a report to show the environmental impact assessment in accordance with the Jordanian Ministry of Environment standards.
• Providing a bank guarantee for the implementation of the business. 5
• Establishing a company to perform the business, and register this company with the Jordanian Ministry of Trade and Industry to oversee the implementation of the requirements.
All the above requestswere successfully carried out and the full amount of (10,000) tones of the oil shale was extracted, crashed, and then transported toMa'an 10 Development City (MDA) where a processing unit to perform the experiment process was built.
After renting a piece of land; the approvals related to import the industrial unit were obtained, which have been imported and interred to Jordan through Jaber border port and then declared in the center of Amman Customs to pay the required fees and 15 customs.
From the second industrial unit was approved and declared, to start the work it was moved to MDA. Engineering plans were developed for the construction of the industrial unit and the distribution of the units partial thereto over the working land.The standard operating processes began which were accompanied by extensive 20 modifications mainly in the development of oil shaletreatment mechanism. At the beginning, several mechanisms were used and all of them failed to give us the desired results that fulfill the high standard ambition. After performing several studies and recording the observations of unsuccessful applications all the failure in performance were studied and then further researches to develop a way for the optimum oil shale 25 setting mechanism inside the reactor were done and all the goals that helped approach the application stage were achieved. The optimum way is described by the way that gives the best outcome in termsof product amount and quality with regarding to the other side effects to be within the acceptable limit such as the environmental impact, the treatment time and cost. 30
The reason why the technique does not have any disastrous sequences even when applied in very wide range is the fact that the present invention performs the heating process which does not depend on pressure (which makes the possibilit of explosions to be nil), moreover, no solvents or catalysts materialsare used (which makes the possibility of dangerous reactions to be nil) during the components separation processes of the oil shale, finally, no enrichment operations are used and concentration of the shale before subjected to treatment which makes the technique 5 fully aware with the materials under treatment with no unexpected bad surprises.
Specifications of the oil shale used in theresearch experience:
The table below shows the specifications of the oil shale under the research:
Figure imgf000063_0001
The two tables below show the results of organic and non-organic chemistry lab tests 10 carried out on a sample of oil shale:
Table 1 : the results of organic chemistry lab tests carried out on a sample of oil shale.
Figure imgf000063_0002
Calorifie 774.5 1547.7 1598.
2026 1210 1221 1088 Value K Cal 8 2 5
C-organic
10.12 10.88 12.66 12.07 11.04 11.35 8.94 wt%
Total S wt% 1.15 2.64 2.94 2.05 1.36 1.43 1.4
Total H
1.27 1.84 1.97 1.73 1.61 1.67 1.25 wt%
Total C
19.76 16.08 21.18 23.74 20.39 20.68 20.75 wt%
Gas loss
5.26 3.97 5.76 5.95 4.84 2.64 1.84 wt%
Spent shale
88.2 84.45 82.94 82.63 86.64 86.64 90.22 wt%
Total oil wt% 4.74 8.85 10 9.67 9.34 9.3 7.34
Total waterwt% 1.8 3 1.3 1.75 1.40 1.60 1.2
Misturecontent
- - - - - - 0.66 mt%
From (m) 95 105 115 70 90 95 116
To To To To To To To To (m)
100 110 120 75 95 100 120
Sample 2130 2287 2292 2197 2211 2212 2153
Table 2: The results of non-organic chemistry lab tests carried out on a sample of oil shale.
Figure imgf000064_0001
L.O.I 26.5 45.2 43.20 45.4 46.5 46 46.3
K20 5.22 5.2 5.11 5.22 5.21 5.21 5.59
S03 2.8 1.37 1.87 .02 0.36 0.44 0.16
Na20 0.08 0.22 0.07 0.17 0.1 0.11 0.07
TvlgO 9.05 0.35 0.45 0.61 0.51 0.53 0.51
A1203 1.8 2.09 1.22 1.81 1.71 1.75 1.12
Si02 16.2 10.08 7.56 9.72 9.72 9.53 10
P2O5 2.16 0.99 2.97 1.72 1.66 1.72 0.86
CaO 28.5 29.8 41.5 36.9 37 37.8 45.5
Ti02 0.08 0.1 0.05 0.08 0.08 0.08 0.05
MnO 0.001 0.002 0.002 0.001 0.002 0.001 0.001
Fe203 0.71 0.79 0.44 75 95 100 0.57
From 105 115 95 70 90 95 116
To To To To To To To
To 110 120 100 100 95 75 120
Sample 2287 2292 2130 2212 2211 2197 2153
Operations to be carried out:
• Secondary crushing - screening - Screening the berries volume - packing - weight - assembly.
• Disposal of small volumes - the adoption of the ideal sizes (1.5-3) cm, 10 preferably approximately equal size to be gathered in the same tray.
• Heating the thermal disassembly unit using liquid fuel (1) until reaching the degree of (650 °C),using the liquid fuel is stopped (1) and using the high fuel till the end of the treatment is begun. So, the liquid fuel is used (1) to start the operation and its consumptionis estimated at (100 - 110) liters. Regarding the 15 high fuel; the used amount is not a problem as whenever a larger amount is burnt, raw materials for other industries are obtained. • When approaching the degree of dispersion (the degree where the organic maters start to be separated from the inorganic maters), the lid of the reactor (Fig.12.1) is opened to insert full trays of more oil shale by a crane, to be treatedinside the reactor (Fig.12.1), then the lid is closedagain and the process of mining extractionbegins.
• The quantity which is subjected to the treatment process is (820 - 890) kg of oil shale.
• Oil shale under treatment lasts for (27-31) minutes inside the reactor (Fig.12.1 ) to be fully treated.
There are several indicators to imply that the mineral extraction process is completed, where as the lid of the reactor (Fig.12.1) is opened by the crane to raise the group of trays. The trays then are placed in the isolation chambers.
When the extremely hot trays contact with air; a good care must be taken from the wary offorming a big flame, specifically when there is a high speed air currency.
After moving the hot trays to the isolation chambersto be isolated;the new full trays are entered into the reactor and afterclosing the reactor lid the new treatment processstarts again. This periodic process is being repeated again and again.
Example: In the mineral extraction operations; the required temperature is in the range of 600°C to 1000°C; while the temperature in the combustion center is 1450°C. So, any temperature can be achieved and controlled. So, this type of the high fuel can easily be introduced to the mining industries that require temperatures above of 2,000 degrees Celsius; all what is needed to achieve this is, to amend the additive materials to the ash and to modify the combustion system till achieving the temperature that is required to work under its limit.
When performing any test; the following operations must be implemented and monitored:
