CN110668440A - Recycling method of tar residue waste - Google Patents

Recycling method of tar residue waste Download PDF

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CN110668440A
CN110668440A CN201911036138.6A CN201911036138A CN110668440A CN 110668440 A CN110668440 A CN 110668440A CN 201911036138 A CN201911036138 A CN 201911036138A CN 110668440 A CN110668440 A CN 110668440A
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tar residue
activation
temperature
residue waste
tar
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常秋连
李文博
孙仲超
毛学峰
胡发亭
赵鹏
马博文
吴艳
钟金龙
黄鹏
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China Coal Research Institute CCRI
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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
    • C01B32/33—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
    • 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
    • C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
    • C10G5/06—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas by cooling or compressing
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas

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Abstract

The invention relates to a recycling method of tar residue waste. The method comprises the following steps: drying and crushing the tar residue; carbonizing under inert atmosphere; physical activation; condensing to normal temperature under inert atmosphere to obtain an activated carbon product; collecting volatile gas, condensing, and carrying out first distillation on a condensation product; wherein, the materials at the top of the tower are condensed and then are subjected to oil-water separation; performing second distillation on the tower bottom material; the non-condensable gas generated when the second volatile gas is condensed is reformed. 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

Recycling method of tar residue waste
Technical Field
The invention belongs to the field of industrial waste utilization and the field of coal chemical industry, and particularly relates to a recycling method of tar residue waste, which is suitable for resource utilization of waste tar residue generated in the coal gasification or coal pyrolysis processing process of a coking plant.
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.
Disclosure of Invention
The invention mainly aims to provide a recycling method of tar residue waste, which aims to solve the technical problems that the tar residue waste is separated into solid matters and non-solid matters through a proper process and a proper device, wherein the solid matters are processed into activated carbon, the non-solid matters are processed into solvent oil, water, light oil distillate oil, heavy oil distillate oil, asphalt and fuel, 100 percent of the tar residue waste is recycled, and waste materials are changed into valuable materials; 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 invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a recycling method of tar residue waste, which comprises the following steps:
drying the tar residue, and collecting a first volatile gas to obtain a first solid residue;
crushing the first solid slag to obtain second solid slag;
carbonizing the second solid slag in an inert atmosphere, and collecting second volatile gas to obtain third solid slag;
physically activating the third solid slag, collecting third volatile gas, and condensing the solid substance to normal temperature in an inert atmosphere to obtain an activated carbon product;
condensing the first volatile gas, the second volatile gas and the third volatile gas, and carrying out first distillation on a condensation product; wherein, the materials at the top of the tower are condensed and then are subjected to oil-water separation, the obtained oil phase is a solvent oil product, and the obtained water phase is conveyed to a sewage treatment station for treatment; performing second distillation on the tower bottom materials, and collecting light oil distillate oil, heavy oil distillate oil and asphalt;
and (4) reforming the non-condensable gas generated when the second volatile gas is condensed to obtain a fuel product.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the method for recycling the tar residue waste, the carbonization temperature in the carbonization step is 700-900 ℃, and the carbonization time is 1-3 h.
Preferably, in the recycling method of tar residue waste, the inert atmosphere is one of nitrogen and helium.
Preferably, in the aforementioned recycling method of tar residue waste, the activation step uses a mixture of carbon dioxide and water vapor as an activator, wherein the volume part of CO is2:H2O is 1: 3-7.
Preferably, in the recycling method of the tar residue waste, the activation temperature in the activation step is 700-900 ℃, and the activation time is 1-3 hours.
Preferably, the method for recycling the tar residue waste comprises a first condensation, a second condensation and a third condensation; the condensation of the first volatile gas and the third volatile gas is first condensation, wherein the temperature of a cooling medium is 40-100 ℃; the condensation of the second volatile gas is second condensation, wherein the temperature of a cooling medium is 110-230 ℃; the condensation of the overhead material is a third condensation, wherein the temperature of the cooling medium is less than 100 ℃.
Preferably, in the recycling method of the tar residue waste, the tar residue is a viscous semi-fluid solid with a water content of 3-15% by mass, and the fixed carbon content of the tar residue is more than or equal to 40 wt%.
Preferably, in the recycling method of the tar residue waste, the drying temperature in the drying step is 100-130 ℃, and the drying time is 1-3 hours.
Preferably, the distillation temperature of the first distillation is less than or equal to 280 ℃.
Preferably, in the method for recycling the tar residue waste, the carbonization temperature in the carbonization step is 800 ℃, and the carbonization time is 2 hours; the physical activation step uses a mixture of carbon dioxide and water vapor as an activator, wherein the CO is present in parts by volume2:H2O is 1: 5; the activation temperature of the activation step is 800 ℃, and the activation time is 2 h.
By the technical scheme, the recycling method of the tar residue waste provided by the invention at least has the following advantages:
