Method for smelting raw material

Abstract

A method for smelting a raw material for recovering copper from the raw material containing Sn, wherein: the raw material is charged into a melting furnace, a calcium source is added as needed, and smelting is performed to produce CaO-FeOx-SnOY-Cu2O-based slag, and the slag is separated; and by controlling one or more selected from the temperature of the slag, the CaO concentration of the slag, the Cu2O concentration of the slag, and the Sn concentration of the slag, the slag is maintained in a molten state.

Description

Method of smelting raw materials

[0001] The present invention relates to a smelting method for recovering copper from raw materials containing Sn. This application claims priority based on Japanese Patent Application No. 2025-051587, filed in Japan on March 26, 2025, the contents of which are incorporated herein by reference.

[0002] The copper melting and smelting method involves 1) oxidizing and melting copper sulfide concentrate, removing some of the Fe in the ore as slag, and removing some of the S as SO ２ Removed as such, while Cu is FeS and Cu ２ 1) A mat smelting process in which the mixture of S is concentrated as mat, 2) The mat obtained thereafter is further oxidized to remove Fe as slag, and white granite (Cu) which contains almost no Fe ２ The process consists of three steps: 1) a white molten metal production process to obtain S), and 2) a copper production process to obtain crude copper by further oxidizing the white molten metal. Self-smelting furnaces are generally used as mat smelting furnaces, and the white molten metal production process and the copper production process are usually carried out in a converter.

[0003] In the converter process, silicate ore is usually added as a solvent to form iron silicate slag. However, when the matte is further oxidized to produce white wax or crude copper, the iron silicate slag is oxidized, causing solid magnetite to precipitate and reducing the fluidity of the slag. Therefore, the process is now a batch process, where the blowing is temporarily interrupted while the white wax and slag are in coexistence, the furnace is tilted to discharge the slag, and only the white wax remains in the converter before oxidation is carried out until it becomes crude copper.

[0004] In these methods, for example, Patent Documents 1 and 2 describe how the deposition of magnetite is avoided by forming a calcium ferrite slag in the converter process, thereby ensuring the fluidity of the slag and enabling the continuous production of crude copper from matte with a copper content of 65-70% by weight. These methods empirically determine the operating conditions that ensure the fluidity of the slag and then operate in a way that maintains those conditions.

[0005] Furthermore, for example, Patent Document 3 proposes a method for recovering copper contained in waste, which involves feeding the waste into a copper refining facility and recovering copper from the waste by utilizing copper oxidation smelting.

[0006] Japanese Patent No. 3838105 (B) Japanese Patent No. 3838106 (B) Japanese Patent No. 3747852 (B)

[0007] Incidentally, among waste materials, a large amount of copper is used in waste materials from various electronic and electrical equipment components such as home appliances, personal computers, mobile phones, smartphones, and network equipment (so-called e-scrap), and it has recently attracted attention as a new source of valuable smelting raw materials (urban mine). Such waste materials (e-scrap) often contain Sn, and as mentioned above, copper smelting is used to produce CaO-FeOx-Cu ２ When O-type slag was produced, solid phase precipitation occurred, potentially leading to the following problems.

[0008] (1) The viscosity or apparent viscosity of the slag increases, hindering the outflow of slag from the furnace outlet or causing foaming, thus impeding operation. (2) To reduce the increased viscosity of the slag, it becomes necessary to operate at a higher temperature than normal, increasing energy costs and accelerating the wear of furnace bricks. (3) If solid phases are mixed in the slag, these solid phases adhere to the furnace body, reducing the effective volume of the furnace. (4) If solid phases are mixed in the slag, the solvent is discharged without dissolving, resulting in waste.

[0009] The present invention has been made in view of the circumstances described above, and aims to provide a raw material smelting method that enables the stable recovery of copper from raw materials (including waste) containing Sn.

[0010] To solve the above problems, the raw material smelting method of embodiment 1 of the present invention is a raw material smelting method for recovering copper from a raw material containing Sn, wherein the raw material is put into a melting furnace and a calcium source is added as necessary to perform smelting, thereby producing CaO-FeOx-SnO Ｙ (1≦y≦2)-Cu ２ The system is configured to generate O-based slag and separate it, and the temperature of the slag, the Sn concentration of the slag, and the Cu of the slag ２The slag is maintained in a molten state by controlling one or more selected from the O concentration and the CaO concentration of the slag.

[0011] In the smelting method for a raw material according to aspect 2 of the present invention, in the smelting method for a raw material according to aspect 1 of the present invention, a calcium source is added to copper matte obtained by smelting a raw material containing copper concentrate, and smelting is performed, thereby generating the slag and blister copper, and the slag is separated.

[0012] In the smelting method for a raw material according to aspect 3 of the present invention, in the smelting method for a raw material according to aspect 1 or 2 of the present invention, CaO, Cu in the slag ２ O, the contents of Sn components, in the coexistence of molten copper (which may contain tin) at the smelting temperature, in CaO-FeOx-SnO Ｙ -Cu ２ O quaternary phase diagram, three components of CaO, Cu ２ O, Sn are specified. In order to fall within the uniform melting range of the expressed function, one or more selected from the temperature of the slag, the CaO concentration of the slag, the Cu ２ O concentration, and the Sn concentration of the slag is / are controlled.

[0013] In the smelting method for a raw material according to aspect 4 of the present invention, in the smelting method for a raw material according to aspect 3 of the present invention, when the smelting temperature is 1300°C, the uniform melting range is obtained by specifying the three components of CaO, Cu ２ O, Sn from the quaternary phase diagram. In the expressed function, when 7.5 ≦ %Cu2O < 17.0, it is defined as the region surrounded by: Formula 1: %Sn = 0; Formula 2: 46.6 × %CaO + 19.1 × %Cu2O - 10.5 × %Sn - 958 = 0; Formula 3: -8.55 × %CaO - 10.1 × %Cu2O - 101 × %Sn + 790 = 0; Formula 4: -38.0 × %CaO + 1.50 × %Cu2O - 23.8 × %Sn + 1030 = 0. Here, %Sn represents the content (weight percent) of Sn. Hereinafter, all % are weight percent.

[0014] In the smelting method for a raw material according to aspect 5 of the present invention, in the smelting method for a raw material according to aspect 3 of the present invention, when the smelting temperature is 1300°C, the uniform melting range is obtained from the quaternary phase diagram with CaO, Cu２ In a function expressed by specifying the three components O and Sn, when 3.7 ≤ %Cu2O < 7.5, it is characterized by being defined within the region enclosed by: Equation 1: %Sn = 0 Equation 5: 20.7 × %CaO - 11.6 × %Cu2O - 4.88 × %Sn - 275 = 0 Equation 6: -1.88 × %CaO - 5.65 × %Cu2O - 20.7 × %Sn + 191 = 0 Equation 7: -18.8 × %CaO - 2.91 × %Cu2O - 11.6 × %Sn + 537 = 0

[0015] The raw material smelting method of embodiment 6 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1300°C, CaO, Cu from the quaternary phase diagram. ２ In a function expressed by specifying the three components O and Sn, when 2.0 ≤ %Cu2O < 3.7, it is characterized by being defined within the region enclosed by: Equation 1: %Sn = 0 Equation 8: 11.8 × %CaO - 36.2 × %Cu2O - 2.64 × %Sn - 46.1 = 0 Equation 9: -1.06 × %CaO - 6.95 × %Cu2O - 12.8 × %Sn + 130 = 0 Equation 10: -10.7 × %CaO - 15.5 × %Cu2O - 6.69 × %Sn + 358 = 0

[0016] The raw material smelting method of embodiment 11 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1300°C, CaO, Cu from the quaternary phase diagram. ２ In a function expressed by specifying the three components O and Sn, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0, it is characterized by being defined by the region enclosed by Equation 1: %Sn = 0 Equation 50: 7.00 × %CaO - 1.40 × %Cu2O - 0.350 × %Sn - 82.6 = 0 Equation 51: 12.1 × %CaO + 13.6 × %Cu2O + 1.91 × %Sn - 209 = 0 and the region enclosed by Equation 1, Equation 51 Equation 52: 4.53 × %CaO + 21.6 × %Cu2O + 12.5 × %Sn - 247 = 0 Equation 53: -5.33 × %CaO - 21.0 × %Cu2O - 3.29 × %Sn + 204 = 0.

[0017] The raw material smelting method of embodiment 12 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1300°C, CaO, Cu from the quaternary phase diagram. ２ In a function expressed with three components O and Sn, when -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, the region enclosed by Equation 1: %Sn = 0 Equation 54: 16.5 × %CaO - 23.5 × %Cu2O - 1.87 × %Sn - 164 = 0 Equation 55: -2.20 × %CaO - 5.00 × %Cu2O + 1.14 × %Sn + 4.25 = 0 Equation 56: 4.50 × %CaO + 118 × %Cu2O + 6.27 × %Sn - 254 = 0 and Equation 1, Equation 56 Equation 57: 0.800 × %CaO + 13.9 × %Cu2O + 2.56 × %Sn - 57.5 = 0 It is characterized by being defined within the region enclosed by equation 58: -3.00 × %CaO + 9.00 × %Cu2O + 0.180 × %Sn + 87.3 = 0.

[0018] The raw material smelting method of embodiment 7 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1250°C, CaO, Cu from the quaternary phase diagram. ２ In a function expressed by specifying the three components O and Sn, when 9.0 ≤ %Cu2O < 20.4, it is characterized by being defined within the region enclosed by: Equation 1: %Sn = 0 Equation 11: 39.9 × %CaO + 10.9 × %Cu2O - 9.12 × %Sn - 848 = 0 Equation 12: -3.42 × %CaO - 2.40 × %Cu2O - 41.0 × %Sn + 249 = 0 Equation 13: -36.5 × %CaO - 5.80 × %Cu2O - 22.8 × %Sn + 925 = 0

[0019] The raw material smelting method of embodiment 8 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1250°C, CaO, Cu from the quaternary phase diagram. ２In a function expressed by specifying the three components O and Sn, when 4.0 ≤ %Cu2O < 9.0, it is characterized by being defined within the region enclosed by: Equation 1: %Sn = 0 Equation 14: 19.5 × %CaO + 5.46 × %Cu2O - 4.50 × %Sn - 416 = 0 Equation 15: -1.00 × %CaO - 1.44 × %Cu2O - 9.50 × %Sn + 69.7 = 0 Equation 16: -18.5 × %CaO - 8.55 × %Cu2O - 11.5 × %Sn + 519 = 0

[0020] The raw material smelting method of embodiment 9 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1250°C, CaO, Cu from the quaternary phase diagram. ２ In a function expressed by specifying the three components O and Sn, when 2.2 ≤ %Cu2O < 4.0, it is characterized by being defined within the region enclosed by Equation 1: %Sn = 0 Equation 17: 8.10 × %CaO - 15.3 × %Cu2O - 1.80 × %Sn - 102 = 0 Equation 18: -0.540 × %CaO - 1.71 × %Cu2O - 4.32 × %Sn + 37.7 = 0 Equation 19: -7.56 × %CaO - 2.76 × %Cu2O - 4.68 × %Sn + 209 = 0.

