CN111217369A - Benzene protection active carbon and preparation method thereof - Google Patents
Benzene protection active carbon and preparation method thereof Download PDFInfo
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- CN111217369A CN111217369A CN202010163001.3A CN202010163001A CN111217369A CN 111217369 A CN111217369 A CN 111217369A CN 202010163001 A CN202010163001 A CN 202010163001A CN 111217369 A CN111217369 A CN 111217369A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The invention provides benzene protection activated carbon and a preparation method thereof. The preparation raw materials comprise the following substances in parts by weight: 70-80 parts of raw material coal and 20-30 parts of binder; wherein the raw material coal comprises a first raw material coal and a second raw material coal; the first raw material coal is bituminous coal, the volatile matter is 24-35 wt%, and the ash content is less than 10 wt%; the second raw material coal is anthracite, the volatile matter is 5-10 wt%, and the ash content is less than 6 wt%; in the raw material coal, the content of the second raw material coal is 50-80 wt%; the volatile content of the raw material coal is 10-20 wt%; the binder comprises coal tar and a solid binder, and the components of the solid binder at least comprise sodium hydroxymethyl cellulose; and the content of the solid binder in the binder is 20-40 wt%. The preparation method comprises the following steps: kneading and pressing strips, carbonizing and activating. The benzene protective activated carbon has high benzene adsorption value on the basis of ensuring the strength; the preparation method is simple and easy to operate, and the prepared product has high strength and benzene adsorption value.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to benzene protection activated carbon and a preparation method thereof.
Background
With the development of industry, the emission of organic waste gas is rapidly increased, and a large amount of multi-component organic waste gas containing benzene and toluene is emitted in the industries of coating, printing, insulating materials, enameled wires, resin processing, leather processing and the like. The recovery of benzene, an organic waste gas, in chemical production is a major problem in the chemical industry at present. After the benzene steam is discharged into the atmosphere, the quality of the atmospheric environment is reduced, serious harm is brought to the human health, and huge loss is caused to national economy. Benzene is used as a harmful substance in the national environmental protection standard, and the concentration of benzene in the air is strictly limited. Therefore, the method has great significance for treating the benzene waste gas.
The activated carbon has strong adsorption performance on benzene and other volatile organic gases, high removal efficiency, mature process and easy popularization, and is a good benzene protection absorbent. At present, no corresponding product is developed specially aiming at benzene protection in the activated carbon market, and the conventional purified water carbon meeting the customer requirements is generally sold as benzene protection carbon according to the market requirements. The conventional water purifying carbon belongs to liquid phase adsorption carbon, is generally prepared by blending low ash anthracite or coal with lower ash content, has strict requirements on product indexes in the market and has higher preparation cost. The benzene protection carbon belongs to gas phase adsorption carbon, and the activated carbon with good liquid phase adsorption effect does not have higher benzene adsorption capacity by utilizing the gas phase adsorption principle of the activated carbon.
Therefore, the development of benzene protective activated carbon with higher benzene adsorption capacity is very necessary.
Disclosure of Invention
A first object of the present invention is to provide a benzene-protecting activated carbon which has high strength and high benzene adsorption capacity.
The second purpose of the invention is to provide a preparation method of the benzene protection activated carbon, which has stable process, can avoid the bubbling phenomenon and ensure the strength of the benzene protection activated carbon product.
In order to achieve the first purpose of the invention, the following technical scheme is adopted:
the benzene protection activated carbon is prepared from the following raw materials in parts by weight:
raw coal 70-80, such as 72.5, 75 and 77.5;
20-30 binders, such as 22.5, 25, and 27.5;
wherein the feed coal comprises a first feed coal and a second feed coal;
the first feedstock coal is bituminous coal having a volatile content of 24-35 wt%, such as 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt% and 34 wt%; ash <10 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% and 9 wt%;
the second raw material coal is anthracite, and the volatile matter of the second raw material coal is 5-10 wt%, such as 6 wt%, 7 wt%, 8 wt% and 9 wt%; ash < 6 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt% and 5 wt%;
and the content of the second raw material coal in the raw material coal is 50-80 wt%, such as 32 wt%, 35 wt%, 37 wt%, 40 wt%, 42 wt%, 45 wt% and 47 wt%; the volatile matter of the raw material coal is 10-20 wt%, such as 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt% and 19 wt%;
the binder comprises coal tar and a solid binder, and the components of the solid binder at least comprise sodium carboxymethyl cellulose; and the content of the solid binder in the binder is 20-40 wt%, such as 25 wt%, 30 wt% and 35 wt%.
