CN110616332B - Purification process of palladium in anode mud - Google Patents

Purification process of palladium in anode mud Download PDF

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Publication number
CN110616332B
CN110616332B CN201911000519.9A CN201911000519A CN110616332B CN 110616332 B CN110616332 B CN 110616332B CN 201911000519 A CN201911000519 A CN 201911000519A CN 110616332 B CN110616332 B CN 110616332B
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block
filtering
clamping
palladium
filter bag
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CN110616332A (en
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姜彩根
王浙民
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Zhejiang Hongda New Material Development Co ltd
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Zhejiang Hongda New Material Development Co ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00Obtaining noble metals
    • C22B11/04Obtaining noble metals by wet processes
    • C22B11/042Recovery of noble metals from waste materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a purification process of palladium in anode mud, which relates to the technical field of palladium purification, and comprises the following process steps: s1: introducing the filtrate obtained after the gold and silver of the anode slime into a reaction kettle, adding ammonia water for regulation, and filtering to remove impurities to obtain filtrate a for later use; s2: adding hydrochloric acid into the filtrate a obtained in the step S1, acidifying, and filtering to obtain a precipitate a for later use; s3: dissolving the precipitate a obtained in the step S2 with ammonia water, adding an impurity removal auxiliary agent, and filtering and removing impurities after clarification to obtain a filtrate b; s4: adding hydrochloric acid into the filtrate b obtained in the step S3, acidifying, and filtering to obtain a precipitate b for later use; s5: and (4) redissolving the precipitate b obtained in the step (S4) by using ammonia water, and then adding hydrazine hydrate for reduction reaction to obtain a precipitate c, namely the product palladium. The preparation method has the advantages of reducing impurity removal steps and improving the purification efficiency and yield of the palladium.

Description

Purification process of palladium in anode mud
Technical Field
The invention relates to the technical field of precious metal purification, in particular to a process for purifying palladium in anode mud.
Background
At present, in the copper electrolytic refining industry, anode copper can generate a lot of anode mud precipitates after being dissolved, and copper anode mud contains a lot of noble metals, mainly containing gold, silver, palladium, platinum, strontium, bismuth and other elements.
The existing purification process of palladium in copper anode slime comprises the steps of firstly generating chlorine gas in acid solution by sodium chlorate used in anode slime to react with free Au in the anode slime so as to separate metal and other noble metals from silver, then adding sodium sulfite to reduce and separate out gold powder, and purifying and separating the residual gold separation liquid through a palladium purification process to obtain the palladium noble metal.
In the existing process for purifying palladium, excessive ammonia water is added into a gold separating solution to precipitate impurities, then acidification is carried out to separate out dichlorodiaminepalladium precipitate, then ammonia water is used for redissolving, and the steps are repeated for multiple times, so that the finally obtained dichlorodiaminepalladium has higher purity. And then adding excessive ammonia water into the dichlorodiamminepalladium precipitate to dissolve the dichlorodiamminepalladium precipitate, and adding hydrazine hydrate to carry out reduction reaction to obtain the product palladium.
The above prior art solutions have the following drawbacks: in the process of purifying the palladium, multiple times of ammoniation, acidification and filtration are needed to remove impurities for multiple times so as to improve the purity of the finally obtained dichlorodiamminepalladium, the process is multiple and long, and the consumption of resources and energy sources is high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a process for purifying palladium in anode mud, which is characterized in that an impurity removal auxiliary agent is added in the impurity removal and filtration process of palladium, so that the impurity removal can achieve higher removal rate after two times of ammoniation, acidification and filtration, and energy and resources are saved.
The above object of the present invention is achieved by the following technical solutions:
a purification process of palladium in anode mud comprises the following process steps:
s1: introducing the filtrate obtained after gold and silver separation of the anode slime into a reaction kettle, adding ammonia water to adjust the pH value to 9-9.2, and filtering to remove impurities to obtain filtrate a for later use;
s2: adding hydrochloric acid into the filtrate a obtained in the step S1, acidifying until the pH value is 0.8-1.2, and filtering to obtain a precipitate a for later use;
s3: dissolving the precipitate a obtained in the step S2 with ammonia water, adjusting the pH value to 10-12, adding an impurity removal auxiliary agent in a mass ratio of 1: 4-10 to the filtrate a, and filtering and removing impurities after clarification to obtain a filtrate b;
s4: adding hydrochloric acid into the filtrate b obtained in the step S3, acidifying until the pH is 0.8-1.2, and filtering to obtain a precipitate b for later use;
s5: and (4) re-dissolving the precipitate b obtained in the step (S4) by using ammonia water with the liquid-solid ratio of 1.8-2.2: 1 to the precipitate b, and then adding hydrazine hydrate for reduction reaction to obtain a precipitate c, namely the product palladium.
