CN101516495A - Activation, refining, and use of oil shale - Google Patents
Activation, refining, and use of oil shale Download PDFInfo
- Publication number
- CN101516495A CN101516495A CNA2007800354131A CN200780035413A CN101516495A CN 101516495 A CN101516495 A CN 101516495A CN A2007800354131 A CNA2007800354131 A CN A2007800354131A CN 200780035413 A CN200780035413 A CN 200780035413A CN 101516495 A CN101516495 A CN 101516495A
- Authority
- CN
- China
- Prior art keywords
- oil shale
- activation
- shale
- described method
- seconds
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
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Images
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
- C10G1/04—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
Abstract
The invention provides the activation, refining and stabilization of oil shale. The stabilization may be performed by recirculative extraction, the activation by electromagnetic irradiation, steam, or by an inorganic base, and the refining by ion beam irradiation. The thus processed oil shale may be used to adsorb organic and inorganic contaminants from a variety of materials including materials of vegetable origin.
Description
Disclosed content is merged among the application by reference at this in the south african patent application 2006/6169, and it constitutes the major part of the disclosed content of the application.
Technical field
The present invention relates to the production and the application of sorbing material, more particularly, it relates to oil shale as the activation of adsorbent, refining, stabilisation and application.
Background technology
Up to the present, the sorbing material kind of extensive use is that (use of term " adsorbent " and " suction-operated " has comprised adsorbent or adsorbing any kind of at this to " activity " carbon products separately.) activated carbon is preparation-for example coal, timber and shuck from the material with high-carbon content, produces a lot of micropores by handling it between carbon atom.Because this porous, activated carbon has a very large surface area (just, specific area) in each unit volume, makes it can be used to the multiple material of absorption from gas or liquid.For example, activated carbon is used in purification for gas, METAL EXTRACTION, desalt, medicine, sewage disposal, air cleaner and many other application.Activation method generally includes some heat and/or chemically treated types.For example, can be converted into activated carbon by pyrolysis based on the material of carbon in stove, a kind of controlled atmosphere and high temperature are used in pyrolysis.
It's a pity, validity that let it be to the greatest extent, the adsorptivity of activated carbon is still strong inadequately for some materials.In addition, the raw material that obtain being used to producing activated carbon may be that cost is high and/or time-consuming.Owing to these reasons, notice relatively turns to and utilizes the activation oil shale as sorbing material recently.
Oil shale is the general name that is used to contain the fine granularity sedimentary rock of a considerable amount of kerabitumens (kerogen) (a kind of solid mixture of organic compound).When oil shale is heated to sufficiently high temperature (just, pyrolysis), steam is driven out of, and it can be distilled or shale oil and a kind of combustible hydrocarbon shale gas of destructive distillation (retort) to produce a kind oil.Pyrolysis is taking place at 250 ℃ under the no oxygen condition in oil shale usually between 550 ℃.Oil shale also can the directly burning as a kind of inferior fuel of generating.
Oil shale has been proposed to use as adsorbent under various state.For example, US1676151 has described in the waste water that the residue that obtains from the oil shale distillation can be used to produce from still-process and has removed impurity.This residue is the solid residue after oil shale retorting, is commonly called the shale of " giving up " or destructive distillation.Spent shale still contains organic carbon (residual carbon), and the common burned energy that is used for the destructive distillation cannel shale with generation.Produce the oil shale ashes by combusting oil shale or spent shale.
In addition, " slightly " (just, do not have usually processed) oil shale also is proposed as the application of adsorbent.For example, how the US4308146 cannel shale that discloses crushing is used as the oil slick adsorbent.The oil that floats on another liquid surface contacts with the cannel shale of crushing, so that oil is adsorbed on the shale.
More recently, in order to obtain being used for the high adsorption material of multiple industry and environmental applications, the proposal of several activation oil shales has been arranged, the activation method of itself and carbon is similar.Unlike thick or spent shale, for can the carbonization carbonaceous material and decompose a part of mineral matter, the oil shale of activation be processed, produces a kind of porous body that active surface area is arranged thus.。
For example, Morocco's patent documentation MA24030 has described and has been used to make the method for oil shale activation and activates the application of oil shale as adsorbent.This activation is to be undertaken by the processing method of heat and/or chemistry (acid).The more detailed method that is used for the activation of oil shale has obtained explanation further at following article:
-" novel sorbents that comes from oil shale: preparation, sign and the adsorption test of uranium thorium isotope " (" New adsorbents from oil shales:Preparation; characterization and U; Thisotope adsorption tests "), Khouya E; Fakhi S; Hannache H; Abbe J C; Andres Y; Naslain R; Pailler R; Nourredine A, Journal of Radioanalytical andNuclear Chemistry, Kluwer Academic Publishers, Do, VOL-260, NR-1, PG-159-166 (2004-04-01)
-" come from complex effects (" Influence of the experimental conditions onporosity and structure of adsorbents elaborated from Moroccan oil shale ofTimahdit by chemical activation ", the Ichcho S of Moroccan Timahdit oil shale experimental condition to adsorbent hole and structure by chemical activation; Khouya E; Fakhi S; Ezzine M; Hannache H; Pallier R; Naslain R, Journal of Hazardous Materials, Elsevier,, VOL-118, NR-1-3, PG-45-51, (2005-02-14)
-“Elaboration et caractérisation d′un nouveau matériau adsorbant àpartirdes schistes bitumineux du Maroc”，Oumam M；Abourriche A；Adil A；Hannache H；Pailler R；Naslain R；Birot M；Puillot J-P，Annales de Chimie，Masson，Paris，FR，VOL-28，NR-4，PG-59-74(2003-07-00)；
-" the synthetic and sign that comes from the carbon alumino-silicate of oil shale activation " (" Synthesis andcharacterization of activated carbo-aluminosilicate material from oil shale "), Shawabkeh R A, Microporous and Mesoporous Materials, Elsevier SciencePublishing, New York, US, VOL-75, NR-1-2, PG-107-114 (2004-10-12);
-" by the prepared novel sorbents of phosphoric acid activation Morocco oil shale: experimental condition is to the influence of adsorbent character " (" New adsorbents prepared by phosphoric acid activation ofMoroccan oil shales:Influence of the experimental conditions on theproperties of the adsorbents ", Khouya E1Hassane; Ichcho Salah; LegrouriKhadija; Hannache Hassan; Fakhi Said; Nourredine Abdelmjid; PaillerRene; Naslain Roger, Ann.Chim.Sci.Mater.; Annales de Chimie:Sciencedes Materiaux September/October 2006, VOL-31, NR-5, PG-583-596 (2006-09-00);
-" the carbon alumino-silicate that comes from the activation of oil shale by use adsorbs chromium ion from solution " (" Adsorption of chromium ions from aqueous solution by using activatedcarbo-aluminosilicate material from oil shale "), Shawabkeh Reyad Awwad, Journal of Colloid and Interface Science Jul 15 2006, VOL-299, NR-2, PG-530-536 (2006-07-15);
-" tolerating the characterization of adsorption of kind from a kind of novel sorbents production that Morocco's oil shale obtains for uranium and thorium with it " (" Production of a new adsorbent fromMoroccan oil shale by chemical activation and its adsorption characteristicsfor U and Th bearing species ") by chemical activation, Khouya E; Fakhi S; Hannache H; Ichcho S; Pailler R; Naslain R; Abbe J C., Journal De Physique.IV:JP; Proceedings-9th International Seminar on the Physical Chemistry of SolidState Materials, REMCES IX 2004 (CONF-REMCES IX:9th InternationalSeminar on the Physical Chemistry of Solid State Materials; Agadir, MoroccoOct 30-Nov 12002), VOL-123, PG-87-93 (2002-10-30); With
-" phosphoric acid activation of Morocco Timahdit oil shale: experimental condition is to the influence of yield and adsorption surface area " (" Phosphoric acid activation of Morrocan oil shale of Timahdit:Influence of the experimental conditions on yield and surface area ofadsorbents "), Ichcho S; Khouya E; Abourriche A; Ezzine M; Hannache H; Naslain R; Pailler R, Journal De Physique.IV:JP; Proceedings-9thInternational Seminar on the Physical Chemistry of Solid State Materials, REMCES IX 2004 (CONF-REMCES IX:9th International Seminar on thePhysical Chemistry of Solid State Materials; Agadir, Morocco Oct 30-Nov 12002), VOL-123, PG-81-85 (2002-10-30).