[0021] The raw material smelting method of embodiment 13 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1250°C, CaO, Cu from the quaternary phase diagram. ２ In a function expressed by specifying the three components O and Sn, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.2, it is characterized by being defined within the region enclosed by Equation 1: %Sn = 0 Equation 59: 3.85 × %CaO - 3.30 × %Cu2O - 0.910 × %Sn - 57.4 = 0 Equation 60: -0.400 × %CaO - 3.72 × %Cu2O - 5.60 × %Sn + 46.2 = 0 Equation 61: -4.59 × %CaO - 22.6 × %Cu2O - 2.79 × %Sn + 177 = 0.

[0022] The raw material smelting method of embodiment 14 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein the uniform melting range is, when the smelting temperature is 1250°C, CaO, Cu from the quaternary phase diagram. ２In a function expressed with three components O and Sn, when -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, the region enclosed by Equation 1: %Sn = 0 Equation 62: 6.37 × %CaO - 7.28 × %Cu2O - 0.600 × %Sn - 92.3 = 0 Equation 63: 7.99 × %CaO + 65.6 × %Cu2O + 5.91 × %Sn - 259 = 0 and Equation 1, Equation 63, Equation 64: 0.350 × %CaO + 1.56 × %Cu2O + 4.06 × %Sn - 33.3 = 0 Equation 65: -3.67 × %CaO - 4.90 × %Cu2O - 2.47 × %Sn + 122 = 0 It is characterized by being defined by the region enclosed by [the specified area].

[0023] The raw material smelting method of embodiment 10 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein when the smelting temperature is greater than 1200°C and less than 1350°C, the uniform melting range is determined from the quaternary phase diagram to be CaO, Cu ２In a function expressed with three components specified as O and Sn, when 9.0 ≤ %Cu2O and the temperature is expressed as T (°C), Equation 20: %CaO = -0.0420 × T + 68.2 %Cu2O = -0.0680 × T + 105 %Sn = 0 Equation 21: %CaO = -0.0360 × T + 61.5 %Cu2O = -0.0680 × T + 105 %Sn = 0.0280 × T - 31.5 Equation 22: %CaO = -0.0383 × T + 66.7 %Cu2O = 9.0 %Sn = 0 Equation 23: %CaO = -0.0320 × T + 59.7 %Cu2O = 9.0 %Sn = 0.0302 × T - 33.8 A plane formed by connecting the four points obtained from the equations of the four lines (if the four points do not lie on a plane, it is considered a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting the four points" will be treated as having the same meaning.) Equations 21, 23, 24: %CaO = 0.104 × T - 110 %Cu2O = -0.0680 × T + 105 %Sn = 0.0160 × T - 16.8 Equation 25: %CaO = 0.0568 × T - 49.4 %Cu2O = 9.0 %Sn = 0.0234 × T - 25.6 A plane formed by connecting the four points obtained from the equations of the four lines, Equations 24, 25, 26: %CaO = 0.114 × T - 120 %Cu2O = -0.0680 × T + 105 The region is defined by a plane formed by connecting four points obtained from the equations of the four lines: %Sn=0 Equation 27: %CaO=0.0717×T-65.7 %Cu2O=9.0 %Sn=0 and the region enclosed by the six planes: Equation 1: %Sn=0 Equation 28: %Cu2O=-0.0680×T+105 Equation 29: %Cu2O=9 Furthermore, when 7.5≦%Cu2O<9.0 and the temperature is expressed in T (°C), Equations 22, 23, and 30: %CaO=-0.0344×T+62.2 %Cu2O=7.5 %Sn=0 Equation 31: %CaO=-0.0272×T+54.2 %Cu2O=7.5 The plane formed by connecting the four points obtained from the equations of the four lines %Sn = 0.0284 × T-31.5, and equations 23, 25, 31, and 32: %CaO = 0.The temperature is defined by a plane formed by connecting four points obtained from the equations of four straight lines: 0422 × T - 30.5 %Cu2O = 7.5 %Sn = 0.0227 × T - 24.5; a plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0561 × T - 45.6 %Cu2O = 7.5 %Sn = 0; and six planes: Equation 1: %Sn = 0 Equation 29: %Cu2O = 9 Equation 34: %Cu2O = 7.5. Furthermore, when 4.0 ≤ %Cu2O < 7.5 and the temperature is expressed in T (°C), Equations 30, 31, and 35: %CaO = -0.0931 × T + 137 %Cu2O = 4.0 %Sn=0 Equation 36: A plane formed by connecting the four points obtained from the equations of the four lines %CaO=-0.0819×T+124 %Cu2O=4.0 %Sn=0.0422×T-48.3 Equations 31, 32, 36, 37: A plane formed by connecting the four points obtained from the equations of the four lines %CaO=0.0129×T+7.5 %Cu2O=4.0 %Sn=0.0352×T-39.8 Equations 32, 33, 37, 38: A plane formed by connecting the four points obtained from the equations of the four lines %CaO=0.0348×T-17.4 %Cu2O=4.0 %Sn=0 Equation 1: %Sn=0 Equation 34: %Cu2O = 7.5 Equation 39: Defined by the region enclosed by the six planes of %Cu2O = 4.0 Furthermore, when 3.7 ≤ %Cu2O < 4.0 and the temperature is expressed in degrees Celsius, Equations 35, 36, 40: %CaO = -0.0847 × T + 125 %Cu2O = 3.7 %Sn = 0 Equation 41: %CaO = -0.0755 × T + 115 %Cu2O = 3.7 %Sn = 0.0403 × T - 45.7 A plane is formed by connecting the four points obtained from the equations of the four lines Equations 36, 37, 41, 42: %CaO = 0.0112 × T + 9.61 %Cu2O = 3.7 The equations of the four lines %Sn = 0.0357 × T-40.3 form a plane connecting four points, and equations 37, 38, 42, and 43: %CaO = 0.0341 × T-16.The region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: 4. %Cu2O = 3.7 %Sn = 0 and the region enclosed by the six planes: Equation 1: %Sn = 0 Equation 39: %Cu2O = 4.0 Equation 44: %Cu2O = 3.7 Furthermore, when 2.2 ≤ %Cu2O < 3.7 and the temperature is expressed in degrees Celsius, the region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: Equation 40, Equation 41, Equation 45: %CaO = -0.0123 × T + 170 %Cu2O = 2.2 %Sn = 0 Equation 46: %CaO = -0.113 × T + 160 %Cu2O = 2.2 %Sn = 0.0460 × T - 52.0 It is characterized by being defined by a region enclosed by a plane formed by connecting four points obtained from the equations of four straight lines: Equations 41, 42, 46, and 47: %CaO = 0.0459 × T - 33.7, %Cu2O = 2.2, and %Sn = 0.0338 × T - 37.1; a plane formed by connecting four points obtained from the equations of four straight lines: Equations 42, 43, 47, and 48: %CaO = 0.0685 × T - 58.8, %Cu2O = 2.2, and %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 44: %Cu2O = 3.7, and Equation 49: %Cu2O = 2.2. Within the defined region described above, the region may be divided into two parts between 1200°C and 1230°C. In such cases, since solid phase precipitation occurs in the region not in contact with Equation 1, only the region in contact with Equation 1 is considered.

[0024] The raw material smelting method of embodiment 15 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein when the smelting temperature is greater than 1200°C and less than 1350°C, the uniform melting range is determined from the quaternary phase diagram to be CaO, Cu ２In a function expressed with three components specified as O and Sn, when 2.0 ≤ %Cu2O < 2.2 and the temperature is expressed as T (°C), Equation 46: %CaO = -0.113 × T + 160 %Cu2O = 2.2 %Sn = 0.0460 × T - 52.0 Equation 66: %CaO = -0.1227 × T + 170.2 %Cu2O = 2.2 %Sn = 0 Equation 67: %CaO = -0.0880 × T + 126.6 %Cu2O = 2.0 %Sn = 0 Equation 68: %CaO = -0.1229 × T + 171.6 %Cu2O = 2.0 %Sn = 0.0213 × T - 19.7 A plane formed by connecting the four points obtained from the equations of the four lines (if the four points do not lie on a plane, it is considered to be a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting the four points" will be treated as having the same meaning.) Equations 46, 47: %CaO = 0.0459 × T - 33.7 %Cu2O = 2.2 %Sn = 0.0338 × T - 37.1 Equations 68, 69: %CaO = 0.0320 × T - 15.3 %Cu2O = 2.0 %Sn = 0.0240 × T - 24.4 A plane formed by connecting the four points obtained from the equations of the four lines, Equations 47, 69, 48: %CaO = 0.0685 × T - 58.8 %Cu2O = 2.2 %Sn = 0 Equation 70: It is characterized by being defined by a region enclosed by a plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0480 × T - 31.9, %Cu2O = 2.0, and %Sn = 0, and by six planes: Equation 1: %Sn = 0, Equation 49: %Cu2O = 2.2, and Equation 71: %Cu2O = 2.0. In addition, within the defined region described above, the region may be divided into two between temperatures exceeding 1200°C and below 1230°C. In such cases, a solid phase precipitates in the region not in contact with Equation 1, so only the region in contact with Equation 1 is considered.

