CN113046557A - Comprehensive recycling method for zinc-containing and iron-containing waste hydrochloric acid - Google Patents
Comprehensive recycling method for zinc-containing and iron-containing waste hydrochloric acid Download PDFInfo
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- CN113046557A CN113046557A CN202011595922.3A CN202011595922A CN113046557A CN 113046557 A CN113046557 A CN 113046557A CN 202011595922 A CN202011595922 A CN 202011595922A CN 113046557 A CN113046557 A CN 113046557A
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- hydrochloric acid
- zinc
- iron
- solution
- ferric trichloride
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 188
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000011701 zinc Substances 0.000 title claims abstract description 105
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 101
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 83
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 59
- 239000012044 organic layer Substances 0.000 claims abstract description 40
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 27
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000005246 galvanizing Methods 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000010410 layer Substances 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000005201 scrubbing Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 33
- 239000012535 impurity Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000007747 plating Methods 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000003651 drinking water Substances 0.000 abstract description 3
- 235000020188 drinking water Nutrition 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 46
- 239000000047 product Substances 0.000 description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- -1 precision etching Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229940118149 zinc sulfate monohydrate Drugs 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 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
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a comprehensive recycling method of waste hydrochloric acid containing zinc and iron, which comprises the steps of oxidizing the waste hydrochloric acid containing zinc and iron into ferric trichloride containing zinc, adding industrial hydrochloric acid and butyl acetate for extraction, standing for layering, taking an organic phase, adding an acid-containing washing liquid containing iron to wash an organic layer, adding a back extractant into the organic layer for back extraction to obtain ferric trichloride with ultralow impurities, and evaporating for concentration and removing organic matters to obtain high-purity ferric trichloride. The organic phase can be recycled, the aqueous phase is extracted for many times until no ferric trichloride exists, ammonia water is added to neutralize hydrochloric acid after evaporation and concentration, and then the ferrate meeting the galvanizing industry can be obtained. The high-purity ferric trichloride product produced by the process has zinc content lower than 5ppm, and can be applied to the fields of drinking water treatment, medical intermediates, analysis and test, precision etching and the like; the plating assistant liquid can be reused in the galvanizing industry.
Description
Technical Field
The invention relates to the field of industrial wastewater treatment, in particular to a method for separating and recycling zinc and iron in waste hydrochloric acid containing zinc and iron.
Background
The zinc-containing iron-containing waste hydrochloric acid is mainly from a galvanizing factory, before galvanizing or spraying is started, iron rust and an oxide film on the surface of steel need to be subjected to acid pickling treatment, while the galvanized layer on the surface of the steel which is unqualified to be galvanized needs to be subjected to zinc stripping treatment by using hydrochloric acid for backwashing, when the hydrochloric acid content of the steel and the galvanized layer is reduced to a certain concentration, the steel and the galvanized layer can not be used continuously to form waste liquid, and the waste liquid generally contains high-concentration hydrochloric acid, ferrous chloride and zinc chloride, so that the waste liquid has good recycling value. Because the difficulty of the zinc and iron separation process is high, the resource recycling of the zinc-containing and iron-containing waste hydrochloric acid is severely restricted, and the global mineral resources are gradually deficient, so that how to realize the resource recycling of the zinc-containing and iron-containing waste hydrochloric acid is very important.
At present, the treatment of waste hydrochloric acid containing zinc and iron mainly comprises four types: 1. adding alkaline substances to precipitate iron or precipitating iron and zinc step by step; 2. adsorbing zinc chloride by resin to separate a hydrochloric acid system from the zinc chloride; 3. adding concentrated sulfuric acid into the solution to replace hydrogen chloride, so that the solution forms a sulfuric acid system, and separating out a mixture of zinc sulfate monohydrate and ferrous sulfate monohydrate; 4. an extractant is used to extract zinc or extract iron. The above treatment methods have common disadvantages: the separation of zinc and iron is not thorough, the purity of the subsequent zinc-containing and iron-containing products is influenced, the product quality cannot stably meet the market demand, and the economic value of the product is low.
Therefore, a method for completely separating zinc and iron is urgently needed so as to improve the economic value of comprehensive recycling of the waste acid containing zinc and iron.
