WO2007114849A2 - Charbon actif obtenu à partir d'un glucide - Google Patents
Charbon actif obtenu à partir d'un glucide Download PDFInfo
- Publication number
- WO2007114849A2 WO2007114849A2 PCT/US2006/060294 US2006060294W WO2007114849A2 WO 2007114849 A2 WO2007114849 A2 WO 2007114849A2 US 2006060294 W US2006060294 W US 2006060294W WO 2007114849 A2 WO2007114849 A2 WO 2007114849A2
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- WO
- WIPO (PCT)
- Prior art keywords
- activated carbon
- group
- carbon
- sulfates
- activation
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This invention relates to a material and means for rendering a substrate to a high surface area by creating significant internal pore structure. More particularly, this invention relates to methods for producing activated carbon having internal pore structure and high adsorptive activity from carbohydrate precursor.
- the invention activated carbons are used in multiple liquid and gas adsorptive applications, and are particularly advantageously used in electrodes for energy storage devices.
- Activated carbon is a microcrystalline, nongraphitic form of carbon that has been processed to increase internal porosity. Characterized by a large specific surface area, typically in the range of 500-2500 m 2 /g, activated carbons have industrial uses in the purification of liquids and gases by the adsorption of gases and vapors from gases and of dissolved or dispersed substances from liquids such as for water purification. Due to their extended surface area and microporous structure, they find applications as filters, membranes, sorbents and catalyst supports for materials in both gas and liquid phases. Additionally, activated carbon has extensively used as electrode material for energy storage devices.
- Pore structures can assume a multitude of shapes and configurations each varying in shape, depth and width. Pores having characteristic dimensions (diameter or width) less than 2 nm are generally defined as micropores, those between 2 nm and 50 m are considered to be mesopores, and those greater than 50 nm dimension are described as macropores.
- activated carbon has been made from material of plant origin, such as hardwood and softwood, corncobs, kelp, coffee beans, rice hulls, fruit pits, nutshells, and wastes such as bagasse.
- Activated carbon also has been made from peat, lignite, soft and hard coals, tars and pitches, asphalt, petroleum residues, and carbon black.
- Powdered carbons are generally used in liquid-phase applications where the carbon is mixed with the liquid being purified and is then separated from the liquid using filtration technology.
- Granular carbons are used in both vapor and liquid-phase applications where, again, the carbon is held in a canister or large column.
- Pelletized carbons are generally used in vapor-phase applications where the carbon is held in a canister or large column.
- activated carbon are useful for most applications involving flowing liquid and vapor-phase streams where an activated carbon-filled canister, column, or filtration apparatus can be installed, such as home and municipal water purification, industrial and residential air purification, and purification of in-process streams in food, chemical and pharmaceutical production processes.
- activated carbon for other applications which are not amenable to having equipment for containing the carbon, more convenient forms of activated carbon have been developed.
- These forms include blends of powdered activated carbon and binder that can be applied directly to a variety of pre-formed substrates, thereby eliminating the need for a canister or column-type device to hold pelletized or granular carbon or a filtration device to capture the powdered carbon.
- Activation of the organic raw material can be accomplished by one of two distinct processes: (1) chemical activation or (2) thermal activation.
- the effective porosity of activated carbon produced by thermal activation is the result of gasification of the carbon at relatively high temperatures after an initial carbonization of the raw material.
- the porosity of chemically activated products generally is created by chemical dehydration reactions occurring at significantly lower temperatures.
- chemical activation process may be performed in the presence of alkali, often known as alkaline activation process (U.S. Patent No. 5,965,483).
- Activated carbons produced by thermal activation are typically more microporous (i.e., pore size no more than 1.8 nm); while carbons produced by chemical activation are typically more mesoporous (i.e., pore size in a range of above 1.8 nm up to 5 nm). Pore size distribution is often a controlling factor in adsorption of liquid and gas-phase contaminants.
- mesoporous activated carbon has been known for its effectiveness in several liquid phase and catalytic applications. There has been a continuing effort to develop a production process for mesoporous activated carbon employing carbon precursors that are abundantly available from natural sources. Furthermore, the process is to be lower in cost and easy to implement and amenable to reliable duplication.
