CN116356148B - Pretreatment method for enriching noble metal by using carbonylation alloy - Google Patents
Pretreatment method for enriching noble metal by using carbonylation alloy Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 32
- 230000006315 carbonylation Effects 0.000 title claims abstract description 30
- 238000002203 pretreatment Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 77
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000002386 leaching Methods 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002893 slag Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 238000005086 pumping Methods 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 20
- 239000010949 copper Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 platinum group metals Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012772 sequence design Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- C22B7/00—Working 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
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- 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
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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
-
- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- 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
- C22B7/00—Working 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
- C22B7/04—Working-up slag
-
- 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
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Abstract
The invention discloses a pretreatment method for enriching noble metals by using a carbonyl alloy, which comprises the following steps: s1, grinding and screening the carbonylation slag containing rare and noble metals to obtain a 300-325 mesh carbonylation alloy; s2, adding the carbonyl alloy obtained in the step S1 into hydrochloric acid to perform presoaking nickel removal, wherein the concentration of hydrochloric acid solution is more than 2.5mol/L, the liquid-solid ratio is 3-4:1, the reaction temperature is controlled to be more than 80 ℃, the reaction time is more than 2 hours, and then, filter pressing is performed to obtain hydrochloric acid leaching residues and hydrochloric acid leaching liquid; s3, adding sulfuric acid into the hydrochloric acid leaching slag obtained in the step S2 for pulping, wherein the liquid-solid ratio is 7-8:1, the sulfuric acid concentration is more than 1mol/L, heating to more than 80 ℃, pumping into a pressurizing kettle, opening an oxygen valve, introducing oxygen, starting timing after the pressure in the kettle is increased to more than 0.8MPa, reacting for more than 3.5 hours, and performing filter pressing after the reaction is finished to obtain the noble metal enriched slag.
Description
Technical Field
The invention relates to the technical field of metal separation and purification, in particular to a pretreatment method for enriching noble metals by using carbonyl alloy.
Background
At present, a nickel carbonyl production line with the scale of 10kt/a is formed, and the main raw material for carbonylation synthesis is water quenched alloy produced by high sulfonium grinding and floating. The water quenched alloy contains about 60% nickel and about 20% copper, under the condition of carbonylation reaction, the nickel is separated to produce gaseous carbonyl compound, and is used for preparing high-purity nickel, the noble metal in the alloy does not undergo carbonylation reaction, and almost all noble metal is enriched in the carbonylation tailings, namely the solid residue after the nickel is extracted by carbonylation, namely the carbonylation alloy, the copper content in the carbonylation alloy is 60-65%, the sulfur content is 16-18%, and the nickel content is about 8-15%. In the traditional process of treatment and extraction, the carbonylated alloy is directly subjected to one-stage pressure leaching, the nickel content in the leaching solution is 30-50g/L, the copper content is 80-90g/L, the specific process is shown in figure 2, and the carbonylated alloy containing platinum group metal is added with H after being screened 2 SO 4 Pulping in the solution, oxidizing the pulped ore pulp with base metal sulfide in high temperature and high pressure and oxidizing atmosphere, and introducing the pulped ore pulp into the solution in the form of sulfate. The noble metals and platinum group metals are still present in a solid phase because of their relatively high oxidation-reduction potential and substantially no oxidation reaction. Filtering after the leaching reaction is finished to realize solid-liquid separation, washing filter residues with pure water to be colorless, taking the filter residues as raw materials for extracting noble metals and platinum group metals, and taking filtrate as raw materials for producing copper salt and nickel salt. Although the method can leach nickel and copper better, the enrichment effect of the produced noble metal concentrate is better, but the method has the problem that nickel and copper cannot be separated and recovered in the leaching process, the leaching solution has high nickel content, and sulfur is produced by the copper salt processThe copper sulfate has great influence on the nickel extraction process in the copper acid process, thus causing the problems of incomplete nickel extraction, influence on the quality of copper sulfate products, rising of production cost and the like. Therefore, a process for separating and recovering nickel and copper and effectively enriching platinum group metals needs to be developed.
