CN110668489A - Method for preparing zinc sulfate monohydrate from zinc-containing waste residue - Google Patents
Method for preparing zinc sulfate monohydrate from zinc-containing waste residue Download PDFInfo
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- CN110668489A CN110668489A CN201911184899.6A CN201911184899A CN110668489A CN 110668489 A CN110668489 A CN 110668489A CN 201911184899 A CN201911184899 A CN 201911184899A CN 110668489 A CN110668489 A CN 110668489A
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- C01—INORGANIC CHEMISTRY
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- C01G9/00—Compounds of zinc
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Abstract
The invention relates to a method for preparing zinc sulfate monohydrate from zinc-containing waste residue, which comprises the following steps of 1) washing the zinc-containing waste residue with an ethanol water solution, then adding the zinc-containing waste residue into a sulfuric acid solution, reacting and filtering to obtain primary filtrate; 2) adding hydrogen peroxide and zinc hydroxide into the primary filtrate, reacting, removing iron impurities and redundant sulfuric acid, and filtering to obtain secondary filtrate; 3) adding zinc powder into the secondary filtrate, performing a displacement reaction, and filtering to obtain filtrate; 4) adding the filtrate into methanol, stirring, standing, filtering, dissolving with water, heating, and filtering to obtain crystallized filtrate; 5) and heating the crystallized filtrate, introducing pure air into the filtrate at the same time to evaporate and crystallize the filtrate, and then drying crystals by microwave to obtain the zinc sulfate monohydrate. The product of the invention has less impurities, simpler processing method and mild reaction conditions.
Description
Technical Field
The invention belongs to the field of chemical production and preparation, and particularly relates to a method for preparing zinc sulfate monohydrate from zinc-containing waste residues.
Background
The zinc sulfate monohydrate is white flowable powder with the density of 3.28g/cm3Soluble in water, slightly soluble in alcohol, very deliquescent in air, and insoluble in acetone. It is generally prepared by reacting zinc oxide or hydroxide with sulfuric acid. The zinc salt is mainly used as a production raw material of other zinc salts, and is used for preparing pure zinc by cable galvanizing and electrolysis, a spraying agent for fruit tree nursery diseases, and a preservative for artificial fibers, wood and leather.
The production process of zinc sulfate mainly comprises the following steps: 1. the synthesis method of zinc salt or zinc oxide and sulfuric acid comprises 2, sulfuric acid leaching zinc ore, 3, calcining zinc blende and the like.
The production flow of producing the zinc sulfate monohydrate by using the zinc oxide generally comprises the following steps: rinsing zinc oxide → zinc oxide + sulfuric acid → middle leaching reaction → rough filtration → adding hydrogen peroxide + deironing → adding zinc oxide, adjusting pH value → filter pressing → adding zinc powder, removing cadmium → filter pressing → multiple-effect evaporation → concentrated crystallization → centrifugal dehydration → drying → packaging.
When the zinc-containing waste residue is used for preparation, because the zinc-containing waste residue contains a large amount of impurities, some of the impurities can be dissolved in a sulfuric acid solution, such as iron and cadmium, and can be removed by adding an oxidant or replacing with zinc powder, but some impurities, such as lead, cadmium, arsenic, iron and the like, can enter zinc sulfate monohydrate crystals if not removed, so that the impurity content of the zinc sulfate monohydrate crystals is over-standard, the growth of the zinc sulfate monohydrate crystals can be directly influenced, the dehydration and drying are difficult, and the subsequent treatment is very troublesome.
