A blast furnace recovery smelting device and method for lead-containing materials

Abstract

A blast furnace recovery smelting device and method for lead-containing materials, belonging to the field of environmental protection technology. The device includes a blast furnace, a powder storage tank, a mixer, a pulverized coal distributor, a lower annular flue, an upper annular flue, a furnace gas lead recovery system I, a furnace gas lead recovery system II, a blower I, a blower II, and a nitrogen sweeper. The present invention uses the blast furnace smelting process to smelt and recover lead-containing materials, and utilizes the lead vapor pressure difference generated by the temperature difference of the flue gas in the blast furnace to introduce part of the lead-containing furnace gas into the lead recovery system for repeated recovery. While smelting iron and steel, the present invention also recovers and processes waste batteries, killing two birds with one stone. Moreover, it will not cause lead pollution to the gas and slag, the molten iron does not have an increase in lead content, and the energy consumption is also very low. The present invention has no risk of secondary pollution, and the lead emission is almost zero; the transformation of the existing iron-making blast furnace has less investment and low operating costs; no waste is generated.

Description

Technical Field

[0001] The present invention belongs to the field of environmental protection technologies, and particularly relates to a blast furnace recovery smelting device and method for lead-containing materials. Background Art

[0002] In recent years, due to the rapid development of automobiles and electric vehicles, the amount of waste batteries has increased sharply. In addition to some plastic casings, waste batteries mainly contain lead metal and lead sulfate waste liquid. Since lead is a heavy metal, battery waste belongs to hazardous waste. Currently, there are problems in flue gas treatment for all existing lead-containing hazardous waste treatment technologies. This is because the low-temperature vapor pressure of lead is very high, so it is difficult for the heavy metals in the flue gas to meet the standards. In particular, the treatment of lead sulfate waste liquid is almost a lead smelting process, and it is difficult to control the process pollution and the energy consumption is also high. Therefore, in order to solve environmental protection problems, it is urgent to develop an environmentally friendly lead-containing material smelting technology. Summary of the Invention

[0003] To solve the above technical problems, the present invention provides a blast furnace recovery smelting device and method for lead-containing materials. The lead-containing materials are smelted and recovered by using the blast furnace smelting process. By utilizing the lead vapor pressure difference generated by the temperature difference of the flue gas in the blast furnace, part of the lead-containing furnace gas is introduced into the lead recovery system for repeated recovery, and then the furnace gas after lead recovery is sent back into the furnace. The uncaught lead vapor is caught by the low-temperature furnace charge during the upward movement with the furnace gas, and then follows the furnace charge downward, is gasified again, and is recovered again. Lead cannot escape from the furnace. The furnace gas is blast furnace gas, and all of it is recovered and utilized after leaving the blast furnace. The recovered blast furnace gas does not contain lead components, so there will be no lead pollution during the combustion of the gas. The specific technical solutions are as follows:

[0004] A blast furnace recovery smelting device for lead-containing materials includes a blast furnace 1, a powder storage tank 2, a mixer 3, a coal injection distributor 4, a lower annular flue 5, an upper annular flue 6, a furnace gas lead recovery system I 12, a furnace gas lead recovery system II 13, a blower I 14, a blower II 15, and a nitrogen sweeper 16;

[0005] The top end of the blast furnace 1 is provided with a feed inlet 7, and the bottom furnace wall is provided with a lead discharge port 8; the melting section of the blast furnace 1 is provided with a furnace wall injection feed hole 9, the furnace wall air intake hole 10 is provided at the furnace temperature of 800 - 650 °C in the transition section, and the furnace wall air return hole 11 is provided at the furnace temperature of 600 - 350 °C in the transition section;

[0006] The powder storage tank 2 is provided with a gas feeding system; the coal injection distributor 4 is connected with a coal injection lance;

[0007] The furnace gas lead recovery system I 12 is composed of a lead collector I 12.1 and a lead collecting tank I 12.2 arranged at the bottom of the lead collector I 12.1. A discharge pipe I is arranged at the upper part of the lead collector I 12.1, and a discharge valve I 12.3 is arranged on the discharge pipe I; a lead discharge pipe is arranged on the lead collecting tank I 12.2, and a discharge valve I 12.4 is arranged on the lead discharge pipe;

[0008] The furnace gas lead recovery system II 13 is composed of a lead collector II 13.1 and a lead collecting tank II 13.2 arranged at the bottom of the lead collector II 13.1. A discharge pipe II is arranged at the upper part of the lead collector II 13.1, and a discharge valve II 13.3 is arranged on the discharge pipe II; a lead discharge pipe is arranged on the lead collecting tank II 13.2, and a discharge valve II 13.4 is arranged on the lead discharge pipe;

[0009] The feed inlet 7 of the blast furnace 1 is connected to an external waste battery plate processing system 25 through a pipeline; the top feed inlet of the powder storage tank 2 is connected to an external waste battery waste liquid dry matter pulverizing system 26 through a pipeline, and the waste battery waste liquid dry matter pulverizing system 26 is connected to a waste battery waste liquid treatment system 27;

[0010] The bottom discharge port of the powder storage tank 2 is connected to the inlet of the mixer 3 through a pipeline, the outlet of the mixer 3 is directly connected to the coal injection distributor 4, and the coal injection distributor 4 is connected to the coal injection lance through a branch pipe, and the coal injection lance is inserted into the furnace wall injection feed hole 9;

