US20090308793A1 - Activation, refining, and use of oil shale - Google Patents

Activation, refining, and use of oil shale Download PDF

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US20090308793A1
US20090308793A1 US12/375,156 US37515607A US2009308793A1 US 20090308793 A1 US20090308793 A1 US 20090308793A1 US 37515607 A US37515607 A US 37515607A US 2009308793 A1 US2009308793 A1 US 2009308793A1
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oil shale
activated
activation
shale
oil
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Pieter Gideo Van Der Merwe
Hassan Hannache
Omar Bekri
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Nanotech Investment 2 Pty Ltd
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Assigned to NANOTECH INVESTMENT 2 (PTY) LTD reassignment NANOTECH INVESTMENT 2 (PTY) LTD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BEKRI, OMAR, HANNACHE, HASSAN, VAN DER MERWE, PIETER GIDEO
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    • 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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/047—Hot water or cold water extraction processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives

Definitions

  • the invention relates to the fields of the production and use of adsorbent materials. More particularly, it relates to the activation, refining, stabilisation, and use of oil shale as an adsorbent.
  • adsorbent By far, the most widely used type of adsorbent materials are “activated” carbon products (the use of the terms “adsorbent” and “adsorption” herein include respectively any type of sorbent or sorption).
  • Activated carbon is made from a substance having high carbon content—such as coal, wood and nut shells—by treating it to create many tiny pores between the carbon atoms. Due to this porosity, the activated carbon has a very large surface area per unit volume (i.e., specific surface) allowing it to be used to adsorb a variety of substances from gases or liquids. For instance, activated carbon is used in gas purification, metal extraction, water purification, medicine, sewage treatment, air filters and many other applications. The activation process typically involves some type of thermal and/or chemical treatment. For example, carbon-based material may be converted to activated carbon by thermal decomposition in a furnace using a controlled atmosphere and heat.
  • activated carbon's adsorption properties for some materials are not sufficiently strong.
  • the raw materials needed to produce activated carbon may be costly and/or time consuming to obtain.
  • Oil shale is a general term applied to a fine-grained sedimentary rock containing significant amounts of kerogen (a solid mixture of organic chemical compounds).
  • kerogen a solid mixture of organic chemical compounds.
  • a vapor is driven off which can be distilled or retorted to yield a petroleum-like shale oil and a combustible hydrocarbon shale gas.
  • the thermal decomposition of oil shale in the absence of oxygen typically occurs between 250 and 550° C. Oil shale can also be burnt directly as a low-grade fuel for power generation.
  • Oil shale has been proposed for use as an adsorbent in various different states.
  • U.S. Pat. No. 1,676,151 describes that residue from oil shale distillation may be used to remove impurities from waste waters produced during distillation.
  • This residue typically referred to as “spent” or retorted shale, is the solid material remaining after the retorting of the oil shale.
  • Spent shale still contains organic carbon (residual carbon) and is often burned to produce energy used for the retorting of raw shale.
  • Oil shale ash is produced by burning oil shale or spent shale.
  • activated oil shale in a manner similar to the activation of carbon, in order to obtain highly adsorbent materials for a variety of industrial and environmental applications.
  • activated oil shale has been treated in order to carbonize the carbon matter and to decompose a portion of the mineral matter thereby to create a porous body having an active surface area.
  • Table 1 shows a specific example of differences between raw, spent and activated oil shale:
  • A The spent shale is the solid residue remained after the retorting of oil shale. In this example, 20 to 30% of the initial organic carbon is left in the spent shale is (residual carbon). Some processes like “Hytort” use pressurized Hydrogen (tens of bars) to transform the maximum amount of carbon into oil vapor further reducing the quantity of residual carbon.
  • B 85% of the Organic Carbon is left in this thermally activated oil shale. The 15% reduction is due to release during the thermal treatment and would typically be recovered as hydrocarbon gases and light oil and used as fuel for the heating of the raw oil shale.
  • C & D The amount of organic carbon actually increases due to the loss of the mineral matter during the activation process(es).
