CN114807603B - Method for extracting zinc from high hydrochloric acid washing liquid - Google Patents
Method for extracting zinc from high hydrochloric acid washing liquid Download PDFInfo
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- CN114807603B CN114807603B CN202210588578.8A CN202210588578A CN114807603B CN 114807603 B CN114807603 B CN 114807603B CN 202210588578 A CN202210588578 A CN 202210588578A CN 114807603 B CN114807603 B CN 114807603B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000011701 zinc Substances 0.000 title claims abstract description 56
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 54
- 239000007788 liquid Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005406 washing Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000000605 extraction Methods 0.000 claims abstract description 72
- 238000000926 separation method Methods 0.000 claims abstract description 54
- 229910052742 iron Inorganic materials 0.000 claims abstract description 50
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims description 70
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- 235000005074 zinc chloride Nutrition 0.000 abstract description 4
- 239000011592 zinc chloride Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- -1 iron ions Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005554 pickling Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000002699 waste material Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 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
- 230000010355 oscillation Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
-
- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The application relates to the technical field of chemical extraction, in particular to a method for extracting zinc from high hydrochloric acid washing liquid. The method uses pyridine carboxylic acid ester extractant to co-extract zinc and a small amount of iron in hydrochloric acid washing liquor, and then realizes primary separation of zinc and iron; and then, oxidizing low-valence iron in the zinc-rich strip liquor obtained by the front-stage process by using an oxidant, and removing iron by using a phosphoric acid extractant to realize thorough separation of zinc and iron and obtain a zinc chloride solution with higher purity. The technical scheme solves the technical problem that the prior art is difficult to extract and recycle zinc from the high hydrochloric acid washing liquid simply and efficiently. The scheme has the characteristics of simple process, rich process production resources, and the obtained finished product has the iron content not more than 10ppm, can effectively realize comprehensive recycling of resources, and has wide application prospect.
Description
Technical Field
The application relates to the technical field of chemical extraction, in particular to a method for extracting zinc from high hydrochloric acid washing liquid.
Background
The steel industry is a representative of the heavy industry in China, is an important component part of the national economy in China, and the world leading steel yield promotes the vigorous development of the infrastructure industry, the automobile industry and the like in China. In the process of preparing steel materials, a surface cleaning agent is required to clean a metal oxide layer and other impurities on the surface of steel materials, and an acid cleaning process using high-concentration hydrochloric acid as a cleaning agent is currently the main process for acid cleaning of the steel materials. The hydrochloric acid pickling waste liquid generally contains 100-200g/L Fe 2+ And Fe (Fe) 3 + 30-50g/L H + A certain amount of Zn 2+ And other metal ions. Because the pickling waste liquid has great harm to water and soil environment, normal physiological activities of aquatic plants and animals can be endangered, the enrichment of metal ions can cause secondary pollution to water, the soil structure is changed to influence the growth of crops, and the phenomenon of metal poisoning occurs after the enrichment in human bodies. Meanwhile, the hydrochloric acid pickling waste liquid has high annual output, strong fluidity and high harmfulness, is difficult to treat, harms the ecological environment and the like, and is listed in the list of the harmful wastes in China. Therefore, the environment-friendly treatment of the pickling solution is a currently developed hot spot, and scientific researchers develop various methods for treating the pickling solution, so as to reduce the pollution of the pickling waste solution to the environment and improve the utilization rate of resources. The method mainly comprises precipitation of metal ions, acid neutralization, extraction method and the like. Due to the specificity of the various isolation methods, there are always respective disadvantages. Such as precipitation and acid neutralization, a large amount of alkaline substances are needed, the cost is high, a large amount of acid in pickling solution is lost, a large amount of waste salt solid slag is generated, and the subsequent treatment is difficult. The extraction method has larger separation difference according to the types of the extracting agents. When the zinc-iron extractant circulated in the current market is used for treating washing liquid containing high iron, high zinc and high hydrochloric acid, the zinc-iron separation effect is poor or the separation cost is higher, and the main reason is that part of the extractant can realize the preliminary separation of metal ions under the high acid condition, but cannot realize the thorough separation of metals; the other part of extractant can realize complete separation of metal ions in the whole system, but a large amount of alkaline substances are needed to be added. Therefore, how to improve the comprehensive recycling value of the high-hydrochloride washing liquid and realize the efficient and simple separation and extraction of zinc is a problem to be solved in the technical field.
