Method and device for recovering rhodium in low-content rhodium liquid

Abstract

The invention discloses a method and a device for recovering rhodium in a low-content rhodium liquid, the rhodium content in the rhodium liquid is lower than 0.12 g / L, the pH value is 1-2, the method for recovering rhodium in the low-content rhodium liquid comprises the following steps: slowly and uniformly adding industrial-grade sodium hydroxide into the rhodium liquid until the solution reaches a preset pH value, stirring, standing and precipitating to obtain rhodium hydroxide, the preset pH value is 11 to 12; slowly adding the obtained rhodium hydroxide into a reaction kettle containing aqua regia to thoroughly dissolve the rhodium hydroxide, and filtering to obtain a first rhodium-containing solution; slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodate; and calcining the obtained ammonium chlororhodate to obtain the finished product rhodium powder.

Description

Technical Field

[0001] The invention relates to the field of chemical technology, and in particular to a method and a device for recovering rhodium from low-content rhodium liquid. Background Art

[0002] Rhodium is a silvery white transition metal and one of the platinum noble metals. It is hard and brittle, has strong reflective ability, and is particularly soft when heated. Rhodium has good chemical stability and strong oxidation resistance, and can maintain its metallic luster for a long time in the air. Rhodium-containing precious metal alloys have more superior physical and chemical properties and are widely used in industry, electronic information, aerospace, military and other fields. For example, Rh and Pt catalytic nets are used in the production of nitric acid; Rh, Pt, and Pd catalysts are used in automobile exhaust purification. The expansion of the industrial application field of precious metals has made it listed as a strategic material by many countries.

[0003] For rhodium liquid (especially rhodium liquid with a rhodium content of less than 0.12 g / L and a pH value of 1-2), conventional recovery methods are used, but the recovery rate is low, the recovery cycle is long, and the cost is high.

[0004] The above contents are only used to assist in understanding the technical solution of the present invention and do not constitute an admission that the above contents are prior art. Summary of the invention

[0005] The main purpose of the present invention is to provide a method and device for recovering rhodium in low-content rhodium liquid, aiming to solve the problems of the prior art.

[0006] To achieve the above object, the present invention provides a method for recovering rhodium in a low-content rhodium liquid, wherein the rhodium content in the rhodium liquid is lower than 0.12 g / L and the pH value is 1-2, comprising:

[0007] Slowly and evenly adding industrial-grade sodium hydroxide to the rhodium solution until the solution reaches a preset pH value, stirring, standing, and precipitating to obtain rhodium hydroxide, wherein the preset pH value is 11-12;

[0008] Slowly adding the obtained rhodium hydroxide into a reaction kettle containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first solution containing rhodium;

[0009] Slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodate;

[0010] The obtained ammonium chlororhodate is calcined to obtain finished rhodium powder.

[0011] Preferably, in the method for recovering rhodium from the low-content rhodium liquid, in the step of slowly adding the obtained rhodium hydroxide into a reactor containing aqua regia to completely dissolve the rhodium hydroxide and filter to obtain a first rhodium-containing solution, the mass ratio of the aqua regia to the rhodium hydroxide is (3-3.5):1.

[0012] Preferably, in the method for recovering rhodium from low-content rhodium liquid, the step of calcining the obtained ammonium chlororhodate to obtain a finished rhodium powder comprises:

[0013] The obtained ammonium chlororhodate is placed in an electric furnace and calcined at a first preset temperature to obtain a finished rhodium powder, wherein the first preset temperature is 600-700°C.

[0014] Preferably, in the method for recovering rhodium from a low-content rhodium solution, industrial-grade sodium hydroxide is slowly and evenly added to the rhodium solution until the solution reaches a preset pH value, and then stirred, allowed to stand, and precipitated to obtain rhodium hydroxide, comprising:

[0015] Industrial-grade sodium hydroxide is slowly and evenly added to the rhodium solution until the solution reaches a pH of 11-12, stirred for 30 min-50 min, and allowed to stand for 1 h-1.5 h to precipitate to obtain rhodium hydroxide.

