CN112791573A - Steelmaking waste cooperative treatment system and method based on ball milling reinforcement - Google Patents

Steelmaking waste cooperative treatment system and method based on ball milling reinforcement Download PDF

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CN112791573A
CN112791573A CN202110031439.0A CN202110031439A CN112791573A CN 112791573 A CN112791573 A CN 112791573A CN 202110031439 A CN202110031439 A CN 202110031439A CN 112791573 A CN112791573 A CN 112791573A
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ball milling
vertical vibration
gas
metallurgical
vibration ball
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CN112791573B (en
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赵青
梅孝辉
刘承军
李文杰
姜茂发
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Northeastern University China
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/025—Other waste gases from metallurgy plants
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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Abstract

The invention provides a system and a method for the cooperative treatment of steelmaking wastes based on ball milling reinforcement. The metallurgical slag of steel is used as a carbon capture raw material to perform carbon capture reaction in cooperation with metallurgical waste gas and metallurgical waste water, so that carbon emission reduction is considered, and CO in the metallurgical waste gas is realized2With CO and N2The separation is efficient and low in cost, and an external heating source is not needed in the whole process. The invention breaks through the difficult problems of low carbonation reaction rate and low reaction degree caused by product film coating in the prior art of direct carbon capture of metallurgical waste residues, gives consideration to the cooperative treatment of various wastes of steel enterprises, and realizes the green sustainable treatment of the steel enterprisesThe development is of great significance.

Description

Steelmaking waste cooperative treatment system and method based on ball milling reinforcement
Technical Field
The invention relates to the technical field of energy conservation, emission reduction and carbon capture, in particular to a system and a method for cooperative treatment of steelmaking waste based on ball milling reinforcement.
Background
As a key industry of energy consumption and waste discharge, the steel industry faces the current situation of large discharge of metallurgical waste gas, waste water and solid waste in the metallurgical production process, and the cooperative treatment of the waste gas, the waste water and the solid waste has important significance for realizing the green sustainable development of steel. How to realize end CO under double pressure of Paris agreement and carbon trading market mechanism2The low cost and emission reduction become the key difficult problems of transformation and upgrading of iron and steel enterprises. In addition, CO and H2The method is the other two main components in the metallurgical waste gas, the chemical products of alcohol and alkene prepared by utilizing the metallurgical waste gas have great potential advantages, and the important reason for limiting the toughening co-production is the high-cost gas separation technology. Therefore, the metallurgical waste slag and the waste water generated in the steel-making process are used for capturing CO in the metallurgical waste gas2Not only can realize the cooperative treatment of the waste, but also can realize the CO and H in the waste gas2The low cost separation of (2) creates conditions.
Currently, Carbon Capture and Sequestration (CCS) technology is considered to be the most economically feasible technology for reducing greenhouse gas emissions and alleviating global warming in the future on a large scale, and mainly comprises marine sequestration, geological sequestration and mineral sequestration. Among them, the mineral sequestration method does not need long-term CO monitoring due to its stable carbonation product (carbonate)2Miss the advantages and the like and are widely concerned. The metallurgical waste slag generated in the steelmaking process has higher content of CaO and MgO, large amount and close distance with the exhaust emission point, and is used for capturing CO on a large scale2Good raw materials of (1). The direct method carbon capture has the characteristics of simple operation, short flow, low equipment cost and the like, and has a higher scale application prospect. However, in the direct carbon capture process, the generated carbonation product layer can cover the surface of the unreacted core, so that the gas diffusion becomes a limiting link and leads toSo that the utilization rate of the metallurgical waste residue is low and the carbon capture efficiency is low.
Aiming at the retardation behavior of a product layer in the direct carbon capture process of metallurgical waste residues, the invention provides a system and a method for mechanically strengthening direct carbon capture in the metallurgical industry.
Disclosure of Invention
Aiming at the technical bottleneck that the generation of a carbonated product layer hinders the carbon capture reaction in the direct method carbon capture process of metallurgical by-products, the invention provides a system and a method for the cooperative treatment of steelmaking wastes based on ball milling reinforcement2The large-scale trapping, sealing and utilization of the waste gas lay a foundation for the commercial application of the subsequent metallurgical waste gas.
The technical scheme of the invention is realized as follows:
a steelmaking waste cooperative treatment system based on ball milling reinforcement comprises a carbon capture system and a carbon and nitrogen gas separation and collection system which are sequentially connected;
the carbon capture system comprises four vertical vibration ball milling reactors (I)1、Ⅰ2、Ⅱ1And II2) Gas transport pipeline, liquid flow rate meter, gas flow rate meter, CO2The device comprises a concentration detector, a computer intelligent switching system, a circular slide rail and a vibrating screen; the carbon and nitrogen gas separating and collecting system comprises a carbon and nitrogen gas separating chamber, a freezing type compressed air dryer, a gas condensing device and a gas storage tank which are connected in sequence.
The carbon capture system comprises vertical vibration ball-milling reactors which are matched with each other for use, wherein the vertical vibration ball-milling reactors firstly vibrate vertically and then rotate along a circular track in an accelerated manner, then the vertical vibration is started, and the carbon capture reaction is carried out in a circulating manner; the vertical vibration ball-milling reactor comprises a stainless steel tank body and stainless steel balls, metallurgical slag and the stainless steel balls are filled in the stainless steel tank body, and when the stainless steel tank body of the vertical vibration ball-milling reactor vibrates or rotates, the metallurgical slag and the stainless steel balls in the tank move along with the movement of the stainless steel tank body.
Further, the vertical vibration ball mill reactor comprises: the device comprises a flange cover, a sealing ring, a heat insulation material, a stainless steel tank body, stainless steel balls with different diameters, a buffer spring, a base, a vertical slideway, a support, a motor and a circular slideway; the flange cover is detachably and hermetically arranged at the upper end of the stainless steel tank body through a sealing ring, a gas inlet, a gas outlet and a liquid input pipeline are arranged on the flange cover, the gas inlet is connected with a metallurgical waste gas transmission pipeline, the gas flow in the metallurgical waste gas transmission pipeline is controlled by a gas flow controller, the gas outlet is connected with a purified gas transmission pipeline, and the purified gas transmission pipeline is formed by a CO (carbon monoxide) gas2Concentration detector for monitoring CO in tube2The liquid input pipeline is connected with a metallurgical waste liquid transmission pipeline, and the metallurgical waste liquid transmission pipeline is controlled by liquid flow control meter; the stainless steel tank body is sleeved with a heat insulation material, stainless steel balls with different diameters are arranged in the stainless steel tank body, a buffer spring is arranged at the lower end of the stainless steel tank body, the side face of the stainless steel tank body is arranged on a support through a vertical slide way, the support is arranged above a base, and a circular slide way is arranged below the base; the vertical vibration ball milling reactor can do 360-degree accelerated rotation motion along the circular slide rail; the vertical vibration ball milling reactor is electrically connected with a motor;
furthermore, the tail end of the liquid input pipeline is averagely divided into four output pipelines, the interval between every two adjacent output pipelines is 90 degrees, the tail end of each output pipeline is provided with a liquid atomizer, liquid can flow through the liquid end atomizers to spray water in a divergent mode, and the spraying range is 120 degrees.
