CN114561221A

CN114561221A - Catalytic pyrolysis gasification method for scrap automobile crushing residue

Info

Publication number: CN114561221A
Application number: CN202210338877.6A
Authority: CN
Inventors: 许开华; 夏甜; 宋华伟; 彭涛; 陈川; 季强东; 库松
Original assignee: GEM Tianjin Urban Mining Recycling Industry Development Co Ltd; GEM Wuhan Urban Mining Industry Group Co Ltd; Henan Mutong Environmental Protection Industry Co Ltd
Current assignee: GEM Tianjin Urban Mining Recycling Industry Development Co Ltd; GEM Wuhan Urban Mining Industry Group Co Ltd; Henan Mutong Environmental Protection Industry Co Ltd
Priority date: 2022-04-01
Filing date: 2022-04-01
Publication date: 2022-05-31

Abstract

The invention discloses a catalytic pyrolysis gasification method of scrap automobile crushed residue, belonging to the technical field of scrap automobile crushed residue recycling, which comprises the following steps: drying and crushing; mixing the ingredients; the method comprises the steps of pyrolysis, gasification and the like, and the scrap automobile crushed residue and the nickel-containing solid waste can be subjected to common pyrolysis treatment, so that the comprehensive utilization rate of the pyrolysis and gasification reaction product of the automobile crushed residue is improved, the using amount of the pyrolysis and gasification catalyst of the automobile crushed residue is reduced, and the cost of the catalytic pyrolysis and gasification process is reduced. And the nickel-containing solid waste is reasonably utilized, so that the cooperative reduction, harmlessness and recycling of bulk industrial solid wastes such as automobile broken residues, nickel-containing solid waste and the like are realized.

Description

Catalytic pyrolysis gasification method for scrap automobile crushing residue

Technical Field

The invention relates to the technical field of recycling of scraped car crushed residues, in particular to a catalytic pyrolysis gasification method of scraped car crushed residues.

Background

Generally, after a scraped car is disassembled and parts are recovered, the rest part is compressed, crushed and sorted to recover metal and non-metal materials, and the rest part which is difficult to recover and is finely crushed is called as car crushing Residue (ASR).

The current ASR disposal methods mainly comprise: landfill method, incineration method, chemical solvent treatment method and pyrolysis gasification method. These methods have some effectiveness in ASR processing, but also have disadvantages. For example, although the landfill method is low in cost and simple in operation, the ASR contains a large amount of harmful heavy metals, chlorobiphenyls (PCBs), polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE) and other environmental load substances, and may pollute soil and groundwater; the incineration method can generate toxic substances such as dioxin, hydrogen chloride and the like, and the residues after incineration contain heavy metals; the chemical solvent treatment method only recovers specific substances and is not suitable for ASR recovery with complex components; the ASR is used as a raw material to produce combustible synthesis gas through a pyrolysis gasification process for energy recycling, and is the processing mode with the greatest application prospect. However, ASR has the problems of low tar and coke yield, insufficient gasification reaction, low calorific value of combustible synthesis gas, and the like in the pyrolysis gasification process. Under the action of the catalyst, the tar or the pyrolysis synthesis gas can be further cracked into smaller molecules. However, the catalyst specially used for the ASR pyrolysis gasification has high cost, large usage amount and large loss amount. In the actual production, the conversion rate of the ASR pyrolysis gasification is low, the catalyst is adopted, the treatment cost is directly increased, and the harmless treatment of the ASR is seriously inhibited.

In view of the above, there is a need to provide a catalytic pyrolysis gasification method for scrap car scrap residues, so as to solve the problem that the existing car scrap residues are difficult to be treated in a harmless manner.

The invention provides a catalytic pyrolysis gasification method for scrap automobile crushing residues, which comprises the following steps:

drying and crushing: drying the automobile crushing residues, and then carrying out multistage crushing to obtain fine crushed materials;

mixing the ingredients: uniformly mixing 30 parts of finely-crushed materials, 1-60 parts of nickel-containing solid wastes, 1-10 parts of forming agents and 1-10 parts of chlorine-fixing agents in parts by weight to obtain mixed materials;

extrusion molding: putting the mixed material into a die, and extruding and shaping the mixed material to obtain a small-size solid material;

pyrolysis and gasification: and putting the solid material into a pyrolysis gasification furnace, heating the solid material in a low-oxygen or oxygen-free atmosphere, and keeping the solid material for a period of time to decompose macromolecular substances in the automobile crushing residues in the solid material into alkanes, carbon monoxide, hydrogen, tar gas, water vapor and coke.

