CN114620725A - Method for green preparation of molded activated carbon from agricultural processing residues - Google Patents
Method for green preparation of molded activated carbon from agricultural processing residues Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims description 25
- 239000005539 carbonized material Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001994 activation Methods 0.000 claims description 17
- 230000004913 activation Effects 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- 238000000197 pyrolysis Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 12
- 230000005484 gravity Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 44
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052740 iodine Inorganic materials 0.000 abstract description 13
- 239000011630 iodine Substances 0.000 abstract description 13
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000012855 volatile organic compound Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 239000000047 product Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 22
- 238000010000 carbonizing Methods 0.000 description 11
- 238000007873 sieving Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 235000021419 vinegar Nutrition 0.000 description 5
- 239000000052 vinegar Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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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
- C01B32/354—After-treatment
- C01B32/378—Purification
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Abstract
The invention discloses a green preparation method of molded activated carbon from agricultural processing residues, and belongs to the technical field of high-valued utilization of agricultural product processing residual waste resources. Taking agricultural processing residues as raw materials, condensing gas after carbonization to obtain pyroligneous liquor and tar, mixing carbon powder, a molding agent and tar, extruding and molding, pyrolyzing and crosslinking molded particles, activating to obtain columnar particles, and washing with the pyroligneous liquor to obtain the columnar activated carbon. The method has the advantages that waste generated in the carbonization process of the agricultural processing residues is collected and utilized, full-value utilization and overall process negative carbon emission are realized, the performance of the prepared activated carbon product is improved, and the application field of the activated carbon product is expanded. The activated carbon product has excellent performance, the wear-resisting strength can reach 95 percent, the iodine adsorption value reaches 800mg/g, and the methylene blue adsorption value is more than 110 mg/g; can be used in the fields of organic solvent recovery, VOCs treatment, coal desulfurization and denitration and the like.
Description
Technical Field
The invention belongs to the technical field of high-value utilization of agricultural product processing residual waste resources, and particularly relates to a green preparation method of formed activated carbon from agricultural processing residues.
Background
The biomass resource is the only renewable resource, wherein the agricultural processing residue in China accounts for more than 50% of the total amount of the biomass resource, and the utilization efficiency is low. At present, most of agricultural processing residues are composted, burned and discarded, the resource utilization efficiency is low, and the environment is seriously polluted. The utilization of agricultural processing residues can increase local economic benefits, reduce the waste of resources, reduce the pollution to the environment and be beneficial to promoting the high-efficiency comprehensive utilization of domestic agricultural residues.
The activated carbon as an adsorption material has excellent performances of high specific surface area, rich pore structure and the like, is widely applied to aspects of environmental governance, energy storage, catalysis, national defense and the like, and is an indispensable product for national economy because the activated carbon is required to be more than 80 ten thousand tons and the demand is stably promoted year by year in China at present.
At present, agricultural processing residues generally have large ash content, uneven shapes and low strength, so that the directly prepared activated carbon has high ash content, low specific gravity and poor strength and is difficult to use, and wood vinegar and tar wastes generated in the carbonization process can also damage the environment if not used, so that resources are wasted. Therefore, the research on the green preparation method of the agricultural processing residue formed activated carbon with low ash content, high specific gravity and high strength plays an important role in high-value utilization of the agricultural processing residue.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing high-performance activated carbon from agricultural processing residues in a green manner. The specific gravity and the strength of the agricultural processing residue activated carbon are improved by using a forming process, the application field is improved, the tar in the carbonization process and the pyroligneous liquor in the carbonization process used in the acid washing are selected as the forming agent, so that byproducts can be effectively utilized, and a green and clean production mode is established. The method can effectively reduce the ash content of the activated carbon by pretreating the raw materials and removing ash by subsequent acid washing, can utilize byproducts generated in the production process, is clean in production process, simple and easy to implement on a large scale, has good adsorption performance of the prepared and formed activated carbon, and has economic and environmental benefits.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing molded activated carbon from agricultural processing residues in a green manner comprises the following steps:
1) taking agricultural processing residues as raw materials, and crushing and screening the raw materials after the raw materials are pretreated; preferably, the particles are sieved to a particle size of 0.15 mm;
2) putting the raw materials prepared in the step 1) into a tubular furnace, carrying out anaerobic carbonization and recovering tail gas, condensing and separating the tail gas to obtain pyroligneous liquor and tar, and crushing the carbonized raw materials into carbon powder;
3) uniformly mixing the carbon powder, the molding agent and the tar in the step 2) in a molding machine for extrusion molding, and drying and hardening after molding to obtain a molded carbonized material;
4) putting the formed carbonized material in the step 3) into a tubular furnace for pyrolysis, crosslinking and activation, and cooling to obtain columnar particles;
5) washing the columnar particles obtained in the step 4) by using the pyroligneous liquor obtained in the step 2), then washing the columnar particles to be neutral, and drying the columnar particles to obtain the columnar activated carbon.