Furthermore, the system is provided with a computer intelligent switching system, the computer intelligent switching system, a gas flow control meter and CO2Concentration detector, metallurgical waste gas transmission pipeline, purified gas transmission pipeline, metallurgical waste liquid transmission pipeline and verticalThe vibrating ball milling reactor is electrically connected.
Further, the 4 vertical vibration ball milling reactors (I)1、Ⅰ2、Ⅱ1And II2) Wherein, the vertical vibration ball milling reactor I1And I2Is a first-stage carbon capture reactor; vertical vibration ball milling reactor II1And II2Is a secondary carbon capture reactor.
Further, the ratio of the diameter D to the height H of the stainless steel tank body is as follows: H/D (1.5-2), the vibration frequency of the stainless steel tank body is 30-120 times/min, and the amplitude is 0.25-0.5 times of the height H of the stainless steel tank body (4); the volume of the metallurgical slag in the vertical vibration ball milling reactor is not more than two fifths of the volume of the stainless steel tank body; the total mass ratio of the metallurgical slag to the stainless steel balls in the stainless steel tank body is 5: 1-20: 1, and the density of the stainless steel balls is 7.8 +/-0.2 g cm-3(ii) a The stainless steel tank body is internally provided with a large sphere and a small sphere, wherein the vertical vibration ball milling reactor I1And I2In the vertical vibration ball milling reactor II, the diameter range of the sphere is 10-20 mm1And II2In the middle, the diameter range of the sphere is 5-10 mm; and the diameter d of the large sphere in the tank body1Diameter d of the small sphere2Ratio d1：d2The number ratio of the large spheres to the small spheres is 3:1 (1.5-2.5); the inner lining of the stainless steel tank body and the heat insulation and preservation material (3) are both medium-temperature heat insulation refractory materials which are more than 700 ℃; the stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started.
A steelmaking waste cooperative treatment method based on ball milling reinforcement comprises the following steps:
the four vertical vibration ball milling reactors (I)1、Ⅰ2、Ⅱ1And II2) In the operation, the device is divided into two groups for switching use, wherein the first group is a vertical vibration ball milling reactor I1And II1(ii) a The second group is a vertical vibration ball milling reactor I2And II2；
(1) First order carbon capture reaction
Placing metallurgical slag in a vertical vibration ball milling reactor I1And II1In the process, the metallurgical waste gas and the metallurgical waste water after dust removal are introduced into a vertical ball milling reactor I1At this time, chemical reaction among the metallurgical slag, the metallurgical waste gas and the metallurgical waste water occurs, and primary carbon capture reaction is carried out;
(2) second order carbon capture reaction
In the carbon capture reaction process, if the vertical vibration ball milling reactor I1Releasing purified gas via CO2CO monitored by concentration detector2Content (wt.)>When the concentration is 1 percent, the purified gas is continuously introduced into the vertical vibration ball milling reactor II by the computer intelligent switching system1Carrying out secondary carbon capture in the process, and simultaneously spraying metallurgical wastewater by an atomizer at the tail end of a liquid inlet and outlet pipeline; vertical vibration ball milling reactor I1And II 1 passing the released gas through CO2CO monitored by concentration detector2Content (wt.)<When 1 percent of the nitrogen is obtained, the obtained purified gas enters a carbon nitrogen gas separation chamber to respectively obtain pure N2And CO and H2The high-heat value coal gas is condensed and compressed into a gas storage tank for storage and utilization after moisture is removed by a refrigeration type compressed air dryer; when vertical vibration ball milling reactor II1Passing the released gas through CO2CO monitored by concentration detector2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1Performing the following steps;
(3) switching vertical vibration ball milling reactor
When CO is present2Vertical vibration ball-milling reactor I for monitoring concentration monitor1CO in connected purge gas lines2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2Concentration (i.e. CO in metallurgical off-gas and purge gas)2Concentration difference is less than or equal to 3%) or when CO is present2Vertical vibration ball-milling reactor II for monitoring concentration monitor1CO at the middle gas outlet2The concentration is kept within 15min>At 1%, the end of the first group of reactions is verified; the metallurgical waste gas and the metallurgical waste water pipeline are switched by an intelligent control system to enter a second group of vertical vibration ball milling reactors I filled with new metallurgical slag2In the second group, a vertical vibration ball milling reactor I2And II2Replacement of a first set of vertical vibratory ball milling reactors I1And II1Repeating the steps (1) and (2);
when CO is present2Vertical vibration ball-milling reactor I for monitoring concentration monitor2CO in connected purge gas lines2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2Concentration (i.e. CO in metallurgical off-gas and purge gas)2Concentration difference is less than or equal to 3%) or when CO is present2Vertical vibration ball-milling reactor II for monitoring concentration monitor2CO at the middle gas outlet2The concentration is kept within 15min>At 1%, the end of the second group of reactions is verified; a metallurgical waste gas pipeline and a metallurgical waste water pipeline are switched by an intelligent control system to enter a first group of vertical vibration ball milling reactors I filled with new metallurgical slag1In the first group, a vertical vibration ball milling reactor I is adopted1And II1Replacement of a second group of vertical vibratory ball milling reactors I2And II2Repeating the steps (1) and (2);
the first group is a vertical vibration ball milling reactor I1And II1And the second group is a vertical vibration ball milling reactor I2And II2Switching to recycle according to the above conditions;
(4) magnetic separation of carbonated metallurgical slag
And (4) performing ball material separation on the carbonated metallurgical slag produced in the step (3) and the stainless steel balls through a vibrating screen, returning the obtained stainless steel balls to the vertical vibrating ball-milling reactor for recycling, and performing magnetic separation on the obtained materials to recover iron-containing magnetic substances for recycling.
Further, the metallurgical slag in the step (1) can be steel slag with alkalinity generated in the steel-making process, the temperature of the steel slag is less than or equal to 600 ℃, and the particle size is less than or equal to 10 mm; the metallurgical waste gas can be CO contained in the steel-making process2The temperature of the waste gas and the metallurgical waste gas is less than or equal to 600 ℃, and CO is2Content (wt.)>5 percent; the metallurgical waste water can be cold rolling waste water, waste liquid generated in the steel-making process, F-、Cr3+、Cr6+And the polluting ions need to be removed in advance.