[0016] Preferably, in the method for recovering rhodium from low-content rhodium liquid, the pH value of the rhodium liquid is 1.

[0017] In order to achieve the above object, the present invention also provides a device for recovering rhodium in a low-content rhodium liquid, which is used for a method for recovering rhodium in the above-mentioned low-content rhodium liquid, comprising:

[0018] A feed barrel, used to hold reaction raw materials;

[0019] A driving device, connected to the lower material barrel, for driving the lower material barrel to move horizontally and vertically;

[0020] A material discharge box is arranged below the material discharge barrel and is used to disperse the reaction raw materials. The material discharge box includes a material discharge front plate and a material discharge back plate. The material discharge front plate and the material discharge back plate are surrounded to form a box structure with upper and lower openings. A plurality of material discharge columns are arranged between the material discharge front plate and the material discharge back plate. Each material discharge column extends from the material discharge front plate to the material discharge back plate. The plurality of material discharge columns form a plurality of column groups along the up and down directions. Each column group includes a plurality of material discharge columns arranged at intervals along the left and right directions. The material discharge columns of two adjacent column groups along the up and down directions are staggered.

[0021] The reaction cylinder is located below the feed box and is used for the reaction of rhodium liquid and industrial-grade sodium hydroxide;

[0022] Among them, the multiple column groups include {a1, a2, ..., ai, ..., an}, ai is the blanking column of the i-th row;

[0023] When i is an odd number, the material cutting columns in the i-th row include {ai 1, ai 2, ai 3, ..., ai k}, and the material cutting columns in the i+1-th row include {a(i+1)1, a(i+1)2, a(i+1)3, ..., a(i+1)(k-1)},

[0024] When aim is set to the left of the center of the i-th row of columns, Xim-X(i+1)s<X(i+1)s-Xi(m-1);

[0025] When aim is set to the right of the center of the i-th row of columns, Xim-X(i+1)s>X(i+1)s-Xi(m-1);

[0026] Where aim is the blanking column in the i-th row and m-th column, and a(i+1)s is located between aim and ai(m-1);

[0027] Xim is the horizontal coordinate corresponding to aim;

[0028] X(i+1)s is the horizontal coordinate corresponding to a(i+1)s;

[0029] Xi(m-1) is the horizontal coordinate corresponding to ai(m-1).

[0030] Preferably, in the device for recovering rhodium from the low-content rhodium liquid, when k is an even number,

[0031] X(i+1)1-Xi 1>Xi2-X(i+1)1, X(i+1)2-Xi2>Xi 3-X(i+1)2,...,

[0032] X(i+1)(k / 2)-Xi(k / 2)=Xi(k / 2+1)-X(i+1)(k / 2),

[0033] Xi(k / 2+2)-X(i+1)(k / 2+1)>X(i+1)(k / 2+1)-Xi(k / 2+1),..., Xi k

[0034] When k is an odd number, X(i+1)1-Xi 1>Xi 2-X(i+1)1, X(i+1)2-Xi2>Xi 3-X(i+1)2, ...,

[0035] X(i+1)((k+1) / 2)-Xi((k+1) / 2)=Xi((k+1) / 2)-X(i+1)((k+1) / 2-1),

[0036] Xi((k+1) / 2+1)-X(i+1)((k+1) / 2)>X(i+1)((k+1) / 2)-Xi((k+1) / 2),..., Xi kX(i+1)(k-1)>

[0037] Preferably, in the device for recovering rhodium from low-content rhodium liquid, the driving device comprises:

[0038] Support frame;

[0039] A lateral moving device is disposed on the support frame so as to be lateral movable;

[0040] A vertical moving device, which is vertically movable on the horizontal moving device;

[0041] The connecting arm is fixed on the vertical moving device and connected to the discharge barrel.

