CN112359205B - Treatment method of platinum group metal beneficiation concentrate strengthened leaching solution - Google Patents
Treatment method of platinum group metal beneficiation concentrate strengthened leaching solution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 28
- 239000012141 concentrate Substances 0.000 title claims abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002386 leaching Methods 0.000 title claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 131
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002893 slag Substances 0.000 claims abstract description 53
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000010970 precious metal Substances 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 99
- 239000007788 liquid Substances 0.000 claims description 69
- 238000001556 precipitation Methods 0.000 claims description 55
- 239000000706 filtrate Substances 0.000 claims description 45
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 43
- 238000006386 neutralization reaction Methods 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 238000006722 reduction reaction Methods 0.000 claims description 26
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 20
- -1 iron-aluminum-chromium-arsenic Chemical compound 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 239000008267 milk Substances 0.000 claims description 10
- 210000004080 milk Anatomy 0.000 claims description 10
- 235000013336 milk Nutrition 0.000 claims description 10
- 238000006073 displacement reaction Methods 0.000 claims description 9
- 235000019738 Limestone Nutrition 0.000 claims description 8
- 239000006028 limestone Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 50
- 239000011651 chromium Substances 0.000 abstract description 49
- 229910052804 chromium Inorganic materials 0.000 abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 25
- 230000003472 neutralizing effect Effects 0.000 abstract description 17
- 238000005728 strengthening Methods 0.000 abstract description 11
- 238000011084 recovery Methods 0.000 abstract description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 5
- 239000013067 intermediate product Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000005070 sampling Methods 0.000 description 30
- 230000001376 precipitating effect Effects 0.000 description 25
- 229910052785 arsenic Inorganic materials 0.000 description 21
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 17
- 238000001914 filtration Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000010953 base metal Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 238000005188 flotation Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- 229910003267 Ni-Co Inorganic materials 0.000 description 4
- 229910003262 Ni‐Co Inorganic materials 0.000 description 4
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for treating a platinum group metal ore dressing concentrate strengthening leachate, which is a method for enriching noble metals and comprehensively recovering valuable metals by adopting a process route of strengthening the leachate, neutralizing residual acid, replacing noble metals with active copper powder, replacing copper with iron powder, and oxidizing and neutralizing iron, aluminum and chromium by compressed air. Compared with the prior art, the valuable metal intermediate product obtained by the invention has the advantages that the precious metal is precious metal replacement slag which contains 300g/t of precious metal; the copper is sponge copper slag, wherein the copper content is 88 percent; the nickel and cobalt is nickel and cobalt hydroxide slag, wherein the nickel and cobalt content is 32%, and the recovery rate of valuable metal elements is more than 98%.
Description
Technical Field
The invention relates to the technical field of rare and precious metal smelting, in particular to a method for treating a platinum group metal ore dressing concentrate strengthening leaching solution.
Background
The platinum ore has the characteristics of large platinum group metal storage capacity, high grade and stable ore body thickness, the platinum group metal storage capacity is 412 tons, and the basic grade is 5.22g/t. Platinum ore is subjected to a conventional semi-autogenous grinding, ball milling and grading crushing process, and a stage flotation stage ore grinding and flotation process of roughing, concentrating, regrinding, recleaning and concentrating of roughed tailings is adopted, so that about 82000 tons of precious metal concentrate containing Cr can be produced each year 2 O 3 0.7 to 3.5 percent of MgO and 12 to 21 percent of MgO. The concentrate can bring about 9.5 tons of platinum group metals every year, and can bring 2492 tons, 1533 tons and 246 tons of nickel, copper and cobalt.
When the platinum concentrate is subjected to a wet-process enhanced leaching process, most of elements such as copper, nickel, cobalt, iron, chromium, magnesium, aluminum and the like are leached and enter the leaching solution, and meanwhile, a small amount of precious metals also enter the leaching solution. Therefore, the method has important significance for efficiently recovering the nickel, the copper and the cobalt.
The complex associated platinum group noble metal ore dressing concentrate acid leaching solution contains valuable metal element ions of Ni, cu and Co, at the same time, it also contains small quantity of noble metal element ions of Pt, pd, rh, ir, os, ru, au and Ag, and in addition, a large quantity of Fe, cr, mg,Ions of impurity elements such as Si and Al, and H 2 SO 4 . Wherein Fe and Cr are mostly Fe 3+ 、Cr 6+ The form exists.
The method has the advantages that the concentration of valuable metal ions in the solution is low, the types of impurity element ions are various, the concentration is high, and an economical and reasonable process is very necessary, so that the method has great significance for separating and recovering precious metals and valuable metal elements such as nickel, cobalt, copper, precious metals and the like by taking the platinum-palladium flotation concentrate enhanced leachate as a raw material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating a platinum group metal ore dressing concentrate strengthening leaching solution.
The invention is realized by the following technical scheme.
A method for treating a platinum group metal beneficiation concentrate enhanced leaching solution, which is characterized by comprising the following steps:
(1) Adding a reducing agent sodium sulfite into the platinum group metal ore dressing concentrate enhanced leaching solution to carry out pre-reduction reaction, and adding Fe in the solution 3+ 、Cr 6+ Separately reduced to Fe 2+ 、Cr 3+ Then, sodium carbonate or limestone is adopted to neutralize residual acid, the pH value of the pre-reduction solution is adjusted to be 1.5-2.0, and a first filtrate and a first filter residue are obtained through solid-liquid separation;
(2) And (3) replacing noble metals by active copper powder: adding active copper powder into the first filtrate obtained in the step (1) to replace precious metals to obtain a replaced liquid and replaced slag;
(3) Adding iron powder into the displaced liquid obtained in the step (2) to perform copper displacement reaction, and performing solid-liquid separation to obtain a second filtrate and a second filter residue;
(4) Performing a first-stage oxidation precipitation iron-aluminum-chromium-arsenic reaction on the second filtrate obtained in the step (3), performing solid-liquid separation, performing a second-stage oxidation precipitation iron-aluminum-chromium-arsenic reaction, performing a second-stage neutralization precipitation nickel-cobalt reaction, and obtaining a tail liquid and a tail slag;
(5) And (4) carrying out a manganese neutralization precipitation reaction on the tail liquid obtained in the step (4), and finally carrying out solid-liquid separation to obtain a neutralization tail liquid and neutralization tailings.