The content of above document is incorporated among the present invention by reference.
The benefit of explanation activation has for example illustrated the specific embodiment of the difference between the oil shale of cannel shale, spent shale and activation in the table 1 below.
Table 1: the spent shale and the organic carbon content and the specific area that activate oil shale that come from the oil shale of tal fibre method Asia (Tarfaya) (Morocco)
According to the organic carbon content and the specific area of spent shale and activating shale, can easily derive the difference of the adsorption capacity between these two kinds of materials.With regard to organic carbon content, be with particularly pointing out:
A: spent shale is the solid residue that stays after oil-shale retorting.In this example, 20～30% initial organic carbon has been left on (residual carbon) in the spent shale.The hydrogen (tens of crust) that uses pressurization such as the certain methods of " being hydrogenated to oil (Hytort) " is transformed into oil vapour with the carbon of maximum, thereby further reduces the amount of residual carbon.
The organic carbon of B:85% has been left in the oil shale of this thermal activation.15% minimizing is because the release in heat treatment process can be recovered as the hydrocarbon gas and light oil usually, and be used as the fuel that heats cannel shale.
C﹠amp; D: in fact the amount of organic carbon can increase owing to the loss of mineral matter in activation process.
Consider the content of being stated in The above results and the above-mentioned list of references, the activation oil shale has the sizable potentiality as a kind of new sorbing material, and under multiple situation, its adsorptivity is better than activated carbon significantly.And, because oil shale resources are a large amount of in a lot of places in the world and are not utilized basically that the raw material that therefore are used for necessity of these adsorbents can obtain under many circumstances widely and cheaply.
Yet method that being used to described in the above-mentioned list of references activates oil shale is to rest on largely based in academic and the research in itself.Especially, these methods may not produce a kind of adsorbent, this kind adsorbent is refining fully and is used for using at coml is stable, for example, formerly the method for technology also may not produce a kind of porous at it be enough uniformly sorbing material and/or hole therein be insufficient " opening " a kind of sorbing material, fully " opening " hole makes their adsorption capacity optimization.Therefore, still have a kind of demand to the oil shale activation method, this method can be produced the adsorbent of preparation improvement on a kind of renewable and business-like scale.
Summary of the invention
According to a first aspect of the invention, provide a kind of method that activates oil shale, this method comprises the one or more treatment steps that are selected from following step:
-use electromagnetic radiation irradiation oil shale, carbonization of partial organic substances matter and part mineral matter in the oil shale are transformed, make the inner gas that produces of oil shale, thereby produce hole in the inside of oil shale;
-heat oil shale by contacting with steam at high temperature; With
-contact the chemical treatment oil shale by making oil shale and inorganic alkaline compound.
The conversion of mineral matter can comprise carbonate decomposition.
The oil shale activation method can comprise purification step, in this step, pass through the method for ion beam irradiation oil shale, organic substance, nitrogen, sulphur, hydrogen and the oxygen that wherein unwelcome material does not for example transform is reacted away in the oil shale of activation, thereby has increased the specific activity surface area that is used to adsorb.
The oil shale activation method can comprise stabilization procedures, and it comprises by the circulation extraction makes oil shale contact with deionized-distilled water.
Other and/or selectable stabilization procedures can comprise:
-activating surface of oil shale is charged; And/or
The activating surface of-charge neutrality oil shale.
According to a second aspect of the present invention, a kind of activation method of oil shale is provided, comprise oil shale to be activated is exposed to electromagnetic radiation, a part of mineral matter in wherein a part of organic substance of carbonization and the transformation oil shale, caused having produced hole in oil shale inside thus at the inner gas that produces of oil shale.
Oil shale can be the form with particle, and granular size is from 0.1 millimeter to 200 millimeters, typically from 1 millimeter to 10 millimeters.
This electromagnetic radiation can be so-called microwave radiation, typically in the frequency of 2450 megahertzes.
Oil shale can use electromagnetic radiation irradiation a period of time, and the described time, perhaps the longer time, this depended on concrete oil shale, granular size and frequency from 1s/g to 60s/g.
The intensity of electromagnetic radiation or power can be from 1W/g to 20W/g, and this depends on the chemistry and the physical property of oil shale, and oil shale is treated the time period of irradiation in radiation.
Typically, for the oil shale particle from 1 millimeter to 10 millimeters sizes, under the intensity of 6W/g, exposure time more typically is 3s/g from 2-4s/g.
Think that the carbonization of organic substance has produced adsorption site thereon.
All oil shale particles can produce the hole equably.
The electromagnetic activation method can be the step in the multistep activation method.
Electromagnetic radiation can be the electromagnetic radiation of ultra-violet radiation, radio frequency plasma radiation or any other suitable type.
