CN210656170U - Recycling system of tar residue waste - Google Patents
Recycling system of tar residue waste Download PDFInfo
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- CN210656170U CN210656170U CN201921832122.1U CN201921832122U CN210656170U CN 210656170 U CN210656170 U CN 210656170U CN 201921832122 U CN201921832122 U CN 201921832122U CN 210656170 U CN210656170 U CN 210656170U
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Abstract
The utility model relates to a cyclic utilization system of tar sediment discarded object. The system comprises a solid matter treatment device and a non-solid matter treatment device, and tar residue is processed into activated carbon, light oil distillate, heavy oil distillate, asphalt, water, fuel and solvent oil. The technical problem to be solved is to recycle 100 percent of tar residue waste and change waste into valuable; the environmental pollution of the tar residue waste is avoided, the heat source of the tar residue waste is recycled by self-produced fuel, the energy and the cost are saved, no chemical reagent is introduced in the process, and the tar residue waste is green and environment-friendly, so that the tar residue waste is more suitable for practical use.
Description
Technical Field
The utility model belongs to industrial waste utilizes field and coal chemical industry field, especially relates to a cyclic utilization system of tar residue discarded object, is applicable to the utilization of resource of the abandonment tar residue that produces in the coal gasification of coke-oven plant or the coal pyrolysis course of working.
Background
The coal tar residue, called tar residue for short, is a black or black brown viscous paste solid generated in the coal gasification or coking process, and has high viscosity and difficult oil-water separation. The tar residue has extremely complex components and mainly contains various pollutants such as benzene series, polycyclic aromatic hydrocarbon, nitrogen-containing heterocyclic compounds, sulfur-containing heterocyclic compounds, heavy metals and the like.
The traditional treatment method of the tar residue is to carry out coal blending coking or mix the tar residue into raw materials for recycling. However, with the rapid development of coal chemical industry in recent years, the production capacity is expanding, and the yield of tar residue is increasing year by year. According to statistics, the byproduct tar residues in China reach millions of tons every year at present. If a large amount of tar residues are mixed in the raw materials for coal blending coking, the quality of downstream products is influenced, and therefore, the mixing amount is limited. At present, the main treatment mode of the tar residues of enterprises is still used as waste accumulation. The accumulated tar residues are subjected to rain wash, underground leakage, air volatilization and the like, and cause serious pollution to the environment and underground water. Therefore, the resource utilization of the tar residue becomes one of the problems to be solved urgently for enterprises, and is also a hot spot concerned by researchers in China at present.
The preparation of the activated carbon product by taking the tar residue as a raw material is one of the main approaches for the resource utilization of the tar residue at present. The activated carbon production process generally comprises two stages of carbonization and activation. The carbonization stage is the thermal decomposition and thermal polycondensation reaction process of the carbon-containing raw material, and starts from about 200 ℃ and basically ends to about 600 ℃. Non-carbon elements such as oxygen, hydrogen, nitrogen and the like in the carbon-containing raw material are thermally decomposed into tar and gas micromolecules to be removed, and meanwhile, part of carbon elements are also replaced by CO and CO2The form of (1) is volatilized, carbon atoms in residual carbide are continuously enriched, atoms of oxygen, hydrogen, nitrogen and the like are continuously reduced, the initial form of the activated carbon is gradually formed, the pore structure of the carbide is not developed enough, the carbide exists in a disordered carbon microcrystal form, gaps around the carbon microcrystal are still blocked by tar or amorphous carbon generated by pyrolysis, and the specific surface area of the carbide can only reach 50-200 m at the moment2(ii) in terms of/g. The activation stage is a process that the carbide removes amorphous carbon under the action of an activator, a large number of micropores are formed on the carbon microcrystal, and a developed pore structure is gradually formed, and the specific surface area of the activated carbon can reach 500-3000 m at the stage2/g。
However, since the tar residue has the characteristics of compact structure and high crystallinity, when the tar residue is used for preparing activated carbon, the tar residue lacks of primary pores required by activation, the carbonization and activation are difficult to perform, a physical activation method is not suitable, and a chemical activation method is required. Therefore, in the prior art, most of researches on the preparation of activated carbon by using tar residues use alkali as an activating agent, and an activated group is generated by the reaction of alkali metal and carbon and is subjected to an activating reaction in the activated group to prepare an activated carbon product. However, the chemical activation method is highly corrosive to equipment, pollutes the environment, and if the cleaning is not thorough, the chemical activation method causes the residue of the activating agent.
SUMMERY OF THE UTILITY MODEL
The utility model mainly aims to provide a recycling system of tar residue waste, the technical problem that will solve is to make tar residue waste separate into solid matter and non-solid matter through appropriate technology and device, wherein the solid matter process is active carbon, the non-solid matter process is solvent oil, water, light oil distillate oil, heavy oil distillate oil, pitch and fuel, make 100% of tar residue waste recycled, changing waste into valuables; on one hand, the environmental pollution of the tar residue waste is avoided, on the other hand, the heat source in the recycling method is the recycling of the self-produced fuel, the energy and the cost are saved, and meanwhile, no chemical reagent is introduced in the process, so that the method is green and environment-friendly, and is more suitable for practical use.