[0011] The furnace wall air inlet hole 10 is connected to the lower annular flue 5 through a branch pipe; the lower annular flue 5 is branched through a three-way pipeline to connect to the flue gas inlets of the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13; the flue gas outlets of the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13 are merged through a three-way pipeline to connect to the upper annular flue 6, and the upper annular flue 6 is connected to the furnace wall air return hole 11 through a branch pipe;

[0012] The nitrogen purger 16 is connected to the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13 respectively through pipelines. A nitrogen valve I 16.1 is arranged on the pipeline connecting the nitrogen purger 16 and the furnace gas lead recovery system I 12; a nitrogen valve II 16.2 is arranged on the pipeline connecting the nitrogen purger 16 and the furnace gas lead recovery system II 13;

[0013] The blower I 14 is connected to the furnace gas lead recovery system I 12 through a pipeline, and the blower II 15 is connected to the furnace gas lead recovery system II 13 through a pipeline;

[0014] Two valves, i.e., a first flue gas inlet valve I (17) and a second flue gas inlet valve I (18), are arranged on the branch connection pipeline between the lower annular flue (5) and the lead recovery system I (12) of furnace gas; two valves, i.e., a first flue gas inlet valve II (19) and a second flue gas inlet valve II (20), are arranged on the branch connection pipeline between the lower annular flue (5) and the lead recovery system II (13) of furnace gas; two valves, i.e., a first flue gas outlet valve I (21) and a second flue gas outlet valve I (22), are arranged on the branch connection pipeline between the lead recovery system I (12) of furnace gas and the upper annular flue (6); two valves, i.e., a first flue gas outlet valve II (23) and a second flue gas outlet valve II (24), are arranged on the branch connection pipeline between the lead recovery system II (13) of furnace gas and the upper annular flue (6).

[0015] A valve is arranged on the connecting branch pipe between the lower annular flue (5) and the furnace wall air inlet hole (10); a valve is arranged on the connecting branch pipe between the upper annular flue (6) and the furnace wall air return hole (11).

[0016] A valve is arranged on the connecting and merging pipeline between the lead recovery system I (12) of furnace gas and the upper annular flue (6) and on the connecting and merging pipeline between the lead recovery system II (13) of furnace gas and the upper annular flue (6).

[0017] The number of the furnace wall injection feed holes (9) is N, and N≥2; the number of the pulverized coal injection guns is the same as that of the furnace wall injection feed holes (9); the pulverized coal injection guns are made of heat-resistant stainless steel pipes.

[0018] The number of the furnace wall air inlet holes (10) is M, and M≥2; the inner side of the lower annular flue (5) is provided with holes having the same number as that of the furnace wall air inlet holes (10).

[0019] The number of the furnace wall air return holes (11) is M, and M≥2; the inner side of the upper annular flue (6) is provided with holes having the same number as that of the furnace wall air return holes (11).

[0020] The motors of the blower I (14) and the blower II (15) are variable frequency motors.

[0021] A blast furnace recovery smelting method for lead-containing materials, adopting the above blast furnace recovery smelting equipment for lead-containing materials, the method comprises the following steps:

[0022] Step 1, pretreatment:

[0023] The waste storage batteries are disassembled, and the large lead plates are subjected to plate pretreatment in the waste storage battery plate processing system (25). The large lead plates are cut into small pieces convenient for feeding to obtain pretreated plate materials; the waste liquid in the waste storage batteries is composed of lead sulfate, sulfuric acid and water. The waste liquid is pretreated in the waste storage battery waste liquid processing system (27). The waste liquid is mixed with lime powder to form a mixed solid of calcium sulfate, calcium hydroxide, calcium oxide and lead sulfate. Then the mixed solid is subjected to crushing treatment in the waste storage battery waste liquid dry matter crushing system (26), and the crushing particle size is ≤80 meshes to obtain pretreated powder.

[0024] Step 2, feeding:

[0025] The pre-treated plate material is added into the blast furnace 1 through the feeding port 7 by the feeding system; the pre-treated powder is added into the powder storage tank 2 through a pipeline, and the gas transmission system of the powder storage tank 2 transports the pre-treated powder into the mixer 3 through a pipeline for mixing, and then it is sprayed into the pulverized coal distributor 4 together with the injection fuel, distributed by the pulverized coal distributor 4 to the pulverized coal guns, and finally sprayed into the blast furnace 1 through the furnace wall injection feeding hole 9;

[0026] Step 3, smelting:

[0027] Normal iron smelting is carried out in the blast furnace 1. The smelting burden is sinter, pellet, porous coke and smelting solvent. The molten iron temperature at the bottom of the blast furnace is 1400 - 1500 °C. In the pulverized coal injection tuyere area, that is, the furnace wall injection feeding hole 9 area, the temperature is 1800 - 2300 °C. The furnace top exhaust gas temperature is 150 - 250 °C. The inside of the furnace is a reducing atmosphere;

[0028] (1) The metallic lead in the plate material added through the feeding port 7 starts to melt at 327 °C, flows through the burden towards the lower part of the furnace, and sinks to the furnace bottom; at the same time, a small amount of lead vaporizes at high temperature and rises during the downward flow. The lead vapor is adsorbed by multiple layers of porous coke and sinter during the upward process, or is cooled and solidified on the surface of the burden by the low-temperature burden, and then descends with the burden. After descending, the temperature rises, and the lead is vaporized again. Finally, it reaches equilibrium in different temperature regions. The lead-containing flue gas in the 800 - 650 °C temperature zone in the blast furnace 1 is led out through the furnace wall air extraction hole 10 and enters the lower annular flue 5;