According to a third aspect of the present invention, a kind of method of thermal activation oil shale is provided, described method comprises that oil shale contacts with the steam of temperature from 150 ℃ to 1000 ℃, typically from 250 ℃ to 900 ℃.
In a specific embodiment, process of thermal activation can be finished from 500 ℃ to 1000 ℃ steam with temperature.
In the another one specific embodiment, process of thermal activation can be finished with the steam of 900 ℃ of temperature.
Oil shale can be the form with particle, and granular size is from 0.1 millimeter to 5 millimeters, typically from 0.5 millimeter to 2 millimeters.
Can be from 120 seconds to 3600 seconds the time of contact of oil shale and steam, typically from 240 seconds to 1800 seconds.Normally be 600 seconds time of contact.
Being considered to time of contact is the function of vapor (steam) temperature and oil shale particle size.
Think that the application of steam has caused the oxidation of organic substance and opening of hole in activation.
Process of thermal activation can be the step in the multistep activation method.
Process of thermal activation can combine with another activation method carries out.
According to a forth aspect of the invention, a kind of method of chemical activation oil shale is provided, described method comprises oil shale contacted with inorganic alkaline compound, and at least a portion organic substance and/or carbonate in transforming in the shale thus produce and/or opened hole in that oil shale is inner.
Inorganic alkaline compound can be to select from the group that comprises NaOH and potassium hydroxide, but is not limited thereto.
The scope for the treatment of the oil shale particle size of chemical activation is from 0.1 millimeter to 10 millimeters, typically from 0.5 millimeter to 2 millimeters.
The time of contact of oil shale can be for from 7200 seconds to 43200 seconds, typically from 10800 seconds to 18000 seconds.
At alkali compounds with after oil shale contacts, subsequently can be under 200 ℃ to 500 ℃ temperature thermally treated mixture 1800 seconds to 10800 seconds, typically 250 ℃ of thermally treated mixtures 3600 seconds to 7200 seconds.
The function that is considered to employed inorganic compound, temperature and oil shale particle size time of contact.
The activation effect of oil shale is the concentration of the kind of oil shale particle size, employed inorganic compound, described inorganic compound, the temperature of handling and the stop of oil shale in this process or the function in processing time.
The chemical activation method can be a step in the multistep activation method.
The chemical activation method can be carried out in conjunction with other activation method, typically one or more in thermal activation and the electromagnetic activation.
According to a fifth aspect of the present invention, a kind of process for purification of activating shale is provided, described method comprises the oil shale with the activation of a kind of ion beam irradiation, to reduce organic substance, nitrogen, sulphur, hydrogen and the oxygen that is not carbonized, increases thus and is used to the specific activity surface area that absorbs and/or adsorb.
Ion beam irradiation can be the oxygen ion beam radiation.
Ion beam irradiation can and carry out to 500 microamperes/square centimeter at 20 microamperes/square centimeter at 50 electron-volts to 1000 electron-volts.Typically, use 200 electron-volts and 200 microamperes/square centimeter of oxygen ion beams.
So the activation oil shale of handling has the carbon that surpasses 90% quality, surpasses 95% quality typically, and has the specific absorption rate of increase.Not this means with there being refining activation oil shale and compare that oil shale is in the enrichment of activated carbon site.
With respect to unpurified activation oil shale, the ratio adsorption rate of every gram adsorbent can increase at least 5%, and the typical case surpasses 8%.
According to another side of the present invention, provide a kind of and be used to activate and/or refining oil shale stabilization method, described stabilization method comprises by the recirculation extraction makes oil shale contact with solvent.
Stabilization procedures can comprise that the extraction solvent that uses heating is from activation oil shale dissolving inorganic compound.
Can use hot water and steam to extract and dissolve, for example in apparatus,Soxhlet's, carry out by circulation.
The extraction solvent of heating can be demineralized water, normally deionized-distilled water.
Stabilization procedures can be included between the pot-life of oil shale, the extraction solvent that uses heating from the oil shale dissolved destruction stability of activation inorganic compound.
The oil shale that it is believed that stable activation does not have a kind of leaching phenomenon of minimizing when being used as a kind of adsorbent and contacting with sewage.
In this connection, to notice that importantly distilled water is to be evaporated and the water that condensed again and it comprise mineral matter and other ion.Whether no matter distill, deionized water is to have passed ion-exchanger and the ion concentration water lower than distilled water.The use of deionized water is considered to important, because it makes a large amount of ions be rinsed the oil shale from activation, more can be used for the activation site of adsorbing thereby stayed in oil shale.
Extract solvent and can be heated to, be lower than 100 ℃ typically from 40 ℃ to 130 ℃ temperature.
This method can be carried out at the vacuum of 20 millibars (Abs) pressure to several millibars.
Other and/or selectable stabilization procedures can comprise:
-activating surface of oil shale is charged; And/or
The activating surface of-charge neutrality oil shale.
Charging can realize by a kind of corona discharge assembly or by electrostatic charging.
Electrostatic charging can be finished by stir the oil shale particle of doing in a cylinder or analog, thereby makes oil shale static electrification lotus.
When in the needs and during oil shale, can use corona discharge assembly or electrostatic charging method to obtain identical effect.
Also further, the scope of application of the present invention extends to the oil shale of activation, refining and/or stabilisation, and it prepares by method described above.
The scope of application of the present invention also extended to a kind of activation, refining and/oil shale of stabilisation removes the application of organic toxin or pollutant, inorganic toxin or pollutant, microorganism and other unwelcome material from gas phase or liquid phase, contain this toxin and/or unwelcome material in this gas phase or the liquid phase, it is by contacting described liquid or gas phase and described oil shale is realized.
Inorganic toxin or pollutant can comprise one or more in cadmium, lead and the arsenic.
Inorganic toxin or pollutant can comprise one or more in nickel, cobalt, mercury, lead and the chromium.
Organic toxin or pollutant can comprise agricultural chemicals and/or nonbiodegradable compound.
Gas phase can be selected from comprise factory chimney gas, the group of air, automobile emission and smog by air handling system circulation, but is not limited thereto.
Liquid phase can be selected from the group that comprises the aqueous solution, organic solvent solution, water slurry, radioactive effluent, plant emissions, mining wastewater, water extract, but is not limited thereto.
The water that liquid phase can be to use a kind of portable water facilities (water facility) to handle.
The inventory that is appreciated that gas phase and liquid phase never be limit and here disclosed principle can be employed across a plurality of industry.
