CN115108576A - Purification method and application of copper sulfate pentahydrate crystal - Google Patents
Purification method and application of copper sulfate pentahydrate crystal Download PDFInfo
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- CN115108576A CN115108576A CN202210688630.7A CN202210688630A CN115108576A CN 115108576 A CN115108576 A CN 115108576A CN 202210688630 A CN202210688630 A CN 202210688630A CN 115108576 A CN115108576 A CN 115108576A
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- copper sulfate
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- sulfate pentahydrate
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- 239000013078 crystal Substances 0.000 title claims abstract description 168
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000000746 purification Methods 0.000 title claims description 18
- 238000001816 cooling Methods 0.000 claims abstract description 59
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 34
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000012043 crude product Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000012258 culturing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 29
- 238000009826 distribution Methods 0.000 abstract description 23
- 238000009713 electroplating Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003883 substance clean up Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000010586 diagram Methods 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 11
- 238000010903 primary nucleation Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VEMHQNXVHVAHDN-UHFFFAOYSA-J [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VEMHQNXVHVAHDN-UHFFFAOYSA-J 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention belongs to the technical field of compound purification, and particularly relates to a method for purifying a copper sulfate pentahydrate crystal and application thereof. Adding seed crystals with a certain size and an addition rate into a copper sulfate crude product solution for culturing, adopting a four-time grading cooling strategy, controlling the cooling rate to keep the solution in a metastable state all the time, and gradually cooling to 25-34 ℃ to obtain a copper sulfate pentahydrate crystal; the purity of the obtained copper sulfate pentahydrate crystal reaches the electroplating grade, the crystal morphology of the copper sulfate pentahydrate crystal is greatly improved, the average particle size of the crystal is large, the particle size distribution is concentrated, and the crystal is not easy to agglomerate; meanwhile, the method has the advantages of simple process, greatly shortened preparation time, no need of using strong acid and strong alkali solution, environmental protection, low resource consumption and contribution to large-scale production.
Description
Technical Field
The invention belongs to the technical field of compound purification. More particularly, relates to a purification method of copper sulfate pentahydrate crystals and application thereof.
Background
Blue vitriol, chalcanthite or copperas are commonly known as blue vitriol, chalcanthite or copperas, are important inorganic chemical products, in the field of electroplating, the demand for electroplating-grade copper sulfate with good quality and high purity is increasing, while the purity of the copper sulfate products produced in China is mostly industrial-grade products, the purity of the products is low, the quality is poor, the particles are fine, the granularity is not uniform, the crystal form is not good, the crystals are not compact, and the products are easy to break in the drying and screening process. Therefore, the preparation of the high-purity copper sulfate pentahydrate crystal has very important significance.
The method is characterized in that a plurality of crude copper sulfate pentahydrate products are produced industrially, the application of the crude copper sulfate pentahydrate products is limited due to the low content of copper sulfate, if the crude copper sulfate pentahydrate products can be purified, resources can be greatly saved, and the utilization rate of the crude copper sulfate pentahydrate products is improved. The method can effectively increase the size of copper sulfate crystals and remove impurities such as ferrous sulfate of crude copper sulfate varieties, but needs to add strong acid and strong alkali solution sulfuric acid in the purification process, which is not in accordance with the green chemical concept, and the supersaturation degree of the solution in the initial stage of the crystallization process is sharply increased to reach a certain peak value and then sharply decreased, so that the supersaturation degree of the crystallization process is maintained at a very low level in a subsequent quite long period of time, thereby causing the problems of primary nucleation phenomenon and low production capacity (limoniangnu. method for increasing copper sulfate crystal particles in the crude copper sulfate purification experiment [ J ]. Huai institute, 2003.). Therefore, the method for purifying the copper sulfate pentahydrate crystals from the crude copper sulfate pentahydrate product, which is green and environment-friendly and has good primary nucleation production capacity, is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problems that the existing method for purifying the copper sulfate pentahydrate crystal from the crude copper sulfate pentahydrate product does not conform to the green chemical concept, has poor control on the primary nucleation phenomenon and low production capacity, and provides the method for purifying the copper sulfate pentahydrate crystal, which is green and environment-friendly, has high yield, high copper sulfate purity, narrow crystal particle size distribution range and regular crystal morphology and can greatly shorten the purification time.