The purpose of the utility model and the technical problem thereof are realized by adopting the following technical scheme. According to the utility model provides a cyclic utilization system of tar sediment discarded object, it includes:
a solid matter treatment device which processes the solid matter in the tar residue into an activated carbon product;
and a non-solid matter treatment device which is connected with the solid matter treatment device and is used for separating the non-solid matters in the tar residue and the non-solid matters generated by the solid matter treatment device and processing the non-solid matters into light oil distillate, heavy oil distillate, asphalt, water, fuel and solvent oil.
The purpose of the utility model and the technical problem thereof can be further realized by adopting the following technical measures.
Preferably, the aforementioned recycling system of tar residue waste, wherein the solid matter treatment device comprises:
a drying unit comprising a drying tower;
the crushing unit comprises a crusher and is connected with the drying unit;
the carbonization unit comprises a carbonization furnace and is connected with the crushing unit;
the activation unit comprises an activation furnace and is connected with the carbonization unit;
wherein, a solid flow channel is arranged among the drying unit, the crushing unit, the carbonization unit and the activation unit.
Preferably, in the recycling system of tar residue waste, the solid flow channel is a belt conveyor.
Preferably, the tar residue waste recycling system comprises a drying unit and a drying unit, wherein the drying unit comprises a first belt conveyor and a drying tower; the crushing unit comprises a second belt conveyor and a crusher; the carbonization unit comprises a third belt conveyor and a carbonization furnace; the activation unit comprises a fourth belt conveyor and an activation furnace; the first belt conveyor, the drying tower, the second belt conveyor, the crusher, the third belt conveyor, the carbonization furnace, the fourth belt conveyor and the activation furnace are sequentially connected.
Preferably, in the recycling system of tar residue waste, the carbonization furnace and the activation furnace are both provided with inert gas inlets.
Preferably, the tar residue waste recycling system is characterized in that the solid matter treatment device is communicated with the non-solid matter treatment device through a pipeline.
Preferably, in the aforementioned system for recycling tar residue waste, the drying unit, the carbonization unit and the activation unit are all communicated with the non-solid matter treatment device through pipes.
Preferably, the recycling system of tar residue waste comprises:
the inlet of the first condensing unit is respectively connected with the drying unit and the activating unit;
the inlet of the second condensation unit is connected with the carbonization unit;
a first distillation unit, wherein the inlet of the first distillation unit is respectively connected with the first condensation unit and the second condensation unit; it comprises a top outlet and a bottom outlet;
a third condensing unit, wherein the inlet of the third condensing unit is connected with the tower top outlet of the first distilling unit;
a second distillation unit, the inlet of which is connected with the bottom outlet of the first distillation unit;
the inlet of the oil-water separation unit is connected with the third condensation unit; which comprises an oil phase outlet and a water phase outlet.
Preferably, in the recycling system for tar residue waste, the second condensing unit is provided with a non-condensable gas outlet.
Preferably, in the recycling system for tar residue waste, the first condensing unit includes a first condenser, a first storage tank and a first pipeline pump which are sequentially arranged; the second condensing unit comprises a second condenser, a second storage tank and a second pipeline pump which are sequentially arranged; the inlet of the first condenser is respectively connected with the drying unit and the activation unit; the inlet of the second condenser is connected with the carbonization unit; and the outlet of the first pipeline pump and the outlet of the second pipeline pump are both connected with the inlet of the first distillation unit.
Borrow by above-mentioned technical scheme, the utility model provides a cyclic utilization system of tar sediment discarded object has following advantage at least:
1. the utility model provides a cyclic utilization system of tar residue discarded object, it is the active carbon product through drying, breakage, carbomorphism and the processing of activation step with the solid component in the tar residue discarded object, the defect that the tar residue is difficult to be carbonized and activated because of compact structure has been overcome through the technology of the structural feature of research tar residue and control carbomorphism, thereby can adopt the mixture of vapor and carbon dioxide to carry out physical activation as the activator, chemical activation has been avoided among the prior art and has been used a large amount of acid-base solution, and the active carbon who makes need not the washing, the environmental pollution problem that brings because of acid-base use, washing etc. among the prior art has been solved; meanwhile, the washing is avoided, so that a large amount of water can be saved, and energy and cost are saved;
2. the utility model provides a cyclic utilization system of tar residue discarded object, its technical means such as carrying out condensation step by step, distillation and oil-water separation with the non-solid component in the tar residue discarded object, process it into water, solvent oil, light oil distillate oil, heavy oil distillate oil, pitch that can recycle respectively; the non-condensable gas obtained by condensation is conveyed to a reforming working section to be processed into fuel, and then the fuel is circularly applied to the treatment process of the tar residue, so that the energy consumption in the treatment process of the tar residue can be avoided, and the energy and cost economy are saved;
3. the utility model provides a pair of cyclic utilization system of tar sediment discarded object, its simple process, easy operation, wherein the volatile that drying, carbomorphism and activation process produced is retrieved, cyclic utilization after the condensation, and all the other solid residue materials are used for preparing the active carbon product, and no waste water, waste residue produce in the whole process, and the utilization ratio of tar sediment almost reaches 100%, has realized resource utilization and the near zero release of tar sediment furthest, and fundamentally has solved the pollution difficult problem to the environment.