By adopting the technical scheme, when the ammonia water is added in the step S1, the palladium ions and other noble metal ions in the solution are gradually precipitated and separated out along with the gradual increase of the pH value of the solution. With the continuous addition of the ammonia water, when the pH value is increased to about 9, the palladium in the precipitate can generate a complex reaction with the ammonia water to generate dichlorodiamminepalladium dissolved in the ammonia water, so that the palladium is separated from other noble metal impurities, and the impurities can be separated and removed by filtering.
Usually, when the pH is adjusted to redissolve the palladium hydroxide, the adjusted pH is about 9, the palladium can be completely complexed with ammonia, most of noble metal ions except the palladium and base metal ions can be completely precipitated, but bismuth element in the noble metal impurities does not reach the pH range capable of being completely precipitated, and the precipitation is difficult to be complete in the pH range, in the prior art, the content of the impurities is reduced by repeatedly performing the steps S1 and S2 for many times, in the invention, when the ammonia water is repeatedly added for the second time, the pH of the solution is adjusted to 10-12, most of other residual impurity metal ions can be completely precipitated, and most of the bismuth ions can be precipitated. However, the content of bismuth ions is still relatively high, and the impurity removal reagent continuously added in the step S3 removes the remaining non-precipitated bismuth ions, so that the purity of the dichlorodiamminepalladium for reduction obtained in the step S4 is greatly improved, impurities are basically removed completely after twice circular impurity removal, the times of circular impurity removal are reduced, and the consumption of energy and resources is saved.
The invention is further configured to: the temperature of the solution before filtration in the step S1 is raised to 80-90 ℃, and the temperature of the solution before filtration in the step S2 is raised to 85-95 ℃.
The invention is further configured to: the impurity removal auxiliary comprises the following components in percentage by weight:
60-80% of montmorillonite particles;
10-30% of disodium ethylene diamine tetraacetate;
5-10% of dimercaprol.
By adopting the technical scheme, the pH value of the palladium hydroxide precipitate dissolved in excessive ammonia water is basically controlled to be about 9, and the pH value of the solution containing the noble metal bismuth ions is about 12, so that the bismuth ions still contain more bismuth ions even in the multiple ammoniation and acidification processes, so that the finally obtained dichlorodiamminepalladium for reduction contains more bismuth ion impurities, and the purity is reduced. Montmorillonite particles in the impurity removal auxiliary agent can adsorb and gather ethylene diamine tetraacetic acid and dimercaprol to enter pores of the impurity removal auxiliary agent, when the impurity removal auxiliary agent is added into filtrate, an ethylene diamine tetraacetic acid disodium chelating system can be formed on the surface of montmorillonite, and a chelating system containing a dimercaprol releasing agent can selectively chelate bismuth ions, so that the concentration of the bismuth ions is reduced to an extremely low range, and the purity of the finally obtained dichloro-diammine palladium-idene is further improved.
The invention is further configured to: the preparation process of the impurity removal auxiliary agent comprises the following steps:
step 1: preparing 2-3 parts of disodium ethylene diamine tetraacetate solution with the mass fraction concentration of 20-30% according to a proportion;
step 2: adding dimercaprol into each part of disodium ethylene diamine tetraacetate solution according to a proportion, and uniformly stirring for later use;
and step 3: adding montmorillonite particles into 1 part of the solution prepared in the step 2, stirring for 5-10 min, and standing for 5-6 h;
and 4, step 4: then filtering off the montmorillonite particles, adding the montmorillonite particles into another part of the solution prepared in the step 2, and repeating the step 3;
and 5: and (4) drying the montmorillonite particles obtained in the step (4) in an oven to obtain the impurity removal auxiliary agent.
By adopting the technical scheme, the montmorillonite particles have strong adsorption capacity, are firstly immersed into 1 part of mixed solution of disodium ethylenediamine tetraacetate and dimercaprol to adsorb the disodium ethylenediamine tetraacetate, and are then immersed into another part of mixed solution of the disodium ethylenediamine tetraacetate and the dimercaprol to adsorb in order to improve the concentration of the disodium ethylenediamine tetraacetate and the dimercaprol adsorbed on the montmorillonite particles, and then the montmorillonite particles after adsorption are dried, so that the moisture on the surface is removed, and the required impurity removal reagent is obtained.
The invention is further configured to: the filtration equipment who adopts during filtration in step S1, S2, S3, S4 is for filtering the jar, install the filter in the filtration jar, the opening has been seted up on the top of filtering the jar, the top of filtering the jar is provided with closed open-ended closing cap, install in the filtration jar and cross the filter bag, be provided with locating component in the filtration bag, locating component crosses the open-ended second locking piece of filter bag with the location including the first locking piece of filter bag bottom in the location, first locking piece includes first magnetic block and second magnetic block, it is provided with a plurality of first magnetic blocks along crossing filter bag circumference even interval on being close to the lateral wall of filter bag to cross the filter bag, be provided with the second magnetic block that cooperatees and use with first magnetic block on the inside wall of filtration jar.