1- Tests: strict tests are performed for the burner, - towers - vacuum pumps - assisting pumps- cooling cycle - motors - high fuel mixer - crusher - sieve, by relying on sensors and pressure and temperature meters, and by using compressors (by pressing). - Readings: Readings should be taken for the meters of (electricity - water - liquid fuels (1 ) and liquid fuels (2)), and make sure of the amount of gas and oil in the compressors, cooling unit and a vacuum unit.
- Maintain all valves and make sure all the opening valves must be in opened condition as well as closing valves that must be in shut down condition. 5- Prepare suitable and measured quantity from the high fuel and configure it for the use.
- Prepare a balanced amount of oil shale to be subjected to the treatment process and distributed on trays, where the estimated quantity to the processed oil shale is from (800 to 870) kg and it is chosen with a good care to be from a 10 good quality.
- Start operating the burner which works with diesel, then the start operation point is recorded with the temperature of the furnace at that moment, keep monitoring and recording the temperature data that serve the experiment till the furnace temperature reaches to 600°C; when the temperature inside the 15 furnace is 600 °C, the high fuel is then provided to the furnace where the burner is completely stopped from the work.
- The high-pressure turbine works with a small frequency,whenever the temperature stops rising in the furnace; the air stream is then changed, and then continue refueling the furnace with the high fuel till reaching the 20 temperature of (800 to 850) Celsius degrees.
- Cooling cycle is early run to secure the amount of cold water which is estimated at 5 m3 and the temperature of cooling water is (2 to 6) ° C to be used in the cooling processes through the mineral extraction processes.
- When the furnace temperature approaching the degree of dispersion (800 to 25 850) Celsius degree (the degree to which the organic prong is separated from the inorganic prong), the reactor lid is opened and the oil shale bearer trays are then inserted into the reactor by the crane, the reactor lid is then closed, observing the reactor temperature which will decrease till it reaches a stable and fixed temperature. When the reactor temperature starts to raise again, the 30 high value of the pressure on the pressure meters is noted; accordingly, the pressure vacuum pumps are then run. In addition, the cold water pumps are then run and the heat exchange processes are observed between the volatile fumes and cold water. - There are physical indicators of the extraction completion such as temperature changes for the pulling tubes, pressure changes of vacuum meters and the stability of the pressure value at a certain value so that it does not rise beyond. - The reactor lid is opened by the crane; the trays are pulled and put in isolation roomsto avoid the resulting flame from contacting the hot trays to the air, so 5 they are totally isolated from the outside atmosphere.
- The reactor lid is then closed, and the new readings are taken for (electricity - water - liquid fuel (1)), and then the products are withdrawn, where the shale gas is gathered in the tank outside the unit, so the process of calculating the shale gas quantity is available and easy. The shale oil is measured while mixed 10 with the water, and then the mixture injected into glass towers of which the oil is separated from the water.
- The trays are then withdrawn from the isolation rooms and then weighed before being discharged. The weight before and after the treatment is matched; to make sure that the law of mass conservation and functioning of the energy 15 flow are maintained.
- The data relating to the operation of the experiment (furnace temperature changes - the amount of spent fuel - electricity consumed amount- the amount of water consumed, the amount of air) are provided. These amounts accurately referred to, and they are almost fixed in every experience, which is regarded as 20 a positive indicator of the accuracy and the success of the experiment.
- When the goal is to ensure the continuity and the stability of the products properties and maintaining its quality, and testing the high fuel to ensure its ability to perform its role in a proper way; new trays which are filled with the almost the same amount of oil shale are prepared; and then inserted into the 25 reactor. The same steps are repeated again. When performing the experiment, the following facts to verify the law of mass conservation should be taken into account: The time it takes to raise the temperature of the furnace from (20 to 600) °C is (120 to 130) minutes, the quantity of diesel consumed during this period (100 to 110) liters, the amount of electricity consumed is from 200 kw 30 to 220 kw,the amount of water consumed is estimated by 0 L, and the quantity of oil consumed is very limited and the oil is replaced after every 20 experiences. Modules ideal for processing oil shale that can treat from 1200 to 1300 tons per day have been designed and studied. The following table shows the quantities of oil shale to be processed and the products:
Figure imgf000069_0001
2.16 Processing Experiment of Poor Shale Oil (Germany):
This experiment is based on the direct combustion process, extracting 700 tons per day of oil shale from the mine; the extracted quantity is transformed to the cement plan by tracks to pass through the fallow treatment processes: cracking till obtaining 10 grains with dimensions of 10 mm, then pushed to the homogeneous mixing unit, and then the direct combustion at equal degrees. The obtained products from the direct combustion possess fixed specifications as it is used as one of the fundamental components of the cement. Thus, the units of mixing and homogenization are fed with the oil shale through the cracker and preparation unit. 15
This heterogeneous mixture is then fed into the furnace from the top with the necessary air to complete the burning. The air is processed by being pressed through jets distributors located on the perimeter of the furnace, to distribute the combustion on a regular basis in the entire furnace; even at the bottom.
The combustion of the oil shale operations are performed at temperatures of 800° to 20 850°, the surface of the combustion increases at the upper part of the oven, till the fully combustion process is performed. The high rates of heat transfer and turbulent movements inside the furnace lead to increase the oil shale temperature very quickly, leading to the ignition of oil shale and this requires feeding the furnace with additional quantities of combustion materials to maintain a constant temperature inside the furnace.
The heat in contact with the combustion gases coming out of the furnace is used in the production of steam through the boiler, which is connected with a generator and turbine.
