CN1120591A - Method for prepn. of zinc oxide from zinc containing material - Google Patents
Method for prepn. of zinc oxide from zinc containing material Download PDFInfo
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- CN1120591A CN1120591A CN 94116676 CN94116676A CN1120591A CN 1120591 A CN1120591 A CN 1120591A CN 94116676 CN94116676 CN 94116676 CN 94116676 A CN94116676 A CN 94116676A CN 1120591 A CN1120591 A CN 1120591A
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Abstract
The process for preparing zinc oxide from zinc-containing materials comprises grinding, leaching by addition of acid, oxidant and ox-hide gelatin, purifying by addition of zinc powder for displacement and then peracid's salts or peroxides for oxidation, sythesizing by addition of ammonia and CO2, and roasting at 760-800 deg.C, and features cyclic use of by-products resulted in each steps, low cost and high purity of product.
Description
The invention relates to the field of hydrometallurgy.
The wet method for producing zinc oxide is gradually regarded as important by people in the later period of the 80 s due to the advantages of small investment scale, strong equipment maneuverability (most of the zinc oxide is general chemical equipment) and the like. Patent documents CN86108798A, CN1053412A, CN1040013A, CN86107218A disclose existing methods for producing zinc oxide by a wet process, but these methods all have some disadvantages. The concrete points are as follows: 1. in the leaching stage, only dilute sulfuric acid is added, so that iron hydroxide colloid and silica gel are formed in the actual production, the filtering speed is low, the filtering is difficult, and the filtering equipment is easy to damage. 2. The oxidizing agents (potassium permanganate, potassium chlorate, sodium hypochlorite, bleaching powder, chlorine, air and the like) added in the purification stage have good effect on removing iron, but the time for removing manganese is too long, some new impurities (Cl<-> and manganese) are brought in, and the manganese cannot be removed; the index of manganese in the finally obtained zinc oxide product can not reach the national standard requirement. 3. ZnSO is used more in the synthesis stage4Solution with NH4HCO3The method for producing alkaline zinc carbonate by reaction requires high-purity NH4HCO3Due to reaction products In the presence of CO2The gas is generated, the effective utilization rate of the synthetic agent is reduced, and a large amount of foam is generated in a reaction system, so that the solution overflows a reactor, the synthetic agent cannot be continuously added, the reaction time is prolonged, the utilization rate of equipment is reduced, and the production cost is greatly increased; in addition, ammonia or (NH) may be used4)2CO3、NaOH、Na2CO3The synthetic agents have the disadvantages of low effective utilization rate and low economy. 4. In the roasting stage, the adopted temperature is higher (above 800 ℃), so that the energy consumption is increased; or the zinc oxide product with high purity (meeting the national standard requirement) can not be obtained by adopting low temperature (below 650 ℃). In addition, the existing method has low waste utilization rate and great environmental pollution.
The invention aims to overcome the defects of the prior art and provide a method for preparing zinc oxide from zinc-containing materials, which has low cost, can obtain high-purity zinc oxide and is convenient to operate.
The technical scheme of the invention is as follows: the method for preparing zinc oxide from zinc-containing materials comprises the following process steps: zinc-containing materials (zinc ore or zinc hypoxide and the like) are ground into powder (below 40 meshes) → leaching → purification → synthesis → roasting → zinc oxide finished products. The method is characterized in that the process in the purification stage comprises the following steps: adjusting pH of the leachate (zinc salt solution) to 5.0-5.4 with common acid or alkali (adjusted by known method), adjusting pH to 0-100 deg.C (without boiling or freezing) while stirring, adding zinc powder in an amount 1-4 times of theoretical amount calculated by reaction formula of Zn and impurities Cu, Cd, Co, Ni, etc., reacting for 0.5-12 hr (sufficient reaction if necessary), and performing displacement reaction(the main reaction formula is: ， ， ， the replaced Cu, Cd, Co, Ni and the like can also form an alloy with unreacted Zn) → filtering and deslagging → keeping the pH value at 5.0-5.4 and 0-100 ℃, and adding perborate salts (such as (NH) with oxidation property in an amount which is 1-8 times (determined according to needs) of theoretical amount required by the reaction formula of the persulfate salts with the manganese and iron impurities inthe solution under stirring4)2S2O3Sodium peracetate and the like) or peroxide (such as sodium peroxide and the like) for 0.5 to 8 hours to carry out oxidation reaction (the reaction is sufficient as required, and the main reaction formula is as follows: → filtration and deslagging → zinc salt purification liquid is obtained, and because peracids or peroxide is used as oxidant, impurity elements of manganese and iron can be completely removed, and the oxidant is 'clean' and does not carry other impurities; the process engineering in the synthesis stage is as follows: adding ammonia and carbon dioxide into the purified solution at room temperature under stirring for 1-3 hr (as required) to make Zn2+The basic zinc carbonate is precipitated and separated out, and the main reaction formula is as follows: ， ， ， ， the total amount of ammonia and carbon dioxide is determined according to the PH6.3-7 at the end of the reaction (determined according to requirements), and the amount of carbon dioxide is determined according to the condition that no bubbles are emitted in the reaction system; because no foam appears, the utilization rate of equipment is improved → filtration and washing → basic zinc carbonate filter cake.
