KR102244729B1 - Method for hydrogen reduction of nickel oxide and molybdenum oxide - Google Patents

Abstract

The present invention relates to a method for hydrogen reduction of nickel oxide and molybdenum oxide, the method comprising the steps of: performing drying and preheating functions; performing a low-temperature hydrogen reduction reaction function; and performing a high-temperature hydrogen reduction reaction function. The present invention has a simple facility, so there is no malfunction.

Description

Method for hydrogen reduction of nickel oxide and molybdenum oxide

The present invention relates to a hydrogen reduction method, and in particular, nickel oxide and molybdenum oxide which can significantly reduce metal oxides through a continuous and automated hydrogen reduction device by dramatically improving the structure and consumption of hydrogen. It relates to a hydrogen reduction method of.

In general, methods of reducing and smelting metal minerals are largely classified into wet smelting methods and dry smelting methods.

The wet smelting method is a method of leaching or dissolving a metal mineral with a chemical solution such as hydrochloric acid or sulfuric acid, and then reducing the metal by a substitution reaction or smelting through electrolysis. The dry smelting method is a large-capacity smelting method that is adopted by most existing metal smelting companies, and is the most common smelting method, which is a smelting method in which ore is melted and reduced. In addition, a thermite reaction is made by heating and melting the metal mineral to be smelted and reducing it by adding a reducing agent such as coke, silicon, and aluminum to it, and by pulverizing and pulverizing the metal oxide, and then mixing metal powder with high heat of oxidation reaction such as aluminum. There is a smelting method that causes (Thermit Reaction) to be reduced.

The above smelting methods have advantages and disadvantages, and in particular, the blast furnace smelting method and the electric furnace smelting method, which are smelting methods employed by most companies, are smelting methods that cause enormous pollution. Because the hydrometallurgical method uses chemicals, water pollution occurs. The development of smelting technology that generates little or no pollution due to these environmental problems is a topic and homework that all smelting companies in the world pursue.

The most environmentally friendly smelting technology developed so far is Hydrogen Reduction, and it has evolved into some mass production technology after the R&D stage. However, there are still limits to smelting all metals due to two difficulties. The first problem is that the price of hydrogen used as a reducing agent is too high. The hydrogen price is expected to drop to less than 30% of the current market price in the near future as engineers from around the world are actively conducting research as the demand for hydrogen increases significantly due to the advent of hydrogen cars. The second is the failure to develop an optimal reactor capable of reacting with hydrogen. In the case of the reactor, the commercially available processor is a method of placing a container (Batt) containing the ore powder to be reduced on a rotating conveyor and transferring it into a chamber filled with hydrogen to cause hydrogen reduction. This has a problem in that low melting point metals such as Fe and Ni adhere to the inner wall of the chamber or the container after reduction.

On the other hand, according to the rotary kiln type metal oxide reduction device of Republic of Korea Patent Publication (B1) No. 10-0844106 (2008.07.04.), a heating zone for heating a metal oxide and a cooling zone for cooling the heated metal oxide are provided. It is composed of an integral muffle, and the metal oxide is configured to be inclined downward from the heating zone to the cooling zone so that the metal oxide can continuously reduce the reaction through heating and cooling, and the muffle is configured to rotate at a constant speed by a motor. It makes it possible to reduce metal oxides such as in large quantities.

However, the above patented technology is not only excessively used despite the use of the above-mentioned expensive hydrogen gas itself as a reducing agent, as well as the use of heat-resistant stainless steel for the interior wall of the chamber, so that it is reduced inside the muffle after a reduction reaction in a high temperature heating zone. The problem of entangled metal is still included.

