JP6896011B2 - Method of recovering iron and zinc from electric furnace dust and its equipment - Google Patents

Description

INDUSTRIAL APPLICABILITY According to the present invention, iron (reduced iron) is produced from electric furnace dust (dust generated in the electric furnace steelmaking process) containing iron oxide and zinc oxide, and iron (reduced iron) is contained in the gas (reduced treatment gas) generated in the reduction treatment. It relates to a method and an apparatus for recovering iron and zinc from electric furnace dust, which recovers the contained metallic zinc.

Due to the soaring price of zinc in recent years, effective utilization of zinc has been required, and recovery from iron-making dust containing a large amount of zinc has been attracting attention. The amount of steelmaking dust, especially electric furnace dust generated in the electric furnace steelmaking process, is about 1.8% of the crude steel production in the electric furnace, and the amount of electric furnace dust generated in Japan was about 520,000 tons in 1999. It is estimated to be about 440,000 tons in 2013.

Normally, in the electric furnace (electric furnace) steelmaking process, iron scrap is used as a raw material, and a large amount of galvanized steel sheet scrap is input. Therefore, the electric furnace dust contains about 25% zinc on average. Various efforts have been made to recover this zinc. In 2013, about 80% of the generated amount was intermediately treated in the zinc recovery industry, and the remaining about 20% was landfilled in managed landfills and closed landfills after detoxification such as chemical injection treatment. There is.

As a method for recovering metallic zinc from electric furnace dust, a method combining the Waelz method and the ISP (Imperial Smelting Process) method has been proposed (Non-Patent Documents 1 and 2). For example, Non-Patent Document 1 describes a method for producing crude zinc oxide (ZnO), which is a raw material for zinc, from steelmaking smoke ash by the Waelz process. Further, Non-Patent Document 2 describes a method in which crude zinc oxide (ZnO) recovered by the Waelz process is finally treated by the ISP method and recovered as metallic zinc. The obtained crude zinc oxide (ZnO) is recovered as zinc by the ISP method, and is commercialized as distilled zinc having a zinc purity of 98.5% or more. For reference, the JIS and ISO standards for distilled zinc are shown here. In JIS H 2107 and ISO 752: 2004, Zinc ingots (MOD), the chemical composition of one type of distilled zinc ingot is Zn: 98.5% or more, Pb: 1.3% or less, Cd: 0.2% or less, Fe: It is set to 0.025% or less.

The zinc grade of crude zinc oxide recovered by the Waelz process is about 60%. Therefore, the dezincination rate (zinc recovery rate) from the electric furnace dust is only about 60% to 70%, and the remaining 30 to 40% of zinc is contained in the clinker and cannot be recovered as zinc.
In addition, recently, there has been an example of reducing electric furnace dust by the rotary hearth method (RHF method). Since the RHF method treats steel dust with granulated briquettes, the recovery rate is slightly higher than that of the Waelz method.
Further, the ISP method not only requires large-scale equipment such as a sintering machine and a hot air furnace in addition to the blast furnace, but also has an economic problem that expensive coke breeze must be used.

Instead of these methods, we focused on the reduction treatment gas containing metallic zinc vapor generated when reducing iron is produced from electric furnace dust containing iron oxide and zinc oxide, and from the viewpoint of process and energy efficiency. Also, a method for producing reduced iron and recovering zinc, which can efficiently recover zinc, and an apparatus therefor have been proposed (Patent Document 1).

In Patent Document 1, electric furnace dust, carbonaceous material, binder and water are mixed and molded to produce a carbon-containing molded product, and the carbon-containing molded product is heated, dried, and further heated in a closed space for oxidation. A method is disclosed in which iron is reduced to reduced iron and recovered, while zinc is recovered from a reduction treatment gas generated during the reduction treatment and containing zinc.

Japanese Patent No. 5881886

Hiroshi Sugimoto, Hiroshi Takizawa, Hiroshi Ueda "Steelmaking Smoke and Ash Treatment at Sotetsu Metal Co., Ltd." Journalof MMIJ Vol. 123 (2007) No. 12 205th and 206th Nishiyama Memorial Technical Lecture "Slag and Dust Utilization and New Development" June 2011, p. 160

According to the method described in Patent Document 1, metallic zinc can be efficiently recovered from electric furnace dust from the viewpoint of process and energy efficiency. On the other hand, the scarcity of zinc raw materials is increasing, and the price of zinc raw materials is soaring. Therefore, further efficiency of zinc recovery is required. Furthermore, it is desired that the recovered zinc does not contain harmful substances and is recovered as recyclable zinc as a normal zinc raw material.

That is, recovery as high-grade zinc of the first class of distilled zinc bullion is required. Here, one type of distilled zinc bullion is used in JIS H 2107 and ISO 752: 2004, Zinc ingots (MOD).
Zn: 98.5% or more,
Pb: 1.3% or less,
Cd: 0.2% or less,
Fe: It is set to 0.025% or less.

Therefore, the present invention efficiently uses a reduction treatment gas containing metallic zinc vapor generated when reducing iron is produced from electric furnace dust containing iron oxide and zinc oxide to achieve high quality in the JIS distilled zinc base metal class 1. The challenge is to recover zinc in a stable manner.

The present inventors have found the following matters as a result of repeated diligent studies based on the process described in Patent Document 1 in order to solve the above-mentioned problems.

(A)
In the process of cooling the reduction treatment gas containing metallic zinc vapor, if CO2 is present in the reduction treatment gas, the metallic zinc vapor is oxidized by CO2 to become crude zinc oxide (ZnO), and the metallic zinc cannot be recovered. There is. This is because the lower the CO / CO2 ratio, the higher the equilibrium temperature at which zinc can exist as a metal vapor.

Approximately 20% of CO2 is contained in the reduction treatment gas of the charcoal-containing molding by the average electric furnace dust. It is known that if the CO2 concentration in the reduction treatment gas is reduced to 3% or less, the oxidation of metallic zinc vapor is suppressed and metallic zinc can be efficiently recovered. According to the research results of the present inventors, if the CO2 concentration in the reduction treatment gas is 3% or less, the metallic zinc recovery rate (the amount of recovered zinc relative to the amount of zinc contained in the electric furnace dust) can be secured at 90% or more. I know it.

Therefore, an effort to reduce the CO2 concentration in the reduction treatment gas by reforming CO2 into CO (hereinafter referred to as CO2 reforming in the present specification, and performing the treatment is referred to as CO2 reforming treatment). Has been made. For example, Patent Document 1 proposes that CO2 can be reformed into CO (CO2 + C → 2CO) by charging a powdered charcoal material into an externally heated rotary kiln, stirring the mixture in the rotary kiln, and bringing it into contact with CO2 gas. There is.

As a result of diligent studies in order to improve the efficiency of this CO2 reforming treatment, the present inventors installed a heat exchange device for the reduction treatment gas between the reduction treatment step and the zinc recovery step, and heated the temperature to 1050 ° C. or higher. It has been found that CO2 can be reformed into CO by arranging the carbon dioxide pellets in the apparatus and bringing the reduction treatment gas into contact with the carbon pellets. By making the coal material into pellets, the contact area with the reduction treatment gas can be increased, and by further heating the reduction treatment gas to a high temperature (1050 ° C. or higher), CO2 reforming can proceed. Is. As the carbonaceous material, for example, artificial graphite or the like is preferable.

(B)
Furthermore, it has been found that as a method for advancing CO2 reforming, it is preferable to pulverize the charcoal material charged in the external heat rotary kiln. In Patent Document 1, powdered coke is charged with powdered coke having a particle size of 1 mm or less for CO2 modification, but by further pulverizing (for example, having a particle size of 1 μm or less), contact with a reduction treatment gas It was found that the area increased and CO2 reforming proceeded. As the pulverized coal material, for example, carbon black may be applied. This is because carbon black has a particle size of about 500 nm (0.5 μm).

(C)
Next, when an iron and zinc recovery test from electric furnace dust was carried out based on the method described in Patent Document 1, although a high zinc recovery rate of about 90% was obtained, the recovered zinc was analyzed. However, Zn: 96.2%, Pb: 3.7%, Cd: 0.03%, and the lead (Pb) of one type of distilled zinc bullion specified in JIS H 2107: 1.3% or less is satisfied. It turns out that it may not be. This is often affected by the quality of scrap and the like input into the electric furnace, and it is difficult to control the components of scrap as an input raw material. Therefore, there is a need for a method for efficiently deleting Pb regardless of the electric furnace dust.

As a result of diligent studies, the present inventors have found a means for separating lead from the reduction-treated gas by heating the reduction-treated gas to 1000 ° C. or higher, utilizing the difference in boiling points between lead and zinc. This is because lead (Pb) has a melting point of 327 ° C and a boiling point of 1749 ° C. On the other hand, since zinc (Zn) has a melting point of 420 ° C. and a boiling point of 907 ° C., by heating the reduction treatment gas to 1000 ° C. or higher, lead (Pb) contained in the reduction treatment gas is condensed and a fine granular liquid. It was found that the concentration of lead in the recovered metallic zinc can be reduced to 1.3% or less by separating lead from the reduction treatment gas by utilizing the fact that it becomes droplets.

Specifically, as a lead (Pb) aggregator (lead removing device), silicon carbide (SiC) pellets heated to 1050 ° C. or higher are filled in the device, and a reduction treatment gas is passed there to exchange heat. Can agglomerate and separate Pb. Since SiC has low reactivity with metal and high thermal conductivity, it is suitable for pellets for agglutination of lead that also serves as heat exchange.

(D)
On the other hand, at present, the number of electric furnaces equipped with iron scrap preheating equipment is increasing with the progress of electric furnace steelmaking technology. It was found that in the electric furnace dust generated in an electric furnace equipped with an iron scrap preheating device, zinc is concentrated by contact with the iron scrap filled in the iron scrap preheating device, and the iron content is reduced. Even if a charcoal material and a binder are added to the electric furnace dust with a reduced iron content to form a charcoal-containing briquette, the strength of the reduced iron (DRI) does not appear, and in some cases, if the charcoal-containing briquette becomes DRI. It was found that the zinc vapor could not be recovered as zinc vapor from the charcoal-containing briquette, and the zinc recovery efficiency was lowered.