Disclosure of Invention
Aiming at the technical problems, the invention provides a pretreatment method for enriching noble metals by using carbonyl alloy.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a pretreatment method for enriching noble metals by using a carbonyl alloy, which comprises the following steps:
s1, grinding and screening the carbonylation slag containing rare and noble metals to obtain a 300-325 mesh carbonylation alloy;
s2, adding the carbonyl alloy obtained in the step S1 into hydrochloric acid to perform presoaking nickel removal, wherein the concentration of hydrochloric acid solution is more than 2.5mol/L, the liquid-solid ratio is 3-4:1, the reaction temperature is controlled to be more than 80 ℃, the reaction time is more than 2 hours, and then, filter pressing is performed to obtain hydrochloric acid leaching residues and hydrochloric acid leaching liquid;
s3, adding sulfuric acid into the hydrochloric acid leaching slag obtained in the step S2 for pulping, wherein the liquid-solid ratio is 7-8:1, the sulfuric acid concentration is more than 1mol/L, heating to more than 80 ℃, pumping into a pressurizing kettle, opening an oxygen valve, introducing oxygen, starting timing after the pressure in the kettle is increased to more than 0.8MPa, reacting for more than 3.5 hours, and performing filter pressing after the reaction is finished to obtain noble metal enrichment slag and pressurized leaching liquid, wherein the noble metal enrichment slag is used as a raw material for extracting platinum noble metals, and the pressurized leaching liquid is used for producing copper sulfate by copper salt.
Wherein, in the step S2, the concentration of the hydrochloric acid solution is 2.5-3.5mol/L, the reaction temperature is controlled to be 80-90 ℃ and the reaction time is controlled to be 2-3h.
In the step S3, the concentration of sulfuric acid is 1-2.5mol/L, after the temperature is raised to 80-90 ℃, the sulfuric acid is pumped into an autoclave, an oxygen valve is opened, oxygen is introduced, the pressure in the autoclave is increased to 0.8-1.0MPa, and then timing is started, and the reaction is carried out for 3.5-6.5 hours.
The beneficial effects of the invention are as follows: the invention firstly grinds and screens the carbonylation slag containing rare noble metals, reduces the granularity of the carbonylation alloy to be capable of fully reacting with subsequent process liquid, improves the reaction efficiency, then carries out process sequence design according to different leaching process requirements of valuable metal nickel and copper, namely, the carbonylation alloy obtained through grinding and screening is added into hydrochloric acid to carry out presoaked nickel removal, then filter-pressing to obtain hydrochloric acid leaching slag and hydrochloric acid leaching liquid, then the obtained hydrochloric acid leaching slag is added into sulfuric acid to carry out slurrying, then pumping into a pressurized kettle, and the pressure in the kettle is increased to more than 0.8MPa, finally, filter-pressing is carried out to obtain noble metal enrichment slag and pressurized leaching liquid, the noble metal enrichment slag is used as a raw material for extracting platinum noble metals, and the pressurized leaching liquid is used for producing copper sulfate, so that the valuable metal nickel and copper in the carbonylation alloy can be selectively separated, the produced leaching liquid containing rich copper and nickel metal can be used as a raw material for extracting nickel and copper, and the platinum group metal platinum group metal is exchanged on a production line after the enrichment of the leaching slag. The invention reduces the complexity of platinum group metal intermediate materials, simultaneously comprehensively recovers valuable impurity metals such as copper, nickel and the like, and improves the resource utilization rate. The process disclosed by the invention is wide in material adaptability and simple to operate, and can be used for efficiently separating copper and nickel from various platinum group metal solutions containing copper and nickel. The method greatly improves the resource utilization rate of valuable elements such as copper and nickel in the refining process of the platinum group metal, and simultaneously effectively eliminates the influence of impurity metals such as copper and nickel on the separation and refining process of the platinum group metal. The invention can lead the nickel leaching rate in the carbonylation alloy to reach more than 98 percent, lead the copper leaching rate to reach more than 88 percent, lead the slag rate to be 15-20 percent, lead the noble metal to be enriched by more than 5 times, and be beneficial to the refining and purification of the follow-up platinum group metals.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is a prior art process flow diagram.