Further, the method also comprises a gas-liquid separation process, wherein gas obtained in the pyrolysis gasification process is introduced into a chiller to be chilled, so that tar gas is separated from other gases.

And further, the method also comprises a gas washing and purifying process, wherein the gas subjected to the gas-liquid separation process is treated and purified by a dry cyclone dust collector and an alkaline liquid spray tower in sequence to obtain clean combustible gas.

Further, the forming agent comprises one or more of sodium silicate, sodium metasilicate, sodium carbonate, sodium hydroxide, calcium sulfate, bentonite, starch or polyvinyl alcohol.

Further, the chlorine fixing agent comprises one or more of oxides or hydroxides of calcium, magnesium and zinc.

Further, in the drying and crushing process, firstly, the automobile crushed residue is put into an industrial oven and dried at the temperature of 100-120 ℃ for 20-70 min, and the water content of the automobile crushed residue is controlled to be 5-25%.

Further, in the drying and crushing process, the dried automobile crushing residue is subjected to secondary crushing of a jaw crusher-hammer crusher, and the particle size of the obtained automobile crushing residue is 0.5mm-1 mm.

Furthermore, the nickel-containing solid waste comprises 3-4% of NiO.

Furthermore, in the process of mixing the ingredients, the ingredients comprise 30 parts of fine crushed materials, 30 parts of nickel-containing solid waste, 5 parts of forming agent and 5 parts of chlorine-fixing agent according to the mass parts of the ingredients.

Further, the automobile scrap residue is a residue obtained by disassembling, compressing, crushing, sorting and recycling steel and nonferrous materials from at least one of a scrap passenger car, a scrap passenger car or a scrap truck, and comprises a mixture of plastic, rubber, paint, synthetic fiber, foam, phenolic resin glass fiber composite, epoxy resin glass fiber composite, wood chips and cloth.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the catalytic pyrolysis gasification method for the scrap automobile crushed residues, the scrap automobile crushed residues and nickel-containing solid wastes can be pyrolyzed and gasified together, so that the comprehensive utilization rate of the pyrolysis gasification reaction products of the automobile crushed residues is improved, the using amount of the pyrolysis gasification catalyst for the automobile crushed residues is reduced, and the cost of the catalytic pyrolysis gasification process is reduced. And the nickel-containing solid waste is reasonably utilized, so that the cooperative reduction, harmlessness and recycling of the bulk industrial solid wastes such as automobile broken residues, the nickel-containing solid waste and the like are realized.

(2) According to the catalytic pyrolysis gasification method for the scrap automobile crushed residues, the pyrolysis gasification reaction is carried out on the automobile crushed residues under the low-oxygen or oxygen-free condition, so that the content of harmful components in gas can be greatly reduced, combustible gas capable of being recycled can be generated, and the environment-friendly reutilization of waste is realized.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:

FIG. 1 is a flow chart of a method provided by the present invention;

FIG. 2 is a table of experimental data for a rough study of the ratio of nickel-containing solid waste to finely divided material in accordance with the present invention;

FIG. 3 is a table of experimental data for accurately investigating the ratio of nickel-containing solid waste to finely divided material in the present invention;

FIG. 4 is a table of test data for the best parts by mass of the forming agent of the present invention;

FIG. 5 is a table of test data for investigating the optimum parts by weight of chlorine-fixing agent in the present invention;

Detailed Description

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.

Referring to fig. 1, the catalytic pyrolysis gasification method for broken residues of scraped car in this embodiment includes the following steps:

drying and crushing: firstly, putting the automobile broken residue into an industrial oven, adjusting the internal temperature of the industrial oven to be 100-120 ℃, continuously drying the automobile broken residue for 20-70 min, and controlling the water content to be 5-25%. Firstly, relatively dry automobile crushing residues are put into a cutting type grinder for coarse crushing, and the automobile crushing residues are crushed into crushing coarse materials with the particle size of 1mm-5 mm. And then, putting the crushed coarse materials into a table jaw crusher for fine crushing to obtain fine crushed materials with the particle size of 0.5mm-1.0 mm.

Mixing the ingredients: evenly mixing 30 parts of finely-divided materials, 1-60 parts of nickel-containing solid waste, 0-10 parts of forming agent and 0-5 parts of chlorine-fixing agent to obtain a mixed material. The nickel-containing solid waste is nickel-containing powdery solid which is baked and crushed, the nickel-containing sludge comprises 3% -4% of NiO, and Ni element can play a catalytic role in the pyrolysis gasification process of macromolecular substances. The cracking of macromolecular substances into light molecular gas is a reversible reaction, and Ni element as a catalyst can promote the reaction balance to move towards the direction of generating the light molecular gas, thereby improving the conversion rate of the light molecular gas to be obtained.