Disclosure of Invention
The application aims to provide a method for extracting zinc from high hydrochloric acid washing liquid, which aims to solve the technical problem that the prior art is difficult to extract and recycle zinc from the high hydrochloric acid washing liquid simply and efficiently.
In order to achieve the above purpose, the application adopts the following technical scheme:
a method for extracting zinc from a high hydrochloric acid wash comprising a first separation step:
s1, extraction: mixing the organic phase A with a high hydrochloric acid washing liquid containing iron and zinc, and extracting to obtain a first loaded organic phase I and a first raffinate I;
s2, back extraction: mixing a stripping agent I with a first loaded organic phase I, and carrying out stripping to obtain a first lean organic phase I and a first stripping liquid I;
s3, circulation: extracting the first raffinate I by using the first lean organic phase I, and adding an acidity constant agent to obtain a second loaded organic phase I and a second raffinate I; carrying out back extraction on the second loaded organic phase I by using the first back extraction liquid I to obtain a second lean organic phase I and a second back extraction liquid I;
extracting the N-1 raffinate I by using the N-1 lean organic phase I, and adding an acidity constant agent to obtain an N loaded organic phase I and an N raffinate I; carrying out back extraction on the N-th loaded organic phase I by using the N-1-th back extraction liquid I to obtain an N-th lean organic phase I and an N-th back extraction liquid I; wherein N is 5-7.
The principle adopting the technical scheme has the beneficial effects that:
in this embodiment, the high hydrochloric acid wash contains a large amount of iron ions (including divalent and trivalent iron, collectively referred to as iron ions in this embodiment) and a small amount of zinc ions, as well as other small amounts of metal ions. The acidity of the wash liquor and the presence of large amounts of iron ions have a major impact on zinc ion enrichment and separation. In the technical scheme, the organic phase A containing pyridine carboxylic acid ester extractant is used for directly extracting the high hydrochloric acid washing liquid, so that a large amount of zinc and a small amount of iron are enriched in the Nth strip liquor I, and the enrichment of zinc and the separation of zinc and iron are preliminarily realized. The technical scheme can directly treat the high hydrochloric acid washing liquid without adjusting the pH value before extraction, thereby simplifying the process flow and reducing the cost.
Further, the method also comprises a second step of separation:
SS1 extraction: extracting the Nth strip liquor I after oxidation treatment by using an organic phase B to obtain a loaded organic phase II and a raffinate II;
SS2 strip: and stripping the loaded organic phase II by using a stripping agent II to obtain a lean organic phase II and a stripping liquid II.
Further, in the first separation step, the organic phase A comprises a diluent and a pyridine carboxylic acid ester extractant with a structural formula shown in a formula I;
wherein R is 1 And R is 2 Respectively selected from alkyl groups with 10-15 carbon atoms.
According to the extraction method and process for zinc in the high hydrochloric acid washing liquid, two kinds of extracting agents are adopted to separate and extract zinc in a high hydrochloric acid system step by step, the zinc and a certain amount of impurities are extracted in the first step, the zinc chloride solution with higher purity is obtained through impurity removal in the second step, the raffinate in the first step and the strip liquor in the second step flow back to the acid washing section, waste of high hydrochloric acid waste liquid after zinc extraction is avoided, acid circulation is realized, and good ecological environment and economic benefits are achieved.
Further, in the first separation step, the volume fraction of the pyridine carboxylic acid ester extractant in the organic phase A is 20-40%. The organic phase with the content can realize the full extraction of zinc ions and is eluted in the pure water back extraction process.