The invention aims to provide an application of a purification method of copper sulfate pentahydrate crystals in purification of the copper sulfate pentahydrate crystals.
The above object of the present invention is achieved by the following technical solutions:
the invention discloses a purification method of copper sulfate pentahydrate crystals, which comprises the following steps:
mixing a copper sulfate crude product with water, heating to 85-100 ℃ for dissolution, filtering while the copper sulfate crude product is hot, cooling to 56-63 ℃ at the speed of 0.05-0.25 ℃/min for the first time, adding seed crystals for culturing for 0.5-1 h, cooling to 50-55 ℃ at the speed of 0.2-0.3 ℃/min for the second time, cooling to 35-45 ℃ at the speed of 0.3-0.4 ℃/min for the third time, cooling to 25-34 ℃ at the speed of 0.4-0.5 ℃/min for the fourth time, standing, and performing post-treatment to obtain the copper sulfate;
when the grain size of the seed crystal is 50-85 meshes, the seed crystal addition rate is 8% -12%; when the grain size of the seed crystal is 90-100 meshes, the seed crystal addition rate is 6-12%.
The method creatively adopts a quartic grading cooling strategy, the solution is always kept in a metastable state by controlling the cooling rate, and compared with uncontrolled natural cooling and constant-speed cooling, the method adopted by the invention ensures that the growth rate of the copper sulfate pentahydrate crystal is completely controlled by the cooling rate, thereby effectively avoiding the primary nucleation phenomenon caused by the solution entering an unstable area. If the natural cooling operation is adopted, the supersaturation degree of the solution is sharply increased to a certain peak value at the initial stage of the crystallization process and then sharply decreased, so that the supersaturation degree of the crystallization process is maintained at a very low level for a subsequent considerable period of time, resulting in the problem of low productivity of primary nucleation. As for the constant-speed cool-down operation, the disadvantage similar to the natural cooling operation still remains.
The seed formula design is the key to the success of crystallization. The more the seed crystal addition rate is, the higher the cost is, besides, the growth speed of the single crystal is inhibited, and the average size of the product is reduced; the less the seed crystal addition rate is, the yield is correspondingly reduced, and the nucleation rate is higher than the growth rate, so that the primary nucleation phenomenon occurs, and the product granularity is irregular.
The narrower the grain size distribution of the seed crystal is, the narrower the grain size distribution of the obtained product is, and the more uniform the grain size distribution of the product is; the smaller size of the seed crystal (less than 100 meshes) can improve the yield of the product, but the generated crystal has smaller grain diameter, and the larger size (more than 50 meshes) is favorable for generating crystals with larger grain diameter, but the yield of the product is lower. Only in the particle size range of the present invention, a large crystal particle size can be achieved with a high yield.
Preferably, the concentration of the copper sulfate crude product after being mixed with water is 750 g/L-890 g/L.
Preferably, the crude copper sulfate is industrial crude copper sulfate.
Preferably, stirring is needed during the first cooling, and the stirring speed is 80-150 r/min.
Preferably, stirring is needed during the second cooling, and the stirring speed is 300-400 r/min.
Preferably, stirring is needed during the third temperature reduction, and the stirring speed is 300-400 r/min.
Preferably, stirring is needed during the fourth temperature reduction, and the stirring speed is 300-400 r/min.
Preferably, the temperature is reduced to 36-40 ℃ for the third time.
Preferably, the fourth temperature reduction is carried out to 28-32 ℃.
Preferably, the seed crystals are screened through a sample-separating screen.
Preferably, the seed crystal is washed with a proper amount of water after being subjected to sample separation and screening.
Washing with proper amount of water can dissolve fine particles adhered to the seed crystal, so that the surface of the seed crystal is smoother, and the particle size distribution is more uniform.
Preferably, the water comprises deionized water.
Preferably, the standing time is 0.5-1.5 h.
The invention further protects the application of the purification method of the copper sulfate pentahydrate crystal in the preparation of the copper sulfate pentahydrate crystal.