Further, step (ii)Step (1), (2) and (3) vertical vibration ball milling reactor I1And I2The particle size of the metallurgical waste residue is 5-10 mm, and the metallurgical waste residue is placed in a vertical vibration ball milling reactor II1And II2The grain diameter of the metallurgical waste residue is less than or equal to 5 mm; the gas flow of the metallurgical waste gas introduced into the vertical vibration ball milling reactor is 5-100 L.h-1(ii) a The mass ratio of the volume of the introduced metallurgical wastewater to the metallurgical slag is as follows: 0.25 to 1.2L/Kg-1The flow rate of the introduced metallurgical wastewater is controlled to be 0.1-2 L.min-1。
Further, the indication of the end of the carbonation reaction of the vertical vibratory ball mill reactor in the step (3) is as follows: the materials separated by the vibrating screen in the step (4) are subjected to magnetic separation treatment, so that iron-containing ore phases in the carbonated metallurgical slag, scrap iron and the like due to collision and grinding loss between the stainless steel ball and the cylinder body can be recovered; residual carbonated material, particle size>5mm, returning to the vertical vibration ball milling reactor I1And I2Returning the carbonated metallurgical slag with the grain diameter of 1-5 mm to the vertical vibration ball milling reactor II1And II2Medium, carbonated metallurgical slag particle size<1mm can be directly applied.
The invention has the following beneficial effects:
(1) the raw materials used in the invention are all wastes generated in the steel smelting production process, including metallurgical waste residues, metallurgical waste gases and metallurgical waste water. The invention uses the metallurgical waste residue and the metallurgical waste water to capture CO in the metallurgical waste gas2On one hand, the cooperative treatment of the wastes of the iron and steel enterprises is realized, and on the other hand, the CO and N in the metallurgical waste gas are realized2、H2With CO2The separation is carried out at low cost, and an external heating source is not needed in the whole process. Meanwhile, the stable carbonate product is generated, so that the sustainable utilization of resources is realized.
(2) Aiming at the blocking effect that a product layer wraps an unreacted interface in the direct carbon capture process, the ball milling effect introduced in the invention can continuously strip a carbonated product layer in the reaction process, expose a fresh unreacted interface and improve the carbonation reaction rate.
(3) The invention can realize the large-scale carbon capture of metallurgical enterprises, has the characteristics of short flow and low cost, and realizes the resource utilization of the metallurgical by-product while improving the capture rate of the metallurgical by-product carbon; has important promotion effect on realizing the green sustainable development of iron and steel enterprises.
Drawings
FIG. 1 is a process flow chart of a steelmaking waste cooperative treatment method based on ball milling reinforcement.
FIG. 2 is a schematic diagram of the configuration of the vertical vibration ball-milling reactor of the present invention.
FIG. 3 is a top view of the construction of the present invention.
FIG. 4 is a top view of the vertical vibration ball milling reactor of the present invention along the running track of the circular slide rail.
In the figure, 1, a flange cover; 2. a seal ring; 3. a thermal insulation material; 4. a stainless steel tank body; 5. stainless steel balls; 6. a buffer spring; 7. a base; 8. a gas inlet; 9. a liquid input conduit; 9.1, a liquid atomizer; 10. a gas outlet; 11. A vertical slideway; 12. a support; 13. a motor; 14. a circular slideway; 15. a vertical vibration ball milling reactor; 16. circular slide rail
Detailed Description
For a more clear understanding of the technical features, objects and advantages of the present invention, reference is now made to the following detailed description of the embodiments of the present invention taken in conjunction with the accompanying drawings, which are included to illustrate and not to limit the scope of the present invention.
Example 1
A steelmaking waste cooperative treatment system based on ball milling reinforcement comprises a carbon capture system and a carbon and nitrogen gas separation and collection system which are sequentially connected; the carbon capture system comprises a vertical vibration ball milling reactor group, a gas transmission pipeline, a liquid flow controller, a gas flow controller and CO2Concentration detector, computer intelligence switched systems, circular slide rail, shale shaker. The computer intelligent switching system, the gas flow controller and the CO2The concentration detector, the metallurgical waste gas transmission pipeline, the purified gas transmission pipeline, the metallurgical waste liquid transmission pipeline and the vertical vibration ball-milling reactor are electrically connected.
The vertical vibration ball milling reactor group is mutually matched for use, and the number of the vertical vibration ball milling reactors is 4 (I)1、Ⅰ2、Ⅱ1And II2) Wherein, the vertical vibration ball milling reactor I1And I2Is a first-stage carbon capture reactor; vertical vibration ball milling reactor II1And II2Is a secondary carbon capture reactor. The vertical vibration ball milling reactor firstly vibrates vertically, then rotates along a circular track in an accelerating way, then starts vertical vibration, and carries out carbon capture reaction circularly; the vertical vibration ball-milling reactor comprises a stainless steel tank body and stainless steel balls, wherein steel-making waste and the stainless steel balls are filled in the stainless steel tank body, and when the stainless steel tank body of the vertical vibration ball-milling reactor vibrates or rotates, the steel-making waste and the stainless steel balls in the tank move along with the movement of the stainless steel tank body.
The vertical vibration ball-milling reactor comprises: the device comprises a flange cover, a sealing ring, a heat insulation material, a stainless steel tank body, stainless steel balls with different diameters, a buffer spring, a base, a vertical slideway, a support, a motor and a circular slideway; the flange cover is detachably and hermetically arranged at the upper end of the stainless steel tank body through a sealing ring, a gas inlet, a gas outlet and a liquid input pipeline are arranged on the flange cover, the gas inlet is connected with a metallurgical waste gas transmission pipeline, the gas flow in the metallurgical waste gas transmission pipeline is controlled by a gas flow controller, the gas outlet is connected with a purified gas transmission pipeline, and the purified gas transmission pipeline is formed by a CO (carbon monoxide) gas2Concentration detector for monitoring CO in tube2The liquid input pipeline is connected with a metallurgical waste liquid transmission pipeline, and the metallurgical waste liquid transmission pipeline is controlled by liquid flow control meter; the stainless steel tank body is sleeved with a heat insulation material at the outer side, stainless steel balls with different diameters are arranged in the stainless steel tank body, a buffer spring is arranged at the lower end of the stainless steel tank body, the side face of the stainless steel tank body is arranged on a support through a vertical slide way, the support is arranged above a base, and a circular slide way is arranged below the base; the vertical vibration ball milling reactor can do 360-degree accelerated rotation motion along the circular slide rail; the vertical vibration ball milling reactionThe device is electrically connected with the motor;
the tail end of the liquid input pipeline is averagely branched into four output pipelines, two adjacent pipelines are spaced by 90 degrees, the tail end of each output pipeline is provided with a liquid atomizer, liquid can flow through the liquid end atomizers to spray water in a divergent mode, and the spraying range is 120 degrees.