An object of the present invention is to solve the problems of the prior art and at the same time install three rotary kilns in which graphite lining tubes are applied horizontally or vertically inside the hydrogen reduction chamber, but drying and preheating in the primary rotary kiln In addition, by implementing a method of performing low-temperature hydrogen reduction in the secondary rotary kiln and performing high-temperature hydrogen reduction in the third rotary kiln, a large amount of metal oxides such as nickel or molybdenum through a continuous and automated hydrogen reduction device are implemented. By adopting electric induction heating or SiC heat heating system for the heat source of the secondary and tertiary rotary kiln, the temperature control can be quickly and accurately, and the structure is simple, so the installation cost and maintenance cost are greatly increased. It provides a hydrogen reduction method of nickel oxide and molybdenum oxide that can be reduced.

According to a feature of the present invention for achieving the above object, in the hydrogen reduction method of nickel oxide and molybdenum oxide, the method comprises a plurality of The blade 120 is welded to the inner diameter, and the ore (NiO or MoO3) powder is charged into the rotatable first chamber 130A, rotated at 1 to 10 RPM, and stirred by the blade, and the LPG or LNG gas burner 140 is A first step of performing drying and preheating functions at 200° C. to 300° C. by spraying directly into the first chamber through; Graphite, silicon carbide (SiC), and silicon nitride (Graphite) molded in the inner diameter of the second chamber 130B of the second rotary kiln apparatus 200 capable of rotating and stirring the dried and preheated ore powder at 1 to 10 RPM. Si3N4) After charging the inside of a selected lining tube, hydrogen injection produced by reforming butane gas through the first water introduction device 260 and the first electricity using high frequency A second step of performing a first low-temperature hydrogen reduction reaction function at 500°C to 700°C by the induction heating device 230; Graphite and silicon carbide (SiC) and After charging any one of silicon nitride (Si3N4) materials into the selected lining tube, the hydrogen injection produced by reforming butane gas through the second water introduction device 360 and high frequency use And a third step of performing a secondary high-temperature hydrogen reduction reaction function at 900°C to 1,300°C by the second electric induction heating device 330; In addition, a fourth step of irradiating ultrasonic waves through the ultrasonic generator 400 to prevent entanglement between the particles of the ore powder during the reduction reaction with hydrogen in the third step and to promote the reduction reaction; A fifth step of cooling the nickel or molybdenum oxide reduced in the third step through a cooling chamber 500 is provided.

According to another embodiment of the present invention, when performing the low-temperature hydrogen reduction reaction of the second step, the first vent hole 270 installed at the upper end of the outlet side of the second chamber 130B is opened. It characterized in that the step is further included.

According to another embodiment of the present invention, when performing the high-temperature hydrogen reduction reaction of the third step, the second vent hole 370 installed at the upper end of the outlet side of the third chamber 130C is opened. It characterized in that the step is further included.

According to another embodiment of the present invention, the first rotary kiln device 100 to the third rotary kiln device 300 is a stacked vertical type in order to enable continuous mass production with high thermal efficiency and automation ( Vertical Type) or a horizontal type (Horizontal Type) installed in a horizontal arrangement further comprises a step of selecting any one.

According to another embodiment of the present invention, the second rotary kiln device 200 and the third rotary kiln device 300 have a fixed structure equipped with an insulation system on the outside, and a cylindrical chamber capable of rotating inside ( Chamber) characterized in that it has the step of forming the structure is further included.

The hydrogen reduction method of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention can expect the following effects.

(1) The present invention is a continuous and automated hydrogen reduction system by installing three rotary kilns vertically or horizontally in the smelting method by hydrogen reduction of nickel oxide (NiO) and molybdenum oxide (MoO3). Nickel and molybdenum can be easily smelted through.

(2) In the present invention, the inside of the secondary and tertiary rotary kiln, which is a hydrogen reduction chamber, is made of graphite, silicon nitride, or silicon carbide, and heated with a high frequency induction current. , It is possible to prevent the phenomenon that reducing metals such as Ni adhere to the inside of the chamber after hydrogen reduction, and obtain high-temperature heating and energy saving effects.

