Reaction method

Abstract

To provide a reaction apparatus and a reaction apparatus component in which durability is hard to deteriorate even in an environment where a treatment object is reacted at 300°C or higher, and a sulfur component is included in at least one of the treatment object and an atmosphere thereof.SOLUTION: A reaction apparatus component according to one embodiment is used for a reaction apparatus in which a treatment object is reacted in an environment where a sulfur component is contained in at least one of the treatment object and an atmosphere thereof, and is composed of an alloy essentially consisting of Fe, comprising Cr of 13 to 35 mass% and comprising Ni and Co of 0 to 35 mass% in total.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to reactors and components for reactors. [Background technology]

[0002] For example, Patent Document 1 discloses a reaction apparatus having a screw feeder body serving as a pressure reaction vessel, a catalyst supplying section for introducing a catalyst into the screw feeder body, and a lower hydrocarbon supplying section for introducing lower hydrocarbons into the screw feeder body. This reaction apparatus also has a screw for transporting the generated nanocarbon, a solid delivery section for delivering the catalyst and nanocarbon transported by the screw, and a gas delivery section for delivering the generated hydrogen to the outside of the feeder body. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2006-290682 A Summary of the Invention [Problem to be solved by the invention]

[0004] The reaction apparatus and its components in Patent Document 1 have a problem in that the durability decreases in an environment where the material to be treated is reacted at a temperature of 300° C. or higher and at least one of the material to be treated and the atmosphere contains sulfur components.

[0005] The present disclosure has been made to solve such problems, and provides a reactor and reactor components that react materials at temperatures of 300°C or higher and are resistant to deterioration in durability even in an environment in which at least one of the materials to be treated and the atmosphere contains sulfur components. [Means for solving the problem]

[0006] The reactor component according to one embodiment comprises: The present invention is used in a reaction apparatus for reacting a material to be treated in an environment in which at least one of the material to be treated and the atmosphere contains a sulfur component, It is composed of an alloy containing Fe as a main component, 13 to 35 mass % of Cr, and 0 to 35 mass % in total of Ni and Co.

[0007] The reactor component according to one embodiment comprises: The present invention is used in a reaction apparatus for reacting a material to be treated in an environment in which at least one of the material to be treated and the atmosphere contains a sulfur component, It is composed of an alloy containing Ni or Co as a main component, 13 to 35 mass % of Cr, and a total of 35 to 87 mass % of Ni and Co.

[0008] The reactor component according to one embodiment comprises: The present invention is used in a reaction apparatus for reacting a material to be treated in an environment in which at least one of the material to be treated and the atmosphere contains a sulfur component, The alloy is mainly composed of Ni or Co, contains less than 13% by mass of Cr, and contains 40 to 80% by mass of Ni and Co in total; The alloy has a coating film formed on its surface.

[0009] In one embodiment, the reactor comprises: reacting the material to be treated in an environment in which at least one of the material to be treated and an atmosphere contains a sulfur component; The cylinder into which the material to be treated is supplied is made of an alloy containing Fe as a main component, 13 to 35 mass % of Cr, and 0 to 35 mass % in total of Ni and Co.

[0010] In one embodiment, the reaction apparatus comprises: reacting the material to be treated in an environment in which at least one of the material to be treated and an atmosphere contains a sulfur component; The cylinder into which the material to be treated is supplied is made of an alloy containing Ni or Co as a main component, 13 to 35 mass % of Cr, and 35 to 87 mass % of Ni and Co in total.

[0011] In one embodiment, the reactor comprises: reacting the treated material in an environment where at least one of the treated material and an atmosphere contains a sulfur component; The cylinder into which the material to be treated is supplied is made of an alloy containing Ni or Co as a main component, less than 13% by mass of Cr, and 40 to 80% by mass of Ni and Co in total; The alloy has a coating film formed on its surface. Effect of the Invention

[0012] According to the present disclosure, it is possible to provide a reactor and reactor components that are resistant to deterioration in durability even in an environment in which a material to be treated is reacted at a temperature of 300°C or higher and at least one of the material to be treated and the atmosphere contains sulfur components. [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a cross-sectional view of a high temperature reaction apparatus according to a first embodiment. [Diagram 2] FIG. 4 is a cross-sectional view of a high temperature reaction apparatus according to a second embodiment. [Diagram 3] FIG. 11 is a cross-sectional view of a high temperature reaction apparatus according to a third embodiment. [Figure 4] FIG. 2 is a ternary diagram showing the compositions of alloys according to Examples E1 to E13 and Comparative Examples C1 to C3. [Diagram 5] 1 is a graph showing the temperature dependence of the thermal expansion coefficient (linear expansion coefficient) of alloys according to Comparative Examples C21 and C22 and Example E21. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, specific embodiments will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. In addition, the following description and drawings are appropriately simplified for clarity of explanation.

[0015] <Preliminary review by the inventor> There are known devices for producing desired products by applying a predetermined temperature to powders. For example, a positive electrode active material for a lithium-ion secondary battery is produced by applying a predetermined temperature to a mixed powder of a plurality of types of powders. For example, a device called a rotary kiln produces a desired positive electrode active material by heating a hollow furnace body that rotates around a central axis and passing the mixed powder through the furnace body while rolling it. Also, for example, a device called a roller hearth kiln produces a desired positive electrode active material by passing a ceramic sheath filled with the mixed powder through a preheated tunnel-shaped furnace body. Various other devices have also been developed.

[0016] In recent years, lithium ion secondary batteries called all-solid-state lithium ion secondary batteries have been developed. In all-solid-state lithium ion secondary batteries, a solid electrolyte is used as an ion conductor instead of a conventional electrolyte solution. That is, not only the positive electrode active material but also the solid electrolyte is produced by applying a predetermined temperature to powder particles.

[0017] On the other hand, unlike the cathode material of conventional lithium ion secondary batteries, when producing the cathode active material or solid electrolyte of the all-solid-state lithium ion secondary battery, it is preferable to strictly control the temperature so that the powder is in a predetermined temperature range. Furthermore, it is preferable that the powder contains sulfur, and in order to prevent the sulfur component from being released, it is preferable to strictly control the atmosphere so that the inside of the furnace is a sulfur atmosphere. Specifically, it is preferable to use a sulfur compound such as lithium sulfide as the powder containing sulfur as a part of the component, and to use hydrogen sulfide as the atmospheric gas.

[0018] However, in the above-mentioned rotary kiln, a thick ceramic material is often used for the inner wall of the hollow furnace body, and such ceramic material usually has a lower thermal conductivity than metal, so there is a problem that it is not possible to precisely control the temperature to appropriately impart a predetermined temperature to the mixed powder at a predetermined position in the hollow furnace body of the rotary kiln.

[0019] On the other hand, in hearth kilns, the powder is transported in a ceramic sheath, so the temperature and atmosphere of the powder near the outside of the sheath are different from that of the powder near the center of the sheath. Therefore, there is a problem that the temperature and atmosphere of the powder cannot be strictly controlled in the hearth kiln. For these reasons, there is a problem that rotary kilns and hearth kilns cannot be used for mass production of products that require strict temperature and atmosphere control, such as positive electrode active materials and solid electrolytes for all-solid-state lithium-ion secondary batteries.

