CN109133057B - Macroporous granular activated carbon and preparation method thereof - Google Patents
Macroporous granular activated carbon and preparation method thereof Download PDFInfo
- Publication number
- CN109133057B CN109133057B CN201811363973.6A CN201811363973A CN109133057B CN 109133057 B CN109133057 B CN 109133057B CN 201811363973 A CN201811363973 A CN 201811363973A CN 109133057 B CN109133057 B CN 109133057B
- Authority
- CN
- China
- Prior art keywords
- columnar
- activated carbon
- catalyst
- mixing
- carbon
- 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.)
- Active
Links
Classifications
-
- 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
- C01B32/354—After-treatment
- C01B32/384—Granulation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
The invention discloses a macroporous granular active carbon and a preparation method thereof, wherein charcoal is ground and sieved, and carbon powder particles smaller than 10 microns are taken; mixing sawdust with a catalyst and water, and heating for 1-3 h at 150 ℃ under a closed condition; mixing carbon powder particles with an adhesive, heating to 80-150 ℃ in a kneading machine, and kneading for 10-60 min to form a plastic material; putting the plastic material into a hydraulic forming machine to be extruded into columnar granules; under the protection of nitrogen, curing the columnar particles at the constant temperature of 200-500 ℃ for 30-120 min to obtain a columnar carbonized material; washing the columnar carbonized material with water to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon. The invention adopts carbon powder extrusion molding to prepare macroporous granular activated carbon, utilizes the gaps of carbon powder granules to form a macroporous structure, and can regulate and control the proportion of macropores by regulating the particle size of the carbon powder granules, molding pressure and the proportion of the carbon powder and an adhesive.
Description
Technical Field
The invention relates to a preparation method of activated carbon, in particular to a method for preparing macroporous granular activated carbon by carbon powder extrusion molding.
Background
Activated carbon is the most widely used material at present, and China is also the first country of production and export of the activated carbon in the world. The granular activated carbon has the advantages of high strength, strong adsorption force, no dust in the using process and suitability for continuous operation, is widely applied to the fields of liquid phase and gas phase adsorption, and has huge application prospects in the fields of environmental protection such as air pollution treatment, water purification and the like. At present, the granular activated carbon mainly comprises micropores and mesopores, has poor adsorption capacity on macromolecular impurities, cannot meet the requirements of capturing PM2.5 in the atmosphere, and can be refined by liquid-phase impurity removal of edible oil, diesel oil, lubricating oil and the like.
Since the invention of activated carbon, there has been a continuous effort to produce granular activated carbon using various methods. The granular activated carbon is prepared by activating the sawdust with phosphoric acid, phosphoric acid with the mass 4 times that of the sawdust is needed, so that a large amount of gas and liquid pollution is caused, the environmental protection treatment cost is high, and the time and the energy are consumed; the granular active carbon is prepared by bonding, molding and activating carbon powder and tar, and the granular active carbon is required to be subjected to the processes of kneading, carbonization, high-temperature steam activation and the like, so that the prepared product has no macropores, and has the problems of high manufacturing cost, low product yield, serious waste gas pollution and the like.
Influence of different phosphoric acid activation processes on the pore structure of activated carbon [ J]Carbon, 2009, 28 (1): 18-21.) bamboo blocks are used as raw materials, 80% concentrated phosphoric acid is used as an activating agent, and the weight ratio of the raw materials to the raw materials is 4: l, the activation temperature is 500 ℃, the activation time is 240min, and the specific surface area is 2127m2Per gram of activated carbon. Preparation of Long-handled almond shell activated carbon [ J ] by the Zinc chloride activation method of Li Bing et al (Li Bing, Li Yan, Xining Xia, et al., at the university of northwest]Northwest university journal (nature science edition) 2010,40 (5): ) The method is characterized in that the long-handled pecan activated carbon is prepared by a zinc chloride activation method, and the best process is that the mass fraction of a zinc chloride solution is 50%, the activation temperature is 600 ℃, and the activation time is 90min under experimental conditions. The specific surface area of the obtained activated carbon is 1633.08m2/g, iodine adsorption value of 883.78mg/g, methylene blue adsorption value of 165 mg/g. The chemical activation method for preparing the activated carbon uses a large amount of chemical reagents, so that certain corrosion is generated on equipment, and secondary pollution is caused to the environment. The patent (patent number ZL98115717.3) of Liulang et al, Shanxi institute of science and technology, of China, utilizes linear thermoplastic phenolic resin as a raw material, adds a curing agent before balling to prepare a blocky mixture, and then pulverizes the blocky mixture to 1.25-2.5mm to obtain the raw material resin; dispersing the raw material resin into a dispersing liquid containing a dispersing agent, and emulsifying to form balls; carbonizing the prepared ball under the protection of inert gas and activating with water vapor or carbon dioxide to obtain the phenolic resin-based spherical activated carbon. However, the related method has close relationship with the mixing, crushing and screening of the curing agent, the pore-forming agent and the phenolic resin, so the loss is large and the cost is high.
