CN103880063A - Method of preparing high purity activated zinc oxide by wet chemistry method - Google Patents
Method of preparing high purity activated zinc oxide by wet chemistry method Download PDFInfo
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- CN103880063A CN103880063A CN201410094319.5A CN201410094319A CN103880063A CN 103880063 A CN103880063 A CN 103880063A CN 201410094319 A CN201410094319 A CN 201410094319A CN 103880063 A CN103880063 A CN 103880063A
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Abstract
The invention provides a method of preparing high purity activated zinc oxide by a wet chemistry method. The method comprises the following steps: leaching raw material zinc ores by sulfuric acid, adding excessive potassium permanganate to oxidize for removing impurities, removing impurities of zinc powder, and secondarily oxidizing with potassium permanganate to prepare a refined zinc sulfate solution; adding a sodium carbonate solution into the refined zinc sulfate solution to neutralize till the pH value is 6.8, heating to 75 DEG C, continuously stirring to react for 1 hour, and finishing reaction when free alkali is 0.4-0.5%; separating solids from the liquid, recovering sodium sulfate or ammonium sulfate from the liquid, washing sulfate and excessive alkali of solids by water, and drying and roasting. According to the method provided by the invention, a control loop is increased based on the original fundamental process. In the conventional process, just pH and temperature are taken as control means, and the final product quality cannot be effectively controlled in the specific guidance of production chains, so that after relative density control to the intermediate product and raw material of the product are added, not only is the yield of the product greatly enhanced, but also the purity of produced activated zinc oxide is greater than 99%. Meanwhile, the activated zinc oxide has high specific surface area and low bulk volume.
Description
Technical field
The present invention relates to a kind of method of hydrometallurgy, particularly a kind of method of wet chemistry method high-purity active zinc flower.
Background technology
Active zinc flower is a kind of white or the spherical fines of micro-yellow, and relative density is 5.47.1975 ℃ of fusing points (5268.9 kPas), are heated to 1800 ℃ of distillations, are yellow when high temperature, recover white when cooling, and odorless is tasteless, is a kind of intermediate oxide.Be insoluble in water and alcohol, can be dissolved in acid, alkali metal hydroxide, ammoniacal liquor, volatile salt and ammonium chloride solution, in air, slowly absorbing carbon dioxide and water generate zinc carbonate.
Be a kind of polyfunctional new inorganic material, its granular size is about 1～100 nanometer.Due to the granular of crystal grain, its Electronic Structure and crystalline structure change, and have produced the features such as the surface effects that macro object does not have, volume effect, quantum size effect and macroscopical tunnel effect and high-clarity, polymolecularity.Record according to data, find that it shows many specific functions at aspects such as catalysis, optics, magnetics, mechanics, make it have important using value in many fields such as pottery, chemical industry, electronics, optics, biology, medicine, there is singularity and purposes that common zinc oxide cannot compare.
Particle is little, specific surface area is large, active high, be easily dispersed in rubber or latex, mainly as natural rubber, the vulcanization leveller of synthetic rubber and latex, strengthening agent, also as the vulcanizing agent of the tinting material of white size and weighting agent, chloroprene rubber.After adding, can make rubber there is good wear resistance, resistance to tearing and elasticity.At natural rubber, in synthetic rubber, substitute indirect process zinc oxide and American process zinc oxide, not only physical and mechanical properties and processing performance are stable, and consumption can reduce 20%-50%.Also can be used for UV-light masking material, antiseptic-germicide, fluorescent material, photocatalyst material etc. at field of textiles.Due to a series of superiority of active zinc flower and very tempting application prospect, therefore researching and developing active zinc flower has become the focus that many scientific and technical personnel pay close attention to.
The preparation method of zinc oxide is divided three classes: i.e. direct method (also claiming U.S. law), indirect method (also claiming method national law) and wet chemistry method, much commercially available zinc oxide mostly is direct method or indirect method product, granularity is micron order, specific surface area is less, and these character have restricted their Application Areas and the performance in goods thereof greatly.Due to the restriction of technique, active oxygen voltinism is difficult to take into account the physical property of high purity, high-specific surface area, low stacking volume in process of production, and therefore, country is decided to be salable product purity 95% ~ 98% for the target level of product quality of zinc oxide, specific surface area>=35 m
2g
-1, tap density≤0.40gcm
-1; Acceptable end product purity 95% ~ 98%, specific surface area>=45m
2g
-1, tap density≤0.35gcm
-1, therefore the active zinc flower of high purity, high-specific surface area, low stacking volume relies on current not high, the special production technique high cost of industrialization production line yield rate, is restricting to a certain extent the development of industry.