[0020] Therefore, as typified by Patent Document 1, the inventors developed an atmosphere-controllable reaction apparatus in which a rotatable screw is laid horizontally inside a cylindrical reaction furnace (cylinder), which makes it possible to continuously produce products such as positive electrode active materials and solid electrolytes for all-solid-state lithium-ion secondary batteries from processed materials consisting of powder and granular materials, thereby solving the above-mentioned problems. However, the reaction apparatus of Patent Document 1 has a problem in that the durability of the reaction apparatus and reaction apparatus parts decreases under conditions where at least one of the material to be treated and the atmosphere contains sulfur components.

[0021] (First embodiment) <Reaction apparatus configuration> First, the configuration of the high temperature reaction apparatus according to the first embodiment will be described with reference to Fig. 1. Fig. 1 is a cross-sectional view of the high temperature reaction apparatus according to the first embodiment. As shown in FIG. 1, a high temperature reaction apparatus 10 according to this embodiment includes a cylinder 100, a heating device 110, and a screw 120.

[0022] The high-temperature reactor 10 is a reactor that reacts materials (e.g., raw materials) at a temperature of 300°C or higher, and is a reactor for producing, for example, a positive electrode active material and a solid electrolyte for an all-solid-state lithium-ion secondary battery. The positive electrode active material and the solid electrolyte produced by the high-temperature reactor 10 are used as components of the all-solid-state lithium-ion secondary battery. In other words, the high-temperature reactor 10 can be said to be a manufacturing device for components for all-solid-state lithium-ion secondary batteries.

[0023] 1, the cylinder 100 has a cylindrical main body 101 extending in the horizontal direction, a supply port 102 extending upward from an upper end portion on the upstream side of the main body 101, and a discharge port 103 extending downward from a lower end portion on the downstream side of the main body 101. A material to be treated R10 is supplied from the supply port 102, and a product R11 is discharged from the discharge port 103. The cylinder 100 has an intermediate portion between the supply port 102 and the discharge port 103.

[0024] The material constituting the cylinder 100 has heat resistance against the processing temperature of the material in the furnace. The processing temperature is 300° C. or higher. The processing temperature may be 500° C. or higher, or even 800° C. or higher.

[0025] In addition, the material constituting the cylinder 100 has sulfur corrosion resistance against the material to be treated and the atmosphere (especially sulfur compounds such as lithium sulfide and hydrogen sulfide) supplied into the furnace. The concentration of hydrogen sulfide in the atmosphere is, for example, 10% by volume or more. The purpose of supplying hydrogen sulfide to the atmosphere is to suppress the desorption of sulfur components from the material to be treated and to form an equilibrium state of the sulfur components. Therefore, the higher the concentration of hydrogen sulfide in the atmosphere, the better, and it is preferably 50% by volume or more, and more preferably 100% by volume. The sulfur components in the atmosphere of the cylinder 100 may form an equilibrium state of the sulfur components by being generated from the material to be treated. Alternatively, the equilibrium state of the sulfur components may be formed by introducing a sulfur compound from the outside of the cylinder 100 separately from the material to be treated.

[0026] Therefore, the cylinder 100 according to this embodiment is made of any one of alloys (1) to (3) having the following compositions. (1) An alloy containing Fe as the main component, 13 to 35 mass% Cr, and 0 to 35 mass% Ni and Co in total. (2) An alloy mainly composed of Ni or Co, containing 13 to 35 mass% Cr, and containing 35 to 87 mass% Ni and Co in total. (3) An alloy mainly composed of Ni or Co, containing less than 13% by mass of Cr, and containing 40 to 80% by mass of Ni and Co in total. Here, a coating film is formed on the surface of the cylinder 100 made of the alloy (3). A coating film may be formed on the surface of the cylinder 100 made of the alloys (1) and (2). The alloys and coating film constituting the cylinder 100 will be described in detail later.

[0027] As shown in Fig. 1, a screw 120 is housed inside the cylinder 100. When the screw 120 rotates, the material R10 to be treated, which is supplied from a supply port 102 into the inside of the cylinder 100, is transported downstream. When the material R10 to be treated passes through an intermediate portion of the cylinder 100, the material R10 reacts to obtain a predetermined product R11. The predetermined product R11 is then discharged from a discharge port 103.

[0028] 1, the heating device 110 is provided so as to cover the outer peripheral surface of the middle part of the cylinder 100, and heats the cylinder 100. The heating device 110 includes any heater capable of adjusting the temperature, such as a sheath heater, a coil heater, or a ceramic heater. The heating device 110 can heat, for example, a predetermined position in the middle part of the cylinder 100 in a range from room temperature to about 900° C.

[0029] Here, the heating device 110 may be able to set different temperatures along the axial direction of the screw 120 for each region in the middle part of the cylinder 100. For example, the heating device 110 may change the heating temperature of the material R10 to be treated in each of the first reaction zone RZ1 and the second reaction zone RZ2. That is, the middle part of the cylinder 100 may have one region (reaction zone), or may have two or more regions. In addition, the temperature set by the heating device 110 may be the same temperature along the axial direction of the screw 120 within the range of one reaction zone, or the temperature may be changed. That is, the first reaction zone RZ1 may be set so that the temperature at the start point is 300°C, the temperature at the end point is 600°C, and the temperature gradient from the start point to the end point is 300°C to 600°C.

[0030] The heating device 110 may also include a control device for controlling heating. For example, the control device controls the heating temperature of the cylinder 100 by controlling the value of a current flowing through the heating device. Furthermore, the heating device 110 may include a temperature sensor at a predetermined position of the cylinder 100. For example, the control device feedback-controls the heating temperature of the cylinder 100 based on the temperature measured by the temperature sensor.

[0031] The heating device 110 may be configured to heat the cylinder 100 by circulating a heat medium such as water or oil. Furthermore, the high temperature reaction apparatus 10 according to this embodiment may include a cooling device for cooling the cylinder 100 in addition to the heating device 110 .

[0032] 1, the screw 120 extends over substantially the entire length of the cylinder 100. The material to be treated R10 supplied from the supply port 102 is transported toward the discharge port 103 by the rotation of the screw 120.

[0033] The screw 120 shown in Fig. 1 has a spiral screw flight 122 formed around a shaft 121 extending in the left-right direction of Fig. 1. The screw flight 122 rotates while contacting the material R10 to be treated, so that the screw 120 transports the material R10 from the upstream side to the downstream side. It should be noted that there may be two or more screws 120. That is, the high temperature reaction apparatus 10 may have a plurality of screws 120 arranged in parallel.

[0034] The material constituting the screw 120 is made of any one of the above-mentioned alloys (1) to (3), similar to the cylinder 100. In addition, a coating film may be formed on the surface of the screw 120 made of the alloy. The details of the alloy and coating film constituting the screw 120 are similar to those of the alloy and coating film constituting the cylinder 100 described later, and therefore will not be described again.

[0035] The shape of the screw flight 122 shown in FIG. 1 is an example, and the shape of the screw flight 122 is not limited to this. The screw flight 122 may have a different shape for each region of the cylinder 100. More specifically, the helical pitch of the screw flight 122 may vary for each region of the cylinder 100. Here, the helical shape of the screw flight 122 may be two-thread instead of one-thread. Furthermore, the screw flight 122 may have a portion that is not helical. Furthermore, the thickness and shape of the shaft 121 of the screw 120 may vary.

[0036] With this configuration, the speed and transport amount of the material R10 transported by the screw 120 can be set for each region of the cylinder 100 in the high temperature reaction apparatus 10. The transport amount of the material R10 can be changed appropriately depending on the application, and for example, 200 grams per hour or more is preferable for prototyping, and for example, 100 kilograms per hour or more is preferable for production. Furthermore, while transporting the material R10 at a predetermined speed, stirring, kneading, or pulverization may be added for each region of the cylinder 100 in the high temperature reaction apparatus 10.