As a further embodiment, in the process of mixing the ingredients, the ingredients are 30 parts of finely-divided materials, 30 parts of nickel-containing solid waste, 5 parts of forming agent and 5 parts of chlorine-fixing agent. Referring to fig. 2, under the condition of not adding forming agent and curing agent, and controlling other reaction conditions to be the same, the part of the fine crushed material is determined to be 30 parts, and the part of the solid waste containing nickel is changed to determine the optimal ratio of the fine crushed material to the solid waste containing nickel. In fig. 2, when the fraction of the nickel-containing solid waste ranges from (0 to 28 parts), the amount of light molecular gas generated increases as the fraction of the nickel-containing solid waste increases. However, when the fraction of nickel-containing solid waste is in the range of (35 to 60 parts), the amount of light molecular gas generated does not increase as the fraction of nickel-containing solid waste increases. The gas conversion rate of the light molecular gas reaches the limit and cannot be increased. In order to obtain the most accurate ratio, referring to fig. 3, in examples 1-22, it can be seen that the light molecular gas generation amount is not increased when the ratio of the fine crushed material and the nickel-containing solid waste reaches 30: 30. That is, under otherwise identical reaction conditions, when the ratio of the finely divided material to the nickel-containing solid waste reaches 1:1, the ratio of the finely divided material to the nickel-containing solid waste is optimized, and the highest conversion rate of the light gas is obtained at the lowest cost.

Referring to fig. 4, in example a-l, the ratio of the mass parts of the fine crushed material and the nickel-containing solid waste is maintained at 30:30, the same mass of the chlorine fixing agent is added, the mass part of the forming agent is changed to explore the optimal mass part of the forming agent, the forming agent can enhance the viscosity among various substances and facilitate the extrusion forming among various substances, and meanwhile, the forming agent can make the contact between the fine crushed material and the catalyst more compact, increase the contact area between the fine crushed material and the catalyst, improve the cracking speed of the fine crushed material and shorten the reaction time. As can be seen from the figure, when the mass part of the molding agent is 5, the time required for generating 43 parts by volume of the light gas is shortest, and is 60 min. When the part of the molding agent is less than 5, the time required to generate 43 parts by volume of the light gas is continuously shortened. When the part of the forming agent is more than 5, the redundant forming agent increases the whole mass and volume of the mixed material, increases the gap between the fine crushed material and the nickel-containing solid waste, and reduces the reaction speed.

Referring to fig. 5, in examples a to L, the ratio of the mass parts of the fine crushed material and the nickel-containing solid waste is maintained at 30:30, the same mass of the forming agent is added, and the mass part of the chlorine fixing agent is changed to explore the optimal mass part of the chlorine fixing agent, so that the chlorine fixing agent can absorb the hydrogen chloride generated during the cracking process of the fine crushed material, thereby preventing the hydrogen chloride from polluting the environment. As can be seen from the figure, when the mass part of the chlorine fixing agent is 5, the hydrogen chloride content in the generated gas is 0.01 parts by volume. When the part of the molding agent is less than 5, the volume part of hydrogen chloride in the generated gas is continuously reduced. When the part of the forming agent is more than 5, the chlorine element in the fine crushed material is consumed by the chlorine fixing agent, the hydrogen chloride can not be consumed by increasing the mass part of the curing agent, and the precision of a hydrogen chloride detecting instrument can only reach 0.01.

The forming agent comprises one or more of sodium silicate, sodium metasilicate, sodium carbonate, sodium hydroxide, calcium sulfate, bentonite, starch and polyvinyl alcohol. The forming agent enhances the viscosity among various substances and facilitates the extrusion forming among various substances. The contact of the fine crushing materials and the catalyst is more compact, the pyrolysis gasification efficiency of macromolecular substances in the fine crushing materials can be further improved, and the waste materials are fully recycled.

The chlorine fixing agent comprises one or more of calcium, magnesium, zinc and other oxides or hydroxides. The chlorine fixing agent can be combined with chlorine (Cl) elements in automobile broken residues to prevent the formation of chlorinated gas and cause unnecessary pollution.

Extrusion molding: putting the mixed material into a die, applying pretightening force to the material through a screw rod of an electronic universal tester, pressurizing the material by using a hydraulic machine of a base (20MPa-80MPa), keeping the maximum pressure for 1min-5min, and then demoulding to obtain the solid material with the diameter of 1mm-5mm and the length of 1mm-10 mm. The fine crushing material and the nickeliferous solid waste plastic that the process of extrusion will the misce bene mould into the tiny particle, increases the area of contact of the two, improves catalysis efficiency.