Further, in the first separation step, the volume ratio of the organic phase A to the high hydrochloric acid washing liquid containing iron and zinc is 4-1:1; the extraction mixing time is at least 5min. The O/A ratio and the extraction time can ensure the sufficient extraction of zinc ions.
Further, in the first separation step, the volume ratio of the stripping agent I to the first loaded organic phase I is 1:1-4; the back extraction mixing time is at least 5min; the back extraction agent I is water. The O/A ratio and the back extraction time can ensure that zinc ions are fully back extracted.
Further, the zinc ion content in the Nth raffinate I is 0.2-0.8g/L; the pH value of the Nth stripping liquid I is 0.1-0.3.
Further, in the second back extraction step, the phosphoric acid extractant is Mextral 204P; the stripping agent II is 3-5mol/L HCl solution; and (3) oxidizing the Nth stripping solution I by using hydrogen peroxide, wherein the use amount of the hydrogen peroxide is 0.1-0.5% of the mass of the Nth stripping solution I, and obtaining the oxidized Nth stripping solution I. By oxidizing to convert ferrous iron into ferric iron, the Mextral 204P has a good extraction effect on ferric iron, and can remove iron in zinc ions and promote zinc-iron separation.
Further, in the second stripping step, the stripping solution II is refluxed to the high hydrochloric acid washing solution containing iron and zinc in S1; the iron content of raffinate II is 0.005-0.01g/L.
Further, the SS1 extraction and the SS2 back extraction both adopt countercurrent extraction processes, the extraction and the back extraction have at least 2 stages, and the single-stage mixing time is at least 3min; the volume ratio of the Nth stripping liquid I after the oxidation treatment to the organic phase B is 1:1-4; the volume ratio of the stripping agent II to the loaded organic phase II is 1:1-4. The two extraction and the two reverse can realize the full separation of zinc and iron.
Detailed Description
The present application will be described in further detail with reference to the following embodiments, but the embodiments of the present application are not limited thereto. The technical means used for the following implementation are, unless otherwise indicated, conventional means well known to those skilled in the art: the materials, reagents, and the like used are all commercially available.
Example 1
A first step of separation:
s1, extraction: the organic phase A was washed with a high hydrochloric acid washing liquid containing iron and zinc (the same batch of high hydrochloric acid washing liquid was used in all examples and comparative examples of this scheme, which was measured to contain about 150g/L of Fe 2+ And Fe (Fe) 3+ 50g/L H + Zn of 46g/L 2+ ) Mixing according to the volume ratio of 4:1, oscillating for 5min, and then separating phases to obtain a first loaded organic phase I and a first raffinate I. The organic phase A consists of pyridine carboxylic ester extractant shown in formula I and sulfonated kerosene diluent, wherein R 1 And R is 2 Are all C 13 H 27 (methods for synthesizing the compounds are described in the literature: synthesis of the metal extractant MextralCLX-50 and copper extraction PropertiesCan be studied, hydrometallurgy, 2013). The volume fraction of the pyridine carboxylic acid ester extractant is 20%.
S2, back extraction: mixing the stripping agent I and the first loaded organic phase I according to the volume ratio of 1:4, and carrying out mixing oscillation on the two phases for 3min to obtain a first lean organic phase I and a first stripping liquid I through stripping. The stripping agent I is water, in this example, particularly preferably purified water.