The first magnetic block is connected with the filter bag through a mounting piece, the mounting piece comprises an elastic mounting rod and a buckling piece, more than one set of lantern ring groups are connected to the side wall, close to the filter plate, of the filter bag along the circumferential direction of the filter bag, each lantern ring group comprises two lantern rings arranged at intervals, the lantern rings are fixedly connected with the outer side wall of the filter bag, a first magnetic block is mounted between the two lantern rings of each set of lantern ring groups, a mounting hole is formed in the first magnetic block, and the mounting rod penetrates through the lantern rings and the mounting hole and is connected end to end through the buckling piece;
the clamping piece comprises an elastic first clamping block and an elastic second clamping block, the first clamping block is fixedly connected to the end face of one end of the mounting rod, the second clamping block is fixedly connected to the side wall of the first clamping block, the limiting groove is formed in the end face of the other end of the mounting rod, the limiting hole communicated with the clamping groove is formed in the side wall of the mounting rod, the first clamping block is in sliding fit with the limiting groove, and the second clamping block is clamped with the limiting hole.
Through adopting above-mentioned technical scheme, when putting into the filtration jar, the bottom of crossing the filter bag corresponds through first magnetism piece and second magnetism piece inter attraction and laminates for the bottom of crossing the filter bag is expanded, and is difficult for producing great fold along with the flow of filtration in-process rivers. The open end of the filter bag is locked through the second locking piece, so that the whole filter bag is positioned and fixed and is not easy to deviate, and the filtering efficiency is improved.
When the first magnetic block is installed, the elastic installation rod penetrates through the lantern ring and the installation hole in the first magnetic block, so that the first magnetic block is fixed on the installation rod, and the installation rod is fixed at the bottom of the filter bag, and therefore the installation of the first magnetic block is achieved. And when the installation rod and the first magnetic block are damaged, the installation rod can be simply and quickly disassembled and replaced. When the mounting rod is connected, the first clamping block and the second clamping block at one end of the mounting rod are inserted into the limiting groove in the end face of the other end of the mounting rod correspondingly. When inserting, the lateral wall of spacing groove is first butt second fixture block for the second fixture block promotes first fixture block downwarping, makes first fixture block and second fixture block peg graft with the spacing groove. When the second clamping block is inserted into the bottom of the limiting groove, the second clamping block corresponds to the limiting hole, pressure on the second clamping block disappears, the first clamping block recovers deformation, the second clamping block is connected with the limiting hole in a clamped mode, and therefore the mounting rod is locked.
The invention is further configured to: the inside wall of the filter tank is provided with a clamping groove matched with the second magnetic block in a clamping manner along the equal interval of the circumferential direction of the filter tank, the second magnetic block is clamped with the clamping groove, and the clamping groove is provided with a closed part for closing the clamping groove.
The closing member includes guide block and closing plate, the both sides fixedly connected with guide block in joint groove, the guiding groove has been seted up on the guide block, the notch in joint groove is provided with the closing plate that seals the joint groove, the both ends and the guiding groove of closing plate slide and link to each other. The tank bottom of the clamping groove is provided with a circulation hole, and the circulation hole is communicated with the inner side wall of the filter tank.
Through adopting above-mentioned technical scheme, the second magnetism piece also can be changed through dismantling and installing simply, through the closure piece with the closure in joint groove with opening for the second magnetism piece is installed and is dismantled at the joint inslot. When the closing member is closed, when closed, the closing plate is inserted along the guiding groove on the guiding block, so that the clamping groove is closed by the closing plate, and the second magnetic block is not easy to slide from the clamping groove. When the closing piece is opened, the closing plate can slide out from the guide groove, so that the clamping groove is opened, and the second magnetic block can be detached.
The circulation hole makes in filtering process, and the solution that gets into the joint inslot can the circulation hole flow back to filter in the jar to make the joint inslot be difficult to ponding, reduce the corruption probability of second magnetism piece, improve its life-span.
The invention is further configured to: the second locking piece includes first locking piece and second locking piece, a plurality of flexible grooves have been seted up along filtering jar circumference even interval equidistance on the inside wall of jar, flexible inslot is provided with the spring, spring one end links to each other with the tank bottom in flexible groove is fixed, the first locking piece of the other end fixedly connected with of spring, first locking piece and flexible groove sliding fit, be connected with on the first locking piece and cross the filter bag open end and cross the inconsistent second locking piece of jar inside wall.
And a rubber layer is arranged on the abutting surface of the second locking block, which abuts against the filter bag.
Through adopting above-mentioned technical scheme, pulling second locking block for form certain gap between second locking block and the filtration jar inside wall. At this moment, first locking piece receives the pulling of first locking piece and slides, and first locking piece is tensile with the spring, then fills in the gap between second locking piece and the inside wall of filter-tank with the edge of crossing the filter bag open end, then loosens the second locking piece for the spring pulls second locking piece will cross the filter bag and support tightly on the lateral wall of filter-tank, thereby will cross the locking of filter bag.