The invention has the following beneficial effects:
adding seed crystals with a certain size and an addition rate into a copper sulfate crude product solution for culturing, adopting a four-time grading cooling strategy, controlling the cooling rate to keep the solution in a metastable state all the time, and gradually cooling to 25-34 ℃ to obtain a copper sulfate pentahydrate crystal; the purity of the obtained copper sulfate pentahydrate crystal reaches the electroplating grade, the crystal morphology of the copper sulfate pentahydrate crystal is greatly improved, the average particle size of the crystal is large, the particle size distribution is concentrated, and the crystal is not easy to agglomerate; meanwhile, the method has the advantages of simple process, greatly shortened preparation time, no need of using strong acid and strong alkali solution, environmental protection, low resource consumption and contribution to large-scale production.
Drawings
FIG. 1 is a crystal morphology diagram of copper sulfate pentahydrate crystals obtained in examples 1 to 3, which is obtained by magnifying the crystals by 40 times through an optical microscope, and the crystal morphology diagrams sequentially include example 1, example 2, and example 3 from left to right.
FIG. 2 is a particle size distribution diagram of copper sulfate pentahydrate crystals obtained in examples 1 to 3 obtained by a laser particle size analyzer, which is shown as example 1, example 2, and example 3 from left to right.
FIG. 3 is a crystal morphology diagram of copper sulfate pentahydrate crystals obtained in comparative examples 1 to 2 of the present invention obtained by magnifying the crystals by 40 times with an optical microscope, and comparative example 1 and comparative example 2 are shown from left to right.
Fig. 4 is a particle size distribution diagram of the copper sulfate pentahydrate crystals obtained in comparative examples 1 to 2 of the present invention obtained by a laser particle size analyzer, which is comparative example 1 and comparative example 2 in the order from left to right.
FIG. 5 is a crystal morphology diagram of copper sulfate pentahydrate crystals obtained in comparative examples 3 to 5 of the present invention obtained by magnifying the crystals by 40 times with an optical microscope, and the crystal morphology diagrams are comparative example 3, comparative example 4, and comparative example 5 in the order from left to right.
Fig. 6 is a particle size distribution diagram of the copper sulfate pentahydrate crystals obtained in comparative examples 3 to 5 of the present invention obtained by a laser particle size analyzer, which is comparative example 3, comparative example 4, and comparative example 5 in the order from left to right.
FIG. 7 is a crystal morphology diagram obtained by magnifying a copper sulfate pentahydrate crystal obtained in comparative example 6 by 40 times with an optical microscope and a particle size distribution diagram obtained by a laser particle size analyzer, the crystal morphology diagram and the particle size distribution diagram being sequentially from left to right.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The main components and contents of the industrial copper sulfate crude product used in the invention are shown in table 1:
TABLE 1 Main Components and contents of crude Industrial copper sulfate
| Item | Industrial copper sulfate |
| Copper sulfate (CuSO) 4 ·5H 2 O) content w/% | 95.63 |
| W/% arsenic (As) content | 0.00011 |
| W/% of lead (Pb) content | 0.00002 |
| Calcium (Ca) content w/%) | 0.00700 |
| Iron (Fe) content w/%) | 0.01364 |
| Cobalt (Co) content w/%) | 0.00002 |
| W/% of nickel (Ni) content | 0.00002 |
| Zinc (Zn) content w/%) | 0.00006 |
| W/% of cadmium (Cd) content | 0.00000 |
| Manganese (Mn) content w/%) | 0.00010 |
| Aluminium (Al) content w/%) | 0.00319 |
| W/% of chromium (Cr) content | 0.00066 |
| W/% chloride (as Cl) content | 0.01250 |
| Water insoluble content w/%) | 0.01630 |
| pH (50g/L solution) | 3.60 |
EXAMPLE 1 preparation of copper sulfate pentahydrate crystals
84.48g of industrial copper sulfate crude product is taken to be mixed with 100ml of deionized water and heated to 85 ℃, clear solution is obtained by suction filtration while the solution is hot, the temperature is reduced to 58.5 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 120r/min, seed crystals which are filtered by a 65-mesh screen and washed by water are added, the adding rate of the seed crystals is 10 percent, the stirring rate is maintained at 120r/min, the crystal crystals grow at the constant temperature of 58.5 ℃ for 0.5h, the obtained seed crystals are evenly and regularly suspended in the whole solution, the temperature is reduced to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, the temperature is reduced to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, the temperature is reduced to 30 ℃ at the stirring rate of 0.4 ℃/min and the stirring rate of 350r/min, the standing is carried out for 1h, the crystal crystals are vacuum filtered, washed by deionized water, the crystals are dried for 3h in vacuum, copper sulfate pentahydrate crystals are obtained.