(3) In the present invention, by irradiating ultrasonic waves through an ultrasonic oscillator inside a rotary kiln, hydrogen reduction efficiency can be increased, as well as entanglement between powder particles or formation of a reduced metal coating film on the surface of the powder can be prevented. , The installation cost and maintenance cost are inexpensive because the device is simple according to the composition of the rotary kiln type reaction chamber.

1 is a diagram showing a conventional technique
2 is a view showing a first rotary kiln apparatus for a hydrogen reduction apparatus of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention
3 is a view showing a second rotary kiln apparatus for a hydrogen reduction apparatus of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention
4 is a view showing a third rotary kiln apparatus for a hydrogen reduction apparatus of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention
5 is a view showing a horizontal method for a hydrogen reduction apparatus of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention
6 is a view showing a vertical method for a hydrogen reduction apparatus of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention
7 is a diagram showing a flow chart of a method for reducing hydrogen of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First of all, in adding reference numerals to elements of each drawing, it should be noted that the same elements are assigned the same numerals as possible even if they are indicated on different drawings. In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

First, a key technical configuration of a hydrogen reduction apparatus of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention will be described in detail with reference to FIGS. 2 to 6.

The present invention includes a first rotary kiln device 100, a second rotary kiln device 200, a third rotary kiln device 300, an ultrasonic generator 400, and a cooling chamber 500.

Referring to FIG. 2, the first rotary kiln device 100 is dried while stirring the ore (NiO or MoO3) powder charged into the chamber 130 through the first hopper 110 for charging, and As a means for preheating, a plurality of blades 120 for stirring the ore (NiO or MoO3) powder charged through the hopper 110 are welded to the inner diameter, and a cylindrical first chamber made of stainless steel While rotating and stirring the (First Chamber, 130A) at 1 to 10 RPM, drying and preheating functions are performed through the LPG or LNG gas burner 140.

Here, the cylindrical first chamber 130A is rotated at 1 to 10 RPM by a pair of opposite rollers (RR) connected to a three-phase motor having a deceleration function or a driving device of a chain, and the first It has a hopper (110) and a sealed structure. In addition, the dried and preheated ore (NiO or MoO3) powder is automatically transferred to the second hopper 210 of the second rotary kiln device 200 through the first outlet 150.

In addition, drying and preheating of the first rotary kiln device 100 according to an embodiment of the present invention is performed by direct injection into the cylindrical chamber 120 using the LPG or LNG gas burner 140. The ore powder charged in the cylindrical chamber 130 may be dried and preheated through heating at 200°C to 300°C.

In addition, referring to FIG. 3, the second rotary kiln device 200 is a means for primarily performing low-temperature hydrogen reduction on a metal oxide such as nickel or molybdenum charged from the first rotary kiln device 100, the The second rotary kiln device 200 is a fixed structure equipped with an insulation system on the outside, and has a second chamber 130B that can rotate in a cylindrical shape, and in the first rotary kiln device 100 After the dried and preheated ore powder is charged into the second chamber 130B, reformed hydrogen is injected and the first electric induction heating is performed while rotating and stirring at 1 to 10 RPM.

Here, the second chamber 130B is rotated at 1 to 10 RPM by a pair of opposed rollers (R-R) driving devices connected to a three-phase motor having a reducer.

In addition, the second rotary kiln device 200 according to an exemplary embodiment of the present invention comprises, first, the ore powder of _{nickel oxide (NiO) or molybdenum oxide (MoO 3) charged from the first rotary kiln device 100.} It includes a second hopper 210 to be charged into the second chamber (130B).

Next, a plurality of ore powders are mounted on the inner diameter of the second chamber 130B, and the powder of ore charged through the second hopper 210 rises along the sidewall of the inner diameter and then freely falls, resulting in a natural agitation with hydrogen. A first screw 220 is provided to accelerate the reduction reaction.

In addition, a first electric induction that is mounted on the outer diameter of the second chamber 130B and capable of controlling the temperature of ore powder charged in the second chamber 130B and the second chamber 130B at 500°C to 700°C A heating device 230 is provided.