[0029] (2) The lead sulfate in the mixed powder sprayed into the blast furnace 1 decomposes rapidly into sulfur oxide and lead oxide at a temperature above 1800 °C. Immediately afterwards, the lead oxide becomes gaseous and is reduced to metallic lead by carbon monoxide and carbon. The metallic lead is immediately vaporized. After the lead vapor rises, it condenses into liquid lead when it encounters the low-temperature burden, and then flows downward and sinks to the furnace bottom; the sulfur oxide is reduced to hydrogen sulfide and carbonyl sulfide and discharged out of the furnace with the furnace gas, captured and removed by the coal gas desulfurization link, or absorbed by the molten iron to increase the sulfur content of the molten iron; the calcium sulfate in the mixed powder enters the furnace slag; the calcium hydroxide in the mixed powder decomposes into water and calcium oxide. The calcium oxide drips into the bottom molten pool with the iron in the softening and melting zone and is captured by the furnace slag to become a slag-making material;

[0030] Step 4, recovery:

[0031] Start the lead recovery system I 12 or the lead recovery system II 13 of the furnace gas. First, connect the nitrogen purger 16 to the high-pressure nitrogen source, and open the nitrogen valve I 16.1 or the nitrogen valve II 16.2. Open the bleed valve I 12.3 or the bleed valve II 13.3 to inject nitrogen into the lead recovery system I 12 or the lead recovery system II 13 of the furnace gas to displace the air with nitrogen. Then start the blower I 14 or the blower II 15. After that, open the first flue gas outlet valve I 21 and the second flue gas outlet valve I 22, or open the first flue gas outlet valve II 23 and the second flue gas outlet valve II 24. Finally, gradually open the first flue gas inlet valve I 17 and the second flue gas inlet valve I 18, or gradually open the first flue gas inlet valve II 19 and the second flue gas inlet valve II 20. By controlling the flue gas inlet valve, control the flue gas extraction volume at 20 - 30%. The extracted flue gas enters the lead recovery system I 12 or the lead recovery system II 13 of the furnace gas through the pipeline, and is cooled down to capture lead, zinc, cadmium, light metal oxides and salts. The cooled lead liquid, zinc, cadmium, light metal oxides and salts flow into the lead collection tank I 12.2 or the lead collection tank II 13.2. The unliquefied flue gas in the lead recovery system I 12 or the lead recovery system II 13 of the furnace gas enters the upper annular flue 6 through the pipeline and is led back to the blast furnace 1 through the gas return holes 11 in the furnace wall.

[0032] In the above method, the air pressure of the flue gas extracted from the gas extraction hole 10 in the furnace wall after being reduced by the pipeline resistance and the resistance of the lead recovery system of the furnace gas is greater than the air pressure of the flue gas in the furnace at the gas return hole 11 in the furnace wall.

[0033] In the above method, the cooling of the lead recovery system I 12 and the lead recovery system II 13 of the furnace gas adopts tube - type or plate - type heat exchange.

[0034] In the above method, the cooling medium for the cooling of the lead recovery system I 12 and the lead recovery system II 13 of the furnace gas adopts air cooling, and the air source is provided by the blower I 14 or the blower II 15.

[0035] A blast furnace recovery smelting device and method for lead - containing materials of the present invention, compared with the prior art, have the following beneficial effects:

[0036] First, there is a small amount of lead in normal iron - making furnace materials, and some lead is deposited at the bottom of the furnace. Therefore, the lead in the molten iron is basically in a saturated state. The blast furnace lead recovery smelting method of the present invention will not cause lead loss and can increase the lead recovery amount.

[0037] Second, the waste liquid in the storage battery is mainly lead sulfate, sulfuric acid and water. The present invention mixes the waste liquid with lime powder. Calcium oxide in the lime powder reacts with sulfuric acid in the waste liquid to form calcium sulfate, and water in the waste liquid reacts with calcium oxide to form calcium hydroxide, making it a dry mixture of lead sulfate, calcium sulfate, calcium hydroxide and calcium oxide, and pulverizing it into powder for easy feeding to maintain a stable blast furnace smelting environment.

[0038] III. Due to the addition of lead sulfate and calcium sulfate, part of the sulfur is absorbed by the molten iron and enters the molten iron, increasing the sulfur content of the molten iron. Therefore, the sulfur content of the molten iron produced by the method of the present invention is relatively high, and the produced molten iron can be used for the production of castings with low sulfur requirements.

[0039] IV. Since the temperature at the top of the blast furnace is relatively low, generally not exceeding 250 °C, the vapor pressure of lead is almost zero at this temperature. The present invention completes the extraction of flue gas and the recovery of lead treatment in the middle of the blast furnace. Therefore, the vapor pressure of lead in the upper part of the blast furnace is in an unsaturated state. In addition, there are more active metals such as zinc and cadmium than lead in the furnace. Therefore, lead oxide will not be generated. In actual operation, lead is hardly detected in the gas, ensuring the normal operation of the blast furnace.

[0040] V. Since the lead sulfate injected into the furnace is decomposed into gaseous substances and has no chance to enter the slag, lead will not cause excessive lead emissions in the blast furnace slag. In actual operation, no increase in the lead content of the slag has been found, ensuring the harmlessness of the slag.

[0041] VI. The way of extracting flue gas of the equipment of the present invention is to open a plurality of air extraction holes around the blast furnace wall. The more holes are opened, the better the lead removal effect and the less impact on the operation of the blast furnace. The specific number of holes opened is determined according to the size and cost of the equipment, and the design is flexible.