The present invention also further extends to the method that reduces undesirable organic substance and inorganic substances from the material that comes from plant, and this method comprises the steps:
-from material, extract soluble substance to enter in the solvent;
-solvent of the soluble substance that contains extraction is contacted with the activation oil shale, no matter whether described activation oil shale is by refining and/or stabilized;
-in the temperature of hope, keep wishing the contact of time; With
-the solvent that will comprise the solable matter of extraction separates with described oil shale, and undesirable organic substance in the solvent and inorganic substances have obtained reducing.
This method can comprise that organic substance and/or inorganic substances are retained in oil shale from oil shale recovery valuable ingredients.
This method can comprise the soluble substance of dry extraction, for example by spray-drying or freeze drying.
This method can comprise from the soluble substance that is extracted evaporation or remove at least a portion solvent with method for distinguishing.
This method can comprise the solable matter that reorganization is extracted and therefrom extract the raw material of solable matter that undesirable organic substance in the soluble substance of extraction and inorganic substances have obtained reducing.
This material can comprise that tea, coffee, cocoa or other are used for human consumption's vegetable matter.
This material can comprise one or more in root, stem and the leaf of plant, and/or its product.
In order to reduce the amount of cadmium, lead and/or arsenic that the smoker sucks, the present invention also further extends to the application of activation oil shale in cigarette filter.
This cigarette filter can comprise refining activation oil shale, this is because the volume of its unpurified activation oil shale of volume ratio is little, therefore the absorption of refining activation oil shale and/or adsorption rate are higher than the ratio absorption and/or the adsorption rate of unpurified activation oil shale than absorption and/or adsorption rate, thereby allow the activation oil shale of smaller size smaller can obtain cadmium, lead and/or the arsenic of removing same degree from cigarette filter.
The inventor thinks that the present invention has many advantages, includes but not limited to respect to known and adsorbent and adsorbent preparation method based on shale that use:
The active surface area of-increase;
-from material, remove toxin or pollutant by simple method; With
-for the high adsorption activity of heavy metal, radioactive substance and similar substance.
Following specific descriptions are the integral part of the disclosure of invention, and under the situation that context allowed, it should normally be explained, and should not be confined to the certain content of any embodiment.
Description of drawings
Concrete description with reference to the accompanying drawings, wherein:
Fig. 1 shows for single oil shale deposit thing, the chart that is collected at varying level and how to produce the product with different adsorption capacities with the sample of same activation mode treatment;
Fig. 2 according to embodiment of the present invention, be applicable to the sketch of the apparatus,Soxhlet's device of stable activation oil shale;
Fig. 3 show contain the solution that activates product use device among Fig. 2, before stabilization step and the chart of the differentiation of pH afterwards; With
Fig. 4 be olive oil extract waste liquid before with activation oil shale processes of the present invention and afterwards uv absorption spectra.
The specific embodiment
The present invention is described by the subsidiary example of reference, but not only is confined to these examples.
According to an aspect of of the present present invention, carry out the activation of oil shale: use the chemical activation of alkali, use the thermal activation and the electromagnetic radiation activation of steam by being selected from the following activation method one or more.Alternatively, a kind of (or multiple) in the above-mentioned activation method also can combine with the method that known being used to activates oil shale, for example uses the chemical activation or the thermal activation in the atmosphere of air or nitrogen of acid.
Following table 1a has listed influences above-mentioned three kinds of new activation patterns and the thermal activation pattern that some is known and the various parameters of chemical activation pattern respectively.
Table 1a activation pattern and operating parameter
Every kind of pattern in the table can be used as main activation pattern or be used as additional activation pattern.Yet according to this aspect of the present invention, at least a of these patterns is: use the chemical activation of alkali, the thermal activation of using steam or electromagnetic radiation activation.In order to access the character that needs, a series of application model 2,3 or 4 can be applied to identical oil shale sample.Described activation pattern can be applied to sample with different orders, so that its generation has the product of different qualities.
The combination of activation pattern and the variation of operating parameter produce the adsorption production based on oil shale of many series, therefore obtain the commercial Application of wide spectrum.
Embodiment 1: the electromagnetic radiation activation of oil shale
During thermal activation, heat is sent to the center of oil shale particle by heat conduction from the outside, changes the organic substance part of oil shale by carbonization, and oil shale the carbonate part or whole decomposition of mineral parts.By these reactions, the gas that is produced expands and produces the hole in granule interior.
For example, using hydrochloric acid to carry out in the situation of chemical activation, the infiltration of acid also is to finish to granule interior from the particle outside.Acid is attacked carbonate and is dissolved some alkaline element, for example calcium, magnesium, sodium and potassium.Emitting in granule interior of carbon dioxide produces the hole.
Opposite with above two kinds of activation patterns, the activation pattern by electromagnetic radiation arrives whole particle at one time, and feasible activation is more even.
Experiment
This experiment is undertaken by using a kind of micro-wave digestion stove (microwave digestion oven, Mars 5, CEM company, Ma Xiusi (Matthews), the U.S.).
The reactor that it is XP 1500 PLUS that this micro-wave oven is equipped with 14 models, it is by ESTPlus Device controlled pressure and temperature.Micro-wave oven is at 2450 megahertzes and can use the power of 300 watts, 600 watts and 1200 watts three kinds of levels to operate.
The result of operating condition and absorption test has been shown among table 2a and the 2b.
The oil shale sample of Timahdit (Morocco) is put into micro-wave oven, use the microwave radiation 10 minutes (600 seconds) of 1200W.After processing, oil shale has become furvous by grey, and this shows the product that obtains the height carbonization.
Table 2a is by the activation-operating condition of microwave radiation
Table 2b is by the activation-absorption test of microwave radiation
The activation oil shale that in turn adds 100 milligrams in the solution that is included in two kinds 100 milliliters is tested in absorption:
Contain the methylene blue that concentration is 40 mg/litre in-the first kind of solution
Contain the nickel that concentration is 25 mg/litre in-the second kind of solution.
After stirring 2 hours, two kinds of solution the analysis showed that oil shale with microwave activation, 100% nickel and 100% methylenum careuleum are adsorbed.
The absorption test result clearly illustrates that by the radioactivated oil shale of microwave and has obtained the adsorption capacity to methylene blue and nickel that equates at least with the thermal activation oil shale.
Embodiment 2: the source of oil shale is to the oil shale Effect on Performance of activation
The activation of oil shale produces adsorption site in the mineral matter of the organic substance of carbonization and decomposition.The absorption quilt of organic compound is owing to the organic substance site, and the absorption of metal quilt is owing to the mineral matter site.
Because the activation oil shale can adsorb the more pollutant of volume, this has represented its a kind of advantage of comparing with activated carbon.Most probably, during the thermal activation of oil shale, a kind of transitional face of being made up of carbon-aluminium-silicate (carbo-alunino-silcates) occurred, thereby increased described adsorption phenomena.The result is that the concrete feature of oil shale can influence the characteristic of activation product significantly.
