CN112830489A - Resourceful treatment method for coal tar residues - Google Patents
Resourceful treatment method for coal tar residues Download PDFInfo
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- CN112830489A CN112830489A CN202110076884.9A CN202110076884A CN112830489A CN 112830489 A CN112830489 A CN 112830489A CN 202110076884 A CN202110076884 A CN 202110076884A CN 112830489 A CN112830489 A CN 112830489A
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- 238000000034 method Methods 0.000 title claims abstract description 66
- 239000011280 coal tar Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000197 pyrolysis Methods 0.000 claims abstract description 34
- 230000003213 activating effect Effects 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000003245 coal Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003546 flue gas Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000003570 air Substances 0.000 claims abstract description 4
- 239000002893 slag Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 11
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003830 anthracite Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000002802 bituminous coal Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000011273 tar residue Substances 0.000 abstract description 23
- 239000002920 hazardous waste Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 13
- 239000002699 waste material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 238000004939 coking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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
- C01B32/312—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
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a resource treatment method of coal tar residues, which comprises the following steps: a. mixing the coal tar residue and coal to obtain a mixture, wherein the coal accounts for 5-15% of the total mass of the mixture, and drying and crushing the mixture to obtain crushed materials; b. pyrolyzing the crushed materials to obtain a pyrolysis material; c. and adding an activating agent into the pyrolysis material for activation to obtain an activated carbon product, wherein the activating agent is selected from at least one of oxygen, air, carbon dioxide or flue gas, the activation temperature is 800-. The resource treatment method of the coal tar residue can recover oil in the tar residue, and the residual residue can be prepared into an activated carbon product by adopting a low-cost environment-friendly method, so that zero emission of hazardous wastes is realized.
Description
Technical Field
The invention belongs to the field of utilization of industrial hazardous wastes and the field of coal chemical industry, and particularly relates to a resource treatment method of coal tar residues.
Background
Coal tar residue (tar residue for short) is a black or black brown viscous paste-like solid discharged from coal during gasification, coking or pyrolysis. The tar residue has complex components, mainly contains various pollutants such as benzene series, polycyclic aromatic hydrocarbon, nitrogen-containing heterocyclic compounds containing sulfur, heavy metals and the like, and is currently listed as HW11 dangerous waste by the nation.
The coal tar residue treatment technologies reported in the literature at present mainly include solvent extraction separation, mechanical centrifugal separation, flash evaporation-horizontal screw centrifugal separation, free settling (or solvent extraction) -centrifugal separation, pyrolysis separation, fuel combustion and the like. Although the method passes through a laboratory verification stage, the method has bottleneck problems in industrial application, for example, although the solvent extraction centrifugal separation has the advantages of high efficiency, economy and large treatment capacity, the problems of economy, toxicity, extraction capacity, energy consumption and the like of an extractant are not overcome; the mechanical centrifugal separation method has simple process flow and strong operability, but has large consumption of electricity, steam and heat energy; the separation quality is unstable and the oil residue is not completely separated; the pyrolysis separation has strong adaptability, and hardly causes secondary pollution, but the economic efficiency is overlarge due to high energy consumption, so that the industrialization is difficult to realize.
At present, the principle of utilizing tar residues by enterprises is to change waste into useful and eliminate pollution on the basis of not increasing economic cost, so that an economic and environment-friendly method for recycling the tar residues is needed to be developed.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: at present, a large number of researchers in China use an alkali-activated method to prepare tar residue-based activated carbon, and have already obtained preliminary research results. However, the preparation technology of the activated carbon by the alkali activation method has the following significant disadvantages: (1) the equipment is seriously corroded due to the use of alkali; (2) the activated carbon product needs to be washed to be neutral, which brings serious water resource waste and environmental pollution; (3) if the cleaning is not thorough, the residue of the activating agent can be caused, and the product quality is influenced; (4) the use of a large amount of the activating agent greatly improves the cost of the product, reduces the economical efficiency and the like. The defects make coking enterprises prefer to select direct recycling and also prefer the preparation technology of the activated carbon.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the embodiment of the invention provides a resource treatment method of coal tar residues, by adopting the method, not only can the oil in the tar residues be recovered, but also the residual residues can be prepared into an activated carbon product by adopting a low-cost and environment-friendly method, and zero emission of dangerous wastes is realized.