Here, the reason for heating to a temperature of 500° C. to 700° C. is because it is the primary hydrogen reduction temperature of NiO or MoO 3, and the temperature is controlled by controlling the supply amount of induction electricity using high frequency.

In addition, the control of the temperature of the first electric induction heating device 230 according to an embodiment of the present invention is a power supply control means 231 for supplying the high frequency induction electricity built in the first electric induction heating device 230 It is done through

Here, the heating source of the second rotary kiln device 200 according to an embodiment of the present invention may adopt an electric induction heating or SiC Heat heating method, and the electric induction heating and SiC Heat heating method have a faster temperature control. There are features that can be done accurately.

In addition, for the inner diameter of the second chamber 130B, any one of graphite, silicon carbide (SiC) and silicon nitride (Si3N4) materials that can be easily heated by the first electric induction heating device 230 is selected. It has a first lining tube (240) molded in a cylindrical shape.

Here, although general refractory materials such as Magnesia and Alumina have high heat resistance, they cannot be used because they have poor thermal conductivity and are not heated by high-frequency induction current. In addition, although a conventional heating system may be installed, there is a disadvantage that the initial heating time is long, and an expensive molybdenum heater must be used for frequent failure rate of the heater and high temperature heating.

Therefore, in the embodiment of the present invention, the melting point and sublimation temperature of graphite is 3,642°C, the melting point of silicon carbide (SiC) is 2,830°C, and the melting point of silicon nitride (Si3N4) is 1,900°C, which has high heat resistance and thermal conductivity. It can be easily heated by electric induction heating or SiC heat heating. In addition, since the graphite and the like have very low wettability with metal and the reduced nickel or molybdenum does not stick to the inner surface of the second rotary kiln device 200, any one of these materials can be selectively applied. .

In addition, when the second chamber 130B is rotated by a pair of rollers RR opposed to the outer diameter of the second chamber 130B, the second chamber 130B is held and the second chamber 130B is held. 2 A first steel sleeve 250 is provided to help the rotating function of the chamber 130B.

Here, by placing the first steel sleeve 250 according to an embodiment of the present invention in the center of the second chamber 130B, the first lining tube is installed inside the second chamber 130B. (240) It is characterized by making it easier to seal both ends.

In addition, a first water introduction quality device 260 is provided at the inlet side of the second chamber 130B and storing and supplying butane gas-reformed hydrogen.

Here, the reason for installing the water introduction quality device 260 is, as mentioned above as a problem in the background art, hydrogen used for reduction can use industrial hydrogen produced through electrolysis, but lower the hydrogen reduction cost. This is because the cost can be greatly reduced by reforming and using cheap butane gas.

Therefore, the water introduction quality device 260 according to an embodiment of the present invention is applied to the third rotary kiln device 300 as well as the second rotary kiln device 200.

In addition, the first vent hole 270 is installed at the upper end of the outlet side of the second chamber 130B and allows the water vapor (H2O) generated in the hydrogen reduction reaction and the reduced hydrogen gas (H2) of hydrogen to be discharged together. ) Is provided.

Here, the reason for installing the vent hole 270 is as follows, as shown in the known hydrogen reduction reaction equation of nickel and molybdenum.

In other words,

NiO + H2 = Ni + H2O

MoO3 + 2H2 = MoO + 2H2O → 1st reduction

MoO + H2 = Mo + H2O → 2nd reduction

It is very insignificant when the equivalent ratio of hydrogen used in the reaction equation is calculated as a weight ratio. This is because Nickel's atomic weight is 54 and Molybdenum's atomic weight is 97, whereas hydrogen's atomic weight is 1. However, it is not possible to react in an airtight state in the reaction chamber. This is because water vapor (H2O) and hydrogen (H2) generated in the reduction reaction must be discharged together through the vent hole (270).