Therefore, as a result of diligent studies on countermeasures, if iron oxide is separately added to the electric furnace dust and the Fe content of the coal-containing briquette is at least 15% or more, preferably 20% or more, high-strength DRI can be obtained and zinc recovery efficiency can be obtained. I found that it also goes up. The present invention has been made based on the above findings, and the gist thereof is as follows.

(1)
A charcoal-containing briquette manufacturing step for producing a charcoal-containing briquette by mixing and molding electric furnace dust containing iron oxide and zinc oxide, carbonaceous material, binder, and water.
A preheating step of heating and drying the charcoal-containing molding, and
A reduction treatment step in which the charcoal-containing briquette that has been dried and heated in the preheating step is further heated in a closed space to reduce iron oxide to reduced iron.
A lead removal step for recovering and removing lead from the reduction treatment gas generated in the reduction treatment step,
A method for recovering iron and zinc from electric furnace dust, which comprises a zinc recovery step for recovering zinc from the reduction treatment gas that has undergone the lead removal step.
(2)
The iron and zinc from the electric furnace dust according to (1), wherein the lead removal step brings the silicon carbide ceramic balls heated to a temperature equal to or higher than the temperature of the reduction treatment gas into contact with the reduction treatment gas. How to collect.
(3)
From the electric furnace dust according to (1) or (2), there is a CO2 reforming step for reforming CO2 in the reduction treatment gas into CO between the lead removal step and the zinc recovery step. How to recover iron and zinc.
(4)
The iron and iron from the electric furnace dust according to (3), wherein in the CO2 reforming treatment step, the pellet-shaped carbonaceous material heated to a temperature equal to or higher than the temperature of the reduction treatment gas is brought into contact with the reduction treatment gas. How to recover zinc.
(5)
The iron from the electric furnace dust according to any one of (1) to (4), wherein in the reduction treatment step, a fine powdery coal material having an average particle size of 10 μm or less is charged into the closed space. And how to recover zinc.
(6)
In the carbon-containing briquette manufacturing step, iron oxide is further mixed to make the Fe content in the briquette-containing mold 15% by weight or more, according to any one of (1) to (5). The method for recovering iron and zinc from the described electric furnace dust.
(7)
Recovery of iron and zinc from the electric furnace dust according to any one of (1) to (6), wherein the heating temperature of the coal-containing molded product in the preheating step is 770 ° C. or higher and 907 ° C. or lower. Method.
(8)
The iron and zinc from the electric furnace dust according to any one of (1) to (7), wherein the heating temperature of the charcoal-containing molded product in the reduction treatment step is 980 ° C. or higher and 1150 ° C. or lower. Collection method.
(9)
The iron from the electric furnace dust and the iron from the electric furnace dust according to any one of (1) to (8), wherein the preheating step is treated with an internal heating type rotary kiln, and the reduction treatment step is treated with an external heating type rotary kiln. How to recover zinc.
(10)
In any of (1) to (9), the zinc recovery step is characterized in that the silicon carbide tube whose inside is cooled is brought into contact with the reduction treatment gas, and then the silicon carbide pellets are brought into contact with the reduction treatment gas. The method for recovering iron and zinc from electric furnace dust according to one of the above.
(11)
In a device that recovers iron and zinc from electric furnace dust containing iron oxide and zinc oxide
A means for producing a charcoal-containing briquette, which is produced by mixing and molding electric furnace dust containing iron oxide and zinc oxide, a carbonaceous material, a binder, and water.
A preheating means for heating and drying the charcoal-containing briquette, and
A reduction treatment means for producing reduced iron by further heating the charcoal-containing briquette that has been dried and heated by the preheating means.
Lead removing means for recovering and removing lead from the reduction treatment gas generated by the reduction treatment means,
An apparatus for recovering iron and zinc from electric furnace dust, which comprises a zinc recovering means for recovering zinc from a reduction treatment gas that has passed through the lead removing means.
(12)
The lead removing means is characterized by having a lead removing device in which a silicon carbide ceramic ball heated to a temperature equal to or higher than the temperature of the reducing treatment gas is brought into contact with the reduction treatment gas to aggregate lead and separate and recover it. (11) The recovery device for iron and zinc from the electric furnace dust.
(13)
From the electric furnace dust according to (11) or (12), the CO2 reforming means for reforming CO2 in the reduction treatment gas to CO is provided between the lead removing means and the zinc recovering means. Iron and zinc recovery equipment.
(14)
The CO2 reforming means has a CO2 reforming device that reforms CO2 into CO by bringing the pellet-shaped carbonaceous material heated to a temperature equal to or higher than the temperature of the reducing gas into contact with the reducing gas. The iron and zinc recovery device from the electric furnace dust according to (13).
(15)
The recovery of iron and zinc from the electric furnace dust according to any one of (11) to (14), wherein the reduction treatment means includes a fine powdered coal material charging means having an average particle size of 10 μm or less. apparatus.
(16)
The iron and zinc from the electric furnace dust according to any one of (11) to (15), wherein the preheating means is an internal heat type rotary kiln and the reduction treatment means is an external heat type rotary kiln. Recovery device.
(17)
Any of (11) to (16), wherein the zinc recovery means has a reduction treatment gas reusing means for using the reduction treatment gas after recovering zinc as a heating fuel for the reduction treatment means. The iron and zinc recovery device from the electric furnace dust according to one.
(18)
One of (11) to (17), wherein the zinc recovery means has a zinc condenser in which the reduction treatment gas is cooled by a tube made of silicon carbide whose inside is cooled to condense zinc and separate and recover it. The iron and zinc recovery device from the electric furnace dust according to one.
(19)
The iron and zinc from the electric furnace dust according to (18), wherein the silicon carbide pellets are arranged on the downstream side of the silicon carbide tube in the zinc condenser, and zinc is further condensed and separated and recovered. Recovery device.

According to the present invention, not only high-grade reduced iron is produced from electric furnace dust having iron oxide and zinc oxide, but also high-grade zinc of JIS distilled zinc base metal class 1 is efficiently and energy-efficient. Can be recovered. That is, the following effects can be obtained.

FIG. 1 is a conceptual diagram of a method / equipment for recovering iron and zinc from electric furnace dust according to the present invention. FIG. 2 is a conceptual diagram of a carbon-containing molded body manufacturing step according to the present invention. FIG. 3 is a conceptual diagram of the test apparatus according to the present invention. FIG. 3A is a conceptual diagram showing an embodiment of the first embodiment. FIG. 3B is a conceptual diagram showing an embodiment of the second embodiment. FIG. 3C is a conceptual diagram showing an embodiment of the third embodiment. It is a conceptual diagram of the lead removing apparatus which concerns on this invention. It is a conceptual diagram of the zinc recovery apparatus which concerns on this invention.

Hereinafter, the details of the present invention will be described by taking the conceptual diagram shown in FIG. 1 as an example. The embodiments shown below are examples, and the embodiments of the present invention are not limited thereto.

[Charcoal-containing molded body manufacturing step]
In the step of producing a charcoal-containing molded product, the electric furnace dust 10 containing iron oxide and zinc oxide is mixed with a carbon material (charcoal material) as a reducing agent, a binder material having a role of connecting particles, and water, and molded. To produce a charcoal-containing molded product (Fig. 2).

As a raw material for reduced iron in the present invention, electric furnace dust, which is dust generated in an electric furnace type steelmaking process of a steel mill or the like, is used. Electric furnace dust has a high iron oxide content and there is a strong need for reuse.

Moreover, since scrap is used in the electric furnace, the electric furnace dust contains not only iron oxide but also zinc oxide in a large amount. The present invention may be of any type as long as it is an electric furnace dust containing not only iron oxide but also zinc oxide.

Since these electric furnace dusts are fine powders, they are difficult to handle. However, since it is a fine powder, its specific surface area (surface area per unit weight) becomes wide, the reduction reaction easily proceeds, and the dezincification property also improves.

Therefore, the present inventors have conceived to use the electric furnace dust as a fine powder in order to improve the reduction reactivity while keeping the specific surface area of the electric furnace dust particles large, and have diligently studied the method of using the fine powder. As a result, if the average particle size of the electric furnace dust (D50: the particle size corresponding to the cumulative frequency of 50% from the fine particles in the cumulative particle size distribution) is 10.0 μm or less, a practically sufficient reduction reactivity can be obtained. I found that I could do it.

The existing electric furnace dust is collected by a bag filter. The recovered electric furnace dust may be converted into pseudo particles (pellets) to prevent dust generation. Since the pellet diameter is about 8 mm, it is preferable to pulverize the pellets with a ball mill or the like to reduce the particle size to 10.0 μm or less before forming a charcoal-containing molded product.

On the other hand, with the progress of electric furnace steelmaking technology, the number of electric furnaces equipped with an iron scrap preheating device is increasing. It was found that in the electric furnace dust generated in an electric furnace equipped with an iron scrap preheating device, zinc is concentrated by contact with the iron scrap filled in the iron scrap preheating device, and the iron content is reduced. Even if a charcoal material and a binder are added to the electric furnace dust with a reduced iron content to form a charcoal-containing briquette, the strength of the reduced iron (DRI) does not appear, and in some cases, if the charcoal-containing briquette becomes DRI. The iron in the coal-containing briquette cannot be recovered as steam, and the zinc recovery efficiency is lowered. Therefore, iron oxide may be further added to increase the T-Fe concentration (Total-Fe (total Fe) concentration) of the charcoal-containing molded product to at least 15% by mass or more, preferably 20% by mass or more. As a result, a high-strength DRI can be obtained, and the zinc recovery efficiency can be increased.

In addition to the electric furnace dust, the crude zinc oxide recovered in Weltkiln and the oxidized roasted zinc concentrate also contain iron oxide and zinc oxide, and thus are the target raw materials of the present invention. However, if the iron concentration is low in either case, iron oxide for iron supply is added to increase the T-Fe concentration of the charcoal-containing briquette to 15% by mass or more, preferably 20% by mass or more after reduction. DRI strength can be ensured.