The rubber layer increases the frictional resistance between the second locking block and the filter bag, so that the positioning of the filter bag is more stable.
The invention is further configured to: the feed pipeline connected with the filtrate of the filter tank in the steps S1, S2, S3 and S4 adopts a double-layer vacuum glass pipeline, and a heat insulation layer is coated on the inner side wall of the double-layer vacuum glass pipeline.
By adopting the technical scheme, when filtering is performed in steps S1, S2, S3 and S4, the reaction solution and the precipitate generated by the reaction need to be filtered and separated through the filter tank, and the temperature in the reaction solution is high and is about 80-90 ℃, but when the reaction solution and the precipitate generated by the reaction are conveyed into the filter tank along with the pipeline, the temperature of the reaction solution is reduced due to the loss of the temperature in the pipeline, so that part of the dichlorodiamminopalladium substance needing to be dissolved in the reaction solution is precipitated due to the reduction of the solubility due to the reduction of the temperature, and the yield is reduced. When the pipeline adopts a vacuum double-layer glass pipeline, the vacuum layer is arranged between the inner layer and the outer layer of the pipeline, so that heat is blocked when the inner layer of the pipeline is outwards transferred, and the loss of liquid flowing heat in the pipeline is reduced. And a layer of heat insulation layer is coated on the inner side wall of the pipeline, so that the heat insulation performance of the pipeline is further improved, the overlarge temperature difference change of the reaction liquid when flowing into the filter tank is reduced, the separation of dichlorodiamminepalladium is reduced, and the purification yield of palladium is improved.
The invention is further configured to: the heat insulation layer comprises the following components in parts by weight:
by adopting the technical scheme, the epoxy resin in the heat-insulating layer is used as a base material together with the epoxy resin curing agent to be cured and coated on the inner side wall of the pipeline, and the cured epoxy resin coating has strong adhesive force and excellent heat resistance and water resistance. The leveling agent is a coating additive, and can enhance the leveling property and uniformity of the epoxy resin film layer in the forming process, so that the obtained film layer is smoother and smoother. Polyvinylidene fluoride is added in the coating, and the polyvinylidene fluoride can improve the hydrophobic property of the coating, so that reaction liquid is not easy to remain in a pipeline when flowing through the pipeline. The thermal conductivity of the ceramic fiber is very low, and after the ceramic fiber is added into the coating, the thermal conductivity of the coating is reduced, and the thermal insulation performance of the pipeline is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the impurity removal auxiliary agent is added in the ammoniation process, so that the bismuth ions which are difficult to remove in the ammoniation process are thoroughly removed, and the ammoniation acidification circulation impurity removal process is reduced, so that the purity of the dichlorodiamminepalladium is improved, and the consumption of energy and resources is reduced;
2. the heat insulation performance of the pipeline is improved by coating the heat insulation coating on the pipeline, so that the precipitation of dichlorodiamminepalladium is reduced in the transfer process, and the yield of palladium is improved;
3. the bottom and the opening end of the filter bag are respectively positioned by arranging the positioning assembly, so that the stability of the filter bag is improved, the filter bag is not easy to wrinkle in the filtering process, and the filtering effect is improved;
4. carry out demountable installation fixed to first magnetism piece and second magnetism piece respectively through setting up installed part and joint groove and closure for first magnetism piece and second magnetism piece can be changed simply fast when taking place to damage.
Drawings
FIG. 1 is a perspective view of a filter canister;
FIG. 2 is a cross-sectional view of a filter canister and filter bag;
FIG. 3 is an enlarged view of A in FIG. 2;
FIG. 4 is a cross-sectional view of the fastener;
fig. 5 is an enlarged view of B in fig. 2.
Reference numerals: 1. a filter tank; 11. a filter plate; 13. a closure cap; 14. a filter bag; 15. A feed pipe; 16. an exhaust gas discharge pipe; 2. a positioning assembly; 21. a first locking member; 211. a first magnetic block; 212. a second magnetic block; 22. a second locking member; 221. a first locking block; 222. A second locking block; 223. a telescopic groove; 224. a spring; 225. a rubber layer; 3. a mounting member; 31. mounting a rod; 321. a collar; 323. a first clamping block; 324. a second fixture block; 325. A limiting hole; 326. a limiting groove; 4. a clamping groove; 41. a flow-through hole; 5. a closure; 51. A guide block; 52. and (3) closing the plate.
Detailed Description
The present invention will be described in detail with reference to examples.