Further, the leachate component comprises: au 0.003-0.004 g/L, pd.0045-0.0050 g/L, pt 0.00092-0.00098 g/L, rh 0.0012-0.0015 g/L, ir 0.0015-0.0017 g/L, ni.02-2.03 g/L, cu.36-6.39 g/L, fe.62-9.63 g/L, co 0.057-0.059 g/L, as 0.0021-0.0026 g/64 zxft 3264.13-1.20 g/82 zxft 3282.22-6.32 g/34 zxft 3234.60-3434.60-3463 g/L.
Further, the sodium sulfite in the step (1) is added in an amount used for adding Fe in the leaching solution 3+ Reduction to Fe 2+ 、Cr 6+ Reduction to Cr 3+ The required amount of sodium sulfite is 78.7 to 78.9g/L of solution (i.e. 78.7 to 78.9 kg/m) 3 Solution), the temperature of the pre-reduction reaction is 60-75 ℃, and the time of the pre-reduction reaction is 60-65 min; adopting sodium carbonate or limestone to neutralize residual acid: the reaction temperature is 60-65 ℃, and the reaction time is 60-65 min.
Further, the step (2) of copper powder replacing precious metal reaction process is as follows: heating the first filtrate obtained in the step (1) to 75-85 ℃, adding active copper powder, and stirring, wherein the adding amount (wet weight) of the active copper powder is 12-16 g/L (namely 12-16 kg/m) of solution 3 Solution), controlling the potential value to be 350 mv-400 mv, controlling the end point pH to be 2.5-2.8, stopping stirring after the reaction time is 60 min-65 min, and carrying out solid-liquid separation when the temperature is reduced to 60-65 ℃.
Furthermore, the active copper powder is obtained by adding zinc powder into copper sulfate solution for replacement.
Further, the step (3) of replacing copper powder with iron powder comprises the following steps: heating the displaced liquid obtained in the step (2) to 75-85 ℃, adding iron powder, controlling the potential value to be 0-100 mv, reacting for 60-120 min, stopping stirring, and performing solid-liquid separation when the temperature is reduced to 60-65 ℃.
Further, the first stage oxidation precipitation reaction process of the step (4) is as follows: heating the second filtrate obtained in the step (3) to 70-75 ℃, introducing compressed air with the flow of 100-130 l/h, adding 20-21% calcium carbonate slurry, controlling the pH value to be 3.5-3.8, reacting for 100-180 min, stopping stirring, and performing solid-liquid separation when the temperature is reduced to 60-65 ℃ to obtain third filtrate and third filter residue (the third filter residue is waste residue); and (2) secondary oxidation precipitation, namely heating the third filtrate to 70-90 ℃, adding a sodium carbonate solution with the concentration of 10%, controlling the reaction time to be 2-2.5 h, controlling the end point pH to be 4.6-4.8, performing solid-liquid separation to obtain a fourth filtrate and a fourth filter residue, and returning the fourth filter residue to the step (1) for neutralization reaction.
Further, the reaction process of neutralizing and precipitating nickel and cobalt in the two stages of the step (4) is as follows: the first-stage nickel and cobalt precipitation is to heat the fourth filtrate to 60-65 ℃, dropwise add a sodium hydroxide solution, adjust the end point pH of the solution to 7.0-7.5, and perform the total reaction for 120-180 min; the second-stage nickel-cobalt precipitation is that the solution after the first-stage nickel-cobalt precipitation is heated to 70-90 ℃, sodium hydroxide solution is dripped, the end point pH of the solution is controlled to be 8.0-8.2, the total reaction time is 120-180 min, and tail liquid and tail slag (the tail slag is waste slag) are obtained through solid-liquid separation.
Further, the sodium hydroxide solution concentration is 5%.
And further, in the step (5), the tail liquid obtained in the step (4) is heated to 45-50 ℃, compressed air is introduced, the flow rate of the compressed air is 100-130L/h, lime milk with the concentration of 20% is added, the pH of the tail liquid is adjusted to 8.5-9, the reaction time is 2-2.5 h, and finally, neutralization tail liquid and neutralization tailings are obtained through solid-liquid separation.
The invention has the beneficial technical effects that: the invention provides a method for strengthening a leaching solution-residual acid neutralization-active copper powder replacement noble metal-iron powder replacement copper-compressed air oxidation neutralization iron aluminum chromium removal process route, enriching noble metals and comprehensively recovering valuable metals. Compared with the prior art, the method has the following advantages:
(1) In the valuable metal intermediate product obtained by the invention, the noble metal is noble metal replacement slag which contains 300g/t of noble metal; the copper is sponge copper slag, wherein the copper content is 88 percent; the nickel and cobalt are nickel and cobalt hydroxide slag containing 32% of nickel and cobalt, and the intermediate product is easier to be processed in the next step.
(2) The content of the valuable metal elements in the neutralization tail liquid is lower than the lower limit of the analysis and detection of an instrument, namely is less than or equal to 0.0002g/L, the iron-aluminum-chromium slag obtained by a first-stage oxidation precipitation reaction and the neutralized magnesium slag have low content of the valuable metal elements (both less than or equal to 0.1 percent), and the recovery rate of the valuable metal elements is more than 98 percent.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
Example 1
A treatment method of a high-chromium high-magnesium platinum group metal ore dressing concentrate strengthening leachate comprises the following steps:
the leaching solution comprises the following components: au 0.003g/L, pd 0.0045.0045 g/L, pt 0.00092g/L, rh 0.0012.0012 g/L, ir 0.0015g/L, ni 2.02.02 g/L, cu 6.36.36 g/L, fe 9.62g/L, co 0.057.057 g/L, as 0.0021.0021 g/L, cr 1.13g/L, mg 6.22.22 g/L, al 2.60.60 g/L.