According to the benzene protection activated carbon, the first raw material coal (bituminous coal) and the second raw material coal (anthracite) are mixed and blended, and are kneaded with the binder and subjected to layering, carbonization and activation treatment, so that the benzene protection activated carbon with high benzene adsorption capacity is obtained.
It is understood by those skilled in the art that the use of a binder can improve the formability of the coal paste and improve the formability and appearance of the carbon rod, making its surface smooth, free of longitudinal and transverse cracks, free of lumpy materials, and free of caking.
Because the metal elements in the solid binder have the combustion-supporting effect, the use of the solid binder can properly improve the activation reaction rate, so that the activation pore-forming speed is improved, and the benzene adsorption performance of the prepared benzene protection activated carbon product is further improved; the solid binder does not generate irritant gas in the using process, has no unpleasant smell and is relatively environment-friendly; preferably, the particle size of the solid binder is D90 < 75 μm.
In a preferred embodiment, the solid binder is a mixture of sodium carboxymethylcellulose and lignin in a mass ratio of (4-6: 1), such as 4.5:1, 5:1 and 5.5: 1. The lignin is an amorphous aromatic high polymer which is widely existed in plants and contains structural units of the oxo-phenylpropanol or the derivative thereof in the molecular structure, and the use of the lignin is helpful for adjusting the pore structure of the benzene protection activated carbon, thereby improving the benzene adsorption performance and the strength of the benzene protection activated carbon.
In one embodiment, the feedstock for making the benzene protected activated carbon further comprises water, and the amount of water is 10 to 25 wt%, preferably 15 to 21 wt%, such as 16 wt%, 17 wt%, 18 wt%, 19 wt% and 20 wt% of the total mass of the feedstock coal and the binder.
In one embodiment, the volatile matter of the first feedstock coal is 25 to 30 wt%, such as 26 wt%, 27 wt%, 28 wt%, and 29 wt%; preferably, the first raw material coal is black mountain coal or Lingwu coal.
The black mountain coal was produced from black mountain coal mines in tokson county, Xinjiang. The Sinkiang coal reserves account for approximately 40 wt% of the total reserves in the country, with the geological reserves of black mountain coal mines located in the Tukson county of Sinkiang being approximately 14 hundred million tons. The coal quality is ultra-low ash, high volatile matter, ultra-low sulfur, ultra-low medium phosphorus, and is a high-quality coal resource. Due to the limitation of regional and economic development, the coal mainly takes raw coal production for a long time, is used as thermal power generation, industrial boilers, civil fuel and the like, has short industrial chain and low additional value, and causes the waste of high-quality resources.
The ash content of the washed black hill coal can be less than 5 wt%, the sulfur content is less than 1 wt%, and the phosphorus content is less than 0.05 wt%, and the properties of the washed black hill coal are very similar to those of low ash, low sulfur and low phosphorus of Taixi anthracite coal, so that the black hill coal is a high-quality raw material for preparing high-quality active carbon. However, the volatile component of the coal is high, generally 25-40 wt%, and the coal is difficult to be directly used for preparing the activated carbon. And because the volatile component of the black mountain coal is higher and belongs to non-caking coal, the black mountain coal is required to be molded and solidified in the production process of the activated carbon by adding a binder, if the black mountain coal is independently used for producing the benzene protection carbon, the volatile component of the molding strip is too high, the bubbling phenomenon can occur in the carbonization and activation processes, and the obtained product has lower strength due to serious burning loss. Therefore, the pure black mountain coal is difficult to be used for preparing the benzene protection carbon.