[0042] Preferably, in the device for recovering rhodium from the low-content rhodium liquid, the lateral moving device comprises:

[0043] A first driving motor is arranged on the supporting frame;

[0044] A first gear is drivingly connected to a first driving motor and is used to drive the first gear to rotate;

[0045] The first rack is meshed with the first gear and is connected to the vertical moving device.

[0046] Preferably, in the device for recovering rhodium from low-content rhodium liquid, the vertical moving device comprises:

[0047] A vertical connecting frame connected to the first rack, the vertical connecting frame being provided with a slide rail for the connecting arm to slide vertically;

[0048] A second driving motor is arranged on the vertical connecting frame;

[0049] The second gear is connected to the second drive motor

[0050] The second rack is meshed with the second gear, and the second rack is connected to the connecting arm.

[0051] The present invention has at least the following beneficial effects:

[0052] The invention provides a method for recovering rhodium in a low-content rhodium liquid. The method comprises the following steps: slowly and evenly adding industrial-grade sodium hydroxide to the rhodium liquid until the solution reaches a preset pH value, stirring, standing and precipitating to obtain rhodium hydroxide, wherein the preset pH value is 11-12; slowly adding the obtained rhodium hydroxide into a reaction kettle containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first rhodium-containing solution; slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodate; calcining the obtained ammonium chlororhodate to obtain a finished rhodium powder, wherein the rhodium recovery rate can reach more than 95%;

[0053] Furthermore, when i is an odd number, the blanking columns in the i-th row include {ai 1, ai 2, ai 3, ..., ai k}, the material discharge columns of the i+1th row include {a(i+1)1, a(i+1)2, a(i+1)3, ..., a(i+1)(k-1)}, when aim is set on the left side of the center of the i-th row column group, Xim-X(i+1)s<X(i+1)s-Xi(m-1); when aim is set on the right side of the center of the i-th row column group, Xim-X(i+1)s>X(i+1)s-Xi(m-1); wherein aim is the bulk material column of the i-th row and m-th column, a(i+1)s is between aim and ai(m-1); Xim is the horizontal coordinate corresponding to aim; X(i+1)s is the horizontal coordinate corresponding to a(i+1)s; Xi(m-1) is the horizontal coordinate corresponding to ai(m-1), so that the raw materials distributed in the material discharge box are more evenly distributed, which can improve the sufficiency of the reaction and further improve the recovery rate of rhodium in the rhodium liquid. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 A schematic diagram of an embodiment of a method for recovering rhodium from a low-content rhodium liquid provided by the present invention;

[0055] Figure 2 It is a schematic diagram of the partial structure of a device for recovering rhodium from low-content rhodium liquid;

[0056] Figure 3 for Figure 2 Schematic diagram at I in the middle;

[0057] Figure 4 for Figure 2 Schematic diagram of the feed box;

[0058] Figure 5 for Figure 4 Schematic diagram from another perspective;

[0059] Figure 6 A schematic diagram of a material discharge column in one embodiment;

[0060] Figure 7 It is a schematic diagram of a blanking column in another embodiment.

[0061] Reference numerals of the present invention:

[0062]

[0063]

[0064] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings in conjunction with the embodiments. DETAILED DESCRIPTION

[0065] The technical solution of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

[0066] In the embodiments of the present invention, the term "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent three situations: A exists alone, A and B exist at the same time, and B exists alone. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.

[0067] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence.

[0068] In the embodiments of the present invention, the term "plurality" refers to two or more than two, and other quantifiers are similar.

[0069] In the present invention, unless otherwise specified, the directional words used, such as "up, down, top, bottom", usually refer to the directions shown in the drawings, or to the components themselves in the vertical, perpendicular or gravity directions; similarly, for ease of understanding and description, "inside and outside" refer to the inside and outside relative to the outline of each component itself, but the above-mentioned directional words are not used to limit the present invention.