[0042] VII. The present invention adopts two sets of furnace gas lead recovery systems, one for use and one for standby, and they are used alternately to prevent equipment failure and facilitate continuous production.

[0043] VIII. The equipment of the present invention recovers lead by relying on the iron-making process, rather than a dedicated lead production equipment, and there is no requirement for the recovery rate. Therefore, when the permeability of the furnace charge can be ensured, the temperature drop of the gas can be minimized as much as possible to reduce heat loss. When the permeability of the blast furnace becomes poor, more furnace gas needs to be extracted to accelerate the reduction of the lead vapor pressure in the furnace. When the permeability of the blast furnace is normal, less furnace gas can be extracted. It can be flexibly adjusted to save operating costs.

[0044] IX. While smelting iron and steel, the present invention also recovers and treats waste batteries, killing two birds with one stone. And it will not cause lead pollution to the gas and slag, and the lead content of the molten iron does not increase. Therefore, the invention is a very good process whether considering the metal yield or the pollutant emissions, and the energy consumption is also very low. The present invention has no risk of secondary pollution, and the lead emissions are almost zero; the transformation of the existing iron-making blast furnace has less investment and low operating costs; no waste is generated.

[0045] X. While recovering lead, the present invention also recovers some low-temperature vaporizable metals such as zinc and cadmium, and can also remove part of the light metal oxides and salts, which is of great significance for improving the permeability of the blast furnace, improving the reaction activity of materials, reducing the system resistance, and increasing the smelting intensity.

[0046] XI. The present invention can solve the problem of affecting the air permeability of materials in the smelting of high-lead ores and high-lead waste materials. Therefore, this equipment is also applicable to the smelting of other high-lead materials and can also be used as a lead smelting equipment.

[0047] XII. The present invention can solve the problem of the enrichment paste of light metal oxides blocking the furnace charge in blast furnace smelting. Therefore, this equipment and method are applicable to the treatment of iron-containing waste materials in hydrometallurgy. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 FIG. is a schematic structural diagram of a blast furnace recovery smelting equipment for lead-containing materials in Embodiment 1 of the present invention: In the figure, 1-blast furnace, 2-powder storage tank, 3-mixer, 4-coal injection distributor, 5-lower annular flue, 6-upper annular flue, 7-top feed port, 8-lead discharge port, 9-furnace wall injection feed hole, 10-furnace wall air intake hole, 11-furnace wall air return hole, 12-furnace gas lead recovery system I, 12.1-lead collector I, 12.2-lead collecting tank I, 12.3-relief valve I, 12.4-discharge valve I, 13-furnace gas lead recovery system II, 13.1-lead collector II, 13.2-lead collecting tank II, 13.3-relief valve II, 13.4-discharge valve II, 14-blower I, 15-blower II, 16-nitrogen purger, 16.1-nitrogen valve I, 16.2-nitrogen valve II, 17-smoke inlet first valve I, 18-smoke inlet second valve I, 19-smoke inlet first valve II, 20-smoke inlet second valve II, 21-smoke outlet first valve I, 22-smoke outlet second valve I, 23-smoke outlet first valve II, 24-smoke outlet second valve II, 25-waste battery plate treatment system, 26-waste battery waste liquid dry matter crushing system, 27-waste battery waste liquid treatment system, and the arrow indicates the material flow direction.

[0049] Figure 2 FIG. is a cross-sectional view of the lower annular flue of a blast furnace recovery smelting equipment for lead-containing materials in Embodiment 1 of the present invention: In the figure, 1-blast furnace, 5-lower annular flue, 10-furnace wall air intake hole;

[0050] Figure 3 FIG. is a cross-sectional view of the upper annular flue of a blast furnace recovery smelting equipment for lead-containing materials in Embodiment 1 of the present invention: In the figure, 1-blast furnace, 6-upper annular flue, 11-furnace wall air return hole; DETAILED DESCRIPTION OF THE INVENTION

[0051] The present invention will be further described below in conjunction with specific implementation cases and attached Figures 1-3 drawings, but the present invention is not limited to these embodiments.

[0052] Embodiment 1

[0053] A certain iron and steel enterprise carried out the transformation of battery recycling on a 230 cubic meter blast furnace.

[0054] As Figures 1-3 shown, a blast furnace recovery smelting device for lead-containing materials includes a blast furnace 1, a powder storage tank 2, a mixer 3, a pulverized coal distributor 4, a lower annular flue 5, an upper annular flue 6, a furnace gas lead recovery system I 12, a furnace gas lead recovery system II 13, a blower I 14, a blower II 15, and a nitrogen sweeper 16;

[0055] The top of the blast furnace 1 is provided with a feed inlet 7, and the bottom furnace wall is provided with a lead discharge port 8; The melting section of the blast furnace 1 is provided with a furnace wall injection feed hole 9, and 8 furnace wall air intake holes 10 are provided at the furnace temperature of 780°C in the transition section. 8 furnace wall air return holes 11 are provided at the furnace temperature of 500°C, 3.5 meters above the furnace wall air intake holes 10;

[0056] The powder storage tank 2 is provided with a gas feeding system; The pulverized coal distributor 4 is connected to a pulverized coal injection gun;

[0057] The furnace gas lead recovery system I 12 is composed of a lead collector I 12.1 and a lead collecting tank I 12.2 arranged at the bottom of the lead collector I 12.1. A discharge pipe I is arranged on the lead collecting tank I 12.2, and a discharge valve I 12.4 is arranged on the discharge pipe I;