[0025] The raw material smelting method of embodiment 16 of the present invention is the raw material smelting method of embodiment 3 of the present invention, wherein when the smelting temperature is greater than 1250°C and less than 1350°C, the uniform melting range is determined from the quaternary phase diagram to be CaO, Cu ２In a function expressed with three components specified as O and Sn, and further, when the temperature is expressed as T (°C) in the case of -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0, then: Equation 72: %CaO = -0.0880 × T + 126.6 %Cu2O = 2.0 %Sn = 0 Equation 73: %CaO = -0.1020 × T + 145.5 %Cu2O = 2.0 %Sn = 0.1400 × T - 168.0 Equation 74: %CaO = -0.0820 × T + 118.7 %Cu2O = 1.5 %Sn = 0 Equation 75: %CaO = -0.0880 × T + 127.6 %Cu2O = -0.0160 × T + 21.2 A plane formed by connecting four points obtained from the equations of four lines %Sn = 0.3460 × T - 426.3 (if the four points do not lie on a plane, it is considered a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting four points" will be treated as having the same meaning.) And a plane A formed by connecting four points obtained from the equations of four lines: Equations 73, 75, 76: %CaO = -0.0960 × T + 138.0 %Cu2O = 2.0 %Sn = 0.0900 × T - 105.5 Equation 77: %CaO = -0.0660 × T + 100.1 %Cu2O = -0.0060 × T + 8.7 %Sn = 0.1360 × T - 163.8 Equation 1: %Sn = 0 Equation 71: %Cu2O = 2.0 Equation 80: %Cu2O = -0.045 × %Sn + 1.5 is defined by the region enclosed by the five planes, and also by the plane A and the four points obtained from the equations of the four lines Equations 76, 77, 69: %CaO = 0.0320 × T - 15.3 %Cu2O = 2.0 %Sn = 0.0240 × T - 24.4 Equation 78: %CaO = 0.0240 × T - 2.0 %Cu2O = -0.0020 × T + 3.8 %Sn = 0.0360 × T - 39.7, and Equations 69, 78, 70: %CaO = 0.0480 × T - 31.9 %Cu2O = 2.0 %Sn = 0 Equation 79: %CaO = 0.0460 × T - 26.2 %Cu2O = 1.5 %Sn = 0 A plane is formed by connecting the four points obtained from the equations of the four lines, and Equation 1: %Sn = 0 Equation 71: %Cu2O = 2.Equation 80: %Cu2O = -0.045 × %Sn + 1.5 is defined by the region enclosed by the six planes, and furthermore, when the temperature is expressed as T (°C) in the case of -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, then Equations 74 and 81: %CaO = -0.0680 × T + 101.6 %Cu2O = -0.0140 × T + 18.6 %Sn = 0.288 × T - 350.9 Equation 82: %CaO = -0.0860 × T + 122.9 %Cu2O = 0.8 %Sn = 0 Equation 83: %CaO = -0.0840 × T + 121.3 %Cu2O = 0.2 One plane is formed by connecting the four points obtained from the equations of the four lines %Sn = 0.0200 × T - 5.5, and one plane is formed by connecting the three points obtained from the equations of the three lines %CaO = 0.0080 × T + 6.3, %Cu2O = -0.0040 × T + 5.2, and %Sn = 0.1800 × T - 205.5, and Equations 81, 84, and 85: %CaO = -0.0580 × T + 89.7, %Cu2O = -0.0060 × T + 8.7, %Sn = 0.1360 × T - 163.8, and Equation 86: %CaO = 0.1000 × T - 102.0, %Cu2O = -0.0020 × T + 3.1 The region is defined by a plane B formed by connecting four points obtained from the equations of four straight lines %Sn = 0.1000 × T - 119.0, and the region enclosed by the six planes: Equation 1: %Sn = 0, Equation 80: %Cu2O = -0.045 × %Sn + 1.5, Equation 90: %Cu2O = -0.029 × %Sn + 0.8. Furthermore, the region is defined by the aforementioned plane B and the following equations: Equations 85, 86, 87: %CaO = 0.1060 × T - 104.5, %Cu2O = 1.3, %Sn = -0.0060 × T + 12.8, Equation 88: %CaO = 0.0480 × T - 31.2, %Cu2O = -0.0020 × T + 3.1, %Sn = 0.0900 × T - 107.0 A plane formed by connecting the four points obtained from the equations of the four lines, and Equations 79, 87, 88, Equation 89: %CaO = 0.0020 × T + 29.5 %Cu2O = 0.8 %Sn = 0 Equation 1: %Sn = 0 Equation 80: %Cu2O = -0.It is characterized by being defined by the region enclosed by the six planes of Equation 90: %Cu2O = -0.029 × %Sn + 0.8. Note that within the defined region, while Cu2O may be less than 0% at certain temperatures, only the region where Cu2O is 0 or greater is considered.

[0026] The raw material smelting method of embodiment 17 of the present invention is, in the raw material smelting method of embodiment 3 of the present invention, when the uniform melting range is greater than 1200°C and less than 1250°C, and in the function expressed by specifying the three components CaO, Cu2O, and Sn from the quaternary phase diagram, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0 and the temperature is expressed in T (°C), then Equation 72: %CaO = -0.0880 × T + 126.6 %Cu2O = 2.0 %Sn = 0 Equation 73: %CaO = -0.1020 × T + 145.5 %Cu2O = 2.0 %Sn = 0.1400 × T - 168.0 Equation 74: %CaO = -0.0820 × T + 118.7 %Cu2O = 1.5 Equation 75: %CaO = -0.0880 × T + 127.6 %Cu2O = -0.0160 × T + 21.2 %Sn = 0.3460 × T - 426.3 A plane formed by connecting four points obtained from the equations of these four lines (if the four points do not lie on the plane, it is considered to be a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting four points" will be treated as having the same meaning.) Equation 73, Equation 75, Equation 69: %CaO = 0.0320 × T - 15.3 %Cu2O = 2.0 %Sn = 0.0240 × T - 24.4 Equation 78: %CaO = 0.0240 × T - 2.0 %Cu2O = -0.0020 × T + 3.8 The region is defined by a plane formed by connecting four points obtained from the equations of four lines %Sn = 0.0360 × T - 39.7, and by the six planes formed by connecting four points obtained from the equations of four lines %CaO = 0.0460 × T - 26.2, %Cu2O = 1.5, %Sn = 0, and by equation 1: %Sn = 0, equation 71: %Cu2O = 2.0, and equation 80: %Cu2O = -0.045 × %Sn + 1.5. Furthermore, when the temperature is expressed in degrees Celsius, in the case of -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, then equations 74 and 81: %CaO=-0.0680×T+101.6 %Cu2O=-0.0140×T+18.6 %Sn=0.2880×T-350.9 Equation 82: %CaO=-0.0860×T+122.9. %Cu2O = 0.8 %Sn = 0 Equation 83: %CaO = -0.0840 × T + 121.3 %Cu2O = 0.2 %Sn = 0.0200 × T - 5.5 A plane formed by connecting four points obtained from the equations of four straight lines, and Equation 85: %CaO = -0.0580 × T + 89.7 %Cu2O = -0.0060 × T + 8.7 %Sn = 0.1360 × T - 163.8 Equation 86: %CaO = 0.1000 × T - 102.0 %Cu2O = -0.0020 × T + 3.1 %Sn = 0.1000 × T - 119.0 Equation 87: %CaO = 0.1060 × T - 104.5 Equation 88: %Cu2O=1.3 %Sn=-0.0060×T+12.8 Equation 88: %CaO=0.0480×T-31.2 %Cu2O=-0.0020×T+3.1 %Sn=0.0900×T-107.0 A plane formed by connecting four points obtained from the equations of four straight lines, and Equations 79 and 87: %CaO=0.1060×T-104.5 %Cu2O=1.3 %Sn=-0.0060×T+12.8 Equation 88: %CaO=0.0480×T-31.2 %Cu2O=-0.0020×T+3.1 %Sn=0.0900×T-107.0 Equation 89: It is characterized by being defined by a region enclosed by a plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0020 × T + 29.5, %Cu2O = 0.8, and %Sn = 0, and six planes: Equation 1: %Sn = 0, Equation 80: %Cu2O = -0.045 × %Sn + 1.5, and Equation 90: %Cu2O = -0.029 × %Sn + 0.8. Note that within the defined region described above, depending on the temperature, the region may be divided into two or more parts, but in that case, a solid phase will precipitate in the region not in contact with Equation 1, so only the region in contact with Equation 1 is considered. In each of the above embodiments, the regions between 1200°C and 1250°C, and between 1300°C and 1350°C were obtained by extrapolating the liquidus curves at 1250°C and 1300°C, while the region between 1250°C and 1300°C was obtained by interpolation.

[0027] According to the present invention, since the slag is maintained in a molten state, the precipitation of solids in the generated slag can be suppressed, the decrease in the fluidity of the slag can be suppressed, and copper can be recovered stably. Therefore, according to the present invention, a raw material smelting method can be provided that enables the stable recovery of copper from raw materials (including waste) containing Sn.

[0028] This is an explanatory diagram showing an example of a continuous copper production facility for carrying out the raw material smelting method according to an embodiment of the present invention. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 17.0%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 7.5%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 3.7%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 2.0%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 20.4%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 9.0%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copperＹ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 4.0%. CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 2.2%. CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is -0.045 × %Sn + 1.5). CaO - FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper or molten tin × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is -0.029 × %Sn + 0.8). The dotted line represents the liquidus line in the presence of molten tin. CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is -0.045 × %Sn + 1.5). CaO - FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is -0.029 × %Sn + 0.8). CaO - FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ This is an enlarged view of the liquid phase portion of the O-system liquidus diagram (1300°C). The dotted line represents CaO-FeO in the presence of molten tin, not molten copper. × ―SnOＹ -Cu ２ O system liquidus diagram. CaO-FeO × -SnO Ｙ is a projection onto the plane of the CaO-FeO system in the coexistence of molten copper × -SnO Ｙ -Cu ２ is an enlarged view of the liquid phase portion of the O system liquidus diagram (1250°C).

[0029] Hereinafter, an example of an embodiment of the present invention will be described with reference to the accompanying drawings. The raw material smelting method according to the present embodiment recovers high-purity copper from a copper-containing raw material containing tin as an impurity metal, such as waste of electronic and electrical equipment parts (E-scrap), for example.

[0030] In the raw material smelting method according to the present embodiment, the above-mentioned copper-containing raw material is charged into a melting furnace and melted to obtain a melt, and a calcium source is added to perform smelting, thereby obtaining CaO-FeOx-SnO containing Sn contained in the melt Ｙ -Cu ２ O-based slag is generated, and this CaO-FeOx-SnO Y -Cu ２ Sn is removed by separating the O-based slag. Here, in the present embodiment, copper is recovered from the copper-containing raw material using the continuous copper production equipment shown in FIG. 1.

[0031] As shown in Figure 1, this continuous copper production facility 1 includes a smelting furnace (S furnace) 10 that heats and melts copper ore (copper concentrate) to produce a molten body L containing matte M and slag S, a separation furnace (CL furnace) 3 that separates the matte M and slag S produced in the smelting furnace 10, a copper production furnace (C furnace) 20 that further oxidizes the matte M separated in the separation furnace 3 to produce crude copper C and slag S, and a refining furnace 5 that refines the crude copper C produced in the copper production furnace 20 to produce higher grade copper. These smelting furnace 10, separation furnace 3, copper production furnace 20, and refining furnace 5 are connected to each other by troughs 6A, 6B, and 6C, and are installed with height differences between them in order so that the molten body moves in the order of smelting furnace 10, separation furnace 3, copper production furnace 20, and refining furnace 5 by the action of gravity. Any of the smelting furnace (S furnace) 10, separation furnace (CL furnace) 3, and copper smelting furnace (C furnace) 20 may be used as the melting furnace of the present invention.

[0032] The smelting furnace 10 comprises a furnace body 12 for smelting non-ferrous metals, and a plurality of lance pipes 15 for supplying ore containing non-ferrous metals (copper ore in this embodiment) to a molten body L stored in the furnace body 12, together with oxygen-enriched air (oxygen gas) and flux. The lance pipes 15 are installed to penetrate vertically through the ceiling wall 11 of the furnace body 12 and are movable up and down relative to the surface of the molten body L.

[0033] The lance pipe 15 is located above the surface of the molten metal L and is designed to allow copper ore and oxygen-enriched air to be blown into the surface of the molten metal L. In addition, the ceiling wall 11 of the smelting furnace 10 is provided with an opening 19 for discharging gas (exhaust gas) generated in the furnace, and a waste heat boiler 7 is connected downstream of this opening 19.

[0034] The separation furnace 3 separates the mat M and slag S in the molten material L fed from the smelting furnace 10 by utilizing the difference in their specific gravity, so that a layer of slag S with a lower specific gravity is formed on top of a layer of mat M with a higher specific gravity. Multiple electrodes 8 are arranged in the separation furnace 3 with their lower ends immersed in the slag. In the separation furnace 3, the molten material L is kept warm by inputting a three-phase alternating current from a transformer to these electrodes 8 to generate Joule heat.