1. according to the recycling method of the tar residue waste, the solid components in the tar residue waste are processed into an activated carbon product through the steps of drying, crushing, carbonizing and activating, the defect that the tar residue is hard to be carbonized and activated due to compact structure is overcome through researching the structural characteristics of the tar residue and controlling the carbonizing process, so that the mixture of water vapor and carbon dioxide is used as an activating agent for physical activation, the situation that a large amount of acid-base solution is used for chemical activation in the prior art is avoided, the prepared activated carbon does not need to be washed with water, and the problem of environmental pollution caused by acid-base washing and the like in the prior art is solved; meanwhile, the washing is avoided, so that a large amount of water can be saved, and energy and cost are saved;
2. the invention provides a recycling method of tar residue waste, which comprises the following steps of carrying out technical means such as stepwise condensation, distillation, oil-water separation and the like on non-solid components in the tar residue waste, and respectively processing the non-solid components into recyclable water, solvent oil, light oil distillate oil, heavy oil distillate oil and asphalt; 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 invention provides a recycling method of tar residue waste, which has simple process and easy operation, wherein volatile matters generated in the drying, carbonization and activation processes are condensed and then recovered and recycled, and other solid residue substances are used for preparing activated carbon products, no waste water and waste residue are generated in the whole process, the utilization rate of the tar residue almost reaches 100 percent, the resource utilization and near zero emission of the tar residue are realized to the maximum extent, and the problem of environmental pollution is fundamentally solved.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic process flow diagram of the recycling method of tar residue waste according to the present invention;
FIG. 2 is a schematic structural diagram of a recycling system for tar residue waste according to the present invention;
FIG. 3 is a schematic view of a solid matter treatment apparatus of the tar residue waste recycling system;
FIG. 4 is a schematic view of a non-solid matter treatment apparatus of a tar residue waste recycling system;
FIG. 5a is an electron micrograph of a third solid residue after charring tar residue at 500 ℃;
FIG. 5b is an electron micrograph of a third solid residue after charring tar residue at 800 ℃;
FIG. 5c is an electron micrograph of a third solid residue after charring tar residue at 1000 ℃;
FIG. 6a is an electron micrograph of activated carbon after tar residue activation at 500 ℃;
FIG. 6b is an electron micrograph of activated carbon after tar residue activation at 800 ℃;
FIG. 6c is an electron micrograph of activated carbon after tar residue activation at 1000 ℃.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to the specific implementation, structure, features and effects of the recycling method of tar residue waste according to the present invention with reference to the accompanying drawings and preferred embodiments.
The invention provides a recycling method of tar residue waste, wherein the tar residue is a viscous semi-flowing solid with the water content of 3-15% in percentage by mass, 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 and 2, the recycling method includes the following steps:
drying the tar residue ①, and collecting the first volatile gas
Figure BDA0002251552160000051
Obtaining first solid slag
Figure BDA0002251552160000052
First solid slag
Figure BDA0002251552160000053
Crushing to obtain second solid slag
Figure BDA0002251552160000054
Second solid slag
Figure BDA0002251552160000055
Carbonizing in inert atmosphere, collecting second volatile gas
Figure BDA0002251552160000056
Obtaining third solid slag
Figure BDA0002251552160000057
Third solid slag
Figure BDA0002251552160000058
Physical activation, collecting the third volatile gas
Figure BDA0002251552160000059
Condensing the solid matter to normal temperature in inert atmosphere to obtain an activated carbon product ⑩;
first volatile gas
Figure BDA00022515521600000510
Second volatile gas
Figure BDA00022515521600000511
Third volatile gas
Figure BDA00022515521600000512
Condensing, the condensation product is subjected to the second stepDistilling, wherein materials at the top of the tower are condensed and then subjected to oil-water separation, the obtained oil phase is a solvent oil ④ product, the obtained water phase is conveyed to a sewage treatment station to be treated into water ⑤, 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 ⑧ are collected;
second volatile gas
Figure BDA00022515521600000513
The non-condensable gas ② generated during condensation is reformed to obtain a fuel ⑨ product.
The recycling refers to a process of changing waste into recyclable materials.
The subject group discovers through previous researches that tar residue waste contains organic matters such as tar, colloidal particles and coal dust, solid matters in the tar residue waste can form various mosaic optical structures which are randomly and disorderly arranged after carbonization treatment, and further form a large number of edge angle edges which can provide a large number of active sites for a subsequent activation process, as shown in a figure 5 b; 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, as shown in figure 6 b.
The specific surface area of the activated carbon prepared by the technical scheme of the invention is more than 900m2(ii) in terms of/g. According to the technical scheme, the micro surface structure of the tar residue is changed by means of carbonization treatment and other technical means, so that the tar residue is developed into an extremely complex spatial three-dimensional structure system to provide active sites for 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; the separated condensable gas is fed intoDistilling, condensing the substance at the top, and separating oil from water, 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 products, and the products can enter a subsequent coal tar processing section for further utilization, so that the tar residue waste is utilized to the maximum value, and the tar residue waste is green, environment-friendly and energy-saving.