Step 1, pre-reducing solution and neutralizing residual acid in solution
Adding sodium sulfite as a reducing agent into the strengthening leachate of the platinum group metal ore dressing concentrate to carry out pre-reduction reaction, wherein the adding amount of the sodium sulfite is 78.7g/L (namely 78.7 kg/m) 3 Solution), fe in the solution is added 3+ 、Cr 6+ Separately reduced to Fe 2+ 、Cr 3+ Then, sodium carbonate or limestone is adopted for neutralization, the content of residual acid in the leaching solution is about 30-40 g/L generally, the pH value of the pre-reduction solution is adjusted to be 1.5, and pre-reduced solution (first filtrate) and pre-reduced slag (first filter residue) are obtained through solid-liquid separation; the reduction and neutralization temperatures are both 60 ℃, and the reduction and neutralization times are both 60min.
Step 2, noble metal replacement
Adding a certain amount of solution obtained after platinum-palladium flotation concentrate enhanced leaching pre-reduction, namely first filtrate, into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 75 ℃, then starting to add reducing agent active copper powder into the beaker or the reactor, adding the active copper powder according to 12g/L of the solution, starting timing, reacting for 60min after a preset potential value of 350mv is reached, controlling the pH value at the end point to be 2.5, stopping stirring, stopping reaction, taking out ore pulp for filtering and washing when the temperature is reduced to about 60 ℃, drying a solid sample, then dividing, sampling and analyzing, and sampling and analyzing the contents of base metals and precious metals after the volume of the solution is measured.
Table 1 results of noble metal displacement by activated copper powder
Step 3, replacing copper with iron powder
Replacing copper ions in the solution with iron powder, taking a certain amount of precious metal replaced solution, adding the iron powder into a beaker or a reactor according to the adding amount of 10.4 g/L of the solution, starting stirring, adjusting the rotating speed, heating to 75 ℃, then starting to add the iron powder into the beaker or the reactor, starting timing to reach a preset potential value of 56mv, stopping stirring after reacting for 60min for a preset time, stopping the reaction, taking out ore pulp for filtering and washing when the temperature is reduced to about 60 ℃, and obtaining iron replaced liquid (second filtrate) and iron replaced slag (second filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the content of the base metal. The end point pH was 2.5 and the results are given in Table 2.
Table 2 substitution of copper by reduced iron powder results
Step 4, performing staged oxidation hydrolysis to precipitate Fe, al, cr and As
The leach solution contains a large amount of Fe2+, al3+, cr3+, H3AsO3, which must be removed beforehand. Because the iron-aluminum-chromium slag is easy to adsorb and precipitate nickel-cobalt ions when precipitating the iron, aluminum and chromium, in order to ensure the recovery rate of nickel and cobalt, a process of precipitating the iron, aluminum and chromium by two-stage oxidation is adopted.
Adding a certain amount of iron-substituted solution, namely a second filtrate, into a beaker or a reactor, starting stirring, adjusting the rotation speed, heating to a set temperature of 70 ℃, then starting introducing compressed air, adding 20% calcium carbonate slurry into the beaker or the reactor, starting timing, reacting for 100min for a predetermined time, stopping stirring, stopping reaction, and when the temperature is reduced to about 60 ℃, taking out ore pulp, filtering and washing to obtain a first-stage iron-removed liquid (a third filtrate) and a first-stage iron-aluminum slag (a third filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the contents of base metals and precious metals.
The technological parameters are as follows: the temperature was 70 ℃ for 100min, and the compressed air flow rate was 100L/h, the results are shown in Table 3.
TABLE 3 first stage oxidation precipitation of Fe, al and Cr results
And (3) performing secondary deep iron removal of aluminum, chromium and arsenic on the first-stage iron-removed liquid, namely the third filtrate, using a 10% sodium carbonate solution as a neutralizing precipitator, wherein the final temperature is 4.6-4.8, the first-stage iron-removed aluminum, chromium and arsenic slag is discarded slag, and the second-stage iron-removed aluminum, arsenic slag (fourth filter residue) returns to the ore pulp for neutralization.
The technological parameters are as follows: the two-stage air oxidation iron-aluminum-chromium deposition adopts a high pH value of 4.6-4.8, a fixed temperature of 70 ℃, a fixed time of 120min and a compressed air flow of 100L/h, and the results are shown in Table 4.
TABLE 4 two-stage results of deep iron removal of AlCr
Step 5, neutralizing and precipitating nickel and cobalt in sections
One-stage sodium hydroxide precipitation of nickel cobalt
The technological parameters are as follows: the concentration of the sodium hydroxide solution was 5%, the temperature was 60 ℃, the second stage deironing aluminum chromium solution, i.e., 1.5L of the fourth filtrate, was added dropwise with the sodium hydroxide solution, the pH of the solution was adjusted, the total reaction time was 120min, and the end point pH of the solution was controlled to 7.0, the results are shown in table 5.
TABLE 5 sodium hydroxide precipitation of nickel cobalt results
Two-stage precipitation of nickel and cobalt
Process parameters; the concentration of the sodium hydroxide solution is 5%, the temperature is 70 ℃, 1.5L of solution after nickel and cobalt are precipitated for one period, the sodium hydroxide solution is dripped, the pH value of the solution is adjusted, a solution sample is taken every 30min for analyzing the concentration and precipitation rate of the nickel and cobalt, the total reaction time is 120min, and the end point pH value of the solution is controlled to be 8.0, and the results are shown in Table 6.
TABLE 6 two stage precipitated Ni-Co results
Step 6, neutralizing and precipitating tail liquid
The solution after nickel and cobalt replacement contains a large amount of metal ions such as magnesium, lime milk can be added to neutralize and precipitate magnesium and manganese, the pH value of the solution is adjusted to 8.5-9, compressed air is introduced for oxidation, harmful element ions in the solution are removed, and the solution is discharged after reaching the standard.
Taking 2.0L of the solution after the second-stage nickel and cobalt precipitation, heating to 45 ℃, introducing compressed air with the flow rate of 100L/h, adjusting the pH value of the solution to 8.5 by using 20% lime milk (the pH value of discharged wastewater is 6-9), reacting for 2h, and inspecting the pH value of the neutralization end point of the tail liquid and the components of the tailings. The results are shown in Table 7.