Based on this construction to generate the electricity; we need 30 tons/h of water steam, steam temperature of 450° and steam pressure of 42 bar, to generate 3 Megawatt.
Products of the combustion are withdrawn from the bottom of the furnace, cooled and mixed with the soft parts that are associated to the combustion gases process, and then stored in silos attached to the manufacturer of cement, the result compounds are then milled and mixed with the clinker that is produced from the rotary furnace in the traditional way, as a result of these operations, shale cement is manufactured, which is equivalent to the well-known Portland cement.
Combustion products is characterized by the property of using the water as interaction intimidator due to the thermal conditions of the furnace, so an electrostatic deposition unit is needed for purifying the combustion gases before directing it to the chimney.
2.16.1 Factory Production
First: Oil shale cement: it is contented of 70% of clinker and 30% of the oil shale combustion products. The property of using the water as an interaction intimidator, of this type of cement are perfectly matched to the properties ofPortland cement at low amount of heat. The annual output of the plant is 300,000 tons.
Second: Road-paving materials: it is contented of 30% of clinker and 70% of the oil shale combustion products.
The economic data for this experiment are:
1- The ratio of the cement rock that is produced to the road paving material is (1 :1) which is equal to 200,000 tons each. 2- The heat content of the oil shale used in the combustion process is 950 kcal/kg.
3- The 1.45 kg of the oil shale gives 1 kg of the oil shale combustion products.
4- The 1.45 kg of the oil shale gives, 1 kg of the shale cement or 1 kg of road pavement materials, taking into consideration that, 1.45 kg of oil shale gives 5 when burned 1460 kcal.
5- The final yield of the power plant is 25% of the total generated power. Which is justified by the low heat content of the oil shale (950 kcal/kg), and the small size of the power station. Accordingly, the net amount of electricity generated from burning 1.4 kg of oil shale is 0.42 kilowatt-hour. 10
6- The amount of the required oil shale is (200,000 χ 1.45) tons per year and combustion products of 308,000 tons per year. The net amount of electricity generated is (200,000 χ 0.42)= 84,000 kilowatt-hour.
7- The power station plan consumes 10% of the generated power, so, the remaining amount of energy is 75600 MW/h, accordingly, the total generated 15 power is 11,7 MW when assuming that one working year is equal to 7200 working hours.
Finally, we should realize that the price of the 200,000 tons of the combustion products should cover the unfixed cost that is spent to produce the required clinker.
2.16.2 Conclusion of the Germany Experiment: 20
The shale oil used in this factory has two utilities; generating the necessary power for the operation of the plant, and raising the production capacity of cement plant.
Figure imgf000072_0001
Practical Experiments
3.1 Introduction
In this section, we show the former experiments that have been performed in Estonia and Germany, and then both are compared with the experiments of the present
invention. 5
3.2 Processing Experiment of Rich Shale Oil (Estonia):
It used the direct combustion method over rich oil shale, which was processed in the steam station No. 2, near the town of Narva in Estonia.
The station is the largest station ever that exploits the oil shale using the direct combustion processes method to generate the electric power. The electric capacity is 10 1600 Mw. The station includes eight groups; the generation capacity is 200 MW for each. The only source of energy available in the Republic of Estonia is the oil shale, which is extracted from surface mines with cover thickness of 2 meters and shale layer thickness of 2.75 meters. There are interface layers placed between oil shale layers. The oil shale is prepared in the mine in the form of blocks with dimensions of 15 (l x l x l) m. The block is then fed into a crasher; the dimensions of exited pieces is (25 x25x25) mm, which then fed to mills with hammers to leave as beads of dimensions 100 Micro meter to 200 Micro meter. The resulting power is then dried to get rid of the moisture before it is sent to the furnace, where the shale powder puffed into the furnace through eight distributors around the furnace. The temperature in the 20 furnace reaches 1400°, so, we need amounts of hot air (primary and secondary), water and steam to complete the combustion operation. The temperature of the steam when leaving the furnace is 450° and the pressure of 105 bars.
Reminders.
1) One kilowatt hours needs 3000 kcal of heat energy, regardless of the energy source. 25
2) One ton of oil shale costs 23 U.S. for extracting and mining operations. 3.2.1 Shale Specifications used in Direct Combustion Processes:
Heat content of: 2400 kcal/kg to 2800 kcal/kg.
Organic matter percentage in the oil shale: 32% to 36% of the oil shale weight.
Sulfur percentage: 1.8% to 2.8%.
Humidity: 12% to 16%. 5
The station consumption: 10 Million tons to 12 Million tons per year.
The station capacity: 9 billion kilowatt hours per year.
Average kilowatt hour per oil shale: 1.25 kg oil shale per kilowatt hour.
Station size: 300 hectares.
Ash storage space size: 1000 hectares. 10
The resulted shale oil ash from the direct combustion per year is estimated by 6 million tons, which are removed from the station using pumped water as means of transportation, and then deposited in specific locations.
The resulted ash from the direct combustion process is used in several areas such as:
Fertilizer to the soil to modify the acidity: 25%. 15
Block cements industry: 10%. Sand for construction work: 15%. Paving roads: 10%.
The remaining 40% is transported by water and stored in the outdoors.
Electrostatic precipitators used to purify the smoke produced by combustion 20 processes.
The amount of water needed to perform the overall mentioned operations are:
55 m3/s, we need 200000 m3/h for ash transport processes, and most of the quantity is recycled after the deposition. 0.45 m3/s, we need 40.000 m3/day to compensate the lost water in the operations.
5.5 m3/s, we need 20.000 m7h for the capacitors cooling system.
This is accurate information about the cost of production of 1 kWh of electricity and the accompanied requirements.
3.3 Processing Experiment of Poor Shale Oil (Germany): 5
This experiment is based on the direct combustion process, extracting 700 tons per day of oil shale from the mine; the extracted quantity is transformed to the cement plan by tracks to pass through the fallow treatment processes: cracking till obtaining grains with dimensions of 10 mm, then pushed to the homogeneous mixing unit, and then the direct combustion at equal degrees. The obtained products from the direct 10 combustion possess fixed specifications as it is used as one of the fundamental components of the cement. Thus, the units of mixing and homogenization are fed with the oil shale through the cracker and preparation unit.