According to the invention, anthracite and black hill coal are blended, so that the bubbling phenomenon can be avoided when the black hill coal is used in the process of preparing the benzene protection activated carbon, the strength of the prepared benzene protection activated carbon product is ensured, high-quality benzene protection activated carbon is obtained, and the additional value and the economic benefit of the black hill coal are further improved; and the obtained product has increased 2-3nm pore volume, which is helpful for improving the benzene adsorption capacity of the benzene protection activated carbon product.
Lingwu coal is produced from the largest coal field in Nindong coal-containing area and is located in Lingwai, the coal area mainly comprises non-sticky coal, and the coal quality has the characteristics of low ash, low sulfur and high activity, and is high-quality chemical coal. The high-quality benzene protection active carbon can be obtained by blending the coal with anthracite.
It is understood by those skilled in the art that the secondary feedstock coal may be anthracite coal commonly used in the art, such as Yangquan anthracite coal, Russian anthracite coal, Jincheng anthracite coal, and Taixi anthracite coal. In one embodiment, the second feedstock coal is taixi anthracite coal produced from the puelia stolonifera ditch coal area.
The taixi anthracite has small ash content and small volatile component, the content of trace metals is higher, particularly the content of silicon and aluminum is higher, wherein the total content of silicon dioxide, aluminum trioxide and calcium oxide accounts for more than 70 wt%, so that a skeleton structure with coordinate bonds is generated after carbonization, the number of active sites is increased, the pore volume of 3-5nm in the obtained product is increased, and the strength of the prepared benzene protection activated carbon is improved.
Preferably, the coal tar has a pitch content of 57 to 68 wt%, such as 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt% and 67 wt%; ash content 0.02-0.5 wt%, such as 0.03 wt%, 0.08 wt%, 0.2 wt%, 0.3 wt% and 0.4 wt%.
In one embodiment, the particle size of the first feedstock coal and the second feedstock coal is D90 < 75 μm.
In the present invention, the particle size D90 < 75 μm means D90 < 75 μm by mass. The particle size is obtained by a sieving method.
In order to achieve the second purpose of the invention, the following technical scheme is adopted:
a preparation method of the benzene protection activated carbon comprises the following steps:
(1) kneading depression bar
Mixing the raw materials according to the weight parts and the weight content, kneading the mixed materials into coal paste, and then carrying out extrusion forming on the coal paste to obtain carbon strips;
generally, the method comprises the steps of kneading in a kneading and stirring device (such as a double-shaft stirring kneader) to obtain uniform coal paste, and extruding and forming on a hydraulic forming machine or a screw extruder to obtain carbon bars with higher compactness;
(2) charring
Heating and carbonizing the carbon strip obtained in the step (1) in an anaerobic state to obtain a carbonized material;
the carbonization is the thermal decomposition and solidification of coal at low temperature and the volatilization of low molecular substances in coal tar; the carbonization process can remove volatile components in the carbon strips and harden the carbon strips, thereby increasing the strength of the carbon strips, forming primary pores to be beneficial to the effective implementation of the subsequent activation process and determining the pore structure of the final product to a certain extent;
(3) activation of
And (3) activating the carbonized material obtained in the step (2) to obtain the benzene protection activated carbon.
The activation is carried out in an activation furnace, and an activating agent (such as water vapor or carbon dioxide) is also introduced into the activation furnace during the activation so as to activate and pore-form the carbonized material in the activation furnace.
As can be understood by those skilled in the art, in the step (1), the first raw material coal, the second raw material coal and the solid binder can be milled to have a particle size D90 of less than 75 μm, and the three materials are uniformly mixed and then kneaded with the coal tar (and water).
As can be understood by those skilled in the art, the carbon strip obtained in step (1) can be carbonized after being dried and cured in various ways, such as drying and curing, preferably for 24-48 h.