[0035] The copper smelting furnace 20 is equipped with multiple lance pipes 25 for supplying chilling material and limestone into the furnace along with oxygen-enriched air such as oxygen gas. The lance pipes 25 are installed through the ceiling wall 21 of the copper smelting furnace 20 and are movable up and down. In addition, the ceiling wall 21 of the copper smelting furnace 20 is provided with an outlet for discharging gas generated in the furnace, and a waste heat boiler 9 is connected to this outlet.

[0036] To smelt copper in this continuous copper production facility 1, dried copper concentrate (non-ferrous metal raw material) and flux (silica sand, lime, etc.) are blown into the molten body L of the smelting furnace 10 through a lance pipe 15, along with oxygen-enriched air. In the smelting furnace 10, the dissolution and oxidation reactions of the copper concentrate proceed, producing matte M, which is mainly composed of a mixture of copper sulfide and iron sulfide, and slag S, which consists of gangue, solvent, etc. from the copper concentrate.

[0037] The matt M and slag S contained in the molten metal L of the smelting furnace 10 are sent to the separation furnace 3 via the trough 6A, where they are separated into a lower layer of matt M and an upper layer of slag S due to the difference in specific gravity. The slag S (Sg) separated in the separation furnace 3 is recovered separately from the matt M. In addition, SO2 generated in the smelting furnace 10, etc. ２ Sulfur-containing gases such as gases are transported to a sulfuric acid plant (not shown) and treated with sulfuric acid or gypsum (CaSO4). ４ It will be collected as follows.

[0038] Meanwhile, the matte M separated in the separation furnace 3 is sent to the copper smelting furnace 20 through the trough 6B. In the copper smelting furnace 20, flux is blown in along with air using the lance pipe 25 to oxidize the sulfur and iron in the matte M, obtaining crude copper C with a purity of 98.5% or higher. The crude copper C continuously produced in the copper smelting furnace 20 is transferred to the refining furnace 5 through the trough 6C. Then, in the refining furnace 5, the crude copper C is refined to produce copper of higher quality.

[0039] In this embodiment of the raw material smelting method, copper-containing raw materials including tin are charged into the smelting furnace 10 in addition to copper concentrate, and copper is recovered by smelting the copper-containing raw materials together with the copper concentrate. The raw materials include those that have undergone pretreatment such as crushing, sorting, granulation, oxidation-reduction reaction, melting, leaching, filtration, and heat treatment for purposes such as roasting, dechlorination, and deorganization. If the pretreatment separates the raw material into two or more phases, such as a copper-concentrated phase (defined as raw materials with a higher copper concentration than the raw materials before pretreatment; typical examples include matte (a copper-containing sulfide) and copper alloys) and other phases, both phases are included in the raw materials.

[0040] Here, in the copper smelting furnace 20, a calcium source is added to the molten material as needed to perform oxidative smelting, resulting in CaO-FeOx-Cu ２ O-based slag is generated, and impurities contained in the molten material are transferred to the slag. Therefore, CaO-FeOx-Cu ２ O-based slag becomes CaO-FeOx-SnO when Sn is supplied. Y - Cu ２ It becomes a quaternary system of O, CaO-FeOx-SnO Ｙ - Cu ２ O quaternary slag (CaO, Fe ２ O ３ (All Fe to Fe ２ O ３ (Amount calculated by converting to) SnO ２ (All Sn to SnO ２ (Amount calculated by converting to) Cu ２ O (All Cu to Cu ２ Slag is defined as having a total converted amount (calculated by converting to oxygen) of 70% or more. It is not limited to this, but for example, at 1250°C, CaO is 16-22% by mass, Fe ２ O ３ It is 54-70 mass%, SnO ２ is 0-3 mass%, Cu ２ O is 2-18% by mass, CaO is 14-25% by mass at 1300°C, Fe ２ O ３ It is 50-73 mass%, SnO ２ is 0-5 mass%, Cu ２The amount of O is 1 to 15% by mass. It is necessary to control the state so that it becomes molten. There are no particular limitations, but CaO-FeOx-SnO Ｙ - Cu ２ For the quaternary slag of O, the numerical range of y may be 1 ≤ y ≤ 2. When this slag is used in the smelting process, it may contain CaO derived from the raw materials. Therefore, the amount of CaO added as flux in the smelting process can be reduced, and in some cases, it may not be necessary to add CaO separately. On the other hand, when this slag is used in the converter process, the CaO component is removed in the smelting process, so CaO is added as flux to obtain the desired slag composition.

[0041] Here, Cd ２ The oxygen concentration can be controlled by the amount of oxygen blown in. Also, SnO Ｙ The concentration (Sn concentration) can be controlled as the amount of raw material supplied. The CaO concentration of the slag can be controlled as the amount of calcium source supplied to be added. The temperature can be controlled by the heating conditions. Therefore, in this embodiment, the temperature of the molten material sent to the copper smelting furnace 20, the Cu of the slag, ２ By controlling one or more of the following: O concentration, Sn concentration in the slag, and CaO concentration in the slag, CaO-FeOx-SnO Ｙ - Cu ２ Maintain the O-type slag in a molten state.

[0042] Figure 2 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 17.0%. Figure 3 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 7.5%. Figure 4 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 3.7%. Figure 5 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The oxygen concentration is 2.0%. Figure 10 shows CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The O concentration (-0.045 × %Sn + 1.5) is shown. Figure 11 shows CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper or molten tin × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1300°C, Cu ２ The O concentration is shown as -0.029 × %Sn + 0.8).

[0043] Figure 6 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 20.4%. Figure 7 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 9.0%. Figure 8 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 4.0%. Figure 9 shows CaO-FeOx-SnO Ｙ CaO-FeOx-SnO projected onto a surface in the presence of molten copper Ｙ ―Cu ２O-system liquidus diagram (1250°C, Cu ２ The oxygen concentration is 2.2%. Figure 12 shows CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The O concentration (-0.045 × %Sn + 1.5) is shown. Figure 13 shows CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ O-system liquidus diagram (1250°C, Cu ２ The O concentration is shown as -0.029 × %Sn + 0.8).

[0044] Figure 14 shows CaO-FeO × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ Figure 15 shows an enlarged view of the liquid phase portion of the O-system liquidus diagram (1300°C). × ―SnO Ｙ CaO-FeO projected onto a surface in the presence of molten copper × ―SnO Ｙ ―Cu ２ This shows an enlarged view of the liquid phase portion of the O-system liquidus diagram (1250°C).

[0045] Here, the uniform melting range of the slag is CaO-FeOx-SnO at a smelting temperature of 1300°C. Ｙ - Cu ２ From the O quaternary phase diagram, CaO, Cu ２In a function expressed by specifying the three components O and Sn, when 7.5 ≤ %Cu2O < 17.0, the region is defined by the following equations: Equation 1: %Sn = 0, Equation 2: 46.6 × %CaO + 19.1 × %Cu2O - 10.5 × %Sn - 958 = 0, Equation 3: -8.55 × %CaO - 10.1 × %Cu2O - 101 × %Sn + 790 = 0, Equation 4: -38.0 × %CaO + 1.50 × %Cu2O - 23.8 × %Sn + 1030 = 0. At a smelting temperature of 1300°C, if 3.7 ≤ %Cu2O < 7.5, the substance is defined by the region enclosed by equation 1: %Sn = 0, equation 5: 20.7 × %CaO - 11.6 × %Cu2O - 4.88 × %Sn - 275 = 0, equation 6: -1.88 × %CaO - 5.65 × %Cu2O - 20.7 × %Sn + 191 = 0, and equation 7: -18.8 × %CaO - 2.91 × %Cu2O - 11.6 × %Sn + 537 = 0. At a smelting temperature of 1300°C, if 2.0 ≤ %Cu2O < 3.7, the region is defined by the following equations: Equation 1: %Sn = 0, Equation 8: 11.8 × %CaO - 36.2 × %Cu2O - 2.64 × %Sn - 46.1 = 0, Equation 9: -1.06 × %CaO - 6.95 × %Cu2O - 12.8 × %Sn + 130 = 0, and Equation 10: -10.7 × %CaO - 15.5 × %Cu2O - 6.69 × %Sn + 358 = 0. At a smelting temperature of 1300°C, if -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0, the %Sn content is defined by the region enclosed by equation 1: %Sn = 0, equation 50: 7.00 × %CaO - 1.40 × %Cu2O - 0.350 × %Sn - 82.6 = 0, and equation 51: 12.1 × %CaO + 13.6 × %Cu2O + 1.91 × %Sn - 209 = 0, and the region enclosed by equations 1, 51, and 52: 4.53 × %CaO + 21.6 × %Cu2O + 12.5 × %Sn - 247 = 0, and equation 53: -5.33 × %CaO - 21.0 × %Cu2O - 3.29 × %Sn + 204 = 0.At a smelting temperature of 1300°C, if -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, then Equation 1: %Sn = 0, Equation 54: 16.5 × %CaO - 23.5 × %Cu2O - 1.87 × %Sn - 164 = 0, Equation 55: -2.20 × %CaO - 5.00 × %Cu2O + 1.14 × %Sn + 4.25 = 0, Equation 56: 4.50 × %CaO + 118 × %C The smelting temperature is defined by the region enclosed by u₂O + 6.27 × %Sn - 254 = 0 and the region enclosed by equations 1, 56, and 57: 0.800 × %CaO + 13.9 × %Cu₂O + 2.56 × %Sn - 57.5 = 0, and equation 58: -3.00 × %CaO + 9.00 × %Cu₂O + 0.180 × %Sn + 87.3 = 0. The smelting temperature is the temperature of the slag.

[0046] Furthermore, at a smelting temperature of 1250°C, when 9.0 ≤ %Cu2O < 20.4, the region is defined by the following equations: Equation 1: %Sn = 0, Equation 11: 39.9 × %CaO + 10.9 × %Cu2O - 9.12 × %Sn - 848 = 0, Equation 12: -3.42 × %CaO - 2.40 × %Cu2O - 41.0 × %Sn + 249 = 0, and Equation 13: -36.5 × %CaO - 5.80 × %Cu2O - 22.8 × %Sn + 925 = 0. At a smelting temperature of 1250°C, if 4.0 ≤ %Cu2O < 9.0, the substance is defined by the region enclosed by equation 1: %Sn = 0, equation 14: 19.5 × %CaO + 5.46 × %Cu2O - 4.50 × %Sn - 416 = 0, equation 15: -1.00 × %CaO - 1.44 × %Cu2O - 9.50 × %Sn + 69.7 = 0, and equation 16: -18.5 × %CaO - 8.55 × %Cu2O - 11.5 × %Sn + 519 = 0. At a smelting temperature of 1250°C, if 2.2 ≤ %Cu2O < 4.0, the region is defined by the following equations: Equation 1: %Sn = 0, Equation 17: 8.10 × %CaO - 15.3 × %Cu2O - 1.80 × %Sn - 102 = 0, Equation 18: -0.540 × %CaO - 1.71 × %Cu2O - 4.32 × %Sn + 37.7 = 0, and Equation 19: -7.56 × %CaO - 2.76 × %Cu2O - 4.68 × %Sn + 209 = 0. At a smelting temperature of 1250°C, if -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.2, then it is defined by the region enclosed by equation 1: %Sn = 0, equation 59: 3.85 × %CaO - 3.30 × %Cu2O - 0.910 × %Sn - 57.4 = 0, equation 60: -0.400 × %CaO - 3.72 × %Cu2O - 5.60 × %Sn + 46.2 = 0, and equation 61: -4.59 × %CaO - 22.6 × %Cu2O - 2.79 × %Sn + 177 = 0. At a smelting temperature of 1250°C, if -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, then the %Sn content is defined by the region enclosed by equation 1: %Sn = 0, equation 62: 6.37 × %CaO - 7.28 × %Cu2O - 0.600 × %Sn - 92.3 = 0, and equation 63: 7.99 × %CaO + 65.6 × %Cu2O + 5.91 × %Sn - 259 = 0, and the region enclosed by equations 1, 63, and 64: 0.350 × %CaO + 1.56 × %Cu2O + 4.06 × %Sn - 33.3 = 0, and equation 65: -3.67 × %CaO - 4.90 × %Cu2O - 2.47 × %Sn + 122 = 0.