[0037] The shaft 121 of the screw 120 is rotatably supported at both ends of the cylinder 100. The upstream end of the screw 120 shown in Fig. 1 is connected to a drive unit MT1. In Fig. 1, a drive gear MG1 fixed to the rotating shaft of the drive unit MT1 and a screw gear SG fixed to the upstream end of the shaft 121 of the screw 120 are engaged with each other.

[0038] Here, the material constituting the drive gear MG1 and the screw gear SG is made of any of the above-mentioned alloys (1) to (3). Furthermore, a coating film may be formed on the surface of the drive gear MG1 and the screw gear SG made of the alloy. The details of the alloy and coating film constituting the drive gear MG1 and the screw gear SG are similar to those of the alloy and coating film constituting the cylinder 100 described later, and therefore will not be described here.

[0039] Here, the drive unit MT1 is a rotation drive mechanism such as a motor, and drives the screw 120 to rotate. The drive unit MT1 may be capable of changing the rotation speed of the screw 120. In this case, the drive unit MT1 may be a motor capable of changing the rotation speed, or may be a combination of a motor with a fixed rotation speed and a reducer with a changeable reduction ratio.

[0040] The first reaction zone RZ1 is an area between the supply port 102 and the second reaction zone RZ2, i.e., an upstream area, in the middle of the cylinder 100. In order to create a predetermined atmosphere in the first reaction zone RZ1, the first reaction zone RZ1 is provided with a first supply part 32 and a first fluid supply pipe 33 capable of supplying a first fluid F11 to the cylinder 100, and further provided with a first discharge part 34 and a first fluid discharge pipe 35 capable of discharging the first fluid F11 from the cylinder 100.

[0041] The first supply unit 32 is a component having a hole for supplying the first fluid F11 into the cylinder 100 in the first reaction zone RZ1. One end of the first fluid supply pipe 33 is connected to the first supply unit 32 connected to the cylinder 100. The number of the first supply units 32 and the first fluid supply pipes 33 may be one each, but it is preferable that the number of each is two or more depending on the length of the first reaction zone RZ1. As shown in FIG. 1, the other end of the first fluid supply pipe 33 may be connected to a first flow control valve 31. The first flow control valve 31 can control the flow rate of the first fluid F11 supplied to the first reaction zone RZ1 via the first fluid supply pipe 33.

[0042] The first discharge part 34 is a part having a hole for discharging at least a part of the first fluid F11 in the first reaction zone RZ1 to the outside of the cylinder 100. One end of a first fluid discharge pipe 35 is connected to the first discharge part 34 connected to the cylinder 100. The number of the first discharge parts 34 and the first fluid discharge pipes 35 may be one each, but preferably they are two or more each, and it is more preferable that one each is provided on the upstream side and downstream side of the first supply part 32.

[0043] The first fluid F11 may be in any form as long as it has fluidity. That is, the first fluid F11 may be a gas, a liquid, a mixture of gas and liquid, or a mixture of liquid and solid. The first fluid F11 may also be one whose form changes in the first reaction zone RZ1. The first fluid F11 may be, for example, a mixed gas in which hydrogen sulfide and nitrogen are mixed in a volume ratio of 2:1. After being supplied to the first reaction zone RZ1 by the first supply unit 32, the first fluid F11 flows in a branched manner toward the upstream and downstream of the cylinder 100, and is discharged from the first discharge unit 34.

[0044] As shown in Fig. 1, the other end of the first fluid discharge pipe 35 may be connected to a first forced discharge device 36. The first forced discharge device 36 has a function of forcibly discharging a fluid, and efficiently discharges at least a part of the first fluid F11 from the first reaction zone RZ1 through the first discharge section 34 and the first fluid discharge pipe 35. The first forced discharge device 36 may be, for example, a pump using the rotation of a motor, or an aspirator or ejector using the Venturi effect. The first forced discharge device 36 is not limited to the above-mentioned configuration as long as it is a mechanism that can forcibly discharge the fluid discharged from the first reaction zone RZ1.

[0045] Here, the materials constituting the first flow control valve 31, the first supply part 32, the first fluid supply pipe 33, the first discharge part 34, the first fluid discharge pipe 35, and the first forced discharge device 36 are made of any of the above-mentioned alloys (1) to (3), similar to the cylinder 100. Moreover, a coating film may be formed on the surfaces of the first flow control valve 31, the first supply part 32, the first fluid supply pipe 33, the first discharge part 34, the first fluid discharge pipe 35, and the first forced discharge device 36 made of the alloy. The details of the alloy and coating film constituting the first flow control valve 31, the first supply section 32, the first fluid supply pipe 33, the first discharge section 34, the first fluid discharge pipe 35, and the first forced discharge device 36 are similar to the alloy and coating film constituting the cylinder 100 described later, and therefore will not be described here.

[0046] The second reaction zone RZ2 is located in the middle of the cylinder 100 between the first reaction zone RZ1 and the discharge port 103, that is, on the downstream side. In order to create a predetermined atmosphere in the second reaction zone RZ2, the second reaction zone RZ2 is equipped with a second supply section 42 and a second fluid supply pipe 43 capable of supplying a second fluid F21, which has a different type and component ratio from the first fluid F11, to the cylinder 100, and further equipped with a second discharge section 44 and a second fluid discharge pipe 45 capable of discharging the second fluid F21 from the cylinder 100.

[0047] The second supply unit 42 is a component having a hole for supplying the second fluid F21 into the cylinder 100 in the second reaction zone RZ2. One end of a second fluid supply pipe 43 is connected to the second supply unit 42 connected to the cylinder 100. The number of the second supply units 42 and the second fluid supply pipes 43 may be one each, but it is preferable that the number of each is two or more depending on the length of the second reaction zone RZ2. As shown in FIG. 1, the other end of the second fluid supply pipe 43 may be connected to a second flow control valve 41. The second flow control valve 41 can control the flow rate of the second fluid F21 supplied to the second reaction zone RZ2 via the second fluid supply pipe 43.

[0048] The second discharge part 44 is a part having a hole for discharging at least a part of the second fluid F21 in the second reaction zone RZ2 to the outside of the cylinder 100. One end of a second fluid discharge pipe 45 is connected to the second discharge part 44 connected to the cylinder 100. The number of the second discharge parts 44 and the second fluid discharge pipes 45 may be one each, but preferably is two or more each, and it is more preferable that one each is provided on the upstream side and downstream side of the second supply part 42.

[0049] The second fluid F21 may be in any form as long as it has fluidity like the first fluid F11. That is, the second fluid F21 may be a gas, a liquid, a mixture of gas and liquid, or a mixture of liquid and solid. The form of the second fluid F21 may change in the second reaction zone RZ2. The second fluid F21 is, for example, hydrogen sulfide. After being supplied to the second reaction zone RZ2 by the second supply unit 42, the second fluid F21 flows in a branched manner toward the upstream and downstream of the cylinder 100, and is discharged from the second discharge unit 44.

[0050] 1, the other end of the second fluid discharge pipe 45 may be connected to a second forced discharge device 46. The second forced discharge device 46 has a function of forcibly discharging a fluid, and efficiently discharges at least a part of the second fluid F21 from the second reaction zone RZ2 via the second discharge part 44 and the second fluid discharge pipe 45. The configuration of the second forced discharge device 46 is similar to that of the first forced discharge device 36.