Chinese patent application No. 201110184452.6 discloses a production method of zinc sulfate monohydrate, which comprises the following process steps:
1) taking waste zinc containing lead, cadmium, arsenic and iron as an initial raw material, taking water as a solvent, adding 550kg of sulfuric acid solution with the concentration of 93-98% into each ton of waste zinc, reacting for 150 minutes at 65-75 ℃, controlling the pH value at the end point of the reaction to be more than 4.5, and performing filter pressing separation after the reaction is finished to obtain zinc sulfate-containing liquid and solid impurities; 2) taking the zinc sulfate-containing liquid obtained in the step 1), and oxidizing the zinc sulfate-containing liquid with air at 65-80 ℃ for 160-200 minutes to obtain a primary purified zinc sulfate-containing liquid; 3) adding 3.5-5g/L zinc powder into the primary purified zinc sulfate-containing liquid obtained in the step 2), adding 0.8-1.2g/L active carbon, and reacting at 35-60 ℃ for 65-85 minutes to obtain secondary purified zinc sulfate-containing liquid and secondary purified slag; 4) adding 2.5-4.5g/L zinc powder into the secondary purified zinc sulfate-containing liquid obtained in the step 3), reacting for 65-85 minutes at 35-60 ℃, and performing filter pressing separation after the reaction is finished to obtain tertiary purified zinc sulfate-containing liquid and tertiary purified slag; 5) taking the third purified zinc sulfate-containing liquid obtained in the step 4), evaporating, concentrating, and performing centrifugal separation to obtain hydrous zinc sulfate and mother liquor; 6) drying the hydrous zinc sulfate obtained in the step 6) to obtain the product zinc sulfate monohydrate. Concentrated sulfuric acid solution is needed to be used in the scheme, and the method has certain limitation, and materials containing other impurities cannot be effectively treated.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing zinc sulfate monohydrate from zinc-containing waste residues, wherein the impurities in the product are less, the treatment method is simpler, and the reaction conditions are mild.
The invention relates to a method for preparing zinc sulfate monohydrate from zinc-containing waste residue, which comprises the following steps,
1) washing the zinc-containing waste residue with an ethanol water solution, then adding the zinc-containing waste residue into a sulfuric acid solution with the weight concentration of 60-80%, reacting, and filtering to obtain primary filtrate;
2) adding hydrogen peroxide and zinc hydroxide into the primary filtrate, reacting, removing iron impurities and redundant sulfuric acid, and filtering to obtain secondary filtrate;
3) adding zinc powder into the secondary filtrate, performing a displacement reaction, and filtering to obtain filtrate;
4) adding the filtrate into methanol, stirring, standing, filtering, dissolving with water, heating to 80-90 deg.C, and filtering to obtain crystallized filtrate;
5) heating the crystallization filtrate at 70-90 deg.C, introducing 70-90 deg.C pure air into the filtrate, and controlling air flow at 0.1-0.5m3And h, evaporating and crystallizing the filtrate, and then drying crystals by microwave to obtain the zinc sulfate monohydrate.
In the ethanol water solution, the volume concentration of ethanol is 50-70%.
The weight of the hydrogen peroxide is 2-3% of the weight of the primary filtrate.
The weight of the zinc hydroxide is 1-2% of the weight of the primary filtrate.
The weight of the zinc powder is 1-2% of the weight of the secondary filtrate.
Controlling air flow rate to 0.1-0.2m3/h。
The microwave drying method comprises drying the crystal under 915 MHz microwave for 5-10 min.
The method has the beneficial effects that the raw materials are placed in the ethanol aqueous solution for washing, the ethanol solution has better erosion effect on substances in the waste residues, and impurities can be better removed.
The method firstly carries out the operation of dissolving the displaced filtrate in the methanol, and the magnesium sulfate is easy to separate out due to the poor solubility of the magnesium sulfate in the methanol, thereby realizing the separation of the magnesium sulfate and the zinc sulfate and having better impurity removal effect of the product.
When the evaporation crystallization is carried out, on one hand, the filtrate is heated, on the other hand, a small amount of pure air is introduced into the filtrate, the flow rate of the air is low, the growth of crystals is influenced by the air when the filtrate is subjected to the evaporation crystallization, the particle size of the crystals is proper and not large or small, and therefore the problems of subsequent drying and storage are well solved.