EXAMPLE 2 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding seed crystals which are filtered by a 100-mesh screen and washed by water, wherein the seed crystal adding rate is 6 percent, the stirring rate is maintained at 120r/min, and the seed crystals are grown at a constant temperature of 58.5 ℃ for 0.5h, are uniformly and regularly suspended in the whole solution, are cooled to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, are cooled to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, are kept stand for 1h, are subjected to vacuum filtration and deionized water washing, are dried for 3h in vacuum, obtaining the blue copperas crystal.
The difference from example 1 is that the seed crystal was passed through a 100 mesh sieve, and the seed crystal addition rate was 6%.
EXAMPLE 3 preparation of copper sulfate pentahydrate crystals
84.48g of industrial copper sulfate crude product is taken to be mixed with 100ml of deionized water and heated to 85 ℃, clear solution is obtained by suction filtration while the solution is hot, the temperature is reduced to 58.5 ℃ at the temperature reduction rate of 0.2 ℃/min and the stirring rate of 120r/min, seed crystals which are filtered by a 100-mesh screen and washed by water are added, the seed crystal addition rate is 10 percent, the stirring rate is maintained at 120r/min, the crystal seeds are grown for 0.5h at the constant temperature of 58.5 ℃, the obtained seed crystals are uniformly and regularly suspended in the whole solution, the temperature is reduced to 50 ℃ at the temperature reduction rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, the temperature is reduced to 38 ℃ at the temperature reduction rate of 0.3 ℃/min and the stirring rate of 350r/min, the temperature is reduced to 30 ℃ at the temperature reduction rate of 0.4 ℃/min and the stirring rate of 350r/min, standing is carried out for 1h, the crystals are vacuum suction filtered and washed by deionized water, the washed crystals are dried for 3h in vacuum, obtaining the blue copperas crystal.
The difference from example 1 is that the seeds were passed through a 100 mesh screen.
Comparative example 1 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding a seed crystal which is sieved by a 65-mesh screen and washed by water, wherein the seed crystal addition rate is 2 percent, the stirring rate is maintained at 120r/min, and the seed crystal is grown for 0.5h at a constant temperature of 58.5 ℃, the obtained seed crystal is uniformly and regularly suspended in the whole solution, cooling to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, cooling to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, standing for 1h, carrying out vacuum suction filtration and deionized water washing, carrying out vacuum drying on the washed crystal for 3h, copper sulfate pentahydrate crystals are obtained.
The difference from example 1 is that the seed crystal addition rate was 2%.
Comparative example 2 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding seed crystals which are sieved by a 65-mesh screen and washed by water, wherein the seed crystal adding rate is 6 percent, the stirring rate is maintained at 120r/min, and the seed crystals are grown at a constant temperature of 58.5 ℃ for 0.5h, the obtained seed crystals are uniformly and regularly suspended in the whole solution, cooling to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, cooling to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, standing for 1h, carrying out vacuum suction filtration and deionized water washing, carrying out vacuum drying on the washed crystals for 3h, obtaining the blue copperas crystal.
The difference from example 1 is that the seed crystal addition rate was 6%.
Comparative example 3 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding seed crystals which are filtered by a 100-mesh screen and washed by water, wherein the seed crystal adding rate is 2 percent, the stirring rate is maintained at 120r/min, and the seed crystals are grown at a constant temperature of 58.5 ℃ for 0.5h, are uniformly and regularly suspended in the whole solution, are cooled to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, are cooled to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, are kept stand for 1h, are subjected to vacuum filtration and deionized water washing, are dried for 3h in vacuum, obtaining the blue copperas crystal.