TABLE 7 neutralization results of the tail liquors
Example 2
A treatment method of a high-chromium high-magnesium platinum group metal ore dressing concentrate strengthening leaching solution comprises the following steps:
the leaching solution comprises the following components: au 0.004g/L, pd 0.0050.0050 g/L, pt 0.00098.00098 g/L, rh 0.0015.0015 g/L, ir 0.0017.0017 g/L, ni 2.03g/L, cu 6.39.39 g/L, fe9.63 g/L, co 0.059.059 g/L, as 0.0026g/L, cr 1.20g/L, mg 6.32.32 g/L, al 2.63.63 g/L.
Step 1, pre-reducing solution and neutralizing residual acid in solution
Adding a reducing agent sodium sulfite into the platinum group metal ore dressing concentrate enhanced leaching solution to carry out pre-reduction reaction, wherein the adding amount of the sodium sulfite is 78.9g/L solution, namely 78.9kg/m 3 Solution of Fe in solution 3+ 、Cr 6+ Separately reduced to Fe 2+ 、Cr 3+ Then, sodium carbonate or limestone is adopted for neutralization, the content of residual acid in the leaching solution is about 30-40 g/L generally, the pH value of the pre-reduction solution is adjusted to be 2.0, and pre-reduced solution (first filtrate) and pre-reduced slag (first filter residue) are obtained through solid-liquid separation; the reduction and neutralization reaction temperature is 65 ℃ and the time is 65min.
Step 2, noble metal substitution
Adding a certain amount of solution obtained after platinum-palladium flotation concentrate enhanced leaching pre-reduction, namely first filtrate, into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 85 ℃, then starting to add reducing agent active copper powder into the beaker or the reactor, adding the amount (wet weight) of the active copper powder into the solution according to 16g/L, starting timing, reacting for a preset time of 65min when the preset potential value is 400mv, stopping stirring, stopping reaction, taking out ore pulp for filtering and washing when the temperature is reduced to about 65 ℃, drying a solid sample, then carrying out division sampling analysis, taking out a sample after measuring the volume of the solution, and carrying out sampling analysis on the contents of base metals and precious metals.
The technological parameters are as follows: 40g of activated copper powder (wet weight) was added, the displacement time was 65min, and the end point pH was 2.8.
Table 8 results of displacement of noble metals by activated copper powder
Step 3, replacing copper with iron powder
Replacing copper ions in the solution with iron powder, taking a certain amount of precious metal replaced solution, adding the precious metal replaced solution into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 85 ℃, then starting to add the iron powder into the beaker or the reactor according to 16g/L of the solution, starting timing, reacting for 120min when the preset potential value is 100mv, stopping stirring, stopping reaction, and taking out ore pulp for filtering and washing when the temperature is reduced to about 65 ℃ to obtain iron replaced liquid (second filtrate) and iron replaced slag (second filter residue). And (4) after drying the solid sample, dividing, sampling and analyzing, and after measuring the volume of the solution, sampling and analyzing the content of the base metal.
The technological parameters are as follows: 32g (dry weight) of reduced iron powder was added thereto, the substitution time was 120min, and the end point pH was 2.5, as shown in Table 9.
TABLE 9 substitution of reduced iron powder for copper results
Step 4, performing staged oxidation hydrolysis to precipitate Fe, al, cr and As
The leaching solution contains a large amount of Fe 2+ 、Al 3+ 、Cr 3+ 、H 3 AsO 3 It must be removed beforehand. Because the iron-aluminum-chromium slag is easy to adsorb and precipitate nickel-cobalt ions when precipitating iron, aluminum and chromium, a two-stage process for precipitating iron, aluminum and chromium is adopted to ensure the recovery rate of nickel and cobalt.
Adding a certain amount of copper-replaced solution, namely second filtrate, into a beaker or a reactor, starting stirring, adjusting the rotation speed, heating to 75 ℃, then starting introducing compressed air, adding 21% calcium carbonate slurry into the beaker or the reactor, starting timing, reacting for 180min, stopping stirring, stopping reaction, and when the temperature is reduced to about 65 ℃, taking out ore pulp, filtering and washing to obtain first-stage iron-removed liquid (third filtrate) and first-stage iron-aluminum slag (third filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the contents of base metals and precious metals.
The technological parameters are as follows: the temperature was 75 ℃ for 180min, and the compressed air flow rate was 130L/h, the results are shown in Table 10.
TABLE 10 first stage oxidation precipitation of Fe, al and Cr results
And (3) performing secondary deep iron removal of aluminum, chromium and arsenic on the liquid after the primary iron removal, wherein the temperature is 90 ℃, the time is 2 hours, a 10% sodium carbonate solution is adopted as a neutralizing precipitator, the end point is pH4.8, the primary iron-removed aluminum, chromium and arsenic slag is discarded slag, and the secondary iron-removed aluminum, chromium and arsenic slag (fourth filter slag) returns to ore pulp for neutralization.
The technological parameters are as follows: the two-stage air oxidation iron-aluminum-chromium deposition adopts a higher pH value of 4.8, a fixed temperature of 90 ℃, a time of 180min and a compressed air flow rate of 130L/h, and the results are shown in Table 11.
TABLE 11 results for two-stage deep iron removal of Al and Cr
Step 5, neutralizing and precipitating nickel and cobalt in sections
Separating nickel and cobalt in the solution by adopting a neutralization hydrolysis precipitation method, precipitating the nickel and cobalt in the solution by using a sodium hydroxide solution, converting the nickel and cobalt into nickel and cobalt hydroxide slag, and simultaneously separating the nickel and cobalt from impurity ions in the solution. The nickel cobalt precipitation is carried out by two-stage precipitation process, namely, one stage is controlled to have lower pH value to obtain nickel cobalt hydroxide products with lower impurities, the other stage is used for precipitating the nickel cobalt and controlling higher pH value to ensure that the nickel cobalt in the solution is completely precipitated, and the second stage of nickel cobalt hydroxide slag is returned to residual acid for neutralization or the first stage is used for precipitating the nickel cobalt.