The resource treatment method of the coal tar residue according to the embodiment of the invention comprises the following steps:
a. mixing the coal tar residue and coal to obtain a mixture, wherein the coal accounts for 5-15% of the total mass of the mixture, and drying and crushing the mixture to obtain crushed materials;
b. pyrolyzing the crushed materials to obtain a pyrolysis material;
c. and adding an activating agent into the pyrolysis material for activation to obtain an activated carbon product, wherein the activating agent is selected from at least one of oxygen, air, carbon dioxide or flue gas, the activation temperature is 800-.
According to the advantages and the technical effects brought by the independent claims, 1, in the method provided by the embodiment of the invention, hazardous waste tar residues which are byproducts in the coal gasification, coking or pyrolysis process are used as raw materials, a small amount of bituminous coal or anthracite is added into the tar residues, and easily-obtained, low-cost and mild gas is used as an activating agent, so that the problem that the tar residues are low in activity and difficult to activate is solved, and the problems of high pollution, high cost and equipment corrosion caused by the adoption of an alkaline activating agent are avoided; 2. the method of the embodiment of the invention solves the problem of environmental pollution caused by stacking of the tar residues, eliminates secondary pollution, changes waste into valuable and realizes the resource utilization of hazardous waste; 3. by adopting the method of the embodiment of the invention, the specific surface area of the prepared activated carbon product can reach 1000m2More than/g, iodine value more than 900mg/g, better adsorption performance, methylene blue value more than 100ml/g, can be used for water treatment.
According to the resource treatment method of the coal tar residue, provided by the embodiment of the invention, the resource treatment method further comprises a step d of condensing the flue gas generated in the drying treatment in the step a and the pyrolysis treatment in the step b, recovering condensable light oil, and introducing non-condensable gas into an acidic aqueous solution for adsorption treatment.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, in the step a, the coal is bituminous coal and/or anthracite.
According to the resource treatment method of the coal tar residue, provided by the embodiment of the invention, in the step a, the drying temperature is 80-140 ℃, and the drying time is 0.5-3h.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, in the step a, the particle size of the crushed material is less than or equal to 80 microns.
According to the resource treatment method of the coal tar slag, disclosed by the embodiment of the invention, in the step b, the pyrolysis temperature is 300-600 ℃, and the pyrolysis time is 20-50 min.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, in the step b, the pyrolysis atmosphere is inert gas.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, in the step b, the crushed material is extruded and formed into a strip material, and the strip material is pyrolyzed at the temperature of 300-600 ℃ in an inert atmosphere to obtain a pyrolysis material.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, the diameter of the strip-shaped material is 2-4mm, and the length of the strip-shaped material is 5-15 mm.
According to the resource treatment method of the coal tar residue, provided by the embodiment of the invention, in the step c, the flow of the activating agent is 15-30 ml/h.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The resource treatment method of the coal tar residue according to the embodiment of the invention comprises the following steps:
a. mixing the coal tar slag and coal to obtain a mixture, wherein the coal accounts for 5-15% of the total mass of the mixture, drying and crushing the mixture to obtain crushed materials, preferably, the drying temperature is 80-140 ℃, the drying time is 0.5-3h, and the particle size of the crushed materials is less than or equal to 80 mu m;
b. pyrolyzing the crushed material to obtain a pyrolysis material, preferably, the pyrolysis temperature is 300-600 ℃, the pyrolysis time is 20-50min, and the pyrolysis atmosphere is inert gas such as nitrogen or helium;
c. and adding an activating agent into the pyrolysis material for activation to obtain an activated carbon product, wherein the activating agent is selected from at least one of oxygen, air, carbon dioxide or flue gas, the activation temperature is 800-.
According to the resource treatment method of the coal tar slag, the hazardous waste tar slag which is a byproduct in the coal gasification, coking or pyrolysis process is used as the raw material, a small amount of bituminous coal or anthracite is added into the tar slag, and the gas which is easy to obtain, low in cost and mild is used as the activating agent, so that the problem that the tar slag is low in activity and difficult to activate is solved, and the problems of large pollution, high cost and equipment corrosion caused by the adoption of an alkaline activating agent are avoided; 2. the method of the embodiment of the invention solves the problem of environmental pollution caused by stacking of the tar residues, eliminates secondary pollution, changes waste into valuable and realizes the resource utilization of hazardous waste; 3. by adopting the method of the embodiment of the invention, the specific surface area of the prepared activated carbon product can reach 1000m2More than/g, iodine value more than 900mg/g, better adsorption performance, methylene blue value more than 100ml/g, can be used for water treatment.