The second kind of process for preparing zinc oxide from zinc-containing material includes the following steps: zinc-containing materials (zinc ore or zinc hypoxide and the like) are ground into powder (below 40 meshes) → leaching → purification → synthesis → roasting → zinc oxide finished products. The method is characterized in that the technical process of the leaching stage comprises the following steps: adding known acid (sulfuric acid, hydrochloric acid, nitric acid, etc.) at 30-95 deg.C (as required), in an amount of 0.9-2 times (as required) the theoretical amount calculated according to the chemical reaction formula, and reacting for 0.5-5 hr (as required)The acid reacts with the zinc-containing material sufficiently to make the zinc enter the solution in the form of zinc salt (the main reaction formula is: ， ， ， ) Controlling end point pH to 1.6-1.8 (adjusted by common acid or alkali) and reacting with known oxidant (hydrogen peroxide, bleaching powder, sodium chlorate, hydrogen peroxide, air, etc.) in an amount 1-3 times of theoretical amount calculated according to chemical reaction formula under the condition of controlling end point pH to 85-95 deg.C (determined as required) to make Fe react2+Conversion to Fe3+Keeping the temperature at 85-95 deg.C, adding ammonium sulfate in an amount 1-5 times (as required) the theoretical amount required by chemical reaction, and reacting for 0.5-1 hr (as long as the reaction is sufficient as required) to obtain Fe3+Large-particle ammonioiarosite precipitate is generated (because the precipitate is large-particle precipitate, the precipitate is easy to filter out, and the Fe in the prior art is avoided3+Form a difficultly filterable gum Fe (OH)3Precipitation, which has the main reaction formula: ， ， → filtering to remove impurities such as iron → adjusting PH3-5.4 with lime water to make the silicic acid sol in the mother liquor generate large-particle calcium silicate precipitate → 70-85 deg.C (as required), adding oxhide gelatin in an amount of 0.9-1.2 times of the theoretical amount calculated by the chemical reaction formula to react for 0.5-1 h (as required, making the silica gel completely aggregate), and making the silica gel aggregate, thereby completely removing impurity silicon, improving filtering performance, increasing filtering speed → filtering, removing residue → leaching solution.
The 3 rd method for preparing zinc oxide from zinc-containing material comprises the following steps: zinc-containing materials (zinc ore or zinc hypoxide) are ground into powder (below 40 meshes) → leaching → purification → synthesis → sintering → zinc oxide finished product. The method is characterized in that the technological process of the roasting stage comprises the following steps: the basic zinc carbonate filter cake is centrifugally dried → dried under 95-250 ℃ (if necessary) → dried under 760-800 ℃ (if necessary) and roasted for 1-3 hours (roasting furnace)The roasting time is determined as required, and the reaction is ensured to be fully carried out) → discharging after cooling → zinc oxide finished products. The reaction formula is as follows: the roasting temperature is moderate, so that the high-purity zinc oxide can be obtained, and the energy consumption is low.
FIG. 1 is a flow chart of the process of the present invention,
FIG. 2 is a process flow diagram of a first method of the present invention,
FIG. 3 is a process flow diagram of a second method of the present invention,
FIG.4 is a process flow diagram of a third method of the present invention.