Adding a certain amount of the solution after the iron, aluminum, chromium and arsenic removal in the second stage into a beaker or a reactor, starting stirring, adjusting the rotating speed, starting to add 5% of sodium hydroxide solution into the beaker or the reactor after the temperature is raised to a set temperature, starting timing, stopping stirring after a preset pH value and a preset reaction time, stopping reaction, taking out ore pulp, filtering and washing, dividing and sampling for analysis after a solid sample is dried, and sampling for analysis after the volume of the solution is measured to analyze the content of metal.
One-stage sodium hydroxide precipitation of nickel cobalt
The technological parameters are as follows: the concentrations of the sodium hydroxide solutions were 5% and at a temperature of 65 ℃, 1.5L of the second-stage deironing aluminum chromium solution (fourth filtrate) was added dropwise to adjust the pH of the solution, the total reaction time was 180min, and the end-point pH of the solution was controlled to 7.5, the results are shown in table 12.
TABLE 12 sodium hydroxide precipitation of nickel cobalt results
Two-stage precipitation of nickel and cobalt
Process parameters; the concentration of the sodium hydroxide solution was 5%, the temperature was 70 ℃, 1.5L of the solution after nickel cobalt precipitation was added dropwise, the pH of the solution was adjusted, a sample of the solution was taken every 30min to analyze the concentration of nickel cobalt and the precipitation rate, the total reaction time was 180min, and the end point pH of the solution was controlled to 8.2, with the results as shown in table 13.
TABLE 13 two stage precipitated Ni-Co results
Step 6, neutralizing and precipitating tail liquid
The solution after nickel and cobalt replacement contains a large amount of metal ions such as magnesium, lime milk can be added to neutralize and precipitate magnesium and manganese, the pH value of the solution is adjusted to 9.0, compressed air is introduced for oxidation, harmful element ions in the solution are removed, and the solution is discharged after reaching the standard.
Taking 2.0L of the solution (namely tail liquid) after the secondary nickel-cobalt precipitation, heating to 50 ℃, introducing compressed air with the flow rate of 130L/h, adjusting the pH of the solution to 9.0 by using 20% lime milk (the pH of discharged wastewater is 6-9), reacting for 2.5h, and inspecting the pH of the tail liquid at the neutralization end point and the components of the tail slag. The results are shown in Table 14.
TABLE 14 results of tail liquid neutralization
Example 3
A treatment method of a high-chromium high-magnesium platinum group metal ore dressing concentrate strengthening leaching solution comprises the following steps:
the leaching solution comprises the following components: au 0.003g/L, pd 0.0047.0047 g/L, pt 0.00095g/L, rh 0.0014.0014 g/L, ir 0.0016g/L, ni 2.02.02 g/L, cu 6.37.37 g/L, fe 9.62g/L, co 0.058.058 g/L, as 0.0024.0024 g/L, cr 1.16g/L, mg 6.26.26 g/L, al 2.61.61 g/L.
Step 1, pre-reducing solution and neutralizing residual acid in solution
Adding a reducing agent sodium sulfite into the platinum group metal ore dressing concentrate enhanced leaching solution to carry out pre-reduction reaction, wherein the adding amount of the sodium sulfite is 78.8g/L solution, namely 78.8kg/m 3 Solution of Fe in solution 3+ 、Cr 6+ Separately reduced to Fe 2+ 、Cr 3+ Then, sodium carbonate or limestone is adopted for neutralization, the content of residual acid in the leaching solution is about 30-40 g/L generally, the pH value of the pre-reduction solution is adjusted to be 1.7, and pre-reduced solution (first filtrate) and pre-reduced slag (first filter residue) are obtained through solid-liquid separation; the reduction and neutralization reaction temperature is 63 ℃ and the time is 63min.
Step 2, noble metal replacement
Adding a certain amount of solution obtained after platinum-palladium flotation concentrate enhanced leaching pre-reduction, namely first filtrate, into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 80 ℃, then starting to add reducing agent active copper powder into the beaker or the reactor, adding the active copper powder according to the addition amount (wet weight) of 12g/L solution, starting timing, reacting for 63min after a preset potential value of 370mv is reached, stopping stirring, stopping reaction, taking out ore pulp for filtering and washing when the temperature is reduced to about 63 ℃, drying a solid sample, then carrying out division sampling analysis, taking out a sample after the volume of the solution is measured, and carrying out sampling analysis on the contents of base metals and precious metals.
The technological parameters are as follows: 35g (wet weight) of activated copper powder was added, and the substitution time was 63min and the end point pH was 2.5.
Table 15 results of noble metal displacement by activated copper powder
Step 3, replacing copper with iron powder
Replacing copper ions in the solution with iron powder, taking a certain amount of precious metal replaced solution, adding the precious metal replaced solution into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 85 ℃, then starting adding the iron powder into the beaker or the reactor, timing, reacting for a preset time of 100min until a preset potential value of 100mv, stopping stirring, stopping reaction, and taking out ore pulp for filtering and washing when the temperature is reduced to about 65 ℃ to obtain iron replaced liquid (second filtrate) and iron replaced slag (second filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the content of the base metal.
The technological parameters are as follows: reduced iron powder (30 g, dry weight) was added thereto, the substitution time was 100min, and the end point pH was 2.5, and the results are shown in Table 16.
TABLE 16 results of copper replacement by reduced iron powder
Step 4, performing staged oxidation hydrolysis to precipitate Fe, al, cr and As
The leach solution contains a large amount of Fe2+, al3+, cr3+, H3AsO3, which must be removed beforehand. Because the iron-aluminum-chromium slag is easy to adsorb and precipitate nickel-cobalt ions when precipitating the iron, aluminum and chromium, in order to ensure the recovery rate of nickel and cobalt, a process of precipitating the iron, aluminum and chromium by two-stage oxidation is adopted.