The above description is only an overview of the technical solution of the present invention, and in order to make the technical means of the present invention clearer and can be implemented according to the content of the description, the following detailed description is made with reference to the preferred embodiments of the present invention and accompanying drawings.
Drawings
FIG. 1 is a schematic structural view of a recycling system for tar residue waste according to the present invention;
FIG. 2 is a schematic view of a solid matter treatment apparatus of the tar residue waste recycling system;
FIG. 3 is a schematic view of a non-solid matter treatment apparatus of a tar residue waste recycling system.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the intended purpose of the present invention, the following detailed description will be given with reference to the accompanying drawings and preferred embodiments of the present invention for the specific embodiments, structures, features and effects of the tar residue waste recycling system according to the present invention.
The utility model provides a recycling method of tar residue waste, which comprises the following steps that the tar residue is a viscous semi-flowing solid with the water content of 3-15% by mass percentage, and the fixed carbon content of the tar residue is more than or equal to 40 wt%; furthermore, the fixed carbon content is more than or equal to 50 wt%.
As shown in fig. 1, the recycling method includes the following steps:
drying tar residue, and collecting the first volatile gas
Obtaining first solid slag
First solid slag
Crushing to obtain second solid slag
Second solid slag
Carbonizing in inert atmosphere, collecting second volatile gas
Obtaining third solid slag
Third solid slag
Physical activation, collecting the third volatile gas
Condensing the solid matter to normal temperature in inert atmosphere to obtain the active carbon product
First volatile gas
Second volatile gas
Third volatile gas
condensing, and performing first distillation on a condensation product, wherein materials at the top of the tower are condensed and then subjected to oil-water separation, an obtained oil phase is a solvent oil product, an obtained water phase is conveyed to a sewage treatment station for treatment, materials at the bottom of the tower are subjected to second distillation, and light oil distillate oil ⑥, heavy oil distillate oil (⑦) and asphalt (eighty percent) are collected;
second volatile gas
non-condensable gas generated during condensation is reformed to obtain a fuel ⑨ product.
The recycling refers to a process of changing waste into recyclable materials.
The research in the early stage discovers that the tar residue waste contains organic matters such as tar, colloidal particles and coal dust, and solid matters in the tar residue waste can form various mosaic optical structures which are randomly and disorderly arranged after carbonization treatment, so that a large number of edge angle edges are formed, and the edge angle edges can provide a large number of active sites for the subsequent activation process; meanwhile, an activated carbon product with industrial value can be prepared by adopting a proper activating agent and activating process and carrying out physical activation.
Through the technical scheme of the utility model, the specific surface area of the prepared active carbon is larger than 900m2(ii) in terms of/g. The technical proposal of the utility model changes the microscopic surface structure of the tar residue through the technical means of carbonization treatment and the like, so that the tar residue is developed into an extremely complex space three-dimensional structure system to provide active sites for the subsequent activation reaction; meanwhile, the tar residue is prepared into a high-quality activated carbon product by using a cheap and easily-obtained and environment-friendly physically-activated activating agent, so that the purpose of resource utilization of the tar residue is realized.
Further, the moisture or volatile gas components except the solid matters in the tar residue waste are condensed, and the separated non-condensable gas mainly contains H2、CH4、CO、CO2Conveying the tar residue to a reforming section for reforming to obtain a fuel product which can be further circularly applied to the treatment process of the tar residue waste; distilling the separated condensable gas, condensing the substances at the top, and then performing oil-water separation, wherein the oil phase part is conveyed to a solvent oil storage tank for later use; wherein the water phase part is conveyed to a sewage treatment station to be treated into water for standby; the aqueous phase conveyed to the sewage treatment station also comprises a part of water entrained from the first distillation unit and a part of water formed by condensation of the third condenser; and distilling the crude tar serving as the bottom material, and collecting fractions at different temperatures, wherein the fraction at a temperature of less than 350 ℃ is used as light oil distillate, the fraction at a temperature of 350-500 ℃ is used as heavy oil distillate, and the fraction at a temperature of more than 500 ℃ is used as asphalt.
The tar residue waste is comprehensively utilized by the technical scheme, the solid components are processed into the activated carbon product with industrial value, other components are separated and processed into various product oils, and the various product oils can enter a subsequent coal tar processing section for further utilization, so that the tar residue waste is utilized at the maximum value, and the tar residue waste is green, environment-friendly and energy-saving.
in one embodiment of the present invention, the tar residue ① is first sent to the drying tower 12 through the first belt conveyer 11 for drying, wherein the drying temperature ① is preferably 100-130 ℃, the drying time ① is preferably 1-3 h, and the gas escaping from the drying process ① is the first volatile gas
Collected and sent to a first condenser 411 for condensation; the temperature of the condensing medium of the first condenser 411 is between 40 ℃ and 100 ℃. The oil-water mixed solution obtained by condensing the oil-water mixed solution to be below 100 ℃ is input into the first storage tank 412 through a pipeline.