[0051] The other ends of the first fluid discharge pipe 35 and the second fluid discharge pipe 45 are connected to, for example, an absorber or a decomposition apparatus (not shown), respectively. With such a configuration, each of the fluids discharged through the first fluid discharge pipe 35 and the second fluid discharge pipe 45 may be made disposable. The absorber is, for example, a scrubber, and dissolves the fluid in the dissolving liquid by spraying the dissolving liquid while passing the fluid through a cylinder filled with a filling. The decomposition apparatus is, for example, a combustor, and burns and decomposes the fluid using a flame from a burner torch or the like.

[0052] Alternatively, the other ends of the first fluid discharge pipe 35 and the second fluid discharge pipe 45 are connected to, for example, a cooling device, a concentration sensor, and a fluid mixing unit, not shown, respectively. With such a configuration, each of the fluids discharged through the first fluid discharge pipe 35 and the second fluid discharge pipe 45 may be supplied again to the cylinder 100 as the first fluid F11 and the second fluid F21. The cooling device cools each of the fluids discharged through the first fluid discharge pipe 35 and the second fluid discharge pipe 45, and converts them into a first cooling fluid and a second cooling fluid (not shown), respectively. The fluid mixing unit adjusts the first cooling fluid and the second cooling fluid to a desired concentration, respectively, to make them reusable.

[0053] In addition to being resupplied to the cylinder 100 via the fluid mixing section, the first cooling fluid and the second cooling fluid may be recovered as reusable fluids by a first cooling fluid recovery section and a second cooling fluid recovery section (not shown), respectively.

[0054] Here, the materials constituting the second flow control valve 41, the second supply part 42, the second fluid supply pipe 43, the second discharge part 44, the second fluid discharge pipe 45, and the second forced discharge device 46 are made of any of the above-mentioned alloys (1) to (3), similar to the cylinder 100. Moreover, a coating film may be formed on the surfaces of the second flow control valve 41, the second supply part 42, the second fluid supply pipe 43, the second discharge part 44, the second fluid discharge pipe 45, and the second forced discharge device 46 made of the alloy. The details of the alloy and coating film constituting the second flow control valve 41, the second supply section 42, the second fluid supply pipe 43, the second discharge section 44, the second fluid discharge pipe 45, and the second forced discharge device 46 are similar to the alloy and coating film constituting the cylinder 100 described later, and therefore will not be described here.

[0055] 1, a third discharge part 54 and a third fluid discharge pipe 55 are provided at the boundary between the first reaction zone RZ1 and the second reaction zone RZ2. The third discharge part 54 is a component having a hole for discharging the first fluid F11, the second fluid F21, or a mixture thereof to the outside of the cylinder 100. One end of the third fluid discharge pipe 55 is connected to the third discharge part 54 connected to the cylinder 100.

[0056] 1, the other end of the third fluid discharge pipe 55 may be connected to a third forced discharge device 56. The third forced discharge device 56 has a function of being able to forcibly discharge a fluid, and efficiently discharges the first fluid F11, the second fluid F21, or a mixture thereof through the third discharge section 54 and the third fluid discharge pipe 55. The configuration of the third forced discharge device 56 is similar to the configurations of the first forced discharge device 36 and the second forced discharge device 46.

[0057] Here, the materials constituting the third discharge part 54, the third fluid discharge pipe 55, and the third forced discharge device 56 are made of any of the above-mentioned alloys (1) to (3), similar to the cylinder 100. Moreover, a coating film may be formed on the surfaces of the third discharge part 54, the third fluid discharge pipe 55, and the third forced discharge device 56 made of the alloy. The details of the alloy and coating film constituting the third discharge portion 54, the third fluid discharge pipe 55, and the third forced discharge device 56 are similar to those of the alloy and coating film constituting the cylinder 100 described later, so that the explanation will be omitted.

[0058] With this configuration, in the high temperature reaction device 10, the treated product R10 that has passed through the first reaction zone RZ1 is further reacted in the second reaction zone RZ2. Then, the treated product R10 that has passed through the second reaction zone RZ2 is transported to the discharge port 103 and discharged as the product R11. The number of reaction zones is not limited to two, and the number of reaction zones may be one or more. In addition, in the reaction zone, a chemical reaction such as a combination reaction or a decomposition reaction may be performed, or a physical reaction such as vaporization, liquefaction, or solidification may be performed. In the reaction zone, even if the above reaction is not involved, preheating (preheating) for efficiently performing a desired reaction in the next reaction zone, or cooling for safely discharging the product R11 from the discharge port 103 may be performed.

[0059] 1, the first supply unit 32 and the second supply unit 42 are disposed on the upper part of the cylinder 100, but may be disposed on the side or lower part of the cylinder 100. Similarly, the first discharge unit 34, the second discharge unit 44, and the third discharge unit 54 are disposed on the upper part of the cylinder 100, but may be disposed on the side or lower part of the cylinder 100. Furthermore, the first supply unit 32 and the second supply unit 42 may be disposed at different positions in the circumferential direction of the cylinder 100. Similarly, the first discharge unit 34, the second discharge unit 44, and the third discharge unit 54 may be disposed at different positions in the circumferential direction of the cylinder 100.

[0060] <Details of the alloy that makes up Cylinder 100> As described above, the cylinder 100 according to this embodiment is made of any one of the following alloys (1) to (3) having the following compositions. (1) An alloy containing Fe as the main component, 13 to 35 mass% Cr, and 0 to 35 mass% Ni and Co in total. (2) An alloy mainly composed of Ni or Co, containing 13 to 35 mass% Cr, and containing 35 to 87 mass% Ni and Co in total. (3) An alloy mainly composed of Ni or Co, containing less than 13% by mass of Cr, and containing 40 to 80% by mass of Ni and Co in total. Here, a coating film is formed on the surface of the cylinder 100 made of the alloy (3). In the alloy (1), the total of Ni and Co is preferably 30% by mass or less, more preferably 25% by mass or less. In the alloy (2), the total of Ni and Co is preferably 40% by mass or more, more preferably 45% by mass or more. On the other hand, the total of Ni and Co is preferably 80% by mass or less, more preferably 75% by mass or less.

[0061] In the above-mentioned alloys (1) and (2), the addition of 13 mass% or more of Cr improves the oxidation resistance and corrosion resistance, and the addition of less than 35 mass% of Cr suppresses the formation of TCP (Topologically Close Packed) phase, which adversely affects ductility and toughness. From the viewpoint of suppressing the formation of TCP phase, the amount of Cr added is preferably 30 mass% or less. The concentrations of Cr, Mo and other alloying elements are measured in accordance with JIS G1256 2013 (Iron and steel - X-ray fluorescence analysis method).

[0062] Moreover, the alloy (particularly alloys (2) and (3)) preferably contains 5 to 20 mass% W. Addition of 5 mass% or more W reduces the difference in thermal expansion coefficient (linear expansion coefficient) between the alloy and the ceramic coating film, and cracking of the ceramic coating film can be suppressed, while addition of 20 mass% or less W can suppress streak-like segregation. Since W is a solid-solution strengthening alloy element, the addition of W improves strength and high-temperature strength. From the viewpoint of suppressing streak-like segregation, the amount of W added is preferably 15 mass% or less.

