CN103303964A - Method for producing food-grade copper sulfate by smelting byproduct-copper sulfate - Google Patents
Method for producing food-grade copper sulfate by smelting byproduct-copper sulfate Download PDFInfo
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- CN103303964A CN103303964A CN2013102776370A CN201310277637A CN103303964A CN 103303964 A CN103303964 A CN 103303964A CN 2013102776370 A CN2013102776370 A CN 2013102776370A CN 201310277637 A CN201310277637 A CN 201310277637A CN 103303964 A CN103303964 A CN 103303964A
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Abstract
The invention discloses a method for producing food-grade copper sulfate by a smelting byproduct-copper sulfate. The method comprises the following steps of: dissolving the industrial smelting byproduct-copper sulfate in ultrapure water, heating to 70-80 DEG C, slowly dropwise adding acid for adjusting the pH value of a solution to be 1.00, stirring for dissolving, and slowly adding an oxidant; mixing polymeric ferric sulfate and basic cupric carbonate according to a mass ratio of 1:(2.0-5.0) to prepare a deposition complexing agent, slowly adding the deposition complexing agent which is 0.6-2.8% of the weight of the solution into the insulation solution, using basic cupric carbonate to adjust the pH value of the solution to be 3.0-4.0, slowly adding an adsorbing agent which is 1.0-2.5% of the weight of the solution, stirring and insulating for 6-8 hours, cooling to room temperature, and standing for a day; and carrying out vacuum filtration on the solution, filtering by using a microporous filter membrane of 0.2-0.3mu m, carrying out ultrasonic-assisted rotary evaporation and concentration on filter liquor for crystallization, and carrying out spray-drying to obtain the food-grade copper sulfate.
Description
Technical field
The present invention relates to the production method of food grade copper sulfate, particularly by the method for smelting by-product product copper sulfate production food grade copper sulfate.
Background technology
Copper sulfate is sky blue or slightly yellow granular crystal, and it is acid that the aqueous solution is, and belongs to the protectiveness inorganic fungicide.Chemical formula CuSO
4, be generally five hydrate CuSO
45H
2O, popular name blue stone, blue vitriol, lapis divinus; Blue rhomboidal crystal, density 2.284 g/cm
3Copper sulfate is the important source material of other copper compounds of preparation, mixes to get " Bordeaux " solution with milk of lime, as sterilant, and the electrolytic solution when copper sulfate also is electrolytical refined copper.
Copper sulfate effect and purposes:
(1) inorganic industry is for the manufacture of other mantoquitas such as cuprous chloride, cupric chloride, cupric pyrophosphate, Red copper oxide, neutralized verdigris, copper carbonate etc.
(2) dyestuff and pigment industry are for the manufacture of cupric monoazo-dyes such as reactive brilliant bule, reactive violet etc.
(3) organic industry is as the catalyzer of synthetic perfume and dyestuff intermediate, the stopper of methyl methacrylate.
(4) coatings industry is as the sterilant of producing ship bottom anti-fouling paint.Electroplating industry is as full acidic copper-plating of bright master salt and cupric ion additive.
(5) printing and dyeing industry is as mordant and smart pro-oxygenic agent of dying cloth.
(6) on the agricultural as sterilant.
(7) aquaculture also is used as the main raw material of fodder additives trace copper.
(8) can use the copper sulfate of food grade as sequestrant and finings in lime-preserved egg and the wine production processes.
(9) be used for the B liquid that the biuret reagent of the fehling reagent of reducing sugar and identification of protein is identified in configuration in the biology, but normally now with the current.
(10) Bordeaux mixture processed.
(11) make copper sulfate crystal, very attractive in appearance.
Therefore, the purity of food grade copper sulfate, cleanliness factor and reliability have very important meaning.
At present, the production method of food grade copper sulfate product has no report, but manufacture mainly contains following several method with high-purity sulphuric acid copper:
1, CN1678532 discloses a kind of high-purity sulfuric acid copper method, and copper sulfate is dissolved in the crystal pure water, it is carried out evaporation concentration, removes the crystal of initial precipitation, further carries out evaporation concentration to realize crystallization, it is filtered obtain high purity copper sulfate.The method is owing to removing the crystal of initial precipitation, and conversion rate of products is low.