The invention discloses a process for purifying palladium in anode mud, which comprises the following process steps:
s1: introducing the filtrate obtained after the gold and silver of the anode slime into a reaction kettle, adding ammonia water to adjust the pH value to 9, and filtering to remove impurities to obtain filtrate a for later use;
s2: adding hydrochloric acid into the filtrate a obtained in the step S1, acidifying to pH 1, and filtering to obtain a precipitate a for later use;
s3: dissolving the precipitate a obtained in the step S2 with ammonia water, adjusting the pH to 10, adding an impurity removal auxiliary agent with the mass ratio of 1: 4 to the filtrate a, and filtering and removing impurities after clarification to obtain a filtrate b;
s4: adding hydrochloric acid into the filtrate b obtained in the step S3, acidifying to pH 1, and filtering to obtain a precipitate b for later use;
s5: and (4) re-dissolving the precipitate b obtained in the step (S4) by using ammonia water with the liquid-solid ratio of 2: 1 to the precipitate b, and then adding hydrazine hydrate for reduction reaction to obtain a precipitate c, namely the product palladium.
The impurity removal auxiliary agent comprises the following components in percentage by weight:
60% of montmorillonite particles;
30% of ethylene diamine tetraacetic acid disodium;
10% of dimercaprol.
The preparation process of the impurity removal auxiliary agent comprises the following steps:
step 1: preparing 3 parts of disodium ethylene diamine tetraacetate solution with the mass fraction concentration of 20-30%;
step 2: adding dimercaprol into each part of disodium ethylene diamine tetraacetate solution according to a proportion, and uniformly stirring for later use;
and step 3: adding montmorillonite particles into 1 part of the solution prepared in the step 2, stirring for 10min, and standing for 5 h;
and 4, step 4: then filtering off the montmorillonite particles, adding the montmorillonite particles into another part of the solution prepared in the step 2, and repeating the step 3;
and 5: and (4) drying the montmorillonite particles obtained in the step (4) in an oven to obtain the impurity removal auxiliary agent.
Referring to fig. 1, the filtering apparatus used for filtering in steps S1, S2, S3, and S4 is a filter tank, and the material of the filter tank 1 is plastic. A filter plate 11 is fixedly arranged in the filter tank 1. The top of the filtering tank 1 is clamped with a closing cover 13 for closing the filtering tank 1. A feed pipe 15 and an exhaust gas discharge pipe 16 are fixedly connected to the closing cap 13.
Referring to fig. 1 and 2, a filter bag 14 is disposed above the filter plate 11. The filter bag 14 and the filter tank 1 are provided with a positioning assembly 2 for positioning the filter bag 14. The positioning assembly 2 comprises a first locking member 21 and a second locking member 22.
Referring to fig. 2 and 3, the first locking member 21 includes a first magnetic block 211 and a second magnetic block 212, and the filter bag 14 is provided with a mounting member 3 at an end thereof adjacent to the filter plate 11. The mounting member 3 comprises a collar set, a resilient mounting rod 31 and a snap. The even interval of edge filter bag 14 circumference on the peripheral lateral wall of filter bag 14 is provided with 4 lantern ring groups, lantern ring group including the lantern ring 321 of two intervals settings, lantern ring 321 and the fixed linking to each other of the lateral wall of filter bag 14. A first magnetic block 211 is installed between the two lantern rings 321 of each lantern ring group, and a mounting hole penetrating through the first magnetic block 211 is formed in the side wall of the first magnetic block 211 facing the two lantern rings 321. The mounting rods 31 pass through the collar and mounting holes circumferentially along the filter bag 14 to secure the first magnetic block 211 to the filter bag 14.
Referring to fig. 3 and 4, a snap is provided on an end surface of one end of the mounting rod 31. The fastener comprises a first fastening block 323 and a second fastening block 324, the end surface of the mounting rod 31 is fixedly connected with the first fastening block 323, and the side wall of the first fastening block 323 is vertically connected with the second fastening block 324. The side wall of the second latch 324 on the side away from the first latch 323 is provided with a cambered surface.
Referring to fig. 4, a limiting groove 326 matched with the first block 323 is formed on an end surface of the other end of the mounting rod 31, and the width of the limiting groove 326 is equal to the sum of the widths of the first block 323 and the second block 324. The side wall of the mounting rod 31 is provided with a limiting hole 325 communicated with the limiting groove 326, the first clamping block 323 is in sliding fit with the limiting groove 326, and the second clamping block 324 is clamped with the limiting hole 325.
Referring to fig. 2 and 3, 4 clamping grooves 4 are formed in the inner side wall of the filter tank 1 at equal intervals along the circumferential direction of the filter tank 1, a plurality of circulation holes 41 are formed in the side wall of one side, close to the filter plate 11, of each clamping groove 4, and the circulation holes 41 are communicated with the inner side wall of the filter tank 1. The second magnetic block 212 for attracting the first magnetic block 211 is snap-fitted in the snap groove 4. The notch of the clamping groove 4 is provided with a closing part 5 for closing the clamping groove 4.
Referring to fig. 2 and 3, the closing member 5 includes a guide block 51 and a closing plate 52. Every joint groove 4 all is provided with guide block 51 along the both sides of filtering jar 1 circumference, and guide block 51 links to each other with the inside wall of filtering jar 1 is fixed. The side wall of the guide block 51 close to one side of the clamping groove 4 is provided with a guide groove, and the guide groove is communicated with the top wall of the guide block 51. The notch of the clamping groove 4 is provided with a closing plate 52 for closing the clamping groove 4, and the closing plate 52 is in inserting fit with the guide groove.