Dried first solid slag
Sending the slag into a crusher 22 through a second belt conveyor 21, and crushing the slag into solid powdery solid slag with 20-100 meshes, namely second solid slag
Second solid slag
The carbonized material is sent into the carbonization furnace 32 through the third belt conveyor 31, the temperature of the carbonization furnace 32 is raised in a temperature programming mode, the carbonization temperature is preferably 700-900 ℃, and the retention time is preferably 1-3 h. When the carbonization temperature is lower than 700 ℃, such as carbonization at 500 ℃, the tar residue is difficult to form a mosaic optical structure which is randomly and disorderly arranged, and the tar residue is difficult to be carbonized and activated; when the carbonization temperature is 700-900 ℃, for example, carbonization is carried out at 800 ℃, the tar residues form mosaic optical structures which are randomly and disorderly arranged, and the edge edges can provide a large amount of active sites for the subsequent activation process, so that the subsequent activation is easy to carry out; when the carbonization temperature is higher than 900 ℃, for example, carbonization is carried out at 1000 ℃, the three-dimensional crystal structure of the tar residue collapses, and the pore channel is blocked, which is not beneficial to the subsequent activation process.
The gas escaping in the carbonization process is the second volatile gas
Collected and sent to a second condenser 421 for condensation; the temperature of the condensing medium in the second condenser 421 is preferably between 110 ℃ and 230 ℃. Condensed in the second condenser 421 and the resulting liquid product is directed to the second storage tank 422.
③ the ③ material ③ in ③ the ③ second ③ storage ③ tank ③ 422 ③ and ③ the ③ material ③ in ③ the ③ first ③ storage ③ tank ③ 412 ③ are ③ respectively ③ pumped ③ into ③ the ③ first ③ distillation ③ unit ③ 43 ③ through ③ a ③ second ③ pipeline ③ pump ③ 423 ③ and ③ a ③ first ③ pipeline ③ pump ③ 413 ③, ③ the ③ distillation ③ temperature ③ of ③ the ③ material ③ in ③ the ③ first ③ distillation ③ unit ③ 43 ③ is ③ preferably ③ less ③ than ③ or ③ equal ③ to ③ 280 ③ ℃ ③, ③ the ③ material ③ at ③ the ③ bottom ③ of ③ the ③ first ③ distillation ③ unit ③ 43 ③ is ③ crude ③ tar ③, ③ the ③ crude ③ tar ③ is ③ guided ③ into ③ a ③ fifth ③ storage ③ tank ③ 451 ③ through ③ a ③ pipeline ③ from ③ a ③ side ③ outlet ③, ③ then ③ the ③ crude ③ tar ③ is ③ pumped ③ into ③ a ③ second ③ distillation ③ tower ③ 453 ③ through ③ a ③ fifth ③ pipeline ③ pump ③ 452 ③, ③ fractions ③ (③ light ③ oil ③) ③ at ③ 350 ③ ℃ ③, ③ fractions ③ (③ heavy ③ oil ③) ③ at ③ 350 ③ - ③ 500 ③ ℃ ③ and ③ fractions ③ (③ asphalt ③) ③ at ③ 500 ③ ℃ ③ are ③ respectively ③ collected ③ by ③ the ③ second ③ distillation ③ tower ③, ③ the ③ material ③ at ③ the ③ top ③ of ③ the ③ first ③ distillation ③ unit ③ 43 ③ enters ③ a ③ third ③ condensation ③ unit ③ 44 ③, ③ after ③ the ③ materials ③ are ③ condensed ③ to ③ be ③ below ③ 100 ③ ℃ ③, ③ the ③ materials ③ are ③ separated ③ through ③ an ③ oil ③ - ③ water ③ separation ③ unit ③ 46 ③, ③ the ③ oil ③ phase ③ is ③ sent ③ into ③ a ③ solvent ③ oil ③ storage ③ tank ③ through ③ a ③ pipeline ③, ③ and ③ the ③ water ③ phase ③ is ③ sent ③ into ③ a ③ water ③ treatment ③ station ③ for ③ treatment ③, ③ and ③ water ③ is ③ obtained ③. ③
the noncondensable gas obtained after condensation by the second condenser 421 mainly contains H2、CH4、CO、CO2and entering a subsequent reforming section, and ninthly, using the reformed product as fuel.
The third solid slag carbonized in the carbonization furnace 3
And (3) feeding the mixture into an activation furnace 52 through a fourth belt conveyor 51, wherein the activation temperature is preferably 700-900 ℃, and the activation time is preferably 1-3 h. It is activated by adopting a 800 ℃ carbonized three-dimensional crystal structure. When the activation temperature is lower than 700 ℃, for example, when the activation is carried out at 500 ℃, the pore channel formed by the tar residue is of a macroporous structure, so that the active carbon with industrial value is difficult to obtain; when the activation temperature is 700-900 ℃, for example, when the activation temperature is 800 ℃, a hierarchical pore structure of macropores, mesopores and micropores can be formed in the tar residue, so that the activated carbon with industrial value can be obtained; when the activation temperature is higher than 900 ℃, such as 1000 ℃, the pore structure in the tar residue collapses and the pore channel is blocked.