[0063] The alloy may further contain 0.3 to 25 mass % Mo. Addition of 0.3 mass % or more of Mo improves high-temperature strength, and addition of 25 mass % or less of Mo can suppress the formation of TCP phases that adversely affect ductility and toughness. In order to improve the high temperature strength, the amount of Mo added may be 1 mass % or more, or even 3 mass % or more, while in order to suppress the formation of the TCP phase, the amount of Mo added may be 20 mass % or less, or even 15 mass % or less.

[0064] The alloy may further contain 1 to 3 mass % of Al, which is a precipitation-strengthening alloying element. The addition of 1 mass % or more of Al improves the strength, and the addition of 3 mass % or less of Al can suppress the deterioration of hot workability and the like.

[0065] The alloy may contain at least one additional element selected from the group consisting of C, B, Si, Ti, Nb, Y, Hf, Zr, Ta, and Mn in an amount of 1 mass % or less each, with a total of 1 to 5 mass %.

[0066] The addition of C forms carbides, which refines the crystal grains and improves the strength and high-temperature strength. B, Hf, and Zr segregate at grain boundaries, improving high-temperature strength. The addition of Mn improves the toughness of the alloy. Silicon functions as a deoxidizer when the alloy is melted.

[0067] Ti, Nb, and Ta are precipitation-strengthening alloy elements. Therefore, the addition of Ti, Nb, and Ta improves strength and high-temperature strength. In addition, the addition of Ti forms carbides, which refines the grains and improves strength and high-temperature strength.

[0068] <Details of the coating film that makes up the cylinder 100> The material of the coating film is not particularly limited, but a material that can be easily formed uniformly on the surface of the parts of the high-temperature reaction device, such as a ceramic film or metal plating, is preferable. The ceramic constituting the ceramic film is not particularly limited, but examples thereof include oxides such as alumina and zirconia, nitrides such as titanium nitride and silicon nitride, carbides such as titanium carbide, and borides such as chromium boride. The ceramic film has a thickness of, for example, 0.01 to 5 mm. Depending on the method for forming the alumina film, a deteriorated layer (diffusion layer) of 0.01 to 5 mm may be formed at the interface between the matrix and the ceramic film. The method for forming the ceramic film is not particularly limited. In the case of an alumina film, for example, a thermal spraying method, a vapor deposition method, a sputtering method, a CVD method, a wet method using a precursor such as an aluminum alkoxide, an anodization method of metallic aluminum, etc. can be used. The metal constituting the metal plating is not particularly limited, but may be, for example, a single plating of chromium, nickel, titanium, a precious metal, or the like, a multi-layer plating having a first layer of nickel and a second and third layers of chromium or a precious metal, or a composite plating of a metal and a ceramic.

[0069] As described above, in the high temperature reaction apparatus 10 according to this embodiment, the cylinder 100 and the screw 120 are made of any one of the following alloys (1) to (3) having the following compositions. (1) An alloy containing Fe as the main component, 13 to 35 mass% Cr, and 0 to 35 mass% Ni and Co in total. (2) An alloy mainly composed of Ni or Co, containing 13 to 35 mass% Cr, and containing 35 to 87 mass% Ni and Co in total. (3) An alloy mainly composed of Ni or Co, containing less than 13% by mass of Cr, and containing 40 to 80% by mass of Ni and Co in total. Here, a coating film is formed on the surface of the cylinder 100 made of the alloy (3). Therefore, the high temperature reaction apparatus 10 according to this embodiment can withstand a severe operating environment of a temperature of 300° C. or higher and an atmosphere containing sulfur compounds.

[0070] At least one of the cylinder 100 and the screw 120 may be made of the above alloy. In addition, other reactor parts used in the high temperature reactor 10 may be made of the alloy, not limited to the cylinder 100 and the screw 120. The reactor parts may include gears such as the drive gear MG1 and the screw gear SG described above, and piping such as the first fluid discharge pipe 35 and the second fluid discharge pipe 45 described above.

[0071] Second embodiment Next, the configuration of a high temperature reaction apparatus according to a second embodiment will be described with reference to Fig. 2. Fig. 2 is a cross-sectional view of the high temperature reaction apparatus according to the second embodiment. 2, the high temperature reactor 20 according to this embodiment includes a cylinder 100 and a heating device 110, but does not include a screw 120, like the high temperature reactor 10 shown in FIG 1. The high temperature reactor 20 according to this embodiment further includes a feeder 140, a kiln foot 150, a fluid supplying device 160, and a fluid discharging device 170.

[0072] In the cylinder 100 of the high temperature reaction apparatus 20 according to this embodiment, a supply port 102 is provided on an upstream end surface of a cylindrical main body 101. On the other hand, a downstream end surface of the main body 101 is opened to form a discharge port 103. In addition, in the high temperature reaction apparatus 20 according to this embodiment, the cylinder 100 is supported rotatably with a central axis C10 as a rotation axis, forming a rotary kiln.

[0073] 2, the cylinder 100 is connected to a driving device MT2 on the upstream side. In FIG. 2, a driving gear MG2 fixed to a rotating shaft of the driving device MT2 and a cylinder gear 106 fixed to an outer circumferential surface of a main body 101 of the cylinder 100 are engaged with each other.

[0074] Here, the material constituting the drive gear MG2 and the cylinder gear 106 is made of any of the above-mentioned alloys (1) to (3), similar to the cylinder 100. Moreover, a coating film may be formed on the surface of the drive gear MG2 and the cylinder gear 106 made of the alloy.

[0075] The details of the alloy and coating film constituting the drive gear MG2 and the cylinder gear 106 are similar to those of the alloy and coating film constituting the cylinder 100 according to the first embodiment, and therefore will not be described.

[0076] Here, the drive device MT2 is a rotation drive mechanism such as a motor, and rotates the cylinder 100. The drive device MT2 may be capable of changing the rotation speed of the cylinder 100. In this case, the drive device MT2 may be a motor capable of changing the rotation speed, or may be a combination of a motor with a fixed rotation speed and a reducer with a changeable reduction ratio.

[0077] 2, the cylinder 100 may be installed with its central axis C10 inclined at a predetermined angle θ (for example, 0°<θ<90°) with respect to the horizontal direction so that the upstream side is higher than the downstream side. As a result, in the cylinder 100, the received predetermined processing object R10 is transported to the discharge port 103 along the central axis C10 while contacting the inner wall of the main body 101.

[0078] A feeder 140 is connected to a supply port 102 of a cylinder 100 shown in Fig. 2 via a bearing 104. That is, an upstream end of the cylinder 100 is rotatably supported by the feeder 140. The material to be processed R10 is fed from an inlet 141 provided at the upper end of the feeder 140 and introduced into the main body 101 of the cylinder 100 via the supply port 102 of the cylinder 100.

[0079] On the other hand, a kiln foot 150 is connected to the discharge port 103 of the cylinder 100 via a bearing 104. That is, the downstream end of the cylinder 100 is rotatably supported by the kiln foot 150. The product R11 discharged from the discharge port 103 of the cylinder 100 is discharged from the high temperature reaction apparatus 10 via a product discharge port 151 provided at the lower end of the kiln foot 150. Furthermore, as shown in FIG. 2, a fluid supply device 160 and a fluid discharge device 170 are fixed by the kiln foot 150.

[0080] Here, the material constituting the feeder 140 and the kiln foot 150 is made of any of the above-mentioned alloys (1) to (3), similar to the cylinder 100. Moreover, a coating film may be formed on the surface of the feeder 140 and the kiln foot 150 made of the alloy.