2, CN1835891 discloses a kind of manufacture method of high purity copper sulfate, make the dissolving of thick cupric sulphate crystal or copper alloy, it is carried out activated carbon treatment or solvent extraction and activated carbon treatment, reach the purpose of purifying with other separation of metal ions, although this method has selected suitable extraction solution to get technology extracting copper ion with extracting-back extraction.But this method efficient is low, can not large-scale application in industrial production.
3, adopt the chemical oxidation method neutralizing hydrolysis to purify tradition and remove iron process, then by adjusting pH iron ion and other impurity metal ions are removed with the form of oxyhydroxide, the quality product of this method is not high.Do not reach the service requirements of food grade copper sulfate, can only reach the feed-grade bluestone user demand.
The product that above three kinds of methods are produced all can not be applicable to Food industry.
Summary of the invention
The object of the present invention is to provide a kind of method by smelting by-product product copper sulfate production food grade copper sulfate of easy handling.
Technical solution of the present invention: the method by smelting by-product product copper sulfate production food grade copper sulfate comprises the steps:
A, get industrial smelting by-product product copper sulfate and be dissolved in the ultrapure water (solid-to-liquid ratio 1:4), be heated to 70-80 ℃, slowly add sulfuric acid regulation solution pH to 1.00-2.00, after the stirring and dissolving, slowly add again (volume ratio 100:3, the hydrogen peroxide of massfraction 3%) oxygenant adds rear insulated and stirred 1 hour, gets A step solution;
B, with bodied ferric sulfate and ventilation breather in mass ratio 1:2.0-5.0 be mixed and made into the precipitation and complexation agent, 0.6-2.8% by A step solution weight slowly adds the precipitation and complexation agent in A step solution, after the precipitation and complexation agent adds, adjust pH value of solution to 3.0-4.0 with ventilation breather, the 1.0-2.5% that presses again A step solution weight continues slowly to add acticarbon, and under 60 ± 2 ℃ of temperature insulated and stirred 6-8 hour, cool to room temperature again, left standstill 24 ± 2 hours, and got B step solution;
C, with behind the B step solution for vacuum suction filtration, use again the filtering with microporous membrane of 0.2-0.3 μ m, filtrate adopts the spray-dryer drying to obtain food grade cupric sulphate crystal product after the auxiliary rotatory evaporator of ultrasonic wave is concentrated.
Among the above-mentioned steps B, be incubated 60 ℃ and stir 6-8 hour the best, the quality 1:2.0-3.0 of bodied ferric sulfate and ventilation breather is best in the precipitation and complexation agent, and precipitation and complexation agent consumption is 1.5% the best of solution weight.
In the condensing crystal process, the scheme that the present invention is preferential: when the normal temperature to 60 ℃, concentrated under the air pressure of working pressure 380-680mmHg with the copper-bath behind the filtering with microporous membrane of 0.2-0.3 μ m, be cooled to 20-30 ℃, when solution density reaches 1.48g/cm
3The time, adopt the spray-dryer drying to obtain food grade cupric sulphate crystal product.
The present invention adopts filtering with microporous membrane, membrane filtration is a kind of screening process relevant with the membrane pore size size, take the pressure difference of film both sides as motivating force, take film as filtration medium, under certain pressure, when stoste flows through the film surface, the many tiny micropore that gathers in the film surface only allows water and small-molecule substance by becoming through liquid, volume then is trapped within the liquid feeding side of film in the stoste greater than the material in film surface micropore footpath, become concentrated solution, thereby realize stoste is effectively separated and concentrated purpose.
The present invention adopts the vacuum filtration method to filter, and filtrate enters in the auxiliary rotatory evaporator of ultrasonic wave and concentrates, when solution density reaches 1.48g/cm
3The time, change spray-dryer over to, obtain the food grade cupric sulphate crystal.Mother liquor returns dissolution process and again recycles, and reclaims filter and mixes.It is short that this technique has flow process, environment amenable characteristics, and product is pure, and transformation efficiency is high, and is very feasible.
The present invention introduces ultrasonic wave auxiliary inductive phase that can obviously shorten the copper-bath crystallisation process, improves crystallization velocity, under low-frequency high-power ultrasonic wave subsidiary conditions, can make that particle is little, the ideal product of even particle size distribution.