At first, the composition of various oil shale deposit thing can change.Table 3 shows the composition of two kinds of Morocco's oil shale deposit things: the Timahdit at middle part, mountain range, Atlas (Atlas) and near the Tarfaya the South Atlantic Coast.
The chemical composition of table 3 oil shale
| Chemical composition (wt%) | Timahdit | Tarfaya |
| The quartzy pyrite clay of calcite dolomite and other mineral oil parent rock | 21.9 15.9 19.1 1 24.0 17.7 | 63.7 3.5 6.5 ＜1 10.0 15.9 |
The Timahdit oil shale contains more quartz than the Tarfaya oil shale and more manys shale, at Tarfaya, is mainly carbonate in the mineral matter matrix (mineral matrix).
In addition, table 4 shows the difference between the composition of Timahdit oil shale layer.This oil shale has more shale and siliceous (aluminium-silicate) in the T zone, dark more carbonate many more (Y, X and M zones).The Tarfaya oil shale layer is more even, and wherein carbonate occupies the majority.It is in fact only along with its organic matter content changes.
Table 4 oil shale layer is formed
Fig. 1 explanation, in a kind of single oil shale deposit thing (for example Timahdit), the product that the sample that is collected at varying level with same activation mode treatment produces has different adsorption capacities.
The result is, except the combination of activation pattern and its operating condition, the selection of oil shale deposit thing or oil shale layer also can be considered as and be used for the major criterion that a kind of adsorbent is produced, and adsorbent is developed and is specifically endeavoured to be used for a kind of solution of specific environment problem.
Embodiment 3: the stabilisation of the activation oil shale that extracts by soxhlet extraction
In case be activated, for the absorption property of oil shale keep as much as possible stable be undoubtedly important.
Apparatus,Soxhlet's is a kind of laboratory installation that goes out as shown in Figure 2, is normally used for extracting from solid material the compound of wanting.In the present invention, extractor is used to eliminate mineral composition, and between the operating period of activation product shale oil, mineral composition may odiously cause eluviation (leaching).
In Fig. 2, Reference numeral is represented following parts: 1: stirring rod; 2: distillation still; 3: the distillation path; 4: sleeve; 5: solid; 6: the siphon pipe top; 7: the siphon pipe outlet; 8: the expansion adapter; 9: condenser; 10: the inlet cooling water; And 11: the outlet cooling water.
A kind of activation oil shale sample (50 gram) is put into the sleeve pipe of being made by thick filter paper 4, and it is loaded in the main chamber of apparatus,Soxhlet's.
Apparatus,Soxhlet's is placed on the distillation still 2 that contains 500 ml deionized water, and deionized water is used as the extraction solvent.Heat described water to reflux.Steam moves up along distillation path 3, pours in the chamber that accommodates the sleeve 4 that the activation oil shale is housed.
The chamber that contains solid material has been full of hot solvent (60-80 ℃) at leisure.Then, some undesirable compounds will be dissolved in the water/solvent of heat.
When the Soxhlet chamber had almost been expired, by automatically emptied, aqueous reflux went down to distilling flask chamber by siphon pipe top 6.Repeat this and follow also several times, repeat 2 hours approximately.
In each cycle period, the destroyed stable mineral composition of part dissolves in water in the oil shale.After a plurality of circulations, the mineral composition of dissolving is concentrated in distilling flask.
The advantage of this system only needs recycling a collection of water for not needing many hot water by sample.Remove this stable product shale oil from sleeve then, dry in drying box at 110 ℃.
Stabilization Control-pH develops
In the time will activating oil shale and contact with water, the differentiation of pH value of solution is a kind of simple and important indicant of leaching phenomenon.
To having implemented the leaching test with two kinds of activation oil shales afterwards before with the apparatus,Soxhlet's stabilisation.
At first kind of product shale oil of 880 ℃ of thermal activations (PTM), second kind of product of thermal activation (PTC) carries out chemical activation with the hydrochloric acid attack subsequently.
For each test, in the retort solution with 100 milliliters of the 1 product addings that restrains.Agitating solution 2 hours also writes down pH.
Fig. 3 be contain activation product P TM and PTC solution before using the apparatus,Soxhlet's stabilisation and the evolution of pH afterwards:
The pH of solution before stabilisation that contains PTM and PTC product become the alkalescence dissolving of the alkaline element of calcium and magnesium (because such as) and acid (owing to the muriatic dissolving that is retained in the product) respectively.
After used the apparatus,Soxhlet's washing, the pH that contains the solution of PTM and PTC product was stabilized in about pH7, thereby has shown the effect of this processing, makes the product stabilisation.
Embodiment 4: activation oil shale refining that uses the oxygen ion beam radiation
Refining further oil shale by the activation of one of described activation method, with increase adsorption capacity and specific area, and the feasible carbonization optimization that activates all residual organic matter in the oil shale.
The ion beam irradiation of activating shale (also being known as ion beam radiation or Ion Beam Treatment) has changed chemical composition, chemical state and surperficial little form (surfacenanomorphology) of activation oil shale.
Ion beam irradiation influences structure by molecule rather than radiation medium thing (radiative vehicle), so its effect is confined within the interface of a certain atom infiltration and diffusion.Some method in common are radio frequency plasma processing, corona discharge and ion beam bombardment.In these methods, ion beam source provides and has been used for the most promising potential that adhesive force improves.On the other hand, has the possibility that the wide beam ion gun that carries out the ability of work in the gas atmosphere of reaction provides chemistry and physical modification.
In an experiment, use oxygen ion beam to bombard the 50 activation oil shales that restrain 5 minutes at 200 electron-volts and 200 microamperes/square centimeter, obtain following result:
Observe quality and reduce 6.8%, absorbing increases by 9.2%.Use column method and MB (methylene blue) to absorb test, this test shows is absorbed with 9.2% increase.This can be oxidized to nitrogen dioxide, water and sulfur dioxide owing to nitrogen, hydrogen, sulphur, and the further carbonization that activates organic substance in the oil shale.
Embodiment 5: olive oil extracts the processing of waste liquid
The physicochemical characteristic of waste liquid
Extract the color that the waste liquid that is produced has dark brown or maroon, outward appearance muddiness by olive oil.These waste liquids have the salt of high-load and very acid, are rich in organic substance and not biodegradable polyphenol.This waste water is characterized as: pH is 4.5～5, electrical conductivity be about 10 megaseconds/centimetre, this mainly is because the existence of potassium, chlorine, calcium and magnesium ion.DCO (COD) can change at the 50-220 grams per liter.
