CN111778519A - Method for digesting solid impurity elements of lead, zinc and selenium in nickel electrolytic solution - Google Patents
Method for digesting solid impurity elements of lead, zinc and selenium in nickel electrolytic solution Download PDFInfo
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- CN111778519A CN111778519A CN202010431393.7A CN202010431393A CN111778519A CN 111778519 A CN111778519 A CN 111778519A CN 202010431393 A CN202010431393 A CN 202010431393A CN 111778519 A CN111778519 A CN 111778519A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000007787 solid Substances 0.000 title claims abstract description 77
- 239000012535 impurity Substances 0.000 title claims abstract description 68
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 55
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 44
- 239000011133 lead Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000011669 selenium Substances 0.000 title claims abstract description 30
- 239000011701 zinc Substances 0.000 title claims abstract description 30
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 28
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 4
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 3
- 239000004744 fabric Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000000184 acid digestion Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000029087 digestion Effects 0.000 description 10
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 229910052745 lead Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910017912 NH2OH Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-M hydrogenselenite Chemical compound O[Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229940000207 selenious acid Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- 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 digesting solid impurity elements of lead, zinc and selenium in a nickel electrolytic solution, which comprises the following steps: washing solid impurities in the nickel electrolytic solution with a dilute hydrochloric acid solution and deionized water, and drying; adding an organic weak acid solution containing a reducing agent into solid impurities in the dried nickel electrolytic solution to obtain a mixed material; the reducing agent is one or two of hydrazine hydrate and hydroxylamine hydrochloride, and the organic weak acid is one or more of formic acid, acetic acid and propionic acid; the mixed materials are stirred and react for 0.2h to 1h at the temperature of 50 ℃ to 80 ℃. The method is different from a strong acid digestion method, does not need to be assisted by ultrasonic and does not need acid dispelling operation, has short reaction time, and can be used as a novel method for digesting the solid impurities.
Description
Technical Field
The invention belongs to the technical field of chemical dissolution, and particularly relates to a method for digesting solid impurity elements of lead, zinc and selenium in a nickel electrolytic solution.
Background
Nickel electrolytic solutions are important electrolytes for electrolytic nickel production. The distinction according to the type of anion can be divided into sulfate Systems (SO)4 2-) Chlorine system (Cl)-) And mixed systems, which are electrolytes formulated with a certain sulfate/chloride ratio, are the most common electrolytic systems. The mixed acid system can obtain the standard nickel electrolyte suitable for electrolytic nickel production through sequentially removing iron (Fe), copper (Cu) and cobalt (Co) plasmas. In the impurity removal process, fine solid impurities can penetrate through the filter cloth and enter the solution to influence the quality of the electrolyteFurther influencing the quality of the electrolytic nickel. Therefore, the understanding of the state of the nickel electrolytic solution has important significance for monitoring and controlling the production conditions of electrolytic nickel and ensuring the quality of products. The content of metallic or non-metallic impurity elements such as lead (Pb), zinc (Zn), selenium (Se) and the like in the electrolytic nickel not only affects the quality of the electrolytic nickel, but also affects the performance of the nickel. Through analysis of solid impurity elements in the nickel electrolyte, the quality of the electrolyte and the quality of finished nickel can be indirectly evaluated. The traditional solid digestion method generally adopts strong inorganic acid (such as hydrochloric acid, nitric acid, hydrofluoric acid and aqua regia) to dissolve and digest the solid, the solution after digestion is heated to remove acid, and dilute inorganic acid with certain concentration is used for preparing the solution suitable for the detection of mass spectrometry (GB/T6041-. The traditional solid digestion method has the problems of long time consumption, more equipment investment, complicated steps and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for digesting solid impurity elements of lead, zinc and selenium in a nickel electrolytic solution, which is simple, convenient to operate and short in time consumption.
The invention adopts the following technical scheme:
a method for digesting solid impurity elements of lead, zinc and selenium in a nickel electrolytic solution is characterized by comprising the following steps:
step (1): washing solid impurities in the nickel electrolytic solution with a dilute hydrochloric acid solution and deionized water, and drying;
step (2): adding an organic weak acid solution containing a reducing agent into solid impurities in the dried nickel electrolytic solution to obtain a mixed material; the reducing agent is one or two of hydrazine hydrate and hydroxylamine hydrochloride, and the organic weak acid is one or more of formic acid, acetic acid and propionic acid;
and (3): the mixed materials are stirred and react for 0.2h to 1h at the temperature of 50 ℃ to 80 ℃.
The method for digesting solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution is characterized in that the nickel electrolytic solution is a mixed solution composed of a nickel sulfate solution and a nickel chloride solution.
The method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution is characterized in that the solid impurities in the nickel electrolytic solution are collected by a double-pipe filter, and the aperture of filter cloth of the double-pipe filter is 1 um.
The method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution is characterized in that in the step (1), the solid impurity in the nickel electrolytic solution is washed for three times by a dilute hydrochloric acid solution with the pH value of 4.0-5.5 and deionized water respectively, and then dried, and the drying process conditions are as follows: the drying temperature is 80-100 ℃, and the drying time is 8-10 h.
The method for digesting solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution is characterized in that the concentration of the reducing agent in the step (2) is 0.01M-0.2M; the concentration of the organic weak acid solution is 30-60%.
The invention has the beneficial technical effects that: the invention applies the weak organic acid to the analysis of solid impurity components in the nickel electrolytic solution, not only can shorten the digestion time in the sample detection process, but also has low price of equipment required for digestion, simple operation method and easy grasp by workers. Meanwhile, the organic weak acid is a monodentate ligand, and the application of the organic weak acid is beneficial to improving the solubility of the metal elements (Pb and Zn) to be detected and enhancing the reliability of analysis data. The method is different from a strong acid digestion method, does not need to be assisted by ultrasonic and does not need acid dispelling operation, has short reaction time, and can be used as a novel method for digesting the solid impurities.
Detailed Description
The invention discloses a method for digesting solid impurity elements of lead, zinc and selenium in a nickel electrolytic solution, which comprises the following steps: step (1): and washing solid impurities in the nickel electrolytic solution with a dilute hydrochloric acid solution and deionized water, and drying, wherein the solid-liquid mass ratio of the solid impurities to the dilute hydrochloric acid solution is 0.25-0.5, and the solid-liquid mass ratio of the solid impurities to the deionized water is 0.25-0.5. Preferably, the solid impurities in the nickel electrolytic solution are washed three times with a dilute hydrochloric acid solution with a pH of 4.0-5.5 and deionized water, and then dried, wherein the drying process conditions are as follows: drying for 8-10 h in a forced air drying oven at 80-100 ℃. The nickel electrolytic solution is sulfuric acidNickel solution and nickel chloride solution. The solid impurities in the nickel electrolytic solution are mainly a mixture of nickel, cobalt, manganese and iron. Solid impurities in the nickel electrolytic solution are solid insoluble substances collected by a sleeve pipe precision filter, and the aperture of filter cloth of the sleeve pipe precision filter is 1 um. Step (2): adding an organic weak acid solution containing a reducing agent into solid impurities in the dried nickel electrolytic solution to obtain a mixed material; the reducing agent is hydrazine hydrate (N)2H4·H2O), hydroxylamine hydrochloride (NH)2OH & HCl), organic weak acid is formic acid (HCO)2H) Acetic acid (AcOH), propionic acid (EtCO)2H) One or more of the above; the concentration of the reducing agent is 0.01M-0.2M; the concentration of the organic weak acid solution is 30-60%. And (3): and (3) carrying out magneton stirring reaction on the mixed material at the temperature of 50-80 ℃ for 0.2-1 h, wherein the solution is light brown after the reaction and basically no solid remains. And detecting the contents of lead, zinc and selenium in the solution by ICP-MS according to GB/T6041-2002.
The chemical reaction equation involved in the digestion process of the solid impurities in the nickel electrolytic solution is as follows:
Ni(OH)2+2RCO2H＝Ni(RCO2)2+2H2O
4Fe(OH)3+8RCO2H+N2H4·H2O＝4Fe(RCO2)2+13H2O+N2↑
2Fe(OH)3+2RCO2H+2NH2OH·HCl＝Fe(RCO2)2+FeCl2+8H2O+N2↑
4Co(OH)3+8RCO2H+N2H4·H2O＝4Co(RCO2)2+13H2O+N2↑
2Co(OH)3+2RCO2H+2NH2OH·HCl＝Co(RCO2)2+CoCl2+8H2O+N2↑
MnO2+2RCO2H+N2H4·H2O＝Mn(RCO2)2+3H2O+N2↑
MnO2+2NH2OH·HCl＝MnCl2+4H2O+N2↑
PbCO3+2RCO2H＝Pb(RCO2)2+H2O+CO2↑
Pb3(OH)2(CO3)2+6RCO2H＝3Pb(RCO2)2+4H2O+2CO2↑
2Pb2O3+8RCO2H+N2H4·H2O＝4Pb(RCO2)2+7H2O+N2↑
Pb2O3+2RCO2H+2NH2OH·HCl＝Pb(RCO2)2+5H2O+N2↑+PbCl2
ZnCO3+2RCO2H＝Zn(RCO2)2+H2O+CO2↑
Zn3(OH)2(CO3)2+6RCO2H＝3Zn(RCO2)2+4H2O+2CO2↑
wherein, RCO2H represents weak organic acid, and R is H, Me or Et.
Selenium is mainly selenious acid (SeO)3 2-) And hydrogen selenite (HSeO)3 -) The corresponding acid radical negative ions gradually enter a solution state along with the dissolution of solid dissolved matters in the solid granular slag through form adsorption.
The invention is further illustrated by the following specific examples.
Example 1
The solid impurities in the nickel electrolytic solution obtained by intercepting the sleeve pipe precision filter (provided with 1um filter cloth) are mixed according to the solid-liquid mass ratio of 1: and 3, washing the solid impurities with a dilute hydrochloric acid solution with the pH value of 5.0 and deionized water for three times respectively, and drying the washed solid impurities in a forced air drying oven at 100 ℃ for 10 hours. The composition of the solid impurities is analyzed, and the mass percentage of each element is as follows 1:
TABLE 1 composition of solid impurities in nickel electrolytic solution and mass percent thereof
0.5g of the above dried solid impurity was weighed into a 50mL round-bottomed flask, and 20mL of a solution containing NH was added to the round-bottomed flask2AcOH solution of OH & HCl to obtain mixed material, NH2The concentration of OH HCl was 0.1M and the concentration of AcOH was 40%. And (3) stirring the mixed materials at 70 ℃ for 30min by magneton stirring, and reacting for 30min until no solid remains. Stopping reaction, filtering the reaction solution through an organic filter membrane (aperture 0.2um), transferring the reaction solution into a 25mL volumetric flask, and detecting the contents of lead, zinc and selenium by using ICP-MS after constant volume, wherein specific data are shown in the following table 2:
TABLE 2 Mass percents of Pb, Zn and Se in solid impurities
Example 2
The solid impurities in the nickel electrolytic solution obtained by intercepting the sleeve pipe precision filter (provided with 1um filter cloth) are mixed according to the solid-liquid mass ratio of 1: and 3, washing the solid impurities with a dilute hydrochloric acid solution with the pH value of 5.0 and deionized water for three times respectively, and drying the washed solid impurities in a forced air drying oven at 100 ℃ for 10 hours. The composition of the solid impurities was analyzed and the mass percentages of the elements are shown in table 1.
0.5g of the dried solid impurities of Table 1 above was weighed into a 50mL round-bottomed flask, and 15mL of a solution containing NH was added to the round-bottomed flask2HCO of OH & HCl2H solution to obtain mixed material, NH2OH & HCl concentration 0.02M, HCO2The concentration of H was 60%. And (3) stirring the mixed materials at 80 ℃ for 12min by magneton stirring, and reacting for 12min until no solid remains. Stopping the reaction, filtering the reaction solution with an organic filter membrane (aperture of 0.2um), transferring the reaction solution into a 25mL volumetric flask, measuring the lead, zinc and selenium content by ICP-MS after constant volume, and obtaining specific data shown in the following table3：
TABLE 3 Mass percents of Pb, Zn and Se in solid impurities
Example 3
The solid impurities in the nickel electrolytic solution obtained by intercepting the sleeve pipe precision filter (provided with 1um filter cloth) are mixed according to the solid-liquid mass ratio of 1: and 3, washing the solid impurities with a dilute hydrochloric acid solution with the pH value of 5.0 and deionized water for three times respectively, and drying the washed solid impurities in a forced air drying oven at 100 ℃ for 10 hours. The composition of the solid impurities was analyzed and the mass percentages of the elements are shown in table 1.
0.5g of the dried solid impurities of Table 1 above was weighed into a 50mL round-bottomed flask, and 20mL of a solution containing NH was added to the round-bottomed flask2EtCO of OH HCl2H solution to obtain mixed material, NH2The concentration of OH & HCl is 0.01M, EtCO2The concentration of H was 30%. And (3) stirring the mixed materials at 60 ℃ for 40min by magneton stirring, and reacting for 40min until no solid remains. Stopping reaction, filtering the reaction solution through an organic filter membrane (aperture 0.2um), transferring the reaction solution into a 25mL volumetric flask, and detecting the contents of lead, zinc and selenium by using ICP-MS after constant volume, wherein specific data are shown in the following table 4:
TABLE 4 Mass percents of Pb, Zn and Se in solid impurities
Comparative example 1
The solid impurities in the nickel electrolytic solution obtained by intercepting the sleeve pipe precision filter (provided with 1um filter cloth) are mixed according to the solid-liquid mass ratio of 1: and 3, washing the solid impurities with a dilute hydrochloric acid solution with the pH value of 5.0 and deionized water for three times respectively, and drying the washed solid impurities in a forced air drying oven at 100 ℃ for 10 hours. The composition of the solid impurities was analyzed and the mass percentages of the elements are shown in table 1.
Weighing 0.5g of the dried solid impurities in the table 1, placing the solid impurities in a 50mL glass beaker, adding 10mL of aqua regia into the glass beaker, covering the glass beaker with a watch glass, placing the glass beaker on a digital display heating plate in a fume hood, adjusting the temperature of the heating plate to ensure that the sample solution is in a slightly boiling state, refluxing until the solids are completely dissolved, taking down the watch glass, and removing the redundant aqua regia. When about 0.5mL of aqua regia remains, adding a proper amount of distilled water, transferring the aqua regia into a 25mL volumetric flask, and after the volume is constant, carrying out content determination on the lead, zinc and selenium elements in the solution by means of ICP-MS. Specific data are shown in table 5 below:
TABLE 5 Mass percents of Pb, Zn and Se in solid impurities
The contents of Pb, Zn and Se elements obtained by the traditional aqua regia digestion method in the embodiments 1 to 3 are all equivalent to those obtained by the comparative example 1, the method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution adopted by the invention has equivalent technical effect to that obtained by the aqua regia digestion method, and can replace the aqua regia digestion method to become a new digestion method.
Claims (5)
1. A method for digesting solid impurity elements of lead, zinc and selenium in a nickel electrolytic solution is characterized by comprising the following steps:
step (1): washing solid impurities in the nickel electrolytic solution with a dilute hydrochloric acid solution and deionized water, and drying;
step (2): adding an organic weak acid solution containing a reducing agent into solid impurities in the dried nickel electrolytic solution to obtain a mixed material; the reducing agent is one or two of hydrazine hydrate and hydroxylamine hydrochloride, and the organic weak acid is one or more of formic acid, acetic acid and propionic acid;
and (3): the mixed materials are stirred and react for 0.2h to 1h at the temperature of 50 ℃ to 80 ℃.
2. The method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution according to claim 1, wherein the nickel electrolytic solution is a mixed solution of a nickel sulfate solution and a nickel chloride solution.
3. The method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution according to claim 2, wherein the solid impurity elements in the nickel electrolytic solution are collected by a double-pipe filter, and the aperture of a filter cloth of the double-pipe filter is 1 um.
4. The method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution according to claim 1, wherein in the step (1), the solid impurity in the nickel electrolytic solution is washed three times with a dilute hydrochloric acid solution with a pH of 4.0-5.5 and deionized water, and then dried, and the drying process conditions are as follows: the drying temperature is 80-100 ℃, and the drying time is 8-10 h.
5. The method for digesting the solid impurity elements of lead, zinc and selenium in the nickel electrolytic solution according to claim 1, wherein the concentration of the reducing agent in the step (2) is 0.01M-0.2M; the concentration of the organic weak acid solution is 30-60%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981458A (en) * | 2021-02-04 | 2021-06-18 | 中国科学院兰州化学物理研究所 | Method for regulating and controlling brightness of appearance of nickel button |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151258A (en) * | 1978-03-06 | 1979-04-24 | Amax Inc. | Dissolution of cobaltic hydroxide with organic reductant |
| EP0176100A1 (en) * | 1984-09-26 | 1986-04-02 | Austria Metall Aktiengesellschaft | Hydrometallurgical process for treating electrolytic copper refinery anode slimes |
| US4606764A (en) * | 1983-08-17 | 1986-08-19 | Resource Technology Associates | Method of recovering metals from ores using a formate reducing agent |
| WO1997036013A1 (en) * | 1996-03-26 | 1997-10-02 | Cabot Corporation | Recovery of metal values from solids by digestion in sulfuric acid medium including a reductant |
| CN101383440A (en) * | 2007-11-16 | 2009-03-11 | 佛山市邦普镍钴技术有限公司 | Method for recycling and preparing superfine nickel powder from nickel-hydrogen cell |
| CN102071323A (en) * | 2010-12-16 | 2011-05-25 | 惠州市奥美特环境科技有限公司 | Method for producing high-purity gold by utilizing electroplating waste liquid containing gold |
| CN102242276A (en) * | 2011-06-13 | 2011-11-16 | 白银万山稀贵金属科技有限责任公司 | Process for extracting noble metal palladium from industrial solid wastes |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
| CN103526040A (en) * | 2013-10-11 | 2014-01-22 | 金川集团股份有限公司 | Process for removing base metals in platinum group metal containing material |
| US20150298988A1 (en) * | 2014-04-18 | 2015-10-22 | Brett A. Helms | Ionic nanocrystalline materials with high surface charge density and composites of the same |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| EP3613863A1 (en) * | 2018-08-21 | 2020-02-26 | Heraeus Deutschland GmbH & Co KG | Method for decomposition of a ruthenium-containing mixture of solid particles |
-
2020
- 2020-05-20 CN CN202010431393.7A patent/CN111778519B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151258A (en) * | 1978-03-06 | 1979-04-24 | Amax Inc. | Dissolution of cobaltic hydroxide with organic reductant |
| US4606764A (en) * | 1983-08-17 | 1986-08-19 | Resource Technology Associates | Method of recovering metals from ores using a formate reducing agent |
| EP0176100A1 (en) * | 1984-09-26 | 1986-04-02 | Austria Metall Aktiengesellschaft | Hydrometallurgical process for treating electrolytic copper refinery anode slimes |
| WO1997036013A1 (en) * | 1996-03-26 | 1997-10-02 | Cabot Corporation | Recovery of metal values from solids by digestion in sulfuric acid medium including a reductant |
| CN101383440A (en) * | 2007-11-16 | 2009-03-11 | 佛山市邦普镍钴技术有限公司 | Method for recycling and preparing superfine nickel powder from nickel-hydrogen cell |
| CN102071323A (en) * | 2010-12-16 | 2011-05-25 | 惠州市奥美特环境科技有限公司 | Method for producing high-purity gold by utilizing electroplating waste liquid containing gold |
| CN102242276A (en) * | 2011-06-13 | 2011-11-16 | 白银万山稀贵金属科技有限责任公司 | Process for extracting noble metal palladium from industrial solid wastes |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
| CN103526040A (en) * | 2013-10-11 | 2014-01-22 | 金川集团股份有限公司 | Process for removing base metals in platinum group metal containing material |
| US20150298988A1 (en) * | 2014-04-18 | 2015-10-22 | Brett A. Helms | Ionic nanocrystalline materials with high surface charge density and composites of the same |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| EP3613863A1 (en) * | 2018-08-21 | 2020-02-26 | Heraeus Deutschland GmbH & Co KG | Method for decomposition of a ruthenium-containing mixture of solid particles |
Non-Patent Citations (1)
| Title |
|---|
| 周通 等: ""铅锌硒在镍电解液固体杂质中的形态分析"", 《冶金分析》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981458A (en) * | 2021-02-04 | 2021-06-18 | 中国科学院兰州化学物理研究所 | Method for regulating and controlling brightness of appearance of nickel button |
| CN112981458B (en) * | 2021-02-04 | 2022-05-17 | 中国科学院兰州化学物理研究所 | Method for regulating and controlling brightness of appearance of nickel button |
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