Disclosure of Invention
The invention aims to comprehensively recycle iron and zinc in the iron-containing and zinc-containing waste hydrochloric acid to obtain a high-purity ferric trichloride solution and a zinc ferrate solution. The high-purity ferric trichloride solution can meet the market demand of high-end ferric trichloride, can be applied to the fields of drinking water, precision etching, chemical analysis, medical intermediates and the like, and the zinc ferrate can be reused in the galvanizing industry.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a comprehensive recycling method of waste hydrochloric acid containing zinc and iron comprises the following steps:
s1 adding waste hydrochloric acid containing zinc and iron into oxidant to make Fe in solution2+Oxidizing completely to obtain zinc-containing ferric trichloride solution;
s2, adding hydrochloric acid and butyl acetate into the zinc-containing ferric trichloride solution, oscillating and standing until layering is complete;
s3, adding the organic layer in the S2 into a washing solution, shaking and standing until the layering is complete;
s4, adding a stripping agent into the organic layer in the S3 to obtain a ferric trichloride solution with ultralow impurity content, evaporating to obtain high-purity ferric trichloride, and returning the organic layer to the system for recycling;
s5, extracting the water layer in the S2 for multiple times by butyl acetate until the iron content is not detected, evaporating and concentrating the water layer, and adding ammonia water to neutralize hydrochloric acid in the solution to obtain a transition aid solution meeting the requirement of the galvanizing industry; or extracting the water layer in S2 with butyl acetate for several times until the iron content is not detected, and electrolyzing the water layer to recover zinc.
Further, the oxidation manner in step S1 may be one or more of oxygen oxidation, air oxidation, ozone oxidation, sodium chlorate oxidation, potassium chloride oxidation, chlorine oxidation, and hydrogen peroxide oxidation. Due to Fe2+Not being mixed with Cl-Complexing, not being extracted by butyl acetate, so Fe in iron-containing chloride is needed2+And (4) oxidizing.
Further, in step S2, the volume ratio of the materials added is, zinc-containing ferric chloride: industrial hydrochloric acid: butyl acetate is 1: 4-6: 2-4. During extraction, the organic phase ratio is too high, so that the emulsification phenomenon is easy to occur, and the delamination is not thorough, slow in delamination speed and even not delamination; if the organic phase ratio is too low, the extraction stages need to be increased to improve the extraction efficiency of iron, so that the organic phase ratio of the aqueous phase to the organic phase is kept 1.5-3: 1, preferably 2-2.5: 1, which is beneficial to complete extraction of iron.
Free state of Fe3+Cannot be extracted by butyl acetate, so high-concentration hydrochloric acid needs to be added to lead Fe to be extracted3+And Cl-Complex synthesis of [ FeCl4]-Can be extracted by butyl acetate. To is coming toMaintaining the uniqueness of the extraction of iron also requires that the solution maintain a high acidity. When the acidity of the aqueous phase is low, a small amount of other impurity metals can be extracted into the organic phase, which is not beneficial to the purification of ferric trichloride and the recovery of zinc. Test results show that the higher the acidity of the aqueous phase is, the lower the extraction capacity of the organic phase to zinc is, and when the acidity in the solution is more than 8mol/L, the zinc content in ferric trichloride can be ensured to be less than 0.01%, and the recovery rate of zinc is more than 99.99%.
Further, the step S2 can be repeated to saturate the iron in the organic layer and then perform back extraction, thereby increasing the iron concentration in the back extraction solution and saving the evaporation cost. The multi-time fractional extraction is favorable for completely extracting the ferric trichloride into an organic phase, and the recovery rate of the iron extraction can be more than 99.99%.
Further, in step S3, the washing solution is low-impurity iron-containing hydrochloric acid, the content of various metals is less than 0.01%, the concentration of hydrochloric acid is greater than 8mol/L, and the content of iron is greater than 0.25%. Wherein the higher the acidity, the higher the iron content and the lower the impurity content, the more beneficial the iron content of the organic layer is to be increased and the impurity content is to be reduced. Through the steps, the zinc in the organic layer can be effectively reduced to be below 0.0005%. The washing liquid can be repeatedly used until the zinc content is more than 0.1 percent.