The method for preparing the molded activated carbon from the agricultural processing residues in an environment-friendly manner is characterized in that the raw material pretreatment is to carry out ash removal treatment on the raw material, and the ash removal mode can be one or a mixture of gravity classification, mechanical vibration sieve and negative pressure fluid.
The green preparation method of the formed activated carbon from the agricultural processing residues comprises the step 2), wherein the carbonization temperature is 450-600 ℃, and the carbonization time is 60-120 min.
The method for preparing the molded activated carbon from the agricultural processing residues in a green manner comprises the step 3) of mixing the tar, the molding agent and the carbon powder in a mass ratio of 1:1: 2-1: 1: 5.
The method for preparing the molded active carbon from the agricultural processing residues in a green manner comprises the step 3) of preparing one or more mixtures of water, sodium carboxymethyl cellulose, starch or polyvinyl alcohol as a molding agent.
The green preparation method of the formed activated carbon from the agricultural processing residues comprises the step 4) of pyrolyzing and crosslinking for 60-120 min at 450-600 ℃ in an inert gas atmosphere; in the activation procedure, the activation temperature is 800-1000 ℃, the activation time is 60-100 min, and the activation gas is one or more of water vapor, carbon dioxide or air.
The green preparation method of the formed activated carbon from the agricultural processing residues comprises the step 5), wherein the mass ratio of the columnar particles to the pyroligneous liquor is 1: 5-1: 15, the pH value of the pyroligneous liquor is 2.0-4.0, and the washing temperature is 50-90 ℃.
Has the advantages that: compared with the prior art, the invention has the advantages that:
the preparation method is simple in preparation process and easy to implement industrially, and can effectively solve the problems of large ash content, low specific gravity, poor strength and the like of the activated carbon of the traditional agricultural processing residues. The activated carbon prepared from the agricultural processing residues is compact in structure through a forming process, so that the strength and the specific gravity are improved, the ash content of the activated carbon can be reduced by pretreating the raw materials and performing subsequent acid washing centrifugation, and a green production mode without byproducts can be realized by using tar in a carbonization process as a binder and using pyroligneous as an acid washing solution.
The activated carbon prepared by the combination of the processes has low ash content, large specific gravity, good strength and adsorption performance, similar performance indexes to those of activated carbon prepared from coal, abrasion resistance strength of more than 90 percent, iodine adsorption value of more than 800mg/g and methylene blue adsorption value of more than 110 mg/g. The method can be used for solvent adsorption, wastewater treatment, coal desulfurization and denitration and the like, and is beneficial to the cleanness, high-valued and negative carbon discharge and utilization of agricultural processing residues.
Drawings
FIG. 1 is a process flow diagram of green preparation of shaped activated carbon from agricultural processing residues.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Materials and reagents: agricultural process residues (moisture 10.01%, ash 16.67%, volatiles 23.62%, fixed carbon 49.70%), sodium carboxymethylcellulose (abbreviated CMC).
Preparing a plasticizer CMC: weighing a proper amount of sodium carboxymethylcellulose, pouring hot water into the beaker, putting the beaker on an electric heating furnace, heating the beaker while stirring until the sodium carboxymethylcellulose is completely dissolved, preparing a 4 wt% solution and cooling the solution; and applied to the following examples and comparative examples in which the mass of the plasticizer refers to the mass of the sodium carboxymethyl cellulose solution.
Example 1
A method for preparing molded activated carbon from agricultural processing residues in a green manner comprises the following steps:
(1) carrying out gravity classification on the agricultural processing residues to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1: 4, uniformly mixing, adding the mixture into a forming machine for extrusion forming, and drying and hardening the formed carbonized material to obtain a formed carbonized material;
(4) putting the molded carbonized material obtained in the step 3) into a tubular furnace, heating to 550 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 90min, heating to 900 ℃, introducing steam for activation for 60min, and cooling to obtain columnar particles;
(5) according to the mass ratio of the columnar particles to the pyroligneous liquor with the pH value of 2.14 of 1:5 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar active carbon product is 10.41 percent, the wear resistance is 94 percent, the iodine adsorption value is 804mg/g, the methylene blue adsorption value is 135mg/g, and the carbon tetrachloride adsorption rate is 51 percent.