The carbonaceous material is a reducing agent for reducing iron oxide to metallic iron, and is added so that the C equivalent is in the range of 0.7 to 1.3. Here, the C equivalent is a ratio to the theoretical carbon amount based on the following formulas 1 and 2. If the total amount of iron oxide in the electric furnace dust is Fe ₂ O ₃ and the total amount of zinc oxide is ZnO, 3 mol of C (carbon) is required to reduce 1 mol of _{Fe 2} O _{3 to obtain 2 mol of metallic iron.} ) Is required, and 1 mol of C is required to reduce 1 mol of ZnO to obtain 1 mol of zinc. This is the theoretical carbon content. It means that C is added 0.7 to 1.3 times the theoretical carbon content.

Fe ₂ O ₃ + 3C + ΔH (1) → 2Fe + 3CO ・ ・ ・ (Equation 1)
ZnO + C + ΔH (2) → Zn + CO ・ ・ ・ (Equation 2)
The chemical reactions of the above formulas 1 and 2 are both endothermic reactions, and the amount of heat absorption is ΔH (1) = 966 × 10 ³ kcal / t (Fe), respectively.
ΔH (2) = 882 × 10 ³ kcal / t (Zn).
In order to cause these reactions, it is necessary to apply an amount of heat corresponding to the above amount of heat absorption from the outside.

The binder is, for example, cornstarch. Add so that the crushing strength of the charcoal-containing molded product after drying is 2 MPa or more. This is because if the crushing strength of the molded body after drying is less than 2 MPa, the molded body is partially destroyed by handling and rolling in the rotary kiln.

Water can be added as necessary to adjust the water content of the molded body to be around 10%.

These raw materials are put into a mixer and the raw materials are mixed. As the mixer, a rotary batch type is usually used, but the method is not particularly limited as long as the raw materials can be mixed uniformly. The mixed raw material passes through a relay tank and is molded by an extrusion molding machine, a roll molding machine, or the like. The molded mixed raw material is referred to as a charcoal-containing molded body 20.

For example, water is added to electric furnace dust, charcoal material, and a binder, and the mixture is kneaded and granulated. At this time, if the kneaded material is pushed into a die having holes and molded by applying pressure, a high-strength charcoal-containing molded body can be obtained. By adjusting the properties of the electric furnace dust and the carbonaceous material, the amount of water to be added, the pore diameter, the depth, the pushing pressure, etc. of the die, the production conditions of the coal-containing molded body suitable for the raw material powder can be obtained.

The shape of the charcoal-containing briquette is generally spherical or columnar, but the shape is not limited to a cube, a rectangular parallelepiped, a triangular prism, and a briquette. The size of the charcoal-containing molded body may be a spherical shape having a diameter of about 10 to 30 mm or a columnar shape having a diameter of 10 to 30 mm and a length of 10 to 30 mm in consideration of the subsequent reduction treatment. If the diameter or length is smaller than 10 mm, the reduced iron after the reduction treatment becomes small. If it is smaller than 10 mm, the pulverization rate due to rolling in the rotary kiln increases as the surface area increases, and in addition, it shrinks by about 40% with reduction, so that the size of reduced iron (DRI) is small. It becomes too much and causes handling problems during recycling. Further, if it is larger than 30 mm, the pulverization rate decreases, but the reduction time increases, so that if the residence time in the reduction furnace is constant, the metallization rate and the dezincification rate decrease. This is because The diameter and length are preferably 10 to 30 mm, more preferably 15 to 25 mm.

By using the molded body, the reduced iron as a product can also be obtained as a molded body although it shrinks, and can be used as it is as a raw material for an electric furnace. An apparatus required for a series of steps from cutting out a raw material to selecting a carbon-containing molded body having a predetermined size is referred to as a carbon-containing molded body manufacturing device 11. The mode of each individual device forming the charcoal-containing briquette manufacturing device 11 is not particularly limited as long as it can achieve the above-mentioned functions.

[Charcoal-containing briquette manufacturing means]
As described above, the raw materials of the charcoal material, the binder, and the water, including the electric furnace dust 10, are put into the mixer, and the raw materials are mixed and molded (FIG. 2). A series of devices for discharging the briquette-containing molded product 20 which has been mixed, molded, and molded from the cut-out of each raw material is a carbon-containing molded body manufacturing means (carbon-containing molding single manufacturing device) 11.

The mode of cutting out each raw material is not limited as long as it can be cut out by measurement. For example, a vibration feeder or the like is applied.

As the mixer, a rotary batch type is usually used, but the method is not particularly limited as long as the raw materials can be mixed uniformly. The mixed raw material passes through a relay tank and is molded by an extrusion molding machine, a roll molding machine, or the like.

The molding machine may be in any mode as long as it can be molded into a predetermined shape. As described above, the shape of the charcoal-containing briquette is generally spherical or columnar, but the shape is not limited to a cube, a rectangular parallelepiped, a triangular prism, and a briquette. For example, when a kneaded material is pushed into a die having holes and molded by applying pressure, a high-strength charcoal-containing molded body can be obtained. By adjusting the properties of the electric furnace dust and the carbonaceous material, the amount of water to be added, the pore diameter, the depth, the pushing pressure, etc. of the die, the production conditions of the coal-containing molded body suitable for the raw material powder can be obtained.

The mode of the charcoal-containing briquette dispensing device is not particularly limited. However, it is better to avoid something that destroys the charcoal-containing molded body.

[Preheating step]
The preheating step in the present invention is to evaporate the water contained in the charcoal-containing molded body by heating the charcoal-containing molded body 20 produced in the charcoal-containing molded body manufacturing step 11, and volatilize chlorine (Cl) and the like. It refers to a series of steps until the charcoal-containing briquette from which the sex impurities have been removed is discharged. Since the charcoal-containing briquette is made from electric furnace dust, various impurities such as chlorine are mixed in it. In particular, volatile impurities such as chlorine are mixed in the reduction treatment gas after the reduction treatment and cause equipment corrosion, so they are removed before the reduction treatment. In addition, when water is also mixed in the reduction treatment gas, it promotes the reoxidation of vaporized zinc, so this is removed.

Zinc has a boiling point of 907 ° C. For this reason, the heating temperature of the coal-containing molded product in the preheating step is preferably 907 ° C. or lower. Above 907 ° C, there is a high possibility that zinc will evaporate. When zinc evaporates, it is mixed in the exhaust gas, reoxidized, recovered as zinc oxide (crude zinc oxide), and reused. This is not appropriate from the viewpoint of processing efficiency. The heating temperature of the charcoal-containing molded product is preferably 890 ° C. or lower. Considering the temperature variation in actual operation, it is better to set the temperature below 880 ° C.

If the lower limit of the heating temperature is too low, volatile impurities (chlorine (Cl) and cadmium (Cd)) cannot be removed. In ordinary electric furnace dust, 10% of zinc is present as zinc chloride (ZnCl2). In addition, although it is a trace amount, cadmium is contained as CdO, which is reduced during heating and volatilizes as cadmium. Since zinc chloride has a boiling point of 756 ° C and cadmium has a boiling point of 767 ° C, the preheating temperature should be 770 ° C or higher. This is because if the temperature is lower than 770 ° C., zinc chloride and cadmium are more likely to be carried into the next reduction treatment step. Considering the temperature variation in the coal-containing molding body, the heating temperature of the coal-containing molding in the preheating step is preferably 780 ° C. or higher, more preferably 790 ° C. or higher, and preferably 800 ° C. or higher.
In this way, the charcoal-containing molded product 30 from which volatile impurities have been removed, heated and dried is transferred to the next reduction treatment step.

[Preheating means]
Since the purpose of the preheating step is to preheat and dry the coal-containing molded body 20 for removing volatile impurities and water, the atmosphere is not particularly limited. Therefore, any mode can be used as long as it is a means capable of heating the charcoal-containing molded body 20. However, since the volatilized zinc chloride is cooled, aggregated and recovered, and used again as a raw material, a structure that does not dissipate the generated gas to the atmosphere is desirable. Further, since it is necessary to avoid mixing of oxygen (atmosphere) when transferring to the reduction treatment step of the next step, the treatment in a closed space is preferable. From this point of view, it is preferable to apply an internally heated rotary kiln as the preheating means 22. Since the internally heated rotary kiln is also applied to the Waelz process, it has a proven track record in heating pellet-shaped electric furnace dust such as coal-containing briquette. In the present invention, preheating the coal-containing molded body using an internally heated rotary kiln will be described as an example.

In the case of reduction treatment with an internally heated rotary kiln represented by the Welts method, the vein stone components (SiO2 and CaO) in the raw material are between Fe ₂ O ₃ which is iron oxide and Fe O which is a reduction intermediate thereof. Therefore, it is easy to form a low melting point substance as shown below.
Fe ₂ O ₃・ CaO: Melting point 1206 ℃
FeO ・ SiO ₂ : Melting point 1180 ℃
FeO / CaO: Melting point 1105 ° C

If the content of the vein stone component is high, the raw material temperature in the firing zone is too high, the temperature of the combustion flame (burner frame) is too high, the shape of the combustion flame (burner frame) is too wide, and the inner wall surface of the rotary kiln is covered. It causes the formation of deposits on the inner wall of the rotary kiln, such as when licking. This deposit is called a dam ring because it forms a ring. The dam ring hinders the movement of the object to be treated (raw material) in the rotary kiln, and a large amount of the dam ring may continuously fall off, which is not preferable from the viewpoint of stable operation. However, as described above, the internally heated rotary kiln used in the preheating step heats only up to about 900 ° C., so that a dam ring is not formed.
Further, since the internally heated rotary kiln sucks and discharges the gas in the kiln from the upstream side thereof, the exhaust gas containing volatile impurities and water can be quickly discharged to the outside of the kiln.