- the present invention is to provide a process for producing mesoporous activated carbon that is simple, highly reproducible and controllable for pore characteristics, and lower in cost. Specifically, the present invention is to provide a process for producing mesoporous activated carbon from a naturally abundant carbon precursor such as carbohydrate. [0010] Another application for activated carbon is used as electrodes for capacitors (U.S. Patent Nos. 5,905,629; 5,926,361; 6,043,183; and 6,060,424).
- Capacitors such as electron double layer (EDLC) capacitor, ultracapacitor and supercapacitor, are based on double-layer capacitance store energy in a polarized liquid layer only a few angstroms thick at the interface between an ionically conducting electrolyte solution and an electronically conducting electrode. The separation of charge in the ionic species at the interface (called a double layer) produces a standing electric field. If other factors are equal, the larger the electrode surface area the more charge can be stored. In addition, because no chemical reactions take place during the charge/discharge cycle, these devices can be cycled many times without degradation.
- EDLC electron double layer
- capacitors contains at least two such electrodes, at least one porous separator interposed between the at least two such electrodes and an electrolytic solution that is in contact with the at least two such electrode structures and the at least one porous separator.
- the electrolytic solution for double layer capacitor devices may be aqueous electrolytes such as potassium hydroxide and sulfuric acid, or organic electrolytes such as NEt 4 BF 4 dissolved in propylene carbonate or acetonitrile.
- U.S. Patent Application No. 2006/0,093,915 teaches the process of producing activated carbon derived from a carbon precursor selected from naturally occurring carbohydrates, pitch derived from coal tar, pitch derived from petroleum and combinations. Nitrogen functionality compound must be added into the carbon prior to activation process. The required level of incorporated nitrogen functionality is greater than 1.0 wt % elemental nitrogen.
- U.S. Patent Application No. 2005/0,207,962 teaches that mesoporous activated carbon can be produced from a mixture comprising at least one carbohydrate, at least one dehydrating component, and at least one nonmetallic cationic component. Both of these processes require that a carbon precursor is activated in the presence of additional component or additional step from conventional carbon activation process.
- the present invention is to provide a process for producing activated carbon suitable for use as in capacitor electrode that is simple, highly reproducible and controllable for pore characteristics, and lower in cost.
- the present invention is to provide a process for producing activated carbon from carbohydrate precursor, which is suitable for use as in capacitor electrode, that does not require additional components to carbon precursor or additional step to the conventional carbon activation process.
- It is another object of the present invention is to provide activated carbon derived from a naturally abundant carbon precursor such as carbohydrate, which is suitable for use as in electrodes for energy storage devices.
- It is yet another object of the present invention is to provide a method for producing activated carbon derived from carbohydrate precursor.
- It is a further object of the present invention is to provide an electrode comprising the activated carbon of the present invention.
- the objectives of this invention are met by pyrolyzing dewatered carbohydrate carbon precursor, and then activating the obtained carbon material.
- the produced activated carbon exhibiting internal pore structure and high surface area is suitable for use in multiple liquid and gas adsorptive applications and advantageously in electrodes for energy storage devices. DESCRIPTION OF THE PREFERRED EMBODIMENT
- the activated carbon of the present invention was prepared by a process comprising:
- the activation process in step (c) may be performed in the presence of carbon dioxide, or high temperature stream, or activating agent selected from the group consisting of alkali metal hydroxides, carbonates, sulfides, and sulfates; alkaline earth carbonates, chlorides, sulfates, and phosphates; phosphoric acid; polyphosphoric acid; pyrophosphoric acid; zinc chloride; sulfuric acid; oleum; and combinations thereof.
- the activated carbon may be further washed to remove the excess activating agent and then dried.
- the activated carbon of the present invention was prepared by a process comprising:
- the activation process in step (c) may be performed in the presence of carbon dioxide, or high temperature stream, or activating agent selected from the group consisting of alkali metal hydroxides, carbonates, sulfides, and sulfates; alkaline earth carbonates, chlorides, sulfates, and phosphates; phosphoric acid; polyphosphoric acid; pyrophosphoric acid; zinc chloride; sulfuric acid; oleum; and combinations thereof.
- the activated carbon may be further washed to remove the excess activating agent and then dried.
- the heat treatment in step (d) may be performed in the presence of at least one compound selected from the group consisting of alkali metal hydroxides, carbonates, sulfides, and sulfates; alkaline earth carbonates, chlorides, sulfates, and phosphates; phosphoric acid; polyphosphoric acid; pyrophosphoric acid; zinc chloride; sulfuric acid; oleum; and combinations thereof.