Detailed Description
Example 1
The method for preparing the zinc sulfate monohydrate from the zinc-containing waste residue comprises the following steps,
1) washing the zinc-containing waste residue with an ethanol water solution with the volume concentration of 50%, then adding the zinc-containing waste residue into a sulfuric acid solution with the weight concentration of 60-80%, reacting, and filtering to obtain primary filtrate;
2) adding hydrogen peroxide and zinc hydroxide into the primary filtrate, reacting, removing iron impurities and redundant sulfuric acid, and filtering to obtain secondary filtrate; the weight of the hydrogen peroxide is 3% of the weight of the primary filtrate, and the weight of the zinc hydroxide is 2% of the weight of the primary filtrate.
3) Adding zinc powder into the secondary filtrate, performing a displacement reaction, and filtering to obtain filtrate; the weight of the zinc powder is 1 percent of the weight of the secondary filtrate.
4) Adding the filtrate into methanol, stirring, standing, filtering, dissolving with water, heating to 80 deg.C, and filtering to obtain crystallized filtrate;
5) heating the crystallization filtrate at 70 deg.C, introducing 70 deg.C pure air into the filtrate, and controlling air flow at 0.1m3And/h, evaporating and crystallizing the filtrate, and then carrying out microwave drying on the crystal at 915 MHz for 5min to obtain the zinc sulfate monohydrate.
Example 2
The method for preparing the zinc sulfate monohydrate from the zinc-containing waste residue comprises the following steps,
1) washing the zinc-containing waste residue with an ethanol water solution with the ethanol volume concentration of 70%, then adding the zinc-containing waste residue into a sulfuric acid solution with the weight concentration of 60-80%, reacting, and filtering to obtain primary filtrate;
2) adding hydrogen peroxide and zinc hydroxide into the primary filtrate, reacting, removing iron impurities and redundant sulfuric acid, and filtering to obtain secondary filtrate; the weight of the hydrogen peroxide is 2% of the weight of the primary filtrate, and the weight of the zinc hydroxide is 1% of the weight of the primary filtrate.
3) Adding zinc powder into the secondary filtrate, performing a displacement reaction, and filtering to obtain filtrate; the weight of the zinc powder is 2 percent of the weight of the secondary filtrate.
4) Adding the filtrate into methanol, stirring, standing, filtering, dissolving with water, heating to 90 deg.C, and filtering to obtain crystallized filtrate;
5) heating the crystallization filtrate at 90 deg.C, introducing 80 deg.C pure air into the filtrate, and controlling air flow at 0.2m3And/h, evaporating and crystallizing the filtrate, and then carrying out microwave drying on the crystal at 915 MHz for 10min to obtain the zinc sulfate monohydrate.
Example 3
The method for preparing the zinc sulfate monohydrate from the zinc-containing waste residue comprises the following steps,
1) washing the zinc-containing waste residue with an ethanol water solution with the volume concentration of ethanol of 60%, then adding the zinc-containing waste residue into a sulfuric acid solution with the weight concentration of 60-80%, reacting, and filtering to obtain primary filtrate;
2) adding hydrogen peroxide and zinc hydroxide into the primary filtrate, reacting, removing iron impurities and redundant sulfuric acid, and filtering to obtain secondary filtrate; the weight of the hydrogen peroxide is 2.5% of the weight of the primary filtrate, and the weight of the zinc hydroxide is 1.5% of the weight of the primary filtrate.
3) Adding zinc powder into the secondary filtrate, performing a displacement reaction, and filtering to obtain filtrate; the weight of the zinc powder is 1.5 percent of the weight of the secondary filtrate.
4) Adding the filtrate into methanol, stirring, standing, filtering, dissolving with water, heating to 85 deg.C, and filtering to obtain crystallized filtrate;
5) heating the crystallized filtrate at 80 deg.C, introducing 80 deg.C pure air into the filtrate, and controlling air flow at 0.3m3And/h, evaporating and crystallizing the filtrate, and then carrying out microwave drying on the crystal at 915 MHz for 8min to obtain the zinc sulfate monohydrate.
The product quality of examples 1-3 above was tested to obtain the data in Table 1.