The difference from example 1 is that the seed crystal was passed through a 100 mesh sieve, and the seed crystal addition rate was 2%.
Comparative example 4 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding seed crystals which are filtered by a 120-mesh screen and washed by water, wherein the seed crystal adding rate is 2 percent, the stirring rate is maintained at 120r/min, and the seed crystals are grown at a constant temperature of 58.5 ℃ for 0.5h, are uniformly and regularly suspended in the whole solution, are cooled to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, are cooled to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, are kept stand for 1h, are subjected to vacuum filtration and deionized water washing, are dried for 3h in vacuum, obtaining the blue copperas crystal.
The difference from example 1 is that the seed crystal was passed through a 120-mesh sieve, and the seed crystal addition rate was 2%.
Comparative example 5 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding seed crystals which are filtered by a 120-mesh screen and washed by water, wherein the seed crystal adding rate is 6 percent, the stirring rate is maintained at 120r/min, and the seed crystals are grown at a constant temperature of 58.5 ℃ for 0.5h, are uniformly and regularly suspended in the whole solution, are cooled to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, are cooled to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, are kept stand for 1h, are subjected to vacuum filtration and deionized water washing, are dried for 3h in vacuum, obtaining the blue copperas crystal.
The difference from example 1 is that the seed crystal was passed through a 120-mesh sieve, and the seed crystal addition rate was 6%.
Comparative example 6 preparation of copper sulfate pentahydrate crystals
Mixing 84.48g of industrial copper sulfate crude product with 100ml of deionized water, heating to 85 ℃, carrying out suction filtration while the solution is hot to obtain a clarified solution, cooling to 58.5 ℃ at a cooling rate of 0.2 ℃/min and a stirring rate of 120r/min, adding seed crystals which are filtered by a 120-mesh screen and washed by water, wherein the seed crystal adding rate is 2 percent, the stirring rate is maintained at 120r/min, and the seed crystals are grown at a constant temperature of 58.5 ℃ for 0.5h, are uniformly and regularly suspended in the whole solution, are cooled to 50 ℃ at the cooling rate of 0.2 ℃/min and the stirring rate of 350r/min in sequence, are cooled to 38 ℃ at the cooling rate of 0.3 ℃/min and the stirring rate of 350r/min, are kept stand for 1h, are subjected to vacuum filtration and deionized water washing, are dried for 3h in vacuum, obtaining the blue copperas crystal.
The difference from example 1 is that the seed crystal is passed through a 120 mesh screen.
Experimental example 1 determination of content of main component in copper sulfate pentahydrate crystal
The main component content of the copper sulfate pentahydrate crystals obtained in the examples 1 to 3 and the comparative examples 1 to 6 is measured by a method derived from HG/T3592 & lt 2020 & gt copper sulfate for electroplating (the standard of the copper sulfate for electroplating is shown in Table 4), and the main component and content results of the copper sulfate pentahydrate crystals are shown in tables 2 to 3.
TABLE 2 main components and contents of copper sulfate pentahydrate crystals obtained in examples 1 to 3
TABLE 3 main components and contents of copper sulfate pentahydrate crystals obtained in comparative examples 1 to 6
TABLE 4 HG/T3592 & 2020 copper sulfate for electroplating
As can be seen from the table 2, the content of the blue vitriod in the examples 1 to 3 is improved compared with that of the raw material, and the comparison table 4 shows that the example 1 reaches the qualified product of the electroplating grade and is close to the first-grade product of the electroplating grade; examples 2 and 3 achieved a first grade of plating, example 3 was close to a first grade of plating; in the aspect of impurity content, the whole Fe content is reduced from 0.0136 percent to 0.0020 to 0.0030 percent, and the requirement of the first-grade electroplating product is met; the Ca content is reduced from 0.0070% to 0.0002% -0.0017% as a whole, and the quality of the Ca is between that of the first-class products and the high-class products of the electroplating grade; the content of chloride is reduced from 0.0125% to 0.0009% -0.0035%, the quality is between the first-class product and the superior product of electroplating grade, in addition, the yield of the blue vitriol in the above embodiment is very in accordance with the production benefit on the basis of the quality optimization to the copper sulfate of electroplating grade, and the yield is respectively 92.6%, 90.51% and 93.2%.