According to the resource treatment method of the coal tar residue, provided by the embodiment of the invention, the resource treatment method further comprises a step d of condensing the flue gas generated in the drying treatment in the step a and the pyrolysis treatment in the step b, recovering condensable light oil, and introducing non-condensable gas into an acidic aqueous solution for adsorption treatment. The method provided by the embodiment of the invention effectively recovers the flue gas generated in the drying and pyrolysis processes, completely recovers the condensable light oil, sends the condensable light oil into the coal tar distillation tower of the plant area, distills and cuts the condensable light oil into the gasoline and diesel oil for recycling, sends the non-condensable gas into the plant area flue gas treatment system after adsorption treatment, can be realized by means of existing equipment of the plant area, and does not generate additional equipment construction investment.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, in the step a, the coal is bituminous coal and/or anthracite. In the method of the embodiment of the invention, the bituminous coal or anthracite with low metamorphism degree is preferably adopted, the activity of the tar residue is improved, the problems of large pollution, high cost and equipment corrosion caused by adopting an alkaline activator are avoided, and the activated carbon product with excellent performance is prepared by adopting a low-cost gas activator.
According to the resource treatment method of the coal tar slag, provided by the embodiment of the invention, in the step b, the crushed material is extruded into strips to be made into strip-shaped materials, preferably, the strip-shaped materials have the diameter of 2-4mm and the length of 5-15mm, and are pyrolyzed at the temperature of 300-600 ℃ in an inert atmosphere to obtain pyrolysis materials. In the embodiment of the invention, the crushed material is preferably made into a strip material, so that the catalyst has wider application space.
The present invention will be described in detail with reference to examples.
Example 1
The results of elemental analysis and industrial analysis of tar residue obtained from coal gasification of Xinjiang are shown in Table 1.
TABLE 1
90g of tar residue and 10g of anthracite are mixed to obtain a mixture. And (3) drying and pretreating the mixture for 2 hours at the temperature of 120 ℃ to obtain a dried material. Wherein the condensable gas is condensed and collected, and the non-condensable gas is subjected to high-temperature combustion treatment after being adsorbed by the acid solution.
And putting the crushed dry material into a strip extruding machine for strip extruding and forming, preparing the dry material into a columnar material with the diameter of 2.5mm, and carrying out low-temperature pyrolysis on the columnar material at the temperature of 500 ℃ for 80min in a nitrogen atmosphere to obtain a pyrolysis material. And mixing the gas generated in the pyrolysis process and the gas generated in the drying process for centralized treatment. And (3) performing high-temperature activation on the pyrolysis material in the atmosphere of carbon dioxide serving as an activating agent, wherein the activation temperature is 1100 ℃, and the activation time is 3 hours, so as to obtain an activated carbon product.
And (3) sending the light oil condensed and collected in the drying and pyrolysis processes into a distillation tower for fraction cutting to obtain distillate oil in different process ranges.
The process parameters adopted by the method of the embodiment are shown in table 2, and the yield of each product after the coal tar residue is treated by the method of the embodiment is shown in table 3. The yield calculation method of each product comprises the following steps: the weight of each product was divided by the weight of the tar residue, multiplied by 100%. The performance indexes of the activated carbon product prepared in this example are shown in table 4, and the detection methods are all performed by using detection methods which are conventional in the art.
Examples 2 to 4
The methods of examples 2-4 are the same as in example 1, except that the process parameters are different, as shown in Table 3, the yields of the respective products are shown in Table 4, and the properties of the obtained activated carbon products are shown in Table 5.
Examples 5 to 6
The coal tar residue used in examples 5 to 6 was coal pyrolysis tar residue from a coke plant in Shandong, which had a water content of 3%, and the physical properties after dehydration were as shown in Table 2.
TABLE 2
The methods of examples 5-6 are the same as in example 1, except that the process parameters are different, as shown in Table 3, the yields of the respective products are shown in Table 4, and the properties of the obtained activated carbon products are shown in Table 5.