Further, in step S4, the stripping agent is pure water or dilute acid water, and the concentration of the dilute acid water is 0.5% to 1%, preferably 0.5% dilute acid water. The aqueous phase has a certain acidity, so that the ferric trichloride can not generate ferric hydroxide hydrolysis in the subsequent evaporation process. And heating ferric trichloride to boiling, keeping boiling for 10-15 min, and removing organic matters in the stripping solution completely, wherein the TOC (total organic carbon) is detected. The process can improve the product concentration and remove organic matters in the ferric trichloride. The condensed water is evaporated and reused as the water for back extraction.
Further, in step S5, the aqueous phase is evaporated and concentrated to have a zinc content of 7% to 9%, and the hydrochloric acid concentration in the aqueous phase is 12% to 14%. Adding ammonia water with the concentration of 20-25% into the concentrated solution, and neutralizing hydrochloric acid to obtain a mixed solution containing 7-9% of zinc chloride and 14-15% of ammonium chloride, so as to meet the requirements of the plating assistant for the galvanizing industry. The concentration of the evaporation condensate hydrochloric acid is 28-31%, and the evaporation condensate hydrochloric acid can be recycled.
Further, in step S5, zinc can be recovered by electrolyzing an aqueous layer containing zinc chloride, hydrochloric acid, and trace impurity metals. The method for recovering the metal zinc by the electrolysis method has the following advantages compared with the method for directly electrolyzing the zinc-containing iron-containing waste liquid: 1. during electrolysis, a large amount of Fe in waste liquid is not needed3+Reduced to Fe first2+And the ferric chloride is oxidized to avoid the waste of energy consumption. Directly electrolyzing and regenerating the zinc-containing and iron-containing etching waste liquid, wherein Fe is required to be firstly added at the cathode of an electrolytic cell3+Reduction to Fe2+Then, Zn is added2+Reducing and depositing on a cathode plate, and transferring the low-zinc waste liquid to an anode to convert Fe2+Is oxidized into Fe3+Direct electrolysis process wastes power consumption to remove Fe3+Reduction to Fe2+Doing useless work; 2. because a large amount of iron ions are extracted from the solution, the concentration of interfering ions in the solution is greatly reduced when copper is extracted by electrolysis, and the current utilization rate can be improved; the zinc plate is not provided with iron, so that the possibility of low purity of the zinc plate is greatly reduced; 3. in the electrolytic process, chlorine generated by the anode can be fully utilized to oxidize Fe in the zinc-containing and iron-containing waste liquid2+The method saves the oxidation cost of the zinc-containing and iron-containing waste liquid, is an oxidation mode without introducing impurities and moisture in a plurality of oxidation modes, and is favorable for purifying and concentrating the ferric trichloride.
In conclusion, the method for extracting and separating the iron-containing and zinc-containing waste hydrochloric acid by butyl acetate has the following beneficial effects:
1. the extraction and separation of zinc and iron are relatively thorough by controlling the acidity of the water layer; the low-impurity iron-containing hydrochloric acid is used as a washing liquid, so that the purity and the concentration of ferric trichloride in the back extraction liquid are improved. By adopting the process, the recovery rates of zinc and iron are both as high as 99.99 percent, high-end ferric trichloride products and zinc ferrate can be obtained, and the economic value is higher.
2. Butyl acetate can be used as edible spice and is nontoxic. The iron trichloride and the ferry liquid are easy to volatilize when heated, can be completely removed by an evaporation process, does not influence the product quality of the iron trichloride and the ferry liquid, and the evaporation condensate can be repeatedly used as a stripping agent without the problem of organic wastewater discharge.
3. The extractant can be repeatedly used after back extraction.
Detailed Description
Test of influence of A solution acidity on extraction separation of zinc and iron from butyl acetate
Taking 10mL of a zinc-containing ferric trichloride sample, adding hydrochloric acid and water to prepare 40mL of ferric trichloride solution with acidity of 5, 6, 7, 8 and 9mol/L, extracting with 20mL of butyl acetate, performing back extraction with 10mL of water, and detecting a back extraction water phase, wherein test data are as follows:
the above data show that: when the acidity of the solution is low, butyl acetate extracts a small amount of zinc, and the acidity of the solution is more than 8mol/L, so that a better zinc-iron separation effect can be ensured.