- saccharide based compounds including, but are not limited to, monosaccharides such as glucose and fructose; disaccharides such as sucrose and lactose; oligosaccharides and polysaccharides such as starch, corn syrup, and cellulose. Furthermore, these saccharide based compounds may be in form of powder, granular, and syrup.
- the invention activated carbon may be produced or formed into a variety of shapes or objects including, but are not limited to, powders, granules, pellets, blocks, monoliths, sheets, filaments, and tubes.
- the invention activated carbon has a pore size in the range of about 0.8 nm to about 50 nm.
- the BET surface area of the activated carbon of the present invention ranges from about 500 m 2 /g to 3,000 m 2 /g.
- the invention activated carbon may be used to produce electrodes for energy storage devices.
- energy storage devices in the present invention refers to electron double layer (EDLC) capacitor, ultracapacitor, supercapacitor, battery, fuel cell and any other devices capable of storing energy for systems such as, but are not limited to, automobile and other transportation, power quality, electronic appliances, and power stabilizer devices.
- EDLC capacitor of the present invention contains electrodes, at least one porous separator interposed between the electrodes and an electrolytic solution that is in contact with the electrode structures and the at least one porous separator.
- Electrolytic solutions may be organic electrolytic solutions and aqueous electrolytic solutions.
- the electrodes comprising typically about 90-95% weight of activated carbon were formed and used for the assembly of EDLC capacitor.
- the capacitance of the EDLC containing electrodes made of the invention activated carbon were evaluated and compared to those containing electrodes made of activated carbon controls.
- the activated carbons were obtained from carbon dioxide activation of sucrose precursor at about 95O 0 C for different activation lengths of time: 1 hour, 2 hours, 4 hours and 8 hours.
- the obtained activated carbon from different activation length of time each was formed into electrodes typically comprising about 90-95% weight of activated carbon.
- the EDLC capacitors were assemblies using electrodes made of activated carbon from different activation time length. The capacitance of these EDLC cells were compared to each other, and to those of the EDLC containing electrodes made of activated carbon controls.
- Three activated carbon controls were used for comparison: YP- 17, RP- 15, and RP-20; all are commercially available from Kuraray.
- EDLC capacitor having electrodes made of activated carbon from sucrose precursor under 2-hour carbon dioxide activation showed the highest cell energy of 47.8 J/cc.
- the cell energies of EDLC capacitors containing sucrose-based activated carbon were 29.0 J/cc for 1-hour activation, 32.7 J/cc for 4-hour activation, and 31.3 J/cc for 8-hour activation.
- EDLC containing electrodes made of sucrose precursor under 2- hour carbon dioxide activation showed superior cell energy to those containing electrodes made of commercial activated carbons YP- 17 and RP-15.
- EDLC containing electrodes made of activated carbon from sucrose precursor at the optimum activation condition showed comparable cell energy to that of EDLC made of RP-20 which is the best known activated carbon for the EDLC application.
- the activated carbons were obtained from alkaline activation of sucrose precursor using potassium hydroxide (KOH).
- KOH potassium hydroxide
- the activated carbon was formed into electrodes which were subsequently assembled to EDLC capacitor.
- the capacitance of the EDLC cell was measured and compared to those of the EDLC containing electrodes made of activated carbon controls.
- Four alkali activated carbons were used as controls: activated carbon from coke; coconut-based activated carbon NACAR G210 commercially available from PICA, another coconut-based activated carbon from PICA, and activated carbon from Rayonier fly ash.
- Both electrode capacitance and electrolyte decomposition voltage of the capacitor cell (EDV) were measured for determination of the EDLC energy capacity.
- EDLC containing electrodes made of sucrose-derived alkali activated carbon showed superior cell energy to those of control.
- the invention activated carbon was also used as electrode for battery.
- the capacity of battery was measured both for irreversible capacity and reversible capacity at different heat treatment temperature (HTT). Furthermore, the ⁇ value which is a ratio of reversible capacity to irreversible capacity was determined and compared to those of battery using conventional electrode. (TABLE III) TABLE III
- the ⁇ values of the batteries containing electrodes made of the invention activated carbon ranged from about 2 to about 14, based on the heat treatment temperature.