The absorption test
The sample that is used for this test comes from the deposit of the olive oil extraction waste liquid in Morocco non-this (Fez) area.The sample that concentrates very much of this waste liquid is a black, and discharges a kind of olive oil smell of corruption.
Sample to same dilution carries out twice absorption test on the product shale oil post of a kind of product shale oil post of thermal activation and a kind of heat and chemical activation respectively.With the solution after described two kinds of product treatment is colourless and tasteless.Begin to occur first kind of color (tangible maroon) after in thermal activation oil shale post, pouring 30 milliliters sample into and in chemistry and thermal activation post, pouring 60 milliliters sample into.
Gathered the measured value of the corresponding adsorption yield of the concentration of the sample after handling by described two kinds of product shale oils and acquisition, the ability that it has demonstrated the activation oil shale shows that particularly heat and chemically treated product have adsorbed that in this refuse almost whole organic substance comprises polyphenol.
After chemistry and thermal activation oil shale adsorption treatment, the COD of waste liquid (DOC) is reduced to 6.72 mg/litre from 57.7 grams per liters, and this has confirmed that set has organic substance in the oil shale riverbed.
Fig. 4 shows olive oil and extracts waste liquid before using activation oil shale processes of the present invention and uv absorption spectra afterwards.
Embodiment 6: the processing of the vegetable oil processing-waste of use
The source of waste liquid sample and feature
Use following steps to obtain and handle the vegetable oil waste liquid sample of use:
The oil that-heating is collected;
-decant(-ation);
-separate organic and mineral matter mutually;
-end product is sent to chemical processing plant, is used to produce aliphatic acid and biodiesel.
-waste water is sent to water treatment plant.
The not biodegradable compound that exists in the waste water makes water treatment become difficulty.Table 5 shows the feature of waste liquid.
The feature of table 5 waste liquid
| COD (grams per liter) | 40 |
| BOD (grams per liter) | 10 |
| |
40 |
| Organic substance | 25 |
| Mineral matter | 15 |
| pH | 5 |
| C/ |
5 |
The absorption test
Carry out the absorption test of waste liquid according to following program:
It is in 3.5 centimetres the glass column that 40 milliliters waste liquid sample is little by little poured into a diameter, contains the product shale oil of 50 gram heat and chemical activation in this post, and the granular size of the product shale oil of preparation is less than 0.63 millimeter and greater than 0.2 millimeter.Mineral wool is placed in the bottom of pillar to hold back the tiny solid particle.
Tenne sample becomes colourless after filtering by pillar.The ultraviolet spectra of waste liquid almost completely disappears after processing at the ultraviolet absorption peak of 235 and 300 nanometers, and these all organic substances that show sample have been trapped within the oil shale riverbed.
Example 7: as a kind of application of cigarette filter
Tobacco industry
Though finished a lot of work improving cigarette filter and to make the cigarette safer use that becomes, cigarette is for human and environment can have a lot of health and hazards but are well-known.
Each smoking, smoker and involuntary smoker can suck nearly 4000 kinds different chemical material, and some are highly toxic, and they are causes of cancer and other heart disease and tuberculosis.
According to pertinent literature, extensive studies has concentrated on the organic principle of mainly measuring cigarette.Because the carcinogenic character of a lot of organic substances, comparatively speaking, the metal analysis of cigarette is still in exploration.Yet, being accompanied by smoking, some is that metal may be in the human body inner accumulated to the poisoning level, this is harmful to equally.
Some elements that may exist with high concentration in a lot of cigarettes are boron, calcium, magnesium, nitrogen, lead, arsenic, cadmium, phosphorus and potassium.
Health perception, legislation and public pressure are just needing a kind of solution that threatens situation for this life.
The heavy metal of the smoke from cigarette on the heavy metal of this embodiment by the common cotton smoke from cigarette beyond the Great Wall that relatively collect to embed and the tampon of collecting after the handling with product of the present invention of embedding has carried out the branch watchman's clapper.
Method and apparatus
Though it is simple, but by using 500 milliliters ceramic vessel of a kind of shape such as funnel, can use a kind of described ceramic vessel of effective and cheap method that is used for simulation " smoker's big tobacco pipe " to be connected with a vacuum hose, described vacuum hose is aspirated by an extractor (extractor).One tampon (10 gram) is as " filter tip " of this control group.During 10 minutes extraction, use the Boxer of 75gm
TMCigarette.
A kind of similar device is used to repeat described experiment (exercise), but the filter paper before placing tampon is enclosed with 2.5 grams activation oil shale of the present invention.
When leaching process was finished, cutting vacuum hose, described vacuum hose comprised water plug (water plug) in the filter tip (be used in the same old way) and the tampon that activates product shale oil are housed.This has been repeated 4 times, and all samples submitted being used for analyzed.
Because the level of expection heavy metal is low-down, therefore combined sample is analyzed in decision in both cases.A kind of do not have a product shale oil, and a kind of have a described powder.
Use Camel
TMCigarette is repeated described experiment.5 volunteers of Xuan Zeing have also participated in " taste and effect " test at random.Prepared 40 cigarettes, 20 are used common filter tips, and 20 are embedded with activation product shale oil powder in filter-tip front portion.There is not people sensation that any departing from or any difference arranged on taste among 5 volunteers.
The laboratory that is used to carry out this test is outside ISO 3001/2000 laboratory.
The application of using is an inductively coupled plasma.
Table 6: activation oil shale and the filter-tip comparison of non-oil shale
| Sample type (ID) | Cadmium μ g Cd | Plumbous μ g Pb | Arsenic μ g As | |
| 1. | Condensate behind the filter tip contains the condensate behind the filter tip of |
9 15 | 5 505 | ＜2 16 |
| 2. | 75 gram Boxer contain 75 gram Boxer of 2.5 gram oil shales | 64 70 | 9 622 | ＜2 27 |
Above result clearly illustrates that a large amount of lead (Pb) and arsenic (As) are collected in the filter tip layer of handling with product shale oil.
Claims (45)
1, a kind of stabilization method of that be used to activate and/or refining oil shale, described stabilization method comprise extracting by circulation makes oil shale contact with a kind of solvent.
2, method according to claim 1 is characterized in that: described method comprises that the extraction solvent with heating dissolves inorganic compound from the oil shale of activation.
3, method according to claim 1 and 2 is characterized in that: described method is finished with hot water and steam.
4, according to the described method of above-mentioned arbitrary claim, it is characterized in that: described solvent is a mineral water, typically deionized-distilled water.