Test of Effect of B Wash solution on Zinc impurity in organic layer
Taking 10mL of zinc-containing ferric trichloride, adding 40mL of hydrochloric acid and 20mL of butyl acetate, extracting, standing for layering, and taking an organic layer. The organic layer was washed with 10mL of different materials and the washed organic layer was examined, with the following results:
and (3) data analysis:
1. the pure water is used as a washing liquid, most of iron and zinc can be back-extracted, so that the iron concentration in the subsequent normal back-extraction liquid is reduced;
2. industrial hydrochloric acid is used as a washing liquid, so that a small amount of iron and most of zinc enter a water phase, and the iron concentration in a subsequent strip liquor is slightly reduced;
3. high-purity ferric trichloride is used as a washing liquid, and iron and impurity metals in a water phase can enter an organic phase, so that the purity of a subsequent strip liquor is reduced;
4. the material with acidity larger than 8mol/L and containing a certain amount of iron is selected as the washing liquid, so that the iron in the organic phase can be improved, the impurity metal in the organic phase can be effectively reduced, the washing liquid is a better washing liquid, and the washing liquid can be repeatedly utilized for multiple times.
The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments.
Example 1
A comprehensive recycling method of waste hydrochloric acid containing zinc and iron comprises the following steps:
s1 mixing 1kg of waste hydrochloric acid A containing zinc and iron0Introducing chlorine gas to lead Fe in the solution2+Oxidizing completely to obtain zinc-containing ferric trichloride solution;
s2, adding the ferric trichloride solution into 4kg of industrial hydrochloric acid and 2kg of butyl acetate, oscillating, standing until the layering is complete, and taking an organic layer;
s3, washing the organic layer in the S2 with 5kg of washing liquid, shaking and standing until the layering is complete, and taking the organic layer;
s4 adding 1kg pure water into the organic layer for back extraction, evaporating the aqueous layer to obtain high purity ferric trichloride A with ultra-low impurity content for 10min1The organic layer returns to the system for recycling;
s5 extracting the water layer in S2 with 2kg butyl acetate for 3 times until the content of iron is not detected, evaporating and concentrating the water layer until the content of zinc is 7.31%, cooling, adding industrial ammonia water to neutralize hydrochloric acid in the solution to obtain transition aid liquid A meeting the requirement of galvanizing industry21.62kg。
The experimental data are shown in the following table.
| Product index | High-purity ferric trichloride A1 | Plating assistant liquid A2 |
| Fe，％ | 10.2 | Not detected out |
| Zn，％ | 0.00014 | 3.52 |
| TOC，mg/L | Not detected out | Not detected out |
| NH4Cl，％ | ---- | 14.56 |
Example 2
A comprehensive recycling method of waste hydrochloric acid containing zinc and iron comprises the following steps:
s1 sample A of waste hydrochloric acid containing zinc and iron0Introducing chlorine gas to lead Fe in the solution2+Oxidizing completely to obtain zinc-containing ferric trichloride solution;
s2, adding 4kg of industrial hydrochloric acid and 2kg of butyl acetate into 1kg of zinc-containing ferric chloride solution, oscillating and standing until layering is complete, and taking an organic layer;
s3, adding 1kg of zinc-containing ferric chloride solution into the organic layer, adding 4kg of industrial hydrochloric acid, oscillating, standing until the layering is complete, and taking the organic layer;
s4 washing the organic layer with 5kg of the washing solution in the example 1, shaking and standing until the layering is complete, and taking the organic layer;
s5 back-extracting the organic layer in S4 with 1kg of 0.5% dilute hydrochloric acid to obtain aqueous layer of ferric trichloride with ultralow impurity content, and evaporating for 10min to obtain high-purity ferric trichloride B1The organic layer returns to the system for recycling;
s6 extracting the water layer of S2 with 2kg butyl acetate for 4 times until the content of iron is not detected, evaporating and concentrating the water layer until the content of zinc is 7.96%, cooling, adding industrial ammonia water to neutralize hydrochloric acid in the solutionCan obtain the ferry aiding liquid B meeting the galvanizing industry21.34kg。
The experimental data are shown in the following table.