- Conventional cobalt electrode systems have ⁇ values of 13-14 and Ni electrode systems 5-6; therefore, the invention activated carbon can be used as electrode for battery having the capacity tailored to match those of the conventional systems using cobalt or Ni electrode.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Engineering & Computer Science (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
L'invention concerne une matière et des moyens permettant d'obtenir un substrat présentant une surface active étendue par création d'une structure poreuse interne importante. Plus particulièrement, l'invention concerne des procédés destinés à produire un charbon actif présentant une structure interne poreuse et une haute activité d'adsorption à partir d'un précurseur de glucide. Les charbons actifs de l'invention sont utilisés dans de multiples applications d'adsorption de liquides et de gaz et sont utilisés de manière particulièrement avantageuse dans des électrodes pour dispositifs de stockage d'énergie.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US73369005P | 2005-11-04 | 2005-11-04 | |
US60/733,690 | 2005-11-04 |
Publications (2)
Publication Number | Publication Date |
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WO2007114849A2 true WO2007114849A2 (fr) | 2007-10-11 |
WO2007114849A3 WO2007114849A3 (fr) | 2007-12-13 |
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PCT/US2006/060294 WO2007114849A2 (fr) | 2005-11-04 | 2006-10-27 | Charbon actif obtenu à partir d'un glucide |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010075053A1 (fr) * | 2008-12-15 | 2010-07-01 | Corning Incorporated | Charbons actifs pour supercondensateurs à haute densité d'énergie |
CN101950683A (zh) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | 超级电容器半球状活性炭电极材料的制备方法 |
US7998898B2 (en) | 2007-10-26 | 2011-08-16 | Corning Incorporated | Sorbent comprising activated carbon, process for making same and use thereof |
US8124213B2 (en) | 2008-05-30 | 2012-02-28 | Corning Incorporated | Flow-through sorbent comprising a metal sulfide |
US8691722B2 (en) | 2008-07-03 | 2014-04-08 | Corning Incorporated | Sorbent comprising activated carbon particles, sulfur and metal catalyst |
US8741243B2 (en) | 2007-05-14 | 2014-06-03 | Corning Incorporated | Sorbent bodies comprising activated carbon, processes for making them, and their use |
CN103991872A (zh) * | 2014-05-09 | 2014-08-20 | 山东大学 | 一种有机醇/酸低温制备高含氧官能团活性炭的方法 |
CN105244473A (zh) * | 2014-07-10 | 2016-01-13 | 北京化工大学 | 一种提高锂离子电池炭负极材料电化学性能的后处理方法 |
WO2016032915A1 (fr) * | 2014-08-23 | 2016-03-03 | Entegris, Inc. | Adsorbant de carbone microporeux à partir de glucides naturels |
WO2017035086A1 (fr) * | 2015-08-22 | 2017-03-02 | Entegris, Inc. | Adsorbant de pyrolysat d'hydrate de carbone ainsi que systèmes et procédés utilisant celui-ci |
WO2017035023A1 (fr) * | 2015-08-22 | 2017-03-02 | Entegris, Inc. | Adsorbants de type pyrolysat à base de cellulose microcristalline et procédés de fabrication et d'utilisation associés |
WO2017205960A1 (fr) | 2016-05-30 | 2017-12-07 | Adven Industries, Inc. | Charbons actifs présentant des aires de surface élevées et procédés pour leur fabrication |
US11060035B2 (en) | 2016-07-07 | 2021-07-13 | Adven Industries, Inc. | Methods for enhancing efficiency of bitumen extraction from oilsands using activated carbon containing additives |
GR1010189B (el) * | 2020-10-01 | 2022-03-17 | Ευσταθιος Βασιλειου Λιακος | Ενεργος ανθρακας απο επιτραπεζια ζαχαρη |