Summary of the invention
A kind of method that the object of the present invention is to provide wet chemistry method high-purity active zinc flower, has higher yield rate, can suitability for industrialized production high purity, the active zinc flower of high-specific surface area, low stacking volume.
In order to achieve the above object, the invention provides a kind of method of wet chemistry method high-purity active zinc flower, comprise the following steps:
(1) acidic leaching: by raw material zinc ore sulfuric acid leaching, make rough solution of zinc sulfate;
(2) impurity removal and purification: add excessive potassium permanganate when the rough solution of zinc sulfate making in step (1) is heated to 80 ℃ ~ 90 ℃, removing impurities by oxidation, after filtering, adjusting pH is 5.2, then be heated to 80 ℃, with excessive zinc powder removal of impurities, after filtering, adjusting pH is 5.4, then heats to 80 ℃ ~ 90 ℃ with making POV zinc solution after potassium permanganate secondary oxidation;
(3) neutralization reaction: by the POV zinc solution input neutralization reactor in step (2), adjusting relative density is 1.16, stirring is warming up to 40 ℃ ~ 43 ℃, add soda ash solution to neutralize, until pH value is 6.8, stopping feeding in raw material is warming up to 75 ℃, continues stirring reaction 1 hour, in the time that free alkali is 0.4% ~ 0.5%, finish reaction.
(4) product separation: by solid-liquid separation, the recyclable sodium sulfate of liquid or ammonium sulfate, solid washes desulfuration hydrochlorate and excess base post-drying with water, and controlling bake out temperature is 250 ℃ ~ 300 ℃, dries to water content≤4%.
(5) roasting: material after drying in step (4) is carried out to roasting, 500 ℃ ~ 550 ℃ of temperature.
Preferably, in the sulfuric acid that described step (1) is 55% ~ 60%, stir and add raw material zinc ore, until pH is 4.5 ~ 5.0, the regulator solution relative density that adds water is 1.394 ~ 1.422.
Preferably, in described step (2) except use mixedly potassium permanganate and zinc powder usage quantity can according to detect analytical results use accurate consumption.
Preferably, in described step (3), the relative density of the soda ash aqueous solution is 1.16.
Preferably, described raw material zinc ore is secondary zinc oxide or oxidized form zinc ore or cadmia or zinc gray.
Beneficial effect of the present invention:
The present invention has increased controlling unit on original technique basis, in traditional technology, only use pH and temperature as control device, in concrete guide production link, find effectively to control final quality product, therefore after adding the relative density control of product intermediate product and raw material, not only the yield rate of product is significantly promoted, and fertile active zinc flower purity is greater than 99%, possessed high-specific surface area, low stacking volume simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, is to be understood that embodiment is used for understanding the present invention, does not limit restriction the present invention.
Embodiment 1:
By secondary zinc oxide sulfuric acid leaching, make rough solution of zinc sulfate; When being heated to 80 ℃, rough solution of zinc sulfate adds excessive potassium permanganate, removing impurities by oxidation, after filtering, adjusting pH is 5.2, then be heated to 80 ℃, with excessive zinc powder removal of impurities, after filtering, adjusting pH is 5.4, then heats to 80 ℃ with making POV zinc solution after potassium permanganate secondary oxidation; By in POV zinc solution input neutralization reactor, adjusting relative density is 1.16, stirring is warming up to 40 ℃, add soda ash solution to neutralize, until pH value is 6.8, stopping feeding in raw material is warming up to 75 ℃, continues stirring reaction 1 hour, in the time that free alkali is 0.4%, finish reaction, by solid-liquid separation, the recyclable sodium sulfate of liquid or ammonium sulfate, solid washes desulfuration hydrochlorate and excess base post-drying with water, controlling bake out temperature is 250 ℃, dry to water content≤4%, material after oven dry is carried out to roasting, 500 ℃ of temperature.
Using EDTA standard titration determination active zinc flower purity is 98.7%, is 0.34gcm with reference to the tap density of determination of test method active zinc flower in HG/T2572-94
-1, be 46.7m with reference to the specific surface area of determination of test method active zinc flower in HB-T2922
2g
-1, product indices is all better than the standard of acceptable end product in active zinc flower target level of product quality (HG/r2572～94).