Example 2
A method for preparing molded activated carbon from agricultural processing residues in a green manner comprises the following steps:
(1) mechanically vibrating and screening the agricultural processing residues to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1:2, uniformly mixing, adding the mixture into a forming machine for extrusion forming, and drying and hardening the formed carbonized material to obtain a formed carbonized material;
(4) putting the molded carbonized material in the step 3) into a tubular furnace, heating to 450 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 90min, heating to 900 ℃, introducing steam for activating for 60min, and cooling to obtain columnar particles;
(5) according to the mass ratio of the columnar particles to the pyroligneous liquor with the pH value of 2.07 of 1: 10 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar active carbon product is 13.42 percent, the abrasion resistance is 83 percent, the iodine adsorption value is 715mg/g, the methylene blue adsorption value is 112.5mg/g, and the carbon tetrachloride adsorption rate is 41 percent.
Example 3
A method for preparing molded activated carbon from agricultural processing residues in a green manner comprises the following steps:
(1) deashing the agricultural processing residue negative pressure fluid to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1: 4, uniformly mixing, adding the mixture into a forming machine for extrusion forming, and drying and hardening after forming to obtain a formed carbonized material;
(4) putting the molded carbonized material in the step 3) into a tubular furnace, heating to 600 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 60min, heating to 850 ℃, introducing steam for activating for 80min, and cooling to obtain columnar particles;
(5) according to the mass ratio of the columnar particles to the pyroligneous liquor with the pH value of 2.43 of 1:15 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar activated carbon product is 9.64 percent, the abrasion resistance is 76 percent, the iodine adsorption value is 884mg/g, the methylene blue adsorption value is 165mg/g, and the carbon tetrachloride adsorption rate is 56 percent.
Example 4
A method for preparing molded activated carbon from agricultural processing residues in an environment-friendly manner comprises the following steps:
(1) mechanically vibrating and screening the agricultural processing residues to remove ash to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1: 3, uniformly mixing, adding the mixture into a forming machine for extrusion forming, and drying and hardening the formed carbonized material to obtain a formed carbonized material;
(4) putting the molded carbonized material in the step 3) into a tubular furnace, heating to 500 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 120min, heating to 850 ℃, introducing steam for activation for 100min, and cooling to obtain columnar particles;
(5) according to the mass ratio of the columnar particles to the pyroligneous liquor with the pH value of 2.17 of 1: 10 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar activated carbon product is 11.45 percent, the abrasion resistance is 79 percent, the iodine adsorption value is 744mg/g, the methylene blue adsorption value is 130mg/g, and the carbon tetrachloride adsorption rate is 49 percent through determination.
Example 5
A method for preparing molded activated carbon from agricultural processing residues in a green manner comprises the following steps:
(1) mechanically vibrating and screening the agricultural processing residues to remove ash to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1:2, uniformly mixing, adding the mixture into a forming machine for extrusion forming, and drying and hardening the formed carbonized material to obtain a formed carbonized material;
(4) putting the molded carbonized material in the step 3) into a tubular furnace, heating to 550 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 90min, heating to 1000 ℃, introducing steam for activation for 100min, and cooling to obtain columnar particles;
(5) according to the mass ratio of the columnar particles to the pyroligneous liquor with the pH value of 3.95 of 1: 10 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar activated carbon product is 13.66 percent, the wear-resisting strength is 54 percent, the iodine adsorption value is 946mg/g, the methylene blue adsorption value is 195mg/g, and the carbon tetrachloride adsorption rate is 63 percent.
Example 6
A method for preparing molded activated carbon from agricultural processing residues in an environment-friendly manner comprises the following steps:
(1) performing gravity grading and ash removal on agricultural processing residues to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a molding agent and carbon powder according to a mass ratio of 1:1:5, uniformly mixing, adding the mixture into a forming machine for extrusion forming, and drying and hardening the formed carbonized material to obtain a formed carbonized material;
(4) putting the molded carbonized material in the step 3) into a tubular furnace, heating to 600 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 120min, heating to 950 ℃, introducing water vapor for activation for 100min, and cooling to obtain columnar particles;
(5) according to the mass ratio of the columnar particles to the pyroligneous liquor with the pH value of 2.04 of 1:15 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar activated carbon product is 7.77 percent, the abrasion resistance is 31 percent, the iodine adsorption value is 1047mg/g, the methylene blue adsorption value is 225mg/g, and the carbon tetrachloride adsorption rate is 69 percent.