| Product index | High-purity ferric trichloride B1 | Plating assistant liquid B2 |
| Fe，％ | 12.4 | Not detected out |
| Zn，％ | 0.00018 | 3.95 |
| TOC，mg/L | Not detected out | Not detected out |
| NH4Cl，％ | ---- | 14.21 |
Example 3
A comprehensive recycling method of waste hydrochloric acid containing zinc and iron comprises the following steps:
s1 mixing 1kg of waste hydrochloric acid A containing zinc and iron0Adding proper amount of industrial hydrochloric acid, adding oxygen and catalyst to make Fe in the solution2+Oxidizing completely to obtain zinc-containing ferric trichloride solution;
s2, adding 6kg of industrial hydrochloric acid and 2.5kg of butyl acetate into the zinc-containing ferric trichloride solution, oscillating and standing until layering is complete, and taking an organic layer;
s3 washing the organic layer with 5kg of the washing solution in the example 2, shaking and standing until the layering is complete, and taking the organic layer;
s4 back extracting the organic layer of S3 with 1kg pure water, evaporating the aqueous layer of ferric trichloride with ultra-low impurity content for 10min to obtain high-purity ferric trichloride C1The organic layer returns to the system for recycling;
s5 extracting the water layer in S2 with 2.5kg butyl acetate for 3 times until the content of iron is not detected, evaporating and concentrating the water layer until the content of zinc is 8.11%, cooling, adding industrial ammonia water to neutralize hydrochloric acid in the solution to obtain the ferry liquid C meeting the requirement of the galvanizing industry21.29kg。
The experimental data are shown in the following table.
| Product index | High-purity ferric trichloride C1 | Plating assistant liquid C2 |
| Fe，％ | 10.33 | Not detected out |
| Zn，％ | 0.00012 | 4.02 |
| TOC，mg/L | Not detected out | Not detected out |
| NH4Cl，％ | ---- | 13.96 |
Example 4
A comprehensive recycling method of waste hydrochloric acid containing zinc and iron comprises the following steps:
s1 mixing 1kg of waste hydrochloric acid A containing zinc and iron0Introducing chlorine gas to lead Fe in the solution2+Oxidizing completely to obtain zinc-containing ferric trichloride solution;
s2, adding a zinc-containing ferric trichloride solution into 6kg of condensate of the evaporated water layer in the step S5 in the embodiment 3 and 2.5kg of butyl acetate in the step S4 in the embodiment 3, oscillating and standing until the layering is complete, and taking an organic layer;
s3 washing the organic layer with 5kg of the washing solution in the example 3, shaking and standing until the layering is complete, and taking the organic layer;
s4 back-extracting the organic layer of S3 with 1kg 1% dilute hydrochloric acid to obtain aqueous layer of ferric trichloride with ultra-low impurity content, and evaporating for 60min to obtain high-purity ferric trichloride D1The organic layer returns to the system for recycling;
s5 extracting the water layer in S2 with 2.5kg of butyl acetate in step S5 of example 3 for 3 times until the iron content is not detected, evaporating and concentrating the water layer until the zinc content is 8.59%, cooling, adding industrial ammonia water to neutralize hydrochloric acid in the solution to obtain the transition aid liquid D meeting the requirement of the galvanizing industry21.22kg。
The experimental data are shown in the following table.
From the experimental data of examples 1 to 4, it can be seen that: by controlling the addition of hydrochloric acid and butyl acetate, the extractant only extracts iron, but not zinc; the zinc in the organic layer can be effectively extracted back to the water layer by using the low-impurity iron-containing hydrochloric acid as a detergent; through simple evaporation, residual organic matters in the ferric trichloride product and the zinc ferry liquid product can be removed. The purified and concentrated ferric trichloride can meet the requirements of high-end ferric trichloride application industries such as drinking water treatment, medical intermediates, analytical tests and precision etching, and the zinc ferrate can be returned to the galvanizing industry for use.