5, according to the described method of above-mentioned arbitrary claim, it is characterized in that: described extraction solvent is heated to 40 ℃～130 ℃ temperature, is lower than 100 ℃ typically.
6, a kind of method with the oil shale activation, described method comprises oil shale to be activated is exposed to electromagnetic radiation, with a part of mineral matter in a part of organic substance in the described oil shale of carbonization and the described oil shale of conversion, caused having produced hole in oil shale inside thus at the inner gas that produces of oil shale.
7, method according to claim 6 is characterized in that: described oil shale is a particle form, and the size of particle is from 0.1 millimeter to 200 millimeters, typically from 1 millimeter to 10 millimeters.
8, according to claim 6 or 7 described methods, it is characterized in that: described electromagnetic radiation is so-called microwave radiation, typically in the frequency of 2450 megahertzes.
9, according to arbitrary described method in the claim 6～8, it is characterized in that: described oil shale is exposed to a period of time in the electromagnetic radiation, and the described time is from 1s/g to 60s/g.
10, method according to claim 9 is characterized in that: the intensity of described electromagnetic radiation or power are that 1W/g is to 20W/g.
11, according to arbitrary described method in the claim 6～10, it is characterized in that: for size is 1 millimeter to 10 millimeters oil shale particle, is under the electromagnetic radiation of 6W/g in intensity, exposure time be 2s/g to 4s/g, more typically be 3s/g.
12, a kind of method of thermal activation oil shale, described method comprise that oil shale contacts with the steam of temperature from 150 ℃ to 1000 ℃, typically from 250 ℃ to 900 ℃.
13, method according to claim 12 is characterized in that: described method is carried out with the steam of temperature from 500 ℃ to 1000 ℃.
14, method according to claim 13 is characterized in that: described method is carried out with the steam of 900 ℃ of temperature.
15, according to arbitrary described method in the claim 12～14, it is characterized in that: described oil shale is the form of particle, and the size of described particle is 0.1 to 5 millimeter, typically from 0.5 millimeter to 2 millimeters.
16, according to arbitrary described method in the claim 12～15, it is characterized in that: can be from 120 seconds to 3600 seconds the time of contact of described oil shale and steam, typically from 240 seconds to 1800 seconds.
17, method according to claim 16 is characterized in that: be 600 seconds described time of contact.
18, a kind of method of oil shale of refining activation, described method comprises the oil shale with a kind of ion beam irradiation activation, be used to the specific activity surface area that absorbs and/or adsorb to reduce the organic substance be not carbonized and in nitrogen, sulphur, hydrogen and the oxygen one or more, to increase thus.
19, method according to claim 18 is characterized in that: described ion beam irradiation is the oxygen ion beam radiation.
20, according to claim 18 or 19 described methods, it is characterized in that: ion beam irradiation be with from 50 electron-volts to 1000 electron-volts and from 20 to 500 microamperes/square centimeter carry out.
21, method according to claim 19 is characterized in that: use described oxygen ion beam with 200 electron-volts and 200 microamperes/square centimeter.
22, according to arbitrary described method in the claim 18～21, it is characterized in that: the ratio adsorption rate of every gram adsorbent increases by 5% at least than the oil shale of unpurified activation, and the typical case surpasses 8%.
23, a kind of method of chemical activation oil shale, described method comprise oil shale are contacted with inorganic alkaline compound, transform at least a portion organic substance and/or carbonate in the shale thus, produce and/or opened hole in that oil shale is inner.
24, method according to claim 23 is characterized in that: described inorganic alkaline compound is selected from the group that comprises NaOH and potassium hydroxide.
25, according to claim 23 or 24 described methods, it is characterized in that: the granular size excursion for the treatment of the oil shale of chemical activation is from 0.1 to 10 millimeter, typically from 0.5 millimeter to 2 millimeters.
26, according to arbitrary described method in the claim 23～25, it is characterized in that: for described oil shale, time of contact is from 7200 seconds to 43200 seconds, typically from 10800 seconds to 18000 seconds.
27, according to arbitrary described method in the claim 23～26, it is characterized in that: after the time of contact of alkali compounds and oil shale, under 200 ℃ to 500 ℃ temperature, described mixture is carried out 1800 seconds to 10800 seconds heat treatment, typically 250 ℃ of heat treatments 3600 seconds to 7200 seconds.
28, a kind of method that activates oil shale, described method comprise as each described two or more treatment steps in the above-mentioned claim.
29, by as above-mentioned claim in the activation, the oil shale of refining and/or stabilisation of each described method preparation.
30, as the purposes of the oil shale of claim 29 activation required for protection, refining and/or stabilisation; it is used for removing organic pollution, inorganic pollution, microorganism and other unwelcome material from gas phase or liquid phase; contain described pollutant and/or unwelcome material in this gas phase or the liquid phase, described purposes is by contacting realization with liquid phase or gas phase with described oil shale.
31, purposes according to claim 30 is characterized in that: described inorganic pollution comprises one or more in cadmium, lead and the arsenic.
32, purposes according to claim 30 is characterized in that: described inorganic pollution comprises one or more in nickel, cobalt, mercury, lead and the chromium.
33, purposes according to claim 30 is characterized in that: described organic pollution comprises agricultural chemicals and/or not biodegradable compound.
34, according to arbitrary described purposes in the claim 30～33, it is characterized in that: described gas phase is selected from comprise factory chimney gas, the group of air, vehicle emission and smog by air handling system circulation.
35, according to arbitrary described purposes in the claim 30～34, it is characterized in that: described liquid phase is selected from following liquid, and described liquid is selected from the group that comprises the aqueous solution, organic solvent solution, water slurry, radioactive effluent, plant chimney stalk, mining wastewater and water extract.
36, according to arbitrary described purposes in the claim 30～34, it is characterized in that: the water that described liquid phase is to use a kind of portable water facilities to handle.
37, a kind of method that reduces the unwelcome organic and inorganic substances in the botanical material, described method comprises the steps:
-from described material extraction soluble substance to solvent;
-the solvent that will comprise the soluble substance of described extraction contacts with a kind of oil shale of activation, and no matter whether described oil shale is by refining and/or stabilisation;
-keep wishing the contact of time in the temperature of hope; With
-with in the described oil shale with comprise the separated from solvent of the soluble substance of extraction, the unwelcome organic and inorganic substances in the described solvent have obtained minimizing.
38, according to the described method of claim 37, it is characterized in that: described method comprises reclaims valuable ingredients that from oil shale wherein, organic and/or inorganic substances have been retained in the described oil shale.
39, according to claim 37 or 38 described methods, it is characterized in that: described method comprises from the soluble substance that is extracted evaporation or removes at least a portion solvent with method for distinguishing.