Referring to fig. 2 and 5, the second locking member 22 includes a first locking block 221 and a second locking block 222, wherein 4 telescopic grooves 223 are formed in one end of the filter tank 1 close to the closing cover 13 at equal intervals along the circumferential direction of the filter tank 1, a spring 224 is arranged in each telescopic groove 223, one end of the spring 224 is fixedly connected with the bottom of each telescopic groove 223, the other end of the spring 224 is fixedly connected with the first locking block 221, and the first locking block 221 is in sliding fit with the telescopic grooves 223. A second locking block 222 is vertically and fixedly connected to a side wall of the first locking block 221 on a side close to the filter plate 11, and a rubber layer 225 is coated on a side wall of the second locking block 222 on a side facing the telescopic groove 223.
The second locking block 222 presses the filter bag 14 against the inner side wall of the filter tank 1 through the rubber layer 225.
The implementation principle of the embodiment is as follows: when the filter bag 14 is installed, the installation rod 31 firstly penetrates through the collar and the first magnetic block 211 between the two collars along the circumferential direction of the filter bag 14, and after the 4 first magnetic blocks 211 are all installed on the installation rod 31, the first block 323 and the second block 324 at one end of the installation rod 31 are inserted into the limit groove 326 on the end face of the other end of the installation rod 31 correspondingly. When the first and second clips 323 and 324 are inserted, the sidewall of the limiting groove 326 first abuts against the second clip 324, so that the second clip 324 pushes the first clip 323 to bend downward, and the first clip 323 and the second clip 324 are inserted into the limiting groove 326. When the second fixture block 324 is inserted into the bottom of the limiting groove 326, the second fixture block 324 corresponds to the limiting hole 325, the pressure on the second fixture block 324 disappears, the first fixture block 323 restores to deform, so that the second fixture block 324 is clamped with the limiting hole 325, and the first magnetic block 211 is mounted on the filter bag 14.
The filter bag 14 is then placed into the filter canister 1, with the bottom of the filter bag 14 held in place due to the attraction between the first magnetic block 211 and the second magnetic block 212.
Then, the second locking block 222 is pulled so that a gap is formed between the second locking block 222 and the inner side wall of the filter tank 1. At this time, the first locking block 221 is pulled by the first locking block 221 to slide, the first locking block 221 stretches the spring 224, then the edge of the opening end of the filter bag 14 is inserted into the gap between the second locking block 222 and the inner side wall of the filter tank 1, and then the second locking block 222 is released, so that the spring 224 pulls the second locking block 222 to press the filter bag 14 against the side wall of the filter tank 1.
The feeding pipeline connected with the filter tank and used for flowing the filtrate in the steps S1, S2, S3 and S4 adopts a double-layer vacuum glass pipeline, and a heat insulation layer is coated on the inner side wall of the double-layer vacuum glass pipeline.
The heat insulation layer comprises the following components in parts by weight:
the difference between the examples 2-9 and the example 1 is that the components in the impurity removal auxiliary agent are as follows in percentage by weight.
The difference between the embodiments 10-13 and the embodiment 1 is that the components in the heat insulation layer are as follows according to weight percentage.
Examples 14 to 17 are different from example 1 in that the mass ratio of the amount of the impurity-removing auxiliary added to the filtrate a is shown in the following table.
Examples Impurity removal auxiliary agent Filtrate a
Example 14 5.5 1
Example 15 7 1
Example 16 8.5 1
Example 17 10 1
Examples 18 to 21 are different from example 1 in that the adjustment ranges of the pH values in the respective steps S1 to S4 are shown in the following table.
Examples pH value in S1 pH value in S2 pH value in S3 pH value in S4
Example 18 9 0.8 10.5 0.8
Example 19 9.1 0.9 11 0.9
Example 20 9.2 1.1 11.5 1.1
Example 21 9 1.2 12 1.2
Examples 22 to 25 are different from example 1 in that the amount of redissolution of ammonia water in step S5 is shown in the following table in terms of the liquid-solid mass ratio of precipitate b.
Examples Amount of ammonia water Precipitation of b
Example 22 1.9 1
Example 23 2 1
Example 24 2.1 1
Example 25 2.2 1
Examples 23 to 26 are different from example 1 in that the temperatures of the reaction liquids in step S1 and step S2 are shown in the following table.
Examples Temperature control in step S1 Temperature control in step S2
Example 23 82.5 87.5
Example 24 85 90
Example 25 87.5 92.5
Example 26 90 95
Comparative example
The difference between the comparative example 1 and the example 1 is that no impurity removal auxiliary agent is added in the palladium purification process;
comparative example 2 differs from example 1 in that the feed line connecting the filter canisters for flowing filtrate is a plastic pipe;
comparative example 3 differs from example 1 in that the feed pipe connecting the filter tank for flowing filtrate is a double-layer vacuum glass pipe, but the inner side wall of the pipe is not coated with an insulating layer.