In one embodiment of the invention, the tar residue ① is firstly sent into a drying tower 12 for drying through a first belt conveyor 11, wherein the drying temperature is preferably 100-130 ℃, the drying time is preferably 1-3 h, and the gas escaping in the drying process is the first volatile gas
Figure BDA0002251552160000061
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 slagSending 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
Figure BDA0002251552160000063
Second solid slag
Figure BDA0002251552160000064
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. As shown in fig. 5a, 5b and 5c, 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 disordered and 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
Figure BDA0002251552160000071
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.
The material in the second storage tank 422 and the material in the first storage tank 412 are respectively pumped into the first distillation unit 43 through a second pipeline pump 423 and a first pipeline pump 413, the distillation temperature of the material in the first distillation unit 43 is preferably less than or equal to 280 ℃, the material at the bottom of the first distillation unit 43 is crude tar ③, the crude tar is guided into the fifth storage tank 451 through a pipeline from a side outlet, then the crude tar is pumped into the second distillation tower 453 through a fifth pipeline pump 452, fractions (light oil) ⑥ at 350 ℃, fractions (heavy oil) ⑦ at 350-500 ℃ and fractions (asphalt) ⑧ at more than 500 ℃ are respectively collected by the second distillation tower, the material at the top of the first distillation unit 43 enters a third condensation unit 44, after the materials are condensed to be below 100 ℃, the materials are separated through an oil-water separation unit 46, the oil phase is sent into a solvent oil ④ through a pipeline, and the water phase is sent into a sewage treatment station for treatment, and then water ⑤.
The non-condensable gas ② obtained after condensation in the second condenser 421 contains H2、CH4、CO、CO2And the like, enters a subsequent reforming section, and is reformed and used as fuel ⑨.
The third solid slag carbonized in the carbonization furnace 3
Figure BDA0002251552160000072
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. As shown in fig. 6a, fig. 6b and fig. 6c, which all adopt a 800 ℃ carbonized three-dimensional crystal structure for activation. 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
Figure BDA0002251552160000073
Performing an activation reaction to obtain an activated carbon ⑩ product, and obtaining the residual gas after the reaction, namely the third volatile gas
Figure BDA0002251552160000081
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 present invention is tar residue waste, which has a dense structure and high crystallinity and lacks primary pores required for activation. In the research of the invention, a great deal of research on the raw materials of the tar residue wastes shows that when the carbonization process temperature is increased to 700-900 ℃, it does not promote the ordered change of graphite microcrystals in the carbonized product like the raw materials of other activated carbon, reduces the gaps among the microcrystals, but instead forms a plurality of mosaic optical structures within, and randomly arranged with respect to each other, as shown in figure 5b, thereby forming a plurality of corner edges which can provide a plurality of active sites for the subsequent activation process, that is, the technical scheme of the invention, 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 scheme of the invention uses a mixture of water vapor and carbon dioxide which is cheap, easy to obtain and 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.
In the technical scheme of the invention, the mixture of water vapor and carbon dioxide is used as an activating agent, and activation can be completed without using chemical reagents such as acid, alkali and the like, so that a large amount of acid-alkali solution in the prior chemical activation technology is avoided, and meanwhile, the prepared activated carbon product does not need a water washing step, the problem of environmental pollution caused by the steps of acid-alkali use, water washing and the like is solved, and energy is greatly saved.
The invention also provides a recycling system of tar residue waste, as shown in the attached fig. 2, 3 and 4, which comprises:
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
Figure BDA0002251552160000101
Third volatilized gas collected from activation Unit 5Are 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 3Is 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.
The first distillation unit 43 distills the components at a certain temperature, wherein the top component is conveyed to a third condensation unit 44 for condensation, the condensed material is conveyed to an oil-water separation unit 46 for separation, the separated oil phase part is solvent oil ④ and is conveyed to a storage tank for storage, the separated water phase is conveyed to a sewage treatment station (not shown in the figure) for treatment to obtain water ⑤ which can be recycled, the bottom component is crude tar ③ and is conveyed to a second distillation unit 45 for distillation, and light oil distillate ⑥, heavy oil distillate ⑦ and asphalt ⑧ are collected according to different distillation ranges.
The present invention is further illustrated by 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
Figure BDA0002251552160000121
TABLE 3 Process parameters for the examples and comparative examples
Figure BDA0002251552160000122
Figure BDA0002251552160000131
Table 4 yield of each product prepared for each example and comparative example
Figure BDA0002251552160000132
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 are carried out on each example and comparative example, the tar residue waste is almost 100 percent utilized, 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
Figure BDA0002251552160000133
Figure BDA0002251552160000141
As can be seen from the test data in Table 5, the microstructure of the activated carbon obtained by the technical scheme of the 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 more 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 and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to 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 to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (10)