The charcoal-containing briquette 30 preheated and dried by the internally heated rotary kiln 22 is discharged from the kiln and transferred to the reduction treatment apparatus in the next step. It is preferable that the discharge device 23 from the internal heat type rotary kiln is considered as one with the charging device 31 to the reduction processing equipment. As will be described later, in the reduction treatment step, since it is necessary to avoid mixing oxygen in the atmosphere as much as possible, both the discharge device 23 from the preheating means (preheating device) and the charging device 31 for the reduction treatment shut off the atmosphere. It is preferable to have a function.

[Reduction processing step]
The reduction treatment step in the present invention means that the carbon-containing molded body 30 preheated and dried in the preheating step is placed in a closed space and heated to reduce iron oxide and zinc oxide in the coal-containing molded body. , Iron and zinc (steam). If air (especially oxygen) is mixed in during the reduction treatment, the reduced iron and zinc will be reoxidized, so it is important to treat in a closed closed space that blocks the mixing of air.

Since the coal-containing briquette mixes the electric furnace dust as fine powder with the carbonaceous material, the specific surface area of the electric furnace dust is wide, the reactivity with the carbonaceous material as a reducing agent can be enhanced, and the reduction treatment temperature can be lowered. it can.

The present inventors have confirmed that if the briquette-containing molded product according to the present invention is heated to about 980 ° C. to 1150 ° C., the reduction reaction proceeds to the extent that there is no practical problem. From the results of the experiment (Table 5), in order to reduce iron oxide by C (carbon) itself, a temperature of 980 ° C. or higher is practically required. Therefore, the lower limit of the reduction treatment temperature is ideally 980 ° C. However, the reduction treatment temperature is preferably 1050 ° C. or higher because factors such as the contact state between the fine iron oxide and carbon in the briquette-containing molding body also affect it.

The upper limit temperature of the reduction treatment depends on the heat resistance of the equipment. For example, in the case of an externally heated rotary kiln, since it is generally made of heat-resistant cast steel, the upper limit temperature for its use is 1200 ° C. Considering the durability of the equipment, the upper limit temperature for use may be set to 1150 ° C. The upper limit is preferably 1130 ° C, more preferably 1100 ° C. Since the reduction treatment proceeds at about 1100 ° C., the temperature can be lowered as compared with 1250 ° C. in the conventional rotary hearth type reduction method (RHF) and 1200 ° C. in the Waelz method. Naturally, if the heat resistance of the equipment is increased, the reduction treatment temperature can be increased.

The GROSS metallization rate was adopted as the quality index of the reduced iron, and the GROSS metallization rate of 60% or more of the RHF method was used as the acceptance criterion. Details will be described in Examples described later.

Further, as can be seen from Equation 1, the gas generated by the reduction treatment of iron oxide is CO (carbon monoxide) gas. The gases generated by the reduction treatment of zinc oxide are zinc vapor (referred to as Zn (gas) for convenience) and CO (Equation 3). Some CO gases _{also become CO 2} (carbon dioxide).
ZnO + C → Zn (gas) + CO ・ ・ ・ (Equation 3)

As shown in Tables 1 and 9, the electric furnace dust also contains lead in the form of lead oxide, although it is a small amount, and at the same time as the reduction of iron oxide and zinc oxide in the carbon-containing molded body by the reduction treatment, Lead oxide is also reduced to metallic lead. As shown in Table 3, the dezincification rate was 98.3% and the lead removal rate was 92.3% in the reduction treatment at 1050 ° C. for 30 minutes, and the lead removal rate was not low. Since the melting points and boiling points of lead are 327 ° C and 1749 ° C, respectively, the reduced lead exists as a liquid at 1050 ° C. Although the vapor pressure of lead is not high, Zn evaporates to the outside of the briquette-containing molding by being pulled by the ejector effect of evaporating at 4 atm. However, since it can exist only in a liquid at 1050 ° C., it condenses into fine droplets. In addition, a small amount of alkali metal salts (NaCl, KCl) are also contained in the electric furnace dust, and the dealkalilation rate is about 70 to 80%. Since the melting points and boiling points are 800 ° C. and 1413 ° C., and 770 ° C. and 1420 ° C., respectively, the alkali metal salt evaporates to the outside of the carbon-containing molded body in the reduction treatment gas at 1050 ° C. and exists as fine droplets. ing.

From the above, the gas generated in the reduction treatment step in the present invention (reduction treatment gas 50) is mainly CO _{gas, contains vapor zinc and CO 2} gas, and also contains a small amount of lead and a small amount of alkali metal salt. Contains fine droplets. Therefore, in order to recover high-grade zinc of JIS distilled zinc bullion class 1, it is important to remove lead so that it is below the standard value.
Furthermore, it is desirable to remove alkali metal salts as much as possible in order to prevent clogging of the ceramic ball packing layer in the zinc recovery step.

In this way, in the reduction treatment step, the volatile components can be separated from the briquette-containing molded product, and the reduced iron 40 having a high metallization rate can be recovered as a solid, while the reduction treatment gas containing zinc vapor can be recovered. 50 can be recovered.

[Reduction processing means]
In the reduction treatment step, the reduction treatment must be performed by heating in a closed space in which the atmosphere (particularly oxygen) is blocked. The mode is not particularly limited as long as it is a means capable of embodying this restriction. Currently, an externally heated rotary kiln 32 can be applied as a means capable of embodying this constraint.

As described above, the inventors have confirmed that the reduction reaction proceeds to the extent that there is no problem in practical use when the charcoal-containing molded product is heated to about 980 ° C. to 1150 ° C. This can achieve a considerably lower temperature than the existing reduced iron production apparatus of 1200 ° C. of the Waelz process and 1250 ° C. of the rotary hearth type reduction method (RHF method). This lowering of the temperature has made it possible to use an externally heated rotary kiln that could not be used in the past. The body of the externally heated rotary kiln is generally made of heat-resistant cast steel manufactured by centrifugal casting, and the upper limit of use is about 1200 ° C. The lower limit of the heating temperature is preferably 1050 ° C. in consideration of temperature variation and the like. On the other hand, from the viewpoint of equipment maintainability, the upper limit temperature is preferably 1150 ° C, preferably 1130 ° C, and more preferably 1100 ° C. As a matter of course, if the heat resistance of the equipment is improved, the reduction treatment temperature can be naturally raised.

Hereinafter, the reduction treatment means (reduction treatment apparatus) will be described by taking the external heat type rotary kiln 32 as an example.

It is desirable that the air (strictly speaking, oxygen) is not mixed when the preheated / dried charcoal-containing briquette 30 is transferred / charged from the internal heat type rotary kiln 22 to the external heat type rotary kiln 32. Similarly, when the reduced iron is discharged from the externally heated rotary kiln 32, it is necessary to maintain airtightness so that the air does not enter the kiln. As described above, the mode of the transfer / charging device 31 (hereinafter, simply charging device) and the discharging device 35 is not limited as long as the airtightness can be ensured. For example, it can be embodied by using a double damper.

The amount of charcoal-containing molding 30 discharged from the internally heated rotary kiln 22 is controlled by a rotary valve, and double dampers (for example, two hoppers are installed in series in the upper and lower directions, and an openable damper is installed at the bottom of each hopper. Transfer to the upper hopper. The dampers of the double damper are opened and closed alternately, and the transferred carbon-containing molded body is transferred (dropped) from the upper hopper to the lower hopper. Then, the lower hopper is opened and the carbon-containing molded body is charged into the external heat type rotary kiln 32. If the charcoal-containing briquette is charged by this method, air contamination can be suppressed as much as possible.

Similarly, when the reduced iron is discharged from the externally heated rotary kiln 32, it is possible to suppress the mixing of air into the kiln by applying the double damper. In this way, zinc can be separated and the reduced iron 40 having a high metallization rate can be recovered as a solid.
The reduction treatment gas 50 in the externally heated rotary kiln 32 is guided to the zinc recovery device 57 in the next process without coming into contact with the atmosphere via a pipe connected to the kiln. By doing so, it becomes possible to recover zinc without reoxidizing the vaporized zinc.

[CO2 reforming]
The CO2 reforming in the present invention is to reform CO2 in the reduction treatment gas generated in the reduction treatment step to CO.
If CO2 is present in the reduction treatment gas in the process of cooling the reduction treatment gas containing metallic zinc vapor, the metallic zinc vapor is oxidized by CO2 to crude zinc oxide (ZnO), and the metallic zinc cannot be recovered. This is because the lower the CO / CO2 ratio (the higher the CO2 concentration), the higher the equilibrium temperature at which zinc can exist as a metal vapor.

For example, when the CO / CO2 ratio is 4, the equilibrium temperature in the direction of ZnO reduction (ZnO + CO → Zn + CO2) is about 1200 ° C., and above this temperature, zinc oxide reduction proceeds. According to the oxide energy / temperature diagram (Ellingham diagram), the equilibrium temperature when the CO / CO2 ratio is 10 is 1100 ° C, the equilibrium temperature when the CO / CO2 ratio is 15 is 1050 ° C, and the CO / CO2 ratio. The equilibrium temperature when = 20 is 1010 ° C., and the equilibrium temperature when the CO / CO2 ratio = 100 is 910 ° C.

Since the treatment temperature of the briquette-containing briquette according to the present invention is about 980 ° C. to 1150 ° C., the CO / CO2 ratio may be about 30 or less in order to promote the reduction of zinc oxide (ZnO). That is, the CO2 concentration may be about 3% or less. In the study by the present inventors, it was found that if the CO2 concentration in the reduction treatment gas is 3% or less, the metallic zinc recovery rate (the amount of recovered zinc relative to the amount of zinc contained in the electric furnace dust) can be secured at 90% or more. It was.

Next, a specific method of CO2 reforming was examined. The CO2 reforming is to reform CO2 in the reduction treatment gas into CO. For example, CO2 can be reformed into CO (CO2 + C → 2CO) by bringing the reduction treatment gas into contact with carbon (C) in some way.
In Patent Document 1, a powdered charcoal material charging device (a device for charging powdered coal material) 36 is installed in an externally heated rotary kiln 32, and the powdered coal material is charged in the externally heated rotary kiln 32. , A method of bringing it into contact with the reduction treatment gas has been proposed.