[0081] The details of the alloy and coating film constituting the feeder 140 and the kiln foot 150 are similar to those of the alloy and coating film constituting the cylinder 100 according to the first embodiment, and therefore will not be described here.

[0082] The fluid supplying device 160 supplies a predetermined fluid to the cylinder 100. The predetermined fluid is a gas or liquid, but may include a solid having flowability such as a powder. The fluid supplying device 160 has a fluid supply pipe 161 and a fluid supply port 162. The fluid supplying device 160 may have a storage section for storing the predetermined fluid, and a pump for pumping the fluid.

[0083] The fluid supply pipe 161 is a pipe extending from one end or the other end of the cylinder 100 to the upstream side of the contact area 105 in the main body 101. A predetermined fluid is introduced into the cylinder 100 through the fluid supply pipe 161. In the example shown in FIG. 2, the fluid supply pipe 161 is fixed to the kiln foot 150 and extends from the kiln foot 150 to the upstream side of the contact area 105 in the main body 101 of the cylinder 100. The fluid supply pipe 161 may be fixed to the high temperature reactor 20 by the feeder 140 or other fixing members instead of the kiln foot 150.

[0084] Fluid supply port 162 is an opening provided at the tip of fluid supply pipe 161 in order to introduce a predetermined fluid pressure-fed by fluid supply pipe 161 into main body 101. Fluid supply port 162 shown in Fig. 2 has a plurality of holes. However, fluid supply port 162 may be composed of only one hole, or may be composed of a porous member that allows the predetermined fluid to pass through.

[0085] The fluid discharge device 170 discharges the fluid inside the cylinder 100 to the outside of the cylinder 100. The fluid discharged by the fluid discharge device 170 is, for example, a fluid supplied from the fluid supply device 160 and has come into contact with the material to be treated R10. The fluid discharge device 170 has a fluid discharge pipe 171 and a fluid discharge port 172. The fluid discharge device 170 may have a pump or the like for discharging the fluid.

[0086] The fluid discharge pipe 171 is a pipe extending from one end or the other end of the cylinder 100 to the downstream side of the contact area 105 in the main body 101. The fluid inside the cylinder 100 is discharged to the outside of the cylinder 100 via the fluid discharge pipe 171. In the example shown in FIG. 2, the fluid discharge pipe 171 is fixed to the kiln foot 150 and extends from the kiln foot 150 to the downstream side of the contact area 105 in the main body 101 of the cylinder 100. The fluid discharge pipe 171 may be fixed to the high temperature reactor 20 by the feeder 140 or other fixing members instead of the kiln foot 150.

[0087] The fluid discharge port 172 is an opening provided at the tip of the fluid discharge pipe 171 in order to discharge the fluid that has passed through the contact area 105. The fluid discharge port 172 shown in Fig. 2 has a plurality of holes. However, the fluid supply port 162 may be composed of only one hole, or may be composed of a porous member that allows a predetermined fluid to pass through.

[0088] The fluid supply device 160 and the fluid discharge device 170 are provided to extend in a direction parallel to the central axis C10 and spaced apart from the inner wall of the main body 101 so as not to impede the rotation of the cylinder 100. In addition, the fluid supply device 160 and the fluid discharge device 170 may be fixed to the kiln foot 150 in a connected state, or may be fixed to the kiln foot 150 independently. Further, the fluid supply device 160 and the fluid discharge device 170 may be fixed to the feeder 140 in addition to the kiln foot 150.

[0089] 2, the fluid supply port 162 is located on the upstream side of the main body 101, and discharges the fluid below where the object to be treated R10 exists. The fluid discharge port 172 is located downstream away from the fluid supply port 162 in the direction along the central axis C10, and discharges the fluid present below. With this configuration, it is possible to provide a contact area 105 between the fluid supply port 162 and the fluid discharge port 172, where the fluid supplied from the fluid supply port 162 comes into contact with the object to be treated R10.

[0090] The contact area 105 is an area where the fluid discharged from the fluid supply port 162 comes into contact with the material to be treated R10. The area indicated by a thick two-dot chain line in FIG. 2 is the contact area 105. In the contact area 105, the material to be treated R10 comes into contact with the fluid supplied from the fluid supply device 160 while rolling and flowing. As a result, the material to be treated R10 becomes a predetermined product R11, and is transported to the discharge port 103. In addition, the fluid supplied from the fluid supply port 162 passes through the contact area 105 and is then discharged to a fluid discharge port 172 located downstream of the contact area 105.

[0091] Here, the material constituting the fluid supplying device 160 and the fluid discharging device 170 is made of any of the above-mentioned alloys (1) to (3) like the cylinder 100. Moreover, a coating film may be formed on the surface of the fluid supplying device 160 and the fluid discharging device 170 made of the alloy.

[0092] The details of the alloy and coating film constituting the fluid supply device 160 and the fluid discharge device 170 are similar to those of the alloy and coating film constituting the cylinder 100 according to the first embodiment, and therefore will not be described. The other configuration is similar to that of the first embodiment, and therefore the description will be omitted.

[0093] (Third embodiment) Next, the configuration of a high temperature reaction apparatus according to a third embodiment will be described with reference to Fig. 3. Fig. 3 is a cross-sectional view of the high temperature reaction apparatus according to the third embodiment. As shown in FIG. 3, the high temperature reaction apparatus 30 according to this embodiment includes a screw 120 in addition to the cylinder 100, the heater 110, the feeder 140, and the kiln foot 150 shown in FIG.

[0094] Here, the heating device 110 according to this embodiment has a plurality of different heating regions along the direction of the central axis C10 in the middle part of the cylinder 100. More specifically, as shown in FIG. 3, the heating device 110 includes a first heating region 110A, a second heating region 110B, and a third heating region 110C. The first heating region 110A is disposed on the most upstream side away from the supply port 102 of the cylinder 100. The second heating region 110B is disposed between the first heating region 110A and the third heating region 110C. The third heating region 110C is disposed on the most downstream side away from the discharge port 103 of the cylinder 100.

[0095] The first heating zone 110A, the second heating zone 110B, and the third heating zone 110C are set to different temperatures, i.e., the heating device 110 can set different temperatures for different zones of the cylinder 100. This allows the high temperature reactor 20 to promote or inhibit a desired reaction depending on the zone of the cylinder 100.

[0096] As shown in Fig. 3, in the high temperature reaction apparatus 30 according to this embodiment, the screw 120 includes an agitator 123, a pulverizer 124, and a spray 125 in addition to the shaft 121 and the screw flight 122 shown in Fig. 1. Specifically, the screw 120 includes, in the longitudinal direction of the shaft 121, the agitator 123, the pulverizer 124, the spray 125, and the screw flight 122 in this order from the upstream side.

[0097] More specifically, an agitator 123 and a grinder 124 are provided at a position on the shaft 121 corresponding to the first heating zone 110A. A spray 125 is provided at a position on the shaft 121 corresponding to the second heating zone 110B. And a screw flight 122 is provided at a position on the shaft 121 corresponding to the third heating zone 110C. In addition, the number and arrangement of the screw flights 122, the agitator 123, the pulverizer 124, and the spray 125 in the shaft 121 are not limited to the above-mentioned number and arrangement. For example, the shaft 121 may be provided with the screw flights 122, the agitator 123, and the spray 125, but may not be provided with the pulverizer 124.