[0058] The furnace gas lead recovery system II 13 is composed of a lead collector II 13.1 and a lead collecting tank II 13.2 arranged at the bottom of the lead collector II 13.1. A discharge pipe II is arranged on the lead collecting tank II 13.2, and a discharge valve II 13.4 is arranged on the discharge pipe II;

[0059] The feed inlet 7 of the blast furnace 1 is connected to an external waste battery plate processing system 25 through a pipeline; The top feed inlet of the powder storage tank 2 is connected to an external waste battery waste liquid dry matter crushing system 26 through a pipeline, and the waste battery waste liquid dry matter crushing system 26 is connected to a waste battery waste liquid treatment system 27;

[0060] The bottom discharge port of the powder storage tank 2 is connected to the inlet of the mixer 3 through a pipeline. The outlet of the mixer 3 is directly connected to the pulverized coal distributor 4. The pulverized coal distributor 4 is connected to the pulverized coal injection gun through a branch pipe, and the pulverized coal injection gun is inserted into the furnace wall injection feed hole 9;

[0061] The furnace wall air inlet hole 10 is connected to the lower annular flue 5 through a branch pipe, and the lower annular flue 5 is branched and connected to the smoke inlets of the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13 through a three-way pipe; the smoke outlets of the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13 are merged and connected to the upper annular flue 6 through a three-way pipe, and the upper annular flue 6 is connected to the furnace wall air return hole 11 through a branch pipe;

[0062] The nitrogen purger 16 is connected to the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13 respectively through pipes, and a nitrogen valve I 16.1 is provided on the connecting pipe between the nitrogen purger 16 and the furnace gas lead recovery system I 12; a nitrogen valve II 16.2 is provided on the connecting pipe between the nitrogen purger 16 and the furnace gas lead recovery system II 13;

[0063] The blower I 14 is connected to the furnace gas lead recovery system I 12 through a pipe, and the blower II 15 is connected to the furnace gas lead recovery system II 13 through a pipe;

[0064] Two valves, namely a smoke inlet first valve I 17 and a smoke inlet second valve I 18, are provided on the branch connecting pipe between the lower annular flue 5 and the furnace gas lead recovery system I 12; two valves, namely a smoke inlet first valve II 19 and a smoke inlet second valve II 20, are provided on the branch connecting pipe between the lower annular flue 5 and the furnace gas lead recovery system II 13; two valves, namely a smoke outlet first valve I 21 and a smoke outlet second valve I 22, are provided on the branch connecting pipe between the furnace gas lead recovery system I 12 and the upper annular flue 6; two valves, namely a smoke outlet first valve II 23 and a smoke outlet second valve II 24, are provided on the branch connecting pipe between the furnace gas lead recovery system II 13 and the upper annular flue 6;

[0065] A valve is provided on the connecting branch pipe between the lower annular flue 5 and the furnace wall air inlet hole 10; a valve is provided on the connecting branch pipe between the upper annular flue 6 and the furnace wall air return hole 11;

[0066] A valve is provided on the connecting and merging pipe between the furnace gas lead recovery system I 12 and the furnace gas lead recovery system II 13 and the upper annular flue 6;

[0067] The coal injection distributor 4 is provided with 8 branch pipes connected to 8 coal injection guns, and the 8 coal injection guns are respectively inserted into 8 furnace wall injection feed holes 9;

[0068] The motors of the blower I 14 and the blower II 15 are variable frequency motors.

[0069] A blast furnace recovery smelting method for lead-containing materials, using the above-mentioned blast furnace recovery smelting device for lead-containing materials, the method comprises the following steps:

[0070] Step 1, pretreatment:

[0071] The waste storage battery is disassembled, and the large lead plates are subjected to plate pretreatment in the waste storage battery plate processing system 25. The large lead plates are cut into small pieces convenient for feeding to obtain pretreated plate materials. The waste liquid in the waste storage battery consists of lead sulfate, sulfuric acid and water. The waste liquid is pretreated in the waste storage battery waste liquid processing system 27. The waste liquid is mixed with lime powder to form a mixed solid of calcium sulfate, calcium hydroxide, calcium oxide and lead sulfate. Then the mixed solid is pulverized in the waste storage battery waste liquid dry matter pulverizing system 26, and the pulverizing particle size is ≤80 mesh to obtain pretreated powder.

[0072] Step 2, feeding:

[0073] The pretreated plate materials are added into the blast furnace 1 through the feeding system via the feed inlet 7; the pretreated powder is added into the powder storage tank 2 through a pipeline. The gas conveying system of the powder storage tank 2 conveys the pretreated powder through a pipeline to the mixer 3 for mixing, and then it is sprayed into the coal injection distributor 4 together with the injected fuel. After being distributed by the coal injection distributor 4 to the coal injection lance, it is finally sprayed into the blast furnace 1 through the furnace wall injection feed hole 9.

[0074] Step 3, smelting:

[0075] Normal iron smelting is carried out in the blast furnace 1. The smelting charge is sinter, pellet, porous coke and smelting solvent. The molten iron temperature at the bottom of the blast furnace is 1400~1500°C. In the coal injection tuyere area, that is, the furnace wall injection feed hole 9 area, the temperature is 1800~2300°C, and the furnace top exhaust temperature is 150~250°C. The inside of the furnace is a reducing atmosphere.