[0047] Furthermore, when the smelting temperature is between 1200°C and 1350°C, and 9.0 ≤ %Cu2O, when the temperature is expressed as T (°C), Equation 20: %CaO = -0.0420 × T + 68.2, %Cu2O = -0.0680 × T + 10⁵, %Sn = 0; Equation 21: %CaO = -0.0360 × T + 61.5, %Cu2O = -0.0680 × T + 10⁵, %S The equations of the four lines n = 0.0280 × T - 31.5, Equation 22: %CaO = -0.0383 × T + 66.7, %Cu2O = 9.0, %Sn = 0, Equation 23: %CaO = -0.0320 × T + 59.7, %Cu2O = 9.0, %Sn = 0.0302 × T - 33.8 form a plane connecting four points, and Equations 21, 23, and 24: %CaO = 0.1 Equation 25: %CaO = 0.0568 × T - 110, %Cu2O = -0.0680 × T + 105, %Sn = 0.0160 × T - 16.8, Equation 25: %CaO = 0.0568 × T - 49.4, %Cu2O = 9.0, %Sn = 0.0234 × T - 25.6. A plane is formed by connecting four points obtained from the equations of these four lines, and Equations 24, 25, and 26: %CaO = 0.114 × T - 120, % The region is defined by a plane formed by connecting four points obtained from the equations of four lines: Cu2O = -0.0680 × T + 10⁵, %Sn = 0, Equation 27: %CaO = 0.0717 × T - 65.7, %Cu2O = 9.0, %Sn = 0, and six planes: Equation 1: %Sn = 0, Equation 28: %Cu2O = -0.0680 × T + 10⁵, Equation 29: %Cu2O = 9. An example of how to obtain four points from the equations of four lines will be explained using Equations 20 to 23. First, substitute T = 1300 into Equation 20, for example, fixing T. Then, one point is obtained in a three-dimensional space with %CaO, %Cu2O, and %Sn as axes. Similarly, by substituting T = 1300 into Equations 21 to 23, one point can be obtained from each equation. In this way, four points can be obtained from the equations of four lines. Furthermore, if the four points obtained from the equations of the four lines do not lie on the same plane, the figure formed by connecting the four points obtained from the equations of the four lines is divided by an arbitrary diagonal, and the resulting plane consisting of two triangular faces is considered "a single plane formed by connecting the four points obtained from the equations of the four lines." This provision for cases where the four points obtained from the equations of the four lines do not lie on the same plane also applies when referring to plane A or plane B. The temperature expressed as T (°C) is the temperature of the slag.

[0048] Furthermore, when the smelting temperature is greater than 1200°C but less than 1350°C, and 7.5 ≤ %Cu2O < 9.0, when the temperature is expressed as T (°C), a plane is formed by connecting four points obtained from the equations of four straight lines: Equations 22, 23, and 30: %CaO = -0.0344 × T + 62.2, %Cu2O = 7.5, %Sn = 0; Equation 31: %CaO = -0.0272 × T + 54.2, %Cu2O = 7.5, %Sn = 0.0284 × T - 31.5, and Equations 23, 25, 31, and 32: It is defined by the region enclosed by one plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0422 × T - 30.5, %Cu2O = 7.5, and %Sn = 0.0227 × T - 24.5; one plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0561 × T - 45.6, %Cu2O = 7.5, and %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 29: %Cu2O = 9, and Equation 34: %Cu2O = 7.5.

[0049] Furthermore, when the smelting temperature is greater than 1200°C but less than 1350°C, and 4.0 ≤ %Cu2O < 7.5, when the temperature is expressed as T (°C), a plane is formed by connecting four points obtained from the equations of four straight lines: Equations 30, 31, 35: %CaO = -0.0931 × T + 137, %Cu2O = 4.0, %Sn = 0, Equation 36: %CaO = -0.0819 × T + 124, %Cu2O = 4.0, %Sn = 0.0422 × T - 48.3, and Equations 31, 32, 36, 37: % It is defined by the region enclosed by one plane formed by connecting four points obtained from the equations of four straight lines CaO = 0.0129 × T + 7.5, %Cu2O = 4.0, %Sn = 0.0352 × T - 39.8; one plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0348 × T - 17.4, %Cu2O = 4.0, %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 34: %Cu2O = 7.5, Equation 39: %Cu2O = 4.0.

[0050] Furthermore, when the smelting temperature is greater than 1200°C but less than 1350°C, and 3.7 ≤ %Cu2O < 4.0, when the temperature is expressed as T (°C), a plane is formed by connecting four points obtained from the equations of four straight lines: Equations 35, 36, and 40: %CaO = -0.0847 × T + 125, %Cu2O = 3.7, %Sn = 0; Equation 41: %CaO = -0.0755 × T + 115, %Cu2O = 3.7, %Sn = 0.0403 × T - 45.7, and Equations 36, 37, 41, and 42: %C It is defined by the region enclosed by one plane formed by connecting four points obtained from the equations of four straight lines: aO = 0.0112 × T + 9.61, %Cu2O = 3.7, %Sn = 0.0357 × T - 40.3; one plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0341 × T - 16.4, %Cu2O = 3.7, %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 39: %Cu2O = 4.0, Equation 44: %Cu2O = 3.7.

[0051] Furthermore, when the smelting temperature is greater than 1200°C but less than 1350°C, and 2.2 ≤ %Cu2O < 3.7, when the temperature is expressed as T (°C), a plane is formed by connecting four points obtained from the equations of four straight lines: Equations 40, 41, 45: %CaO = -0.0123 × T + 170, %Cu2O = 2.2, %Sn = 0, and Equation 46: %CaO = -0.113 × T + 160, %Cu2O = 2.2, %Sn = 0.0460 × T - 52.0, and Equations 41, 42, 46, 47: %C It is defined by the region enclosed by one plane formed by connecting four points obtained from the equations of four straight lines: aO = 0.0459 × T - 33.7, %Cu2O = 2.2, %Sn = 0.0338 × T - 37.1; one plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0685 × T - 58.8, %Cu2O = 2.2, %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 44: %Cu2O = 3.7, Equation 49: %Cu2O = 2.2.

[0052] Furthermore, when the smelting temperature is greater than 1200°C but less than 1350°C, and 2.0 ≤ %Cu2O < 2.2, when the temperature is expressed as T (°C), formula 46: %CaO Equation 66: %CaO = -0.1227 × T + 170.2, %Cu2O = 2.2, %Sn = 0, Equation 67: %CaO = -0.0880 × T + 126.6, %Cu2O = 2.0, %Sn = 0, Equation 68: %CaO = -0.1229 × T + 171.6, %Cu2O = 2.0, %Sn = 0.0213 × T - 19.7. A plane is formed by connecting four points obtained from the equations of the four lines, and Equations 46 and 47: %CaO = 0.0459 × T - 33.7, %Cu2O = 2.2, %Sn = 0.0338 × T - It is defined by a region enclosed by a plane formed by connecting four points obtained from the equations of four straight lines: 37.1, Equation 68, Equation 69: %CaO = 0.0320 × T - 15.3, %Cu2O = 2.0, %Sn = 0; a plane formed by connecting four points obtained from the equations of four straight lines: 47, Equation 48: %CaO = 0.0685 × T - 58.8, %Cu2O = 2.2, %Sn = 0; Equation 69, Equation 70: %CaO = 0.0480 × T - 31.9, %Cu2O = 2.0, %Sn = 0; and six planes: Equation 1: %Sn = 0; Equation 49: %Cu2O = 2.2; Equation 71: %Cu2O = 2.0.

[0053] Furthermore, when the smelting temperature is greater than 1250°C but less than 1350°C, and -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0, and the temperature is expressed as T (°C), then Equation 72: %CaO = -0.0880 × T + 126.6, %Cu2O = 2.0, %Sn = 0; Equation 73: %CaO = -0.1020 × T + 145.5, %Cu2O = 2.0, %Sn = 0.1400 × T - 168.0; Equation 74: %CaO = -0.0820 × T + 118.7. A plane formed by connecting four points obtained from the equations of four straight lines: %Cu2O = 1.5, %Sn = 0, Equation 75: %CaO = -0.0880 × T + 127.6, %Cu2O = -0.0160 × T + 21.2, %Sn = 0.3460 × T - 426.3, and Equations 73, 75, and 76: %CaO = -0.0960 × T + 138.0, %Cu2O = 2.0, %Sn = 0.0900 × T - 105.5, Equation 77: %CaO = -0.0660 × T + 100.1 The region is defined by a plane (plane A) formed by connecting four points obtained from the equations of four straight lines: %Cu2O = -0.0060 × T + 8.7, %Sn = 0.1360 × T - 163.8, and the region enclosed by five planes: Equation 1: %Sn = 0, Equation 71: %Cu2O = 2.0, Equation 80: %Cu2O = -0.045 × %Sn + 1.5. Furthermore, the region is defined by plane A and equations 69, 76, 77, and 78: %CaO = 0.0240 × T - 2.0, %Cu2O = -0.0020 × It is defined by the region enclosed by one plane formed by connecting four points obtained from the equations of four straight lines with T+3.8 and %Sn = 0.0360 × T-39.7, one plane formed by connecting four points obtained from the equations of four straight lines with %CaO = 0.0460 × T-26.2, %Cu2O = 1.5, and %Sn = 0, and six planes with equations 1: %Sn = 0, 71: %Cu2O = 2.0, and 80: %Cu2O = -0.045 × %Sn+1.5.

