CN102797018A

CN102797018A - Method for separating and purifying platinum by adopting holding potential

Info

Publication number: CN102797018A
Application number: CN2012103135069A
Authority: CN
Inventors: 贺小塘; 吴喜龙; 王欢; 郭俊梅; 明潇; 施秋杰; 韩守礼; 李锟; 李勇; 郑允�
Original assignee: Your Research Resources (yimen) Co Ltd
Current assignee: Your Research Resources (yimen) Co Ltd
Priority date: 2012-08-30
Filing date: 2012-08-30
Publication date: 2012-11-28
Anticipated expiration: 2032-08-30
Also published as: CN102797018B

Abstract

The invention mainly relates to a novel method for separating and purifying platinum from complex platinum family metal solution. Base metal impurities in the solution are removed through ion exchange, pure platinum family metal solution can be obtained, ammonium chloride precipitate platinum is added under a certain oxidation-reduction potential, the electric potential is adjusted, precipitate containing platinum is reduced by a specific reducing agent, the platinum deposit is enabled to be resolved, then the oxidation-reduction potential is adjusted again, the platinum is oxidized to be high valence state again, the ammonium chloride is added so as to enable the platinum to be deposited again, the process of precipitation and resolution are repeated in such a way according to the complexity of raw materials until the ammonium chloroplatinate deposit with purity meeting the requirements can be obtained, and high-purity spongy platinum is obtained from the qualified ammonium chloroplatinate through the processes of reduction, washing, calcination and the like. The method has the advantages of short process, simplicity in operation, and high platinum recovery.

Description

A kind of method that adopts CONTROLLED POTENTIAL to separate purification platinum

Technical field

The present invention relates to redox potential, realize the method for the Separation & Purification of platinum in the complicated precious metal feed liquid through adjustment solution.

Background technology

The superior performance of platinum, purposes are very extensively. BullionThe industry in, mainly as ornamental with ArtworkIn the chemical industry, in order to make senior chemical ware, platinum crucible, ElectrodeAnd acceleration Chemical reactionSpeed CatalyzerIn the exotic materials field, also very extensively, common is platinum iridium alloy, platinum rhodium etc. to the purposes of platinum, is the important source material of producing pyrometer couple.

Because the character of each element of platinum metals is very approaching, it is the important directions of precious metals metallurgy area research that the separation of platinum metals is purified always.Development so far; The separating and purifying method of platinum commonly used has selective precipitation, SX, IX etc.; But all exist problems such as material flexibility is not strong, selectivity is not high, purification efficiency is lower, obtain the purification that highly purified platinum must pass through repeated multiple times, different types of material all will be adjusted purifying technique; And other platinum metals of association disperses easily, and the precious metal comprehensive recovery is not high.These technology are looser to control of process condition, and the result who therefore obtains is often unsatisfactory.

The present invention has paid close attention to the variation of valence of platinum under various conditions, through accurate control, realizes the controlled adjustment of platinum metals valence state, utilizes the valence state difference The properties to be realized the Separation & Purification of platinum.

Summary of the invention

The purpose of this invention is to provide a kind of method of purification, realize efficient, the purification fast of platinum material flexibility platinum strong, simple to operate.

Realize the method for the described purification platinum of the object of the invention, comprise the following steps: successively

1. material is adjusted into hydrochloric acid system, realizes the separation of base metal through Zeo-karb;

2. the solution after the exchange is through adjustment acidity and adding oxygenant A, and the controlled oxidation reduction potential is 650 ~ 850mV, adds an amount of ammonium chloride and makes platinum generate deposition;

3. the platiniferous deposition is removed the impurity of deentrainment with the ammonium chloride solution washing;

4. through adjustment acidity and adding reductive agent B, control solution oxide reduction potential is 200 ~ 600mV, and the platiniferous deposition is converted into soluble substance, transfers solution to;

5. adjust solution acidity, add oxygenant C, control solution oxide reduction potential is 910 ~ 1000mV, adds an amount of greening ammonium, and platinum is converted into yellow mercury oxide once more;

6. the platiniferous deposition with the ammonium chloride solution washing, is further removed impurity once more, obtains purified platinum throw out;

7. purified platinum throw out adds water slurryization, uses hydrazine hydrate reduction after the adjustment acidity, and the black powder of generation with calcining behind the pure water repetitive scrubbing, promptly obtains purity at the spongy platinum more than 99.95%.

Be the better the present invention of realization, can carrying out the 7. before the step, repeat 4., 5., 6. step, strengthen the effect of purifying, improve the purity of platinum.The 2., 3., 5., the deposition that 4. obtains of the solution that 6. obtains and the should properly collect, to improve the comprehensive recovery of precious metal.