Finally, the nickel or molybdenum metal oxide, which is installed at the lower end of the outlet side of the second chamber 130B, and which is firstly reduced in the first tube 240 of the second chamber 130B, is used in a third rotary kiln device 300 A second outlet 280 for charging into the third hopper 310 of) is provided.

Referring to FIG. 4, the third rotary kiln device 300 is a means for secondaryly performing high-temperature hydrogen reduction on a metal oxide such as nickel or molybdenum charged from the second rotary kiln device 200. 3 The outside of the rotary kiln device 300 is a fixed structure equipped with an insulation system, and the inside has a third chamber (130C) capable of rotating a cylindrical shape, and 1 in the second rotary kiln device 200 After charging ore powder subjected to hydrogen reduction reaction by car into the inside of the third chamber (130C), reformed hydrogen is injected while rotating and agitating at 1 to 10 RPM and secondly performing a high-temperature hydrogen reduction reaction function by second electric induction heating. do.

Here, the third chamber (130C) is rotated at 1 to 10 RPM by a driving device of a pair of opposed rollers (R-R) connected to a three-phase motor having a reducer.

On the other hand, the detailed technical configuration of the third rotary kiln device 300 according to an embodiment of the present invention includes detailed technical components of the second rotary kiln device 200, and there is a degree of difference in code and some configurations. .

That is, the third rotary kiln device 300 may first transfer the ore powder of _{nickel oxide (NiO) or molybdenum oxide (MoO 3} ) that has undergone a primary hydrogen reduction reaction from the second rotary kiln device 200 to the third. It has a third hopper 310 to be charged into the chamber (130C).

Next, a plurality of ore powders are mounted on the inner diameter of the third chamber 130C, and the powder of ore charged through the third hopper 310 rises along the sidewall of the inner diameter and then freely falls. A second screw (Screw, 320) is provided to accelerate the reduction reaction of.

In addition, a second high frequency induction mounted on the outer diameter of the third chamber 130C and capable of controlling the temperature of ore powder charged in the third chamber 130C and the third chamber 130C at 900°C to 1.300°C. A heating device 330 is provided.

In addition, in the inner diameter of the third chamber 130B, any one of graphite, silicon carbide (SiC) and silicon nitride (Si3N4) materials that can be easily heated by the second electric induction heating device 330 is selected. It has a second lining tube (2nd Lining Tube 340) to be molded.

In addition, when the third chamber 130B is rotated by a pair of rollers RR opposed to the outer diameter of the third chamber 130B, the third chamber 130B is held and the third chamber 130B is held. 3 A second steel sleeve 350 is provided to help the rotating function of the chamber 130B.

In addition, a second water introduction device 360 is provided at the inlet side of the third chamber 130C and is provided to store and supply hydrogen converted from butane gas.

In addition, the second vent hole 370 is installed at the upper end of the outlet side of the third chamber 130C and allows the water vapor (H2O) generated in the hydrogen reduction reaction and the reduced hydrogen gas (H2) of hydrogen to be discharged together. ) Is provided.

Finally, it is installed at the lower end of the outlet side of the third chamber (130C), and discharges the secondly reduced nickel or molybdenum metal oxide from the tube 340 of the third chamber (130C) to a cooling chamber (500). A third outlet 380 is provided.

Meanwhile, referring to FIG. 4, in the third rotary kiln device 300 according to an embodiment of the present invention, nickel oxide or molybdenum oxide undergoes a reduction reaction with hydrogen. An ultrasonic generator 400 serving as a catalyst to cause the reaction to occur is further included.

Here, nickel has a low melting point of 1,455°C, so it melts down between particles or on the surface of the particles, which can interfere with the continuous reaction of hydrogen, thus contributing to preventing such a phenomenon. That is, by irradiating ultrasonic waves through the ultrasonic generator 310 inside the third rotary kiln device 300, the hydrogen reduction efficiency is improved, as well as preventing the formation of a nickel oxide or molybdenum oxide coating film due to entanglement between nickel powder particles. There are features that can be done.