Comparative example 1
The method for preparing the activated carbon by utilizing the agricultural processing residues comprises the following steps:
(1) carrying out gravity classification on the agricultural processing residues to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain wood vinegar liquid, crushing carbonized material, and sieving to obtain carbon powder with particle size of 0.075 mm;
(3) uniformly mixing a plasticizer and carbon powder according to the mass ratio of 1:4, and then putting the mixture into a forming machine to form columnar particles by extrusion;
(4) putting the columnar particles into a tubular furnace, heating to 550 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 90min, heating to 900 ℃, and introducing water vapor for activation for 60 min;
(5) cooling, and then mixing the activated material with wood vinegar with pH 2.14 according to the mass ratio of 1: and 5, washing and centrifuging, washing to be neutral by using distilled water, and drying to obtain the activated carbon.
The ash content of the activated carbon is 17.42 percent, the abrasion resistance is 64 percent, the iodine adsorption value is 771mg/g, the methylene blue adsorption value is 105mg/g, and the carbon tetrachloride adsorption rate is 31 percent. Compared with the example 1, the comparative example shows that the ash content of the product is lower, the wear-resisting strength is higher and the adsorption performance is better due to the addition of the byproduct tar in the forming process.
Comparative example 2
The method for preparing the activated carbon by utilizing the agricultural processing residues comprises the following steps:
(1) mechanically vibrating and screening the agricultural processing residues to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1:2, uniformly mixing, and then extruding and forming the mixture into columnar particles in a forming machine;
(4) putting the columnar particles into a tubular furnace, heating to 450 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 90min, heating to 800 ℃, and introducing steam for activation for 60 min;
(5) after cooling, the mixture is cooled according to the mass ratio of the activated material to the pyroligneous liquor with the pH value of 2.07 of 1: 10 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar activated carbon product is 12.01 percent, the wear-resisting strength is 91 percent, the iodine adsorption value is 766mg/g, the methylene blue adsorption value is 120mg/g, and the carbon tetrachloride adsorption rate is 44 percent. Compared with example 2, the comparative example shows that the pyrolysis crosslinking temperature reaches 900 ℃, all indexes of the product are reduced, and the performance of the product is reduced due to overhigh pyrolysis crosslinking temperature.
Comparative example 3
The method for preparing the activated carbon by utilizing the agricultural processing residues comprises the following steps:
(1) deashing the agricultural processing residue negative pressure fluid to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting and separating to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1: 4, uniformly mixing and forming into columnar particles;
(4) putting the columnar particles into a tubular furnace, heating to 600 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 120min, heating to 850 ℃, and introducing water vapor to activate for 80 min;
(5) cooling, and then mixing the activated material with wood vinegar with pH 2.43 according to the mass ratio of 1:15 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
Through determination, the ash content of the columnar activated carbon product is 13.07 percent, the wear-resisting strength is 90 percent, the iodine adsorption value is 744mg/g, the methylene blue adsorption value is 120mg/g, and the carbon tetrachloride adsorption rate is 41 percent. In comparison with example 3, it can be compared that an excessively long pyrolysis crosslinking time leads to an increase in ash content of the activated carbon, a decrease in adsorption performance, but an increase in abrasion resistance.
Comparative example 4
The method for preparing the activated carbon by utilizing the agricultural processing residues comprises the following steps:
(1) mechanically vibrating and screening the agricultural processing residues to remove ash to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas in carbonization process, collecting to obtain pyroligneous liquor and tar, crushing carbonized raw materials, and sieving to obtain carbon powder with particle size of about 0.075 mm;
(3) mixing tar, a molding agent and carbon powder according to a mass ratio of 1:1: 3, uniformly mixing and then forming into columnar particles;
(4) and (3) putting the columnar particles into a tube furnace, heating to 500 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 120min, heating to 850 ℃, introducing steam to activate for 100min, and cooling to obtain a columnar activated carbon product.