[0054] Furthermore, when the smelting temperature is greater than 1250°C but less than 1350°C, and -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, and the temperature is expressed as T (°C), then Equations 74 and 81: %CaO = -0.0680 × T + 101.6, %Cu2O = -0.0140 × T + 18.6, %Sn = 0.2880 × T - 350.9, Equation 82: %CaO = -0.0860 × T + 122.9, %Cu2O = 0.8, %Sn = 0, Equation 83: %CaO = -0.0840 × T + 121.3, %Cu2O = 0.2, % One plane is formed by connecting four points obtained from the equations of four lines with Sn = 0.0200 × T - 5.5, and another plane is formed by connecting three points obtained from the equations of three lines with equations 81, 83, and 84: %CaO = 0.0080 × T + 6.3, %Cu2O = -0.0040 × T + 5.2, %Sn = 0.1800 × T - 205.5, and equations 81, 84, and 85: %CaO = -0.0580 × T + 89.7, %Cu2O = -0.0060 × T + 8.7, %Sn = 0.1360 × T - 163.8, and equation 86: %CaO = 0.1000 × T - 102. The region is defined by a plane (plane B) formed by connecting four points obtained from the equations of four straight lines: 0, %Cu2O = -0.0020 × T + 3.1, and %Sn = 0.1000 × T - 119.0, and by the region enclosed by six planes: equation 1: %Sn = 0, equation 80: %Cu2O = -0.045 × %Sn + 1.5, and equation 90: %Cu2O = -0.029 × %Sn + 0.8. Furthermore, the region is defined by plane B and equations 85, 86, and 87: %CaO = 0.1060 × T - 104.5, %Cu2O = 1.3, %Sn = -0.0060 × T + 12.8, and equation 88: %CaO = 0.0 The region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: 480 × T - 31.2, %Cu2O = -0.0020 × T + 3.1, %Sn = 0.0900 × T - 107.0; a plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0020 × T + 29.5, %Cu2O = 0.8, %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 80: %Cu2O = -0.045 × %Sn + 1.5, Equation 90: %Cu2O = -0.029 × %Sn + 0.8. Furthermore, within the defined region described above, regions where Cu2O is less than 0% at certain temperatures are excluded.

[0055] Furthermore, when the smelting temperature is between 1200°C and 1250°C, and -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0, the region is defined by the area enclosed by a plane formed by connecting four points obtained from the equations of the four lines in equations 72, 73, 74, and 75; a plane formed by connecting four points obtained from the equations of the four lines in equations 69, 73, 75, and 78; a plane formed by connecting four points obtained from the equations of the four lines in equations 69, 70, 78, and 79; and six planes: equation 1: %Sn = 0, equation 71: %Cu2O = 2.0, and equation 80: %Cu2O = -0.045 × %Sn + 1.5.

[0056] Furthermore, when the smelting temperature is between 1200°C and 1250°C, and -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, the region is defined by the area enclosed by the plane formed by connecting four points obtained from the equations of the four lines in equations 74, 81, 82, and 83; the plane formed by connecting four points obtained from the equations of the four lines in equations 85, 86, 87, and 88; the plane formed by connecting four points obtained from the equations of the four lines in equations 79, 87, 88, and 89; and the six planes of equation 1: %Sn = 0, equation 80: %Cu2O = -0.045 × %Sn + 1.5, and equation 90: %Cu2O = -0.029 × %Sn + 0.8.

[0057] In this embodiment, the temperature of the molten material in the copper furnace 20, the Cu of the slag ２ Control one or more of the following: O concentration, Sn concentration in the slag, and CaO concentration in the slag, and CaO-FeOx-SnO Ｙ - Cu ２ By operating the process so that the composition of the O-based slag is located in the liquid phase portion of the phase diagrams from Figures 2 to 15 (i.e., within the uniform melting range), it becomes possible to stably recover copper from raw materials containing Sn. The composition of the liquid phase portion of the phase diagrams from Figures 2 to 15 coincides with the compositional range of each claim.

[0058] According to the raw material smelting method of this embodiment, which has the above configuration, the temperature of the molten material sent to the copper furnace 20, the Cu of the slag ２By controlling one or more of the following: O concentration, Sn concentration in the slag, and CaO concentration in the slag, CaO-FeOx-SnO Ｙ - Cu ２ Since the system is configured to maintain the O-based slag in a molten state, the precipitation of solids in the generated slag can be suppressed, the decrease in the fluidity of the slag can be suppressed, and copper can be recovered stably.

[0059] Although embodiments of the present invention have been described above, the present invention is not limited thereto and can be modified as appropriate without departing from the technical spirit of the invention. In this embodiment, the invention has been described as being carried out using the continuous copper production equipment shown in Figure 1, but the invention is not limited thereto, and the raw material smelting method of the present invention may be carried out using a batch-type melting furnace.

[0060] The following additional information is disclosed regarding the above embodiments. (Addendum 1) A method for smelting a raw material to recover copper from a raw material containing Sn, wherein the raw material is put into a melting furnace and melted to obtain a molten body, and a calcium source is added and smelted to obtain CaO-FeOx-SnO Ｙ - Cu ２ The system is configured to generate and separate O-based slag, and the temperature of the slag, the CaO concentration of the slag, and the Cu of the slag ２ A method for smelting raw materials, characterized by maintaining the slag in a molten state by controlling one or more of the following: the O concentration and the Sn concentration of the slag.

[0061] The results of the verification experiments conducted to confirm the effectiveness of the present invention are described below.

[0062] In the commercial copper smelting furnace (Furnace C) of the Mitsubishi continuous copper smelting process shown in Figure 1, the target control temperature for calcium ferrite slag is set to 1250°C during operation. The temperature of the slag is measured at 30-minute intervals using a consumable thermocouple, and the Cu of the slag is measured using an X-ray fluorescence analyzer. ２ A component analysis of O, CaO, and Sn will be performed. The values ​​that can be measured with a fluorescence X-ray analyzer are the Cu and Ca concentrations of the slag, so these will be converted assuming that all of them are Cu₂O and CaO in the slag.

[0063] Here, the smelting temperature may fluctuate depending on the degree of oxidation of the crude copper and the increase or decrease in the amount of copper matte flowing into the copper smelting furnace (C furnace). For example, at 1250°C, the % Cu of the slag ２ When O (equivalent to the partial pressure of oxygen) is 9.0, %CaO is 20, and %Sn is 1.0, the slag is sufficiently within the uniform melting range, and even if the slag temperature drops to 1230°C due to fluctuations in operating conditions, no solid precipitates will form in the slag. (At a temperature of 1250°C, the melting range is inside the point connecting (%CaO, %Cu2O, %Sn) = (18.8, 9.0, 0) (19.7, 9.0, 3.9) (21.60, 9.0, 3.7) (23.9, 9.0, 0) from equations 1, 11, 12, and 13, and the above point falls within that region. The melting range at a temperature of 1230°C is (%CaO, from equations 1, 20-27) (%CaO, The solubility of Cu in slag increases as the temperature decreases, so in this case, we assumed that the Cu2O concentration in the slag increased from 9.0 to 10.0 as a result of the temperature decrease.

[0064] Thus, during operation, % Cu of the slag ２ The amount of solvent (CaO source) added and the amount of oxygen blown in (% Cu) are adjusted so that O, % CaO, and % Sn are within a uniform melting range. ２ If you control the amount of O (which changes), even if the slag temperature temporarily drops, Fe ３ O ４ Ca ２ Fe ２ O ５ CaSnO ３ Furthermore, Ca2SnO4 does not precipitate, and the slag has low viscosity and good fluidity. In addition, slag does not adhere to the furnace's slag outlet or trough, and magnetite does not accumulate. The slag temperature is measured using a consumable thermocouple, and %Cu ２ O, %CaO, and %Sn can each be measured in a short time using the above-mentioned X-ray fluorescence analyzer.

[0065] Based on the results of the above verification experiments, it has been confirmed that the present invention provides a raw material smelting method that enables the stable recovery of copper from raw materials containing Sn.

[0066] (CaO-FeOx-SnO Ｙ -Cu ２ (Creation of a quaternary phase diagram) Calcium ferrite slag containing Cu2O and Sn was prepared using reagents and held together with a copper-tin alloy in a magnesium vat at temperatures of 1250°C and 1300°C. This yielded calcium ferrite slag with a composition range of 0-25% Cu2O, 10-40% CaO, 0-30% Sn, and the remainder being substantially iron oxide (FeOx, 1 ≤ x ≤ 1.5). The individual components of this calcium ferrite slag were determined by chemical analysis, and its molten state was determined by solid-phase separation, resulting in CaO-FeOx-SnO Ｙ -Cu ２ The uniform melting range of the O quaternary phase diagram was determined. The results are shown in Tables 1, 1A, 2, and 2A.

[0067] The solid-phase separation method is carried out as follows. First, when a small amount of solid phase coexists in the molten material, if it is allowed to settle sufficiently, the solid phase will concentrate in the upper or lower part depending on the density difference between the molten material and the solid phase. Therefore, if this solidified sample is divided into two halves, upper and lower, and chemically analyzed, a compositional difference will be created between the upper and lower halves, and the molten composition when a solid phase coexists in the molten material can be determined relatively easily by chemical analysis alone. This method is effective when the viscosity and interfacial tension are low, such as with calcium ferrite slag. Based on the results obtained in the above test, the domain of the claim is an approximation of the quaternary phase diagram, in which only the CaO-Cu2O-Sn three components are represented, such that the melting range is an assembly of polyhedra. For information on solid-phase separation methods, see "Yoichi Takeda, Akira Yazawa: "Thermodynamics of Solid Iron Saturated Fe-O-CaO System Slag - Equilibrium Study of Ferrite Slag (Part 1)", Journal of the Mining Society of Japan, 96(1980), 901-905." and "Yoichi Takeda, Shigeatsu Nakazawa, Akira Yazawa: "Phase Equilibrium of CaO-FeO-Fe2O3 System - Equilibrium Study of Ferrite Slag (Part 2)", Journal of the Mining Society of Japan, 97(1981), 473-478."

[0068]

[0069]

[0070]

[0071]

[0072] According to the present invention, it is possible to provide a raw material smelting method that enables the stable recovery of copper from raw materials containing Sn.

Claims

1. A method for smelting a raw material to recover copper from a raw material containing Sn, wherein the raw material is placed in a melting furnace, and a calcium source is added as needed to perform smelting, thereby producing CaO-FeOx-SnO Ｙ - Cu ２ The system is configured to generate and separate O-based slag, and the temperature of the slag, the CaO concentration of the slag, and the Cu of the slag ２ A method for smelting raw materials, characterized by maintaining the slag in a molten state by controlling one or more of the following: the O concentration and the Sn concentration of the slag.

2. The method for smelting a raw material according to claim 1, characterized in that the raw material containing Sn includes copper matte obtained by smelting a material containing copper concentrate, and smelting is carried out by adding the calcium source to produce slag and crude copper, and the slag is separated.

3. CaO, Cu in the slag ２ The amount of O and Sn components in CaO-FeOx-SnO in the presence of molten copper (which may also contain tin) at the smelting temperature. Y - Cu ２ From the O quaternary phase diagram, CaO, Cu ２ The temperature of the slag, the CaO concentration of the slag, and the Cu of the slag are adjusted so that the function expressed by specifying the three components O and Sn is within the uniform melting range. ２ A method for smelting raw materials according to claim 1 or 2, characterized by controlling one or more selected from the O concentration and the Sn concentration of the slag.