This heterogeneous mixture is then fed into the furnace from the top with the necessary air to complete the burning. The air is processed by being pressed through 15 jets distributors located on the perimeter of the furnace, to distribute the combustion on a regular basis in the entire furnace; even at the bottom.
The combustion of the oil shale operations are performed at temperatures of 800° to 850°, the surface of the combustion increases at the upper part of the oven, till the fully combustion process is performed. 20
The high rates of heat transfer and turbulent movements inside the furnace lead to increase the oil shale temperature very quickly, leading to the ignition of oil shale and this requires feeding the furnace with additional quantities of combustion materials to maintain a constant temperature inside the furnace.
The heat in contact with the combustion gases coming out of the furnace is used in the 25 production of steam through the boiler, which is connected with a generator and turbine. Based on this construction to generate the electricity; we need 30 tons/h of water steam, steam temperature of 450° and steam pressure of 42 bar, to generate 3 Megawatt.
Products of the combustion are withdrawn from the bottom of the furnace, cooled and mixed with the soft parts that are associated to the combustion gases process, and then 5 stored in silos attached to the manufacturer of cement, the result compounds are then milled and mixed with the clinker that is produced from the rotary furnace in the traditional way, as a result of these operations, shale cement is manufactured, which is equivalent to the well-known Portland cement.
Combustion products is characterized by the property of using the water as interaction 10 intimidator due to the thermal conditions of the furnace, so an electrostatic deposition unit is needed for purifying the combustion gases before directing it to the chimney.
3.3.1 Factory Production
First: Oil shale cement: it is contented of 70% of clinker and 30% of the oil shale combustion products. The property of using the water as an interaction intimidator, of 15 this type of cement are perfectly matched to the properties ofPortland cement at low amount of heat. The annual output of the plant is 300,000 tons.
Second: Road-paving materials: it is contented of 30% of clinker and 70% of the oil shale combustion products.
The economic data for this experiment are: 20
8- The ratio of the cement rock that is produced to the road paving material is (1 : 1) which is equal to 200,000 tons each.
9- The heat content of the oil shale used in the combustion process is 950 kcal/kg.
10- The 1.45 kg of the oil shale gives 1 kg of the oil shale combustion products. 25
1 1 - The 1.45 kg of the oil shale gives, 1 kg of the shale cement or 1 kg of road pavement materials, taking into consideration that, 1.45 kg of oil shale gives when bumed 1460 kcal. 12- The final yield of the power plant is 25% of the total generated power. Which is justified by the low heat content of the oil shale (950 kcal/kg), and the small size of the power station. Accordingly, the net amount of electricity generated from burning 1.4 kg of oil shale is 0.42 kilowatt-hour.
13- The amount of the required oil shale is (200,000 χ 1.45) tons per year and 5 combustion products of 308,000 tons per year. The net amount of electricity generated is (200,000 χ 0.42)= 84,000 kilowatt-hour.
14- The power station plan consumes 10% of the generated power, so, the remaining amount of energy is 75600 MW h, accordingly, the total generated power is 11 ,7 MW when assuming that one working year is equal to 7200 10 working hours.
Finally, we should realize that the price of the 200,000 tons of the combustion products should cover the unfixed cost that is spent to produce the required clinker.
3.3.2 Conclusion of the Germany Experiment:
The shale oil used in this factory has two utilities; generating the necessary power for 15 the operation of the plant, and raising the production capacity of cement plant.
3.4 Processing Experiment of Average Oil Shale (Jordan):
This experiment based on the extraction of oil shale from the mine, and then subjected to mining and initializing operations before entering it to the processing unit to extract shale gas, shale oil and ash. 20
An application to the Natural Resources Authority had been submitted in the Hashemite Kingdom of Jordan to extract 10,000 tons of oil shale from Alsultani opened miner. Jordanian government required several things for the approval of the Action Plan, which are, obtaining the environmental impact assessment approval, submit the Action Plan for the extraction of the sample, and the rehabilitation of the 25 site after the extraction of the sample. The three requests had been implemented and the sample was extracted and transferred to the area of development in the Jordanian city of Ma'an. Experiments of the standard operation were carried out to adjust the industrial half unit operation processes that can handle 50 tons per day in order to implement a continuous experiment to be sure from the stability of the product 30 specifications drawn from the treatment processes. The main objective of this technique is to transform this scientific research project to an industrial project with commercial production economically viable and consistent with the environmental allowed standards for soil, water, air and life.
The strategic dimension of this technique is to achieve the following equation: 5 Oil shale = Coal + Crude oil + Natural Gas.
Based on the law of conservation of mass, which is derived from the law of conservation of energy, and the law of the determinants of energy which is based on energy conversion processes from one to another.
3.4.1 Specifications of the Oil Shale used in the present invention's 10 Experiment are:
Density: 2.1 to 2.6
Volumetric weight: 1.3 to 2.5 ton/m3.
Heat content of the oil shale:859kCal/kg to 1585 kCal/kg.
Organic matter percentage in the oil shale: 10% to 22% of the oil shale weight. 15
Sulfur percentage: 0.5 % to 2.8% of the oil shale weight.
Humidity: 6% to 10% of the oil shale weight.
Rigidity coefficient \ degrees a Yaconov recession: 6 to 9 degrees.
Durability limit at displacement: (17 to 78) x 10° Pascal.
Durability limit when the pressure: (170 to 920) χ 10° Pascal. 20 Durability limit when pull: (21 to 110) χ 10° Pascal.
Processes that are needed for the treatment process: extraction, transport, initial cracking, secondary cracking, packaging so that the dimensions of the grains is from 1.5 cm to 3 cm and preferably with equal dimensional, and then enter the unit of the thermal dismantling. The quantity of the treatment amount of the oil shale is 1 ton, 25 and the treatment period is from 22 minutes to 27minutes. We do not use any amount of water during the treatment process.