S3, circulation: the first lean organic phase I is returned to the first raffinate I, meanwhile, an acidity constant agent HCl solution (the added amount is 0.04% of the volume of the first raffinate I and the mass fraction of the HCl solution is 36%) is added, and the second loaded organic phase I and the second raffinate I are obtained by shaking for 5 minutes and phase separation. And mixing the first stripping liquid I and the second loaded organic phase I, oscillating for 5min, and phase-separating to obtain a second lean organic phase I and a second stripping liquid I. Extracting the N-1 raffinate I by using the N-1 lean organic phase I, and simultaneously adding an acidity constant HCl solution (the adding amount is the same as the adding amount) to obtain an N loaded organic phase I and an N raffinate I (the N raffinate I returns to a high hydrochloric acid washing liquid containing iron and zinc); and carrying out back extraction on the N-th loaded organic phase I by using the N-1-th back extraction liquid I to obtain an N-th lean organic phase I and an N-th back extraction liquid I. This step was repeated 5 times (n=5) to obtain a fifth lean organic phase i and a fifth strip i, and a fifth raffinate i. The zinc ion content in the fifth raffinate I was 0.8g/L (this fraction was returned to the high hydrochloric acid wash), and the fifth strip I contained mainly zinc ions (for the second separation step) and contained a small amount of impurities including iron ions. The primary separation of zinc and iron is realized through the first separation step.
And a second step of separation:
SS1 extraction and SS2 stripping: and the pH value of the fifth stripping solution I is 0.1, hydrogen peroxide is added to oxidize low-valence iron ions in the fifth stripping solution I, the dosage of the hydrogen peroxide is 0.4% of the mass of the fifth stripping solution I, and the fifth stripping solution I after the oxidation treatment is obtained.
In the embodiment, a two-extraction two-reverse-flow extraction process is adopted, the ratio (volume ratio) of the organic phase B to the fifth reverse-extraction liquid I after oxidation treatment is 4:1, the single-stage mixing time is 3min, and the loaded organic phase II and the raffinate II are obtained after two-stage extraction. The organic phase B consists of phosphoric acid extractant and diluent, wherein the phosphoric acid extractant is specifically Mextral 204P (P204), the diluent is sulfonated kerosene, and the volume percentage of the Mextral 204P is 10%. In the back extraction process, the ratio (volume ratio) of the back extraction agent II to the loaded organic phase II is 1:4, the single-stage mixing time is 3min, and the lean organic phase II and the back extraction liquid II are obtained after two-stage back extraction. Wherein, the stripping agent II is 5mol/L HCl solution. The main component in the raffinate II is zinc chloride, and the content of impurity iron ions is 0.01g/L, so that the raffinate II is used for further producing the zinc chloride. The zinc-iron ratio in the stripping solution II is smaller, and the stripping solution is returned to the original high hydrochloric acid washing solution. Through the second separation step, the zinc and iron are thoroughly separated.
Examples 2-5 are basically the same as example 1, except that some parameters are selected, see table 1 for details, and the flow chart is shown in fig. 1. Fig. 1 is an overall flow.
Table 1: parameter settings of examples 1 to 5
In Table 1, the zinc-iron separation is complete with respect to the amount of iron impurities present in raffinate II, and strip II is recycled back to the pickling solution, so that the zinc-iron ratio does not exhibit the separation effect. The main investigation indexes of the process effect are an Nth strip liquor I and a raffinate II, wherein the Nth strip liquor I shows the extraction effect of zinc in the pickling solution, and the raffinate II shows the thorough separation effect of zinc and iron. According to the experimental data in table 1, the process method can realize relatively efficient separation and recovery of zinc in pickling solution, and realize extraction of zinc in a high hydrochloric acid system.
Comparative example 1
This comparative example is substantially the same as example 1 except that the oxidation treatment of the strip liquor I with hydrogen peroxide is not performed in the second separation step. The content of iron ions in the raffinate II is more than 2g/L, so that the zinc-iron separation cannot be realized thoroughly.
Comparative example 2
This comparative example is substantially the same as example 1, except that in the second separation step, the stripping agent II was 2mol/L HCl solution and 5.5mol/L HCl solution. The excessive acidity of the stripping agent II does not affect the separation result, but the acidity of the pickling solution is gradually increased after the stripping solution II returns to the pickling solution, which affects the first separation step and increases the acid consumption. The too low acid degree of the stripping agent II influences the stripping effect of the organic phase B, so that the stripping is incomplete, the extraction capacity of the organic phase B in the subsequent circulation process is reduced, and the zinc-iron separation effect in the second separation step is gradually influenced.