The following further illustrates embodiments of the invention:
example 1: the method for preparing zinc oxide from zinc-containing materials comprises the following process steps: 500 g of zinc hypoxide powder → grinding to powder of-150 mesh → 30 ℃ under stirring, 250ml of a 20% sulfuric acid solution is added under stirring for reaction for 3 hours → the pH value is adjusted to 1.6 → 85 ℃, 5ml of 30% hydrogen peroxide is added under stirring for reaction for 0.5 hour → 85 ℃, 500ml of an ammonium sulfate solution is added for reaction for 0.5 hour → filtration and washing → lime water is added under adjusting the pH value to 5.2 → 70 ℃, 15 g of oxhide gelatin is added for reaction for 0.5 hour → filtration and deslagging → 10 g of zinc powder is added under stirring for reaction for 0.5 hour, displacement reaction → filtration and deslagging → maintaining the pH value at 5.2 under stirring, 10 g of ammonium persulfate is added for reaction for 2 hours → filtration and washing at room temperature under stirring, ammonia and carbon dioxide are added into the purified solution for reaction for 1 hour, so that Zn2+ is precipitated and basic zinc carbonate is precipitated, the amount of ammonia is 330ml, and the total amount of ammonia and carbon dioxide is adjusted to the reaction end point of pH8.5, keeping the reaction system from bubbling → filtering, washing → basic zinc carbonate filter cake → centrifugally drying the alkali and the zinc carbonate filter cake by a centrifugal machine → drying in a 120 ℃ oven → sending into a muffle furnace, roasting at 780 ℃ for 2 hours → cooling the discharged material (zinc oxide) and recovering the byproduct carbon dioxide for the synthesis stage.
Example 2: the process for preparing zinc oxidefrom zinc-containing materialThe process is as follows: taking 700 g of Zn 30%The calamine (35% loss on ignition) is ground to-200 mesh → 2000ml water → 90 ℃ is added, 200ml 98% sulfuric acid is added for reaction for 0.5 hour → pH value is adjusted to 1.8 → 95 ℃, 10ml 30% hydrogen peroxide is added → 95 ℃ is added, 700ml ammonium sulfate solution is added for reaction for 1 hour → filtration, washing and residue recovery, washing liquid is added, pH value is adjusted to 5.2 → 85 ℃ is added with 25 g oxhide glue for reaction for 1 hour → filtration, residue removal → 85 ℃ is added with 15 g zinc powder for reaction for 12 hours → filtration, residue removal → pH5.2, at 25 ℃ sodium peracetate 3 g is added for reaction for 3 hours → filtration, residue removal → greenhouse is added with ammonia and carbon dioxide under stirring for reaction for 3 hours, the amount of ammonia is 180ml, the total amount of ammonia and carbon dioxide is based on the reaction end point pH6.8, and no bubble is added in the reaction system → filtration, washing and mother liquor (NH) is recovered (NH)4)4SO4→ drying filter cake → drying at 250 deg.C → roasting at 800 deg.C for 1 h → cooling the discharged material (zinc oxide) and recovering carbon dioxide.
Example 3: the method for preparing zinc oxide from zinc-containing materials comprises the following technical processes: 500 g of heteropolar zinc ore containing 30 percent of zinc → grinding into powder of-40 meshes → leaching by a common method → purification → synthesis → roasting by a common method → finished product of zinc oxide. The purification stage comprises the following processes: adjusting pH of leachate to 5.0 → 45 deg.C with lime water under stirring, adding 15 g zinc powder for reaction for 3 hr, performing displacement reaction → filtering, removing residue → 95 deg.C, maintaining pH at 5.0, and adding 12 g oxidant(NH)4)2S2O8Reacting for 4 hours, performing oxidation reaction → filtering, deslagging → obtaining purified liquid; the process engineering in the synthesis stage is as follows: adding ammonia and carbon dioxide into the purified solution to react for 1 hour at room temperature under stirring to ensure that Zn is obtained2+And (3) precipitating and separating out basic zinc carbonate, wherein the adding amount of ammonia is 150ml, the adding amount of ammonia and carbon dioxide is based on the reaction end point PH6.3, and no bubbling is kept in the reaction system → filtering and washing → a basic zinc carbonate filter cake.