[Charge of pulverized coal material in the reduction treatment step]
Therefore, as a result of further studying measures to promote CO2 reforming, we focused on increasing the contact area between the reduction treatment gas and the carbonaceous material, and focused on the powdered coal material to be charged into the reduction treatment step (for example, an external heat rotary kiln). It was found that it would be better to atomize. In Patent Document 1, powdered coke is charged with powdered coke having a particle size of 1 mm or less for CO2 reforming, but by further micronizing (for example, particle size of 100 μm or less), even a carbonaceous material having the same weight can be used. It was found that the contact area with the reduction treatment gas increased and CO2 reforming proceeded. The average particle size of the pulverized pulverized coal material (fine pulverized coal material) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 10 μm or less. The type of pulverized coal material is not particularly limited. For example, carbon black can be applied. This is because carbon black has an average particle size of about 500 nm (0.5 μm). By charging the fine powdered carbonaceous material, the CO2 concentration can be reduced from 0.5% to 1.0%, and the CO2 concentration in the reduction treatment gas on the exit side of the reduction treatment step can be reduced to 2.5% or less. it can.

[CO2 reforming steps and means]
However, in the method of charging pulverized coal or fine pulverized coal into a reduction treatment apparatus such as an externally heated rotary kiln and contacting the reduction treatment gas, the amount of the contacting gas is limited, so that the reduction treatment is performed. It is difficult to further reduce the CO2 concentration in the gas.
Therefore, the CO2 reforming step is not a reduction treatment step using an externally heated rotary kiln or the like, but is an independent step in which the reduction treatment gas and the carbon dioxide material are brought into contact with each other more efficiently to proceed with the reforming of CO2. In order to efficiently contact the reduction treatment gas with the carbonaceous material, it is advisable to increase the carbonaceous material density in the space. That is, it is preferable to increase the area of the carbonaceous material in the cross section of the gas flow path.

As long as the area of the carbonaceous material in the cross section of the gas flow path can be increased, the means thereof is not particularly limited. As an example of a specific CO2 reforming means, a pellet of powdered charcoal material (charcoal material pellet) filled in a dedicated container (CO2 reformer) (charcoal material pellet moving layer). , Found a means to pass the reformed gas. As a result, the area of the carbonaceous material in the cross section of the flow path of the reduction treatment gas can be increased, and the reduction treatment gas flows in the gap between the coal material pellets, and at that time, the carbon material pellets and the reduction treatment gas come into contact with each other. .. With this method, it was confirmed that the two were well contacted and the CO2 reforming reaction (CO2 + C → 2CO) proceeded efficiently.

At that time, it is preferable that the temperature of the carbonaceous material pellets is at least equal to or higher than the temperature of the reduction treatment gas. By doing so, CO2 reforming can proceed without lowering the temperature of the reduction treatment gas. This CO2 reforming and CO2 concentration can be 2% or less. Therefore, the carbonaceous material pellet temperature is preferably 980 ° C. or higher, more preferably 1000 ° C. or higher, and even more preferably 1050 ° C. or higher.

The size of the charcoal pellets is not particularly limited. The smaller the average particle size is, the better the contact efficiency between the reduction treatment gas and the carbonaceous material pellets. CO2 reforming progresses by that amount, and the CO concentration can be further reduced. On the other hand, if the average particle size is too small, the strength of the carbonaceous material pellets decreases, and the pellets collapse, causing clogging. Therefore, from the viewpoint of securing an appropriate gap, it is easy to handle if the size of the carbonaceous pellet is a cylinder with a diameter of about 5 to 10 mm and a height of about 5 to 10 mm, or a spherical shape with a diameter of about 5 to 10 mm, and an appropriate gap. It is preferable because it can secure.

The charcoal pellets may be continuously supplied and moved in a container for discharge. By doing so, the temperature of the carbonaceous pellets in the container can be maintained. Of course, the carbonaceous material pellets may be replaced after flowing the reduction treatment gas at a constant flow rate in a so-called batch system.

Further, the CO2 reforming step may be performed between the lead removal step and the zinc recovery step described later. This is because if the CO2 reforming step is performed before the lead removing step (upstream side), lead and alkali metal salts are coagulated and separated during the CO2 reforming step and impregnated into the carbonaceous material pellets.

[Lead removal steps and means]
The lead removal step in the present invention is a series of steps for recovering and removing lead (Pb) in the reduction treatment gas generated in the reduction treatment step. Alkali metal salts (particularly NaCl, KCl) can also be removed in the lead removal step, as described below.

As shown in Tables 1 and 9, the electric furnace dust contains a small amount of lead (Pb) and alkali metal salts (NaCl, KCl) in the form of lead oxide, although the amount is small. When the reduction treatment gas generated in the reduction treatment step as in Patent Document 1 was directly treated in the zinc recovery step described later to recover zinc, the zinc recovery rate was as high as about 90%, but the recovered zinc was obtained. As a result of analysis, it was Zn: 96.2%, Pb: 3.7%, Cd: 0.03%, and one kind of distilled zinc bullion specified by JIS H 2107 (Zn: 98.5% or more, Pb: 1). .3% or less, Cd: 0.2% or less, Fe: 0.025% or less) may not be satisfied. This is often affected by the quality of scrap and the like input into the electric furnace, and it is difficult to control the components of scrap as an input raw material.

Similarly, alkali metal salts (for example, NaCl and KCl) are also contained in the input raw material, and may be contained in zinc recovered as it is.

As long as lead (Pb) can be removed, the means thereof is not particularly limited. As a specific example of lead removing means, we have found a means for removing and separating lead from the reduction treatment gas by utilizing the difference in boiling points between lead and zinc. With this method, alkali metal salts such as NaCl and KCl can also be removed.

Zinc (Zn) has a melting point of 420 ° C. and a boiling point of 907 ° C. On the other hand, lead (Pb) has a melting point of 327 ° C and a boiling point of 1749 ° C. Similarly, NaCl has a melting point of 800 ° C. and a boiling point of 1413 ° C., and KCl has a melting point of 770 ° C. and a boiling point of 1420 ° C.
Since the reduction treatment gas generated in the reduction treatment step is 980 ° C. to 1150 ° C., Pb, NaCl, and KCl exist in the form of fine droplets rather than steam because their boiling points are higher than that. Therefore, by passing the packed layer of the ceramic ball, fine droplets of Pb, NaCl, and KCl are aggregated on the surface of the ceramic ball, and dropped as large droplets on the lower part of the packed layer for recovery. It was found that it can be separated and removed from the reduction treatment gas.

The temperature of the packed bed of the ceramic balls should be maintained at the same temperature as or higher than the temperature of the reduction treatment gas. This is because the reduction treatment gas temperature is not lowered.

The material of the ceramic balls is not particularly limited. Silicon carbide (SiC) ceramics are preferable in consideration of thermal conductivity and wettability with metal (preferably not wet with metal). In addition, the whole may be made of ceramics, or pellets coated with ceramics may be used.

The size of the ceramic balls is also not particularly limited. The smaller the average particle size is, the better the contact efficiency with the reduction treatment gas. Coagulation removal of Pb, Na, and K proceeds accordingly. On the other hand, if the average particle size is too small, clogging will occur. Therefore, from the viewpoint of securing an appropriate gap, it is preferable that the size of the ceramic ball is a sphere having a diameter of about 5 to 10 mm because it is easy to handle. The shape is not limited to a spherical shape, and may be, for example, a cylindrical shape having a diameter of about 5 to 10 mm and a height of about 5 to 10 mm, or a rugby ball type.

The number of ceramic balls to be arranged is not particularly limited as long as it is a plurality (two or more), but since it is desirable that the gas comes into contact with the pellet surface evenly, it is preferable to fill the cross section through which the gas passes. Further, by stacking the pellets in a plurality of layers, the gas and the pellet surface come into contact with each other, and the removal performance of lead and alkali metal salts is improved.

By recovering zinc after passing the reduction treatment gas through such a lead removal step (or means), the content of Pb, NaCl, and KCl in the recovered zinc can be reduced, and the distilled zinc bullion class 1 , Or even higher purity zinc can be recovered.

[Zinc recovery step]
The zinc recovery step in the present invention is a series of steps for recovering zinc from the reduction treatment gas 50 generated in the reduction treatment step. In order to suppress the reoxidation of zinc in the gas, it is necessary to guide the reduction treatment gas so that the atmosphere is not mixed.

The method for recovering zinc from a gas containing zinc is not particularly limited. As a method for separating and recovering zinc from the reduction treatment gas, for example, there is a method of applying a lead splash condenser. However, the equipment is large and the collection efficiency is not good. Therefore, the present inventors have repeated studies and found that the reduction treatment gas can be directly cooled to condense zinc and recover it as hot-dip zinc. According to this, the equipment configuration can be made more compact than the lead splash capacitor, and zinc can be separated and recovered with high efficiency. For example, the gas may be cooled directly by a cooling tube. When the cooling tube is made of metal (for example, steel or copper), it reacts with zinc to form an alloy, so the material of the cooling tube should be other than metal. For example, ceramics are good. Therefore, the inventors have confirmed that the reduction treatment gas can be cooled by a cooling tube made of silicon carbide (SiC) having good thermal conductivity, and zinc can be condensed and recovered. The part of the cooling tube that comes into contact with the reduction treatment gas may be ceramics. For example, a metal tube may be coated with ceramics (for example, SiC).

The condensed zinc in the fine droplets is aggregated in the ceramic ball packing layer installed on the downstream side of the cooling tube and collected as droplets. It may be stored as molten zinc in the lower part of the zinc recovery device, or it may be cooled while being dropped as droplets and recovered as zinc particles. The collection method is not particularly limited.

[Zinc recovery means]
The mode of the zinc recovery means (zinc recovery device) is not particularly limited as long as it is a means capable of separating and recovering zinc contained in the reduction treatment gas. For example, a zinc splash capacitor may be applied as described above.