Detailed Description
The present invention will be further described in detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Example 1
As shown in fig. 1, a pretreatment method for enriching noble metals from a carbonyl alloy is characterized by comprising the following steps:
s1, grinding and screening the carbonylation slag containing the rare and noble metals by using a Raymond mill to obtain a carbonylation alloy with the granularity of 325 meshes, wherein the content of the carbonylation slag containing the rare and noble metals is shown in a table 1;
s2, adding the carbonyl alloy into hydrochloric acid for pre-soaking and nickel removal, wherein the concentration of a hydrochloric acid solution is 3.5mol/L, the liquid-solid ratio is 4:1, the reaction temperature is controlled to be 90 ℃, the reaction time is 3 hours, then, filter pressing is carried out to obtain hydrochloric acid leaching residues and hydrochloric acid leaching liquid, the hydrochloric acid leaching liquid is subjected to nickel factory production to obtain metallic nickel, and the hydrochloric acid leaching residues are treated in the step S3;
s3, adding sulfuric acid into the hydrochloric acid leaching residue obtained in the step S2 for pulping, wherein the liquid-solid ratio is 8:1, the sulfuric acid concentration is 2.5mol/L, heating to 90 ℃, pumping into an autoclave, opening an oxygen valve, introducing oxygen, increasing the pressure in the autoclave to 1.0MPa, starting timing, and reacting for 6.5 hours. After the reaction is finished, filter pressing is carried out to obtain noble metal enriched slag and pressurized leaching liquid; the noble metal enriched slag is used as raw material for extracting platinum group noble metal, the copper salt is added to the pressurized leaching solution to produce copper sulfate, the removal rate of nickel copper is 99.89 percent, 90.23 percent, the slag rate is 15.16 percent, and the noble metal is enriched by more than 5 times. The specific results are shown in Table 2:
。
example 2
As shown in fig. 1, a pretreatment method for enriching noble metals from a carbonyl alloy is characterized by comprising the following steps:
s1, grinding and screening the carbonylation slag containing the rare and noble metals by using a Raymond mill to obtain a carbonylation alloy with 300 meshes, wherein the content of the carbonylation slag containing the rare and noble metals is shown in a table 3;
s2, adding the carbonyl alloy into hydrochloric acid for pre-soaking and nickel removal, wherein the concentration of a hydrochloric acid solution is 2.5mol/L, the liquid-solid ratio is 3:1, the reaction temperature is controlled to be 80 ℃, the reaction time is 2 hours, then, filter pressing is carried out to obtain hydrochloric acid leaching residues and hydrochloric acid leaching liquid, the hydrochloric acid leaching liquid is subjected to nickel factory production to obtain metallic nickel, and the hydrochloric acid leaching residues are treated in the step S3;
s3, adding sulfuric acid into the hydrochloric acid leaching residue obtained in the step S2 for pulping, wherein the liquid-solid ratio is 7:1, the sulfuric acid concentration is 1mol/L, heating to 80 ℃, pumping into an autoclave, opening an oxygen valve, introducing oxygen, increasing the pressure in the autoclave to 0.8MPa, starting timing, and reacting for 3.5 hours. After the reaction is finished, filter pressing is carried out to obtain noble metal enriched slag and pressurized leaching liquid; the noble metal enriched slag is used as raw material for extracting platinum group noble metal, the copper salt is added to the pressurized leaching solution to produce copper sulfate, the removal rate of nickel copper is 99.68 percent and 88.24 percent respectively, the slag rate is 20.01 percent, and the noble metal is enriched by more than 5 times. The specific results are shown in Table 4:
。
as shown in fig. 2, in order to further embody the technical effects of the present invention, the applicant has given an example of application of the direct pressure leaching process for the original carbonylation alloy:
the composition of the carbonylation alloy is shown in table 5, and the granularity of the obtained carbonylation alloy is 200 meshes through grinding and screening by using a dry ball mill; adding 5L of sulfuric acid with the concentration of 1.23mol/L into a reaction kettle, heating the sulfuric acid solution to 50 ℃, adding the carbonylation alloy into the reaction kettle, and controlling the liquid-solid ratio to be 8:1, oxygen is blown into the solution, the partial pressure of the oxygen is kept at 0.4Mpa, the temperature of the reaction solution starts to rise, the leaching temperature is stabilized at 170 ℃, and the reaction time lasts for 6 hours. After the reaction is finished, the solution is cooled to below 50 ℃ and filtered, filter residues are washed by pure water, and the washing is stopped when the color of the washing liquid is consistent with that of the pure water. And (5) transferring the filter residues to corresponding procedures for drying, and continuously extracting the platinum group metals and the noble metals. The nickel-copper removal rates were 93.33%,83.68% and the slag rate was 17.33%, respectively. The specific results are shown in table 6,
comparing this example with examples 1 and 2 of the present invention, it can be seen that the original direct pressure leaching process does not perform the previous separation of copper and nickel, which results in the mutual influence of copper and nickel in the separation process, and the leaching effect is not particularly ideal, and meanwhile, nickel copper is enriched in the pressure liquid to a certain extent, which causes a certain influence on the subsequent copper sulfate preparation process. The invention adopts the hydrochloric acid presoaking and pressurizing leaching technology, which can well solve the problems, the nickel simple substance and the nickel sulfide in the raw materials are leached out by the hydrochloric acid presoaking to generate nickel chloride, the nickel electrolysis system can be returned to produce electrolytic nickel, the leaching residue after the nickel leaching is subjected to pressurizing leaching, the concentration of nickel ions in the produced pressurizing liquid is reduced to below 1g/L, the separation and recovery of nickel and copper can be well realized, and the noble metal is further enriched.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (3)
1. A pretreatment method for enriching noble metals by using a carbonylation alloy, which is characterized by comprising the following steps:
s1, grinding and screening the carbonylation slag containing rare and noble metals to obtain a 300-325 mesh carbonylation alloy;
s2, adding the carbonyl alloy obtained in the step S1 into hydrochloric acid to perform presoaking nickel removal, wherein the concentration of hydrochloric acid solution is more than 2.5mol/L, the liquid-solid ratio is 3-4:1, the reaction temperature is controlled to be more than 80 ℃, the reaction time is more than 2 hours, and then, filter pressing is performed to obtain hydrochloric acid leaching residues and hydrochloric acid leaching liquid;
s3, adding sulfuric acid into the hydrochloric acid leaching slag obtained in the step S2 for pulping, wherein the liquid-solid ratio is 7-8:1, the sulfuric acid concentration is more than 1mol/L, heating to more than 80 ℃, pumping into a pressurizing kettle, opening an oxygen valve, introducing oxygen, starting timing after the pressure in the kettle is increased to more than 0.8MPa, reacting for more than 3.5 hours, and performing filter pressing after the reaction is finished to obtain noble metal enrichment slag and pressurized leaching liquid, wherein the noble metal enrichment slag is used as a raw material for extracting platinum noble metals, and the pressurized leaching liquid is used for producing copper sulfate by copper salt.