Comparative example 1
The process of comparative example 1 is the same as example 1 except that water vapor is used as the activating agent.
The product yields of comparative example 1 are shown in Table 4, and the properties of the obtained activated carbon products are shown in Table 5.
In comparative example 1, water vapor is used as an activating agent, the activating effect on tar residues is obviously reduced, and the specific surface area of the prepared activated carbon is only 832m2The iodine value is only 769mg/g, and the methylene blue value is only 96 ml/g.
Comparative example 2
The process of comparative example 2 is the same as example 1 except that no anthracite coal is added to the coal tar residue.
The product yields of comparative example 2 are shown in Table 4, and the properties of the obtained activated carbon products are shown in Table 5.
Comparative example 2 with no added smokelessThe coal and tar residues can not be effectively activated, and the specific surface area of the prepared activated carbon is only 675m2Iodine value of 576mg/g and methylene blue value of 54 ml/g.
TABLE 3
TABLE 4
As can be seen from Table 4, after the tar residue waste is recycled by the method of the embodiment of the invention, the tar residue waste is almost 100% utilized, the waste is changed into valuable, and the tar residue waste can be processed into various products with industrial use values. Wherein the yields of the various products amount to slightly more than 100% due to the introduction of oxygen and activating agent during the activation of the solid matter, which results in the total amount of material fed into the system being greater than the weight of the tar residue waste, which is expressed in combination with the losses of the individual processes.
TABLE 5
| Specific surface area m2/g | Iodine value/mg/g | Methylene blue value/ml/g | |
| Example 1 | 1230 | 1108 | 179 |
| Example 2 | 1032 | 915 | 115 |
| Example 3 | 1143 | 1028 | 129 |
| Example 4 | 1023 | 897 | 123 |
| Example 5 | 1137 | 1003 | 136 |
| Example 6 | 965 | 893 | 132 |
| Comparative example 1 | 832 | 769 | 96 |
| Comparative example 2 | 675 | 576 | 54 |
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A resource treatment method of coal tar residues is characterized by comprising the following steps:
a. mixing the coal tar residue and coal to obtain a mixture, wherein the coal accounts for 5-15% of the total mass of the mixture, and drying and crushing the mixture to obtain crushed materials;
b. pyrolyzing the crushed materials to obtain a pyrolysis material;
c. and adding an activating agent into the pyrolysis material for activation to obtain an activated carbon product, wherein the activating agent is selected from at least one of oxygen, air, carbon dioxide or flue gas, the activation temperature is 800-.
2. The method for recycling coal tar slag according to claim 1, further comprising a step d of condensing flue gas generated in the drying treatment in the step a and the pyrolysis treatment in the step b to recover condensable light oil, and introducing non-condensable gas into an acidic aqueous solution for adsorption treatment.
3. The method for recycling coal tar slag according to claim 1, wherein in the step a, the coal is bituminous coal and/or anthracite.
4. The resource treatment method of the coal tar slag according to any one of claims 1 to 3, wherein in the step a, the drying temperature is 80 to 140 ℃, and the drying time is 0.5 to 3 hours.
5. The resource treatment method of the coal tar slag according to any one of claims 1 to 3, wherein the particle size of the crushed material in the step a is less than or equal to 80 μm.
6. The resource treatment method for the coal tar slag as claimed in any one of claims 1 to 3, wherein in the step b, the pyrolysis temperature is 300-600 ℃, and the pyrolysis time is 20-50 min.
7. The resource treatment method of the coal tar slag according to any one of claims 1 to 3, wherein in the step b, the pyrolysis atmosphere is inert gas.
8. The resource treatment method for the coal tar slag as claimed in any one of claims 1-3, wherein in the step b, the crushed material is extruded into strips to be made into strips, and the strips are pyrolyzed at 300-600 ℃ in an inert atmosphere to obtain pyrolyzed material.
9. The resource treatment method of the coal tar slag according to claim 8, wherein in the step b, the diameter of the strip-shaped material is 2-4mm, and the length of the strip-shaped material is 5-15 mm.
10. The resource treatment method of the coal tar slag according to any one of claims 1 to 3, wherein the flow rate of the activating agent in the step c is 15 to 30 ml/h.
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