In addition, referring to FIG. 4, the third rotary kiln device 300 according to an embodiment of the present invention further includes a cooling chamber 500 for cooling the reduced nickel or molybdenum metal.

Meanwhile, referring to FIGS. 5 and 6, the first rotary kiln device 100 to the third rotary kiln device 300 reduce metal oxides such as nickel or molybdenum in large quantities through a continuous and automated hydrogen reduction device. For investment and maintenance, any one of a vertical type and a horizontal type can be selected and installed.

This arrangement method has a feature that not only can greatly reduce the consumption of hydrogen and reduce metal oxides such as nickel or molybdenum in a large amount, but also greatly reduce the installation cost and maintenance cost of the hydrogen reduction reaction device.

In this way, depending on the structure of the hydrogen reduction reaction chamber, the amount of hydrogen used may be several times to several tens of times the theoretical required amount. Existing reaction chambers for hydrogen reduction are generally manufactured in the form of a long tunnel like a train, and a rotating device for transport made of a mesh belt is installed at the bottom of the chamber, and a batt made of ceramic is installed on the mesh belt. Here, NiO or MoO3 powder to react with hydrogen is put and driven. This structure requires several times more space than the space required for the reaction, so the required amount of hydrogen is excessive, and the drive windows such as the mesh belt must be made of heat-resistant steel, so the failure rate is high and the installation cost of the device is very high. In particular, sulfur contained in the ore powder and water (H ₂ O) generated during the reduction reaction react to become sulfuric acid (H ₂ SO ₄ ), and this sulfuric acid corrodes the heat-resistant steel chamber, causing an accident that a hole is punctured. In addition, NiO or MoO ₃ contained in Batt undergoes a reduction reaction with hydrogen from the upper layer, and the reaction efficiency inevitably decreases as it reacts in a stationary state. For this reason, the existing mesh belt type hydrogen reduction device increases the consumption of hydrogen and is therefore economical. Another existing hydrogen reduction system is a fluidizing process, and this method puts NiO or MoO ₃ in a long rectangular reaction chamber and injects hydrogen gas to the bottom of the chamber, so that NiO and MoO ₃ flow together with the gas. ) To cause a reduction reaction. This method has the advantage of maximizing the contact area between hydrogen and metal oxide, but it is _{difficult to selectively discharge the reaction gas, water vapor (H 2} O), and it is difficult to grasp the degree of reduction of nickel or molybdenum. In addition, batch type is also possible, but continuous mass production is difficult. In addition, there is a problem in that the production cost is increased by increasing the consumption of hydrogen, and not only the investment cost of the reduction reactor is required, but also the maintenance cost is high.

Therefore, in the embodiment of the present invention, the ore powder of nickel oxide (NiO) or molybdenum oxide (MoO3) is preheated and dried in the first rotary kiln 100, and in the second rotary kiln 200, at a low temperature (500 degrees C ~ 700). In Fig. C), a hydrogen reduction reaction is performed, and in the third rotary kiln 300, a hydrogen reduction reaction is performed at a high temperature (900°C to 1300°C) to complete the reduction reaction. In addition, the first rotary kiln 100 to the third rotary kiln 300 may be vertically arranged in a stacked manner, or installed in a horizontal arrangement arranged in a row, thereby solving all of the conventional problems mentioned above. There are features.

Hereinafter, a method for reducing hydrogen of nickel oxide and molybdenum oxide according to a preferred embodiment of the present invention will be described in detail.

The method for hydrogen reduction of nickel oxide and molybdenum oxide according to the present invention includes constituting means of a hydrogen reduction apparatus for nickel oxide and molybdenum oxide described in detail above.

First, the hydrogen reduction method of nickel oxide and molybdenum oxide is by charging ore (NiO or MoO3) powder into the rotatable first chamber 130A through the first hopper 110 of the first rotary kiln device 100. It has a first step (S100) of performing a drying and preheating function through the gas burner 140 while stirring.