As can be seen from Table 3, in comparative examples 1 to 3, although the purity is close to that of electroplating-grade copper sulfate, the yield is low, and the actual production is not suitable, and the prepared copper sulfate pentahydrate crystal is unqualified only by changing the combination of the mesh number of the seed crystal passing through the screen and the addition rate of the seed crystal.
Experimental example 2 morphology and particle size analysis of copper sulfate pentahydrate crystals
The copper sulfate pentahydrate crystals obtained in examples 1 to 3 and comparative examples 1 to 6 were subjected to particle size distribution analysis, and crystal microscopic morphology analysis was performed by an optical microscope.
As shown in fig. 1 to 7: the particle size distribution of the copper sulfate pentahydrate crystals obtained in the examples 1-3 is narrow, wherein the particle size distribution of the example 3 is unimodal distribution, the particle size distribution is mainly between 1000-1200 um, the distribution range of the example 1 is wide, but the particle size distribution is mainly between 1000-2000 um, the example 2 is close to unimodal distribution, and the particle size distribution is mainly between 900-1200 um, which shows that the combination of the mesh number of the seed crystal passing through the screen and the seed crystal addition rate in the seed crystal formula has a small probability of primary nucleation in the crystallization process, so that the crystals precipitated in the cooling crystallization process can be regularly attached to the seed crystal for regular growth, the average particle size is large, and the crystal form of the examples 1-3 is very regular from a crystal morphology chart, and the mother liquor is not easy to adhere to carry impurities, thereby improving the product purity.
The particle size distribution, the particle size, the crystal morphology and the like of the blue copperas crystals obtained in the comparative examples 1 to 6 can not be considered at the same time, for example, the particle size distribution range of the comparative examples 5 and 6 is narrow and is in monomodal distribution, but the particle sizes are mainly distributed between 250 to 300um, the crystal morphology can show that the crystal forms are disordered and have serious primary nucleation phenomenon, and in addition, the fine crystals are difficult to wash and filter, and the purity is easily influenced by inclusion of mother liquor.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for purifying copper sulfate pentahydrate crystals is characterized by comprising the following steps:
mixing a copper sulfate crude product with water, heating to 85-100 ℃ for dissolving, filtering while the mixture is hot, cooling to 56-63 ℃ at the rate of 0.05-0.25 ℃/min for the first time, adding seed crystals, and culturing for 0.5-1 h; cooling to 50-55 ℃ at the speed of 0.2-0.3 ℃/min for the second time, cooling to 35-45 ℃ at the speed of 0.3-0.4 ℃/min for the third time, cooling to 25-34 ℃ at the speed of 0.4-0.5 ℃/min for the fourth time, standing, and performing post-treatment to obtain the final product;
when the grain size of the seed crystal is 50-85 meshes, the seed crystal addition rate is 8% -12%; when the grain size of the seed crystal is 90-100 meshes, the seed crystal addition rate is 6% -12%.
2. The purification method of claim 1, wherein the concentration of the crude copper sulfate mixed with water is 750g/L to 890 g/L.
3. The purification method according to claim 1, wherein stirring is required during the first temperature reduction, and the stirring speed is 80-150 r/min.
4. The purification method according to claim 1, wherein stirring is further required during the second temperature reduction, and the stirring speed is 300-400 r/min.
5. The purification method according to claim 1, wherein stirring is further required during the third temperature reduction, and the stirring speed is 300-400 r/min.
6. The purification method according to claim 1, wherein stirring is further required during the fourth temperature reduction, and the stirring speed is 300-400 r/min.
7. The purification method according to claim 1, wherein the third temperature reduction is carried out to 36-40 ℃.
8. The purification method according to claim 1, wherein the fourth temperature reduction is carried out to 28-32 ℃.
9. The purification method according to claim 1, wherein the standing time is 0.5 to 1.5 hours.
10. Use of the method for purifying copper sulfate pentahydrate crystals as claimed in any one of claims 1 to 9 for the preparation of copper sulfate pentahydrate crystals.
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