The reaction gas from the high-pressure gas cylinder 50, for example, uses a mixture of carbon dioxide and water vapor as an activator, wherein CO is present in parts by volume2:H2O is 1: 3-7, and the mixture is conveyed into an activation furnace 52 together with the third solid slag
activated reaction to obtain activated carbon ⑩ product, and the residual gas after reaction, i.e. third volatile gas
To the first condensing unit 41.
The basic reaction formula of the above gas activation is as follows: c + H2O→H2+CO，C+CO2→CO。
In the recycling method, the inert atmosphere in the carbonization stage and the cooling stage is one of nitrogen or helium.
In the conventional production process of activated carbon, the carbonization stage is a reaction process of thermal decomposition and thermal polycondensation of a carbon-containing raw material, and generally carbonization is started from about 200 ℃ to about 600 ℃. The carbonization temperature directly influences the pore structure and strength of the carbonized material. When the temperature is too low, the carbonized product cannot develop sufficient mechanical strength; when the temperature is too high, the graphite microcrystals in the carbonized product can be promoted to change orderly, so that the gaps among the microcrystals are reduced, and the subsequent activation pore-forming process is influenced. However, the raw material of the utility model is the tar residue waste, and the structure of the tar residue waste is compact, the crystallinity is high, and the tar residue waste lacks the primary pores required by activation. In the research of the utility model, a large amount of researches on the raw materials of the tar residue waste show that when the process temperature of carbonization is increased to 700-900 ℃, it does not promote the ordered change of graphite microcrystals in the carbonized product and reduces the gaps among the microcrystals like the raw materials of other activated carbon, but forms a plurality of mosaic optical structures which are randomly and disorderly arranged in the interior of the microcrystals, thereby forming a plurality of corner edges which can provide a plurality of active sites for the subsequent activation process, that is, the technical proposal of the utility model, through technical means such as carbonization treatment at a higher carbonization temperature, the microscopic surface structure of the tar residue is changed, so that the tar residue is developed into an extremely complex spatial three-dimensional structure system, an active site is provided for subsequent activation reaction, and the activation mode of the subsequent activation process can be selected in various ways.
The technical proposal of the utility model is to use the mixture of water vapor and carbon dioxide which is cheap and easy to obtain and is environment-friendly as an activating agent. During the activation process, a gas activating agent, such as carbon dioxide, water vapor, air, etc., is introduced. The activation reaction finally achieves the purpose of activating pore-forming through the following three stages: the first stage is as follows: the original occluded pores were opened. At high temperature, the activated gas firstly reacts with disordered carbon atoms and heteroatoms, pores which are formed during carbonization but are blocked by the disordered carbon atoms and the disordered heteroatoms are opened, and the surface of basic microcrystal is exposed; and a second stage: enlarging the original pores. The carbon atoms on the surface of the basic microcrystal exposed at the stage are burnt out by oxidation reaction with the activated gas, so that the opened pores are continuously enlarged, run through and develop deeply; and a third stage: new pores are formed. The loss of carbon atoms on the surface of the crystallites is not uniform, the loss rate in parallel with the carbon layer is higher than in perpendicular direction, and the carbon atoms, i.e. active sites, at the edges and defect sites of the crystallites are more reactive with the activating gas. Meanwhile, as the activation reaction continues, new active sites are exposed on the surface of the microcrystal, and then the new active sites can react with the activation gas. This uneven burning of the surface of the crystallites constantly leads to the formation of new pores. Along with the progress of the activation reaction, the pores are continuously enlarged, the pore walls between adjacent micropores are completely burned off to form larger pores, so that the pore volumes of the mesopores and the macropores are increased, and thus, a pore structure formed by connecting the macropores, the mesopores and the micropores of the activated carbon has a developed specific surface area. By proper proportion of the activating agent and the parameters of the activating process, activation can be completed without using chemical reagents such as acid, alkali and the like, and an activated carbon product with industrial value is obtained, so that the problem of environmental pollution caused by a chemical activation technology is avoided.
The technical scheme of the utility model in, use the mixture of vapor and carbon dioxide as the activator, need not to use chemical reagents such as acid, alkali and can accomplish the activation to avoid a large amount of uses of acid-base solution among the current chemical activation technique, the active carbon product that makes simultaneously need not the washing step, has solved the environmental pollution problem because of using steps such as acid-base, washing to bring, simultaneously very big saving the energy.
The utility model discloses still provide a cyclic utilization system of tar sediment discarded object, as shown in figure 1, figure 2 and figure 3, it includes:
a solid matter treatment device which processes the solid matter in the tar residue into an activated carbon product;
and a non-solid matter treatment device 4 connected to the solid matter treatment device, for separating and processing the non-solid matter in the tar residue and the non-solid matter generated by the solid matter treatment device into light oil distillate, heavy oil distillate, asphalt, water, fuel, and solvent oil.