In this embodiment, the high hydrochloric acid wash contains a large amount of iron ions (including divalent and trivalent iron, collectively referred to as iron ions in this embodiment) and a small amount of zinc ions, as well as other small amounts of metal ions. The acidity of the wash liquor and the presence of large amounts of iron ions have a major impact on zinc ion enrichment and separation. In the technical scheme, the organic phase A containing pyridine carboxylic acid ester extractant is used for directly extracting the high hydrochloric acid washing liquid, so that a large amount of zinc and a small amount of iron are enriched in the Nth stripping liquid I. Pyridine carboxylic acid ester type extractant is suitable for extraction of copper ions, but it is not known whether it is suitable for extraction of zinc ions. Attempts have been made to find that pyridine carboxylic acid ester extractants can also be used for extraction of zinc ions. However, due to the particularity of the pickling solution, even if pyridine carboxylic acid ester extractant is used, the extraction effect on zinc is good, and the effective separation of zinc and iron cannot be completely realized under the working condition. The inventors were faced with two options, namely, iron ion removal prior to use of the pyridine carboxylate extractant, and separation of zinc and iron in the nth strip liquor i after extraction with the pyridine carboxylate extractant.
The inventors first tried to separate and remove iron ions using various extractants, as exemplified by P204, see in comparative example 3.
Comparative example 3:
this comparative example is substantially the same as the first separation step of example 1 (the second separation step was not performed), except that in the first separation step, the extractant of the organic phase A used was P204, and the stripping agent I was 4mol/L HCl, which was circulated five times.
The Nth stripping liquid I (fifth stripping liquid I) contains 1g/L zinc ions and 110g/L iron ions, and the Nth stripping liquid I contains 45g/L zinc ions and 40g/L iron ions. Therefore, the extractant such as P204 and the like cannot effectively separate zinc and iron, and the N raffinate I contains a small amount of cadmium, manganese and other metal ions besides the metal ions, so that the impurity content is high, and even though the zinc ions in the N raffinate I are extracted and separated later, the technical difficulty is high and the separation effect is poor. In addition, in many cases, the acidity of the high hydrochloric acid wash is very high (higher than the one used in this comparative example), which results in the acidity reaching the limit of P204 itself, and various metal ions in the Nth raffinate I mix and cannot be separated.
After a number of attempts, the inventors have not found suitable extractants and working processes, and have therefore forgoed the step of separating iron ions prior to the use of pyridine carboxylic acid ester extractants. In addition, the comparison of the first separation step of comparative example 3 with that of example 1 also demonstrates that both P204 alone and picolinate extractant alone are difficult to achieve zinc enrichment and zinc-iron separation. However, the combination of the two can achieve the effect of fully separating zinc and iron by using the two in a certain sequence.
The inventors further tried to conduct zinc-iron separation treatment after directly extracting the high hydrochloric acid washing liquid using the organic phase a containing the pyridine carboxylic acid ester extractant. In this process, a number of candidate extractants were also tried, as illustrated by comparative example 4.
Comparative example 4
This comparative example is substantially the same as example 1, except that in the first separation step, the extractant used was the pyridinecarboxylate extractant of example 1, and in the second separation step, the extractant used was P507. The raffinate II contained 44.1g/L zinc ions and 8.4g/L iron ions. This demonstrates that the combination of pyridine carboxylic acid ester extractant and P204 provides the most excellent extraction of zinc from high hydrochloric acid environments.
In addition, the inventors have tried extractants such as P272, 292P and 471P in the second separation step, and found that the raffinate II contains iron ions in an amount of more than 5g/L, and zinc and iron cannot be separated effectively. It is illustrated that under this condition, P204 is the most suitable extractant for use with pyridine carboxylic acid ester extractants.