Description of drawings

Accompanying drawing 1 is for realizing schema of the present invention.

Embodiment

Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.

Embodiment one

Raw material is that nitric acid industry is used the ammonia oxidation catalysis net, catches up with nitre through aqua regia dissolution, hydrochloric acid, obtains the solution of hydrochloric acid medium.Material liquid volume is 35.00L, and table 1. is seen in composition analysis

Table 1 embodiment one material composition table

1. adjusting solution acidity to pH value is 1 ~ 1.5, and with resin cation exchange 2 times, sampling detects, and the massfraction of the relative Pt of each element such as Ni, Fe, Al, Cr all can reach in the solution GB 1419-2004 " spongy platinum" standard of 99.95% spongy platinum in the standard; 2. add hydrochloric acid; Adjustment pH value of solution value is 0.5 ~ 1, and controlled temperature is more than 90 ℃, under whipped state, slowly adds industrial ydrogen peroxide 50; Monitor the redox potential of solution simultaneously in real time with pHSJ-3F type potentiometer; When solution potential is stabilized in the 700mV left and right sides, stop to add ydrogen peroxide 50, keep more than the 30min; 3. add SILVER REAGENT ammonium chloride 1800g, fully stir 10min, leave standstill cool overnight; 4. leach yellow platiniferous deposition, add 5% SILVER REAGENT ammonium chloride solution 10L, stir pulp, be heated to boiling, and keep leaving standstill more than the 30min, naturally cool to below 50 ℃, leach the platiniferous deposition; 5. add pure water 40L in the deposition, reagent grade hydrochloric acid 10L is stirred and heated to 85 ℃, adds the S-WAT of SILVER REAGENT; Monitor the redox potential of solution simultaneously with pHSJ-3F type potentiometer in real time, when solution potential is stabilized in the 500mV left and right sides, stop to add S-WAT, keep more than the 10min; The dissolving basically fully of xanchromatic platinum deposition, reactor bottom has a small amount of white precipitate, stops heating and stirring; Leave standstill, naturally cool to below 50 ℃, leach solution; 6. add reagent grade hydrochloric acid, the pH value of adjustment solution is below 0.5, when stirring heating, temperature reach 85 ℃; Begin to add Youxiaolin, monitor the redox potential of solution simultaneously with pHSJ-3F type potentiometer in real time, when solution potential reaches 950mV, stop to add Youxiaolin; Add SILVER REAGENT ammonium chloride 1500g, continue to stir 10min, stop heating and stirring; Leave standstill, naturally cooling leaches yellow ammonium chloroplatinate deposition; 7. leach yellow platiniferous deposition, add 5% SILVER REAGENT ammonium chloride solution 10L, stir pulp, be heated to boiling, and keep leaving standstill more than the 30min, naturally cool to below 50 ℃, leach the platiniferous deposition; 8. add water 50L in the deposition, stir pulp, using SILVER REAGENT sodium hydroxide adjustment pH value is about 10, slowly adds SILVER REAGENT Hydrazine Hydrate 80 800mL; And boil 10min, leach the black fine powder, with pure water washing 8 times; Use the quartz boat splendid attire, high-temperature calcination in retort furnace is in 750 ℃ of insulation 3h; 9. naturally cooling, taking-up is weighed, and obtains pure platinum 1463.12g.

Sampling analysis, product purity meets GB 1419-2004 " spongy platinum" requirement of 99.95% spongy platinum in the standard, the direct yield of platinum is 97.33%.

Embodiment two

Raw material is to obtain feed liquid after the concentrate of vehicle exhaust spent catalyst enrichment dissolves, hydrochloric acid medium, and liquor capacity is 27.30L, table 2. is seen in composition analysis

Table 2 embodiment two material composition tables

Element

Pt

Pd

Rh

Cu

Fe

Pb

Al

Zn

Content g/L

45.80

31.26

7.78

0.42

1.30

0.31

0.75

1.21

Total amount g

1250.34?

853.40?

212.39?

11.47?

35.49?

8.46?

20.48?

33.03?