[0070] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings. However, it can be understood by those skilled in the art that in the embodiments of the present invention, many technical details are proposed in order to enable the reader to better understand the present invention. However, even without these technical details and various changes and modifications based on the following embodiments, the technical scheme claimed in the present invention can also be implemented. The division of the following embodiments is for the convenience of description and should not constitute any limitation on the specific implementation of the present invention. The various embodiments can be combined and referenced with each other under the premise of no contradiction.

[0071] The invention provides a method for recovering rhodium in a low-content rhodium liquid, wherein the rhodium content in the rhodium liquid is lower than 0.12 g / L and the pH value is 1-2. Figure 1 The present invention provides a schematic diagram of an embodiment of a method for recovering rhodium from a low-content rhodium liquid.

[0072] In step S100, industrial-grade sodium hydroxide is slowly and evenly added to the rhodium solution until the solution reaches a preset pH value, and then stirred, allowed to stand, and precipitated to obtain rhodium hydroxide. The preset pH value is 11-12. In this embodiment, the preset pH value is 12.

[0073] Specifically, industrial-grade sodium hydroxide is slowly and evenly added to the rhodium solution until the solution reaches a pH of 11-12, stirred for 30 min-50 min, and allowed to stand for 1 h-1.5 h to precipitate to obtain rhodium hydroxide.

[0074] The rhodium liquid reacts with sodium hydroxide to generate rhodium hydroxide, and after the reaction is complete, the rhodium hydroxide is precipitated, filtered, and washed out.

[0075] In step S200, the obtained rhodium hydroxide is slowly added into a reactor containing aqua regia to completely dissolve the rhodium hydroxide and filter to obtain a first rhodium-containing solution. The mass ratio of the aqua regia to the rhodium hydroxide is (3-3.5):1. In this embodiment, the mass ratio of the aqua regia to the rhodium hydroxide can also be 3.2:1. At this time, the rhodium exists as rhodium hydroxide, and the rhodium is directly dissolved by the aqua regia.

[0076] In step S300, solid industrial ammonium chloride is slowly added to the first solution to obtain ammonium chlororhodate. The first solution contains rhodium, and by slowly adding solid industrial ammonium chloride, rhodium can be completely precipitated, and the reaction obtains ammonium chlororhodate. By filtering and washing the ammonium chlororhodate, a purer ammonium chlororhodate is obtained.

[0077] In step S400, the obtained ammonium chlororhodate is calcined to obtain finished rhodium powder.

[0078] Specifically, the obtained ammonium chlororhodate is placed in an electric furnace and calcined at a first preset temperature to obtain a finished rhodium powder, wherein the first preset temperature is 600-700° C. The first preset temperature can also be 650° C.

[0079] The invention slowly adds industrial-grade sodium hydroxide until the pH value of the solution is 11-12, stirs for 30-50 minutes, and then stands for 1-1.5 hours before testing the tail liquid. The rhodium in the rhodium liquid is recovered in this way. The rhodium exists in the form of rhodium hydroxide and is directly dissolved in aqua regia after filtering, so the recovery period is short and the cost is low.

[0080] In order to verify the beneficial effects of the present invention, the following examples and comparative examples are used for comparison and explanation. 2L of rhodium solution is taken respectively, the rhodium content in the rhodium solution is less than 0.12g / L, and the pH value is 1 for experiment.

[0081] Example 1

[0082] S1, slowly and evenly add industrial grade sodium hydroxide to 2L rhodium solution until the solution reaches a pH of 11-12, stir for 30min-50min, let stand for 1h-1.5h to obtain a tail liquid, and obtain rhodium hydroxide after precipitation to obtain a tail liquid;

[0083] S2, slowly adding the obtained rhodium hydroxide into a reactor containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first rhodium-containing solution. The mass ratio of the aqua regia to the rhodium hydroxide is (3-3.5):1;

[0084] S3, slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodiumate;

[0085] S4, putting the obtained ammonium chlororhodate into an electric furnace, and calcining it at a first preset temperature to obtain a finished rhodium powder, wherein the first preset temperature is 600-700°C.