Embodiment 2:
Implementation step is with embodiment 1, and institute's difference is only to use raw material zinc ore for cadmia, in acidic leaching process, cadmia is added while stirring in 60% sulfuric acid, until pH is 5.0, the regulator solution relative density that adds water is 1.394 to make rough solution of zinc sulfate; When being heated to 90 ℃, rough solution of zinc sulfate adds excessive potassium permanganate, removing impurities by oxidation, after filtering, adjusting pH is 5.2, then be heated to 80 ℃, with excessive zinc powder removal of impurities, after filtering, adjusting pH is 5.4, then heats to 90 ℃ with making POV zinc solution after potassium permanganate secondary oxidation; By in POV zinc solution input neutralization reactor, adjusting relative density is 1.16, stirring is warming up to 41 ℃, add soda ash solution to neutralize, until pH value is 6.8, stopping feeding in raw material is warming up to 75 ℃, continues stirring reaction 1 hour, in the time that free alkali is 0.5%, finish reaction, by solid-liquid separation, the recyclable sodium sulfate of liquid or ammonium sulfate, solid washes desulfuration hydrochlorate and excess base post-drying with water, controlling bake out temperature is 300 ℃, dry to water content≤4%, material after oven dry is carried out to roasting, 550 ℃ of temperature.
Using EDTA standard titration determination active zinc flower purity is 99.1%, is 0.35gcm with reference to the tap density of determination of test method active zinc flower in HG/T2572-94
-1, be 45.7m with reference to the specific surface area of determination of test method active zinc flower in HB-T2922
2g
-1, product indices is all better than the standard of acceptable end product in active zinc flower target level of product quality (HG/r2572～94).
Embodiment 3:
Implementation step is with embodiment 1, institute's difference is only to use raw material zinc ore for zinc gray, except the usage quantity of using mixedly potassium permanganate and zinc powder can be used accurate consumption according to detecting analytical results, slightly excessive while adding, with the check of potassiumiodide ~ starch, the relative density of alkali aqueous solution is also 1.16, the amount of free alkali is 5%, in the present embodiment cited to index be in actual production, production cost is compared with situation low and that productive rate is higher, using EDTA standard titration survey product to determine active zinc flower purity is 99.4%, be 0.32gcm with reference to the tap density of determination of test method active zinc flower in HG/T2572-94
-1, be 47.7m with reference to the specific surface area of determination of test method active zinc flower in HB-T2922
2g
-1, product indices is all better than the standard of acceptable end product in active zinc flower target level of product quality (HG/r2572～94).
Should be noted that the explanation during above-mentioned three embodiment are using point value as specific experiment process, in actual production, the control of some production link should be a wider value range, be particularly for: (1) is by raw material zinc ore sulfuric acid leaching, make rough solution of zinc sulfate, more optimizedly to stirring and add raw material zinc ore in 55% ~ 60% sulfuric acid, until pH is 4.5 ~ 5.0, the regulator solution relative density that adds water is 1.394 ~ 1.422;
(2) the rough solution of zinc sulfate making adds excessive potassium permanganate while being heated to 80 ℃ ~ 90 ℃, removing impurities by oxidation, after filtering, adjusting pH is 5.2, then be heated to 80 ℃, with excessive zinc powder removal of impurities, after filtering, adjusting pH is 5.4, then heats to 80 ℃ ~ 90 ℃ with making POV zinc solution after potassium permanganate secondary oxidation;
(3) in POV zinc solution input neutralization reactor, adjusting relative density is 1.16, stirs and is warming up to 40 ℃ ~ 43 ℃, add soda ash solution to neutralize, until pH value is 6.8, stopping feeding in raw material is warming up to 75 ℃, continue stirring reaction 1 hour, in the time that free alkali is 0.4% ~ 0.5%, finish reaction.
(4) by solid-liquid separation, the recyclable sodium sulfate of liquid or ammonium sulfate, solid washes desulfuration hydrochlorate and excess base post-drying with water, and controlling bake out temperature is 250 ℃ ~ 300 ℃, dries to water content≤4%.
(5) dry rear material and carry out roasting, 500 ℃ ~ 550 ℃ of temperature.
Except the usage quantity of using mixedly potassium permanganate and zinc powder can be used accurate consumption according to detecting analytical results, thus production control cost and reaction times.For the relative density that can better obtain less low stacking volume and the higher specific surface area soda ash aqueous solution is 1.16, while selecting free alkali to be 0.5%, finish reaction, when roasting, maintain a stable temperature as far as possible.The claimed interval of contriver is more rational production range, and super going beyond the scope also can be produced but productive rate and production input can corresponding increases, or product performance can be affected.
The raw material zinc ore that the present invention uses can be secondary zinc oxide or oxidized form zinc ore or cadmia or zinc gray, the present invention has increased controlling unit on original technique basis, in traditional technology, only use pH and temperature as control device, in concrete guide production link, find effectively to control final quality product, therefore after adding the relative density control of product intermediate product and raw material, not only the yield rate of product is significantly promoted, and fertile active zinc flower purity is greater than 99%, possessed high-specific surface area, low stacking volume simultaneously.