The ratio of the diameter D to the height H of the stainless steel tank body (4) is as follows: H/D (1.5-2), the vibration frequency of the stainless steel tank body (4) is 30-120 times/min, and the amplitude is 0.25-0.5 times of the height H of the stainless steel tank body (4); the volume of the metallurgical waste residue in the vertical vibration ball milling reactor is not more than two fifths of the volume of the stainless steel tank body; the total mass ratio of the metallurgical waste residues to the stainless steel balls (5) in the stainless steel tank body (4) is 5: 1-20: 1, and the density of the stainless steel balls (5) is 7.8 +/-0.2 g cm-3(ii) a The stainless steel tank body (4) is provided with big spheres and small spheres, wherein the vertical vibration ball milling reactor I1And I2In the vertical vibration ball milling reactor II, the diameter range of the sphere is 10-20 mm1And II2In the middle, the diameter range of the sphere is 5-10 mm; and the diameter d of the large sphere in the tank body1Diameter d of the small sphere2Ratio d1：d2The number ratio of the large spheres to the small spheres is 3:1 (1.5-2.5); the inner lining of the stainless steel tank body and the heat insulation and preservation material are both medium-temperature heat insulation refractory materials which are more than 700 ℃; the stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started.
The carbon and nitrogen gas separation and collection system comprises a carbon and nitrogen gas separation chamber, a freezing type compressed air dryer, a gas condensing device and a gas storage tank which are connected in sequence, wherein the carbon and nitrogen gas separation chamber is made of a copper molecular sieve.
The system also comprises a vibrating screen, and stainless steel balls and carbonated saturated metallurgical slag are separated through the vibrating screen.
Example 2
The metallurgical waste slag is blast furnace slag with the temperature of 600 ℃, the particle size is 6-8 mm, and the specific chemical components are shown in table 1. Placing blast furnace slag in a vertical position with a diameter of 1m and a height of 1.2mFormula vibration ball-milling reactor I1And I2The volume of the stainless steel tank body is one fifth of the tank body. 108 large balls with the diameter of 15mm and 36 small balls with the diameter of 10mm are arranged in the tank body.
The metallurgical waste slag is ladle refining slag, the particle size is 2-3 mm, and the specific chemical components are shown in table 2. Placing the ladle refining slag in a vertical vibration ball milling reactor II with the diameter of 1m and the height of 1.2m1And II2The volume of the stainless steel tank body accounts for one third of the tank body. 120 big balls with the diameter of 8mm and 40 small balls with the diameter of 4mm are arranged in the tank body.
Vertical vibration ball milling reactor I1Blast furnace gas was fed into the vessel, and the composition thereof is shown in table 3. The temperature is 200 ℃, and the gas flow is 10 L.h-1. The flow rate of the introduced metallurgical wastewater is 0.1 L.min-1At this time, a chemical reaction occurs among the blast furnace slag, the metallurgical waste water, and the metallurgical waste gas, and a carbon capture reaction of the blast furnace slag is performed. The vibration frequency of the stainless steel tank body is 50 times/min, and the amplitude is 20 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. When the volume of the metallurgical wastewater reaches 710m3And stopping introducing the metallurgical wastewater or stopping the reaction. Vertical vibration ball milling reactor I1CO in the purge gas released from the tank2Concentration of>When 1 percent of the reaction solution is added into a vertical vibration ball milling reactor II1In the tank body, the vibration frequency of the stainless steel tank body is 120 times/min, and the amplitude is 10 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. The gas flow is 5 L.h-1. When the volume of the metallurgical wastewater reaches 236m3And stopping introducing the metallurgical wastewater or stopping the reaction.
Vertical vibration ball milling reactor I1And II1CO in the released purge gas2Content (wt.)<1%, the obtained purified gas enters carbon and nitrogenGas separation chamber to obtain pure N2And CO and H2The high heating value gas. After moisture is removed by a refrigeration type compressed air dryer, the mixture is condensed and compressed into a gas storage tank for storage and utilization. When vertical vibration ball milling reactor II1CO of released gas2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1In (1).
By CO2Concentration monitor, monitoring vertical vibration ball milling reactor I1CO at the middle and air outlet2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2Concentration, i.e. CO2The content is more than or equal to 9 percent, and the proving type vibration ball milling reactor I1The carbonation reaction is complete, the metallurgical waste gas and the metallurgical waste water pipeline are intelligently switched and are led into the vertical vibration ball milling reactor I2And II2In the above steps, the carbonation reaction is carried out repeatedly.
A vertical vibration ball milling reactor I1And separating the ball material by a vibrating screen, and magnetically separating the obtained material to recover iron-containing ore phases in the metallurgical waste slag, scrap iron and the like due to collision and grinding loss between the stainless steel ball and the cylinder. Resulting spheres and particle sizes>5mm carbonated slag returns to the vertical vibration ball milling reactor I1And adding new blast furnace slag for standby. Returning the carbonated slag with the particle size of 1-5 mm to the vertical vibration ball milling reactor II2Medium and small carbonated slag particle size<1mm can be directly applied.
The carbonation calculation is carried out on the blast furnace slag after the carbon capture, and 380g of CO can be fixed per kilogram of blast furnace slag on average2The average per kilogram of ladle refining slag can be fixed with 410g of CO2The obtained carbonated material can be applied to road construction.
TABLE 1 blast furnace slag chemistry (wt.%)
Figure RE-GDA0003001101570000081
TABLE 2 ladle refining slag chemical composition (wt.%)
Figure RE-GDA0003001101570000082
TABLE 3 blast furnace gas chemistry (vol.%)
Figure RE-GDA0003001101570000083
Example 3
The metallurgical waste slag is the electric furnace slag cooled to 600 ℃, the particle size is 7-10 mm, and the specific chemical components are shown in Table 4. The electric furnace slag is placed in a vertical vibration ball milling reactor I with the diameter of 1.8m and the height of 2.1m1And I2The volume of the stainless steel tank body accounts for three tenths of the tank body. 1000 large balls with the diameter of 20mm and 334 small balls with the diameter of 12mm are arranged in the tank body.
The metallurgical waste slag is converter slag, the particle size is 3-5 mm, and the specific chemical components are shown in Table 5. Placing the ladle refining slag in a vertical vibration ball milling reactor II with the diameter of 1.8m and the height of 2.1m1And II2The volume of the stainless steel tank body is one fifth of the tank body. 300 large balls with the diameter of 10mm and 100 small balls with the diameter of 6mm are arranged in the tank body.