[0086] Example 2

[0087] S1, slowly and evenly add industrial grade sodium hydroxide to 2L rhodium solution until the solution reaches a pH of 11-12, stir for 30min-50min, let stand for 1h-1.5h, obtain rhodium hydroxide after precipitation, and obtain tail liquid;

[0088] S2, slowly adding the obtained rhodium hydroxide into a reactor containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first rhodium-containing solution. The mass ratio of the aqua regia to the rhodium hydroxide is (3-3.5):1;

[0089] S3, slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodiumate;

[0090] S4, putting the obtained ammonium chlororhodate into an electric furnace, and calcining it at a first preset temperature to obtain a finished rhodium powder, wherein the first preset temperature is 600-700°C.

[0091] Example 3

[0092] S1, slowly and evenly add industrial grade sodium hydroxide to 2L rhodium solution until the solution reaches a pH of 11-12, stir for 30min-50min, let stand for 1h-1.5h to obtain a tail liquid, and obtain rhodium hydroxide after precipitation to obtain a tail liquid;

[0093] S2, slowly adding the obtained rhodium hydroxide into a reactor containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first rhodium-containing solution. The mass ratio of the aqua regia to the rhodium hydroxide is (3-3.5):1;

[0094] S3, slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodiumate;

[0095] S4, putting the obtained ammonium chlororhodate into an electric furnace, and calcining it at a first preset temperature to obtain a finished rhodium powder, wherein the first preset temperature is 600-700°C.

[0096] Comparative Example 1

[0097] Slowly add 100g of iron powder to 2L of rhodium solution for replacement (make sure there is excess iron powder), stir for 30min, let stand for 1h, and then test the tail liquid.

[0098] Comparative Example 2

[0099] Slowly add 100g of zinc wire to 2L of rhodium solution for replacement (make sure there is excess zinc wire), stir for 30min, let stand for 1h, and then test the tail liquid.

[0100] The tail liquid obtained in the embodiment and the comparative example was tested to compare the recovery rates of rhodium.

[0101] Table 1 Effect comparison of embodiments and comparative examples

[0102] Rhodium content in tail liquid / ppm Example 1 7.1 Example 2 7.3 Example 3 7.5 Comparative Example 1 23 Comparative Example 2 18

[0103] The lower the rhodium content in the tail liquid, the higher the rhodium recovery rate is. It can be seen from the above examples and comparative examples that after rhodium is replaced by rhodium, comparative examples 1 and 2 exist as elemental rhodium, and not only the tail liquid content is high, but also the rhodium cannot be dissolved by the common aqua regia dissolution method, and the rhodium needs to be recovered by melting method or fragmentation method, resulting in a long recovery period and high cost. In the embodiment, the rhodium in the rhodium liquid is recovered, and the rhodium exists in the form of rhodium hydroxide and directly dissolves the rhodium by aqua regia after filtration, and the recovery period is short and the cost is low, and the rhodium recovery rate is greater than 95%.

[0104] The present invention also provides a device for recovering rhodium from a low-content rhodium liquid. The method for recovering rhodium from a low-content rhodium liquid adopts the device for recovering rhodium from a low-content rhodium liquid to recover rhodium. Figure 2 and Figure 3 As shown, the device for recovering rhodium in the low-content rhodium liquid includes a feed barrel, a driving device 2, and a reaction cylinder 4.

[0105] The driving device 2 includes a support frame 21, a lateral moving device 22, a vertical moving device 23 and a connecting arm 24. The lateral moving device 22 is movably disposed on the support frame 21, the vertical moving device 23 is movably disposed on the lateral moving device 22, and the connecting arm 24 is fixed on the vertical moving device 23. The connecting arm 24 is used to take and place the reaction raw materials.

[0106] Specifically, the lateral moving device 22 includes a first driving motor 221, a first gear 222, and a first rack 223. The first driving motor 221 is disposed on the support frame 21. The first gear 222 is drivingly connected to the first driving motor 221, and is used to drive the first gear 222 to rotate. The first rack 223 is meshed with the first gear 222, and the first rack 223 is connected to the vertical moving device 23.