In conclusion, the method for preparing the granular activated carbon by adopting the chemical activation, the carbon powder and resin molding, carbonization and activation has the advantages of complex operation process, low product yield and secondary pollution to the environment.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a preparation method of granular activated carbon, which has the advantages of small environmental pollution, simplicity, easy implementation, good forming performance, high strength, large porosity of products and controllable pore diameter.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of macroporous particle activated carbon comprises the following steps:
(1) crushing carbon powder: grinding charcoal, and sieving to obtain charcoal powder particles smaller than 10 μm;
(2) preparing an adhesive: mixing the sawdust with a catalyst and water according to a mixing mass ratio of 10 (1-2) to 10-30, and heating for 1-3 hours at 150 ℃ under a closed condition;
(3) mixing: mixing the carbon powder particles obtained in the step (1) with the adhesive prepared in the step (2) according to the mass ratio of 10 (1-3), heating the mixture to 80-150 ℃ in a kneading machine, and kneading the mixture for 10-60 min to form a plastic material;
(4) molding: putting the plastic material obtained in the step (3) into a hydraulic forming machine, and extruding into columnar particles;
(5) and (3) curing: under the protection of nitrogen, curing the columnar particles at the constant temperature of 200-500 ℃ for 30-120 min to obtain a columnar carbonized material;
(6) recovering the catalyst: and (5) washing the columnar carbonized material obtained in the step (5) to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon.
Wherein, in the step (2), the catalyst is one or a mixture of more than two of phosphoric acid, zinc chloride or sulfuric acid.
Preferably, the catalyst is a mixture of phosphoric acid and zinc chloride in a mass ratio of 3: 1.
Preferably, the catalyst is a mixture of sulfuric acid and zinc chloride in a mass ratio of 2: 1.
Preferably, in the step (5), the curing process is to heat the mixture from room temperature to 200-500 ℃ at a speed of 10 ℃/min and keep the temperature for 30-120 min.
The macroporous granular activated carbon prepared by the preparation method has the specific surface area of 400-700 m2(ii) a pore volume of 0.1 to 1.0ml/mg, D>The 50nm macropore volume ratio is 70-95%, the iodine adsorption value is 545-1000 mg/g, and the caramel decolorization ratio is 50-120%.
Has the advantages that:
1. according to the invention, carbon powder is extruded and molded to prepare macroporous active carbon particles, a macroporous structure is formed by utilizing gaps among the carbon powder particles, and the proportion of macropores can be regulated by regulating the particle size of the carbon powder particles, molding pressure and the proportion of the carbon powder and an adhesive;
2. the invention mixes the wood dust, the catalyst and the water as the adhesive, and the carbon powder particles are matched to have good forming performance and high strength, thereby being beneficial to forming a macroporous structure;
3. compared with the existing method for preparing granular activated carbon by using sawdust phosphoric acid activated hair, the method provided by the invention can obviously reduce the consumption of phosphoric acid in raw materials, reduce the cost, reduce the pollution to the environment, is simple and feasible, does not need chemical reagents or high-temperature activation, has a high product macroporosity and a controllable pore diameter, and is suitable for gas phase PM2.5 and oil product refining.
Detailed Description
The invention will be better understood from the following examples.