4. When the smelting temperature is 1300°C, the uniform melting range is determined from the quaternary phase diagram for CaO, Cu ２ O and Sn in a function expressed by specifying the three components, which is defined as a region surrounded by the following formulas when 7.5≦%Cu2O<17.0: Formula 1: %Sn=0; Formula 2: 46.6×%CaO+19.1×%Cu2O-10.5×%Sn-958=0; Formula 3: -8.55×%CaO-10.1×%Cu2O-101×%Sn+790=0; Formula 4: -38.0×%CaO+1.50×%Cu2O-23.8×%Sn+1030=0, the raw material smelting method according to claim 3.

5. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1300°C, and the components of CaO and Cu are... ２ A method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when 3.7 ≤ %Cu2O < 7.5, the region is defined by: Equation 1: %Sn = 0 Equation 5: 20.7 × %CaO - 11.6 × %Cu2O - 4.88 × %Sn - 275 = 0 Equation 6: -1.88 × %CaO - 5.65 × %Cu2O - 20.7 × %Sn + 191 = 0 Equation 7: -18.8 × %CaO - 2.91 × %Cu2O - 11.6 × %Sn + 537 = 0 6. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1300°C, and the components of CaO and Cu are... ２ A method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when 2.0 ≤ %Cu2O < 3.7, the region is defined by the following equations: Equation 1: %Sn = 0 Equation 8: 11.8 × %CaO - 36.2 × %Cu2O - 2.64 × %Sn - 46.1 = 0 Equation 9: -1.06 × %CaO - 6.95 × %Cu2O - 12.8 × %Sn + 130 = 0 Equation 10: -10.7 × %CaO - 15.5 × %Cu2O - 6.69 × %Sn + 358 = 0 7. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1250°C, and the components of CaO and Cu are... ２ A method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when 9.0 ≤ %Cu2O < 20.4, the region is defined by the following equations: Equation 1: %Sn = 0 Equation 11: 39.9 × %CaO + 10.9 × %Cu2O - 9.12 × %Sn - 848 = 0 Equation 12: -3.42 × %CaO - 2.40 × %Cu2O - 41.0 × %Sn + 249 = 0 Equation 13: -36.5 × %CaO - 5.80 × %Cu2O - 22.8 × %Sn + 925 = 0 8. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1250°C, and the components of CaO and Cu are... ２ A method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when 4.0 ≤ %Cu2O < 9.0, the region is defined by the following equations: Equation 1: %Sn = 0 Equation 14: 19.5 × %CaO + 5.46 × %Cu2O - 4.50 × %Sn - 416 = 0 Equation 15: -1.00 × %CaO - 1.44 × %Cu2O - 9.50 × %Sn + 69.7 = 0 Equation 16: -18.5 × %CaO - 8.55 × %Cu2O - 11.5 × %Sn + 519 = 0 9. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1250°C, and the components of CaO and Cu are... ２ A method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when 2.2 ≤ %Cu2O < 4.0, the region is defined by: Equation 1: %Sn = 0 Equation 17: 8.10 × %CaO - 15.3 × %Cu2O - 1.80 × %Sn - 102 = 0 Equation 18: -0.540 × %CaO - 1.71 × %Cu2O - 4.32 × %Sn + 37.7 = 0 Equation 19: -7.56 × %CaO - 2.76 × %Cu2O - 4.68 × %Sn + 209 = 0 10. When the smelting temperature is greater than 1200°C and less than 1350°C, the uniform melting range is determined from the quaternary phase diagram by CaO, Cu ２ In a function expressed with three components specified as O and Sn, when 9.0 ≤ %Cu2O and the temperature is expressed as T (°C), Equation 20: %CaO = -0.0420 × T + 68.2 %Cu2O = -0.0680 × T + 105 %Sn = 0 Equation 21: %CaO = -0.0360 × T + 61.5 %Cu2O = -0.0680 × T + 105 %Sn = 0.0280 × T - 31.5 Equation 22: %CaO = -0.0383 × T + 66.7 %Cu2O = 9.0 %Sn = 0 Equation 23: %CaO = -0.0320 × T + 59.7 %Cu2O = 9.0 %Sn = 0.0302 × T - 33.8 A plane formed by connecting the four points obtained from the equations of the four lines (if the four points do not lie on a plane, it is considered a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting the four points" will be treated as having the same meaning.) Equations 21, 23, 24: %CaO = 0.104 × T - 110 %Cu2O = -0.0680 × T + 105 %Sn = 0.0160 × T - 16.8 Equation 25: %CaO = 0.0568 × T - 49.4 %Cu2O = 9.0 %Sn = 0.0234 × T - 25.6 A plane formed by connecting the four points obtained from the equations of the four lines, Equations 24, 25, 26: %CaO = 0.114 × T - 120 %Cu2O = -0.0680 × T + 105 The region is defined by a plane formed by connecting four points obtained from the equations of the four lines: %Sn=0 Equation 27: %CaO=0.0717×T-65.7 %Cu2O=9.0 %Sn=0 and the region enclosed by the six planes: Equation 1: %Sn=0 Equation 28: %Cu2O=-0.0680×T+105 Equation 29: %Cu2O=9 Furthermore, when 7.5≦%Cu2O<9.0 and the temperature is expressed in T (°C), Equations 22, 23, and 30: %CaO=-0.0344×T+62.2 %Cu2O=7.5 %Sn=0 Equation 31: %CaO=-0.0272×T+54.2 %Cu2O=7.5 The plane formed by connecting the four points obtained from the equations of the four lines %Sn = 0.0284 × T-31.5, and equations 23, 25, 31, and 32: %CaO = 0.The region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: 0422 × T - 30.5, %Cu2O = 7.5, %Sn = 0.0227 × T - 24.5; a plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0561 × T - 45.6, %Cu2O = 7.5, %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 29: %Cu2O = 9, Equation 34: %Cu2O = 7.

5. Furthermore, when 4.0 ≤ %Cu2O < 7.5, and the temperature is expressed in degrees Celsius, Equations 30, 31, 35: %CaO = -0.0931 × T + 137 %Cu2O=4.0 %Sn=0 Equation 36: A plane formed by connecting the four points obtained from the equations of the four lines %CaO=-0.0819×T+124 %Cu2O=4.0 %Sn=0.0422×T-48.3 Equation 31, Equation 32, Equation 36, Equation 37: A plane formed by connecting the four points obtained from the equations of the four lines %CaO=0.0129×T+7.5 %Cu2O=4.0 %Sn=0.0352×T-39.8 Equation 32, Equation 33, Equation 37, Equation 38: %CaO=0.0348×T-17.4 %Cu2O=4.0 %Sn=0 Equation 1: %Sn=0 The region is defined by the six planes of equation 34: %Cu2O = 7.5 and equation 39: %Cu2O = 4.

0. Furthermore, when 3.7 ≤ %Cu2O < 4.0 and the temperature is expressed in degrees Celsius, one plane is formed by connecting the four points obtained from the equations of the four lines: equations 35, 36, and 40: %CaO = -0.0847 × T + 125 %Cu2O = 3.7 %Sn = 0 and equation 41: %CaO = -0.0755 × T + 115 %Cu2O = 3.7 %Sn = 0.0403 × T - 45.7, and equations 36, 37, 41, and 42: %CaO = 0.0112 × T + 9.61 %Cu2O = 3.7 The equations of the four lines %Sn = 0.0357 × T-40.3 form a plane connecting four points, and equations 37, 38, 42, and 43: %CaO = 0.0341 × T-16.The region is defined by a plane formed by connecting four points obtained from the equations of four straight lines:

4. %Cu2O = 3.7 %Sn = 0 and the region enclosed by the six planes: Equation 1: %Sn = 0 Equation 39: %Cu2O = 4.0 Equation 44: %Cu2O = 3.7 Furthermore, when 2.2 ≤ %Cu2O < 3.7 and the temperature is expressed in degrees Celsius, the region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: Equation 40, Equation 41, Equation 45: %CaO = -0.0123 × T + 170 %Cu2O = 2.2 %Sn = 0 Equation 46: %CaO = -0.113 × T + 160 %Cu2O = 2.2 %Sn = 0.0460 × T - 52.0 The method for smelting raw materials according to claim 3, characterized in that the region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: Equations 41, 42, 46, and 47: %CaO = 0.0459 × T - 33.7, %Cu2O = 2.2, and %Sn = 0.0338 × T - 37.1; a plane formed by connecting four points obtained from the equations of four straight lines: Equations 42, 43, 47, and 48: %CaO = 0.0685 × T - 58.8, %Cu2O = 2.2, and %Sn = 0; and six planes: Equation 1: %Sn = 0, Equation 44: %Cu2O = 3.7, and Equation 49: %Cu2O = 2.

2. In some cases, the defined region may be divided into two or more parts depending on the temperature. In such cases, since a solid phase precipitates in the region not in contact with Equation 1, only the region in contact with Equation 1 is considered.

11. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1300°C, and the components of CaO and Cu are... ２ The method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0, the region is defined by the region enclosed by Equation 1: %Sn = 0 Equation 50: 7.00 × %CaO - 1.40 × %Cu2O - 0.350 × %Sn - 82.6 = 0 Equation 51: 12.1 × %CaO + 13.6 × %Cu2O + 1.91 × %Sn - 209 = 0 and the region enclosed by Equation 1, Equation 51, Equation 52: 4.53 × %CaO + 21.6 × %Cu2O + 12.5 × %Sn - 247 = 0 Equation 53: -5.33 × %CaO - 21.0 × %Cu2O - 3.29 × %Sn + 204 = 0 12. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1300°C, and the components of CaO and Cu are... ２ In a function expressed with three components O and Sn, when -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, the region enclosed by Equation 1: %Sn = 0 Equation 54: 16.5 × %CaO - 23.5 × %Cu2O - 1.87 × %Sn - 164 = 0 Equation 55: -2.20 × %CaO - 5.00 × %Cu2O + 1.14 × %Sn + 4.25 = 0 Equation 56: 4.50 × %CaO + 118 × %Cu2O + 6.27 × %Sn - 254 = 0 and Equation 1, Equation 56, Equation 57: 0.800 × %CaO + 13.9 × %Cu2O + 2.56 × %Sn - 57.5 = 0 Equation 58: The method for smelting raw materials according to claim 3, characterized in that it is defined by the region enclosed by -3.00 × %CaO + 9.00 × %Cu2O + 0.180 × %Sn + 87.3 = 0.

13. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1250°C, and the components of CaO and Cu are... ２ A method for smelting raw materials according to claim 3, characterized in that, in a function expressed by specifying the three components O and Sn, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.2, the region is defined by the following equations: Equation 1: %Sn = 0 Equation 59: 3.85 × %CaO - 3.30 × %Cu2O - 0.910 × %Sn - 57.4 = 0 Equation 60: -0.400 × %CaO - 3.72 × %Cu2O - 5.60 × %Sn + 46.2 = 0 Equation 61: -4.59 × %CaO - 22.6 × %Cu2O - 2.79 × %Sn + 177 = 0 14. The uniform melting range is determined from the quaternary phase diagram when the smelting temperature is 1250°C, and the components of CaO and Cu are... ２ In a function expressed with three components O and Sn, when -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, the region enclosed by Equation 1: %Sn = 0 Equation 62: 6.37 × %CaO - 7.28 × %Cu2O - 0.600 × %Sn - 92.3 = 0 Equation 63: 7.99 × %CaO + 65.6 × %Cu2O + 5.91 × %Sn - 259 = 0 and Equation 1, Equation 63, Equation 64: 0.350 × %CaO + 1.56 × %Cu2O + 4.06 × %Sn - 33.3 = 0 Equation 65: -3.67 × %CaO - 4.90 × %Cu2O - 2.47 × %Sn + 122 = 0 A method for smelting raw materials according to claim 3, characterized in that it is defined by a region enclosed by [a certain symbol].