40, according to the described method of claim 39, it is characterized in that: described method comprises the soluble substance drying that will extract.
41, according to arbitrary described method in the claim 37～40, it is characterized in that: described method comprises that soluble substance that reconfigures extraction and the raw material that therefrom extract soluble substance, unwelcome organic matter in the soluble substance of described extraction and inorganic matter have obtained reducing.
42, according to arbitrary described method in the claim 37～41, it is characterized in that: described material is from comprising that tea, coffee, cocoa power or other are used for selecting in human consumption's one or more the group of vegetable matter.
43, according to the described method of claim 42, it is characterized in that: described material comprises one or more in root, stem and the leaf of plant.
44, Huo Hua oil shale is used for the purposes of cigarette filter, and it is used to reduce the amount of cadmium, lead and/or arsenic that the smoker sucks.
45, according to the described purposes of claim 44, it is characterized in that: described cigarette filter comprises refining activation oil shale, this be since the volume of refining activation oil shale less than the volume of unpurified activation oil shale, therefore absorption of the ratio of refining activation oil shale and/or adsorption rate are higher than the ratio absorption and/or the adsorption rate of unpurified activation oil shale, thereby make the activation oil shale of smaller size smaller can obtain to remove the cadmium of same degree, lead and/or arsenic from cigarette smoke.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA2006/06169 | 2006-07-26 | ||
| ZA200606169 | 2006-07-26 | ||
| PCT/ZA2007/000043 WO2008014526A2 (en) | 2006-07-26 | 2007-07-19 | Activation, refining, and use of oil shale |
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| CN101516495A true CN101516495A (en) | 2009-08-26 |
| CN101516495B CN101516495B (en) | 2013-04-10 |
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|---|---|
| US (2) | US20090308793A1 (en) |
| EP (1) | EP2046494A2 (en) |
| CN (1) | CN101516495B (en) |
| AU (1) | AU2007278836B2 (en) |
| CA (1) | CA2658841C (en) |
| IL (1) | IL196597A (en) |
| MA (1) | MA30646B1 (en) |
| RU (1) | RU2443468C2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961073A (en) * | 2019-12-05 | 2020-04-07 | 中国石油大学(北京) | Shale adsorption material for oil-water separation and preparation method thereof |
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| US7931784B2 (en) | 2008-04-30 | 2011-04-26 | Xyleco, Inc. | Processing biomass and petroleum containing materials |
| US9387454B2 (en) | 2008-06-18 | 2016-07-12 | Xyleco, Inc. | Processing material with ion beams |
| LT2300148T (en) * | 2008-06-18 | 2018-12-27 | Xyleco, Inc. | Processing materials with ion beams |
| NZ610074A (en) * | 2008-10-28 | 2014-07-25 | Xyleco Inc | Processing biomass |
| WO2010083574A1 (en) * | 2010-01-17 | 2010-07-29 | Botanical Water Holdings Pty Ltd | Recovering water |
| AU2010100800B9 (en) * | 2010-01-17 | 2011-04-07 | Botanical Water Holdings Pty Ltd | Recovering water |
| AU2010342762B2 (en) | 2010-01-17 | 2015-11-26 | Kambouris Shares Pty Ltd | Recovering water |
| CN105478076B (en) * | 2016-01-18 | 2017-09-22 | 宁波大红鹰学院 | A kind of preparation method of bentonite base porous functional material |
| CN111157517A (en) * | 2020-01-03 | 2020-05-15 | 吉林烟草工业有限责任公司 | Method for detecting hexavalent chromium in cigarette mainstream smoke |
| US11584889B2 (en) * | 2021-01-04 | 2023-02-21 | Saudi Arabian Oil Company | Synthetic source rock with tea |
| CN113466397B (en) * | 2021-05-21 | 2022-05-03 | 中国地质大学（武汉） | Method for quantitatively evaluating contribution of organic pores to shale adsorbed gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1676151A (en) * | 1924-09-16 | 1928-07-03 | Ralph H Mckee | Filtering material and process of filtering |
| US4032305A (en) * | 1974-10-07 | 1977-06-28 | Squires Arthur M | Treating carbonaceous matter with hot steam |
| US4308146A (en) | 1977-05-02 | 1981-12-29 | Phillips Petroleum Company | Crushed raw oil shale as oil spill adsorbent |
| US4508743A (en) * | 1980-05-28 | 1985-04-02 | Societe D'assistance Technique Pour Produits Nestle S.A. | Caffeine adsorption |
| US4408999A (en) * | 1981-05-11 | 1983-10-11 | Exxon Research And Engineering Co. | Coal and oil shale beneficiation process |
| US5041210A (en) * | 1989-06-30 | 1991-08-20 | Marathon Oil Company | Oil shale retorting with steam and produced gas |
| US5554739A (en) * | 1994-12-15 | 1996-09-10 | Cabot Corporation | Process for preparing carbon materials with diazonium salts and resultant carbon products |
| US6030698A (en) * | 1994-12-19 | 2000-02-29 | Lockheed Martin Energy Research Corporation | Activated carbon fiber composite material and method of making |
| US6576145B2 (en) * | 1997-02-27 | 2003-06-10 | Continuum Environmental, Llc | Method of separating hydrocarbons from mineral substrates |
| US20060229476A1 (en) * | 2005-04-08 | 2006-10-12 | Mitchell Robert L Sr | Activated carbon monolith catalyst, methods for making same, and uses thereof |
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- 2007-07-19 US US12/375,156 patent/US20090308793A1/en not_active Abandoned
- 2007-07-19 CN CN2007800354131A patent/CN101516495B/en not_active Expired - Fee Related
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| CN110961073A (en) * | 2019-12-05 | 2020-04-07 | 中国石油大学(北京) | Shale adsorption material for oil-water separation and preparation method thereof |
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| RU2443468C2 (en) | 2012-02-27 |
| MA30646B1 (en) | 2009-08-03 |
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| IL196597A0 (en) | 2009-11-18 |
| US20090308793A1 (en) | 2009-12-17 |
| CA2658841C (en) | 2015-11-24 |
| CA2658841A1 (en) | 2008-01-31 |
| AU2007278836A1 (en) | 2008-01-31 |
| IL196597A (en) | 2013-11-28 |
| WO2008014526A2 (en) | 2008-01-31 |
| EP2046494A2 (en) | 2009-04-15 |
| CN101516495B (en) | 2013-04-10 |
| AU2007278836B2 (en) | 2012-04-05 |
| US20140202930A1 (en) | 2014-07-24 |
| WO2008014526A3 (en) | 2008-06-19 |
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