  • activated oil shale boasts considerable potential as a new adsorbent material, in many cases with adsorption properties that are significantly superior to activated carbon. Furthermore, because oil shale resources in many parts of the world are vast and largely unexploited, the necessary raw material for these adsorbents is in many cases widely and inexpensively available.
  • an oil shale activation process including one or more process steps selected from:
  • the transformation of the mineral matter may include carbonate decomposition.
  • the oil shale activation process may include a refining step in which undesired species such as unconverted organic material, N, S, H, and O are reacted in the activated oil shale by means of ion beam irradiation of activated oil shale thereby to increase the specific surface area active for adsorption.
  • undesired species such as unconverted organic material, N, S, H, and O are reacted in the activated oil shale by means of ion beam irradiation of activated oil shale thereby to increase the specific surface area active for adsorption.
  • the oil shale activation process may include a stabilization process which includes contacting the oil shale with distilled de-ionized water by recirculative extraction.
  • stabilization processes may include:
  • an oil shale activation process comprising exposing oil shale to be activated to electromagnetic radiation to carbonize a portion of organic matter and transform a portion of mineral matter in the oil shale resulting in generation of gases within the oil shale thereby creating pores inside the oil shale.
  • the oil shale may be in the form of particles having a particle size of from 0.1 mm to 200 mm, typically from 1 mm to 10 mm.
  • the electromagnetic radiation may be so called microwave radiation, typically at a frequency of 2450 MHz.
  • the oil shale may be exposed to the electromagnetic radiation for a period of from 1 s/g to 60 s/g, or more depending on the specific oil shale, particle size, and frequency.
  • the intensity, or power, of the electromagnetic radiation may be from 1 W/g to 20 W/g, depending on the chemical and physical properties of the oil shale, and the period for which the oil shale is to be exposed to the radiation.
  • the exposure time is from to 2 to 4 s/g, more typically 3 s/g.
  • the pores may be created homogeneously throughout an oil shale particle.
  • the electromagnetic activation process may be a step in a multi-step activation process.
  • the electromagnetic radiation may be ultraviolet radiation, RF plasma radiation, or any other suitable type of electromagnetic radiation.
  • a thermal oil shale activation process including contacting oil shale with steam at a temperature of from 150° C. to 1000° C., typically from 250° to 900° C.
  • the thermal activation process may be carried out with steam at a temperature of from 500° C. to 1000°.
  • thermal activation may be carried out with steam at 900° C.
  • the oil shale may be in the form of particles having a particle size of from 0.1 to 5 mm, typically from 0.5 mm to 2 mm.
  • the contact time for the oil shale and steam may be from 120 s to 3600 s, typically from 240 s to 1800 s. Usually the contact time will be 600 s.
  • the contact time is a function of the steam temperature and the oil shale particle size.
  • the thermal activation process may be a step in a multi-step activation process.
  • the thermal activation process may be carried out in combination with another activation process.
  • a chemical oil shale activation process including contacting oil shale with inorganic base compounds thereby to transform at least a portion of organic matter and/or carbonates in the oil shale creating and/or opening pores inside the oil shale.
  • the inorganic base compounds may be selected from the group including, but not limited to, sodium hydroxide and potassium hydroxide.
  • the particle size of oil shale to be activated chemically ranges from 0.1 to 10 mm typically from 0.5 to 2 mm.
  • the contact time for the oil shale may be from 7200 s to 43 200, typically from 10 800s to 18 000s.
  • the mixture may be followed by a thermal treatment at a temperature ranging from 200 to 500° C. for a period of from 1800 s to 10 800 s, typically at 250° C. for 3600 s to 7200 s.
  • the contact time is a function of the inorganic compound used, the temperature, and the oil shale particle size.
  • the effectiveness of the activation of the oil shale is a function of the particle size of the oil shale, the type of inorganic compound used, the concentration of said inorganic compound, the temperature at which the process is performed, and the residence or treatment time of the oil shale by the process.
  • the chemical activation process may be a step in a multi-step activation process.
  • the chemical activation process may be carried out in combination with another activation process, typically one or more of thermal and electromagnetic activation.
  • an activated shale refining process including irradiating activated oil shale with an ion beam to reduce uncarbonized organic material, N, S, H, and O thereby to increase the specific surface area active for absorption and/or adsorption.