The solid matter treatment device and the non-solid matter treatment device 4 are communicated with each other through a gas flow passage. Non-solid matter produced during operation of the solid matter treatment device can be conveyed via the gas stream channel to the non-solid matter treatment device 4 for treatment.
Preferably, the solid matter treatment apparatus includes:
a drying unit 1 including a drying tower 12;
a crushing unit 2 comprising a crusher 22 connected to said drying unit 1;
the carbonization unit 3 comprises a carbonization furnace 32 and is connected with the crushing unit 2;
an activation unit 5 which comprises an activation furnace 52 and is connected with the carbonization unit 3;
wherein, a solid flow channel is arranged among the drying unit 1, the crushing unit 2, the carbonization unit 3 and the activation unit 5, so that the solid material is sequentially conveyed among the drying unit 1, the crushing unit 2, the carbonization unit 3 and the activation unit 5 to obtain the activated carbon product.
Preferably, the solid flow channel is a belt conveyor.
Preferably, the drying unit 1 comprises a first belt conveyor 11 and a drying tower 12; the crushing unit 2 comprises a second belt conveyor 21 and a crusher 22; the carbonization unit 3 comprises a third belt conveyor 31 and a carbonization furnace 32; the activation unit 5 comprises a fourth belt conveyor 51 and an activation furnace 52; the first belt conveyor 11, the drying tower 12, the second belt conveyor 21, the crusher 22, the third belt conveyor 31, the carbonization furnace 32, the fourth belt conveyor 51 and the activation furnace 52 are connected in sequence.
Preferably, the carbonization furnace 32 and the activation furnace 52 are both provided with inert gas inlets; the cooling process after carbonization and activation are both in inert atmosphere.
Preferably, the solid matter processing device is communicated with the non-solid matter processing device 4 through a pipeline.
Preferably, the drying unit 1, the carbonization unit 3 and the activation unit 5 are all communicated with the non-solid substance treatment device 4 through pipelines.
Preferably, the non-solid matter treatment device 4 comprises:
a first condensing unit 41, the inlets of which are respectively connected with the drying unit 1 and the activating unit 5;
a second condensing unit 42, the inlet of which is connected with the carbonization unit 3;
a first distillation unit 43, the inlets of which are respectively connected with the first condensation unit 41 and the second condensation unit 42; it comprises a top outlet and a bottom outlet;
a third condensing unit 44, the inlet of which is connected to the top outlet of the first distillation unit 43;
a second distillation unit 45, the inlet of which is connected with the bottom outlet of the first distillation unit 43;
an inlet of the oil-water separation unit 46 is connected with the third condensation unit 44; which comprises an oil phase outlet and a water phase outlet.
Preferably, the second condensing unit 42 is provided with a non-condensable gas outlet.
Preferably, the first condensing unit 41 comprises a first condenser 411, a first storage tank 412 and a first pipeline pump 413 which are arranged in sequence; the second condensing unit 42 comprises a second condenser 421, a second storage tank 422 and a second pipeline pump 423 which are arranged in sequence; the inlet of the first condenser 411 is respectively connected with the drying unit 1 and the activation unit 5; the inlet of the second condenser 421 is connected with the carbonization unit 3; the outlet of the first pipeline pump 413 and the outlet of the second pipeline pump 423 are both connected with the inlet of the first distillation unit 43.
The first volatile gas collected from the drying unit 1
Third volatilized gas collected from activation Unit 5
Are all sent to the first condensing unit 41 for condensation, and the condensed products are sent to the first distilling unit 43 for distillation treatment; the second volatile gas collected from the carbonization unit 3
Is sent to the second condensing unit 42 for condensation, wherein the condensable gas component is sent to the first distilling unit 43 for distillation, and the non-condensable gas component is sent to a reforming section (not shown) from the non-condensable gas outlet for reforming processing, so as to obtain a fuel product.
③ the ③ first ③ distillation ③ unit ③ 43 ③ distills ③ the ③ components ③ at ③ a ③ certain ③ temperature ③, ③ wherein ③ the ③ top ③ component ③ is ③ conveyed ③ to ③ a ③ third ③ condensation ③ unit ③ 44 ③ for ③ condensation ③, ③ the ③ condensed ③ material ③ is ③ conveyed ③ to ③ an ③ oil ③ - ③ water ③ separation ③ unit ③ 46 ③ for ③ separation ③, ③ the ③ separated ③ oil ③ phase ③ part ③ is ③ solvent ③ oil ③, ③ ④ ③ and ③ is ③ conveyed ③ to ③ a ③ storage ③ tank ③ for ③ storage ③, ③ the ③ separated ③ water ③ phase ③ is ③ conveyed ③ to ③ a ③ sewage ③ treatment ③ station ③ (③ not ③ shown ③ in ③ the ③ figure ③) ③ for ③ treatment ③, ③ recyclable ③ water ③ is ③ obtained ③, ③ the ③ bottom ③ component ③ is ③ crude ③ tar ③, ③ the ③ crude ③ tar ③ is ③ conveyed ③ to ③ a ③ second ③ distillation ③ unit ③ 45 ③ for ③ distillation ③, ③ and ③ light ③ oil ③ distillate ③ oil ③, ③ heavy ③ oil ③ distillate ③ oil ③ and ③ asphalt ③ are ③ collected ③ according ③ to ③ different ③ distillation ③ ranges ③. ③
The present invention will be further described with reference to the following more specific examples.