2. The pretreatment method for enriching noble metals of oxo-alloy according to claim 1, wherein in the step S2, the concentration of hydrochloric acid solution is 2.5-3.5mol/L, the reaction temperature is controlled to be 80-90 ℃, and the reaction time is controlled to be 2-3h.
3. The pretreatment method for enriching noble metals by using the carbonylation alloy according to claim 1, wherein in the step S3, the concentration of sulfuric acid is 1-2.5mol/L, after the temperature is raised to 80-90 ℃, the sulfuric acid is pumped into a pressurized kettle, an oxygen valve is opened, oxygen is introduced, and after the pressure in the kettle is increased to 0.8-1.0MPa, the time counting is started, and the reaction is carried out for 3.5-6.5 hours.
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| CN116356148B true CN116356148B (en) | 2023-08-22 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3967958A (en) * | 1970-07-17 | 1976-07-06 | Ethyl Corporation | Method of winning copper, nickel, and other metals |
| US4828809A (en) * | 1983-10-18 | 1989-05-09 | Falconbridge, Limited | Separation of nickel from copper in autoclave |
| CN100999784A (en) * | 2006-12-29 | 2007-07-18 | 金川集团有限公司 | Process of recovering noble metal from hydroxylating metallurgy slag |
| CN101348864A (en) * | 2008-09-04 | 2009-01-21 | 中国恩菲工程技术有限公司 | Leaching process of copper nickel coarse grain alloy |
| RU2398030C1 (en) * | 2009-05-26 | 2010-08-27 | Учреждение Российской академии наук Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра РАН (ИХТРЭМС КНЦ РАН) | Procedure for processing residues of carbonyl nickel synthesis |
| CN105803203A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Method for multicycle selective leaching of copper, zinc and nickel from sludge in waste water produced by copper smelting |
| CN113957243A (en) * | 2021-10-22 | 2022-01-21 | 金川镍钴研究设计院有限责任公司 | Method for realizing respective open circuit of nickel, copper and iron in high-nickel matte and enriching precious metals |
-
2023
- 2023-05-31 CN CN202310631799.3A patent/CN116356148B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3967958A (en) * | 1970-07-17 | 1976-07-06 | Ethyl Corporation | Method of winning copper, nickel, and other metals |
| US4828809A (en) * | 1983-10-18 | 1989-05-09 | Falconbridge, Limited | Separation of nickel from copper in autoclave |
| CN100999784A (en) * | 2006-12-29 | 2007-07-18 | 金川集团有限公司 | Process of recovering noble metal from hydroxylating metallurgy slag |
| CN101348864A (en) * | 2008-09-04 | 2009-01-21 | 中国恩菲工程技术有限公司 | Leaching process of copper nickel coarse grain alloy |
| RU2398030C1 (en) * | 2009-05-26 | 2010-08-27 | Учреждение Российской академии наук Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра РАН (ИХТРЭМС КНЦ РАН) | Procedure for processing residues of carbonyl nickel synthesis |
| CN105803203A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Method for multicycle selective leaching of copper, zinc and nickel from sludge in waste water produced by copper smelting |
| CN113957243A (en) * | 2021-10-22 | 2022-01-21 | 金川镍钴研究设计院有限责任公司 | Method for realizing respective open circuit of nickel, copper and iron in high-nickel matte and enriching precious metals |
Non-Patent Citations (1)
| Title |
|---|
| 贾振海.从含高品位贵金属镍冰铜回收镍、铜和贵金属精矿.中国有色冶金.1977,(第01期),18-21. * |
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