  • the ion beam irradiation may be oxygen ion beam irradiation.
  • the ion beam irradiation may be carried out at from eV 50 to eV 1000 and from 20 to 500 ⁇ A/cm 2 .
  • an oxygen ion beam at eV 200 and 200 ⁇ A/cm 2 is used.
  • the thus treated activated oil shale has in excess of 90 mass % Carbon, typically in excess of 95 mass % and an increased specific absorption rate. This means that the oil, shale is enriched in active carbon sites in comparison to unrefined activated oil shale.
  • the specific adsorption rate per gram of adsorbent may be increased over unrefined activated oil shale by at least 5%, typically in excess of 8%.
  • a stabilization process for activated and/or refined oil shale including contacting the oil shale with a solvent by recirculative extraction.
  • the stabilization process may include the dissolving of mineral compounds from the activate oil shale with heated extraction solvent.
  • the dissolving may be carried out by recirculative extraction with hot water and steam, such as that performed in a Soxhlet extractor.
  • the heater extraction solvent may be demineralised water, typically de-ionised distilled water.
  • the stabilization process may include dissolving the mineral compounds destabilized during the activation of oil shale from the activated oil shale with heated extraction solvent.
  • the stabilized activated oil shale doesn't has a reduced leaching phenomenon when used as an adsorbent in contact with polluted water.
  • distilled water is water which has been evaporated and recondensed and which includes minerals and other ions.
  • De-ionised water is water, whether distilled or not, which has been passed through an ion exchanger and has a lower ionic content than distilled water. The use of de-ionised water is believed to be important as this permits a greater amount of ions to be flushed from the activated oil shale thereby leaving more active sites available for adsorption within the oil shale.
  • the extraction solvent may be heated to a temperature of from 40° C. to 130° C., typically below 100° C.
  • the process may be carried out at a pressure of from 20 mBar(Abs) vacuum to several Bar (Abs) pressure.
  • stabilization processes may include:
  • the electrical charging may be performed by a corona discharge device or by electrostatic charging.
  • Electrostatic charging may be performed by agitating dry oil shale particles in a drum or the like thereby to impart an electrostatic charge to the oil shale.
  • the corona discharge device or the electrostatic charging method may be used to achieve same.
  • the invention extends to activated, refined, and/or stabilized oil shale prepared by a process as described above.
  • the invention also extends to the use of an activated, refined, and or stabilized oil shale in the removal of organic toxins or contaminants, inorganic toxins or contaminants, micro-organisms, and other undesired substances from a gaseous or a liquid phase containing said toxins and/or undesired substances by contacting said liquid or gaseous phase with said oil shale.
  • the inorganic toxins or contaminants may include one or more of cadmium, lead, and arsenic.
  • the inorganic toxins or contaminants may include one or more of nickel, cobalt, mercury, lead, and chromium.
  • the organic toxins or contaminants may include pesticides and/or non-biodegradable compounds
  • the gaseous phase may be selected from the group including, but not limited to, factory chimney gasses, air circulating through air conditioning systems, vehicle emissions, and smoke.
  • the liquid phase may be selected from liquids selected from the group including, but not limited to, aqueous solutions, organic solvent solutions, aqueous suspensions, radioactive effluents, factory effluents, mining effluents, and aqueous extracts.
  • the liquid phase may be water being treated in a potable water facility.
  • the invention extends yet further to a method for the reduction of undesired organic and inorganic substances from a vegetable origin material, said method including the steps of:
  • the method may include recovery of valuable components from the oil shale in which the organic and/or inorganic substances have been retained.
  • the method may include evaporating or otherwise removing at least a portion of the solvent from the extracted soluble substances.
  • the method may include drying the extracted soluble substances, for example by spray drying or freeze drying.
  • the method may include the recombining of the extracted soluble substances in which the undesirable organic and inorganic substances have been reduced with its source material from which it was extracted.
  • the material may include tea, coffee, cocoa, or other vegetable material for human consumption.
  • the material may include one or more of the roots, stem, and leaves of a plant, and/or products thereof.
  • the invention extends yet further to the use of activated oil shale in cigarette filters in order to reduce the amount of cadmium, lead and/or arsenic inhaled by a smoker.