Detection method
Bismuth ion assay
And (3) determining the content of bismuth ions in the product dichlorodiamminepalladium before reduction by adopting an atomic absorption spectrophotometry. The method comprises the following specific steps:
1) preparing bismuth standard solution
Weighing 0.100g of metal bismuth, adding 10ml of nitric acid solution mixed by 98% of concentrated nitric acid and water according to the volume ratio of 1: 1, heating with slow fire to assist dissolution, cooling, transferring to a 1000ml volumetric flask, and adding water to fix the volume.
2) Sample processing
Weighing 5.0g of a sample, adding 5ml of water, mixing, adding 5ml of a nitric acid solution prepared by mixing 98% of concentrated nitric acid and water in a volume ratio of 1: 1, and heating to dissolve the solution to obtain a solution to be detected.
3) Testing
Absorbing the bismuth standard solution, preparing 1ml of standard series containing 2-80 ng of bismuth by using 0.2% of dilute nitric acid in mass concentration, respectively injecting the standard series into a graphite tube, recording the absorbance value, and drawing a standard curve. And then sucking the sample, injecting the sample into a graphite tube, measuring the absorbance value, and obtaining the bismuth ion content in the sample according to the standard curve.
The results of the measurements are shown in the following table
And (4) conclusion: through the test, the content of bismuth ions in the dichlorodiaminepalladiumidene to be reduced finally obtained in the process without adding the impurity removal reagent can be higher than that of the dichlorodiaminepalladiumidene obtained in the process with the impurity removal reagent, and the addition of the impurity removal reagent is proved to have a good effect on the removal of the bismuth ions, so that the bismuth ions can be reduced to a very low range, and the yield and the purity of the purification of the palladium are improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (8)

1. The purification process of palladium in anode mud is characterized by comprising the following process steps:
s1: introducing the filtrate obtained after gold and silver separation of the anode slime into a reaction kettle, adding ammonia water to adjust the pH value to 9-9.2, and filtering to remove impurities to obtain filtrate a for later use;
s2: adding hydrochloric acid into the filtrate a obtained in the step S1, acidifying until the pH is = 0.8-1.2, and filtering to obtain a precipitate a for later use;
s3: dissolving the precipitate a obtained in the step S2 with ammonia water, adjusting the pH value to 10-12, adding an impurity removal auxiliary agent in a mass ratio of 1: 4-10 to the filtrate a, and filtering and removing impurities after clarification to obtain a filtrate b; the impurity removal auxiliary comprises the following components in percentage by weight:
60-80% of montmorillonite particles;
10-30% of disodium ethylene diamine tetraacetate;
5-10% of dimercaprol;
s4: adding hydrochloric acid into the filtrate b obtained in the step S3, acidifying until the pH is = 0.8-1.2, and filtering to obtain a precipitate b for later use;
s5: and (4) re-dissolving the precipitate b obtained in the step (S4) by using ammonia water with the liquid-solid ratio of 1.8-2.2: 1 to the precipitate b, and then adding hydrazine hydrate for reduction reaction to obtain a precipitate c, namely the product palladium.
2. The process of claim 1, wherein the purification process of palladium in anode mud is as follows: the temperature of the solution before filtration in the step S1 is raised to 80-90 ℃, and the temperature of the solution before filtration in the step S2 is raised to 85-95 ℃.
3. The process of claim 1, wherein the purification process of palladium in anode mud is as follows: the preparation process of the impurity removal auxiliary agent comprises the following steps:
step 1: preparing 2-3 parts of disodium ethylene diamine tetraacetate solution with the mass fraction concentration of 20-30% according to a proportion;
step 2: adding dimercaprol into each part of disodium ethylene diamine tetraacetate solution according to a proportion, and uniformly stirring for later use;
and step 3: adding montmorillonite particles into 1 part of the solution prepared in the step 2, stirring for 5-10 min, and standing for 5-6 h;
and 4, step 4: then filtering off the montmorillonite particles, adding the montmorillonite particles into another part of the solution prepared in the step 2, and repeating the step 3;
and 5: and (4) drying the montmorillonite particles obtained in the step (4) in an oven to obtain the impurity removal auxiliary agent.