[0107] The vertical moving device 23 includes a vertical connecting frame 231, a second driving motor 232, a second rack, and a second gear. The vertical connecting frame 231 is connected to the first rack 223, and a slide rail is provided on the vertical connecting frame 231 for the connecting arm 24 to slide vertically. The second driving motor 232 is provided on the vertical connecting frame 231. The second gear is drivingly connected to the second driving motor 232, the second rack is meshed with the second gear, and the second rack is connected to the connecting arm 24, so that the connecting arm 24 can be driven to slide vertically.

[0108] The reaction cylinder 4 is used for the reaction of rhodium in the low-content rhodium liquid with sodium hydroxide to generate rhodium hydroxide. In order to facilitate uniform feeding and avoid uneven reaction, the rhodium recovery device in the low-content rhodium liquid also includes a feeding box 3, which includes a feeding front plate 31 and a feeding back plate 32. The feeding front plate 31 and the feeding back plate 32 are surrounded to form a box structure with upper and lower openings. A plurality of feeding columns 33 are arranged between the feeding front plate 31 and the feeding back plate 32. Each feeding column 33 extends from the feeding front plate 31 to the feeding back plate 32. The plurality of feeding columns 33 form a plurality of column groups in the up and down directions. Each column group includes a plurality of feeding columns 33 arranged at intervals in the left and right directions. The feeding columns 33 of two adjacent column groups in the up and down directions are staggered. When the connecting arm 24 of the driving device 2 moves the reaction raw materials to the top of the reaction cylinder 4, the reaction raw materials are poured into the feeding box 3, and the raw materials fall out from the lower end outlet of the feeding box 3 and enter the reaction cylinder 4.

[0109] For ease of observation, Figure 4 and Figure 5 As shown, at least one of the blanking front plate 31 and the blanking back plate 32 is transparent.

[0110] In addition, the plurality of column groups include {a1, a2, ..., ai, ..., an}, where ai is the blanking column 33 of the i-th row;

[0111] When i is an odd number, the material unloading columns 33 in the i-th row include {ai 1, ai 2, ai 3, ..., ai k}, and the material unloading columns 33 in the i+1-th row include {a(i+1)1, a(i+1)2, a(i+1)3, ..., a(i+1)(k-1)},

[0112] When aim is set to the left of the center of the i-th row of columns, Xim-X(i+1)s<X(i+1)s-Xi(m-1);

[0113] When aim is set to the right of the center of the i-th row of columns, Xim-X(i+1)s>X(i+1)s-Xi(m-1);

[0114] Wherein, aim is the blanking column 33 in the i-th row and the m-th column, and a(i+1)s is located between aim and ai(m-1);

[0115] Xim is the horizontal coordinate corresponding to aim;

[0116] X(i+1)s is the horizontal coordinate corresponding to a(i+1)s;

[0117] Xi(m-1) is the horizontal coordinate corresponding to ai(m-1).

[0118] Since the materials are likely to fall on the middle of the box structure after falling from the discharge barrel, the present invention can distribute the materials entering the box structure to both sides through the position setting of each discharge column 33 in the multiple column groups, making the materials distributed in the box structure more even.

[0119] Specifically, when k is an even number,

[0120] X(i+1)1-Xi 1>Xi2-X(i+1)1, X(i+1)2-Xi2>Xi 3-X(i+1)2,...,

[0121] X(i+1)(k / 2)-Xi(k / 2)=Xi(k / 2+1)-X(i+1)(k / 2),

[0122] Xi(k / 2+2)-X(i+1)(k / 2+1)>X(i+1)(k / 2+1)-Xi(k / 2+1),..., Xi kX(i+1)(k-1)>

[0123] When i is an odd number, i+1 is an even number. Figure 7, for example, the column group includes {a1, a2, a3, a4, a5}, i is 1, i+1 is 2. a1 includes {a11, a12, a13, a14, a15}, a2 includes {a21, a22, a23, a24}. At this time, a13 is located at the center of the first row of column groups, and a22 and a23 are located on both sides of a13. At this time:

[0124] X13-X22=X23-X13;

[0125] X22-X12>X13-X22;

[0126] X12-X21>X22-X12;

[0127] X14-X23>X23-X13;

[0128] X15-X24>X24-X14.