Example 4: the method for preparing zinc oxide from zinc-containing materials comprises the following technical processes: 50 g of zinc ore powder → ground into-80 mesh powder → leaching → common method purification → common method synthesis → common method roasting → zinc oxideAnd (5) finishing. The technical process of the leaching stage comprises the following steps: adding 20ml of 25% sulfuric acid at 70 deg.C for reaction for 3 hours, controlling the end point pH to 1.7 → 85 deg.C, adding 2ml of hydrogen peroxide to make Fe2+Conversion to Fe3+Reacting at 85 deg.C with 50ml ammonium sulfate for 1 hr to obtain Fe3+Large-particle ammonioiarosite precipitation is generated → is filtered, impurities such as iron and the like are removed → is adjusted with lime milk to pH5.0, so that large-particle calcium silicate precipitation is generated from silicic acid sol in mother liquor → is added with 3 g of oxhide gelatin to react for 0.6 hour at the temperature of 75 ℃, so that the silica gel is precipitated, → is filtered, and dregs are removed → the leaching solution.
Example 5: the method for preparing zinc oxide from zinc-containing materials comprises the following technical processes: zinc powder → powder ground to-100 meshes → common method leaching → common method purification → common method synthesis → roasting → zinc oxide finished product. The technological process of the roasting stage comprises the following steps: and (3) centrifuging and drying the basic zinc carbonate filter cake → drying at 200 ℃, → roasting at 770 ℃ for 1.5 hours (in a roasting furnace) → cooling and discharging → obtaining a zinc oxide finished product.
Example 6: the method for preparing zinc oxide from zinc-containing materials comprises the following process steps: 650 g of zincite containing Zn 35% is ground to-320 mesh → 2500ml of water → 60 ℃ is added, 180ml of 93% sulfuric acid is added for reaction for 2 hours → the pH value is adjusted to 1.7 → 90 ℃, 8ml of 30% hydrogen peroxide → 500ml of ammonium sulfate solution is added for reaction for 45 minutes → filtration, washing → lime water is added for adjustment of pH value to 5.3 → 75 ℃ is added with 35 g of oxhide gelatin for reaction for 50 minutes → filtration, deslagging → 75 ℃, 12 g of zinc powder is added for reaction for 6 hours → deslagging, filtration → pH5.3, 10 g of sodium peroxide is slowly added at 60 ℃, reaction for 4 hours → filtration, deslagging → room temperature, ammonia and carbon dioxide are added for reaction for 2 hours under stirring, the adding amount of ammonia is 200ml, the adding amount of ammonia and carbon dioxide is based on the PH8.8 at the end of the reaction, no air bubble appears in the reaction system → filtration, washing → filter cake drying → drying at 95 deg.C → roasting at 770 deg.C for 2 hours → cooling and discharging and recovering carbon dioxide.
By sampling and analyzing, the zinc oxide product obtained in this example has the following components:
Zn 99.7％；
Mn 0.0001％；
Fe2+0.0002％；
Fe3+0.0001％；
Cu 0.0001％；
Pb 0.0002％；
Na 0.00003％；
Cr 0.001％；
V 0.001％；
Co 0.001％；
Ni 0.001％；
Si 0.001％；
SO4 2-0.01％；
cd is zero;
the metal substance is absent.
The invention adopts different technical processes from the prior art, and has the advantages of high utilization rate of raw materials and equipment in each process, convenient filtration, time saving, convenient operation, low cost and high purity of the obtained product.
Claims (3)
1. A method for preparing zinc oxide from zinc-containing materials comprises the following process steps: the zinc-containing material is ground → leached → purified → synthesized → roasted → zinc oxide finished product, which is characterized in that the process of the purification stage is as follows: adjusting the pH value of the leaching solution (zinc salt solution) to 5.0-5.4 by using common acid or alkali, adding zinc powder according to the amount which is 1-4 times of the theoretical amount required by the calculation of the reaction formula of Zn and impurities such as Cu, Cd, Co, Ni and the like under stirring for reaction for 0.5-12 hours, carrying out displacement reaction → filtering, removing residues → keeping the pH value to 5.0-5.4, adding peracids or peroxides with oxidation property according to the amount which is 1-3 times of the theoretical amount required by the calculation of the reaction formula of the impurities such as manganese, iron and the like in the solution under stirring at 0-100 ℃, and carrying out reaction for 0.5-8 hours, filtering, removing residues → obtaining zinc salt purified solution; the process of the synthesis stage comprises the following steps: adding ammonia and carbon dioxide into the purified solution to react for 1-3 hours at room temperature under stirring to ensure that Zn is formed2+The generated basic zinc carbonate is precipitated and separated out,the adding amount of the carbon dioxide is based on no bubble in the reaction system, and the adding amount of the ammonia and the carbon dioxide is based on the reaction end point PH6.3-7 → filtering, washing → basic zinc carbonate filter cake.