The foregoing is merely exemplary of the present application, and specific technical solutions and/or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (9)
1. A method for extracting zinc from a high hydrochloric acid wash solution, comprising a first separation step of:
s1, extraction: mixing the organic phase A with a high hydrochloric acid washing liquid containing iron and zinc, and extracting to obtain a first loaded organic phase I and a first raffinate I;
s2, back extraction: mixing a stripping agent I with a first loaded organic phase I, and carrying out stripping to obtain a first lean organic phase I and a first stripping liquid I;
s3, circulation: extracting the first raffinate I by using the first lean organic phase I, and adding an acidity constant agent to obtain a second loaded organic phase I and a second raffinate I; carrying out back extraction on the second loaded organic phase I by using the first back extraction liquid I to obtain a second lean organic phase I and a second back extraction liquid I;
extracting the N-1 raffinate I by using the N-1 lean organic phase I, and adding an acidity constant agent to obtain an N loaded organic phase I and an N raffinate I; carrying out back extraction on the N-th loaded organic phase I by using the N-1-th back extraction liquid I to obtain an N-th lean organic phase I and an N-th back extraction liquid I; wherein N is 5-7;
the organic phase A comprises a diluent and a pyridine carboxylic ester extractant with a structural formula shown in formula I;
wherein R is 1 And R is 2 Respectively selected from alkyl groups with 10-15 carbon atoms.
2. The method for extracting zinc from a high hydrochloric acid wash solution according to claim 1, further comprising a second separation step of:
SS1 extraction: extracting the Nth strip liquor I after oxidation treatment by using an organic phase B to obtain a loaded organic phase II and a raffinate II;
SS2 strip: and stripping the loaded organic phase II by using a stripping agent II to obtain a lean organic phase II and a stripping liquid II.
3. A method for extracting zinc from a high hydrochloric acid wash liquor according to claim 1, characterized in that in the first separation step, the volume fraction of pyridine carboxylic acid ester extractant in the organic phase a is 20-40%.
4. A method for extracting zinc from a high hydrochloric acid wash liquor according to claim 3, characterized in that in the first separation step the volume ratio of organic phase a to the high hydrochloric acid wash liquor containing iron and zinc is 4-1:1; the extraction mixing time is at least 5min.
5. A process for extracting zinc from a high hydrochloric acid wash liquor according to claim 4, wherein in the first separation step the volume ratio of stripping agent I to first loaded organic phase I is from 1:1 to 4; the back extraction mixing time is at least 5min; the back extraction agent I is water.
6. The process for extracting zinc from a high hydrochloric acid wash solution according to claim 5, wherein the zinc ion content in the nth raffinate i is 0.2-0.8g/L; the pH value of the Nth stripping liquid I is 0.1-0.3.
7. The method for extracting zinc from a high hydrochloric acid wash solution according to claim 2, wherein in the second stripping step, the phosphoric acid extractant is Mextral 204P; the stripping agent II is 3-5mol/L HCl solution; and (3) oxidizing the Nth stripping solution I by using hydrogen peroxide, wherein the use amount of the hydrogen peroxide is 0.1-0.5% of the mass of the Nth stripping solution I, and obtaining the oxidized Nth stripping solution I.
8. The method for extracting zinc from a high hydrochloric acid wash solution according to claim 7, wherein in the second stripping step, the strip solution ii is refluxed to the high hydrochloric acid wash solution containing iron and zinc in S1; the iron content of raffinate II is 0.005-0.01g/L.
9. The method for extracting zinc from high hydrochloric acid washing liquor according to claim 8, wherein the steps of the extraction and the back extraction of SS1 and SS2 are at least 2 steps and the single-stage mixing time is at least 3min; the volume ratio of the Nth stripping liquid I after the oxidation treatment to the organic phase B is 1:1-4; the volume ratio of the stripping agent II to the loaded organic phase II is 1:1-4.
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