4. The process of claim 1, wherein the purification process of palladium in anode mud is as follows: the filtering device that adopts during filtration in step S1, S2, S3, S4 is for filtering the jar, install filter plate (11) in filtering jar (1), the opening has been seted up on the top of filtering jar (1), the top of filtering jar (1) is provided with seals open-ended closing cap (13), install filter bag (14) in filtering jar (1), be provided with locating component (2) in filtering bag (14), locating component (2) are including location first locking piece (21) of crossing filter bag (14) bottom and location filter bag (14) open-ended second locking piece (22), first locking piece (21) are including first magnetic block (211) and second magnetic block (212), filter bag (14) are close to on the lateral wall of filter plate (11) along being provided with a plurality of first magnetic blocks (211) of crossing filter bag (14) circumference even interval, a second magnetic block (212) matched with the first magnetic block (211) for use is arranged on the inner side wall of the filter tank (1);
the first magnetic block (211) is connected with the filter bag (14) through the mounting piece (3), the mounting piece (3) comprises an elastic mounting rod (31) and a clamping piece, more than one set of lantern ring group is connected to the side wall, close to the filter plate (11), of the filter bag (14) along the circumferential direction of the filter bag (14), the lantern ring group comprises two lantern rings (321) arranged at intervals, the lantern ring (321) is fixedly connected with the outer side wall of the filter bag (14), a first magnetic block (211) is installed between the two lantern rings (321) of each set of lantern ring group, a mounting hole is formed in the first magnetic block (211), the mounting rod (31) penetrates through the lantern rings and the mounting hole and is connected end to end through the clamping piece;
the clamping piece comprises an elastic first clamping block (323) and an elastic second clamping block (324), the first clamping block (323) is fixedly connected to the end face of one end of the mounting rod (31), the second clamping block (324) is fixedly connected to the side wall of the first clamping block (323), a limiting groove (326) is formed in the end face of the other end of the mounting rod (31), a limiting hole (325) communicated with the clamping groove is formed in the side wall of the mounting rod (31), the first clamping block (323) is in sliding fit with the limiting groove (326), and the second clamping block (324) is clamped with the limiting hole (325).
5. The process of claim 4, wherein the purification process of palladium in anode mud is as follows: clamping grooves (4) which are matched with the second magnetic blocks (212) in a clamping mode are formed in the inner side wall of the filtering tank (1) at equal intervals along the circumferential direction of the filtering tank (1), the second magnetic blocks (212) are clamped with the clamping grooves (4), and closing pieces (5) for closing the clamping grooves (4) are arranged on the clamping grooves (4);
a circulation hole (41) is formed in the side wall of the clamping groove (4), and the circulation hole (41) is communicated with the inner side wall of the filter tank (1);
the sealing member (5) comprises a guide block (51) and a sealing plate (52), the guide block (51) is fixedly connected to the two sides of the clamping groove (4), a guide groove is formed in the guide block (51), the sealing plate (52) for sealing the clamping groove (4) is arranged at the notch of the clamping groove (4), and the two ends of the sealing plate (52) are connected with the guide groove in a sliding mode.
6. The process of claim 4, wherein the purification process of palladium in anode mud is as follows: the second locking piece (22) comprises a first locking block (221) and a second locking block (222), a plurality of telescopic grooves (223) are uniformly arranged on the inner side wall of the filter tank (1) at intervals along the circumferential direction of the filter tank (1), springs (224) are arranged in the telescopic grooves (223), one ends of the springs (224) are fixedly connected with the bottoms of the telescopic grooves (223), the other ends of the springs (224) are fixedly connected with the first locking block (221), the first locking block (221) is in sliding fit with the telescopic grooves (223), and the first locking block (221) is connected with the second locking block (222) which enables the opening end of the filter bag (14) to be tightly abutted against the inner side wall of the filter tank (1);
a rubber layer (225) is arranged on the abutting surface of the second locking block (222) abutting against the filter bag (14).
7. The process of claim 1, wherein the purification process of palladium in anode mud is as follows: the feed pipeline connected with the filtrate of the filter tank in the steps S1, S2, S3 and S4 adopts a double-layer vacuum glass pipeline, and a heat insulation layer is coated on the inner side wall of the double-layer vacuum glass pipeline.
8. The process of claim 7, wherein the purification process of palladium in anode mud is as follows: the heat insulation layer comprises the following components in parts by weight:
30-60 parts of epoxy resin;
8-10 parts of an epoxy resin curing agent;
0.4-1 part of polyvinylidene fluoride;
1-2 parts of a leveling agent;
3-6 parts of ceramic fiber.
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* Cited by examiner, † Cited by third party
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CN1087687A (en) * 1992-12-02 1994-06-08 北京有色金属研究总院 A kind of processing method of cleaning copper electrolyte
CN102994771A (en) * 2011-09-13 2013-03-27 郴州市金贵银业股份有限公司 Method for extracting palladium sponge from silver electrolysis anode slime parting liquid

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* Cited by examiner, † Cited by third party
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JPH0696997A (en) * 1992-09-10 1994-04-08 Taiyo Yuden Co Ltd Conductive paste for internal electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087687A (en) * 1992-12-02 1994-06-08 北京有色金属研究总院 A kind of processing method of cleaning copper electrolyte
CN102994771A (en) * 2011-09-13 2013-03-27 郴州市金贵银业股份有限公司 Method for extracting palladium sponge from silver electrolysis anode slime parting liquid

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