Preferably, in said step (1), the kneading temperature is 70 to 80 ℃, such as 72 ℃, 74 ℃, 76 ℃ and 78 ℃; kneading for 10-15min (such as 12min and 14 min) to obtain coal paste with uniform mixing and good molding property.
Preferably, in the step (2), the carbonization temperature is 550-650 ℃, such as 575 ℃, 600 ℃ and 625 ℃, and the volatile matter of the carbonized material obtained after carbonization is 6-10 wt%, such as 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt% and 9.5 wt%; preferably, the carbonization time is 20-40min, and further preferably 20-30min, such as 22min, 24min, 26min and 28min, so that a carbonized material with high strength and preliminary pores is obtained, and a better activated material can be obtained in the subsequent activation step to serve as a benzene protection activated carbon product; the strength of the carbonized material obtained after carbonization reaches 95 wt%.
Preferably, in the step (3), the activation is carried out by using water vapor or carbon dioxide as an activation medium, the activation temperature is 860-920 ℃, preferably 890-910 ℃, such as 895 ℃, 900 ℃ and 905 ℃, on one hand, the problem that the activation time is too long due to too low temperature is avoided, and on the other hand, the problems of serious burning loss, low yield, serious oxidation of the surface and large ash floating of the activated material due to too high temperature are avoided; the activation time is 60-150min, such as 80min, 100min, 120min and 140 min.
Preferably, the activation is with carbon dioxide as the activation medium.
When the carbonized material is activated by taking water vapor as an activating medium, water gas reaction, namely C + H, occurs2O(g)＝H2+ CO, at high temperature; the water gas reaction is easy to carry out, the reaction speed is high, the pore size of pores in the obtained activated material is not uniform, and the benzene adsorption capacity can be influenced.
Feeding carbonized material by using carbon dioxide as activating mediumWhen activated, the reaction that takes place is C + CO22CO, the reaction conditions are high temperature; the reaction speed of the reaction is low, the reaction is gentle, the pore size of pores in the obtained activated material is uniform, and the benzene adsorption capacity is high, so that the carbon dioxide is more suitable to be used as an activation medium to prepare the activated material with high benzene adsorption capacity to be used as a benzene protection activated carbon product compared with water vapor.
The benzene adsorption capacity is expressed by a benzene adsorption value, and the calculation formula is as follows: b ═ G-W)/W × 100 wt%; wherein B is a benzene adsorption value (wt%), G is a weight (mg) of the activated carbon after adsorbing benzene vapor, and W is a weight (mg) of the activated carbon sample.
The invention also provides benzene protection activated carbon prepared by the preparation method.
The benzene protection activated carbon and the preparation method thereof have the following beneficial effects:
(1) according to the benzene protection activated carbon, bituminous coal and anthracite are mixed to prepare coal, and the binder is added into the coal, so that the formability of coal paste is improved, the formability and the appearance of carbon bars are improved, and the surface of the carbon bars is smooth, free of longitudinal and transverse cracks, free of blocky materials and free of agglomeration; the strength of the benzene protection activated carbon product is improved by utilizing the characteristic that the pitch contained in the coal tar can generate a skeleton structure after loss of the pitch; the combustion supporting effect of metal elements in the solid binder is utilized to properly improve the activation reaction rate, so that the activation pore-forming speed is improved, and the benzene adsorption performance of the benzene protection activated carbon product is further improved; the solid binder does not generate irritant gas in the using process, has no unpleasant smell and is beneficial to environmental protection; the prepared benzene protection activated carbon product has higher benzene adsorption capacity and can better remove benzene waste gas;