The present invention removes the metal ion methods such as arsenic, mercury, antimony, bismuth and iron: the arsenic in the copper-bath mainly exists with the arsenite form, and the solubility product of ferric arsenate is very little, is 5.7 * 10
-21, therefore, add (hydrogen peroxide of massfraction 3%) oxygenant in the copper-bath, with As
3+Be oxidized to As
5+After, Fe is being arranged
3+Under the existence effect, pH value of solution＜4 make it to generate the ferric arsenate precipitation, thereby reach the purpose of removing arsenic, iron.In like manner, this method also can be simultaneously to remove the metal ions such as antimony, bismuth, mercury, lead, and principal reaction is as follows:
AsO
3 3-+H
2O
2+3H
+→H
3AsO
4+H
2O；
H
3AsO
4+Fe
3+→FeAsO
4↓+3H
+；
H
3AsO
4+Sb
3+→SbAsO
4↓+3H
+；
H
3AsO
4+Bi
3+→BiAsO
4↓+3H
+；
H
3AsO
4+Hg
2+→HgHAsO
4↓+2H
+；
H
3AsO
4+Pb
2+→PbHAsO
4↓+2H
+；
H
3AsO
4+Pb
2+→Pb
3(AsO
4)
2↓+3H
+。
The present invention removes the metal ion methods such as de-iron, lead, cadmium, chromium, magnesium, ?, calcium, barium, cobalt, manganese and nickel: add ventilation breather and adjust pH value of solution to 3.0-4.0, hydrolysis can make Fe
3+, Cr
3+With Fe (OH)
3, Cr (OH)
3Precipitation forms is removed, and the partial impurities ion is removed with the carbonate deposition form, and principal reaction is as follows:
Ca
2++CO
3 2-→CaCO
3↓；
Pb
2++CO
3 2-→PbCO
3↓；
Cd
2++CO
3 2-→CdCO
3↓；
Mg
2++CO
3 2-→MgCO
3↓；
Zn
2++CO
3 2-→ZnCO
3↓；
Mn
2++CO
3 2-→MnCO
3↓；
Ba
2++CO
3 2-→BaCO
3↓；
Co
2++CO
3 2-→CoCO
3↓；
Ni
2++CO
3 2-→NiCO
3↓；
2H
++?CO
3 2-→CO
2↑+H
2O。
The present invention adopts the production method of oxidation, neutralization, complexing, precipitation, adsorption treatment, vacuum filtration, membrane filtration, the auxiliary rotary evaporation crystallization of ultrasonic wave, spray drying technology associating, remove the impurity metal ions such as organism, foreign matter, oil film, arsenic, chromium, cadmium, antimony, iron, bismuth, lead, mercury and iron in the industrial smelting by-product product copper sulfate raw material, the finished product outward appearance is the blue powder crystallization, CuSO
45H
2O 〉=99.9%; Pigment and oil film clearance 〉=more than 99%; Foreign matter content (weight) index: plumbous (Pb)≤4ppm; iron (Fe)≤0.01%, chromium (Cr)≤1ppm, arsenic (As)≤3ppm; cadmium (Cd)≤1ppm; hydrogen sulfide is throw out≤0.26% not, meets food grade GB29210-2012 standard, reached the specification of quality of food grade copper sulfate product; be produced on a large scale; equipment is simple, and is easy and simple to handle, constant product quality.
Embodiment
Utensil used in the present invention is prior art.
Embodiment one:
A, in being housed, 20 liters of reactors of stirring, thermometer and reflux condensing tube add 10 liters of ultra-pure water and 2.5 kilograms of industrial smelting by-product product copper sulfate, be heated to 70 ℃ of stirring and dissolving, slowly drip sulfuric acid and adjust pH value of solution to 1.20, slowly add while hot an amount of (volume ratio 100:3, the hydrogen peroxide of massfraction 3%) oxygenant, with at a middle or low price metal ion oxidation of solution, the speed that drips oxygenant is advisable not produce the bubble fierceness, add rear insulated and stirred 1 hour, get A step solution;
B, then add slowly bodied ferric sulfate and the agent of ventilation breather precipitation and complexation that 1:3.0 in mass ratio mixes, the precipitation and complexation agent is 1.5% of A step solution weight, after the precipitation and complexation agent adds, adjust pH value of solution to 3.0-4.0 with ventilation breather, and slowly add the activated carbon of sorbent of A step solution weight 1%, 60 ℃ of insulated and stirred 6 hours, be cooled to 20 ℃ of room temperatures, left standstill 24 hours, and got B step solution;
C, with behind the B step solution for vacuum suction filtration, use again 0.25 μ m filtering with microporous membrane, filtrate adopts the auxiliary rotatory evaporator reduction vaporization of ultrasonic wave concentrated, temperature 60 C, vacuum tightness 388mmHg is cooled to 20-30 ℃, when solution density reaches 1.48g/cm
3The time, re-use the spray-dryer drying, obtain 2.16 kilograms of food grade copper sulfate blue colored crystals.