TABLE 1 quality Performance Table of the products of the different examples
| Quality performance | Standard (HG2934-2000) | Example 1 | Example 2 | Example 3 |
| ZnSO4·H2O | ≥94.7％ | 97.8％ | 97.4％ | 97.2％ |
| Particle size% (250 μm sieve) | ≥95 | 98.6 | 98.1 | 98.8 |
| The content of Mg is less than or equal to | -- | 0.0001 | 0.0002 | 0.0001 |
| The content of arsenic is less than or equal to | 0.0005 | 0.0002 | 0.0001 | 0.0003 |
| Lead content is less than or equal to | 0.002 | 0.0005 | 0.001 | 0.0012 |
| Cadmium content is less than or equal to | 0.003 | 0.0024 | 0.0017 | 0.0016 |
From the data in table 1, it can be seen that the content of impurities in the product of the present invention meets the requirement, and the complex waste residue can be effectively treated to utilize the value thereof.
Claims (7)
1. A method for preparing zinc sulfate monohydrate from zinc-containing waste residue is characterized by comprising the following steps,
1) washing the zinc-containing waste residue with an ethanol water solution, then adding the zinc-containing waste residue into a sulfuric acid solution with the weight concentration of 60-80%, reacting, and filtering to obtain primary filtrate;
2) adding hydrogen peroxide and zinc hydroxide into the primary filtrate, reacting, removing iron impurities and redundant sulfuric acid, and filtering to obtain secondary filtrate;
3) adding zinc powder into the secondary filtrate, performing a displacement reaction, and filtering to obtain filtrate;
4) adding the filtrate into methanol, stirring, standing, filtering, dissolving with water, heating to 80-90 deg.C, and filtering to obtain crystallized filtrate;
5) heating the crystallization filtrate at 70-90 deg.C, introducing 70-90 deg.C pure air into the filtrate, and controlling air flow at 0.1-0.5m3And h, evaporating and crystallizing the filtrate, and then drying crystals by microwave to obtain the zinc sulfate monohydrate.
2. The method for producing zinc sulfate monohydrate as claimed in claim 1, wherein the volume concentration of ethanol in said aqueous ethanol solution is 50-70%.
3. The method for producing zinc sulfate monohydrate as claimed in claim 1, wherein the weight of the hydrogen peroxide is 2-3% of the weight of the primary filtrate.
4. A process as claimed in any one of claims 1 to 3, wherein the weight of zinc hydroxide is from 1 to 2% of the weight of the primary filtrate.
5. A process as claimed in any one of claims 1 to 3, wherein the zinc powder is present in an amount of 1 to 2% by weight of the secondary filtrate.
6. A process for the production of zinc sulphate monohydrate as claimed in any one of claims 1 to 3 and characterised by controlling the air flow rate to between 0.1 and 0.2m3/h。
7. The method for producing zinc sulfate monohydrate as claimed in any one of claims 1 to 3, wherein said microwave drying is carried out by drying the crystal under a microwave having a frequency of 915 MHz for 5 to 10 minutes.
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| CN111977683A (en) * | 2020-08-07 | 2020-11-24 | 衡阳华宏化工实业有限公司 | Preparation method of zinc sulfate monohydrate |
| CN113277547A (en) * | 2021-05-11 | 2021-08-20 | 湖南博一环保科技有限公司 | Method for producing zinc sulfate by using low-zinc material |
| CN114480842A (en) * | 2021-12-30 | 2022-05-13 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method and device for removing magnesium from zinc smelting zinc sulfate solution |
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|---|---|---|---|---|
| CN111977683A (en) * | 2020-08-07 | 2020-11-24 | 衡阳华宏化工实业有限公司 | Preparation method of zinc sulfate monohydrate |
| CN113277547A (en) * | 2021-05-11 | 2021-08-20 | 湖南博一环保科技有限公司 | Method for producing zinc sulfate by using low-zinc material |
| CN113277547B (en) * | 2021-05-11 | 2023-05-30 | 湖南博一环保科技有限公司 | Method for producing zinc sulfate by using low-zinc material |
| CN114480842A (en) * | 2021-12-30 | 2022-05-13 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method and device for removing magnesium from zinc smelting zinc sulfate solution |
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