When we perform an experiment on approximately 1 ton of oil shale during the period mentioned above (22 minutes to 27 minutes), the products in table 5 are obtained:
Table 5: The obtained products from 1 ton using the present invention's technique. 5
Figure imgf000078_0001
When comparing the experiment of the present invention , which already have been implemented over an average quality oil shale, heat content of (850 to 1585) kcal/kg and the percentage of organic matter is from (10 to 22)%, the reliable results show that all of the products which are treated from 1 ton of oil shale give a total of 10 thermal energy estimated at 7.394 million kcal as shown in the main results table.
If the results have a direct comparison of energy resulting from the Esotnian experiment which is implemented over a superior quality (2800 kcal/kg and 40% organic matters), we note that the treatment for this type of high-quality of the shale give thermal energy with a total capacity of approximately 2,8 million kcal per ton for 15 all products derived by the direct combustion manner.
Clearly we can note the superiority of the present technology in oil shale processing and that do not use direct combustion. Indeed, with a much lower quality oil shale than the quality of the Estonian oil shale we got more than three folders of the thermal energy which better environment impact and cheaper treatment cost. Moreover, it is a vital point to proudly confirm that this experiment produces 40 to 60 liters of water, which is unlike the Estonian experiment which needs huge amount of water. In addition, the resulting ash from the present 5 invention is much better for the industry and less in the amount from the Estonian experiment.
Based on this direct and realistic comparison; it can confidently be said that it is advised and recommended that the Estonians direct combustion method of treatment should stop. 10
Finally, it is important to deduce that the burning of the sources of energy is not the only way and not necessarily to turn product sources of energy to heat energy, the wet gas shale can be directed to the areas of petrochemicals, shale oil is directly subjected to the refinery, and then its products are separated and directed to the industries of: Plastic, Fertilizers, Pharmaceuticals, dyes, and pesticides in addition to its use as a 15 fuel.
Leading improvement techniques in the oil shale
1- The remainder of the oil shale treatment process is around 56% to 86% of the weight of the rock which is nothing but ash. The quality of this ash has been the main impediment to deter the oil shale industry's progress. However, by 20 adding appropriate components to this ash to change into a solid fuel called High fuel, makes it possible to beused in the internal thermal energy in various industrial fields, from the water purification/desalination to the mineral industries.
2- The remainder from burning the high oil is then called high oil residual, which 25 is an important raw material for the manufacturing of cement and other building materials, if fact; settable additives can be added to the high oil at the first place to end up with ready clinker after burning the high fuel.
3- The economic feasibility of extracting oil and gas from shale is connected to the price of crude oil, and its various by-products (whether this involves the 30 on-site shallow treatment, or off-site treatment of oil shale). The price of extracting a barrel of oil shale has been totally segregated from the cost of the traditional energy sources and their by-products, thus confirming that the oil shale industry cannot succeed as long as it is dependent on the cost of extracting a barrel of petroleum.
- There is a lack of a focused inclination to invest in oil shale. Direct combustion, liquefaction, milling and distillation, and on-site and off location 5 treatment, are all options that have been put forth to heat oil shale. A method to treat oil shale has been developed, and its experience has succeeded in producing the following by-products: shale gas, shale oil, high fuel, high fuel residual, water and hot air.
- The methods normally used in the treatment of oil shale require consumption 10 of massive amounts of water. Techniques used for the treatment of oil shale do not consume any amount of water, in fact water is considered asa by-product of this treatment technique in term of 40 L to 60 L per 1 treated ton.
- The extracted shale oil by using different methods; whether it involves on-site or out-site extraction methods, is not sent to the refineries, is not used in the 15 petro-chemical industries, and is not fit for burning. In fact, it needs to be treated and stabilized;it's thermal standard is low, it is saturated with unstable active components, and it contains nitrogen elements, sulphur, and oxygen, in addition to various heavy minerals. Therefore, it must be put through a treatment unit prior to being refined to eliminate these components. Only then 20 can this be considered for a refining process. These problems have been successfully modified in the shale oil quality and type resulting to extracting such good quality of shale oil and shale gas which are very similar to the natural gas and petroleum in the Middle East. The present invention's shale oil can be immediately directed to the refinery in the same way the Middle East 25 oil is directed.
- The specifications of oil and gas shale, and high fuel, have been met in terms of quantity and quality. Water and energy consume a major portion of a country' s budget, and are considered the biggest challenge to the human race, Thus, based on the principles of energy flow, and those of safeguarding 30 energy, oil shale has been employed completely in industrial processes, in addition to the heat energy used, and the water that is extracted.
- The present invention has met the international criteria for scientific research, beginning with the Fisher Apparatus using lOOg of oil shale, and has identified a wide range of data about oil shale which has been proven. This was followed with an experimental apparatus that can treat up to 3kg, which participated in increasing the data base and proved vital values that can be depended on for the treatment process. This was an introduction to the building of a semi- industrial unit with the ability to treat one ton every 30 minutes. The treatment 5 processes were based on a scientific methodology that is also economically, as well as environmentally, feasible.
- When extracting oil shale, mining it and preparing it for treatment, the present invention does not undertake any enrichment processes, and does not use solvents in the treatment process, moreover, does not consume any water or 10 any gases such as (H20(9) - - C02 - CO) to separate the organic from the non-organic elements. The inventionbasesits technology from the method of the formation of the oil itself, and its migration to the final base.