[0098] As shown in Fig. 3, in the high temperature reaction apparatus 30 according to this embodiment, the upstream end of the shaft 121 extending along the central axis C10 of the cylinder 100 is rotatably supported by a bearing 180 provided in the feeder 140. The downstream end of the shaft 121 is rotatably supported by a bearing 180 provided in the kiln foot 150. The downstream end of the screw 120 shown in Fig. 3 is connected to a driving device MT1. In Fig. 3, a driving gear MG1 fixed to a rotating shaft of the driving device MT1 and a screw gear SG fixed to a downstream end of a shaft 121 of the screw 120 are engaged with each other.

[0099] The agitator 123 agitates the material to be treated R10 received from the supply port 102. The agitator 123 is composed of, for example, a rod-shaped member protruding in the radial direction from the shaft 121. The agitator 123 shown in FIG. 3 is composed of a rod-shaped member having an angular U-shape when viewed from a direction perpendicular to the shaft 121. In the example shown in FIG. 3, the agitator 123 has two of these rod-shaped members. As the shaft 121 rotates, the agitator 123 agitates the material to be treated R10.

[0100] The crusher 124 crushes the material to be processed R10 stirred by the stirrer 123. The crusher 124 is composed of, for example, a plurality of plate-like members having an elliptical shape in a plan view fixed to the shaft 121. The major axis of each of the elliptical plate-like members extends to the vicinity of the inner wall of the main body 101. Therefore, as the shaft 121 rotates, the lump-shaped material to be processed R10 is sandwiched between the crusher 124 and the main body 101 and crushed.

[0101] The spray 125 injects a predetermined fluid into the main body 101, and brings the fluid into contact with the object to be treated R10. The shaft 121 has a fluid inlet 125A at the upstream end and a pipe for leading the fluid to the spray 125. The spray 125 injects the fluid introduced from the fluid inlet 125A from the fluid injection port 125B. That is, the object to be treated R10 pulverized by the pulverizer 124 comes into contact with the fluid injected from the spray 125. The fluid injected from the spray 125 may be an inert gas or a predetermined gas for promoting a reaction. The fluid injected from the spray 125 may include a powder or liquid having flowability. The screw flights 122 transport downstream a given product produced by passing through the area in which the sprays 125 are located. The other configurations are similar to those of the first or second embodiment, and therefore will not be described.

[0102] Although the high-temperature reactor according to the first to third embodiments has been described above, the high-temperature reactor is not limited to the above-mentioned embodiments. In addition, the high-temperature reactor is not limited to the use for manufacturing components for all-solid-state lithium-ion secondary batteries. That is, the high-temperature reactor may be used for manufacturing components for batteries other than all-solid-state lithium-ion secondary batteries.

[0103] The high-temperature reactor may also be used as a reactor for decomposing, for example, vulcanized materials or waste plastics, which are treated materials R10, at a molecular level to recover various substances as valuable materials. The valuable materials are not limited to resins, but may include alcohol, ammonia, or hydrocarbons. These substances recovered by the high-temperature reactor are reused as gas, oil, or chemically treated materials. In other words, the high-temperature reactor may be used as a so-called chemical recycling device.

[0104] Alternatively, the high-temperature reactor may be used as a reactor for producing hydrogen from resources such as natural gas. In this case, the product to be treated R10 may include a powdered catalyst. The powdered catalyst is made by supporting fine metal particles such as iron on a ceramic catalyst support such as porous alumina. In other words, the high-temperature reactor may be used as a so-called hydrogen production device.

[0105] <First Example> Hereinafter, the characteristics of the alloy used in the high temperature reactor 10 according to the first embodiment will be described with reference to comparative examples and examples. However, the alloy used in the high temperature reactor 10 according to the first embodiment is not limited to the following examples.

[0106] The compositions of the alloys according to Examples E1 to E13 and Comparative Examples C1 to C3 are summarized in Table 1 below. Specifically, as shown in Table 1, the concentrations of Cr, Ni, Co, Fe, and others are shown in mass %. As shown in Table 1, the other added elements are Mo, W, C, P, S, Si, Mn, Nb, Cu, and N. The balance (Bal.) in the table means the main component.

[0107] Here, Fig. 4 is a ternary diagram showing the compositions of the alloys according to Examples E1 to E13 and Comparative Examples C1 to C3, in which the a-axis represents the Cr concentration (% by mass), the b-axis represents the Ni+Co concentration (% by mass), and the c-axis represents the Fe and other concentrations (% by mass). In Table 1, the a-axis is classified as Cr, the b-axis as Ni+Co, and the c-axis as Fe and others.

[0108] As shown in Table 1, the alloys according to Examples E1 to E5 all belong to alloy (1) containing Fe as a main component, 13 to 35 mass% of Cr, and 0 to 35 mass% in total of Ni and Co. The composition range of alloy (1) is also shown in Figure 4.

[0109] Alloys according to Examples E6 to E11 belong to alloy (2) containing Ni or Co as a main component, 13 to 35 mass% of Cr, and 35 to 87 mass% in total of Ni and Co. The composition region of alloy (2) is also shown in FIG.

[0110] The alloys according to Examples E12 and E13 all belong to alloy (3) which contains Ni or Co as a main component, less than 13 mass% of Cr, and a total of 40 to 80 mass% of Ni and Co. The composition region of alloy (3) is also shown in FIG.

[0111] [Table 1]

[0112] <Testing and Judging Methods> A sulfuration corrosion test and a high-temperature tensile test were carried out on 16 types of alloys according to Examples E1 to E13 and Comparative Examples C1 to C3, which are summarized in Table 1 below. In the high temperature tensile test, if the tensile strength at a test temperature of 800° C. was 200 MPa or more and if the iron-based alloys according to Examples E1 to E5 did not undergo a phase change during the heating process, they were judged to have passed.

[0113] In the sulfidation corrosion test, test pieces made of the alloys according to Examples E1 to E13 and Comparative Examples C1 to C3 were immersed in molten salt heated to 850°C for 2 hours and then furnace-cooled. The molten salt used had a molar ratio of sodium sulfide (Na2So4) and sodium chloride (NaCl) of 1:1.

[0114] In order to prevent bumping of the molten salt and to ensure uniform temperature, it is preferable to make the temperature rise rate slower as the temperature rises. Therefore, the temperature rise rate of the molten salt was set to 10°C / min up to 500°C, 5°C / min from 500 to 550°C, 2.5°C / min from 550 to 650°C, and 1°C / min from 650 to 850°C.

[0115] If the amount of corrosion on the cross section of the test piece was 0.05 mm or less as a result of the sulfur corrosion test, it was judged to be acceptable. The amount of corrosion is preferably 0.01 mm or less, and it is preferable that the surface maintains its metallic luster. The amount of corrosion is not the thickness of the corrosive organism, but the distance between the surface of the test piece before the sulfur corrosion test and the boundary between the corrosive organism and the bulk after the sulfur corrosion test.

[0116] <Test Results> The alloys according to Examples E1 to E11 passed both the high-temperature tensile test and the sulfurization corrosion test.

[0117] The alloys according to Examples E12 and E13 passed the high temperature tensile test but failed the sulfidation corrosion test. However, when a coating film made of an alumina film having a thickness of 1 mm was formed on the surface of the alloys according to Examples E12 and E13, the alloys also passed the sulfidation corrosion test.

[0118] On the other hand, the alloys according to Comparative Examples C1 to C3 failed both the high-temperature tensile test and the sulfurization corrosion test. In the high-temperature tensile test, a phase change was observed during the temperature rise.