Vertical vibration ball milling reactor I1Converter gas was introduced into the vessel, and the composition thereof is shown in Table 6. The temperature is 600 ℃, and the gas flow is 20 L.h-1. The flow rate of the introduced metallurgical wastewater is 1.0 L.min-1At this time, a chemical reaction occurs among the blast furnace slag, the metallurgical waste water, and the metallurgical waste gas, and a carbon capture reaction of the blast furnace slag is performed. The vibration frequency of the stainless steel tank body is 30 times/min, and the amplitude is 50 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. When the volume of the metallurgical wastewater reaches 100m3And stopping introducing the metallurgical wastewater or stopping the reaction. Vertical vibration ball milling reactor I1CO in the purge gas released from the tank2Concentration of>When the concentration is 1 percent, introducing into a vertical vibration ball millReactor II1In the tank body, the vibration frequency of the stainless steel tank body is 100 times/min, and the amplitude is 20 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. The gas flow is 15 L.h-1. When the volume of the metallurgical wastewater reaches 236m3And stopping introducing the metallurgical wastewater or stopping the reaction.
Vertical vibration ball milling reactor I1And II1CO in the released purge gas2Content (wt.)<1 percent, the obtained purified gas enters a carbon nitrogen gas separation chamber to respectively obtain pure N2And CO and H2The high heating value gas. After moisture is removed by a refrigeration type compressed air dryer, the mixture is condensed and compressed into a gas storage tank for storage and utilization. When vertical vibration ball milling reactor II1CO of released gas2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1In (1).
By CO2Concentration monitor, monitoring vertical vibration ball milling reactor I1CO at the middle and air outlet2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2The concentration is more than or equal to 18 percent, and the proving type vibration ball milling reactor I1The carbonation reaction is complete, the metallurgical waste gas and the metallurgical waste water pipeline are intelligently switched and are led into the vertical vibration ball milling reactor I2And II2In the above steps, the carbonation reaction is carried out repeatedly.
A vertical vibration ball milling reactor I1Separating the balls and the carbonation materials by a vibrating screen, magnetically separating the obtained materials, and recovering iron-containing ore phases in the metallurgical waste residues, scrap iron and the like due to collision and grinding loss between the stainless steel balls and the cylinder. Resulting spheres and particle sizes>5mm carbonated slag returns to the vertical vibration ball milling reactor I1And adding new blast furnace slag for standby. Returning the carbonated slag with the particle size of 1-5 mm to the vertical vibration ball milling reactor II2Medium and small carbonated slag particle size<1mm is directly applied.
To carbon captureThe integrated blast furnace slag is subjected to carbonation calculation, and the average amount of CO can be fixed to 400g per kg of the electric furnace slag2390g CO per kg slag of converter can be fixed on average2The obtained carbonated material can be applied to road construction.
Table 4 electric furnace slag chemistry (wt.%)
Figure RE-GDA0003001101570000091
TABLE 5 converter slag chemistry (wt.%)
Figure RE-GDA0003001101570000101
TABLE 6 chemical composition of converter coal (wt.%)
Figure RE-GDA0003001101570000102
Example 4
The metallurgical waste slag is the electric furnace slag cooled to 300 ℃, the particle size is 5-7 mm, and the specific chemical components are shown in Table 7. The electric furnace slag is placed in a vertical vibration ball milling reactor I with the diameter of 1m and the height of 1.3m1And I2The volume of the stainless steel tank body is one tenth of the tank body. 400 large balls with the diameter of 15mm and 133 small balls with the diameter of 12mm are arranged in the tank body.
The metallurgical waste slag is ladle slag with the grain size of 1-3 mm, and the specific chemical components of the metallurgical waste slag are shown in Table 8. Placing the ladle refining slag in a vertical vibration ball milling reactor II with the diameter of 1m and the height of 1.2m1And II2The volume of the stainless steel tank body is one fifth of the tank body. 300 big balls with the diameter of 7mm and 100 small balls with the diameter of 3mm are arranged in the tank body.
Vertical vibration ball milling reactor I1Converter gas was introduced into the vessel, and the composition thereof is shown in Table 9. The temperature is 500 ℃, and the gas flow is 50 L.h-1. The flow rate of the introduced metallurgical wastewater is 0.2 L.min-1At this time, blast furnace slag and smeltingThe gold wastewater and the metallurgical waste gas react chemically to carry out the carbon capture reaction of the blast furnace slag. The vibration frequency of the stainless steel tank body is 50 times/min, and the amplitude is 30 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. When the volume of the metallurgical wastewater reaches 210m3And stopping introducing the metallurgical wastewater or stopping the reaction. Vertical vibration ball milling reactor I1CO in the purge gas released from the tank2Concentration of>When 1 percent of the reaction solution is added into a vertical vibration ball milling reactor II1In the tank body, the vibration frequency of the stainless steel tank body is 120 times/min, the amplitude is 11mm, the stainless steel tank body in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank body is started. The gas flow rate is 40 L.h-1. When the volume of the metallurgical wastewater reaches 306m3And stopping introducing the metallurgical wastewater or stopping the reaction.
Vertical vibration ball milling reactor I1And II1CO in the released purge gas2Content (wt.)<1 percent, the obtained purified gas enters a carbon nitrogen gas separation chamber to respectively obtain pure N2And CO and H2The high heating value gas. After moisture is removed by a refrigeration type compressed air dryer, the mixture is condensed and compressed into a gas storage tank for storage and utilization. When vertical vibration ball milling reactor II1CO of released gas2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1In (1).
By CO2Concentration monitor, monitoring vertical vibration ball milling reactor I1CO at the middle and air outlet2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2The concentration is more than or equal to 15 percent, and the proving type vibration ball milling reactor I1The carbonation reaction is complete, the metallurgical waste gas and the metallurgical waste water pipeline are intelligently switched and are led into the vertical vibration ball milling reactor I2And II2In the above steps, the carbonation reaction is carried out by repeating the above steps。
A vertical vibration ball milling reactor I1Separating the balls and the carbonation materials by a vibrating screen, magnetically separating the obtained materials, and recovering iron-containing ore phases in the metallurgical waste residues, scrap iron and the like due to collision and grinding loss between the stainless steel balls and the cylinder. Resulting spheres and particle sizes>5mm carbonated slag returns to the vertical vibration ball milling reactor I1And adding new blast furnace slag for standby. Returning the carbonated slag with the particle size of 1-5 mm to the vertical vibration ball milling reactor II2Medium and small carbonated slag particle size<1mm is directly applied.
The carbonation of the blast furnace slag after the carbon capture is calculated, and 410g of CO can be fixed per kilogram of electric furnace slag on average2405g CO per kg of converter slag can be fixed on average2The obtained carbonated material can be applied to road construction.