1. adjusting solution acidity to pH value is 1 ~ 1.5, with resin cation exchange 4 times; 2. add hydrochloric acid; Adjustment pH value of solution value is 0.5 ~ 1, and controlled temperature is more than 90 ℃, under whipped state, slowly adds the technical grade ydrogen peroxide 50; Monitor the redox potential of solution simultaneously in real time with pHSJ-3F type potentiometer; When solution potential is stabilized in the 700mV left and right sides, stop to add ydrogen peroxide 50, keep more than the 30min; 3. add SILVER REAGENT ammonium chloride 1500g, fully stir 10min, leave standstill cool overnight; 4. leach yellow platiniferous deposition, add 5% SILVER REAGENT ammonium chloride solution 10L, stir pulp, be heated to boiling, and keep leaving standstill more than the 30min, naturally cool to below 50 ℃, leach the platiniferous deposition; 5. add pure water 40L in the deposition, reagent grade hydrochloric acid 10L is stirred and heated to 85 ℃, adds the S-WAT of SILVER REAGENT; Monitor the redox potential of solution simultaneously in real time with pHSJ-3F type potentiometer, solution potential is stabilized in about 500mV, stops to add S-WAT, keeps more than the 10min; The dissolving basically fully of xanchromatic platinum deposition, reactor bottom has a small amount of white precipitate, stops heating and stirring; Leave standstill, naturally cool to below 50 ℃, leach solution; 6. add reagent grade hydrochloric acid, the pH value of adjustment solution is below 0.5, when stirring heating, temperature reach 85 ℃; Begin to add Youxiaolin, monitor the redox potential of solution simultaneously with pHSJ-3F type potentiometer in real time, when solution potential reaches 950mV, stop to add Youxiaolin; Add SILVER REAGENT ammonium chloride 1250g, continue to stir 10min, stop heating and stirring; Leave standstill, naturally cooling leaches yellow ammonium chloroplatinate deposition; 7. leach yellow platiniferous deposition, add 5% SILVER REAGENT ammonium chloride solution 10L, stir pulp, be heated to boiling, and keep leaving standstill more than the 30min, naturally cool to below 50 ℃, leach the platiniferous deposition; 8. repeat 5., 6., 7. step 2 time; 9. add water 40L in the deposition, stir pulp, using SILVER REAGENT sodium hydroxide adjustment pH value is about 10, slowly adds SILVER REAGENT Hydrazine Hydrate 80 700mL; And boil 10min, leach the black fine powder, with pure water washing 8 times; Use the quartz boat splendid attire, high-temperature calcination in retort furnace is in 750 ℃ of insulation 3h; 10. naturally cooling, taking-up is weighed, and obtains pure platinum 1212.85g,

Sampling analysis, product purity meets GB 1419-2004 " spongy platinum" requirement of 99.95% spongy platinum in the standard, the direct yield of platinum is 97.00%.

Embodiment three

Raw material is the omplicated solution that contains platinum, palladium, rhodium iridium that obtains after the refining residues dissolving, and medium is a hydrochloric acid system, and volume is 38.50L, and table 3. is seen in composition analysis

Table 3 embodiment three material composition tables

1. adjusting solution acidity to pH value is 1 ~ 1.5, with resin cation exchange 3 times; 2. add hydrochloric acid; Adjustment pH value of solution value is 0.5 ~ 1, and controlled temperature is more than 90 ℃, under whipped state, slowly adds the technical grade ydrogen peroxide 50; Monitor the redox potential of solution simultaneously in real time with pHSJ-3F type potentiometer; When solution potential reaches 650 ~ 700mV, stop to add ydrogen peroxide 50, keep more than the 30min; 3. add SILVER REAGENT ammonium chloride 1600g, fully stir 10min, leave standstill cool overnight; 4. leach yellow platiniferous deposition, add 5% SILVER REAGENT ammonium chloride solution 10L, stir pulp, be heated to boiling, and keep leaving standstill more than the 30min, naturally cool to below 50 ℃, leach the platiniferous deposition; 5. add pure water 40L in the deposition, reagent grade hydrochloric acid 10L is stirred and heated to 85 ℃, adds the S-WAT of SILVER REAGENT; Monitor the redox potential of solution simultaneously in real time with pHSJ-3F type potentiometer, solution potential is stabilized in about 500mV, stops to add S-WAT, keeps more than the 10min; The dissolving basically fully of xanchromatic platinum deposition, reactor bottom has a small amount of white precipitate, stops heating and stirring; Leave standstill, naturally cool to below 50 ℃, leach solution; 6. add reagent grade hydrochloric acid, the pH value of adjustment solution is below 0.5, when stirring heating, temperature reach 85 ℃; Begin to add Youxiaolin, monitor the redox potential of solution simultaneously with pHSJ-3F type potentiometer in real time, when solution potential reaches 950mV, stop to add Youxiaolin; Add SILVER REAGENT ammonium chloride 1350g, continue to stir 10min, stop heating and stirring; Leave standstill, naturally cooling leaches yellow ammonium chloroplatinate deposition; 7. leach yellow platiniferous deposition, add 5% SILVER REAGENT ammonium chloride solution 10L, stir pulp, be heated to boiling, and keep leaving standstill more than the 30min, naturally cool to below 50 ℃, leach the platiniferous deposition; 8. repeat 5., 6., 7. step 3 time; 9. add water 40L in the deposition, stir pulp, using SILVER REAGENT sodium hydroxide adjustment pH value is about 10, slowly adds SILVER REAGENT Hydrazine Hydrate 80 750mL; And boil 10min, leach the black fine powder, with pure water washing 8 times; Use the quartz boat splendid attire, high-temperature calcination in retort furnace is in 750 ℃ of insulation 3h; 10. naturally cooling, taking-up is weighed, and obtains pure platinum 1297.88g,