[0119] From the above experimental results, it was found that by constructing the parts used in the reaction apparatus from any of the above-mentioned alloys (1) to (3), the parts can withstand the harsh operating environment of temperatures of 300°C or higher and an atmosphere containing sulfur compounds.

[0120] <Second Example> Hereinafter, the characteristics of the alloy used in the high temperature reactor 10 according to the first embodiment will be described with reference to comparative examples and examples. However, the alloy used in the high temperature reactor 10 according to the first embodiment is not limited to the following examples.

[0121] 5 is a graph showing the temperature dependence of the thermal expansion coefficient (linear expansion coefficient) of the alloys according to Comparative Examples C21 and C22 and Example E21. The horizontal axis represents temperature (° C.), and the vertical axis represents the average linear expansion coefficient (×10 -6 / ℃).

[0122] As shown in FIG. 5, the alloys according to Comparative Examples C21 and C22 and Example E21 were measured using a push rod type thermal expansion measuring device to measure the average linear expansion coefficient (×10 -6 / ℃) was measured.

[0123] In FIG. 5, the alloy according to Comparative Example C21 is a SUS316 alloy, and the alloy according to Comparative Example C22 is an Inconel (registered trademark) 625 alloy. The alloy according to Example E21 is a Ni-based superalloy having a composition of Ni-10Co-12Cr-10W-4Mo-1Al (values ​​are mass%). That is, this alloy belongs to alloy (3) and further contains 10 mass% W.

[0124] As shown in Fig. 5, at each temperature, the average linear expansion coefficient was smallest in the order of Comparative Example C21, Comparative Example C22, and Example E21. That is, the average linear expansion coefficient of the alloy according to Example E21 was the smallest at each temperature. The average linear expansion coefficient of the ceramic such as alumina constituting the ceramic film formed on the surface is even smaller than that of the alloy according to Example E21. Therefore, the difference in the thermal expansion coefficient (linear expansion coefficient) between the alloy and the ceramic is the smallest in Example E21.

[0125] From the above experimental results, it was found that by constructing the parts used in the reaction apparatus from the above-mentioned alloy (2) or alloy (3) containing 5 to 20 mass % W, it is possible to suppress cracking of the ceramic film formed on the surface.

[0126] The present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit and scope of the present invention. [Explanation of symbols]

[0127] 10, 20, 30 High temperature reactor 100 cylinders 101 Main body 102 Supply port 103 Outlet 105 Contact area 106 Cylinder gear 110 Heating device 120 Screw 121 Shaft 122 Screw Flight 123 Stirrer 124 Crusher 125 Spray 125A Fluid Inlet 125B Fluid injection port 140 Feeder 141 Inlet 150 Kilnfoot 151 Product outlet 160 Fluid supply device 161 Fluid supply pipe 162 Fluid supply port 170 Fluid discharge device 171 Fluid discharge pipe 172 Fluid outlet C10 center axis MG1, MG2 drive gear MT1, MT2 drive unit R10 Processing material R11 product RZ1 First reaction zone RZ2 Second reaction zone SG screw gear

Claims

1. A cylinder is provided having a supply port at one end for receiving a raw material to be supplied and an outlet port at the other end for discharging a reaction product; providing a screw extending from the one end side to the other end side of the cylinder; The raw material supplied from the supply port is conveyed toward the delivery port by the screw; Supplying a gas into the cylinder in which 50 volume % or more of the gas is hydrogen sulfide gas; A reaction method in which the raw materials are reacted in an environment at a temperature of 300° C. or higher, a temperature control section for controlling a temperature at a predetermined position in an intermediate portion between the supply port and the delivery port of the cylinder for each of a plurality of zones; At least one of the plurality of zones is controlled so that a temperature gradient between a start point and an end point is 300° C. or more and 600° C. or less; At least one of the cylinder and the screw is The alloy is mainly composed of Ni or Co, contains less than 13 mass% Cr, contains 40 to 80 mass% Ni and Co in total, contains 5 to 20 mass% W, contains 0 to 25 mass% Mo, contains 0 to 3 mass% Al, and contains at least one additional element selected from the group consisting of C, B, Si, Ti, Nb, Y, Hf, Zr, Ta, and Mn in an amount of 1 mass% or less each, and in total, contains 5 mass% or less, with the balance being unavoidable impurities; A coating film is formed on the surface of the alloy, When a test piece of the alloy on which the coating film is formed is immersed in a molten salt having a molar ratio of sodium sulfide and sodium chloride of 1:1 at 850°C for 2 hours and then cooled in a furnace, the amount of erosion in a cross section of the test piece is 0.05 mm or less. Reaction method.

2. A cylinder is provided having a supply port at one end for receiving a raw material to be supplied and an outlet port at the other end for discharging a reaction product; providing a screw extending from the one end side to the other end side of the cylinder; The raw material supplied from the supply port is conveyed toward the delivery port by the screw; Supplying a gas into the cylinder in which 50 volume % or more of the gas is hydrogen sulfide gas; A reaction method in which the raw materials are reacted in an environment at a temperature of 300° C. or higher, a temperature control section for controlling a temperature at a predetermined position in an intermediate portion between the supply port and the delivery port of the cylinder for each of a plurality of zones; At least one of the plurality of zones is controlled so that a temperature gradient between a start point and an end point is 300° C. or more and 600° C. or less; At least one of the cylinder and the screw is An alloy containing 13 to 35 mass% Cr, 0 to 35 mass% Ni and Co in total, 0 to 20 mass% W, 0 to 25 mass% Mo, 0 to 3 mass% Cu, and 0 to 3 mass% Al, the alloy containing at least one additional element selected from the group consisting of C, B, Si, Ti, Nb, Y, Hf, Zr, Ta, and Mn in an amount of 1 mass% or less each, and 5 mass% or less in total, with the balance being Fe and unavoidable impurities; When a test piece of the alloy is immersed in a molten salt having a molar ratio of sodium sulfide and sodium chloride of 1:1 at 850°C for 2 hours and then cooled in a furnace, the amount of erosion in a cross section of the test piece is 0.05 mm or less. Reaction method.

3. A cylinder is provided having a supply port at one end for receiving a raw material to be supplied and an outlet port at the other end for discharging a reaction product; providing a screw extending from the one end side to the other end side of the cylinder; The raw material supplied from the supply port is conveyed toward the delivery port by the screw; Supplying a gas into the cylinder in which 50 volume % or more of the gas is hydrogen sulfide gas; A reaction method in which the raw materials are reacted in an environment at a temperature of 300° C. or higher, a temperature control section for controlling a temperature at a predetermined position in an intermediate portion between the supply port and the delivery port of the cylinder for each of a plurality of zones; At least one of the plurality of zones is controlled so that a temperature gradient between a start point and an end point is 300° C. or more and 600° C. or less; At least one of the cylinder and the screw is The alloy is made of an alloy containing 13 to 35 mass% Cr, 35 to 87 mass% Ni and Co in total, 0 to 20 mass% W, 0 to 25 mass% Mo, 0 to 5 mass% Nb, and 0 to 3 mass% Al, the alloy containing at least one additional element selected from the group consisting of C, B, Si, Ti, Cu, Y, Hf, Zr, Ta, and Mn in an amount of 1 mass% or less each, and 5 mass% or less in total, with the remainder being unavoidable impurities; When a test piece of the alloy is immersed in a molten salt having a molar ratio of sodium sulfide and sodium chloride of 1:1 at 850°C for 2 hours and then cooled in a furnace, the amount of erosion in a cross section of the test piece is 0.05 mm or less. Reaction method.

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