Embodiment two:
A, in being housed, 20 liters of reactors of stirring, thermometer and reflux condensing tube add 10 liters of ultra-pure water and 2.5 kilograms of industrial smelting by-product product copper sulfate, be heated to 80 ℃ of stirring and dissolving, slowly drip sulfuric acid and adjust pH value of solution to 1.50, slowly add while hot an amount of (volume ratio 100:3, the hydrogen peroxide of massfraction 3%) oxygenant, with at a middle or low price metal ion oxidation of solution, the speed that drips oxygenant is advisable not produce the bubble fierceness, add rear insulated and stirred 1 hour, get A step solution.
B, then add slowly bodied ferric sulfate and the agent of ventilation breather precipitation and complexation that 1:5.0 in mass ratio mixes, the precipitation and complexation agent is 2.5% of A step solution weight, after the precipitation and complexation agent adds, adjust pH value of solution to 3.0-4.0 with ventilation breather, and slowly add the activated carbon of sorbent of A step solution weight 2%, 60 ℃ of insulated and stirred 8 hours, be cooled to 25 ℃ of room temperatures, left standstill 24 hours, and got B step solution.
C, with behind the B step solution for vacuum suction filtration, use again 0.25 μ m filtering with microporous membrane.Filtrate adopts the auxiliary rotatory evaporator reduction vaporization of ultrasonic wave concentrated, temperature 60 C, and vacuum tightness 580mmHg is cooled to 20-30 ℃, when solution density reaches 1.48g/cm
3The time, re-use the spray-dryer drying, obtain 2.18 kilograms of food grade copper sulfate blue colored crystals.
Product appearance is good, homogeneous grain size, and wherein crystal grain diameter 30-80 purpose accounts for 80%, and crystal grain diameter 30 orders are following and respectively account for 10% more than 80 orders.
Raw material and product leading indicator (weight content) contrast that obtains are as follows:
| Project | Raw material | Product after processing |
| Content (CuSO 45H 2O) | 97.5% | 99.9% |
| Color and luster | Blue | Blue |
| State | The particulate state crystal | Granular or mealy crystal |
| Hydrogen sulfide is throw out w/% not | — | ≤0.3 |
| Arsenic (As)/(mg/kg) | 6 | ≤3 |
| Plumbous (Pb)/(mg/kg) | 5 | ≤3 |
| Iron (Fe)/w/% | 0.005 | ≤0.01 |
Claims (3)
1. by the method for smelting by-product product copper sulfate production food grade copper sulfate, it is characterized in that: comprise the steps:
A, get industrial smelting by-product product copper sulfate and be dissolved in the ultrapure water (solid-to-liquid ratio 1:4), be heated to 70-80 ℃, slowly add sulfuric acid regulation solution pH to 1.00-2.00, after the stirring and dissolving, slowly add again (volume ratio 100:3, the hydrogen peroxide of massfraction 3%) oxygenant adds rear insulated and stirred 1 hour, gets A step solution;
B, with bodied ferric sulfate and ventilation breather in mass ratio 1:2.0-5.0 be mixed and made into the precipitation and complexation agent, 0.6-2.8% by A step solution weight slowly adds the precipitation and complexation agent in A step solution, after the precipitation and complexation agent adds, adjust pH value of solution to 3.0-4.0 with ventilation breather, the 1.0-2.5% that presses again A step solution weight continues slowly to add acticarbon, and under 60 ± 2 ℃ of temperature insulated and stirred 6-8 hour, cool to room temperature again, left standstill 24 ± 2 hours, and got B step solution;
C, with behind the B step solution for vacuum suction filtration, use again the filtering with microporous membrane of 0.2-0.3 μ m, filtrate adopts the spray-dryer drying to obtain food grade cupric sulphate crystal product after the auxiliary rotatory evaporator of ultrasonic wave is concentrated.
2. the method by smelting by-product product copper sulfate production food grade copper sulfate according to claim 1, it is characterized in that: in step C condensing crystal process, with the copper-bath behind the filtering with microporous membrane of 0.2-0.3 μ m at normal temperature to 60 ℃, concentrated under the air pressure of working pressure 380-680mmHg, be cooled to 20-30 ℃, when solution density reaches 1.48g/cm
3The time, adopt the spray-dryer drying to obtain food grade cupric sulphate crystal product.