[0076] (1) The metallic lead in the plate materials added through the feed inlet 7 starts to melt at 327°C, flows through the charge towards the lower part of the furnace, and sinks to the furnace bottom; at the same time, a small amount of lead vaporizes at high temperature and rises during the downward flow. The lead vapor is adsorbed by the porous coke and sinter in multiple layers during the upward process, or is cooled and solidified on the surface of the charge by the low-temperature charge, and then descends with the charge. After descending, the temperature rises, and the lead is vaporized again. Finally, it reaches equilibrium in different temperature regions. The lead-containing flue gas in the 800~650°C temperature zone in the blast furnace 1 is led out through the furnace wall air inlet hole 10 and enters the lower annular flue 5.

[0077] (2)The lead sulfate in the mixed powder injected into the blast furnace 1 rapidly decomposes into sulfur oxide and lead oxide at temperatures above 1800 °C. Immediately afterwards, the lead oxide becomes gaseous and is reduced to metallic lead by carbon monoxide and carbon. The metallic lead is then vaporized immediately. After the lead vapor rises, it condenses into liquid lead when it encounters the low-temperature burden, and then flows downward and sinks to the bottom of the furnace; the sulfur oxide is reduced to hydrogen sulfide and carbonyl sulfide and discharged out of the furnace with the furnace gas, and is captured and removed in the gas desulfurization section, or absorbed by the hot metal, increasing the sulfur content of the hot metal; the calcium sulfate in the mixed powder enters the furnace slag; the calcium hydroxide in the mixed powder decomposes into water and calcium oxide, and the calcium oxide enters the bottom molten pool with the iron dripping from the softening and melting zone and is captured by the furnace slag to become a slag-making material;

[0078] Step 4, recovery:

[0079] The furnace gas lead recovery system I 12 is used for lead recovery. First, connect the nitrogen sweeper 16 to the high-pressure nitrogen source, open the nitrogen valve I 16.1, and open the blow-off valve I 12.3 to inject nitrogen into the furnace gas lead recovery system I 12 to displace the air with nitrogen; then start the blower I 14; then open the first flue gas outlet valve I 21 and the second flue gas outlet valve I 22, and finally gradually open the first flue gas inlet valve I 17 and the second flue gas inlet valve I 18, and control the amount of flue gas drawn out at 20 - 30% by controlling the inlet flue gas valve; the drawn flue gas enters the furnace gas lead recovery system I 12 through the pipeline to cool down and capture lead, zinc, cadmium, light metal oxides and salts, and the cooled lead liquid, zinc, cadmium, light metal oxides and salts flow into the lead collection tank I 12.2; the unliquefied flue gas in the furnace gas lead recovery system I 12 enters the upper annular flue 6 through the pipeline and is led back to the blast furnace 1 through the furnace wall return air holes 11; the air pressure of the flue gas drawn out at the furnace wall air intake hole 10 after being reduced by the pipeline resistance and the resistance of the furnace gas lead recovery system is greater than the air pressure of the flue gas in the furnace at the furnace wall return air hole 11.

[0080] In the above method, the lead collector I 12.1 adopts plate heat exchange.

[0081] In the above method, the medium for cooling is air cooling, and the air source is provided by the blower I 14.

[0082] In this embodiment, the pretreated plate material is evenly added with the blast furnace burden, and the coke ratio is calculated and adjusted according to the added amount. It is adjusted by increasing the coke ratio by 45 kg per ton of lead; the coke ratio of the burden is first increased by 150 kg of coke per ton of powder, and fine-tuning is performed according to the furnace temperature change during the operation. In this case, the actual increased coke ratio is 120 kg / ton of powder.

[0083] After the equipment in this embodiment runs for 4 - 5 hours, open the discharge valve of the furnace gas lead recovery system I to discharge lead for the first time, and then discharge lead regularly according to the lead collection speed and the volume of the lead collection tank; perform the first lead discharge at the bottom of the blast furnace after the equipment runs for 8 hours, and then discharge lead one to two times a day, which is determined according to the amount of lead-containing materials input for smelting.

[0084] The lead discharge port of the furnace gas lead recovery system I becomes blocked once every two months of operation. The operation of the furnace gas lead recovery system I is stopped and repaired. At the same time, the furnace gas lead recovery system II is started for recovery, without delaying continuous production.

[0085] According to the input-output measurement for two months, the total lead recovery rate of the lead recovered by the upper lead collector and the lead discharged from the lead discharge port at the bottom of the blast furnace is above 99%. The crude lead collected by the deleading equipment contains some zinc and cadmium metals, and the three metals are separated during refining.

[0086] During the four-month operation of the equipment, except for the blockage of the lead discharge port of the furnace gas deleading equipment once, no problems occurred, the operation was normal, and the air permeability of the furnace charge was not affected by the treatment of lead waste. The deleading system discharges a maximum of 5 tons of lead per day. When no lead is discharged, the air permeability of the furnace charge becomes poor, and the air permeability of the furnace charge improves quickly after lead is discharged. No lead component has been found in the blast furnace gas, and there is no change in the lead concentration in the slag.

[0087] During the operation of the blast furnace in this embodiment, the maximum daily dosage of the mixed powder injection is 55 tons, and the maximum amount of plate waste added from the furnace top is 100 tons.