The following examples test methods for specific surface area and adsorption properties of the prepared granular activated carbon as follows:
(1) determination of specific surface area: measuring a nitrogen adsorption isotherm by using carbon microspheres under a liquid nitrogen condition, and calculating the specific surface area according to a BET formula;
(2) determination of iodine adsorption value and methylene blue adsorption value: the iodine adsorption value is measured according to GB/T12496.8-1999 "measurement of iodine adsorption value of wood activated carbon test method"; the methylene blue adsorption value was measured according to GB/T12496.9-1999 "method for testing Wood activated carbon for methylene blue adsorption value".
Example 1
(1) Crushing carbon powder: grinding charcoal, and sieving to obtain charcoal powder particles smaller than 10 μm;
(2) preparing an adhesive: mixing the wood chips with phosphoric acid and water according to the mass ratio of 10:1:10, and heating for 1h at 150 ℃ under a closed condition to prepare an adhesive;
(3) mixing: mixing carbon powder particles and an adhesive according to a mass ratio of 10:1, heating to 80 ℃ in a kneading machine, and kneading for 60min to form a plastic material;
(4) molding: putting the kneaded plastic material into a hydraulic forming machine, adjusting the pressure to be 2MPa, and extruding into columnar particles;
(5) and (3) curing: heating the columnar granular carbon to 200 ℃ at a heating rate of 10 ℃/min, and keeping the temperature for 120min for solidification to obtain a columnar carbonized material;
(6) recovering the catalyst: and (3) washing the carbonized material with water to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon. The prepared granular activated carbon has the strength of 93 percent and the specific surface area of 400m2Per g, pore volume of 0.1ml/mg, macropore (D)>50nm) volume ratio of 71 percent, iodine adsorption value of 545mg/g and caramel decolorization ratio of 50 percent.
Example 2
(1) Crushing carbon powder: grinding charcoal powder, sieving, and collecting charcoal powder particles smaller than 10 μm;
(2) preparing an adhesive: mixing the wood chips with zinc chloride and water according to the mass ratio of 10:2:30, and heating for 3 hours at 150 ℃ under a sealed condition;
(3) mixing: mixing carbon powder particles and an adhesive according to a mass ratio of 10:3, heating to 150 ℃ in a kneading machine, and kneading for 10min to form a plastic material;
(4) molding: putting the kneaded plastic material into a hydraulic forming machine, adjusting the pressure to be 20MPa, and extruding into columnar particles;
(5) and (3) curing: heating the columnar granular carbon to 500 ℃ at a heating rate of 10 ℃/min, and curing at a constant temperature for 30min to obtain a columnar carbonized material;
(6) recovering the catalyst: and (3) washing the carbonized material with water to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon. The strength of the prepared granular activated carbon is 99 percent, and the specific surface area is 550m2A pore volume of 1.0ml/mg, a large pore (D)>50nm) volume ratio of 85 percent, iodine adsorption value of 780mg/g and caramel decolorization ratio of 90 percent.
Example 3
(1) Crushing carbon powder: grinding charcoal powder, sieving, and collecting charcoal powder particles smaller than 10 μm.
(2) Preparing an adhesive: mixing sawdust with a catalyst and water according to a mass ratio of 10:2:20, heating for 2 hours at 150 ℃ under a closed condition, wherein the catalyst is a mixture of phosphoric acid and zinc chloride according to a mass ratio of 3: 1;
(3) mixing: mixing carbon powder particles and an adhesive according to a mass ratio of 10:2, heating to 120 ℃ in a kneader, and kneading for 30min to form a plastic material;
(4) molding: putting the kneaded plastic material into a hydraulic forming machine, adjusting the pressure to be 20MPa, and extruding into columnar particles;
(5) and (3) curing: heating the columnar granular carbon to 300 ℃ at the heating rate of 10 ℃/min, and curing at constant temperature for 90min to obtain a columnar carbonized material;
(6) recovering the catalyst: and (3) washing the carbonized material with water to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon. Granule activityThe strength of the charcoal is 99 percent, and the specific surface area is 700m2A pore volume of 1.0ml/mg, a large pore (D)>50nm) volume ratio of 95 percent, iodine adsorption value of 1000mg/g and caramel decolorization ratio of 120 percent.