In addition, drying and preheating in the first step according to an embodiment of the present invention are dried and preheated by spraying directly into the first chamber 130A using the LPG or LNG gas burner and heating to 200°C to 300°C. It may include more to order.

Next, after charging the dried and preheated ore powder into the second chamber 130B of the second rotary kiln device 200 capable of rotating and stirring at 1 to 10 RPM, reformed hydrogen injection and electric induction heating using high frequency It has a second step (S200) of firstly performing a low-temperature hydrogen reduction reaction function by.

In addition, the low-temperature hydrogen reduction reaction of the second step according to an embodiment of the present invention may further include heating to 500°C to 700°C through the first electric induction heating device 230.

In addition, the inner diameter of the second chamber 130B according to an embodiment of the present invention is made of graphite, silicon carbide (SiC), and silicon nitride (Si3N4) that can be easily heated by the first electric induction heating device 230. The step of selecting any one of the first lining tubes 240 may be further included.

Here, selecting any one of graphite, silicon carbide (SiC), and silicon nitride (Si3N4) materials in the forming step of the first lining tube 240 is high in heat resistance and thermal conductivity. In addition, it is not only easy to heat by high frequency induction heating, but also has a very low wettability with metal so that the reduced nickel or molybdenum does not stick to the inner surface of the chamber of the rotary kiln device.

In addition, when performing the low-temperature hydrogen reduction reaction of the second step according to an embodiment of the present invention, the step of opening the first vent hole 270 installed at the upper end of the outlet side of the second chamber 130B It can be included more.

Here, the reason for opening the first vent hole 270 is that the atomic weight of Nickel is 54 and the atomic weight of Molybdenum is 97, whereas the atomic weight of hydrogen is 1. There is a feature that can solve the problems that cannot be solved.

Next, the ore powder subjected to the first hydrogen reduction reaction is charged into the third chamber 130C of the third rotary kiln device 300 capable of rotating and stirring at 1 to 10 RPM, and then reformed hydrogen is injected and high frequency is used. It has a third step (S300) of performing a secondary high-temperature hydrogen reduction reaction function by electric induction heating.

In addition, the high-temperature hydrogen reduction reaction in the third step according to an embodiment of the present invention may further include heating to 900°C to 1,300°C through the second electric induction heating device 330.

In addition, in the inner diameter of the third chamber 130B according to an embodiment of the present invention, graphite, silicon carbide (SiC) and silicon nitride (Si3N4) that can be easily heated by the second high frequency induction heating device 330 The step of forming a second lining tube 340 by selecting any one of the materials may be further included.

In addition, when performing the high-temperature hydrogen reduction reaction of the third step according to an embodiment of the present invention, the step of opening the second vent hole 370 installed at the upper end of the outlet side of the third chamber 130C It can be included more.

Here, the reason for opening the second ventilation hole 370 is that it has the same characteristics as the reason for opening the first ventilation hole 270 in the second step above.

In addition, the third step further comprises a fourth step of irradiating ultrasonic waves through the ultrasonic generator 400 to prevent entanglement between the particles of the ore powder during the reduction reaction with hydrogen and to promote the reduction reaction, and the third step A fifth step of cooling the nickel or molybdenum oxide reduced in the step through the cooling chamber 500 is further included.

On the other hand, according to another embodiment of the present invention, the first rotary kiln device 100 to the third rotary kiln device 300 is a stacked vertical type in order to enable continuous mass production with high thermal efficiency and automation. The step of selecting any one of (Vertical Type) or a horizontal type installed in a horizontal arrangement may be further included.

In addition, the second rotary kiln device 200 and the third rotary kiln device 300 have a fixed structure equipped with an insulation system on the outside, and a cylindrical chamber structure capable of rotating inside is molded. It can be included more.

In addition, the reformed hydrogen injection in the second and third steps according to an embodiment of the present invention is produced by reforming butane gas through the first water introduction device 260 and the second water introduction device 360. One hydrogen can be used.