15. When the smelting temperature is greater than 1200°C and less than 1350°C, the uniform melting range is determined from the quaternary phase diagram by CaO, Cu ２ In a function expressed with three components specified as O and Sn, when 2.0 ≤ %Cu2O < 2.2 and the temperature is expressed as T (°C), Equation 46: %CaO = -0.113 × T + 160 %Cu2O = 2.2 %Sn = 0.0460 × T - 52.0 Equation 66: %CaO = -0.1227 × T + 170.2 %Cu2O = 2.2 %Sn = 0 Equation 67: %CaO = -0.0880 × T + 126.6 %Cu2O = 2.0 %Sn = 0 Equation 68: %CaO = -0.1229 × T + 171.6 %Cu2O = 2.0 %Sn = 0.0213 × T - 19.7 A plane formed by connecting the four points obtained from the equations of the four lines (if the four points do not lie on a plane, it is considered a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting the four points" will be treated as having the same meaning.) Equations 46, 47, 68, 69: %CaO = 0.0320 × T - 15.3 %Cu2O = 2.0 %Sn = 0.0240 × T - 24.4 A plane formed by connecting the four points obtained from the equations of the four lines Equations 47, 48, 69, 70: %CaO = 0.0480 × T - 31.9 %Cu2O = 2.0 %Sn = 0 Equation 1: %Sn = 0 Equation 49: %Cu2O = 2.2 Equation 71: A method for smelting a raw material according to claim 3, characterized in that it is defined by a region enclosed by six planes of %Cu2O = 2.

0. Of the defined region described above, depending on the temperature, the region may be divided into two or more parts, but in that case, a solid phase will precipitate in the region not in contact with Equation 1, so only the region in contact with Equation 1 is considered.

16. When the smelting temperature is greater than 1250°C and less than 1350°C, the uniform melting range is determined from the quaternary phase diagram by CaO, Cu ２ In a function expressed with three components specified as O and Sn, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0 and the temperature is expressed as T (°C), Equation 72: %CaO = -0.0880 × T + 126.6 %Cu2O = 2.0 %Sn = 0 Equation 73: %CaO = -0.1020 × T + 145.5 %Cu2O = 2.0 %Sn = 0.1400 × T - 168.0 Equation 74: %CaO = -0.0820 × T + 118.7 %Cu2O = 1.5 %Sn = 0 Equation 75: %CaO = -0.0880 × T + 127.6 %Cu2O = -0.0160 × T + 21.2 A plane formed by connecting four points obtained from the equations of four lines %Sn = 0.3460 × T - 426.3 (if the four points do not lie on a plane, it is considered a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting four points" will be treated as having the same meaning.) And a plane A formed by connecting four points obtained from the equations of four lines: Equations 73, 75, 76: %CaO = -0.0960 × T + 138.0 %Cu2O = 2.0 %Sn = 0.0900 × T - 105.5 Equation 77: %CaO = -0.0660 × T + 100.1 %Cu2O = -0.0060 × T + 8.7 %Sn = 0.1360 × T - 163.8 Equation 1: %Sn = 0 Equation 71: %Cu2O = 2.0 Equation 80: %Cu2O = -0.045 × %Sn + 1.5 is defined by the region enclosed by the five planes, and also by the plane A and the four points obtained from the equations of the four lines Equations 76, 77, 69: %CaO = 0.0320 × T - 15.3 %Cu2O = 2.0 %Sn = 0.0240 × T - 24.4 Equation 78: %CaO = 0.0240 × T - 2.0 %Cu2O = -0.0020 × T + 3.8 %Sn = 0.0360 × T - 39.7, and Equations 69, 78, 70: %CaO = 0.0480 × T - 31.9 %Cu2O = 2.0 %Sn = 0 Equation 79: %CaO = 0.0460 × T - 26.2 %Cu2O = 1.5 %Sn = 0 The plane formed by connecting the four points obtained from the equations of the four lines is given by Equation 1: %Sn = 0 Equation 71: %Cu2O = 2.Equation 80: %Cu2O = -0.045 × %Sn + 1.5 is defined by the region enclosed by the six planes, and furthermore, when the temperature is expressed as T (°C) in the case of -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, then Equations 74 and 81: %CaO = -0.0680 × T + 101.6 %Cu2O = -0.0140 × T + 18.6 %Sn = 0.2880 × T - 350.9 Equation 82: %CaO = -0.0860 × T + 122.9 %Cu2O = 0.8 %Sn = 0 Equation 83: %CaO = -0.0840 × T + 121.3 %Cu2O = 0.2 One plane is formed by connecting the four points obtained from the equations of the four lines %Sn = 0.0200 × T - 5.5, and one plane is formed by connecting the three points obtained from the equations of the three lines %CaO = 0.0080 × T + 6.3, %Cu2O = -0.0040 × T + 5.2, and %Sn = 0.1800 × T - 205.5, and Equations 81, 84, and 85: %CaO = -0.0580 × T + 89.7, %Cu2O = -0.0060 × T + 8.7, %Sn = 0.1360 × T - 163.8, and Equation 86: %CaO = 0.1000 × T - 102.0, %Cu2O = -0.0020 × T + 3.1 The region is defined by a plane (plane B) formed by connecting four points obtained from the equations of four lines %Sn = 0.1000 × T - 119.0, and the region enclosed by the six planes: Equation 1: %Sn = 0, Equation 80: %Cu2O = -0.045 × %Sn + 1.5, Equation 90: %Cu2O = -0.029 × %Sn + 0.

8. Furthermore, the region is defined by plane B and the following equations: Equations 85, 86, 87: %CaO = 0.1060 × T - 104.5, %Cu2O = 1.3, %Sn = -0.0060 × T + 12.8, Equation 88: %CaO = 0.0480 × T - 31.2, %Cu2O = -0.0020 × T + 3.1, %Sn = 0.0900 × T - 107.0 The plane formed by connecting the four points obtained from the equations of the four lines is given by equations 79, 87, 88, and 89: %CaO = 0.0020 × T + 29.5 %Cu2O = 0.A method for smelting raw materials according to claim 3, characterized in that the region is defined by a plane formed by connecting four points obtained from the equations of four straight lines representing 8%Sn=0, and six planes representing equations 1: %Sn=0, 80: %Cu2O=-0.045 × %Sn+1.5, and 90: %Cu2O=-0.029 × %Sn+0.

8. Of the regions defined above, only the region where the Cu2O concentration is less than 0% at certain temperatures, but where Cu2O is 0 or greater, is targeted.

17. When the smelting temperature is greater than 1200°C and less than 1250°C, the uniform melting range is determined from the quaternary phase diagram to include CaO and Cu. ２ In a function expressed with three components specified as O and Sn, when -0.045 × %Sn + 1.5 ≤ %Cu2O < 2.0 and the temperature is expressed as T (°C), Equation 72: %CaO = -0.0880 × T + 126.6 %Cu2O = 2.0 %Sn = 0 Equation 73: %CaO = -0.1020 × T + 145.5 %Cu2O = 2.0 %Sn = 0.1400 × T - 168.0 Equation 74: %CaO = -0.0820 × T + 118.7 %Cu2O = 1.5 %Sn = 0 Equation 75: %CaO = -0.0880 × T + 127.6 %Cu2O = -0.0160 × T + 21.2 A plane formed by connecting four points obtained from the equations of the four lines %Sn = 0.3460 × T - 426.3 (if the four points do not lie on a plane, it is considered a plane consisting of two triangular faces divided by an arbitrary diagonal. Hereafter, "a plane formed by connecting four points" will be treated as having the same meaning.) Equations 73, 75, 69: %CaO = 0.0320 × T - 15.3 %Cu2O = 2.0 %Sn = 0.0240 × T - 24.4 Equation 78: %CaO = 0.0240 × T - 2.0 %Cu2O = -0.0020 × T + 3.8 %Sn = 0.0360 × T - 39.7 A plane formed by connecting four points obtained from the equations of the four lines, Equations 69, 70, 78, 79: The region is defined by a plane formed by connecting four points obtained from the equations of four straight lines: %CaO = 0.0460 × T - 26.2, %Cu2O = 1.5, %Sn = 0, and six planes: Equation 1: %Sn = 0, Equation 71: %Cu2O = 2.0, Equation 80: %Cu2O = -0.045 × %Sn + 1.

5. Furthermore, when the temperature is expressed in degrees Celsius, in the case of -0.029 × %Sn + 0.8 ≤ %Cu2O < -0.045 × %Sn + 1.5, Equation 74, Equation 81: %CaO = -0.0680 × T + 101.6, %Cu2O = -0.0140 × T + 18.6, %Sn = 0.2880 × T - 350.9, Equation 82: %CaO=-0.0860×T+122.9 %Cu2O=0.8 %Sn=0 Equation 83: %CaO=-0.0840×T+121.3 %Cu2O=0.2 %Sn=0.0200×T-5.From the equations of the four lines in equation 5, a plane is formed by connecting the four points, and Equation 85: %CaO = -0.0580 × T + 89.7 %Cu2O = -0.0060 × T + 8.7 %Sn = 0.1360 × T - 163.8 Equation 86: %CaO = 0.1000 × T - 102.0 %Cu2O = -0.0020 × T + 3.1 %Sn = 0.1000 × T - 119.0 Equation 87: %CaO = 0.1060 × T - 104.5 %Cu2O = 1.3 %Sn = -0.0060 × T + 12.8 Equation 88: %CaO = 0.0480 × T - 31.2 %Cu2O = -0.0020 × T + 3.1 A plane formed by connecting four points obtained from the equations of four lines %Sn = 0.0900 × T - 107.0, and a plane formed by connecting four points obtained from the equations of four lines %CaO = 0.1060 × T - 104.5 %Cu2O = 1.3 %Sn = -0.0060 × T + 12.8 Equation 88: %CaO = 0.0480 × T - 31.2 %Cu2O = -0.0020 × T + 3.1 %Sn = 0.0900 × T - 107.0 Equation 89: %CaO = 0.0020 × T + 29.5 %Cu2O = 0.8 %Sn = 0, and Equation 1: %Sn = 0 Equation 80: The method for smelting raw materials according to claim 3, characterized in that the region is defined by the six planes of equation 90: %Cu2O = -0.045 × %Sn + 1.5, and equation 90: %Cu2O = -0.029 × %Sn + 0.

8. Of the regions defined above, depending on the temperature, the region may be divided into two or more parts. In such cases, a solid phase will precipitate in the region not in contact with Equation 1, so only the region in contact with Equation 1 will be considered.

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