Example 1
The tar residue obtained from a coal gasification company in Xinjiang has a water content of 12% by mass, and the elemental analysis and industrial analysis of the tar residue are shown in Table 1.
TABLE 1 elemental and Industrial analysis of tar residue
Conveying the tar residues into a drying tower for drying through a belt, wherein the drying temperature of the drying tower is 120 ℃, gas escaping in the drying process is sent into a first condenser for condensation, the temperature of a condensation medium is set to be 100 ℃, and an oil-water mixed solution obtained after condensation is pumped into a first storage tank through a pipeline.
And conveying the dried first solid slag into a crusher through a belt, and crushing the dried material into solid powder of 20-100 meshes to obtain second solid slag. And conveying the second solid slag into a carbonization furnace through a belt, wherein the temperature of the carbonization furnace is set to be 700 ℃, and the retention time is 2 h. And gas escaping in the carbonization process enters a second condenser for condensation, wherein the temperature of a condensation medium is set to be 230 ℃.
The liquid product obtained by condensation in the second condenser is introduced into a second storage tank. And the material in the second storage tank and the material from the first storage tank are pumped into a first distillation unit together, the distillation temperature of the material in the first distillation unit is less than or equal to 280 ℃, the material (crude tar) at the bottom of the first distillation unit is introduced into a fifth storage tank through a pipeline from a side outlet, and then the material is pumped into a second distillation tower, and the fraction (light oil) at the temperature of 350 ℃, the fraction (heavy oil) at the temperature of 350 ℃ to 500 ℃ and the fraction (asphalt) at the temperature of 500 ℃ are respectively collected by the second distillation tower.
And the material at the top of the first distillation unit enters a third condenser, is condensed to below 60 ℃, enters an oil-water separator for separation, and then the oil phase is sent to a solvent storage tank and the water phase is sent to a sewage treatment station through pipelines.
And the non-condensable gas obtained after condensation by the second condenser enters a subsequent reforming section.
Conveying the third solid slag carbonized by the carbonization furnace into an activation furnace through a belt, and adding CO2Mixed gas of CO and water vapor as activator2And H2The volume ratio of O is 1:3, the activation temperature is 900 ℃, and the activation time is 2 h. And (3) the reaction gas from the high-pressure gas cylinder enters an activation furnace, and is subjected to activation reaction with the third solid slag to obtain an activated carbon product, and the residual gas after the reaction is merged into the first condenser.
The yield of each product after the coal gasification tar residue is subjected to the grading treatment process is shown in Table 4. 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 index of the activated carbon product prepared in this example is shown in table 5. The detection method is carried out by the conventional detection method in the field.
Examples 2 to 8 and comparative examples 1 to 6
The process steps are the same as example 1, the specific process parameters are shown in table 3, the yield of each product is shown in table 4, and the performance indexes of the prepared activated carbon product are shown in table 5.
Wherein, the tar residue raw material adopted in example 8 is coal pyrolysis tar residue from a certain coke-oven plant in Shandong, the water content of the tar residue is 3%, and the physical property parameters after dehydration are shown in the following table 2.
TABLE 2 elemental and Industrial analysis of tar residue in example 8
TABLE 3 Process parameters for the examples and comparative examples
Table 4 yield of each product prepared for each example and comparative example
As can be seen from the yield data in Table 4, after the treatment of the recycling method and the recycling system of the technical scheme of the invention, the tar residue waste is almost 100% recycled, so that the waste is changed into valuable, and the tar residue waste is processed into various products with industrial use value. The yields of the individual products amounting to slightly more than 100%, since the introduction of the activating agent during the activation of the solid matter leads to a total amount of material fed into the system which is greater than the weight of tar residue waste, as a result of which this is shown in combination with losses in the individual processes.
TABLE 5 Properties of activated carbon prepared in examples and comparative examples
| Specific surface area m2/g | Iodine value/mg/g | Methylene blue value/ml/g | |
| Example 1 | 996 | 932 | 125 |
| Example 2 | 1298 | 1006 | 195 |
| Example 3 | 1030 | 993 | 107 |
| Example 4 | 964 | 982 | 135 |
| Example 5 | 1043 | 902 | 163 |
| Example 6 | 989 | 900 | 103 |
| Example 7 | 905 | 943 | 132 |
| Example 8 | 959 | 931 | 157 |
| Comparative example 1 | 543 | 482 | 64 |
| Comparative example 2 | 596 | 501 | 82 |
| Comparative example 3 | 695 | 600 | 147 |
| Comparative example 4 | 623 | 546 | 132 |
| Comparative example 5 | 592 | 499 | 100 |
| Comparative example 6 | 634 | 513 | 149 |
As can be seen from the test data in Table 5, the microstructure of the activated carbon obtained by the technical solution of the present invention is characterized by the specific surface area, and the specific surface areas of the activated carbons prepared in examples 1 to 8 are all larger than 900m2Per g, the adsorption property is good, and the industrial application value is good. The iodine value is an index for representing the adsorption performance of the activated carbon, generally, the correlation between the numerical value and the number of micropores in the activated carbon is considered to be good, and the iodine values of the activated carbon prepared in examples 1 to 8 are all larger than 900mg/g, so that the activated carbon has good adsorption performance. The methylene blue value mainly represents the liquid phase adsorption capacity of the activated carbon, and the iodine value of the activated carbon prepared in the examples 1 to 8 is between 100 and 200ml/g, and the activated carbon can be used for water treatment.