Example 4
(1) Crushing carbon powder: grinding charcoal powder, sieving, and collecting charcoal powder particles smaller than 10 μm;
(2) preparing an adhesive: mixing sawdust with a catalyst and water according to a mass ratio of 10:2:30, heating for 2 hours at 150 ℃ under a closed condition, wherein the catalyst is a mixture of sulfuric acid and zinc chloride according to a mass ratio of 2: 1;
(3) mixing: mixing carbon powder particles and an adhesive according to a mass ratio of 10:2, heating to 120 ℃ in a kneader, and kneading for 30min to form a plastic material;
(4) molding: putting the kneaded plastic material into a hydraulic forming machine, adjusting the pressure to be 20MPa, and extruding into columnar particles;
(5) and (3) curing: heating the columnar granular carbon to 300 ℃ at the heating rate of 10 ℃/min, and curing at constant temperature for 90min to obtain a columnar carbonized material;
(6) recovering the catalyst: and (3) washing the carbonized material with water to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon. The strength of the granular activated carbon is 99 percent, and the specific surface area is 690m2Per g, pore volume of 0.99ml/mg, macropore (D)>50nm) volume ratio of 94.5 percent, iodine adsorption value of 982mg/g and caramel decolorization rate of 120 percent.
Example 5
(1) Crushing carbon powder: grinding charcoal powder, sieving, and collecting charcoal powder particles smaller than 10 μm;
(2) preparing an adhesive: mixing the wood chips with sulfuric acid and water according to the mass ratio of 10:2:20, and heating for 1h at 150 ℃ under a sealed condition;
(3) mixing: mixing carbon powder particles and an adhesive according to a mass ratio of 10:2, heating the mixture in a kneader to 100 ℃, and kneading the mixture for 60min to form a plastic material;
(4) molding: putting the kneaded plastic material into a hydraulic forming machine, adjusting the pressure to 10MPa, and extruding into columnar particles;
(5) and (3) curing: heating the columnar granular carbon to 400 ℃ at the heating rate of 10 ℃/min, and curing at constant temperature for 60min to obtain a columnar carbonized material;
(6) recovering the catalyst: and (3) washing the carbonized material with water to recover the catalyst, rinsing to be neutral, and drying to obtain the macroporous granular activated carbon. The strength of the prepared granular activated carbon is 96 percent, and the specific surface area is 650m2Per g, pore volume of 0.8ml/mg, macropore (D)>50nm) volume ratio of 91 percent, iodine adsorption value of 920mg/g and caramel decolorization ratio of 110 percent.
The invention provides a large-pore granular activated carbon and a preparation method thereof, and a plurality of methods and ways for realizing the technical scheme, and the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (1)
1. A preparation method of macroporous particle activated carbon is characterized by comprising the following steps:
(1) crushing carbon powder: grinding charcoal, and sieving to obtain charcoal powder particles smaller than 10 μm;
(2) preparing an adhesive: mixing the sawdust with a catalyst and water according to a mixing mass ratio of 10 (1-2) to 10-30, and heating for 1-3 hours at 150 ℃ under a closed condition;
(3) mixing: mixing the carbon powder particles obtained in the step (1) with the adhesive prepared in the step (2) according to the mass ratio of 10 (1-3), heating the mixture to 80-150 ℃ in a kneading machine, and kneading the mixture for 10-60 min to form a plastic material;
(4) molding: putting the plastic material obtained in the step (3) into a hydraulic forming machine, and extruding into columnar particles;
(5) and (3) curing: under the protection of nitrogen, curing the columnar particles at the constant temperature of 200-500 ℃ for 30-120 min to obtain a columnar carbonized material;
(6) recovering the catalyst: washing the columnar carbonized material obtained in the step (5) with water to recover the catalyst, rinsing to be neutral, and drying to obtain macroporous granular activated carbon;
in the step (5), the curing process is to heat the mixture from room temperature to 200-500 ℃ at a speed of 10 ℃/min and keep the temperature for 30-120 min;
the specific surface area of the prepared macroporous particle activated carbon is 400-700 m2(ii) a pore volume of 0.1 to 1.0ml/mg, D>The 50nm macropore volume ratio is 70-95%, the iodine adsorption value is 545-1000 mg/g, and the caramel decolorization ratio is 50-120%;
the catalyst is a mixture of phosphoric acid and zinc chloride according to a mass ratio of 3:1, or a mixture of sulfuric acid and zinc chloride according to a mass ratio of 2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811363973.6A CN109133057B (en) | 2018-11-16 | 2018-11-16 | Macroporous granular activated carbon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811363973.6A CN109133057B (en) | 2018-11-16 | 2018-11-16 | Macroporous granular activated carbon and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109133057A CN109133057A (en) | 2019-01-04 |