TABLE 7 electric furnace slag chemistry (wt.%)
Figure RE-GDA0003001101570000111
TABLE 8 converter slag chemistry (wt.%)
Figure RE-GDA0003001101570000112
TABLE 9 chemical composition of converter coal (wt.%)
Figure RE-GDA0003001101570000113
Example 5
The metallurgical slag is converter slag cooled to 500 ℃, the particle size is 7-9 mm, and the specific chemical components are shown in Table 10. The electric furnace slag is placed in a vertical vibration ball milling reactor I with the diameter of 1.6m and the height of 2m1And I2The volume of the stainless steel tank body in (1) accounts for one fourth of the tank body. 820 big balls with the diameter of 19mm and 274 small balls with the diameter of 11mm are arranged in the tank body.
The metallurgy usedThe gold waste slag is electric furnace slag with the grain diameter of 1-3 mm, and the specific chemical components of the gold waste slag are shown in Table 11. Placing the ladle refining slag in a vertical vibration ball milling reactor II with the diameter of 1.6m and the height of 2m1And II2The volume of the stainless steel tank body is one fifth of the tank body. 510 big balls with the diameter of 6mm and 170 small balls with the diameter of 4mm are arranged in the tank body.
Vertical vibration ball milling reactor I1Converter gas was introduced into the vessel, and the composition thereof is shown in Table 12. The temperature is 400 ℃, and the gas flow is 100 L.h-1. The flow rate of the introduced metallurgical wastewater is 0.8 L.min-1At this time, a chemical reaction occurs among the blast furnace slag, the metallurgical waste water, and the metallurgical waste gas, and a carbon capture reaction of the blast furnace slag is performed. The vibration frequency of the stainless steel tank body is 30 times/min, and the amplitude is 10 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. When the volume of the metallurgical wastewater reaches 700m3And stopping introducing the metallurgical wastewater or stopping the reaction. Vertical vibration ball milling reactor I1CO in the purge gas released from the tank2Concentration of>When 1 percent of the reaction solution is added into a vertical vibration ball milling reactor II1In the tank body, the vibration frequency of the stainless steel tank body is 100 times/min, and the amplitude is 10 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. The gas flow rate is 80 L.h-1. When the volume of the metallurgical wastewater reaches 520m3And stopping introducing the metallurgical wastewater or stopping the reaction.
Vertical vibration ball milling reactor I1And II1CO in the released purge gas2Content (wt.)<1 percent, the obtained purified gas enters a carbon nitrogen gas separation chamber to respectively obtain pure N2And CO and H2The high heating value gas. After moisture is removed by a refrigeration type compressed air dryer, the mixture is condensed and compressed into a gas storage tank for storage and utilization. When vertical vibration ball milling reactor II1CO of released gas2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1In (1).
By CO2Concentration monitor, monitoring vertical vibration ball milling reactor I1CO at the middle and air outlet2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2The concentration is more than or equal to 14 percent, and the proving type vibration ball milling reactor I1The carbonation reaction is complete, the metallurgical waste gas and the metallurgical waste water pipeline are intelligently switched and are led into the vertical vibration ball milling reactor I2And II2In the above steps, the carbonation reaction is carried out repeatedly.
A vertical vibration ball milling reactor I1Separating the balls and the carbonation materials by a vibrating screen, magnetically separating the obtained materials, and recovering iron-containing ore phases in the metallurgical waste residues, scrap iron and the like due to collision and grinding loss between the stainless steel balls and the cylinder. Resulting spheres and particle sizes>5mm carbonated slag returns to the vertical vibration ball milling reactor I1And adding new blast furnace slag for standby. Returning the carbonated slag with the particle size of 1-5 mm to the vertical vibration ball milling reactor II2Medium and small carbonated slag particle size<1mm is directly applied.
Carbonating calculation is carried out on the converter slag after carbon capture, and 390g of CO can be fixed per kilogram of electric furnace slag on average2The average per kilogram of the electric furnace slag can be fixed with 400g of CO2The obtained carbonated material can be applied to road construction.
TABLE 10 converter slag chemistry (wt.%)
Figure RE-GDA0003001101570000121
TABLE 11 electric furnace slag chemistry (wt.%)
Figure RE-GDA0003001101570000131
TABLE 12 chemical composition of converter coal (wt.%)
Figure RE-GDA0003001101570000132
Example 6
The metallurgical waste slag is blast furnace slag cooled to 200 ℃, the particle size is 6-8 mm, and the specific chemical components are shown in Table 13. The electric furnace slag is placed in a vertical vibration ball milling reactor I with the diameter of 1.8m and the height of 2.7m1And I2The volume of the stainless steel tank body is two fifths of the tank body. 1600 large balls with the diameter of 20mm and 533 small balls with the diameter of 13mm are arranged in the tank body.
The metallurgical waste slag is refining slag with the particle size of 1-3 mm, and the specific chemical components of the metallurgical waste slag are shown in Table 14. Placing the refining slag in a vertical vibration ball milling reactor II with the diameter of 1.8m and the height of 2.7m1And II2The volume of the stainless steel tank body is one fifth of the tank body. 800 large balls with the diameter of 5mm and 267 small balls with the diameter of 2mm are arranged in the tank body.
Vertical vibration ball milling reactor I1Blast furnace gas was introduced into the vessel, and the composition thereof is shown in table 15. The temperature is 500 ℃, and the gas flow is 70 L.h-1. The flow rate of the introduced metallurgical wastewater is 2 L.min-1At this time, a chemical reaction occurs among the blast furnace slag, the metallurgical waste water, and the metallurgical waste gas, and a carbon capture reaction of the blast furnace slag is performed. The vibration frequency of the stainless steel tank body is 50 times/min, and the amplitude is 12 mm. The stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started. When the volume of the metallurgical wastewater reaches 2000m3And stopping introducing the metallurgical wastewater or stopping the reaction. Vertical vibration ball milling reactor I1CO in the purge gas released from the tank2Concentration of>When 1 percent of the reaction solution is added into a vertical vibration ball milling reactor II1In the tank body, the vibration frequency of the stainless steel tank body is 120 times/min, and the amplitude is 18 mm. Stopping vibrating the stainless steel tank body in the vertical vibration ball milling reactor every 15min, and performing 3-turn anticlockwise 360-degree accelerated rotation on the vertical vibration ball milling reactor along a circular trackAfter the movement, the vertical vibration of the stainless steel tank body is started. The gas flow rate is 50 L.h-1. When the volume of the metallurgical wastewater reaches 1200m3And stopping introducing the metallurgical wastewater or stopping the reaction.