However, it is preferable to condense and recover zinc by direct cooling of the gas as described above from the viewpoint of efficiency and zinc quality. The mode is not particularly limited as long as it is a means having this function. Further, as found by the inventors, an apparatus may be used in which the reduction treatment gas 50 containing zinc is directly cooled to condense and recover zinc. In particular, the inventors have found that a zinc condenser (zinc condenser) that condenses zinc in a gas by bringing the cooling tube 56 into direct contact with the gas is efficient. FIG. 4A shows a conceptual diagram thereof. Zinc condensed by the cooling tube 56 falls in a molten state and accumulates in the lower part of the zinc condenser. Of course, after condensation, it can be cooled during dropping and recovered as zinc particles.

It is preferable to install one or a plurality of cooling tubes 56 and arrange them so as to be orthogonal to the gas flow. This is because if it is installed in the gas flow direction, it will solidify and stick on the pipe. Further, the cooling tube 56 is preferably arranged horizontally. If not leveled, the hot-dip galvanized zinc on the cooling tube may move on the cooling tube due to gravity and solidify and stick. By arranging it horizontally, the molten zinc can be dropped before it solidifies. When a plurality of cooling tubes 56 are installed, the arrangement of the tubes is not particularly limited. It may be set from the viewpoint of cooling efficiency.

The gas that passes between the cooling tubes and does not come into contact with the tube surface remains containing zinc vapor and hot-dip zinc particles. Therefore, in order to increase the zinc recovery rate, it is preferable to arrange a plurality of pellets made of ceramics or coated with ceramics on the downstream side of the cooling tube in the flow direction of the zinc vapor-containing gas (FIG. 4 (b)). This is because when the gas containing zinc vapor or hot-dip zinc fine particles passes through the gaps between the ceramic pellets, it comes into contact with the surface of the pellets, and zinc is condensed / aggregated and separated. At this time, what is condensed and aggregated into molten zinc becomes droplets and is dropped downward and collected.

The size of the pellet is not particularly limited, but a cylindrical shape having a diameter of about 5 to 10 mm and a height of about 5 to 10 mm or a spherical shape having a diameter of about 5 to 10 mm is easy to handle and an appropriate void can be secured.

The material of the ceramics is not particularly limited, but like the cooling tube, silicon carbide (SiC) having good thermal conductivity is preferable. If it is SiC, it can be easily separated and recovered without getting wet with molten zinc.

The number of pellets to be arranged is not particularly limited as long as it is a plurality (two or more), but since it is desirable that the gas comes into contact with the pellet surface evenly, it is preferable to fill the cross section through which the gas passes. Further, by stacking the pellets in a plurality of layers, the gas and the pellet surface come into contact with each other, and the zinc recovery rate is improved.

The gas introduction pipe from the external heat type rotary kiln 32 to the zinc recovery device 51 needs to have good airtightness that shuts off the atmosphere so that zinc in the reduction treatment gas is not reoxidized. The blower 54 that sucks the reduction treatment gas is preferably installed downstream of the zinc recovery device. This is because zinc does not adhere to the blower blades because the zinc is separated. From the viewpoint of protecting the equipment of the blower, it is preferable to arrange the dust collector 53 in front of the blower.

Furthermore, when the zinc-containing gas is cooled, when the zinc-containing gas comes into contact with metallic iron, CO2 (carbon dioxide) is generated by the carbon deposition reaction (2CO → CO2 + C), and this CO2 reoxidizes the vapor zinc. It becomes crude zinc oxide (ZnO). As described above, once it becomes crude zinc oxide (ZnO), metallic zinc cannot be recovered, so it is desirable to suppress this carbon deposition reaction.

If the zinc recovery device is made of steel, it is advisable to coat its inner surface so that the zinc-containing gas does not come into direct contact with the steel. The coating is not particularly limited, but for example, it may be painted. The paint is not limited, but there are, for example, heat resistant paints. Alternatively, for example, a lining may be used. For example, there are linings such as ceramic paints and castables.

The method and equipment for extracting iron (reduced iron) and zinc (reduced zinc) from electric furnace dust have been described above, but the method and equipment that can be added for effective use of discharged gas and the like have also been described. To do.

[Reduction treatment gas reuse steps and means]
The reduction treatment gas after zinc recovery is mainly composed of CO (partly CO ₂ ) because zinc is separated. Of course, it may be released to the atmosphere, but it is preferable to effectively utilize CO as a fuel. For example, it may be used as fuel for the heating means of the reduction treatment means (for example, the combustion burner 34 of the externally heated rotary kiln 32). Further, for example, it may be reused as fuel for the heating means of the preheating device 22 (for example, combustion gas of an internally heated rotary kiln). Of course, it may be reused in other equipment.

For that purpose, it is necessary to purify the reduction treatment gas 50. For example, a recuperator 52 that recovers the sensible heat of the gas to lower the gas temperature, a dust collector 53 that removes dust in the gas, a blower 54, and a gas holder 55 that stabilizes the gas pressure may be installed. The gas passed through these facilities can be used as fuel for the combustion burner 34 of the externally heated rotary kiln. The purification method / equipment of the reduction treatment gas is not particularly limited to this embodiment, and the purification method and equipment may be appropriately selected according to the use of the gas.

[Other incidental devices]
In the preheating step, the exhaust gas 80 generated after heating and drying the carbon-containing molded body contains dust containing zinc chloride, iron oxide, and zinc oxide as described above. Therefore, it is desirable to separate and recover these components from the exhaust gas generated in the preheating step. Therefore, for example, the exhaust gas 80 generated from the preheating device (for example, an internally heated rotary kiln) 22 may be passed through a dust collector (bag filter) 81 to collect zinc chloride and dust 84, and then dissipate to the atmosphere. Of course, the blower 82 that sucks the exhaust gas may be installed downstream of the dust collector. The gas treatment method / equipment may be appropriately selected according to the use of the exhaust gas in the preheating step.

[Example 1]
Hereinafter, examples of the present invention in a test plant will be described.
Table 1 shows the chemical components of the electric furnace dust A used in the test operation and the coke breeze as a carbonaceous material. The numerical value indicates mass%. The particle size distribution of the electric furnace dust was measured by a laser diffraction / scattering type particle size distribution measuring device (Microtrack), and was D50 = 1.5 μm and D50 = 36.2 μm of coke breeze. D50 is a particle size corresponding to a cumulative frequency of 50% from fine particles in the cumulative particle size distribution.

Table 2 shows the raw material mixing ratio of the charcoal-containing briquette used in the test operation. Add powdered coke as a charcoal material so that the C equivalent is 1.0, add water for moisture adjustment and cornstarch as a binder, mix well with a double-arm kneader, and then use a semi-dry extrusion molding machine to make the bottom diameter. A charcoal-containing molded product 20 having a diameter of 20 mm and a length of 25 mm was produced. The water content of the charcoal-containing molded product was 10.3%. The raw strength (strength immediately after molding) of the charcoal-containing molded product was 0.853 MPa, and the strength after drying after drying at 150 ° C. for 2 hours was 3.63 MPa.

<Equipment specifications of test plant>
A conceptual diagram of the entire test plant is shown in FIG. 3 (a). The processing capacity is 50 dkg of the charcoal-containing molded product (indicating the weight (Kg) in the dry state. The same applies hereinafter) / h. The basic configuration is similar to the actual equipment shown in Fig. 1, but the external heating furnace of the external heating rotary kiln is an electric heating type for the sake of simplicity. A hot air generator (burner for preheating device) was used to heat the internally heated rotary kiln. In addition, the exhaust gas of the externally heated rotary kiln is cooled by a zinc recovery device, and then the CO gas is burned by the exhaust gas combustion device to make it harmless and then discharged outdoors.

The main equipment specifications are shown below.
[Internal heat rotary kiln]
-Stainless steel: inner diameter 500 mm x length 4 m
・ Heating method: Hot air generator [External heat type rotary kiln]
-Made of heat-resistant cast steel: inner diameter 300 mm x length 4 m, maximum operating temperature 1150 ° C
・ External heating furnace: Electric heating type, total length 2m
[Charcoal-containing briquette supply / discharge device]
・ Supply device to internal heat type rotary kiln: Room temperature type double damper ・ Transfer device from internal heat type rotary kiln to external heat type rotary kiln: 2 units in series with high temperature type water-cooled rotary valve ・ Discharge device from external heat type rotary kiln: Normal temperature type Double damper

[Powdered charcoal material charging device]
-A powdered coal material charging device 36 capable of charging powdered coal material (including fine powdered coal material) was installed in the external heat type rotary kiln 33. Furthermore, a protrusion was installed on the inner surface of the externally heated rotary kiln, and the pulverized coal material was lifted upward by the inner surface protrusion by the rotation of the kiln, and then dropped into the kiln.

[Lead removal device (Fig. 4)]
-The lead remover is made of heat-resistant cast steel and is made of heat-resistant cast steel by filling a vertically long tubular container with a rectangular cross section of 180 mm x 350 mm with SiC ceramic balls with a diameter of 5 to 10 mm to a thickness of 400 mm. An electric heater installed outside the tubular container made it possible to maintain the temperature at the center of the packed bed at 1050 ° C.
-SiC ceramic balls have a high thermal conductivity of 200 W / mk, which is close to that of aluminum, and have a structure that makes it easy to maintain the temperature at the center of the packed bed by heating the long side of the rectangular cross section. The lead recovery device and the CO2 reformer were installed so as to be removable in the reduction treatment gas line after the external heat type rotary kiln.

[CO2 reformer]
The CO2 reformer was made of heat-resistant cast steel and filled with a vertically long tubular container having a rectangular cross section of 180 mm × 350 mm and an artificial graphite pellet having a diameter of 5 to 10 mm so as to have a thickness of 600 mm. The structure is such that the temperature at the center of the packed bed can be controlled between 1050 ° C and 1150 ° C by an electric heater installed outside the heat-resistant cast steel tubular container. The artificial graphite pellets have a high thermal conductivity of 250 W / mk, which is higher than that of aluminum, and have a structure that makes it easy to maintain the temperature at the center of the packed bed by heating the long side of the rectangular cross section.