Adding a certain amount of copper-replaced solution, namely the second filtrate, into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to 73 ℃, then starting introducing compressed air, adding 20% calcium carbonate slurry into the beaker or the reactor, starting timing, removing iron, aluminum, chromium and arsenic by first-stage oxidation to a preset pH value of 3.6, reacting for 150min, stopping stirring, stopping reaction, and when the temperature is reduced to about 63 ℃, taking out ore pulp, filtering and washing to obtain first-stage iron-removed liquid (third filtrate) and first-stage iron and aluminum slag (third filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the contents of base metals and precious metals.
The technological parameters are as follows: the temperature was 73 ℃ for 150min, and the compressed air flow rate was 120L/h, the results are shown in Table 17.
TABLE 17 first stage oxidation deposition of Fe, al and Cr results
And (3) performing secondary deep iron removal of aluminum, chromium and arsenic on the solution after the primary iron removal, wherein the temperature is 80 ℃, the time is 2.5 hours, a neutralizing and precipitating agent adopts a 10% sodium carbonate solution, the end point is pH 4.6-4.8, the primary iron removal aluminum, chromium and arsenic slag is discarded slag, and the secondary iron removal aluminum, chromium and arsenic slag (fourth filter residue) returns to the ore pulp for neutralization.
The technological parameters are as follows: the two-stage air oxidation iron-aluminum-chromium deposition adopts a higher pH value of 4.6, a fixed temperature of 80 ℃, a time of 150min and a compressed air flow rate of 130L/h, and the results are shown in Table 18.
TABLE 18 two-stage results for deep iron removal of Al and Cr
Step 5, segmented neutralization and precipitation nickel cobalt test
Separating nickel and cobalt in the solution by adopting a neutralization hydrolysis precipitation method, precipitating the nickel and cobalt in the solution by using a sodium hydroxide solution, converting the nickel and cobalt into nickel and cobalt hydroxide slag, and simultaneously separating the nickel and cobalt from impurity ions in the solution. The nickel cobalt precipitation is carried out by two-stage precipitation process, namely, one stage is controlled to have lower pH value to obtain nickel cobalt hydroxide products with lower impurities, the other stage is used for precipitating the nickel cobalt and controlling higher pH value to ensure that the nickel cobalt in the solution is completely precipitated, and the second stage of nickel cobalt hydroxide slag is returned to residual acid for neutralization or the first stage is used for precipitating the nickel cobalt.
Adding a certain amount of the solution after the iron, aluminum, chromium and arsenic removal in the second stage into a beaker or a reactor, starting stirring, adjusting the rotating speed, starting to add 5% of sodium hydroxide solution into the beaker or the reactor after the temperature is raised to a set temperature, starting timing, stopping stirring after a preset pH value and a preset reaction time, stopping reaction, taking out ore pulp, filtering and washing, dividing and sampling for analysis after a solid sample is dried, and sampling for analysis after the volume of the solution is measured to analyze the content of metal.
One-stage sodium hydroxide precipitation of nickel cobalt
The technological parameters are as follows: the concentrations of the sodium hydroxide solutions were 5% and at a temperature of 62 ℃ respectively, 1.5L of the second-stage deironing aluminum chromium solution (fourth filtrate) was added dropwise thereto to adjust the pH of the solution, the total reaction time was 120min, and the end-point pH of the solution was controlled to 7.3, the results are shown in Table 19.
TABLE 19 sodium hydroxide precipitation of nickel cobalt results
Two-stage sodium hydroxide precipitation of nickel cobalt
Process parameters; the concentration of the sodium hydroxide solution was 5%, the temperature was 90 ℃, 1.5L of the nickel cobalt solution was precipitated for one stage, the sodium hydroxide solution was added dropwise, the pH of the solution was adjusted, a sample of the solution was taken every 30min to analyze the nickel cobalt concentration and the precipitation rate, the total reaction time was 140min, and the end point pH of the solution was controlled to 8.1, with the results as in table 20.
TABLE 20 two stage precipitated Ni-Co results
Step 6, neutralizing and precipitating tail liquid
The solution after nickel-cobalt replacement contains a large amount of metal ions such as magnesium, lime milk can be added to neutralize and precipitate magnesium and manganese, the pH value of the solution is adjusted to 8.5-9, compressed air is introduced for oxidation, harmful element ions in the solution are removed, and the solution is discharged after reaching the standard.
Taking 2.0L of the solution (namely tail liquid) after the secondary nickel-cobalt precipitation, heating to 48 ℃, introducing compressed air with the flow rate of 120L/h, adjusting the pH of the solution to 8.6 (the pH of discharged wastewater is 6-9) by using 20% lime milk, reacting for 2.3h, and inspecting the pH of the tail liquid at the neutralization end point and the components of the tail slag. The results are shown in Table 21.
TABLE 21 results of tail liquid neutralization
Example 4
A treatment method of a high-chromium high-magnesium platinum group metal ore dressing concentrate strengthening leaching solution comprises the following steps:
the leaching solution comprises the following components: au 0.004g/L, pd 0.0048.0048 g/L, pt 0.00094.00094 g/L, rh 0.0013.0013 g/L, ir 0.0016.0016 g/L, ni 2.02g/L, cu 6.38g/L, fe 9.63.63 g/L, co 0.058g/L, as 0.0025g/L, cr 1.18.18 g/L, mg 6.30.30 g/L, al 2.61.61 g/L.
Step 1, pre-reducing solution and neutralizing residual acid in solution
Adding sodium sulfite as a reducing agent into the strengthening leachate of the platinum group metal ore dressing concentrate to carry out pre-reduction reaction, wherein the adding amount of the sodium sulfite is 78.78g/L solution, namely 78.78kg/m 3 Reducing Fe3+ and Cr6+ in the solution into Fe2+ and Cr3+ respectively, then neutralizing by using sodium carbonate or limestone, wherein the content of residual acid in the leaching solution is about 30-40 g/L generally, adjusting the pH value of the pre-reduction solution to be 1.8, and performing solid-liquid separation to obtain pre-reduced liquid (first filtrate) and pre-reduced slag (first filter residue); the reduction reaction temperature is 75 ℃, the neutralization reaction temperature is 62 ℃, and the time is 62min.