0- The ideal time for the extraction of oil and gas from shale is 18-22 minutes for the quantity that is needed to treat it, irrespective of how much, and this is 15 relevant to the thermal dissolution unit which depends on the time of thermal energy exchange between the quantity of oil being treated and the dissolution unit. The invention then has a state of thermal stability after which it starts the extraction process, which ends with the production of (shale gas - shale oil - high fuel - high fuel residue - water and hot air). 201 - The techniques that are currently being used have failed to achieve the economic and environmental feasibility standards, and have therefore focused on developing heating methods, failing to segregate the process of extracting a barrel of shale oil, from the process of extracting a barrel of crude oil (petroleum). Additionally, these techniques have failed to prove the values 25 they have included in the economic feasibility studies that they presented. The reality of extracting a barrel of oil shale rises with the on-going cultural progress that people live.
2- The present invention on the other hand, is accurately able to prove and set the temperature at which organic elements separate from non-organic ones, and 30 has created the appropriate environment for the formation of the chemicals bonds between the weak radicals, which has made oil shale highly similar to crude oil, and shale gas similar to natural gas. - The way petroleum is formed is based on the presence of large amounts of organic matter, and the transformation methods (heat - pressure - the rotation of the earth), which are all elements that the present invention has benefitted from, with the major advantage of having the ability to distinguish between distillation under pressures, and distillation in a vacuum. 5- The treatment of oil shale, whether on-site or off-site,is undertaken using various heating methods to achieve a temperature of 400-500°C. Consequently the quality of the oil is close to the required specification, but different in terms of chemical structure. But the similarity in these methods is that the extracted oil cannot be sent to the refineries, and its drops separated, thus 10 having to go through a treatment process prior to being sent to the refinery. When using the present method of extraction and treatment of oil shale, there is no need for such a process, and the oil can be sent directly to the refinery, and the gas can be sent for immediate use, or directly to the condensation unit. The chemical analysis conducted on random samples of oil and gas, all prove 15 this, and show the specifications of each of them, and therefore the present inventionis able to determine the indicators for the fields in which they can be used, and their economic and environmental feasibility of the process.
- The current extraction techniques of separating organic from non-organic components involve the consumption of water in order to facilitate the release 20 of the kerosene, which is a major problem, because the small water particles seep into the particles of the oil, thus requiring a highly advanced method to separate them. As mentioned, this invention does not use water during the separation process, and depends on neither water nor air to eliminate the ashes.- The oil shale treatment units, and the direct burning of oil shale units treat 25 shale that has at least 1 OOOkcal/kg, and undertake enrichment processes to the oil shale so that can be treated. As for the American oil shale treatment units, for example, they need to be amended drastically for the treatment of Jordanian oil shale. Thistechnology can be used on all kinds of oil shale with a thermal energy of 750kcal/kg without having to make any amendments to the 30 treatment unit, because the metallic compounds carrying the organic matter have almost the same structural units, with the latter having the same metallic elements, which can have either a negative or a positive effect on the high fuel, and the high fuel residue, and limits the scopes in which high fuel can be used.
- Oil shale is impermeable and is an isolator that prevents the exchange of thermal energy. It must be broken in a certain manner and placed in a treatment unit in a specific way. Also the distance between the particles must 5 be equal and there should be smooth particles among these equal-sized particles. These factors helped in the transfer of thermal energy. All the particles of oil shale are equal until the oil and gas are extracted at the same time from all the particles. This data reflects on the mechanical extraction of the shale oil, and indicates the presence of a large quantity of organic matter 10 stored in the oil shale.
- The quantity and type of organic material extracted from oil shale depends on the temperature of extraction, and the time it takes to do so, in addition to the chemical and physical composition of the oil shale. There are no elements whose quantity or quality will change by changing the temperature or the 15 duration of the treatment, because at the degree of fixation, a complete separation between the organic and non-organic components will occur. The purpose of increasing the temperature will change the compound kerosene and the bitumen mixed in with it, to gaseous and liquid hydrocarbon, and thus there will no longer be between any difference in the chemical structure of the 20 kerosene and the bitumen.
- The present invention does not agree with the German experiment, but base this work on present experience which has proved that the treatment of oil shale can fulfill the requirements for energy and the shortage in cement, as well. In addition to providing the water and the energy necessary for the 25 industries that consume both water and energy for individual profits, and that have not impact on the development of the country. Saving water and energy means that the treatment of the oil shale should involve the same process of manufacturing cement, since high fuel changes into cement, without the need to have a separate cement-manufacturing entity, and the experience and 30 relevant analysis have proved this.
- In all ways of oil shale process; (spatial or out-situ) treatment methods; the only product that is taken advantage of it is the shale oil. The shale gas is burnt to be used to complete the heating processes which are required in the oil shale process. Taking into consideration that this oil is in need for tough hydrogenation process to be ready to sent to the refineries. In our proposed thermal dismantling method; the resulting products are shale gas, shale oil, water, ash, high fuel, high fuel residual and hot air, while the oil does not need hydrogenation process, so, it is sent directly to refineries. 5- Processing of oil shale in the direct combustion method depends on the consumption of water in huge varying amounts, mainly when it is used for electric power generation. In our proposed technique, the water is produced rather than consumed.