Pyrolysis and gasification: putting the solid material into a pyrolysis gasification furnace, heating to 400-1600 ℃ in a low-oxygen or oxygen-free atmosphere, and keeping for a period of time, wherein the plastic, rubber, paint, synthetic fiber, foam material, phenolic resin glass fiber composite material, epoxy resin glass fiber composite material, wood chip and macromolecular substances in the cloth in the automobile crushing residue can be subjected to pyrolysis gasification reaction to finally produce alkanes, carbon monoxide, hydrogen, tar gas, water vapor and coke, and the coke can be further reacted with the water vapor to form the hydrogen and the carbon monoxide. Finally, all pyrolysis gasification products can be output in the form of gas. The residual solid waste can be directly used for mixing with automobile crushing residues and can be reused in the pyrolysis gasification reaction.

Gas-liquid separation: the alkanes, the carbon monoxide, the hydrogen and the tar gas obtained by pyrolysis and gasification are introduced into a chiller, the tar gas is condensed into liquid to be separated from other gases, and the oil phase of the tar can be enriched and stored in a tar storage tank to be used as an industrial raw material.

Washing and purifying: the residual gas after gas-liquid separation treatment comprises alkanes, carbon monoxide and hydrogen, and the combustible gas firstly passes through a dry cyclone dust collector to remove dust possibly existing in the gas, so that relatively pure mixed gas is obtained. And then, the mixed gas is input into an alkaline liquid spray tower, acid gases possibly doped in the mixed gas are removed, and acid pollutants in the mixed gas are reduced. Finally, the obtained pure combustible gas can be used as fuel to provide heat.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the present invention.

Claims

1. A catalytic pyrolysis gasification method for crushed residues of scraped cars is characterized by comprising the following steps:

mixing the ingredients: uniformly mixing 30 parts of finely-divided materials, 1-60 parts of nickel-containing solid waste, 1-10 parts of forming agent and 1-10 parts of chlorine-fixing agent according to parts by mass to obtain a mixed material;

extrusion forming: putting the mixed material into a die, and extruding and shaping the mixed material to obtain a small-size solid material;

2. The catalytic pyrolysis gasification method for crushed residues of scraped cars according to claim 1, further comprising a gas-liquid separation process, wherein the gas obtained in the pyrolysis gasification process is introduced into a chiller to be chilled, so that tar gas is separated from other gases.

3. The catalytic pyrolysis gasification method for crushed residues of scraped cars according to claim 2, characterized in that the method further comprises a scrubbing purification process, wherein the gas after the gas-liquid separation process is sequentially treated and purified by a dry cyclone dust collector and an alkaline liquid spray tower to obtain clean combustible gas.

4. The catalytic pyrolysis gasification method of crushed residues of scraped cars of claim 1, wherein the forming agent comprises one or more of sodium silicate, sodium metasilicate, sodium carbonate, sodium hydroxide, calcium sulfate, bentonite, starch or polyvinyl alcohol.

5. The catalytic pyrolysis gasification method for crushed residues of scraped cars as claimed in claim 1, wherein the chlorine fixing agent comprises one or more of oxides or hydroxides of calcium, magnesium and zinc.

6. The catalytic pyrolysis gasification method for crushed automobile residues as claimed in claim 1, wherein in the drying and crushing process, the crushed automobile residues are firstly put into an industrial oven and dried at 100-120 ℃ for 20-70 min, and the water content of the crushed automobile residues is controlled at 5-25%.

7. The catalytic pyrolysis gasification method for crushed residues of scraped cars according to claim 6, characterized in that, during the drying and crushing process, the dried crushed residues of scraped cars are subjected to the secondary crushing of jaw crusher-hammer crusher to obtain crushed residues of scraped cars with a particle size of 0.5mm-1 mm.

8. The catalytic pyrolysis gasification method for crushed residues of scraped cars according to claim 1, characterized in that the nickel-containing solid waste contains 3% -4% of NiO.

9. The catalytic pyrolysis gasification method for crushed residues of scraped cars according to claim 1, characterized in that in the process of blending, the blending ratio is 30 parts of finely-crushed materials, 30 parts of nickel-containing solid wastes, 5 parts of forming agents and 5 parts of chlorine-fixing agents according to the mass parts.

10. The catalytic pyrolysis gasification method of scrap car scrap residue according to claim 1, wherein the scrap car scrap residue is a mixture of scrap car scrap.