Step 2, noble metal replacement
Adding a certain amount of solution obtained after the platinum-palladium flotation concentrate is subjected to enhanced leaching and prereduction, namely first filtrate, into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 78 ℃, then starting to add reducing agent active copper powder into the beaker or the reactor, adding the active copper powder according to 13g/L of the solution, starting timing, reacting for 62min after a preset potential value of 380mv is reached, stopping stirring, stopping reaction, taking ore pulp out when the temperature is reduced to about 62 ℃, filtering and washing, drying a solid sample, then carrying out division sampling analysis, taking out a sample after the volume of the solution is measured, and carrying out sampling analysis on the contents of base metals and precious metals.
The technological parameters are as follows: 33g (wet weight) of activated copper powder was added, the displacement time was 62min, and the end point pH was 2.5.
Table 22 results of noble metal displacement by activated copper powder
Step 3, replacing copper by iron powder
Replacing copper ions in the solution with iron powder, taking a certain amount of precious metal replaced solution, adding the precious metal replaced solution into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 83 ℃, then starting adding the iron powder into the beaker or the reactor, timing, reacting for 115min after a preset potential value of 10mv, stopping stirring, stopping reaction, and taking out ore pulp for filtering and washing when the temperature is reduced to about 63 ℃ to obtain iron replaced liquid (second filtrate) and iron replaced slag (second filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the content of the base metal.
The technological parameters are as follows: 32g (dry weight) of reduced iron powder was added thereto, the substitution time was 110min, and the end point pH was 2.5, the results are shown in Table 23.
TABLE 23 substitution of reduced iron powder for copper results
Step 4, performing staged oxidation hydrolysis to precipitate Fe, al, cr and As
The leach solution contains a large amount of Fe2+, al3+, cr3+, H3AsO3, which must be removed beforehand. Because the iron-aluminum-chromium slag is easy to adsorb and precipitate nickel-cobalt ions when precipitating the iron, aluminum and chromium, in order to ensure the recovery rate of nickel and cobalt, a process of precipitating the iron, aluminum and chromium by two-stage oxidation is adopted.
Adding a certain amount of the solution after copper replacement, namely the second filtrate, into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to the set temperature of 74 ℃, then starting introducing compressed air, adding 20% calcium carbonate slurry into the beaker or the reactor, starting timing, removing iron, aluminum, chromium and arsenic by first-stage oxidation to the preset pH value of 3.7, stopping stirring after reacting for 145min for preset time, stopping reaction, and taking out ore pulp for filtering and washing when the temperature is reduced to about 62 ℃ to obtain first-stage iron-removed liquid (third filtrate) and first-stage iron and aluminum slag (third filter residue). And (4) carrying out division sampling analysis after drying the solid sample, and carrying out sampling analysis after measuring the volume of the solution to analyze the contents of base metals and precious metals.
The technological parameters are as follows: the temperature was 74 ℃, the time was 2.4h, and the compressed air flow rate was 118L/h, the results are shown in Table 24.
TABLE 24 first stage oxidation precipitation of Fe, al and Cr results
And (3) performing secondary deep iron removal of aluminum, chromium and arsenic on the solution after the primary iron removal at the temperature of 78 ℃ for 2.3h, wherein a 10% sodium carbonate solution is adopted as a neutralization precipitator, the end point is pH4.7, the primary iron removal aluminum, chromium and arsenic removal slag is discarded slag, and the secondary iron removal aluminum, arsenic removal slag (fourth filter residue) returns to ore pulp for neutralization.
The technological parameters are as follows: the two-stage air oxidation iron-aluminum-chromium deposition adopts a higher pH value of 4.7, a fixed temperature of 78 ℃, a time of 2.3h and a compressed air flow rate of 128L/h, and the results are shown in Table 25.
TABLE 25 two-stage results of deep iron removal of AlCr
Step 5, segmented neutralization and precipitation nickel cobalt test
Separating nickel and cobalt in the solution by adopting a neutralization hydrolysis precipitation method, precipitating the nickel and cobalt in the solution by using a sodium hydroxide solution, converting the nickel and cobalt into nickel and cobalt hydroxide slag, and simultaneously separating the nickel and cobalt from impurity ions in the solution. The nickel cobalt precipitation is carried out by two-stage precipitation process, namely, one stage is controlled to have lower pH value to obtain nickel cobalt hydroxide products with lower impurities, the other stage is used for precipitating the nickel cobalt and controlling higher pH value to ensure that the nickel cobalt in the solution is completely precipitated, and the second stage of nickel cobalt hydroxide slag is returned to residual acid for neutralization or the first stage is used for precipitating the nickel cobalt.
Adding a certain amount of the solution after the iron, aluminum, chromium and arsenic removal in the second stage into a beaker or a reactor, starting stirring, adjusting the rotating speed, heating to a set temperature of 62 ℃, adding a 5% sodium hydroxide solution into the beaker or the reactor, starting timing, stopping stirring after a preset pH value and a preset reaction time, stopping reaction, taking out ore pulp, filtering and washing, dividing and sampling a solid sample after drying, and sampling and analyzing the volume of the solution to analyze the content of metal.
One-stage sodium hydroxide precipitation of nickel cobalt
The technological parameters are as follows: the concentrations of the sodium hydroxide solutions were 5% and at a temperature of 62 ℃ respectively, 1.5L of the second-stage deironing aluminum chromium solution (fourth filtrate) was added dropwise thereto to adjust the pH of the solution, the total reaction time was 128min, and the end-point pH of the solution was controlled to 7.2, and the results are shown in Table 26.
TABLE 26 sodium hydroxide precipitation of nickel cobalt results
Two-stage precipitation of nickel and cobalt
Process parameters; the concentration of the sodium hydroxide solution was 5%, the temperature was 72 ℃, 1.5L of the nickel cobalt solution was precipitated for the first time, the sodium hydroxide solution was added dropwise, the pH of the solution was adjusted, samples of the solution were taken every 30min to analyze the nickel cobalt concentration and the precipitation rate, the total reaction time was 145min, and the end-point pH of the solution was controlled to 8.0, respectively, with the results as shown in table 27.