[0129] When k is an odd number, X(i+1)1-Xi 1>Xi 2-X(i+1)1, X(i+1)2-Xi2>Xi 3-X(i+1)2, ...,

[0130] X(i+1)((k+1) / 2)-Xi((k+1) / 2)=Xi((k+1) / 2)-X(i+1)((k+1) / 2-1),

[0131] Xi((k+1) / 2+1)-X(i+1)((k+1) / 2)>X(i+1)((k+1) / 2)-Xi((k+1) / 2),..., Xi kX(i+1)(k-1)>

[0132] See also Figure 6 , a1 includes {a11, a12, a13, a14, a15, a16}, a2 includes {a21, a22, a23, a24, a25}, and a13 and a14 are located at the center of the first row of columns. At this time:

[0133] X23-X13=X14-X23;

[0134] X13-X22>X23-X13;

[0135] X22-X12>X13-X22;

[0136] X21-X11>X12-X21;

[0137] X15-X24>X24-X14;

[0138] X16-X25>X25-X15.

[0139] In addition, the device for recovering rhodium in the low-content rhodium liquid also includes a rinsing tank, etc., which are not listed here one by one.

[0140] Obviously, the embodiments described above are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, ordinary technicians in this field can make other different forms of changes or modifications without creative work, which should fall within the scope of protection of the present invention.

Claims

1. A method for recovering rhodium in a low-content rhodium liquid, wherein the rhodium content in the rhodium liquid is less than 0.12 g / L and the pH value is 1-2, characterized in that: include: Slowly and evenly adding industrial-grade sodium hydroxide to the rhodium solution until the solution reaches a preset pH value, stirring, standing, and precipitating to obtain rhodium hydroxide, wherein the preset pH value is 11-12; Slowly adding the obtained rhodium hydroxide into a reaction kettle containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first solution containing rhodium; Slowly adding solid industrial ammonium chloride into the first solution to obtain ammonium chlororhodate; The obtained ammonium chlororhodate is calcined to obtain finished rhodium powder.

2. The method for recovering rhodium in the low-content rhodium liquid as claimed in claim 1, wherein: In the step of slowly adding the obtained rhodium hydroxide into a reactor containing aqua regia to completely dissolve the rhodium hydroxide and filtering to obtain a first rhodium-containing solution, the mass ratio of the aqua regia to the rhodium hydroxide is (3-3.5):

1.

3. A method for recovering rhodium in a low-content rhodium liquid as claimed in claim 1, characterized in that, The step of calcining the obtained ammonium chlororhodate to obtain a finished rhodium powder comprises: The obtained ammonium chlororhodate is placed in an electric furnace and calcined at a first preset temperature to obtain a finished rhodium powder, wherein the first preset temperature is 600-700°C.

4. the recovery method of rhodium in the low-content rhodium liquid as claimed in claim 1, is characterized in that, The step of slowly and evenly adding industrial-grade sodium hydroxide to the rhodium solution until the solution reaches a preset pH value, stirring, standing, and precipitating to obtain rhodium hydroxide comprises: Industrial-grade sodium hydroxide is slowly and evenly added to the rhodium solution until the solution reaches a pH of 11-12, stirred for 30 min-50 min, and allowed to stand for 1 h-1.5 h to precipitate to obtain rhodium hydroxide.

5. the recovery method of rhodium in the low-content rhodium liquid as claimed in claim 1, is characterized in that, The pH value of the rhodium solution is 1.