Vertical vibration ball milling reactor I1And II1CO in the released purge gas2Content (wt.)<1 percent, the obtained purified gas enters a carbon nitrogen gas separation chamber to respectively obtain pure N2And CO and H2The high heating value gas. After moisture is removed by a refrigeration type compressed air dryer, the mixture is condensed and compressed into a gas storage tank for storage and utilization. When vertical vibration ball milling reactor II1CO of released gas2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1In (1).
By CO2Concentration monitor, monitoring vertical vibration ball milling reactor I1CO at the middle and air outlet2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2At a concentration of>10% proof vertical vibration ball mill reactor I1The carbonation reaction is complete, the metallurgical waste gas and the metallurgical waste water pipeline are intelligently switched and are led into the vertical vibration ball milling reactor I2And II2In the above steps, the carbonation reaction is carried out repeatedly.
A vertical vibration ball milling reactor I1Separating the balls and the carbonation materials by a vibrating screen, magnetically separating the obtained materials, and recovering iron-containing ore phases in the metallurgical waste residues, scrap iron and the like due to collision and grinding loss between the stainless steel balls and the cylinder. Resulting spheres and particle sizes>5mm carbonated slag returns to the vertical vibration ball milling reactor I1And adding new blast furnace slag for standby. Returning the carbonated slag with the particle size of 1-5 mm to the vertical vibration ball milling reactor II2Medium and small carbonated slag particle size<1mm is directly applied.
Carbonating calculation is carried out on the converter slag after carbon capture, and 390g of CO can be fixed per kilogram of electric furnace slag on average2The average per kilogram of the electric furnace slag can be fixed with 400g of CO2The obtained carbonated material can be applied to road construction.
TABLE 13 blast furnace slag chemistry (wt.%)
Figure RE-GDA0003001101570000141
TABLE 14 refining slag chemistry (wt.%)
Figure RE-GDA0003001101570000142
TABLE 15 blast furnace gas chemistry (wt.%)
Figure RE-GDA0003001101570000143
The above embodiments are merely provided to help understand the method and core principle of the present invention, and the main steps and embodiments of the present invention are described in detail by using specific examples. To those skilled in the art, the various conditions and parameters may be varied as desired in a particular implementation in accordance with the principles of the invention, and in view of the foregoing, the description is not to be taken as limiting the invention.

Claims (10)

1. A steelmaking waste cooperative treatment system based on ball milling reinforcement is characterized in that: comprises a carbon capture system and a carbon and nitrogen gas separation and collection system which are connected in sequence; the carbon capture system comprises four vertical vibration ball milling reactors (I)1、Ⅰ2、Ⅱ1And II2) Gas transport pipeline, liquid flow rate meter, gas flow rate meter, CO2The device comprises a concentration detector, a computer intelligent switching system, a circular slide rail and a vibrating screen; the carbon and nitrogen gas separating and collecting system comprises a carbon and nitrogen gas separating chamber, a freezing type compressed air dryer, a gas condensing device and a gas storage tank which are connected in sequence.
2. The ball milling strengthening based steelmaking scrap according to claim 1Abandonment thing cooperative treatment system, its characterized in that: the vertical vibration ball-milling reactor comprises: the device comprises a flange cover, a sealing ring, a heat insulation material, a stainless steel tank body, stainless steel balls with different diameters, a buffer spring, a base, a vertical slideway, a support, a motor and a circular slideway; the flange cover is detachably and hermetically arranged at the upper end of the stainless steel tank body through a sealing ring, a gas inlet, a gas outlet and a liquid input pipeline are arranged on the flange cover, the gas inlet is connected with a metallurgical waste gas transmission pipeline, the gas flow in the metallurgical waste gas transmission pipeline is controlled by a gas flow controller, the gas outlet is connected with a purified gas transmission pipeline, and the purified gas transmission pipeline is formed by a CO (carbon monoxide) gas2Concentration detector for monitoring CO in tube2The liquid input pipeline is connected with a metallurgical waste liquid transmission pipeline, and the metallurgical waste liquid transmission pipeline is controlled by liquid flow control meter; the stainless steel tank body is sleeved with a heat insulation material at the outer side, stainless steel balls with different diameters are arranged in the stainless steel tank body, a buffer spring is arranged at the lower end of the stainless steel tank body, the side face of the stainless steel tank body is arranged on a support through a vertical slide way, the support is arranged above a base, and a circular slide way is arranged below the base; the vertical vibration ball milling reactor can do 360-degree accelerated rotation motion along the circular slide rail; the vertical vibration ball-milling reactor is electrically connected with a motor.
3. The steelmaking waste cooperative treatment system based on ball milling reinforcement as claimed in claim 2, wherein: the tail end of the liquid input pipeline is averagely branched into four output pipelines, two adjacent pipelines are spaced by 90 degrees, the tail end of each output pipeline is provided with a liquid atomizer, liquid can flow through the atomizers to spray water in a divergent mode, and the spraying range is 120 degrees.
4. The steelmaking waste cooperative treatment system based on ball milling reinforcement as claimed in claim 2, wherein: the system is provided with a computer intelligent switching system, the computer intelligent switching system, a gas flow control meter and CO2Concentration detector, metallurgical waste gas transmission pipeline and purified gasThe body transmission pipeline, the metallurgical waste liquid transmission pipeline and the vertical vibration ball-milling reactor are electrically connected.
5. The ball milling strengthening based steelmaking waste cooperative treatment system as claimed in claim 1 or 2, wherein: the 4 vertical vibration ball milling reactors (I)1、Ⅰ2、Ⅱ1And II2) Wherein, the vertical vibration ball milling reactor I1And I2Is a first-stage carbon capture reactor; vertical vibration ball milling reactor II1And II2Is a secondary carbon capture reactor.
6. The ball milling strengthening based steelmaking waste cooperative treatment system as claimed in claim 1 or 2, wherein: the ratio of the diameter D to the height H of the stainless steel tank body is as follows: H/D (1.5-2), the vibration frequency of the stainless steel tank body is 30-120 times/min, and the amplitude is 0.25-0.5 times of the height H of the stainless steel tank body; the volume of the metallurgical slag in the vertical vibration ball milling reactor is not more than two fifths of the volume of the stainless steel tank body; the total mass ratio of the metallurgical slag to the stainless steel balls in the stainless steel tank body is 5: 1-20: 1, and the density of the stainless steel balls is 7.8 +/-0.2 g cm-3(ii) a The stainless steel tank body is internally provided with a large sphere and a small sphere, wherein the vertical vibration ball milling reactor I1And I2In the vertical vibration ball milling reactor II, the diameter range of the sphere is 10-20 mm1And II2In the middle, the diameter range of the sphere is 5-10 mm; and the diameter d of the large sphere in the tank body1Diameter d of the small sphere2Ratio d1：d2The number ratio of the large spheres to the small spheres is 3:1 (1.5-2.5); the inner lining of the stainless steel tank body and the heat insulation and preservation material are both medium-temperature heat insulation refractory materials which are more than 700 ℃; the stainless steel tank in the vertical vibration ball milling reactor stops vibrating every 15min, and after the vertical vibration ball milling reactor performs 3 circles of anticlockwise 360-degree accelerated rotation motion along the circular track, the vertical vibration of the stainless steel tank is started.