3. the method by smelting by-product product copper sulfate production food grade copper sulfate according to claim 1, it is characterized in that: one of scheme: A, stirring is being housed, add 10 liters of ultra-pure water and 2.5 kilograms of industrial smelting by-product product copper sulfate in 20 liters of reactors of thermometer and reflux condensing tube, be heated to 70 ℃ of stirring and dissolving, slowly drip sulfuric acid and adjust pH value of solution to 1.20, slowly add while hot volume ratio 100:3, the hydrogen peroxide oxidant of massfraction 3%, with at a middle or low price metal ion oxidation of solution, the speed that drips oxygenant is advisable not produce the bubble fierceness, add rear insulated and stirred 1 hour, get A step solution;
B, then add slowly bodied ferric sulfate and the agent of ventilation breather precipitation and complexation that 1:3.0 in mass ratio mixes, the precipitation and complexation agent is 1.5% of A step solution weight, after the precipitation and complexation agent adds, adjust pH value of solution to 3.0-4.0 with ventilation breather, and slowly add the activated carbon of sorbent of A step solution weight 1%, 60 ℃ of insulated and stirred 6 hours, be cooled to 20 ℃ of room temperatures, left standstill 24 hours, and got B step solution;
C, with behind the B step solution for vacuum suction filtration, use again 0.25 μ m filtering with microporous membrane, filtrate adopts the auxiliary rotatory evaporator reduction vaporization of ultrasonic wave concentrated, temperature 60 C, vacuum tightness 388mmHg is cooled to 20-30 ℃, when solution density reaches 1.48g/cm
3The time, re-use the spray-dryer drying, obtain 2.16 kilograms of food grade copper sulfate blue colored crystals.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN104108738A (en) * | 2013-04-22 | 2014-10-22 | 广东致卓精密金属科技有限公司 | Method for using copper sulfate waste liquid to prepare high-purity spherical copper oxide |
| CN106379928A (en) * | 2016-10-26 | 2017-02-08 | 西陇科学股份有限公司 | Preparation method of high-purity copper chloride dihydrate |
| CN111170354A (en) * | 2019-12-31 | 2020-05-19 | 东莞市广华化工有限公司 | Purification device for recovering basic copper carbonate from acidic etching waste liquid and use method thereof |
| CN111204792A (en) * | 2020-01-21 | 2020-05-29 | 中国科学院福建物质结构研究所 | Method for regulating and controlling growth morphology of copper sulfate pentahydrate crystal by using urea |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826584A (en) * | 2012-09-22 | 2012-12-19 | 西陇化工股份有限公司 | Production method of high-purity copper sulphate |
-
2013
- 2013-07-04 CN CN2013102776370A patent/CN103303964A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826584A (en) * | 2012-09-22 | 2012-12-19 | 西陇化工股份有限公司 | Production method of high-purity copper sulphate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108738A (en) * | 2013-04-22 | 2014-10-22 | 广东致卓精密金属科技有限公司 | Method for using copper sulfate waste liquid to prepare high-purity spherical copper oxide |
| CN104108738B (en) * | 2013-04-22 | 2015-08-19 | 广东致卓精密金属科技有限公司 | A kind of method being prepared high pure spherical cupric oxide by bluestone waste |
| CN103693672A (en) * | 2013-12-25 | 2014-04-02 | 广州科城环保科技有限公司 | Method for preparing electroplating grade copper sulfate pentahydrate by copper-bearing acid waste liquid without containing ammonia nitrogen |
| CN103693672B (en) * | 2013-12-25 | 2015-08-26 | 广州科城环保科技有限公司 | A kind of cupric acid waste liquid not containing ammonia nitrogen prepares the method for plating level cupric sulfate pentahydrate |
| CN106379928A (en) * | 2016-10-26 | 2017-02-08 | 西陇科学股份有限公司 | Preparation method of high-purity copper chloride dihydrate |
| CN111170354A (en) * | 2019-12-31 | 2020-05-19 | 东莞市广华化工有限公司 | Purification device for recovering basic copper carbonate from acidic etching waste liquid and use method thereof |
| CN111204792A (en) * | 2020-01-21 | 2020-05-29 | 中国科学院福建物质结构研究所 | Method for regulating and controlling growth morphology of copper sulfate pentahydrate crystal by using urea |
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Application publication date: 20130918 |