Claims

1. A blast furnace recovery smelting device for lead-containing materials, characterized in that, It includes a blast furnace (1), a powder storage tank (2), a mixer (3), a pulverized coal distributor (4), a lower annular flue (5), an upper annular flue (6), a furnace gas lead recovery system I (12), a furnace gas lead recovery system II (13), a blower I (14), a blower II (15), and a nitrogen sweeper (16); The top of the blast furnace (1) is provided with a feed inlet (7), and the bottom furnace wall is provided with a lead discharge port (8); in the melting section of the blast furnace (1), there is a furnace wall injection feed hole (9), in the transition section at a furnace temperature of 800 - 650 °C, there is a furnace wall air intake hole (10), and in the transition section at a furnace temperature of 600 - 350 °C, there is a furnace wall air return hole (11); The powder storage tank (2) is provided with a gas feeding system; the pulverized coal distributor (4) is connected to a pulverized coal injection gun; The furnace gas lead recovery system I (12) consists of a lead collector I (12.1) and a lead collecting tank I (12.2) arranged at the bottom of the lead collector I (12.1). An exhaust pipe I is arranged at the upper part of the lead collector I (12.1), and an exhaust valve I (12.3) is arranged on the exhaust pipe I; a lead discharge pipe I is arranged on the lead collecting tank I (12.2), and a discharge valve I (12.4) is arranged on the lead discharge pipe I; The furnace gas lead recovery system II (13) consists of a lead collector II (13.1) and a lead collecting tank II (13.2) arranged at the bottom of the lead collector II (13.1). An exhaust pipe II is arranged at the upper part of the lead collector II (13.1), and an exhaust valve II (13.3) is arranged on the exhaust pipe II; a lead discharge pipe II is arranged on the lead collecting tank II (13.2), and a discharge valve II (13.4) is arranged on the lead discharge pipe II; The feed inlet (7) of the blast furnace (1) is connected to an external waste battery plate treatment system (25) through a pipeline; the top feed inlet of the powder storage tank (2) is connected to an external waste battery waste liquid dry matter pulverizing system (26) through a pipeline, and the waste battery waste liquid dry matter pulverizing system (26) is connected to a waste battery waste liquid treatment system (27); The bottom discharge port of the powder storage tank (2) is connected to the inlet of the mixer (3) through a pipeline. The outlet of the mixer (3) is directly connected to the pulverized coal distributor (4). The pulverized coal distributor (4) is connected to the pulverized coal injection gun through a branch pipe, and the pulverized coal injection gun is inserted into the furnace wall injection feed hole (9); the furnace wall air intake hole (10) is connected to the lower annular flue (5) through a branch pipe. The lower annular flue (5) is branched and connected to the smoke inlets of the furnace gas lead recovery system I (12) and the furnace gas lead recovery system II (13) through a three-way pipeline; the smoke outlets of the furnace gas lead recovery system I (12) and the furnace gas lead recovery system II (13) are merged and connected to the upper annular flue (6) through a three-way pipeline, and the upper annular flue (6) is connected to the furnace wall air return hole (11) through a branch pipe; The nitrogen purger (16) is connected to the furnace gas lead recovery system I (12) and the furnace gas lead recovery system II (13) through pipelines respectively. A nitrogen valve I (16.1) is arranged on the connecting pipeline between the nitrogen purger (16) and the furnace gas lead recovery system I (12); A nitrogen valve II (16.2) is arranged on the connecting pipeline between the nitrogen purger (16) and the furnace gas lead recovery system II (13); The blower I (14) is connected to the furnace gas lead recovery system I (12) through a pipeline, and the blower II (15) is connected to the furnace gas lead recovery system II (13) through a pipeline; Two valves, namely a flue gas inlet valve I (17) and a flue gas inlet valve II (18), are arranged on the branch connecting pipeline between the lower annular flue (5) and the furnace gas lead recovery system I (12); Two valves, namely a flue gas inlet valve I (19) and a flue gas inlet valve II (20), are arranged on the branch connecting pipeline between the lower annular flue (5) and the furnace gas lead recovery system II (13); Two valves, namely a flue gas outlet valve I (21) and a flue gas outlet valve II (22), are arranged on the branch connecting pipeline between the furnace gas lead recovery system I (12) and the upper annular flue (6); Two valves, namely a flue gas outlet valve I (23) and a flue gas outlet valve II (24), are arranged on the branch connecting pipeline between the furnace gas lead recovery system II (13) and the upper annular flue (6); A valve is arranged on the combined connecting pipeline between the furnace gas lead recovery system I (12) and the furnace gas lead recovery system II (13) and the upper annular flue (6); The number of the furnace wall air return holes (11) is M, and M≥2; The same number of holes as the furnace wall air return holes (11) are opened on the inner side of the upper annular flue (6).

2. The blast furnace recovery and smelting equipment for lead-containing materials according to claim 1, characterized in that, A valve is arranged on the connecting branch pipe between the lower annular flue (5) and the furnace wall air inlet hole (10); A valve is arranged on the connecting branch pipe between the upper annular flue (6) and the furnace wall air return hole (11).

3. The blast furnace recovery and smelting equipment for lead-containing materials according to claim 1, characterized in that, The number of the furnace wall injection feed holes (9) is N, and N≥2; The number of the pulverized coal injection guns is the same as that of the furnace wall injection feed holes (9); The pulverized coal injection guns are heat-resistant stainless steel pipes.

4. The blast furnace recovery smelting equipment for lead-containing materials according to claim 1, characterized in that, The number of the furnace wall air inlet holes (10) is M, and M≥2; The same number of holes as the furnace wall air inlet holes (10) are opened on the inner side of the lower annular flue (5).

5. The blast furnace recovery and smelting equipment for lead-containing materials according to claim 1, characterized in that, The motors of the blower I (14) and the blower II (15) are variable frequency motors.