[Zinc recovery device]
-The zinc recovery device is a vertically long tubular container having a square cross section, and has a double structure of an outer wall and an inner wall made of steel plate. Inside the inner wall, a 20 mm thick heat insulating material and an 80 mm thick castable are arranged in this order. Further, the outer wall and the inner wall were separated by 50 mm, and nitrogen was passed between them to prevent air from being mixed in the reduction treatment gas. The portion through which the reduction treatment gas flows has a square cross section with a side of 250 mm.
-Twenty-five SiC pipes (SiC: 99%) having an outer diameter of 30 mm and an inner diameter of 20 mm, which are water-cooled inside, are arranged in a staggered manner on the upper part of the zinc recovery device as cooling tubes. By placing a SiC triangular prism (25 cm in length) whose bottom was cut so as to be in close contact with the pipe on the upper part of the pipe, the accumulation of metallic zinc on the pipe was prevented.
-In order to absorb expansion and contraction due to heating and cooling of the SiC pipe and shut off the outside air, an O-ring was installed at the attachment part of the SiC pipe.
-As shown in FIG. 5, the downstream side (lower part) of the cooling tube 65 of the zinc recovery device 57 was filled with SiC ceramic balls. The SiC ceramic balls had a diameter of 5 to 10 mm, and the SiC ceramic balls were filled so that the cross section (cross section of 250 mm square) of the zinc recovery device had a thickness of 400 mm.
-Furthermore, heat-resistant paint was applied to the inner surface of the piping from the externally heated rotary kiln to the zinc recovery device as a measure against carbon deposition. The inner surface of the inner wall of the zinc recovery device is lined with castables, but just in case, heat-resistant paint was applied to the inner surface of the inner wall.

<Test method>
The test was conducted according to the following procedure.
(1) After operating the hot air generator 24 of the internally heated rotary kiln 22, the charcoal-containing briquette manufactured by the above-mentioned method via the charging device (double damper) 21 in the internally heated rotary kiln 22. 20 was charged at a rate of 50 dkg / h. The fuel combustion amount of the hot air generator 24 and the rotation speed of the internal heat type rotary kiln were controlled so that the temperature when the carbon-containing molded body was preheated and dried and discharged from the internal heat type rotary kiln 22 was 900 ° C.

(2) The external heat type rotary kiln 32 raised the outer surface temperature to 1050 ° C. After the charcoal-containing molded body heated to 900 ° C. was started to be charged into the external heating type rotary kiln 32 via the charging device (two series water-cooled rotary valves) 31, the external heating furnace length was 2 m. The rotation speed of the external heat type rotary kiln was adjusted so that the residence time was 30 minutes, and at the same time, the power input amount of the external heat type rotary kiln was controlled so that the outer surface temperature of the external heat type rotary kiln was maintained at 1050 ° C.

(3) The reason why the reduction treatment temperature was set to 1050 ° C. and the reduction treatment time was set to 30 minutes is that a test in which the reduction treatment temperature and the reduction treatment time were variously changed was carried out in advance as shown in Table 5 described later, and the reduction treatment time was 30 at 1050 ° C. This is because it was confirmed that a metallization rate and a dezincification rate of 95% or more can be obtained by the reduction treatment for minutes.

(4) In order to reform CO2 in the reduction treatment gas into CO, carbon black was charged into an externally heated rotary kiln as a fine powdered coal material from the powdered coal material charging device 36. As for the charge amount of carbon black, 2 d-kg / h was charged per 50 d-kg / h of the carbon-containing molded body. Carbon black is an extremely fine carbonaceous material having a diameter of 500 nm (0.5 μm) or less, and was selected because it has a large surface area and high reactivity with CO2. When the CO2 in the exhaust gas 67 on the exit side of the zinc recovery device was analyzed, the CO2 that was 20% before the carbon black was charged decreased to 2.5% after the carbon black was charged.

(5) Inside the externally heated rotary kiln 32, the carbon-containing molded body is reduced to generate zinc vapor, CO gas, CO2 gas, and fine droplets of lead / alkali metal salt. The exhaust gas 50 was sucked by the exhaust blower 62 and passed through a steam zinc recovery device 57 composed of a SiC water-cooled pipe and a SiC pellet filling layer 66. First, steam zinc is condensed into zinc droplet fine particles by a water-cooled pipe made of SiC, and then the fine particles are aggregated by passing through a SiC pellet packing layer and dropped as raindrop-sized zinc droplets, and molten zinc installed under a zinc recovery device. It was stored in the reservoir 59. The amount of water in the SiC water-cooled pipe was adjusted so that the temperature of the zinc droplets was maintained at 500 ° C. or higher. The stored hot-dip zinc was periodically poured into a mold and recovered.

Table 3 shows the results of the reduction test carried out at a reduction treatment temperature of 1050 ° C. and a reduction treatment time of 30 minutes. The metallization rate was 96.3%, the dezincification rate was 98.3%, and the lead removal rate was 92.3%. The analytical values of the recovered metallic zinc are shown in Table 4. At this time, the recovery rate of metallic zinc was as high as 90.5% of zinc in electric furnace dust, but the analytical values of Zn and Pb were out of the standard of JIS distilled zinc type 1.

(6) The charcoal-containing briquette becomes reduced iron (DRI) 40 when the reduction is completed. The reduced iron at 1050 ° C. was cooled to 100 ° C. or lower in a water cooling box installed at the discharge port of the externally heated rotary kiln 32, and then discharged to the outside via a discharge device (double damper) 35 for recovery.

(7) The exhaust gas 50 at 500 ° C. after the exhaust gas 50 of the externally heated rotary kiln 32 is rapidly cooled by the zinc recovery device 57 is burned under excess air by the exhaust gas combustion device 64, and then diluted with a large amount of air to achieve 50 ° C. After cooling to the following, the dust was further reduced by a dust collector (bag filter) 61, and then the dust was released to the atmosphere.

(8) The case where the reduction treatment temperature is 1050 ° C. and the reduction treatment time is 30 minutes has been described above, but the reduction treatment temperature is between 950 ° C. and 1150 ° C., and the reduction treatment time is between 10 minutes and 40 minutes. The 9-level test was carried out with various changes in the above, and the analysis results of the recovered DRI are shown in Table 5.

(9) The NET metallization rate is the metallization rate increased by reduction. The GROSS metallization rate is the total metallization rate of the reduced sample to which M · Fe (metallic iron (metallic Fe)) originally present in the electric furnace dust is added. The definitions of the metallization rates of GROSS and NET are shown in Equations 5 and 6. Hereinafter, T / Fe indicates total Fe (total iron content), and the weight% of M / Fe and T / Fe indicates the weight% with respect to the coal-containing molded product.
GROSS metallization rate = (M · Fe (% by weight) after reduction) / (T · Fe (% by weight) after reduction) ... (Equation 5)
NET metallization rate = {[(M · Fe (% by weight) after reduction × total weight of carbon-containing molded body after reduction)-(M · Fe (% by weight) before reduction × carbon-containing molded body before reduction) (Total weight of)] / (total weight after reduction)} / (T · Fe (% by weight) after reduction) ... (Equation 6)

(10) For comparison, Table 5 shows the results when the electric furnace dust was treated by the Waelz method and the RHF method. The RHF method using a charcoal-containing molding has better results than the Waelz method. The metallization rate of DRI reduced by RHF is 60 to 70%, the entire amount of DRI is recycled in an electric furnace as an iron source, and the dezincification rate is as high as 70 to 90%. Therefore, the test results in which the GROSS metallization rate and the dezincification rate equivalent to those of RHF were obtained are indicated by ◯, and the test results in which the dezincification rate was equal to that of RHF but the dezincification rate was RHF or less were indicated by Δ.

[Example 2]
In the same test apparatus as in Example 1, in order to remove fine droplets of lead and alkali metal salts in the reduction treatment gas generated in the externally heated rotary kiln 32, the zinc recovery apparatus 57 as shown in FIG. 3 (b). A lead removing device 51 was installed in front of the above. By passing the reduction treatment gas through this lead removing device, the molten lead and the molten alkali metal salt aggregated and dropped by the SiC ceramic ball packing layer are stored in the recovery device 58 installed under the device, and are periodically put into a mold. It was poured and collected.

Using the test device shown in FIG. 3 (b) equipped with the lead removing device in the reduction treatment gas described above, a reduction test was carried out on the briquette-containing molded body of the electric furnace dust A in the same manner as in Example 1. .. The results are shown in Table 6. Although the metal zinc recovery rate decreased from 90.5% in Example 1 to 87.7% due to the removal of lead, the analytical values of Zn and Pb were JIS distilled zinc 1 type. The results satisfied the criteria of.

[Example 3]
In the same test apparatus as in Example 2, in order to reform CO2 in the reduction treatment gas into CO, the CO2 reformer 54 between the lead removing apparatus 51 and the zinc recovery apparatus 57 as shown in FIG. 3C. Was installed. The packed artificial graphite pellets weighed 32.620 kg, and the weight was measured before and after the reduction test, and the amount of artificial graphite pellets consumed by the reaction with CO2 was grasped in the reduction test.

Using the test device shown in FIG. 3 (C) in which the CO2 reformer 54 is installed, a reduction test was carried out at two levels on the charcoal-containing molded body of the electric furnace dust A in the same manner as in Example 1. .. At level 1, the temperature at the center of the coal pellet packed bed was maintained at 1050 ° C, and at level 2, the temperature was maintained at 1150 ° C. At level 1, when CO2 in the exhaust gas 67 on the exit side of the zinc recovery device was analyzed, what was 2.5% after carbon black was charged decreased to 2%. At level 2, it further decreased to 1%. The test results of Level 1 are shown in Table 7, and the test results of Level 2 are shown in Table 8. By thoroughly reforming CO2 to CO, the metal zinc recovery rate is higher than 87.7% in Example 2. It was confirmed that the improvement was up to 90.0% and 92.4%, respectively.
In the reduction test, the treatment time was set to 6 hours for both levels, but the weight loss of the artificial graphite pellets due to the reaction with CO2 before and after the test was 305 g and 610 g, respectively.