2. A method for preparing zinc oxide from zinc-containing materials comprises the following process steps: the zinc-containing material is ground → leached → purified → synthesized → roasted → zinc oxide finished product, which is characterized in that the technological process of the leaching stage is as follows: adding known acid in 0.9-2 times of theoretical amount required by chemical reaction formula at 30-95 deg.C for reaction for 0.5-5 hr, controlling end point pH to 1.6-1.8 → 85-95 deg.C, adding known oxidant in 1-3 times of theoretical amount required by chemical reaction formula to make Fe2+Conversion to Fe2+Keeping the temperature between 85 and 95 ℃, adding ammonium sulfate in an amount which is 1 to 5 times of the theoretical amount required by chemical reaction for 0.5 to 1 hour to ensure that Fe3+Large-particle ammonioiarosite precipitation → filtration, iron removal and other impurities → regulation of PH3-5.4 by lime water, generation of large-particle calcium silicate precipitation from silicic acid sol in mother liquor → reaction of 0.9-1.2 times of theoretical amount required by chemical reaction formula at 70-85 ℃ for 0.5-2 hours by adding oxhide gelatin, coagulation of silica gel → filtration, deslagging and leaching solution → filtration.
3. A method for preparing zinc oxide from zinc-containing materials comprises the following process steps: the zinc-containing material is ground → leached → purified → synthesized → roasted → zinc oxide finished product, which is characterized in that the technological process of the roasting stage is as follows: and (3) centrifuging and drying the basic zinc carbonate filter cake → drying at 95-250 ℃ → roasting at 800 ℃ for 1-3 hours → cooling and discharging (zinc oxide).
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| CN94116676A CN1039921C (en) | 1994-10-13 | 1994-10-13 | Method for prepn. of zinc oxide from zinc containing material |
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| CN94116676A CN1039921C (en) | 1994-10-13 | 1994-10-13 | Method for prepn. of zinc oxide from zinc containing material |
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| CN1120591A true CN1120591A (en) | 1996-04-17 |
| CN1039921C CN1039921C (en) | 1998-09-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503009A (en) * | 2011-10-09 | 2012-06-20 | 成都大中华焊接材料有限公司 | Recycling method of chemical copper plating waste liquid |
| CN103086419A (en) * | 2013-01-30 | 2013-05-08 | 金章法 | Wet-method zinc oxide preparation method |
| CN104973627A (en) * | 2014-04-02 | 2015-10-14 | 中国科学院过程工程研究所 | Method for producing chromic oxide from carbon ferrochrome |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1147971A (en) * | 1980-05-08 | 1983-06-14 | George J. Houlachi | Process for the oxidation of ferrous ions to the ferric state in sulfate leach solutions |
| CN1033695C (en) * | 1993-04-09 | 1997-01-01 | 洛阳市蓝天化工厂 | Preparation of high-active zinc oxide by improved all-wet method of ammonium bicarbonate |
-
1994
- 1994-10-13 CN CN94116676A patent/CN1039921C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503009A (en) * | 2011-10-09 | 2012-06-20 | 成都大中华焊接材料有限公司 | Recycling method of chemical copper plating waste liquid |
| CN103086419A (en) * | 2013-01-30 | 2013-05-08 | 金章法 | Wet-method zinc oxide preparation method |
| CN103086419B (en) * | 2013-01-30 | 2014-12-10 | 金章法 | Wet-method zinc oxide preparation method |
| CN104973627A (en) * | 2014-04-02 | 2015-10-14 | 中国科学院过程工程研究所 | Method for producing chromic oxide from carbon ferrochrome |
| CN104973627B (en) * | 2014-04-02 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of method for producing chrome green as raw material with carbon ferrochrome |
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| CN1039921C (en) | 1998-09-23 |
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