TABLE 27 two stage precipitated Ni-Co results
Step 6, neutralizing and precipitating tail liquid
The solution after nickel and cobalt replacement contains a large amount of metal ions such as magnesium, lime milk can be added to neutralize and precipitate magnesium and manganese, the pH value of the solution is adjusted to 8.5-9, compressed air is introduced for oxidation, harmful element ions in the solution are removed, and the solution is discharged after reaching the standard.
Taking 2.0L of the solution after the second-stage nickel-cobalt precipitation, heating to 47 ℃, introducing compressed air with the flow rate of 100L/h, adjusting the pH of the solution to 8.7 by using 20% lime milk (the pH of discharged wastewater is 6-9), reacting for 2.2h, and inspecting the pH of the tail liquid at the neutralization end point and the tailings components. The results are shown in Table 28.
TABLE 28 Tail solution neutralization results
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (7)
1. A method for treating a platinum group metal beneficiation concentrate strengthened leaching solution, which is characterized by comprising the following steps:
(1) Adding a reducing agent sodium sulfite into the platinum group metal ore dressing concentrate enhanced leaching solution to carry out pre-reduction reaction, and adding Fe in the solution 3+ 、Cr 6+ Separately reduced to Fe 2+ 、Cr 3+ Then, sodium carbonate or limestone is adopted to neutralize residual acid, the pH value of the pre-reduction solution is adjusted to be 1.5-2.0, and a first filtrate and a first filter residue are obtained through solid-liquid separation; the addition amount of the sodium sulfite is 78.7-78.9 g/L solution, the temperature of the pre-reduction reaction is 60-75 ℃, and the time of the pre-reduction reaction is 60-65 min; adopting sodium carbonate or limestone to neutralize residual acid: the reaction temperature is 60-65 ℃, and the reaction time is 60-65 min;
(2) Replacing precious metals with active copper powder, adding the active copper powder into the first filtrate obtained in the step (1) to replace the precious metals, and obtaining replaced liquid and replaced slag; the reaction process for replacing the noble metal by the copper powder comprises the following steps: heating the first filtrate obtained in the step (1) to 75-85 ℃, adding active copper powder, stirring, controlling the addition amount of the active copper powder to be 12-16 g/L solution, controlling the potential value to be 350-400 mv, controlling the end point pH to be 2.5-2.8, reacting for 60-65 min, stopping stirring, and performing solid-liquid separation when the temperature is reduced to 60-65 ℃;
(3) Adding iron powder into the displaced liquid obtained in the step (2) for copper displacement reaction, and performing solid-liquid separation to obtain a second filtrate and a second filter residue; the process of replacing copper powder by iron powder is as follows: heating the displaced liquid obtained in the step (2) to 75-85 ℃, adding iron powder, wherein the adding amount of the iron powder is 10.4-16 g/L solution, controlling the potential value to be 0-100 mv, reacting for 60-120 min, stopping stirring, and performing solid-liquid separation when the temperature is reduced to 60-65 ℃;
(4) Performing a first-stage oxidation precipitation iron-aluminum-chromium-arsenic reaction on the second filtrate obtained in the step (3), performing solid-liquid separation, performing a second-stage oxidation precipitation iron-aluminum-chromium-arsenic reaction, performing a two-stage neutralization precipitation nickel-cobalt reaction, and obtaining a tail liquid and a tail slag;
(5) And (4) carrying out a manganese neutralization precipitation reaction on the tail liquid obtained in the step (4), and finally carrying out solid-liquid separation to obtain a neutralization tail liquid and neutralization tailings.
2. The method of claim 1, wherein the leachate composition comprises: au 0.003-0.004 g/L, pd.0045-0.0050 g/L, pt 0.00092-0.00098 g/L, rh 0.0012-0.0015 g/L, ir 0.0015-0.0017 g/L, ni.02-2.03 g/L, cu.36-6.39 g/L, fe.62-9.63 g/L, co 0.057-0.059 g/L, as 0.0021-0.0026 g/64 zxft 3264.13-1.20 g/82 zxft 3282.22-6.32 g/34 zxft 3234.60-3434.60-3463 g/L.
3. The method of claim 1 wherein said activated copper powder is produced by adding zinc powder to a copper sulfate solution for displacement.
4. The method according to claim 1, wherein the step (4) of the one-stage oxidation precipitation reaction process is as follows: heating the second filtrate obtained in the step (3) to 70-75 ℃, introducing compressed air with the flow rate of 100-130 l/h, adding 20-21% calcium carbonate slurry, controlling the pH value to be 3.5-3.8, reacting for 100-180 min, stopping stirring, and performing solid-liquid separation when the temperature is reduced to 60-65 ℃ to obtain third filtrate and third filter residue; and the second-stage oxidation precipitation is to heat the third filtrate to 70-90 ℃, add a sodium carbonate solution with the concentration of 10%, control the reaction time for 2-2.5 h, control the end point pH to 4.6-4.8, and obtain a fourth filtrate and a fourth filter residue through solid-liquid separation.
5. The method of claim 4, wherein the neutralization and precipitation nickel cobalt reaction process in the two stages of step (4) is: the first-stage nickel-cobalt precipitation is to heat the fourth filtrate to 60-65 ℃, dropwise add a sodium hydroxide solution, adjust the end point pH of the solution to 7.0-7.5, and perform the total reaction for 120-180 min; the second-stage nickel and cobalt precipitation is to heat the first-stage nickel and cobalt precipitation liquid to 70-90 ℃, dropwise add sodium hydroxide solution, control the end point pH of the solution to 8.0-8.2, control the total reaction time to 120-180 min, and obtain tail liquid and tailings through solid-liquid separation.
6. The method of claim 5, wherein the sodium hydroxide solution is at a concentration of 5%.
7. The method according to claim 1, wherein in the step (5), the tail liquid obtained in the step (4) is heated to 45-50 ℃, compressed air is introduced, the flow rate of the compressed air is 100-130L/h, lime milk with the concentration of 20% is added, the pH value of the tail liquid is adjusted to 8.5-9, the reaction time is 2-2.5 h, and finally, the neutralized tail liquid and the neutralized tail slag are obtained through solid-liquid separation.
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