(2) according to the invention, the black mountain coal is further used as a bituminous coal raw material to be blended with the anthracite coal, so that the bubbling phenomenon generated when the black mountain coal is used for preparing the benzene protection activated carbon can be avoided, the strength of the prepared benzene protection activated carbon product is ensured, and the high-quality benzene protection activated carbon is obtained, so that the black mountain coal which cannot be used for preparing the benzene protection activated carbon originally can be used for preparing the high-quality benzene protection activated carbon, and the additional value and the economic benefit of the black mountain coal are improved; the pore volume of 2-3nm in the obtained product is increased, which is beneficial to improving the benzene adsorption capacity of the prepared benzene protection activated carbon product;
(3) the invention further utilizes the Taixi anthracite and the Heishan coal for coal blending, thereby being beneficial to generating a skeleton structure with coordination bonds after carbonization, improving the number of active sites and improving the benzene adsorption capacity of the obtained benzene protection activated carbon product; the pore volume of 3-5nm in the obtained benzene protection activated carbon product is increased, which is beneficial to improving the strength of the prepared benzene protection activated carbon;
(4) according to the preparation method, the formed carbon strips are directly carbonized at high temperature without baking and hardening; in the preparation process, the bubbling phenomenon can be prevented, and the strength of the prepared benzene protection activated carbon product is ensured; the burning loss rate of the prepared benzene protection activated carbon is controlled by controlling the activation temperature and time in the activation process, so that the benzene adsorption capacity (namely benzene adsorption value) is improved;
(5) the benzene protection activated carbon prepared by the preparation method has high strength and good benzene adsorption capacity;
(6) the benzene adsorption value of the common activated carbon can only reach 35 wt%, while the benzene adsorption value of the benzene protective activated carbon can reach 43 wt% on the basis that the strength can ensure that the benzene protective activated carbon reaches 94 wt%.
Detailed Description
The technical solution and effects of the present invention will be further described below by way of specific embodiments. The following embodiments are merely illustrative of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
In the following examples, all the raw materials used were analytically pure and purchased from Tanshino Chemicals, Inc. In the coal tar, the content of asphalt is 60 wt%, and the ash content is 0.025 wt%;
the test items and the test standards of the product benzene protection activated carbon are as follows:
benzene adsorption value: solvent vapor adsorption performance in Japanese Industrial Standard JIS K1474-1999;
strength: and the national standard GB/T7702.3-2008.
Example 1
(1) Kneading depression bar
Grinding black mountain coal with the volatile content of 30.5 wt% and the ash content of 7 wt% and Taixi anthracite coal with the volatile content of 8.6 wt% and the ash content of 7 wt% into powder until D90 is less than 75 mu m; 1200g of coal dust from Heishan coal and 1800g of coal dust from Taixi coal are mixed, and 3000g of raw material coal obtained is 17.5 wt% of volatile matter; adding 700g of coal tar, 300g of sodium carboxymethylcellulose and 600g of water into 3000g of the obtained raw material coal, kneading the mixture in a double-shaft stirring kneader at 70 ℃ for 15min to obtain coal paste, and extruding the coal paste on a hydraulic forming machine to obtain carbon strips;
(2) charring
Airing and curing the carbon strips obtained in the step (1) for 48 hours, and then entering a carbonization furnace to perform carbonization treatment for 25min at 600 ℃ in an oxygen-free state to obtain a carbonized material with the volatile component of 8 wt%;
(3) activation of
And (3) feeding the carbonized material obtained in the step (2) into an activation furnace, introducing high-temperature water vapor (taking the water vapor as an activation medium), and performing activation treatment for 120min at 900 ℃ to obtain benzene protection activated carbon, which is marked as a product A.
The benzene adsorption value of the product A was 42 wt%, and the strength was 95 wt%.