In the invention, hydrochloric acid is added to improve the acidity of the solution, and washing liquid is preferably selected, so that various impurity metals in ferric trichloride can be reduced to below 1ppm, the requirements of various high-purity ferric trichloride can be met, and the zinc ferrate can be returned to the galvanizing industry for use. The method has simple equipment, can effectively separate zinc and iron, the iron in the zinc is not detected, the zinc in the iron is less than 5ppm, the recovery rates of the zinc and the iron can reach 99.99 percent, the extracting agent can be repeatedly used, the purification cost is relatively low, and the method has popularization value.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The comprehensive recycling method of the zinc-containing and iron-containing waste hydrochloric acid is characterized by comprising the following steps of:
s1 adding waste hydrochloric acid containing zinc and iron into oxidant to make Fe in solution2+Oxidizing completely to obtain zinc-containing ferric trichloride solution;
s2, adding hydrochloric acid and butyl acetate into the zinc-containing ferric chloride solution, oscillating and standing until layering is complete;
s3, adding a washing solution into the organic layer in the S2, shaking and standing until the layering is complete;
s4, adding a stripping agent into the organic layer in the S3 to obtain a ferric trichloride solution, evaporating to obtain ferric trichloride, and returning the organic layer to the system for recycling;
s5, extracting the water layer in the S2 for multiple times by butyl acetate until the iron content is not detected, evaporating and concentrating the water layer, and adding ammonia water to neutralize hydrochloric acid in the solution to obtain a transition aid solution meeting the requirement of the galvanizing industry; or extracting the water layer in S2 with butyl acetate for several times until the iron content is not detected, and electrolyzing the water layer to recover zinc.
2. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 1, wherein the oxidation mode in step S1 is one or more of oxygen oxidation, air oxidation, ozone oxidation, sodium chlorate oxidation, potassium chlorate oxidation, hydrogen peroxide oxidation and chlorine oxidation.
3. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 1, wherein the volume ratio of the materials added in step S2 is, zinc-containing ferric chloride solution: hydrochloric acid: butyl acetate is 1: 4-6: 2-4.
4. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 3, wherein the hydrochloric acid added in step S2 makes the concentration of aqueous phase hydrochloric acid more than 8 mol/L.
5. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 3, wherein the water/oil ratio in step S2 is 1.5-3: 1.
6. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 1, wherein the organic layer in step S2 is subjected to repeated extraction of different aqueous phases for multiple times until the organic layer becomes saturated with iron, and the aqueous phase is subjected to 3-5-stage extraction, so that the iron in the aqueous phase completely enters the organic phase.
7. The method of claim 1, wherein the scrubbing solution of step S3 is one of industrial hydrochloric acid and ferric chloride solution with acidity greater than 8 mol/L.
8. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 1, wherein the stripping agent in step S4 is one of pure water and 0.5-1% dilute hydrochloric acid.
9. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 1, wherein the evaporation concentration temperature in step S4 is greater than 80 ℃ and the evaporation time is greater than 10 min.
10. The comprehensive recycling method of waste hydrochloric acid containing zinc and iron according to claim 1, wherein the water layer is evaporated and concentrated in step S5 to a zinc concentration of 7-9%.
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| CN114807603A (en) * | 2022-05-26 | 2022-07-29 | 重庆康普化学工业股份有限公司 | Method for extracting zinc from high-hydrochloric-acid washing liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108193052A (en) * | 2017-12-28 | 2018-06-22 | 江苏永葆环保科技有限公司 | Resource utilization prepares the method without ammonium fluxing agent using low acid waste water containing zinc |
| CN111443079A (en) * | 2020-04-16 | 2020-07-24 | 斯瑞尔环境科技股份有限公司 | Method for simultaneously detecting contents of trace As, Pb, Cd, Zn, Cr, Co and V elements in ferric trichloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108193052A (en) * | 2017-12-28 | 2018-06-22 | 江苏永葆环保科技有限公司 | Resource utilization prepares the method without ammonium fluxing agent using low acid waste water containing zinc |
| CN111443079A (en) * | 2020-04-16 | 2020-07-24 | 斯瑞尔环境科技股份有限公司 | Method for simultaneously detecting contents of trace As, Pb, Cd, Zn, Cr, Co and V elements in ferric trichloride |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807603A (en) * | 2022-05-26 | 2022-07-29 | 重庆康普化学工业股份有限公司 | Method for extracting zinc from high-hydrochloric-acid washing liquor |
| CN114807603B (en) * | 2022-05-26 | 2023-08-22 | 重庆康普化学工业股份有限公司 | Method for extracting zinc from high hydrochloric acid washing liquid |
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