1. A recycling method of tar residue waste is characterized by comprising the following steps:
drying the tar residue, and collecting a first volatile gas to obtain a first solid residue;
crushing the first solid slag to obtain second solid slag;
carbonizing the second solid slag in an inert atmosphere, and collecting second volatile gas to obtain third solid slag;
physically activating the third solid slag, collecting third volatile gas, and condensing the solid substance to normal temperature in an inert atmosphere to obtain an activated carbon product;
condensing the first volatile gas, the second volatile gas and the third volatile gas, and carrying out first distillation on a condensation product; wherein, the materials at the top of the tower are condensed and then are subjected to oil-water separation, the obtained oil phase is a solvent oil product, and the obtained water phase is conveyed to a sewage treatment station for treatment and then is used; performing second distillation on the tower bottom materials, and collecting light oil distillate oil, heavy oil distillate oil and asphalt;
and (4) reforming the non-condensable gas generated when the second volatile gas is condensed to obtain a fuel product.
2. The recycling method of tar residue waste according to claim 1,
the carbonization temperature of the carbonization step is 700-900 ℃, and the carbonization time is 1-3 h.
3. The recycling method of tar residue waste according to claim 1,
the inert atmosphere is one of nitrogen or helium.
4. The recycling method of tar residue waste according to claim 1,
the physical activation step uses a mixture of carbon dioxide and water vapor as an activator, wherein the CO is present in parts by volume2:H2O is 1: 3-7.
5. The recycling method of tar residue waste according to claim 1,
the activation temperature of the activation step is 700-900 ℃, and the activation time is 1-3 h.
6. The recycling method of tar residue waste according to claim 1,
said condensing comprises a first condensing, a second condensing, and a third condensing;
the condensation of the first volatile gas and the third volatile gas is first condensation, wherein the temperature of a cooling medium is 40-100 ℃;
the condensation of the second volatile gas is second condensation, wherein the temperature of a cooling medium is 110-230 ℃;
the condensation of the overhead material is a third condensation, wherein the temperature of the cooling medium is less than 100 ℃.
7. The recycling method of tar residue waste according to claim 1,
the tar residue is a viscous semi-flowing solid with the water content of 3-15% in percentage by mass, and the fixed carbon content of the tar residue is more than or equal to 40 wt%.
8. The recycling method of tar residue waste as claimed in claim 1, wherein the drying temperature in the drying step is 100-130 ℃ and the drying time is 1-3 h.
9. The method of claim 1, wherein the distillation temperature of the first distillation is less than or equal to 280 ℃.
10. The recycling method of tar residue waste according to claim 1, wherein the carbonization temperature in the carbonization step is 800 ℃, and the carbonization time is 2 h; the activation step uses a mixture of carbon dioxide and water vapor as an activator, wherein the CO is present in parts by volume2:H2O is 1: 5; the activation temperature of the activation is 800 ℃, and the activation time is 2 h.
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CN117509638A (en) * 2023-11-08 2024-02-06 武汉中科先进材料科技有限公司 Method and system for continuously preparing silicon-carbon material by coupling organic solid waste and silicon-rich solid waste

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