Example 2
(1) Kneading depression bar
Grinding the black mountain coal with the volatile content of 28.7 wt% and the ash content of 8 wt% and the Taixi anthracite with the volatile content of 9.1 wt% and the ash content of 4 wt% into powder until the D90 is less than 75 mu m; 1500g of coal dust from Heishan coal dust and 1500g of Taixi anthracite dust are mixed, and 3000g of raw material coal is obtained, wherein the volatile matter is 19.1 wt%; adding 450g of coal tar, 300g of sodium carboxymethylcellulose and 937.5g of water into 3000g of the obtained raw material coal, kneading the mixture in a double-shaft stirring kneader at 80 ℃ for 10min to obtain coal paste, and extruding the coal paste on a hydraulic forming machine to obtain carbon strips;
(2) charring
After the carbon strips obtained in the step (1) are aired and cured for 24 hours, the carbon strips enter a carbonization furnace to be carbonized at 650 ℃ for 30min in an oxygen-free state, and a carbonized material with the volatile component of 6 wt% is obtained;
(3) activation of
And (3) feeding the carbonized material obtained in the step (2) into an activation furnace, introducing high-temperature water vapor (taking the water vapor as an activation medium), and performing activation treatment for 110min at 860 ℃ to obtain benzene protection activated carbon, which is marked as a product B.
The benzene adsorption value of the product B was 40.7 wt%, and the strength was 96 wt%.
Example 3
(1) Kneading depression bar
Grinding 25.8 wt% of coal with volatility and 6 wt% of ash content in Heishan coal and 7.9 wt% of coal with volatility and 3 wt% of ash content in Taixi anthracite into powder with D90 smaller than 75 μm; 600g of coal dust from Heishan coal and 2400g of Taixi anthracite coal are mixed, and 3000g of raw coal is obtained, wherein the volatile matter is 11.8 wt%; adding 1029g of coal tar, 257g of sodium carboxymethylcellulose and 428.6g of water into 3000g of raw material coal, kneading the mixture in a double-shaft stirring kneader at 80 ℃ for 10min to obtain coal paste, and extruding the coal paste on a hydraulic forming machine to obtain carbon strips;
(2) charring
After the carbon strips obtained in the step (1) are aired and cured for 36 hours, the carbon strips enter a carbonization furnace to be carbonized at 550 ℃ for 40min in an oxygen-free state, and a carbonized material with 7 wt% of volatile matter is obtained;
(3) activation of
And (3) feeding the carbonized material obtained in the step (2) into an activation furnace, introducing high-temperature water vapor (taking the water vapor as an activation medium), and performing activation treatment for 80min at 920 ℃ to obtain benzene protection activated carbon, which is marked as a product C.
The benzene adsorption value of the product C was 40.9 wt%, and the strength was 97 wt%.
Example 4
The taixi anthracite coal used in example 2 having a volatile content of 9.1 wt% and an ash content of 4 wt% was replaced with yangquan anthracite coal having a volatile content of 6.7 wt% and an ash content of 5 wt%, and the remainder was the same as in example 2, to obtain benzene-protected activated carbon, which was designated as product D.
The benzene adsorption value of product D was 39.2 wt%, and the strength was 94.5 wt%.
Example 5
The coal from black mountain having a volatile matter of 28.7 wt% and an ash content of 8 wt% used in example 2 was replaced with Lingwu coal having a volatile matter of 28.7 wt% and an ash content of 6 wt%, and the remainder was the same as in example 2, to obtain benzene-protected activated carbon, which was designated as product E.
The benzene adsorption value of product E was 39 wt% and the strength was 95.5 wt%.
Example 6
The same procedure as in example 2 was repeated except that the coal from Heishan used in example 2 having a volatile matter of 28.7 wt% and an ash content of 8 wt% was replaced with Lingwu coal having a volatile matter of 28.7 wt% and an ash content of 6 wt%, and the coal from Taixi having a volatile matter of 9.1 wt% and an ash content of 4 wt% was replaced with Yangquan coal having a volatile matter of 6.7 wt% and an ash content of 5 wt%, to obtain benzene-protected activated carbon, which was designated as product F.
The benzene adsorption value of the product F was 38.8 wt%, and the strength was 94 wt%.
Example 7
The procedure used in example 1 was repeated except for replacing "300G of carboxymethylcellulose sodium" with "250G of carboxymethylcellulose sodium and 50G of lignin" to give benzene-protected activated carbon, designated as product G.