Claims

1- Oil shale dismantling process in order to transform any quality oil shale into directly refinable shale oil and to shale gas equal to natural gas, without using oil for temperature rise and without using water for cooling system, resulting 5 in ash production where the ash could be transformed into high fuel by adding organic and non organic additives and ash of burned fuel is used as other industrial products such as clinker, insulation material and as a by product producing water and hot air; comprising; mining, transforming, crushing, separation, packaging, weighting, processing, and dissolution and 10 characterized in that;
• the dismantling process is conducted in between 600 °C and 950 °C,
• shale gas, shale oil, water and hot air are extracted separately after the step of dissolution,
2- Oil shale dismantling process as claimed in Claim 1, and characterized in that 15 shale gas and water vapour are separated by using vacuum pump to be directed to in condenser, after the condenser the shale oil and the water are liquidised while the gas has been directed to gas tank.
3- Oil shale dismantling process as claimed in Claim 1 and characterized in that shale oil is separated from the water by using separation tower and water is 20 directed to the water tank.
4- Oil shale dismantling process as claimed in Claim 1 and characterized in that the hot air is pulled from the oven and directed to the purification unit, after that the hot air is directed to the heat exchange unit.
5- Oil shale dismantling process as claimed in Claim 1 and characterized in that 25 the remaining ash is treated by adding organic and non-organic additives to obtain high fuel to be used as thermal energy source.
6- Oil shale dismantling process as claimed in Claim 1 and characterized in that the ash obtained after burned high fuel is used in industry such as clinker, thermal insulation material, building material industry, thermal isolation 30 industry, road pavement industry, and sand stabilization materials. 7- Oil shale dismantling process in order to transform any quality oil shale into directly refmable shale oil and to shale gas equal to natural gas, without using oil for temperature rise and without using water for cooling system, resulting in ash production where the ash could be transformed into high fuel by adding organic and non organic additives and ash of burned fuel is used as other 5 industrial products such as clinker, insulation material and as a by product producing water and hot air; comprising; mining, transforming, crushing, separation, packaging, weighting, processing, and dissolution and characterized in that the process is operated by the units of;
• Thermal Dismantling Unit for oil shale dismantling process to obtain final 10 product which are shale oil, shale gas, hot air, water, ash to produce high fuel and ash to produce high fuel residual
• Pulling, condensing and vacuum unit for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure, 15
• Gas pulling and liquidizing unit for extracting the shale gas in its liquid form by pulling and liquidizing operations.
8- Thermal Dismantling Unit for oil shale dismantling process to obtain final product which are shale oil, shale gas, hot air, water, ash to produce high fuel and ash to produce high fuel residualas claimed in Claim 7, characterized in 20 that it comprises;
• Reactor (12.1.2) and furnace (12.1.1) unit (12.1): To heat the oil shale using the heating exchange method to reach any temperature in between 600 °Cto 3500°C, but working in between 600°C to 950°C for processing the oil shale. 25
• Purification and combustion products washing unit (12.2): To purify the combustion gags and deposing the planktons.
• Turbine (pull - push combustion products) (12.3): To pull the combustion gases from inside the oven and then push it to the washing and purification
30 unit.
• Multi-stage heat exchanger and plankton precipitator (12.4): To spread the hot air over the usage fields, beside the help in precipitating the planktons • Roasting, moisture pulling and oil shale drying unit (12.5): To dry the oil shale before inserting it to the oven.
• Cooling and condensation unit which is related to the oil shale moisture (12.5): To condense the moisture gases to convert it into water.
• Condensate water collection tank (12.6): To collect the condensed water inside it.
• Nutrition unit entrance (roasting and drying unit) (12.7): To provide the oil shale to the roaster.
• Centri I ligation and pulling the washing outputs unit (12.8): To pull the
10 water from the washing unit.
• Centrifuge unit (pull, process, pushing) of the purified water (12.9): To purify the water and washing the gases planktons.
• Treatment water collection tank (12. 10): To collect the washed water.
• Combustion products exit after purification (12. 1 1 ): The exit path of the
15 treated combustion gases.
9- Pulling, condensing and vacuum unit for extracting the shale gas, shale oil and water by pulling, condensing and vacuuming operations at low pressure as claimed in Claim 7, characterized in that it comprises;
• Reactor (13.1): To heat the oil shale in indirect way to reach any 20 temperature in between 600 °Cto 950°C.
• Compiling and condensing vapors of heavy components tower (13.2): To pull and condense the heavy materials.
• Intensification of Towerl (13.3): To condense initial produced gages.
• Intensification of Tower2 (13.4): To condense the light gases. 25
• The distillates collection tankl (13.5): To collect the distillated liquids that condensed in Tower 1.
• The distillates collection tank 2 (13.6): To collect the distillated liquids that condensed in Tower 2.
• Viscosity breaking tower (13.7): To condense the maximum possible 30 amount of gases.
• Vacuum tower (13.8): To collect the gases which are corning 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.
10
10- Gas pulling and liquidizing unit for extracting the shale gas in its liquid form
by pulling and liquidizing operations claimed in Claim 7, characterized in that it comprises;
• Gas absorber device from the reservoir (14.1): To absorb the gas from the gas tank to prepare it to be liquefied.
• Pump fitted with twin-engines (pull and push) (14.2): To pull the liquidized gas.
• Heat Exchanger (14.3): To cool gas under liquidizing process.
• Surveyor device (14.4): To purify the gases from the joined liquids.
• Kettle (14.5): To initially heat the gas.
• Cooler -intensive (14.6): To cool the gas.
• Accumulator of spraying (14.7): To wash the gases and to separate the liquids.
• Rich gas entrance to be liquidized (14.8): The entrance of the gas that is under liquidizing process.
• Poor gas outlet (14.9): The outer of the poor gas.
• LNG as a major product (14.10): The liquidized gas.
PCT/TR2013/000319 2013-10-11 2013-10-11 High range temperature thermal dismantling method in processing oil shale WO2015053721A1 (en)

Priority Applications (23)

Application Number Priority Date Filing Date Title
PCT/TR2013/000319 WO2015053721A1 (en) 2013-10-11 2013-10-11 High range temperature thermal dismantling method in processing oil shale
EA201690568A EA201690568A1 (en) 2013-10-11 2014-05-13 USE OF PROCESSED Clay shale OR ASH, OBTAINED BY DECOMPOSITION OF OIL SHAFT, WITH ADDITION OR WITHOUT THEM IN THE FORM OF SOLID FUEL
CA2926955A CA2926955A1 (en) 2013-10-11 2014-05-13 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel
CA2926952A CA2926952A1 (en) 2013-10-11 2014-05-13 A thermal dismantling unit and a high temperature furnace
CN201480058816.8A CN105765051A (en) 2013-10-11 2014-05-13 High range temperature thermal dismantling method in processing oil shale
EA201690569A EA201690569A1 (en) 2013-10-11 2014-05-13 METHOD OF HIGH-TEMPERATURE THERMAL DECOMPOSITION IN THE PROCESSING OF OILBOXY SHAFTS
PCT/TR2014/000163 WO2015053723A1 (en) 2013-10-11 2014-05-13 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel
US15/028,027 US20160251577A1 (en) 2013-10-11 2014-05-13 Thermal dismantling unit and a high temperature furnace
CN201480058561.5A CN105745308A (en) 2013-10-11 2014-05-13 Thermal dismantling unit and high temperature furnace
CN201480060382.5A CN105722952A (en) 2013-10-11 2014-05-13 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel
PCT/TR2014/000162 WO2015053722A1 (en) 2013-10-11 2014-05-13 A thermal dismantling unit and a high temperature furnace
EP14742607.6A EP3055384A1 (en) 2013-10-11 2014-05-13 A thermal dismantling unit and a high temperature furnace
US15/028,030 US20160251578A1 (en) 2013-10-11 2014-05-13 High range temperature thermal dismantling method in processing oil shale
EP14742608.4A EP3055404A1 (en) 2013-10-11 2014-05-13 High range temperature thermal dismantling method in processing oil shale
AU2014332590A AU2014332590A1 (en) 2013-10-11 2014-05-13 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel
CA2926956A CA2926956A1 (en) 2013-10-11 2014-05-13 High range temperature thermal dismantling method in processing oil shale
PCT/TR2014/000164 WO2015053724A1 (en) 2013-10-11 2014-05-13 High range temperature thermal dismantling method in processing oil shale
EA201690566A EA201690566A1 (en) 2013-10-11 2014-05-13 INSTALLATION OF THERMAL DECOMPOSITION AND HIGH-TEMPERATURE OVEN
EP14741996.4A EP3055383A1 (en) 2013-10-11 2014-05-13 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel
US15/028,029 US20160236977A1 (en) 2013-10-11 2014-05-13 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel
AU2014332589A AU2014332589A1 (en) 2013-10-11 2014-05-13 A thermal dismantling unit and a high temperature furnace
IL244994A IL244994A0 (en) 2013-10-11 2016-04-10 High range temperature thermal dismantling method in processing oil shale
IL244996A IL244996A0 (en) 2013-10-11 2016-04-10 Use of spent shale or ash obtained from oil shale dismantling methods with or without additives as solid fuel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/TR2013/000319 WO2015053721A1 (en) 2013-10-11 2013-10-11 High range temperature thermal dismantling method in processing oil shale