6. A blast furnace recovery smelting method for lead-containing materials, using the blast furnace recovery smelting equipment for lead-containing materials according to any one of claims 1 to 5, the method comprising the following steps: Step 1, pretreatment: The waste storage battery is disassembled, and the large lead plates are subjected to plate pretreatment in the waste storage battery plate treatment system (25). The large lead plates are cut into small pieces convenient for feeding to obtain pretreated plate materials. The waste liquid in the waste storage battery is composed of lead sulfate, sulfuric acid and water. The waste liquid is pretreated in the waste storage battery waste liquid treatment system (27). The waste liquid is mixed with lime powder to form a mixed solid of calcium sulfate, calcium hydroxide, calcium oxide and lead sulfate. Then the mixed solid is subjected to crushing treatment in the waste storage battery waste liquid dry matter crushing system (26), and the crushing particle size is ≤80 mesh to obtain pretreated powder. Step 2, feeding: The pretreated plate materials are added into the blast furnace (1) through the feeding port (7) via the feeding system; the pretreated powder is added into the powder storage tank (2) through a pipeline. The gas transmission system of the powder storage tank (2) transports the pretreated powder to the mixer (3) through a pipeline for mixing, and then it is sprayed into the coal injection distributor (4) together with the injected fuel. After being distributed by the coal injection distributor (4) to the coal injection lance, it is finally sprayed into the blast furnace (1) through the furnace wall injection feed hole (9). Step 3, smelting: Normal iron smelting is carried out in the blast furnace (1). The smelting burden is sinter, pellet, porous coke and smelting solvent. The molten iron temperature at the bottom of the blast furnace is 1400~1500°C. In the coal injection tuyere area, that is, the area of the furnace wall injection feed hole (9), the temperature is 1800~2300°C, and the furnace top smoke exhaust temperature is 150~250°C. The atmosphere inside the furnace is a reducing atmosphere. (a) The metallic lead in the plate materials added through the feeding port (7) starts to melt at 327°C, flows through the burden towards the lower part of the furnace, and sinks to the furnace bottom; at the same time, a small amount of lead will vaporize at high temperature and rise during the downward flow. The lead vapor is adsorbed by the porous coke and sinter in multiple layers during the upward process, or is cooled and solidified on the surface of the burden by the low-temperature burden, and then descends with the burden. After descending, the temperature rises, and the lead is vaporized again. Finally, it reaches equilibrium in different temperature regions. The lead-containing flue gas in the 800~650°C temperature zone inside the blast furnace (1) is led out through the furnace wall air intake hole (10) and enters the lower annular flue (5). (b) The lead sulfate in the mixed powder sprayed into the blast furnace (1) rapidly decomposes into sulfur oxide and lead oxide at a temperature above 1800°C. Immediately afterwards, the lead oxide becomes gaseous and is reduced to metallic lead by carbon monoxide and carbon. The metallic lead is immediately vaporized. After the lead vapor rises, it condenses into liquid lead when it encounters the low-temperature burden, and then flows downward and sinks to the furnace bottom; the sulfur oxide is reduced to hydrogen sulfide and carbonyl sulfide and discharged out of the furnace with the furnace gas, and is captured and removed by the gas desulfurization link, or is absorbed by the molten iron to increase the sulfur content of the molten iron; the calcium sulfate in the mixed powder enters the furnace slag; the calcium hydroxide in the mixed powder decomposes into water and calcium oxide. The calcium oxide drips into the bottom molten pool with the molten iron in the softening-melting zone and is captured by the furnace slag to become a slag-making material. Step 4, recovery: Start the furnace gas lead recovery system I (12) or the furnace gas lead recovery system II (13). First, connect the nitrogen purge device (16) to the high-pressure nitrogen source, open the nitrogen valve I (16.1) or the nitrogen valve II (16.2), open the vent valve I (12.3) or the vent valve II (13.3), and inject nitrogen into the furnace gas lead recovery system I (12) or the furnace gas lead recovery system II (13) to replace the air with nitrogen; then start the blower I (14) or the blower II (15); then open the first smoke outlet valve I (21), the second smoke outlet valve I (22), or open the first smoke outlet valve II (23), the second smoke outlet valve II (24), and finally gradually open the first smoke inlet valve I (17), the inlet valve I (18), the second smoke outlet valve I (29), and the second smoke outlet valve II (21). The second smoke inlet valve I (18) or the first smoke inlet valve II (19) and the second smoke inlet valve II (20) are gradually opened, and the smoke inlet valve is controlled to control the smoke extraction volume at 20-30%; the extracted smoke enters the furnace gas lead recovery system I (12) or the furnace gas lead recovery system II (13) through a pipeline, and is cooled to capture lead, zinc, cadmium, light metal oxides and salts. The cooled lead liquid, zinc, cadmium, light metal oxides and salts flow into the lead collecting tank I (12.2) or the lead collecting tank II (13.2); the unliquefied smoke in the furnace gas lead recovery system I (12) or the furnace gas lead recovery system II (13) enters the upper annular flue (6) through a pipeline, and is introduced back to the blast furnace (1) through the furnace wall return air hole (11).

7. A blast furnace recovery smelting method for lead-containing materials according to claim 6, characterized in that, The pressure of the flue gas drawn out from the furnace wall air intake hole (10) after being reduced by the pipe resistance and the furnace gas lead recovery system resistance is greater than the flue gas pressure in the furnace at the furnace wall air return hole (11).

8. A blast furnace recovery smelting method for lead-containing materials according to claim 6, characterized in that, The furnace gas lead recovery system I (12) and the furnace gas lead recovery system II (13) are cooled by tubular or plate heat exchange; the cooling medium of the furnace gas lead recovery system I (12) and the furnace gas lead recovery system II (13) is air cooling, and the air source is provided by the blower I (14) or the blower II (15).

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