The benzene adsorption value of product G was 43 wt% and the strength 94 wt%.
Example 8
The procedure of example 1 was repeated except for replacing "300 g of carboxymethylcellulose sodium" with "240 g of carboxymethylcellulose sodium and 60g of lignin" used in example 1 to obtain benzene-protected activated carbon, which was designated as product H.
The benzene adsorption value of product H was 42.7 wt%, and the strength was 94 wt%.
Example 9
The procedure used in example 3 was repeated except for replacing 257g of sodium carboxymethylcellulose with 220.3g of sodium carboxymethylcellulose and 36.7g of lignin, and the residue was the same as in example 3 to obtain benzene-protected activated carbon designated as product I.
The benzene adsorption value of product I was 42.4 wt% and the strength was 93 wt%.
Claims (10)
1. The benzene protection activated carbon is characterized in that raw materials for preparing the benzene protection activated carbon comprise the following substances in parts by weight:
70-80 parts of raw material coal,
20-30 parts of a binder;
wherein the feed coal comprises a first feed coal and a second feed coal;
the first raw material coal is bituminous coal, the volatile matter of the first raw material coal is 24-35 wt%, and the ash content of the first raw material coal is less than 10 wt%;
the second raw material coal is anthracite, the volatile matter of the second raw material coal is 5-10 wt%, and the ash content of the second raw material coal is less than 6 wt%;
in the raw material coal, the content of the second raw material coal is 50-80 wt%; the volatile content of the raw material coal is 10-20 wt%;
the binder comprises coal tar and a solid binder, and the components of the solid binder at least comprise sodium carboxymethyl cellulose; and the content of the solid binder in the binder is 20-40 wt%.
2. The benzene protective activated carbon according to claim 1, wherein the solid binder is a mixture of sodium carboxymethyl cellulose and lignin, and the mass ratio of sodium carboxymethyl cellulose to lignin is (4-6): 1.
3. The benzene protective activated carbon according to claim 1 or 2, wherein the raw material for preparing the benzene protective activated carbon further comprises water, and the amount of water is 10 to 25 wt% of the total mass of the raw material coal and the binder.
4. The benzene protection activated carbon according to any one of claims 1 to 3, wherein the volatile content of the first raw material coal is 25 to 30 wt%, preferably the first raw material coal is Heishan coal or Lingwu coal; preferably, the second feedstock coal is taixi anthracite.
5. The benzene protective activated carbon according to any one of claims 1 to 4, wherein the coal tar contains 57 to 68 wt% of pitch and 0.02 to 0.5 wt% of ash.
6. The benzene protected activated carbon according to any one of claims 1 to 5, wherein the particle size of the first feedstock coal and the second feedstock coal is D90 < 75 μm.
7. The method of preparing benzene protected activated carbon of any one of claims 1 to 6, comprising the steps of:
(1) kneading depression bar
Mixing the raw materials according to the weight parts and the weight content, kneading the mixed materials into coal paste, and then carrying out extrusion forming on the coal paste to obtain carbon strips;
(2) charring
Heating and carbonizing the carbon strip obtained in the step (1) in an anaerobic state to obtain a carbonized material;
(3) activation of
And (3) activating the carbonized material obtained in the step (2) to obtain the benzene protection activated carbon.
8. The preparation method according to claim 7, characterized in that in the step (2), the carbonization temperature is 550-650 ℃, and the carbonization is carried out until the volatile content of the obtained carbonized material is 6-10 wt%, and the preferable carbonization time is 20-40 min.
9. The method according to claim 7 or 8, wherein in the step (3), the activation is carried out by using water vapor or carbon dioxide as an activation medium, the activation temperature is 860 to 920 ℃, and the activation time is 60 to 150 min; preferably, the activation is with carbon dioxide as the activation medium.
10. The production method according to any one of claims 7 to 9, wherein in the step (1), the kneading temperature is 70 to 80 ℃ and the kneading time is 10 to 15 min.
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