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US5403809A (en) * | 1992-12-21 | 1995-04-04 | W. R. Grace & Co.-Conn. | Composite inorganic supports containing carbon for bioremediation |
US20050191230A1 (en) * | 2004-03-01 | 2005-09-01 | Ryusuke Shigematsu | Production process for carbonized product and carbonized product obtained by the same process |
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Cited By (25)
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---|---|---|---|---|
US8741243B2 (en) | 2007-05-14 | 2014-06-03 | Corning Incorporated | Sorbent bodies comprising activated carbon, processes for making them, and their use |
US7998898B2 (en) | 2007-10-26 | 2011-08-16 | Corning Incorporated | Sorbent comprising activated carbon, process for making same and use thereof |
US8124213B2 (en) | 2008-05-30 | 2012-02-28 | Corning Incorporated | Flow-through sorbent comprising a metal sulfide |
US8691722B2 (en) | 2008-07-03 | 2014-04-08 | Corning Incorporated | Sorbent comprising activated carbon particles, sulfur and metal catalyst |
WO2010075053A1 (fr) * | 2008-12-15 | 2010-07-01 | Corning Incorporated | Charbons actifs pour supercondensateurs à haute densité d'énergie |
JP2012512129A (ja) * | 2008-12-15 | 2012-05-31 | コーニング インコーポレイテッド | 高エネルギー密度ウルトラキャパシタ用活性炭材料 |
US8318356B2 (en) | 2008-12-15 | 2012-11-27 | Corning Incorporated | Activated carbon materials for high energy density ultracapacitors |
CN101950683A (zh) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | 超级电容器半球状活性炭电极材料的制备方法 |
CN103991872A (zh) * | 2014-05-09 | 2014-08-20 | 山东大学 | 一种有机醇/酸低温制备高含氧官能团活性炭的方法 |
CN105244473A (zh) * | 2014-07-10 | 2016-01-13 | 北京化工大学 | 一种提高锂离子电池炭负极材料电化学性能的后处理方法 |
TWI663123B (zh) * | 2014-08-23 | 2019-06-21 | 恩特葛瑞斯股份有限公司 | 來自天然醣類的微孔碳吸附劑 |
KR102130196B1 (ko) | 2014-08-23 | 2020-07-03 | 엔테그리스, 아이엔씨. | 천연 탄수화물로부터의 미세다공성 탄소 흡착제 |
US10335763B2 (en) | 2014-08-23 | 2019-07-02 | Entegris, Inc. | Microporous carbon monoliths from natural carbohydrates |
KR20170044664A (ko) * | 2014-08-23 | 2017-04-25 | 엔테그리스, 아이엔씨. | 천연 탄수화물로부터의 미세다공성 탄소 흡착제 |
CN106660009A (zh) * | 2014-08-23 | 2017-05-10 | 恩特格里斯公司 | 来自天然碳水化合物的微孔碳吸附剂 |
WO2016032915A1 (fr) * | 2014-08-23 | 2016-03-03 | Entegris, Inc. | Adsorbant de carbone microporeux à partir de glucides naturels |
CN108136365A (zh) * | 2015-08-22 | 2018-06-08 | 恩特格里斯公司 | 微晶纤维素热解吸附剂和其制造与使用方法 |
WO2017035023A1 (fr) * | 2015-08-22 | 2017-03-02 | Entegris, Inc. | Adsorbants de type pyrolysat à base de cellulose microcristalline et procédés de fabrication et d'utilisation associés |
WO2017035086A1 (fr) * | 2015-08-22 | 2017-03-02 | Entegris, Inc. | Adsorbant de pyrolysat d'hydrate de carbone ainsi que systèmes et procédés utilisant celui-ci |
CN109195907A (zh) * | 2016-05-30 | 2019-01-11 | 爱德温工业公司 | 具有高表面积的活性炭及其制备方法 |
WO2017205960A1 (fr) | 2016-05-30 | 2017-12-07 | Adven Industries, Inc. | Charbons actifs présentant des aires de surface élevées et procédés pour leur fabrication |
US11124418B2 (en) | 2016-05-30 | 2021-09-21 | Adven Industries, Inc. | Activated carbons with high surface areas and methods of making same |
CN109195907B (zh) * | 2016-05-30 | 2023-07-25 | 爱德温工业公司 | 具有高表面积的活性炭及其制备方法 |
US11060035B2 (en) | 2016-07-07 | 2021-07-13 | Adven Industries, Inc. | Methods for enhancing efficiency of bitumen extraction from oilsands using activated carbon containing additives |
GR1010189B (el) * | 2020-10-01 | 2022-03-17 | Ευσταθιος Βασιλειου Λιακος | Ενεργος ανθρακας απο επιτραπεζια ζαχαρη |
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