The ash content of the columnar activated carbon product is 24.03 percent, the wear resistance is 66 percent, the iodine adsorption value is 543mg/g, the methylene blue adsorption value is 60mg/g, and the carbon tetrachloride adsorption rate is 21 percent. This comparison, in comparison with example 4, shows an increase in the index of the product washed with the by-product pyroligneous liquor.
Comparative example 5
The method for preparing the activated carbon by utilizing the agricultural processing residues comprises the following steps:
(1) mechanically vibrating and screening the agricultural processing residues to remove ash to obtain a raw material with the thickness of about 0.15 mm;
(2) carbonizing at 550 deg.C for 120min under nitrogen protection, cooling tail gas during carbonization, and collecting to obtain pyroligneous liquor and tar;
(3) mixing tar, a plasticizer and carbon powder according to a mass ratio of 1:1: 3, uniformly mixing and then forming into columnar particles;
(4) putting the columnar particles into a tubular furnace, heating to 500 ℃ under the protection of nitrogen, carrying out pyrolysis crosslinking for 120min, heating to 850 ℃, and introducing steam for activation for 100 min;
(5) cooling, and then mixing the activated material with wood vinegar with pH of 3.87 according to the mass ratio of 1: 10 washing and centrifuging, washing with water, and drying to obtain the columnar activated carbon product.
The ash content of the columnar activated carbon product is 16.87 percent, the wear-resisting strength is 77 percent, the iodine adsorption value is 672mg/g, the methylene blue adsorption value is 75mg/g, and the carbon tetrachloride adsorption rate is 30 percent. This comparative example is compared with example 4 and it can be seen that washing with a lower pH pyroligneous liquor results in a product with lower ash content and better adsorption properties, but results in a product with reduced attrition resistance.
Claims (7)
1. The method for preparing the molded activated carbon from the agricultural processing residues in a green manner is characterized by comprising the following steps of:
1) taking agricultural processing residues as raw materials, and crushing and screening the raw materials after the raw materials are pretreated;
2) putting the raw materials prepared in the step 1) into a tubular furnace, carrying out anaerobic carbonization and recovering tail gas, condensing and separating the tail gas to obtain pyroligneous liquor and tar, and crushing the carbonized raw materials into carbon powder;
3) uniformly mixing the carbon powder, the molding agent and the tar in the step 2) in a molding machine for extrusion molding, and drying and hardening after molding to obtain a molded carbonized material;
4) putting the formed carbonized material in the step 3) into a tubular furnace for pyrolysis, crosslinking and activation, and cooling to obtain columnar particles;
5) washing the columnar particles obtained in the step 4) by using the pyroligneous liquor obtained in the step 2), then washing the columnar particles to be neutral, and drying the columnar particles to obtain the columnar activated carbon.
2. The method for preparing the formed activated carbon from the agricultural processing residues in a green manner according to the claim 1, wherein in the step 1), the raw material is pretreated by performing ash removal treatment on the raw material, and the ash removal mode can be one or a mixture of gravity classification, mechanical vibration sieve and negative pressure fluid.
3. The method for preparing the molded activated carbon from the agricultural processing residues in a green manner according to claim 1, wherein in the step 2), the carbonization temperature is 450-600 ℃, and the carbonization time is 60-120 min.
4. The method for preparing the molded activated carbon from the agricultural processing residues in a green manner according to claim 1, wherein in the step 3), the mass ratio of the tar to the molding agent to the carbon powder is 1:1: 2-1: 1: 5.
5. The method for preparing the formed activated carbon from the agricultural processing residues in a green manner according to claim 1, wherein in the step 3), the plasticizer is one or a mixture of water, sodium carboxymethyl cellulose, starch or polyvinyl alcohol.
6. The method for preparing the formed activated carbon from the agricultural processing residues in the green way according to the claim 1, wherein in the step 4), the pyrolysis crosslinking is carried out for 60-120 min at 450-600 ℃ in an inert gas atmosphere; in the activation procedure, the activation temperature is 800-1000 ℃, the activation time is 60-120 min, and the activation gas is one or a mixture of water vapor, carbon dioxide or air.
7. The method for preparing the green shaped activated carbon from the agricultural processing residues according to claim 1, wherein in the step 5), the mass ratio of the columnar particles to the pyroligneous liquor is 1: 5-1: 15, the pH value of the pyroligneous liquor is 2.0-4.0, and the washing temperature is 50-90 ℃.
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