Sampling analysis, product purity meets GB 1419-2004 " spongy platinum" requirement of 99.95% spongy platinum in the standard, the direct yield of platinum is 96.02%.

Claims

1. the separating and purifying method of platinum in the precious metal solution is characterized in that comprising following process step:

(1) precious metal solution is a hydrochloric acid system, and solution is passed through ion exchange resin;

(2) solution after the exchange is regulated acidity and temperature, adds oxygenant A, and the adjustment redox potential adds a certain amount of chloride precipitation platinum, leaches the platiniferous deposition;

(3) the platiniferous deposition that obtains adds water and stirs pulp, and adds quantitative ammonium chloride, boils and washes for some time, filters, and leaches the platiniferous deposition;

(4) add entry, hydrochloric acid in the deposition, stir pulp, be heated to certain temperature, the controlled oxidation reduction potential adds reductive agent B, precipitate dissolvedly, and filtration leaches solution;

(5) solution adjustment acidity adds oxygenant C, and the adjustment redox potential adds ammonium chloride, and platinum generates yellow mercury oxide once more, and cooling is filtered, and leaches yellow platiniferous throw out;

(6) yellow mercury oxide adds water stirring pulp once more, adds quantitative ammonium chloride, boils and washes, and leaches more purified ammonium chloroplatinate deposition;

(7) purified ammonium chloroplatinate water pulp adds alkali adjustment acidity, uses hydrazine hydrate reduction, leaches black platinum deposition, deionized water wash, and calcining obtains the spongy platinum product.

2. the separating and purifying method of platinum in a kind of precious metal solution according to claim 1; It is characterized in that: the ion exchange resin in the said step (1) is Zeo-karb; The mixing of one or more that can be, the exchange number of times is 1 ~ 4 time, the base metal element is qualified until detecting.

3. the separating and purifying method of platinum in a kind of precious metal solution according to claim 1; It is characterized in that: the oxygenant A in the described step (2) is a kind of in Textone, ydrogen peroxide 50, Youxiaolin, sulfurous gas, the chlorine; Solution potential is 650 ~ 850mV, and the ammonium chloride consumption is 0.8 ~ 1.2 times of platinum quality.

4. the separating and purifying method of platinum in a kind of precious metal solution according to claim 1; It is characterized in that: the add-on of the water in the described step (3) is 3 ~ 10 times of platinum quality; The ammonium chloride consumption is 0.05 ~ 0.2 times of quality, boils the time of washing to be controlled at 0.5 ~ 1 hour.

5. the separating and purifying method of platinum in a kind of precious metal solution according to claim 1; It is characterized in that: the concentration that adds control platinum behind the water in the said step (4) is 10 ~ 100g/L; The hydrochloric acid consumption is 20% ~ 50% of the water yield; Temperature is 50 ~ 100 ℃, and used reductive agent B is a kind of in sulfurous gas, S-WAT, ydrogen peroxide 50, formic acid, the formaldehyde, and solution potential is 200 ~ 600mV.

6. the separating and purifying method of platinum in a kind of precious metal solution according to claim 1; It is characterized in that: in the said step (5) oxygenant C be a kind of in VAL-DROP, Textone, Youxiaolin, chlorine, the sodium bromate, solution potential is 910 ~ 1000mV.

7. the separating and purifying method of platinum in a kind of precious metal solution according to claim 1; It is characterized in that: the reducing acidity of the ammonium chloroplatinate in the said step (7) is that the pH value is about 10; The Hydrazine Hydrate 80 consumption is every gram platinum 0.5 ~ 1mL; Calcining temperature is 600 ~ 850 ℃, and soaking time was not less than 1 hour.