Above-described is only preferred embodiment of the present invention.Should be understood that for the person of ordinary skill of the art, under technology enlightenment provided by the present invention, as the common practise of this area, can also make other equivalent modifications and improvement, also should be considered as protection scope of the present invention.
Claims (5)
1. a method for wet chemistry method high-purity active zinc flower, is characterized in that: said method comprising the steps of:
(1) acidic leaching: by raw material zinc ore sulfuric acid leaching, make rough solution of zinc sulfate;
(2) impurity removal and purification: add excessive potassium permanganate when the rough solution of zinc sulfate making in step (1) is heated to 80 ℃～90 ℃, removing impurities by oxidation, after filtering, adjusting pH is 5.2, then be heated to 80 ℃, with excessive zinc powder removal of impurities, after filtering, adjusting pH is 5.4, then heats to 80 ℃ ~ 90 ℃ with making POV zinc solution after potassium permanganate secondary oxidation;
(3) neutralization reaction: by the POV zinc solution input neutralization reactor in step (2); adjusting relative density is 1.16; stirring is warming up to 40 ℃～43 ℃; add soda ash solution to neutralize; until pH value is 6.8, stopping feeding in raw material is warming up to 75 ℃, continues stirring reaction 1 hour; in the time that free alkali is 0.4%～0.5%, finish reaction;
(4) product separation: by solid-liquid separation, the recyclable sodium sulfate of liquid or ammonium sulfate, solid washes desulfuration hydrochlorate and excess base post-drying with water, and controlling bake out temperature is 250 ℃～300 ℃, dries to water content≤4%;
(5) roasting: material after drying in step (4) is carried out to roasting, 500 ℃～550 ℃ of temperature.
2. a kind of method of wet chemistry method high-purity active zinc flower according to claim 1, it is characterized in that: in the sulfuric acid that described step (1) is 55%～60%, stir and add raw material zinc ore, until pH is 4.5～5.0, the regulator solution relative density that adds water is 1.394～1.422.
3. a kind of method of wet chemistry method high-purity active zinc flower according to claim 1, is characterized in that: in described step (2) except the usage quantity of using mixedly potassium permanganate and zinc powder can be used accurate consumption according to detecting analytical results.
4. a kind of method of wet chemistry method high-purity active zinc flower according to claim 1, is characterized in that: in described step (3), the relative density of the soda ash aqueous solution is 1.16.
5. a kind of method of wet chemistry method high-purity active zinc flower according to claim 1, is characterized in that: described raw material zinc ore is secondary zinc oxide or oxidized form zinc ore or cadmia or zinc gray.
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Cited By (5)
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| CN104058447A (en) * | 2014-06-30 | 2014-09-24 | 桂林理工大学 | Method for preparing nano-zinc oxide by taking zinc slag oxygen powder as raw materials |
| CN104671278A (en) * | 2015-02-10 | 2015-06-03 | 济源市鲁泰纳米材料有限公司 | Method for preparing high-activity nano zinc oxide |
| CN105819495A (en) * | 2016-05-30 | 2016-08-03 | 安徽省含山县锦华氧化锌厂 | Preparation method for high-activity nano-zinc oxide |
| CN107162040A (en) * | 2017-06-19 | 2017-09-15 | 广汉隆达饲料有限公司 | The production method of feed zinc oxide |
| CN114906871A (en) * | 2022-06-08 | 2022-08-16 | 桂林理工大学 | Method for preparing nano zinc oxide by using secondary zinc oxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058447A (en) * | 2014-06-30 | 2014-09-24 | 桂林理工大学 | Method for preparing nano-zinc oxide by taking zinc slag oxygen powder as raw materials |
| CN104671278A (en) * | 2015-02-10 | 2015-06-03 | 济源市鲁泰纳米材料有限公司 | Method for preparing high-activity nano zinc oxide |
| CN105819495A (en) * | 2016-05-30 | 2016-08-03 | 安徽省含山县锦华氧化锌厂 | Preparation method for high-activity nano-zinc oxide |
| CN107162040A (en) * | 2017-06-19 | 2017-09-15 | 广汉隆达饲料有限公司 | The production method of feed zinc oxide |
| CN107162040B (en) * | 2017-06-19 | 2019-01-04 | 广汉隆达饲料有限公司 | The production method of feed zinc oxide |
| CN114906871A (en) * | 2022-06-08 | 2022-08-16 | 桂林理工大学 | Method for preparing nano zinc oxide by using secondary zinc oxide |
| CN114906871B (en) * | 2022-06-08 | 2023-05-26 | 桂林理工大学 | Method for preparing nano zinc oxide by using secondary zinc oxide |
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Application publication date: 20140625 |