Here, the reason why butane gas is reformed and used is that expensive industrial hydrogen produced through electrolysis may be used, but the present invention has a characteristic of lowering the hydrogen reduction cost.

The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications and variations without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain the technical idea, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: first rotary kiln device 110: first hopper
120: stirring blade
130A, 130B, 130C: 1st chamber to 3rd chimber
140: gas burner 200: first rotary kiln device
210: second hopper 220: first screw
230: first electric induction heating device 231: first power supply control means
240: first lining tube 250: first steel sleeve
260: first water introduction quality device 270: first ventilation hole
280: second outlet 300: third rotary kiln device
310: third hopper 320: second screw
330: second electric induction heating device 331: second power supply control means
340: second lining tube 350: second steel sleeve
360: second water introduction quality device 370: second ventilation hole
380: third outlet 400: ultrasonic generator
500: cooling chamber

Claims (10)

In the hydrogen reduction method of nickel oxide and molybdenum oxide,
In the method, a plurality of blades 120 are welded to the inner diameter through the first hopper 110 of the first rotary kiln device 100, and the ore (NiO or MoO3) powder is transferred to the rotatable first chamber 130A. The first step of performing drying and preheating functions at 200°C to 300°C by charging, rotating at 1 to 10 RPM, stirring by the blades, and spraying directly into the first chamber through the LPG or LNG gas burner 140 at the same time. Wow;
Graphite, silicon carbide (SiC), and silicon nitride (Graphite) molded in the inner diameter of the second chamber 130B of the second rotary kiln apparatus 200 capable of rotating and stirring the dried and preheated ore powder at 1 to 10 RPM. Si3N4) After charging the inside of a selected lining tube, hydrogen injection produced by reforming butane gas through the first water introduction device 260 and the first electricity using high frequency A second step of performing a first low-temperature hydrogen reduction reaction function at 500°C to 700°C by the induction heating device 230;
Graphite and silicon carbide (SiC) molded in the inner diameter of the third chamber 130C of the third rotary kiln device 300 capable of rotating and stirring the ore powder subjected to the first hydrogen reduction reaction at 1 to 10 RPM, and After charging any one of silicon nitride (Si3N4) materials into the selected lining tube, the hydrogen injection produced by reforming butane gas through the second water introduction device 360 and high frequency use And a third step of performing a secondary high-temperature hydrogen reduction reaction function at 900°C to 1,300°C by the second electric induction heating device 330;
In addition, a fourth step of irradiating ultrasonic waves through the ultrasonic generator 400 to prevent entanglement between the particles of the ore powder during the reduction reaction with hydrogen in the third step and to promote the reduction reaction;
The nickel oxide and molybdenum oxide hydrogen reduction method further comprises a fifth step of cooling the nickel or molybdenum oxide reduced in the third step through a cooling chamber (500).
delete delete delete delete delete The method of claim 1,
When performing the low-temperature hydrogen reduction reaction of the second step, the step of opening the first vent hole 270 installed at the upper end of the outlet side of the second chamber 130B is further included. Hydrogen reduction method of nickel and molybdenum oxide.
The method of claim 1,
When performing the high-temperature hydrogen reduction reaction of the third step, the step of opening the second vent hole 370 installed at the upper end of the outlet side of the third chamber 130C is further included. Hydrogen reduction method of nickel and molybdenum oxide.
The method of claim 1,
The first rotary kiln device 100 to the third rotary kiln device 300 are horizontally installed in a stacked vertical type or horizontally arranged to enable continuous mass production with high thermal efficiency and automation. A method for reducing hydrogen of nickel oxide and molybdenum oxide, characterized in that the step of selecting any one of horizontal types is further included.
The method of claim 1,
The second rotary kiln device 200 and the third rotary kiln device 300 further include a step of forming a fixed structure equipped with an insulation system on the outside and a cylindrical chamber structure capable of rotating inside. Nickel oxide and molybdenum oxide hydrogen reduction method, characterized in that it has.

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