[Example 4]
Know the effect of Fe concentration of briquette on the DRI strength after reduction treatment for electric furnace dust containing high concentration zinc but low iron concentration generated in an electric furnace equipped with an iron scrap preheating device. Tests were conducted. First, a charcoal-containing briquette produced by changing the target Fe concentration between 10 and 25% was produced, and then a reduction test was carried out using the test apparatus shown in FIG. 3 (b) of Example 2. .. Table 9 shows the analytical values of the electric furnace dust B used in the test, the converter dust for iron supply, and the coke breeze. The average D50 particle size of the electric furnace dust B was 4.4 μm, the average D50 particle size of the converter dust was 6.9 μm, and the average D50 particle size of the coke breeze was 44.9 μm.

Raw material compounding ratio for producing a coal-containing molded product in which the target T-Fe concentration is changed between 10 and 25%, and the crushing strength measurement result of DRI before and after the reduction test of each level of the carbon-containing molded product. Is shown in Table 10. From Table 10, regarding the DRI strength, the strength is not exhibited at all when T-Fe is 10%, and it is so fragile that it breaks immediately when pinched by fingers, and powder is also mixed in the products discharged from the external heating type rotary kiln. It was. However, when T-Fe was increased to 15%, the DRI intensity was improved to 2.83 MPa, the discharge from the externally heated rotary kiln was also sound, and it was found that rolling in the kiln was stopped. .. It was also confirmed that an extremely high-strength DRI can be obtained by setting T-Fe to 20% or more.

[Example 5]
In the ISP method, zinc concentrate, which is the main raw material, and crude zinc oxide (ZnO) recovered by the Weltzkirn method are mixed and granulated in a predetermined ratio together with a solvent, and then desintered and sintered with a sinter to obtain a sintered ore. It is charged into a blast furnace and finally recovered as metallic zinc. Table 11 shows the analysis values of the zinc concentrate roasted product obtained by oxidizing and roasting crude zinc oxide and zinc concentrate. Although all of them contain a high concentration of zinc, the iron concentration is as low as about 10% or less, and the properties are similar to those of the electric furnace dust B generated in the electric furnace equipped with the iron scrap preheating device shown in Example 4. Therefore, as in Example 4, a charcoal-containing briquette in which the target Fe concentration was increased to 15 to 25% was produced, and then a reduction test was conducted using the test apparatus shown in FIG. 3 (b) of Example 2. Carried out. The average D50 particle size of crude zinc oxide was 5.5 μm, and the average D50 particle size of roasted zinc concentrate was 9.4 μm. The converter dust and coke breeze for iron supply are the same as in Example 4.

Raw material compounding ratio for producing a coal-containing molded product in which the target T-Fe concentration is changed between 15 and 25%, and measurement of the crushing strength of DRI before and after the reduction test of each level of the carbon-containing molded product. The results are shown in Table 12. From Table 12, when T-Fe was increased to 15% for both crude zinc oxide and roasted zinc oxide, the DRI intensity exceeded 2.5 MPa, and the products discharged from the externally heated rotary kiln were also sound. It was confirmed that it can withstand rolling in the kiln and that extremely high-strength DRI can be obtained by setting T-Fe to 20% or more. From the results of Examples 4 and 5, the Fe content of the electric furnace dust, the crude zinc oxide, and the roasted zinc concentrate, which contain a high concentration of zinc but have a low iron content, is 15% by weight or more, preferably 20%. It was found that by containing iron oxide as described above, a sound DRI can be obtained in the reduction test by the test apparatus shown in FIG. 3 (b).

Since the present invention can separate and recover reduced iron and zinc from electric furnace dust generated in an electric furnace-based steelmaking plant, it can be used in the electric furnace-based steelmaking industry.

10 Electric furnace dust
11 Charcoal-containing briquette manufacturing equipment (means)
20 Charcoal-containing molded body
21 Loading device
22 Preheating device (internal heating type rotary kiln)
23 Discharge device
24 Burner for preheating device (hot air generator)
30 Preheated and dried charcoal-containing molding
31 Loading device
32 Reduction processing equipment (external heat type rotary kiln)
33 Heating equipment for reduction processing equipment
34 Combustion burner
35 Discharge device
36 Powdered charcoal material charging device
40 reduced iron
50 Reduction processing gas
51 Lead remover
53 Charcoal pellets (supply side)
54 CO2 reformer
55 Charcoal pellets (discharge side)
57 Zinc recovery device
58 Recovery of lead and alkali metal salts
59 Zinc recovered product
60 heat exchanger
61 Dust collector
62 Blower
63 Gas holder
64 Exhaust gas combustion device
65 cooling tube
66 Ceramic pellet packing layer
70 Heating equipment exhaust gas
80 Preheater exhaust gas
81 Dust collector
82 blower
83 chimney
84 Dust (recycled)

Claims (17)

A charcoal-containing briquette manufacturing step for producing a charcoal-containing briquette by mixing and molding electric furnace dust containing iron oxide and zinc oxide, carbonaceous material, binder, and water.
A preheating step of heating and drying the charcoal-containing molding, and
A reduction treatment step in which the charcoal-containing briquette that has been dried and heated in the preheating step is further heated in a closed space to reduce iron oxide to reduced iron.
A lead removal step for recovering and removing lead from the reduction treatment gas generated in the reduction treatment step,
The have a zinc recovery step of recovering the zinc from the reducing process gas through the lead removal step, the lead removal step, the reduction treatment the reducing process gas and silicon carbide ceramics balls heated to a temperature above the temperature of the gas iron and zinc mETHOD recovery from electric furnace dust, wherein Rukoto contacting the. Between the zinc recovery step and the lead removal step, iron and zinc from electric furnace dust according to claim 1, characterized in that it comprises a CO2 reforming step of reforming the CO2 of the reducing process gas in the CO How to collect. The iron and iron from the electric furnace dust according to claim 2 , wherein in the CO2 reforming treatment step, the pellet-shaped carbonaceous material heated to a temperature equal to or higher than the temperature of the reduction treatment gas is brought into contact with the reduction treatment gas. How to recover zinc. The iron and zinc from the electric furnace dust according to any one of claims 1 to 3 , wherein in the reduction treatment step, a pulverized coal material having an average particle size of 10 μm or less is charged into the closed space. How to collect. The method according to any one of claims 1 to 4 , wherein in the step of producing the briquette-containing briquette, iron oxide is further mixed to bring the Fe content in the briquette-containing mold to 15% by weight or more. How to recover iron and zinc from electric furnace dust. The method for recovering iron and zinc from electric furnace dust according to any one of claims 1 to 5 , wherein the heating temperature of the charcoal-containing briquette in the preheating step is 770 ° C. or higher and 907 ° C. or lower. The method for recovering iron and zinc from electric furnace dust according to any one of claims 1 to 6 , wherein the heating temperature of the charcoal-containing molded product in the reduction treatment step is 980 ° C. or higher and 1150 ° C. or lower. .. The iron and zinc from the electric furnace dust according to any one of claims 1 to 7 , wherein the preheating step is treated with an internal heating type rotary kiln, and the reduction treatment step is treated with an external heating type rotary kiln. Collection method. Any one of claims 1 to 8 , wherein in the zinc recovery step, the silicon carbide tube whose inside is cooled is brought into contact with the reduction treatment gas, and then the silicon carbide pellet is brought into contact with the reduction treatment gas. The method for recovering iron and zinc from the electric furnace dust described in the section. In a device that recovers iron and zinc from electric furnace dust containing iron oxide and zinc oxide
A means for producing a charcoal-containing briquette, which is produced by mixing and molding electric furnace dust containing iron oxide and zinc oxide, a carbonaceous material, a binder, and water.
A preheating means for heating and drying the charcoal-containing briquette, and
A reduction treatment means for producing reduced iron by further heating the charcoal-containing briquette that has been dried and heated by the preheating means.
Lead removing means for recovering and removing lead from the reduction treatment gas generated by the reduction treatment means,
Have a zinc recovery means for recovering zinc from the reducing process gas through the lead removal unit, the lead removal unit, the reduction treatment and the silicon carbide ceramics balls heated to a temperature above the temperature of said reducing process gas gas is contacted with iron and zinc recovery device from electric furnace dust, characterized in that to have a lead removal apparatus for separating and recovering by aggregating the lead. Between the zinc recovery means and the lead removal unit, iron from EAF dust according to claim 1 0, characterized in that it comprises a CO2 reforming means for reforming CO2 of the reducing process gas in the CO and Zinc recovery device. The CO2 reforming means has a CO2 reforming device that reforms CO2 into CO by bringing the pellet-shaped carbonaceous material heated to a temperature equal to or higher than the temperature of the reducing gas into contact with the reducing gas. iron and zinc recovery device from electric furnace dust according to claim 1 1,. The reduction in processing means, the recovery of iron and zinc from electric furnace dust according to any one of claims 1 0 to 1 2, characterized in that it comprises the following pulverulent carbonaceous material charged means an average particle size of 10μm apparatus. The preheating means is a inner-heat rotary kiln, of the iron and zinc from electric furnace dust according to any one of claims 1 0 to 1 3, wherein the reduction treatment means is externally heated rotary kiln Recovery device. Claim 1 0-1 4, characterized in that a reducing process gas recycling means for the reducing process gas after the recovery of zinc in the zinc recovery means for heating fuel in the reduction treatment means The device for recovering iron and zinc from electric furnace dust according to item 1. The zinc recovery means, the reducing process gas by silicon carbide tube was cooled internal cooling, claim 1 0-1 5, characterized in that it has a zinc condenser for separating recovered by condensing the zinc The device for recovering iron and zinc from electric furnace dust according to item 1. The iron and iron from the electric furnace dust according to claim 16 , wherein in the zinc condenser, pellets made of silicon carbide are arranged on the downstream side of the tube made of silicon carbide, and zinc is further condensed and separated and recovered. Zinc recovery device.

Images