Publications (1)

Publication Number Publication Date
WO2015053721A1 true WO2015053721A1 (en) 2015-04-16

Family

ID=49880914

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2013/000319 WO2015053721A1 (en) 2013-10-11 2013-10-11 High range temperature thermal dismantling method in processing oil shale

Country Status (1)

Country Link
WO (1) WO2015053721A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104833787A (en) * 2015-05-29 2015-08-12 沈阳煤层甲烷气开发中心 Shale sample smashing desorption device
CN107356498A (en) * 2017-05-18 2017-11-17 江苏中能科研仪器发展有限公司 A kind of heavy oil wells viscosity reducing test device
CN109682713A (en) * 2019-02-21 2019-04-26 吉林大学 A kind of oil content of oil shale apparatus for automatically measuring and measuring method
CN113254854A (en) * 2021-06-04 2021-08-13 中国电建集团成都勘测设计研究院有限公司 Method for measuring and calculating natural volume weight of giant-grained soil

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1396018A (en) * 1971-09-06 1975-05-29 Petroleo Brasileiro Sa Pyrolysis of oil-containing materials
US4069132A (en) * 1975-11-12 1978-01-17 Union Oil Company Of California Oil shale retorting process with desulfurization of flue gas
CA1251133A (en) * 1983-01-20 1989-03-14 Walter Kaminsky Method of recovering oil and gas from oil sand, oil chalk, and oil shale

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1396018A (en) * 1971-09-06 1975-05-29 Petroleo Brasileiro Sa Pyrolysis of oil-containing materials
US4069132A (en) * 1975-11-12 1978-01-17 Union Oil Company Of California Oil shale retorting process with desulfurization of flue gas
CA1251133A (en) * 1983-01-20 1989-03-14 Walter Kaminsky Method of recovering oil and gas from oil sand, oil chalk, and oil shale

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104833787A (en) * 2015-05-29 2015-08-12 沈阳煤层甲烷气开发中心 Shale sample smashing desorption device
CN107356498A (en) * 2017-05-18 2017-11-17 江苏中能科研仪器发展有限公司 A kind of heavy oil wells viscosity reducing test device
CN109682713A (en) * 2019-02-21 2019-04-26 吉林大学 A kind of oil content of oil shale apparatus for automatically measuring and measuring method
CN109682713B (en) * 2019-02-21 2024-04-19 吉林大学 Automatic determination device and determination method for oil content of oil shale
CN113254854A (en) * 2021-06-04 2021-08-13 中国电建集团成都勘测设计研究院有限公司 Method for measuring and calculating natural volume weight of giant-grained soil
CN113254854B (en) * 2021-06-04 2022-07-26 中国电建集团成都勘测设计研究院有限公司 Method for measuring and calculating natural volume weight of giant-grained soil

Similar Documents

Publication Publication Date Title
US20160251578A1 (en) High range temperature thermal dismantling method in processing oil shale
Speight The chemistry and technology of coal
Gosselin et al. Environmental and health impacts of Canada’s oil sands industry
Speight Shale oil production processes
Goraya et al. Coal bed methane enhancement techniques: a review
Roussak et al. Applied chemistry: a textbook for engineers and technologists
Speight Handbook of natural gas analysis
WO2015053721A1 (en) High range temperature thermal dismantling method in processing oil shale
Speight et al. Peak Energy: Myth Or Reality?
Dufour The Costs and Implications of Our Demand for Energy: A Comparative and comprehensive Analysis of the available energy resources
Gong et al. Study on the migration characteristics of As, Pb, and Ni during oily sludge incineration with CaO additive
Hanif et al. Renewable and Alternative Energy Resources
Wang et al. Analysis of Pyrolysis Characteristics of Oily Sludge in Different Regions and Environmental Risk Assessment of Heavy Metals in Pyrolysis Residue
Cui et al. Hydrothermal treatment of the pristine and contaminated Cd/Zn hyperaccumulators for bio-oil production and heavy metal separation
Hu et al. Influence of water-rock interaction on the pH and heavy metals content of groundwater during in-situ oil shale exploitation
Gharaibeh Environmental impact assessment on oil shale extraction in Central Jordan
AU2014332591A1 (en) High range temperature thermal dismantling method in processing oil shale
Abu-Hamatteh et al. An overview of the Jordanian oil shale: its chemical and geologic characteristics, exploration, reserves and feasibility for oil and cement production
Jia et al. Advancements and Environmental Implications in Oil Shale Exploration and Processing
Nov et al. Neutralization of Acidic Industrial Wastes and Fixation of Trace Element by Oil Shale Ash: Formation of a Green Product
Coyle et al. Reflections on Energy, Greenhouse Gases, and Carbonaceous Fules
Mulvaney et al. Energy and the environment I: Fossil Fuels
Chatterjee Uses of energy, minerals and changing techniques
Nov et al. Treated Oil Shale Ashes as Cement and Fine Aggregates Substitutes for the Concrete Industry
Archer et al. Metallic Wastes into New Process Catalysts: Life Cycle and Environmental Benefits within Integrated Analyses Using Selected Case Histories

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13812205

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 05.08.2016)

122 Ep: pct application non-entry in european phase

Ref document number: 13812205

Country of ref document: EP

Kind code of ref document: A1