  • the cigarette filters may include refined, activated oil shale as the volume thereof is less than that of unrefined activated oil shale and the specific absorption and/or adsorption rates are higher thereby permitting a smaller volume of the activated oil shale to achieve the same degree of removal of cadmium, lead and/or arsenic from the cigarette smoke.
  • FIG. 1 is a chart illustrating how, for a single oil shale deposit, samples collected at different levels and treated by the same activation mode(s) yield to products having different adsorption capacities;
  • FIG. 2 is a diagram of a Soxhlet extractor apparatus suitable for use in stabilizing activated oil shale in accordance with an embodiment of the invention
  • FIG. 3 is a chart illustrating the evolution of the pH of the solutions containing activated products before and after a stabilization step using the apparatus of FIG. 2 ;
  • FIG. 4 is a UV adsorption spectrum chart of olive oil extraction effluent both before and after treatment with the activated oil shale of the invention.
  • the activation of oil shale is carried out by one or more activation processes selected from chemical activation by a base, thermal activation by steam, and electromagnetic radiation activation.
  • one (or more) of the above activation processes may also be combined with a known process for activating oil shale, such as chemical activation by an acid or thermal activation in an atmosphere of air or nitrogen.
  • Table 1a sets out the various parameters affecting each of the three novel activation modes indicated above, as well as certain known thermal and chemical activation modes.
  • Each mode in the table may be used as a primary activation mode or as a complementary activation mode.
  • at least one of these modes is: chemical activation by a base, thermal activation by steam, or electromagnetic radiation activation.
  • a series of 2, 3 or 4 application modes could be applied to the same oil shale sample to achieve the desired properties.
  • the activation modes may be applied in different order to the sample so that they yield to products having different properties.
  • the penetration of the acid is also achieved from outside the particle towards the interior of the particle.
  • the acid attacks the carbonates and dissolves certain alkaline elements like calcium, magnesium, sodium or potassium.
  • the evolution of CO 2 creates pores inside the grains.
  • the activation mode by electromagnetic radiation reaches the entire particle at the same time allowing a more homogeneous activation.
  • the microwave oven is equipped with 14 reactors type XP 1500 PLUS and controlled by the EST Plus Device both for pressure and temperature control.
  • the microwave oven operates at 2450 MHz and three levels of power may be used: 300 W, 600 W and 1200 W.
  • Timahdit (Morocco) oil shale samples were introduced into the microwave oven and submitted to a 1200 W microwave radiation for 10 min (600 s).
  • the gray color of the oil shale becoming dark black after the treatment indicates that a high carbonization yield has been achieved.
  • the adsorption tests consisted of introducing 100 mg of the activated oil shale successively in two 100 ml solutions:
  • the activation of the oil shales creates adsorption sites in the carbonized organic matter and in the decomposed mineral matter.
  • the adsorption of the organic compounds is attributed to the organic matter sites and the adsorption of metals is attributed to the mineral matter sites.
  • composition varies from one oil shale deposit to another.
  • Table 3 shows the composition of twoixie oil shale deposits: Timahdit in the Middle Atlas mountains and Tarfaya near the southern Atlantic coast.
  • Timahdit oil shales contain more quartz and are more argillaceous than those of Tarfaya where the carbonates dominate the mineral matrix.
  • Table 4 shows the difference between the compositions of the Timahdit oil shale layers.
  • the oil shales are more argillaceous and siliceous (alumino-silicates) in the T zone and became more and more carbonated in depth (Y, X and M zones).
  • the Tarfaya oil shale layers are more homogenous with carbonate predominance. They vary practically only by their organic matter content.
  • FIG. 1 illustrates that, in a single oil shale deposit (Timahdit for example), samples, collected at different levels and treated by the same activation mode(s) yield to products having different adsorption capacities.
  • the selection of the oil shale deposit or the oil shale layer may also be considered as an important criterion for the production of an adsorbent developed and dedicated specifically for the solution of a particular environmental issue.
  • the Soxhlet extractor is a laboratory apparatus shown in FIG. 2 , normally used to extract a desired compound from a solid material.