The features of the invention claimed in the claims and/or in the description may be combined, but the combination is not limited to the combination defined in the claims by the reference. The technical solution obtained by combining the technical features in the claims and/or the specification is also the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made by the technical spirit of the present invention to the above embodiments are all within the scope of the technical solution of the present invention.
Claims (10)
1. A recycling system of tar residue waste is characterized by comprising:
a solid matter treatment device which processes the solid matter in the tar residue into an activated carbon product;
and a non-solid matter treatment device which is connected with the solid matter treatment device and is used for separating the non-solid matters in the tar residue and the non-solid matters generated by the solid matter treatment device and processing the non-solid matters into light oil distillate, heavy oil distillate, asphalt, water, fuel and solvent oil.
2. The tar residue waste recycling system as claimed in claim 1, wherein the solid matter treatment apparatus comprises:
a drying unit comprising a drying tower;
the crushing unit comprises a crusher and is connected with the drying unit;
the carbonization unit comprises a carbonization furnace and is connected with the crushing unit;
the activation unit comprises an activation furnace and is connected with the carbonization unit;
wherein, a solid flow channel is arranged among the drying unit, the crushing unit, the carbonization unit and the activation unit.
3. The tar slag waste recycling system of claim 2, wherein the solids flow path is a belt conveyor.
4. The tar residue waste recycling system of claim 2, wherein the drying unit comprises a first belt conveyor and a drying tower; the crushing unit comprises a second belt conveyor and a crusher; the carbonization unit comprises a third belt conveyor and a carbonization furnace; the activation unit comprises a fourth belt conveyor and an activation furnace; the first belt conveyor, the drying tower, the second belt conveyor, the crusher, the third belt conveyor, the carbonization furnace, the fourth belt conveyor and the activation furnace are sequentially connected.
5. The recycling system of tar slag waste as claimed in claim 2, wherein the carbonization furnace and the activation furnace are provided with inert gas inlets.
6. The tar slag waste recycling system as claimed in claim 1, wherein the solid matter treatment device is in communication with the non-solid matter treatment device via a pipe.
7. The tar residue waste recycling system of claim 2, wherein the drying unit, the carbonization unit and the activation unit are all communicated with a non-solid matter treatment device through pipes.
8. The tar residue waste recycling system of claim 2, wherein the non-solid matter treatment device comprises:
the inlet of the first condensing unit is respectively connected with the drying unit and the activating unit;
the inlet of the second condensation unit is connected with the carbonization unit;
a first distillation unit, wherein the inlet of the first distillation unit is respectively connected with the first condensation unit and the second condensation unit; it comprises a top outlet and a bottom outlet;
a third condensing unit, wherein the inlet of the third condensing unit is connected with the tower top outlet of the first distilling unit;
a second distillation unit, the inlet of which is connected with the bottom outlet of the first distillation unit;
the inlet of the oil-water separation unit is connected with the third condensation unit; which comprises an oil phase outlet and a water phase outlet.
9. The tar slag waste recycling system of claim 8, wherein the second condensing unit is provided with a non-condensable gas outlet.
10. The recycling system of tar residue waste as claimed in claim 8,
the first condensing unit comprises a first condenser, a first storage tank and a first pipeline pump which are sequentially arranged; the second condensing unit comprises a second condenser, a second storage tank and a second pipeline pump which are sequentially arranged; the inlet of the first condenser is respectively connected with the drying unit and the activation unit; the inlet of the second condenser is connected with the carbonization unit; and the outlet of the first pipeline pump and the outlet of the second pipeline pump are both connected with the inlet of the first distillation unit.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114192555A (en) * | 2021-10-11 | 2022-03-18 | 北京清新环境技术股份有限公司 | Method for recycling and comprehensively utilizing high-carbon-content hazardous solid wastes, product and application thereof |
| CN114958425A (en) * | 2022-01-10 | 2022-08-30 | 新疆宣力环保能源股份有限公司 | Coal tar hydrogenation process using coal tar residue |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114192555A (en) * | 2021-10-11 | 2022-03-18 | 北京清新环境技术股份有限公司 | Method for recycling and comprehensively utilizing high-carbon-content hazardous solid wastes, product and application thereof |
| CN114958425A (en) * | 2022-01-10 | 2022-08-30 | 新疆宣力环保能源股份有限公司 | Coal tar hydrogenation process using coal tar residue |
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