6. A device for recovering rhodium in a low-content rhodium liquid, used for the method for recovering rhodium in a low-content rhodium liquid as claimed in any one of claims 1 to 5, characterized in that: include: A feed barrel, used to hold reaction raw materials; A driving device, connected to the lower material barrel, for driving the lower material barrel to move horizontally and vertically; A material discharge box is arranged below the material discharge barrel and is used to disperse the reaction raw materials. The material discharge box includes a material discharge front plate and a material discharge back plate. The material discharge front plate and the material discharge back plate are surrounded to form a box structure with upper and lower openings. A plurality of material discharge columns are arranged between the material discharge front plate and the material discharge back plate. Each material discharge column extends from the material discharge front plate to the material discharge back plate. The plurality of material discharge columns form a plurality of column groups along the up and down directions. Each column group includes a plurality of material discharge columns arranged at intervals along the left and right directions. The material discharge columns of two adjacent column groups along the up and down directions are staggered. The reaction cylinder is located below the feed box and is used for the reaction of rhodium liquid and industrial-grade sodium hydroxide; Among them, the multiple column groups include {a1, a2, ..., ai, ..., an}, ai is the blanking column of the i-th row; When i is an odd number, the material cutting columns in the i-th row include {ai 1, ai 2, ai 3, ..., aik}, and the material cutting columns in the i+1-th row include {a(i+1)1, a(i+1)2, a(i+1)3, ..., a(i+1)(k-1)}, When aim is set to the left of the center of the i-th row of columns, Xim-X(i+1)s<X(i+1)s-Xi(m-1); When aim is set to the right of the center of the i-th row of columns, Xim-X(i+1)s>X(i+1)s-Xi(m-1); Where aim is the blanking column in the i-th row and m-th column, and a(i+1)s is located between aim and ai(m-1); Xim is the horizontal coordinate corresponding to aim; X(i+1)s is the horizontal coordinate corresponding to a(i+1)s; Xi(m-1) is the horizontal coordinate corresponding to ai(m-1).

7. The rhodium recovery device in the low-content rhodium liquid as claimed in claim 6, characterized in that, When k is an even number, X(i+1)1-Xi 1>Xi2-X(i+1)1, X(i+1)2-Xi2>Xi 3-X(i+1)2,..., X(i+1)(k / 2)-Xi(k / 2)=Xi(k / 2+1)-X(i+1)(k / 2), Xi(k / 2+2)-X(i+1)(k / 2+1)>X(i+1)(k / 2+1)-Xi(k / 2+1),..., Xik-X(i+1)(k-1)> When k is an odd number, X(i+1)1-Xi 1>Xi2-X(i+1)1, X(i+1)2-Xi2>Xi 3-X(i+1)2, ..., X(i+1)((k+1) / 2)-Xi((k+1) / 2)=Xi((k+1) / 2)-X(i+1)((k+1) / 2-1), Xi((k+1) / 2+1)-X(i+1)((k+1) / 2)>X(i+1)((k+1) / 2)-Xi((k+1) / 2),..., 8. A rhodium recovery device in a low-content rhodium liquid as claimed in claim 6, characterized in that, The driving device comprises: Support frame; A lateral moving device is disposed on the support frame so as to be lateral movable; A vertical moving device, which is vertically movable on the horizontal moving device; The connecting arm is fixed on the vertical moving device and connected to the discharge barrel.

9. The rhodium recovery device in the low-content rhodium liquid as claimed in claim 8, characterized in that, The lateral movement device comprises: A first driving motor is arranged on the supporting frame; A first gear is drivingly connected to a first driving motor and is used to drive the first gear to rotate; The first rack is meshed with the first gear and is connected to the vertical moving device.

10. A rhodium recovery device in a low-content rhodium liquid as claimed in claim 9, characterized in that, The vertical moving device comprises: A vertical connecting frame connected to the first rack, the vertical connecting frame being provided with a slide rail for the connecting arm to slide vertically; A second driving motor is arranged on the vertical connecting frame; The second gear is connected to the second drive motor The second rack is meshed with the second gear, and the second rack is connected to the connecting arm.

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