| CN109133057B true CN109133057B (en) | 2020-09-25 |
Family
ID=64805990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811363973.6A Active CN109133057B (en) | 2018-11-16 | 2018-11-16 | Macroporous granular activated carbon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109133057B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626637A (en) * | 1993-10-25 | 1997-05-06 | Westvaco Corporation | Low pressure methane storage with highly microporous carbons |
| US6060424A (en) * | 1995-09-28 | 2000-05-09 | Westvaco Corporation | High energy density carbons for use in double layer energy storage devices |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151961C (en) * | 1999-08-31 | 2004-06-02 | 林天安 | Method for preparing vehicular active carbon by using straw stalks and saw dust |
| CN1511784A (en) * | 2002-12-28 | 2004-07-14 | 谢仁智 | Process for preparing large and medium pore high performance active carbon |
| CN103922338A (en) * | 2014-04-15 | 2014-07-16 | 浙江省林业科学研究院 | Granulating method and equipment for producing granular activated carbon without additional binding agent |
| CN107381571A (en) * | 2017-07-21 | 2017-11-24 | 广东韩研活性炭制造有限公司 | A kind of preparation method of automobile canister special-purpose activated charcoal |
-
2018
- 2018-11-16 CN CN201811363973.6A patent/CN109133057B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626637A (en) * | 1993-10-25 | 1997-05-06 | Westvaco Corporation | Low pressure methane storage with highly microporous carbons |
| US6060424A (en) * | 1995-09-28 | 2000-05-09 | Westvaco Corporation | High energy density carbons for use in double layer energy storage devices |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109133057A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kang et al. | Preparation of activated carbon with highly developed mesoporous structure from Camellia oleifera shell through water vapor gasification and phosphoric acid modification | |
| CN103482597B (en) | A kind of preparation method of middle macropore carbon | |
| CN103663450B (en) | A kind of high-specific surface area carbosphere and preparation method thereof | |
| CN101890336B (en) | Activated alumina and activated carbon compounded material and preparation method thereof | |
| CN100497170C (en) | Granule decoloration active carbon and preparation method thereof | |
| CN104226256B (en) | Spherical forming Cu base metal organic skeleton-graphene oxide composite material and preparation method of spherical forming Cu base metal organic skeleton-graphene oxide composite material | |
| CN1986401A (en) | Improved process for preparing porous microsphere active carbon | |
| CN105293491A (en) | KOH solid activated active carbon preparation and forming method | |
| JPH01230414A (en) | Activated carbon and production thereof | |
| KR20150119368A (en) | Granular activated carbon having many mesopores, and manufacturing method for same | |
| CN106587047B (en) | A kind of preparation method of nano-pore charcoal | |
| CN110064367A (en) | A kind of biomass-based activated carbon microballon and its preparation method and application | |
| CN102432004B (en) | Active carbon for deeply purifying drinking water and preparation method thereof | |
| Ridassepri et al. | Activated carbon from bagasse and its application for water vapor adsorption | |
| CN102862983A (en) | Preparation method of spherical active carbon for capturing CO2 | |
| CN102674346A (en) | Process for preparing high-specific surface area composite pore structure coal-based activated carbon by using low dosage of KOH | |
| CN109133057B (en) | Macroporous granular activated carbon and preparation method thereof | |
| CN109019591B (en) | Preparation method of asphalt-based spherical activated carbon with low cost and hierarchical pore structure | |
| CN105129770A (en) | Morphological control method for functional hydrothermal carbon | |
| CN107617426A (en) | A kind of preparation method of high adsorption capacity crystalline substance glue microsphere particle | |
| CN104445145A (en) | Simple preparation method of porous carbon with hierarchical pore structure | |
| CN109052396A (en) | A kind of preparation method of household water-purifying machine active carbon | |
| CN107285311B (en) | Method for preparing mesoporous bamboo activated carbon through physical activation | |
| CN111762779B (en) | Coal-based activated carbon, columnar activated carbon and preparation method thereof | |
| CN109775707A (en) | A kind of preparation process for the new-energy automobile absorbent charcoal material that specific surface area is high |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |