CN114959711A - Comprehensive utilization method of stainless steel etching waste liquid - Google Patents
Comprehensive utilization method of stainless steel etching waste liquid Download PDFInfo
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- CN114959711A CN114959711A CN202210474428.4A CN202210474428A CN114959711A CN 114959711 A CN114959711 A CN 114959711A CN 202210474428 A CN202210474428 A CN 202210474428A CN 114959711 A CN114959711 A CN 114959711A
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- 239000007788 liquid Substances 0.000 title claims abstract description 99
- 238000005530 etching Methods 0.000 title claims abstract description 97
- 239000002699 waste material Substances 0.000 title claims abstract description 85
- 239000010935 stainless steel Substances 0.000 title claims abstract description 69
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 60
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 26
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 229910000599 Cr alloy Inorganic materials 0.000 claims abstract description 13
- 239000000788 chromium alloy Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 109
- 239000000243 solution Substances 0.000 claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 42
- 239000000706 filtrate Substances 0.000 claims description 42
- 229910052742 iron Inorganic materials 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000012265 solid product Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- 238000010907 mechanical stirring Methods 0.000 claims description 20
- 238000006722 reduction reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 235000021190 leftovers Nutrition 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 238000009628 steelmaking Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 description 23
- 239000011651 chromium Substances 0.000 description 20
- 229910052804 chromium Inorganic materials 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000562569 Riodinidae Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000015073 liquid stocks Nutrition 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to the technical field of comprehensive utilization of metallurgical resources, and particularly relates to a comprehensive utilization method of stainless steel etching waste liquid. A process for comprehensive utilization of the waste liquid generated by etching stainless steel includes adding reducer to said waste liquid, filtering to obtain FeCl 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 Then adjusting the pH value of the solution, precipitating, and carrying out solid-liquid separation to obtain an iron-chromium precipitate product and FeCl-containing solution 2 And NiCl 2 The iron-chromium precipitate is subjected to carbothermal reduction to obtain iron-chromium alloy, and then FeCl is added into the iron-chromium alloy 2 And NiCl 2 Solution of (2)Adding a reducing agent into the solution, and performing solid-liquid separation to obtain iron-nickel powder and FeCl-containing powder 2 To FeCl 2 Adding oxidant into the solution to regenerate FeCl 3 And (4) etching solution. The iron-chromium alloy, the iron-nickel powder and the FeCl obtained by the invention 3 The etching solution can be widely applied to industries such as metallurgy production, metal processing and the like, and can realize waste utilization and green circulation.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of metallurgical resources, and particularly relates to a comprehensive utilization method of stainless steel etching waste liquid.
Background
The stainless steel has good corrosion resistance, long service life, good mechanical property and high decoration, and is mainly applied to daily life and industrial production. The stainless steel etching technology can process patterns and texture structures on stainless steel, so that various decorative articles and precise devices, such as common metal marks, hollow models, various medals, nameplates and the like, can be obtained, and more precise application of the stainless steel etching technology comprises a stainless steel etching net, a grating photoetching plate, loudspeaker meshes and the like. FeCl 3 The solution has strong oxidability, good etching capability and low price, and is often used as an etching solution in the surface processing processes of stainless steel engraving, printing and the like.
In the stainless steel etching process, FeCl is accompanied 3 The reaction between the etching solution and the stainless steel is carried out, ferric ions in the etching solution are continuously consumed, and finally, a large amount of Fe is contained 3+ 、Fe 2+ And a small amount of Cr 3+ 、Ni 2+ In the national records of hazardous waste, the etching waste liquid belongs to HW17 surface treatment waste, is from the metal surface treatment and heat treatment processing industry, has the hazardous characteristics of corrosivity and toxicity, and can cause the problems of environmental pollution and resource waste due to direct discharge. Therefore, how to comprehensively utilize the stainless steel etching waste liquid and realize the harmless treatment and resource utilization of the etching waste liquid is a considerable problem.
A large amount of Fe element in the stainless steel etching waste liquid can be prepared into iron salt products. Patent CN1540036A proposes a method for regenerating etching waste liquid containing nickel ferric trichloride. Firstly, the methodConcentrating the waste liquid, cooling and supplementing the waste liquid stock solution, and finally adding water into the obtained ferric trichloride crystal containing trace nickel to prepare FeCl 3 And (4) etching liquid. The regenerated etching solution contains a large amount of Fe 2+ And a trace amount of Ni 2+ Complete separation was not achieved. Patent CN102965667A proposes a method for regenerating and recycling waste etching solution in stainless steel etching production line. Firstly, adding oxidant and hydrochloric acid into the etching waste liquid, and then keeping the waste liquid circularly flowing for a period of time to complete regeneration. The method does not recycle Cr and Ni elements in the waste liquid, and the resource recovery is incomplete. Patent CN101497484A proposes a method for treating ferric trichloride etching waste liquid. Two-stage extraction is utilized to remove iron, so that Fe element in the waste liquid is regenerated into liquid ferric trichloride, and Ni element is regenerated into a nickel chloride product. The method has the advantages of complex operation and higher cost.
Although Cr and Ni elements in the stainless steel etching waste liquid are pollutants, the stainless steel etching waste liquid can be prepared into alloy products with certain value after being recycled. Patent CN101269889A proposes a method for treating stainless steel pickling wastewater. Firstly, pH is adjusted by alkaline substances to form ferric hydroxide, chromium hydroxide and nickel hydroxide precipitates, and then solid-liquid separation is carried out. The method has high treatment cost, and the discharged wastewater has high salt content to cause resource waste. Patent CN108928953A discloses a method for recycling stainless steel pickling wastewater. Firstly, adjusting the pH value of the waste liquid to precipitate Fe, Cr and Ni elements together to generate hydroxide, then carrying out carbothermic reduction reaction on the precipitate, and finally carrying out magnetic separation to obtain an iron-chromium-nickel alloy product. The alloy product prepared by the method has low chromium and nickel metal grade and low product value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems of high treatment cost, incomplete recovered resources, low alloy product preparation value and the like of the existing stainless steel etching waste liquid, and provides a treatment method with low treatment cost, complete recovered resources and high alloy product preparation value. The method selectively extracts Cr and Ni elements in the stainless steel etching waste liquid, and prepares the iron-chromium alloy product with higher chromium metal grade and the iron-nickel powder with higher nickel metal grade by echelon recovery, and finally reserves the Fe element in the solutionRegeneration into high yield FeCl 3 And (4) etching solution. The invention can give consideration to harmless treatment and resource utilization, thereby realizing the aims of processing waste by waste and changing waste into valuable.
The technical scheme of the invention is realized as follows:
a comprehensive utilization method of stainless steel etching waste liquid comprises the following steps:
(1) diluting the etching waste liquid generated by the stainless steel etching process to ensure that the total ion concentration is 0.6-1.5 g/mL;
(2) adding a reducing agent into the diluted stainless steel etching waste liquid obtained in the step (1), heating and reacting for 1-3 hours at a constant temperature of 50-90 ℃ under the condition of mechanical stirring, and obtaining FeCl-containing material after reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 1, a filtrate of (a);
(3) adding a pH regulator into the filtrate 1 obtained in the step (2), mechanically stirring at room temperature to ensure that the pH of the solution is more than or equal to 4 and less than or equal to 6, and aging for 1-3 h;
(4) after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (2);
(5) washing and drying the solid product obtained in the step (4) to obtain an iron-chromium precipitate, and carrying out a carbothermic reduction reaction for 1-3 h at 1300-1600 ℃ to obtain an iron-chromium alloy;
(6) adding a pH regulator into the filtrate 2 obtained in the step (4) to ensure that the pH of the solution is more than or equal to 0 and less than or equal to 2, adding a reducing agent, mechanically stirring, and heating at a constant temperature of 80-95 ℃ for reaction for 2-4 hours;
(7) after the reaction in the step (6) is finished, performing solid-liquid separation to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (a);
(8) washing and drying the solid product obtained in the step (7) to obtain iron-nickel powder;
(9) adding an oxidant into the filtrate 3 obtained in the step (8), and reacting under an acidic condition to obtain FeCl 3 And (4) etching liquid.
The stainless steel etching waste liquid treated by the comprehensive utilization method of the stainless steel etching waste liquid is preferably Cr-Ni stainless steel etching waste liquid.
The total ion concentration in the invention refers to the sum of the concentrations of all ions in the solution.
In the method for comprehensively utilizing the stainless steel etching waste liquid, in the step (1), the main body of the etching waste liquid is FeCl 3 The solution has pH less than or equal to 1 and contains FeCl as component 3 10.0-20.0 percent of mass fraction and FeCl 2 5.0-20.0 percent of CrCl 3 1.5-6.1 percent of NiCl 2 The mass fraction is 1.1-4.5%, and the total ion concentration is 0.6-1.5 g/mL.
In the method for comprehensively utilizing the stainless steel etching waste liquid, in the step (2), the reducing agent is one or more of iron powder, iron particles, iron sheet, waste iron scrap, leftovers of iron making and steel making and iron leftover materials, the reducing component is zero-valent iron, and the using amount of the reducing agent is Fe 3+ Reduction to Fe 2+ 1 to 2 times the theoretical molar amount of (A).
In the comprehensive utilization method of the stainless steel etching waste liquid, in the step (2), the mechanical stirring speed is 100-300 rpm, and the heating mode is a common industrial heating method; in the step (3), the mechanical stirring speed is 200-400 rpm, and the heating mode is a common heating method in the industry.
In the comprehensive utilization method of the stainless steel etching waste liquid, the step (2) is as follows: adding a reducing agent into the diluted stainless steel etching waste liquid obtained in the step (1), heating and reacting for 1-3 hours at a constant temperature of 50-90 ℃ under the condition of mechanical stirring, wherein the pH range is not less than 0 and not more than 3 after the reaction, and obtaining FeCl containing chromium and nickel after the reaction 2 And (3) solution.
In the method for comprehensively utilizing the stainless steel etching waste liquid, in the step (3), the pH regulator is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、NH 4 OH and Ca (OH) 2 One or more of (a); in the step (6), the pH regulator is HCl and CH 3 One or more of COOH.
In the comprehensive utilization method of the stainless steel etching waste liquid, in the step (5), the solid product is washed by distilled water for 0.5-1 h and then dried, the drying time is 3-6 h, and the drying temperature is 90-120 ℃; the carbothermic reduction reaction uses sufficient carbon powder as a reducing agent.
In the method for comprehensively utilizing the stainless steel etching waste liquid, in the step (6), the reducing agent is one or more of iron powder, iron particles, iron sheet, waste iron scrap, leftovers of iron making and steel making and iron leftover materials, and the amount of the reducing agent is Ni 2+ Reducing the Ni to be 1-5 times of the theoretical molar weight of Ni; the mechanical stirring speed is 100-300 rpm.
In the comprehensive utilization method of the stainless steel etching waste liquid, the step (6) is as follows: adding nickel-containing FeCl obtained in the step (4) 2 Adding a pH regulator into the solution to ensure that the pH of the solution is more than or equal to 0 and less than or equal to 2, adding a reducing agent, mechanically stirring, heating at a constant temperature of 80-95 ℃ for reaction for 2-4 h, wherein the pH after the reaction is more than or equal to 4 and less than or equal to 6; in the comprehensive utilization method of the stainless steel etching waste liquid, in the step (8), the solid product is washed by distilled water for 0.5-1 h and then dried, the drying time is 3-6 h, and the drying temperature is 90-120 ℃.
In the method for comprehensively utilizing the stainless steel etching waste liquid, in the step (9), the oxidant is H 2 O 2 、Cl 2 And O 3 One or more of them.
In the method for comprehensively utilizing the stainless steel etching waste liquid, the step (9) is included. To the obtained FeCl 2 Adding the solution into the solution according to the volume ratio of 1: 1H 2 O 2 And HCl mixed solution with the dosage of FeCl obtained 2 0.5 to 1 time of the volume of the solution, H 2 O 2 The concentration is 10-50%, the HCl concentration is 10-50%, and the reaction is carried out for 0.5-2 h under the condition of constant temperature heating at 20-70 ℃.
The invention has the following beneficial effects: the raw material used by the invention is waste generated in the process of stainless steel etching technology, namely stainless steel etching waste liquid. The invention can realize the valence of the waste, and realize the graded recovery of the valuable components in the stainless steel etching waste liquid in the treatment process of the stainless steel etching waste liquid, so that the valuable elements Cr and Ni are fully recovered in the respective elementsIn the separated phase, the higher nickel grade in the iron-nickel powder is ensured, and the higher chromium grade in the iron-chromium alloy is ensured to be prepared into an alloy product with higher value; the invention can also realize harmlessness, and after valuable components are recovered, a large amount of Fe element is remained in the liquid phase and can be regenerated into new etching solution, thereby reducing the amount of solid waste and reducing the environmental pollution. The method has great significance for improving the utilization value of the chromium-nickel element and reducing the problem of environmental pollution, and the obtained iron-chromium alloy, iron-nickel powder and FeCl 3 The etching solution can be widely applied to industries such as metallurgy production, metal processing and the like.
Description of the drawings:
FIG. 1 is a process flow diagram for comprehensive utilization of waste stainless steel etching solution.
FIG. 2 is a scanning electron microscope image of the Fe-Cr precipitate obtained as a recovered Cr product in example 2 of the present invention.
FIG. 3 is a scanning electron microscope image of iron-nickel powder as a recovered nickel product obtained in example 2 of the present invention.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
One of the specific implementation modes is as follows:
a comprehensive utilization method of stainless steel etching waste liquid comprises the following steps:
(1) diluting the etching waste liquid generated by the stainless steel etching process to ensure that the total ion concentration is 0.6-1.5 g/mL;
(2) adding a reducing agent into the diluted stainless steel etching waste liquid obtained in the step (1), heating and reacting for 1-3 hours at a constant temperature of 50-90 ℃ under the condition of mechanical stirring, and obtaining FeCl-containing material after reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 Filtrate 1 of (1);
(3) adding a pH regulator into the filtrate 1 obtained in the step (2), mechanically stirring at room temperature to ensure that the pH of the solution is more than or equal to 4 and less than or equal to 6, and aging for 1-3 h;
(4) after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (2);
(5) washing and drying the solid product obtained in the step (4) to obtain an iron-chromium precipitate, and carrying out a carbothermic reduction reaction for 1-3 h at 1300-1600 ℃ to obtain an iron-chromium alloy;
(6) adding a pH regulator into the filtrate 2 obtained in the step (4) to ensure that the pH of the solution is more than or equal to 0 and less than or equal to 2, adding a reducing agent, mechanically stirring, and heating at a constant temperature of 80-95 ℃ for reaction for 2-4 hours;
(7) after the reaction in the step (6) is finished, performing solid-liquid separation to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (2);
(8) washing and drying the solid product obtained in the step (7) to obtain iron-nickel powder;
(9) adding an oxidant into the filtrate 3 obtained in the step (8), and reacting under an acidic condition to obtain FeCl 3 And (4) etching liquid.
In the method for comprehensively utilizing the stainless steel etching waste liquid, in the step (1), the stainless steel is Cr-Ni series stainless steel in the step (1); the etching waste liquid is mainly FeCl 3 The solution has an acidic pH of less than or equal to 1 and contains FeCl 3 10.0-20.0 percent of mass fraction and FeCl 2 5.0-20.0 percent of CrCl 3 1.5 to 6.1 percent of NiCl 2 The mass fraction is 1.1-4.5%, the total ion concentration is 0.6-1.5 g/mL, the concentration is high, and the ion is diluted and fully dissolved, so that the reduction reaction is facilitated.
Preferably, in the step (2), the reducing agent is one or more of iron powder, iron particles, iron sheet, scrap iron, iron and steel leftovers and iron scraps, and the reducing component is zero-valent iron in an amount of Fe 3+ Reduction to Fe 2+ 1 to 2 times the theoretical molar amount of (A).
Preferably, in the step (2), the reduction reaction conditions are as follows: the mechanical stirring speed is 100-300 rpm, the constant temperature heating temperature is 50-90 ℃, and the reaction time is 1-3h, reduction of Fe 3+ After the reaction is finished, the pH value of the solution after the reaction is less than or equal to 3.
Preferably, in the step (3), the pH regulator is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、NH 4 OH and Ca (OH) 2 One or more of them.
Preferably, in the step (3), the precipitation reaction conditions are as follows: the mechanical stirring speed is 200-400 rpm, the room temperature, the pH adjusting range is not less than 4 and not more than 6, and the aging time is 1 h.
Preferably, the solid product is washed and dried in the step (5), and is washed by distilled water for 0.5-1 h, the drying time is 3-6 h, and the drying temperature is 90-120 ℃; in the step (5), the carbothermic reduction reaction conditions are as follows: sufficient carbon powder is used as a reducing agent, the reducing temperature is 1300-1500 ℃, and the reducing time is 1-3 h.
Preferably, in the step (6), the pH regulators are HCl and CH 3 One or more of COOH.
Preferably, in the step (6), the reducing agent is reduced iron powder.
Preferably, in the step (6), a pH regulator is added to regulate the pH of the solution to be 0-2, and a reducing agent is one or more of iron powder, iron particles, iron sheet, scrap iron, leftovers of iron making and steel making and iron leftover materials, and the amount of the reducing agent is relative reduction Ni 2+ Is 1 to 5 times of the theoretical molar weight of Ni, the mechanical stirring speed is 100 to 300rpm, the reaction is carried out for 2 to 4 hours under the condition of constant temperature of 80 to 95 ℃, and the Ni is reduced 2+ After the reaction is finished, the pH value is less than or equal to 6.
Preferably, the solid product is washed and dried in the step (8), and is washed with distilled water for 0.5-1 h, the drying time is 3-6 h, and the drying temperature is 90-120 ℃.
Preferably, in the step (9), the oxidant is H 2 O 2 、Cl 2 And O 3 One or more of them.
Preferably, in the step (9), FeCl is added to the obtained 2 Adding the solution into the solution according to the volume ratio of 1: 1H 2 O 2 And HCl mixed solution with the dosage of FeCl obtained 2 Liquid body0.5 to 1 times of product, H 2 O 2 The concentration is 10-50%, the HCl concentration is 10-50%, and the reaction is carried out for 0.5-2 h under the condition of constant temperature heating at 20-70 ℃.
The treated stainless steel etching waste liquid is FeCl 3 The main component of the waste liquid obtained after the Cr-Ni series stainless steel is etched by the solution is FeCl 3 、FeCl 2 、CrCl 3 、NiCl 2 . So-called echelon recovery of Cr, Ni and regenerated FeCl 3 The etching solution is obtained by adding a certain amount of pH regulator into the stainless steel etching waste solution to recover Cr, adding a certain amount of reducing agent to recover Ni, and finally adding a certain amount of oxidizing agent to regenerate FeCl 3 And (4) etching liquid.
Example 1
Step 1: the stainless steel etching waste liquid contains FeCl 3 10.0 percent of FeCl 2 Mass fraction of 5.0%, CrCl 3 1.5% of NiCl 2 The mass fraction is 1.1%, and the etching waste liquid generated by the stainless steel etching process is diluted so that the total ion concentration is 0.6g/mL and the pH value is 1.
Step 2: adding 4.0g of iron powder into 150mL of the stainless steel etching waste liquid obtained in the step (1), reacting in a constant-temperature heating pot at 50 ℃ and a mechanical stirring speed of 100rpm for 1h, wherein the pH value is 2 after the reaction, and obtaining FeCl-containing material after the reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 Filtrate 1 of (1).
And 3, step 3: to the resulting filtrate 1 was added (NH) 4 ) 2 CO 3 Mechanically stirring at room temperature for 200rpm, adjusting the pH of the solution to 4, and aging for 1 h.
And 4, step 4: after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (1).
And 5: washing and drying the obtained solid product, washing the solid product for 0.5h by using distilled water, wherein the drying time is 3h, and the drying temperature is 90 ℃ to obtain an iron-chromium precipitate; and carrying out carbothermic reduction reaction for 1h at 1300 ℃ in an atmosphere reburning furnace in argon atmosphere and sufficient carbon powder to obtain the iron-chromium alloy.
Step 6: adding HCl into the obtained filtrate 2 to adjust the pH value of the solution to 1, adding 1.1g of iron powder, and reacting in a constant-temperature heating pot for 2 hours under the conditions of mechanical stirring at 100rpm and 80 ℃, wherein the pH value is 4 after the reaction.
And 7: after the reaction in the step (6) is finished, performing solid-liquid separation to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (2).
And 8: and (4) washing and drying the solid product obtained in the step (7), washing with distilled water for 0.5h, wherein the drying time is 3h, and the drying temperature is 90 ℃, so as to obtain iron-nickel powder.
And step 9: adding H into the filtrate 3 obtained in the step (7) 2 O 2 And HCl (1: 1) in an amount of FeCl 2 The volume of the solution is 0.5 time, the reaction is carried out for 0.5h in a constant temperature heating pot at the temperature of 20 ℃, and FeCl is obtained 3 And (4) etching liquid.
Example 2
Step 1: the stainless steel etching waste liquid contains FeCl 3 20.0 percent of FeCl 2 Mass fraction of 20.0%, CrCl 3 1.5 percent of NiCl 2 The mass fraction is 1.1%, and the etching waste liquid generated by the stainless steel etching process is diluted so that the total ion concentration is 0.7g/mL and the pH value is 1. 0.5
Step 2: adding 8.0g of iron powder into 300mL of the stainless steel etching waste liquid obtained in the step (1), reacting in a constant-temperature heating pot at 90 ℃ and a mechanical stirring speed of 200rpm for 2h, wherein the pH value is 2 after the reaction, and obtaining FeCl-containing material after the reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 Filtrate 1 of (1).
And step 3: to the resulting filtrate 1, Ca (OH) was added 2 Mechanically stirring at room temperature for 300rpm, adjusting the pH of the solution to 5, and aging for 1 h.
And 4, step 4: after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (1).
And 5: washing and drying the obtained solid product, washing the solid product for 1h by using distilled water, wherein the drying time is 6h, and the drying temperature is 100 ℃ to obtain an iron-chromium precipitate; and carrying out carbothermic reduction reaction for 3 hours at 1400 ℃ in an atmosphere reburning furnace in argon atmosphere and sufficient carbon powder to obtain the iron-chromium alloy.
Step 6: adding HCl into the obtained filtrate 2 to adjust the pH value of the solution to 1, adding 3.2g of iron powder, and reacting in a constant-temperature heating pot for 3 hours under the conditions of mechanical stirring at 200rpm and 90 ℃, wherein the pH value is 4 after the reaction.
And 7: after the reaction in the step (6) is finished, performing solid-liquid separation to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (2).
And 8: and (4) washing and drying the solid product obtained in the step (7), washing with distilled water for 1h, drying for 6h, and drying at 100 ℃ to obtain iron-nickel powder.
And step 9: adding H into the filtrate 3 obtained in the step (7) 2 O 2 And HCl (1: 1) in an amount to yield FeCl 2 The volume of the solution is 1 time, the solution reacts for 2 hours in a constant temperature heating pot at the temperature of 40 ℃ to obtain FeCl 3 And (4) etching liquid.
And (3) determining the content of each ion in the solution obtained in the step (2) by adopting chemical titration and ICP-OES detection methods. The results showed that the use of 8.0g of iron powder to reduce the waste liquid resulted in a chromium extraction of 3.9%, a nickel extraction of 6.7%, and a Fe extraction 3+ Conversion to Fe 2+ The conversion of (2) was 95.3%, and at this time, FeCl containing chromium and nickel mainly in the solution 2 And (3) solution.
And (4) carrying out SEM-EDS and XRD detection analysis on the recovered product obtained in the step (4). The result shows that the main phase of the recovered product is FeOOH, the electron microscope result shows that Cr element is extracted from the ferrochrome coprecipitate, the chromium content is lower than the iron content, and the ratio of partial particles of chromium to iron is about 1: 2.3, the scanning electron micrograph of the iron chromium precipitate which is the recovered chromium product is shown in figure 2.
And (4) determining the content of each ion in the solution obtained in the step (4) by adopting chemical titration and ICP-OES detection methods. As a result, the waste liquid was reduced with 8.0g of iron powder and then treated with Ca (OH) 2 The pH was adjusted to 5, the chromium extraction was 99.9%, the nickel extraction was 7.6%, and the iron loss was 15.0%, at which time the solution was mainly FeCl containing nickel 2 And (3) solution.
And (4) performing SEM-EDS and XRD detection analysis on the recovered product obtained in the step 7. The result shows that the main phases of the recovered product are Fe and Ni, the electron microscope result shows that the Ni element is attached to iron powder in the form of tiny particles after being separated out, the nickel exists in gaps among the particles and small particles on the surface, and the nickel-iron ratio is about 1: 3, the scanning electron micrograph of the iron-nickel powder recovered from the nickel product is shown in FIG. 3.
And (4) measuring the content of each ion in the solution obtained in the step (7) by adopting a chemical titration method and an ICP-OES detection method. As a result, the waste liquid was reduced with 8.0g of iron powder and then treated with Ca (OH) 2 Adjusting pH to 5, extracting chromium completely, adding 3.2g iron powder at pH of 1 to extract nickel with nickel extraction rate of 90.0%, wherein the main body of the solution is FeCl 2 Solution oxidizable to regenerate FeCl 3 And (4) etching liquid.
Example 3
Step 1: the stainless steel etching waste liquid contains FeCl 3 20.0 percent of FeCl 2 Mass fraction of 20.0%, CrCl 3 1.5% of NiCl 2 The mass fraction is 1.1%, and the etching waste liquid generated by the stainless steel etching process is diluted so that the total ion concentration is 0.6g/mL and the pH value is 1.
Step 2: adding 8.0g of iron powder into 300mL of the stainless steel etching waste liquid obtained in the step (1), reacting in a constant-temperature heating pot at 90 ℃ and a mechanical stirring speed of 200rpm for 2h, wherein the pH value is 2 after the reaction, and obtaining FeCl-containing material after the reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 Filtrate 1 of (1).
And step 3: to the obtained filtrate 1, NH was added 4 OH, mechanically stirring at room temperature for 300rpm, adjusting the pH value of the solution to 6, and aging for 2 hours.
And 4, step 4: after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (1).
And 5: washing and drying the obtained solid product, washing the solid product for 1h by using distilled water, wherein the drying time is 6h, and the drying temperature is 100 ℃ to obtain an iron-chromium precipitate; and carrying out carbothermic reduction reaction for 3 hours in an atmosphere reburning furnace under the argon atmosphere and at 1500 ℃ with sufficient carbon powder to obtain the iron-chromium alloy.
Step 6: adding HCl into the obtained filtrate 2 to adjust the pH value of the solution to 1, adding 4.2g of iron powder, and reacting in a constant-temperature heating pot for 3 hours under the conditions of mechanical stirring at 200rpm and 90 ℃, wherein the pH value is 4 after the reaction.
And 7: after the reaction in the step (6) is finished, performing solid-liquid separation to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (2).
And 8: and (4) washing and drying the solid product obtained in the step (7), washing with distilled water for 1h, drying for 6h, and drying at 100 ℃ to obtain iron-nickel powder.
And step 9: adding H into the filtrate 3 obtained in the step (7) 2 O 2 And HCl (1: 1) in an amount to yield FeCl 2 The volume of the solution is 1 time, the reaction is carried out for 2 hours in a constant temperature heating pot at the temperature of 60 ℃, and FeCl is obtained 3 And (4) etching liquid.
Example 4
Step 1: the stainless steel etching waste liquid contains FeCl 3 20.0 percent of FeCl 2 Mass fraction of 20.0%, CrCl 3 6.1% of NiCl 2 The mass fraction is 4.5%, and the etching waste liquid generated by the stainless steel etching process is diluted so that the total ion concentration is 1.5g/mL and the pH value is 1.
Step 2: adding 15.0g of iron powder into 150mL of stainless steel etching waste liquid obtained in the step (1), reacting for 3 hours in a constant-temperature heating pot at the temperature of 90 ℃ and the mechanical stirring speed of 300rpm, and obtaining FeCl-containing material after reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 Filtrate 1 of (1).
And step 3: to the obtained filtrate 1, NH was added 4 HCO 3 Mechanically stirring at room temperature at 400rpm, adjusting the pH of the solution to 6, and aging for 3 h.
And 4, step 4: after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (1).
And 5: washing and drying the obtained solid product, washing the solid product for 1h by using distilled water, wherein the drying time is 6h, and the drying temperature is 120 ℃ to obtain an iron-chromium precipitate; and carrying out carbothermic reduction reaction for 3 hours in an atmosphere reburning furnace under the argon atmosphere and under the condition of 1600 ℃ by using sufficient carbon powder to obtain the iron-chromium alloy.
Step 6: to the obtained filtrate 2, CH was added 3 Adjusting the pH value of the COOH solution to 2, adding 16.8g of iron powder, and mechanically stirring the mixture for 30 minutesReacting for 4 hours in a constant temperature heating pot at 0rpm and 95 ℃, wherein the pH value is 6 after the reaction.
And 7: after the reaction in the step (6) is finished, performing solid-liquid separation to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (2).
And step 8: and (4) washing and drying the solid product obtained in the step (7), washing with distilled water for 1h, drying for 6h, and drying at 120 ℃ to obtain iron-nickel powder.
And step 9: adding H into the filtrate 3 obtained in the step (7) 2 O 2 And HCl (1: 1) in an amount to yield FeCl 2 The volume of the solution is 1 time, the reaction is carried out for 2 hours in a constant temperature heating pot at the temperature of 70 ℃, and FeCl is obtained 3 And (4) etching liquid.
Claims (10)
1. A comprehensive utilization method of stainless steel etching waste liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) diluting the etching waste liquid generated by the stainless steel etching process to ensure that the total ion concentration is 0.6-1.5 g/mL;
(2) adding a reducing agent into the diluted stainless steel etching waste liquid obtained in the step (1), heating and reacting for 1-3 hours at a constant temperature of 50-90 ℃ under the condition of mechanical stirring, and obtaining FeCl-containing material after reaction 2 、CrCl 3 、NiCl 2 And a small amount of FeCl 3 1, a filtrate of (a);
(3) adding a pH regulator into the filtrate 1 obtained in the step (2), mechanically stirring at room temperature to ensure that the pH of the solution is more than or equal to 4 and less than or equal to 6, and aging for 1-3 h;
(4) after the reaction in the step (3) is finished, carrying out solid-liquid separation to respectively obtain iron-chromium precipitate and FeCl-containing FeCl 2 And NiCl 2 Filtrate 2 of (1);
(5) washing and drying the solid product obtained in the step (4) to obtain an iron-chromium precipitate, and carrying out a carbothermic reduction reaction for 1-3 h at 1300-1600 ℃ to obtain an iron-chromium alloy;
(6) adding a pH regulator into the filtrate 2 obtained in the step (4) to ensure that the pH of the solution is more than or equal to 0 and less than or equal to 2, adding a reducing agent, mechanically stirring, and heating at a constant temperature of 80-95 ℃ for reaction for 2-4 hours;
(7) step (ii) of(6) After the reaction is finished, solid-liquid separation is carried out to respectively obtain iron-nickel powder and FeCl-containing powder 2 Filtrate 3 of (a);
(8) washing and drying the solid product obtained in the step (7) to obtain iron-nickel powder;
(9) adding an oxidant into the filtrate 3 obtained in the step (8), and reacting under an acidic condition to obtain FeCl 3 And (4) etching liquid.
2. The method of claim 1, wherein: in the step (1), the etching waste liquid is mainly FeCl 3 The solution has pH less than or equal to 1 and contains FeCl as component 3 10.0-20.0 percent of mass fraction and FeCl 2 5.0-20.0 percent of CrCl 3 1.5-6.1 percent of NiCl 2 The mass fraction is 1.1-4.5%, and the total ion concentration is 0.6-1.5 g/mL.
3. The method of claim 1, wherein: in the step (2), the reducing agent is one or more of iron powder, iron particles, iron sheet, scrap iron, iron and steel making leftovers and iron leftover materials, the reducing component is zero-valent iron, and the using amount of the reducing agent is Fe 3+ Reduction to Fe 2+ 1 to 2 times the theoretical molar amount of (A).
4. The method of claim 1, wherein: in the step (2), the mechanical stirring speed is 100-300 rpm, and the heating mode is a common heating method in the industry; in the step (3), the mechanical stirring speed is 200-400 rpm, and the heating mode is a common heating method in the industry.
5. The method of claim 1, wherein: in the step (3), the pH regulator is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、NH 4 OH and Ca (OH) 2 One or more of; in the step (6), the pH regulator is HCl and CH 3 One or more of COOH.
6. The method of claim 1, further comprising: in the step (5), the solid product is washed by distilled water for 0.5-1 h and then dried, wherein the drying time is 3-6 h, and the drying temperature is 90-120 ℃; the carbothermic reduction reaction uses sufficient carbon powder as a reducing agent.
7. The method of claim 1, further comprising: in the step (6), the reducing agent is one or more of iron powder, iron particles, iron sheet, scrap iron, iron and steel leftovers and iron leftover materials, and the amount of the reducing agent is Ni 2+ Reducing the Ni into 1-5 times of the theoretical molar weight of Ni; the mechanical stirring speed is 100-300 rpm.
8. The method of claim 1, further comprising: in the step (8), the solid product is washed by distilled water for 0.5-1 h and then dried, wherein the drying time is 3-6 h, and the drying temperature is 90-120 ℃.
9. The method of claim 1, wherein: in the step (9), the oxidant is H 2 O 2 、Cl 2 And O 3 One or more of them.
10. The method of claim 1, wherein: in the step (9), FeCl is added to the obtained 2 Adding the solution into a reactor according to the volume ratio of 1: 1H 2 O 2 And HCl mixed solution with the dosage of FeCl obtained 2 0.5-1 times of the volume of the solution, its H 2 O 2 The concentration is 10-50%, the HCl concentration is 10-50%, and the reaction is carried out for 0.5-2 h under the condition of constant temperature heating at 20-70 ℃.
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| CN1309194A (en) * | 2000-11-28 | 2001-08-22 | 华东理工大学 | Process for regenerating waste etching liquid containing Ni and FeCl3 and recovering Ni |
| CN1899976A (en) * | 2006-07-13 | 2007-01-24 | 烟台海利化工有限公司 | Method for recovering and utilizing valuable metals from nickel and iron etching waste liquid |
| JPWO2007122855A1 (en) * | 2006-04-25 | 2009-09-03 | 鶴見曹達株式会社 | Etching solution, method for regenerating waste liquid, and method for recovering valuable metal from waste liquid |
| CN107162276A (en) * | 2017-07-10 | 2017-09-15 | 惠州市斯瑞尔环境化工有限公司 | A kind of method for removing chromium of ferric trichloride etching waste liquor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309194A (en) * | 2000-11-28 | 2001-08-22 | 华东理工大学 | Process for regenerating waste etching liquid containing Ni and FeCl3 and recovering Ni |
| JPWO2007122855A1 (en) * | 2006-04-25 | 2009-09-03 | 鶴見曹達株式会社 | Etching solution, method for regenerating waste liquid, and method for recovering valuable metal from waste liquid |
| CN1899976A (en) * | 2006-07-13 | 2007-01-24 | 烟台海利化工有限公司 | Method for recovering and utilizing valuable metals from nickel and iron etching waste liquid |
| CN107162276A (en) * | 2017-07-10 | 2017-09-15 | 惠州市斯瑞尔环境化工有限公司 | A kind of method for removing chromium of ferric trichloride etching waste liquor |
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