  • the extractor is used to eliminate the mineral elements which may undesirably cause leaching during the utilisation of the activated oil shale products.
  • the reference numerals identify the following components: 1 : stirrer bar; 2 : still pot; 3 : distillation path; 4 : thimble; 5 : solid; 6 : siphon top; 7 : siphon exit; 8 : expansion adapter; 9 : condenser; 10 : cooling water in valve; and 11 : cooling water out valve.
  • An activated oil shale sample (50 g) is placed inside the thimble 4 made from thick filter paper, which is loaded into the main chamber of the Soxhlet extractor.
  • the condenser 9 ensures that any steam cools and drips back down into the chamber housing the solid material.
  • the Soxhlet extractor is placed onto a still pot 2 containing 500 ml of distilled de-ionised water which is used as the extraction solvent.
  • the water is heated to reflux.
  • the steam travels up the distillation path 3 , and floods into the chamber housing the thimble 4 of activated oil shale.
  • the chamber containing the solid material slowly fills with warm solvent (60-80° C.). Some of the undesired compound will then dissolve in the warm water/solvent.
  • An advantage of this system is that instead of many portions of hot water being passed through the sample, just one batch of water is recycled.
  • the stabilised oil shale product is then removed from the thimble and dried in a drying oven at 110° C.
  • the first oil shale product (PTM) was activated thermally at 880° C. and the second one (PTC) activated thermally and then chemically by hydrochloric acid attack.
  • FIG. 3 shows the diagrams of the evolution of the pH of the solutions containing activated products PTM and PTC before and after their stabilisation by Soxhlet extractor:
  • Oil Shale activated by one of the activation processes was further refined to increase adsorption capacity and to increase the specific surface and to optimize the carbonization of all the residual organic matter in the activated oil shale.
  • Ion beam irradiation also referred to as ion beam radiation or ion beam treatment
  • ion beam radiation modifies the chemical composition, chemical state and surface nanomorphology of the activated oil shale.
  • the ion beam irradiation affects structures via a molecular and not a radiative vehicle, thus confining their effect within a certain atomic penetration and diffusion boundaries.
  • Some common methods are RF plasma treatment, corona discharges and ion beam bombardments. Of these methods ion beam sources offer the most promising capabilities for adhesion improvements.
  • broad beam ion sources having the ability to operate in reactive gas atmospheres offer the possibility of chemical as well as physical modification.
  • the effluents produced by the extraction of the olive oil have a dark brown or brown-reddish colour with a turbid aspect. These effluents have a high load of salts and are very acid, rich in organic matter and non-biodegradable poly-phenols.
  • This waste water is characterized by a pH from 4.5 to 5 and a conductivity of about 10 msec./cm, mainly due to the potassium, chloride, calcium and magnesium ions.
  • the DCO chemical demand for oxygen
  • the sample used for the tests comes from a deposit of olive oil extraction waste in the area of Fez, Morocco.
  • the very concentrated sample of this effluent has a black is colour and releases a putrefied olive oil odour.
  • FIG. 4 A UV adsorption spectrum of olive oil extraction effluent both before and after treatment with the activated oil shale of the invention is shown in FIG. 4 .
  • Some of the elements which could be present in concentrations in many tobaccos are Boron, Calcium, Magnesium, Nitrogen, Lead, Arsenic, Cadmium, Phosphorous and Potassium.
  • This example carries out an analysis of normal tobacco smoke trapped onto embedded cotton plug for heavy metals vs. tobacco smoke through cotton plug treated with the product of the invention.
  • the vacuum hose, containing the water plug (for the control) and the cotton plug with activated oil shale product in the filter was cut. This was repeated 4 times and all samples were submitted for analysis.
  • the laboratory which was used to conduct the testing is an external ISO 3001/2000 laboratory.
  • the application which was used was the Inductively Coupled Plasma.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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IL196597A0 (en) 2009-11-18
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US20140202930A1 (en) 2014-07-24
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EP2046494A2 (fr) 2009-04-15
RU2009103556A (ru) 2010-09-10
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CA2658841A1 (fr) 2008-01-31
RU2443468C2 (ru) 2012-02-27
ZA200900587B (en) 2010-02-24

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