7. A steelmaking waste cooperative treatment method based on ball milling reinforcement is characterized by comprising the following steps:
the four vertical vibration ball milling reactors (I)1、Ⅰ2、Ⅱ1And II2) In the operation, the device is divided into two groups for switching use, wherein the first group is a vertical vibration ball milling reactor I1And II1(ii) a The second group is a vertical vibration ball milling reactor I2And II2；
(1) First order carbon capture reaction
Placing metallurgical slag in a first group of vertical vibration ball milling reactors I1And II1In the process, the metallurgical waste gas and the metallurgical waste water after dust removal are introduced into a vertical ball milling reactor I1At this time, chemical reaction among the metallurgical slag, the metallurgical waste gas and the metallurgical waste water occurs, and primary carbon capture reaction is carried out;
(2) second order carbon capture reaction
In the carbon capture reaction process, if the vertical vibration ball milling reactor I1Releasing purified gas via CO2CO monitored by concentration detector2Content (wt.)>When the concentration is 1 percent, the purified gas is continuously introduced into the vertical vibration ball milling reactor II by the computer intelligent switching system1Carrying out secondary carbon capture in the process, and simultaneously spraying metallurgical wastewater by an atomizer at the tail end of a liquid inlet and outlet pipeline; vertical vibration ball milling reactor I1And II1Passing the released gas through CO2CO monitored by concentration detector2Content (wt.)<When 1 percent of the nitrogen is obtained, the obtained purified gas enters a carbon nitrogen gas separation chamber to respectively obtain pure N2And CO and H2The high-heat value coal gas is condensed and compressed into a gas storage tank for storage and utilization after moisture is removed by a refrigeration type compressed air dryer; when vertical vibration ball milling reactor II1Passing the released gas through CO2CO monitored by concentration detector2Content (wt.)>At 1%, the obtained gas returns to the vertical vibration ball milling reactor II1Performing the following steps;
(3) switching vertical vibration ball milling reactor
When CO is present2Vertical vibration ball-milling reactor I for monitoring concentration monitor1CO in connected purge gas lines2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2Concentration (i.e. CO in metallurgical off-gas and purge gas)2Concentration difference is less than or equal to 3%) or when CO is present2Vertical vibration ball-milling reactor II for monitoring concentration monitor1CO at the middle gas outlet2The concentration is kept within 15min>At 1%, the end of the first group of reactions is verified; the metallurgical waste gas and the metallurgical waste water pipeline are switched by an intelligent control system to enter a second group of vertical vibration ball milling reactors I filled with new metallurgical slag2In the second group, a vertical vibration ball milling reactor I2And II2Replacement of a first set of vertical vibratory ball milling reactors I1And II1Repeating the steps (1) and (2);
when CO is present2Vertical vibration ball-milling reactor I for monitoring concentration monitor2CO in connected purge gas lines2The concentration of the CO in the original metallurgical waste gas is continuously close to that of the CO in the original metallurgical waste gas within 15min2Concentration (i.e. CO in metallurgical off-gas and purge gas)2Concentration difference is less than or equal to 3%) or when CO is present2Vertical vibration ball-milling reactor II for monitoring concentration monitor2CO at the middle gas outlet2The concentration is kept within 15min>At 1%, the end of the second group of reactions is verified; a metallurgical waste gas pipeline and a metallurgical waste water pipeline are switched by an intelligent control system to enter a first group of vertical vibration ball milling reactors I filled with new metallurgical slag1In the first group, a vertical vibration ball milling reactor I is adopted1And II1Replacement of a second group of vertical vibratory ball milling reactors I2And II2Repeating the steps (1) and (2);
the first group is a vertical vibration ball milling reactor I1And II1And the second group is a vertical vibration ball milling reactor I2And II2Switching to recycle according to the above conditions;
(4) magnetic separation of carbonated metallurgical slag
And (4) performing ball material separation on the carbonated metallurgical slag produced in the step (3) and the stainless steel balls through a vibrating screen, returning the obtained stainless steel balls to the vertical vibrating ball-milling reactor for recycling, and performing magnetic separation on the obtained materials to recover iron-containing magnetic substances for recycling.
8. The method according to claim 7The ball-milling reinforced steelmaking waste cooperative treatment method is characterized by comprising the following steps: the metallurgical slag in the step (1) can be steel slag with alkalinity generated in the steel-making process, the temperature of the steel slag is less than or equal to 600 ℃, and the grain size is less than or equal to 10 mm; the metallurgical waste gas can be CO contained in the steel-making process2The temperature of the waste gas and the metallurgical waste gas is less than or equal to 600 ℃, and CO is2Content (wt.)>5 percent; the metallurgical waste water can be cold rolling waste water, waste liquid generated in the steel-making process, F-、Cr3+、Cr6+And the polluting ions need to be removed in advance.
9. The steelmaking waste cooperative treatment method based on ball milling reinforcement as claimed in claim 7, wherein: step (1), (2) and (3) vertical vibration ball milling reactor I1And I2The particle size of the metallurgical waste residue in the vertical vibration ball milling reactor II 1 and II 2 is 5-10 mm, and the particle size of the metallurgical waste residue in the vertical vibration ball milling reactor II 1 and II 2 is not more than 5 mm; the gas flow of the metallurgical waste gas introduced into the vertical vibration ball milling reactor is 5-100 L.h-1(ii) a The mass ratio of the volume of the introduced metallurgical wastewater to the metallurgical slag is as follows: 0.25 to 1.2L/Kg-1The flow rate of the introduced metallurgical wastewater is controlled to be 0.1-2 L.min-1。
10. The steelmaking waste cooperative treatment method based on ball milling reinforcement as claimed in claim 7, wherein: the materials separated by the vibrating screen in the step (4) are subjected to magnetic separation treatment, so that iron-containing ore phases in the carbonated metallurgical slag, scrap iron and the like due to collision and grinding loss between the stainless steel ball and the cylinder body can be recovered; residual carbonated material, particle size>5mm, returning to the vertical vibration ball milling reactor I1And I2Returning the carbonated metallurgical slag with the grain diameter of 1-5 mm to the vertical vibration ball milling reactor II1And II2Medium, carbonated metallurgical slag particle size<1mm can be directly applied.
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