CN109487084B - Crystallization method of nickel sulfate solution - Google Patents
Crystallization method of nickel sulfate solution Download PDFInfo
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- CN109487084B CN109487084B CN201811524997.5A CN201811524997A CN109487084B CN 109487084 B CN109487084 B CN 109487084B CN 201811524997 A CN201811524997 A CN 201811524997A CN 109487084 B CN109487084 B CN 109487084B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for crystallizing nickel sulfate from a nickel solution. The method comprises the following steps: concentrating the nickel sulfate solution to a density of 1.01g/cm3～5.0g/cm3(ii) a Stirring the concentrated nickel sulfate solution at normal temperature, cooling to 30-65 ℃, and adding a load into the concentrated solution; standing and crystallizing for 2-48 h at normal temperature; and after the crystallization is finished, taking out the load to separate the mother liquor from the crystallization, drying the crystallization, and taking the crystal off the load to obtain the nickel sulfate crystal. According to the method, most of crystals are quickly and stably precipitated on a load by adding the load into a nickel sulfate concentrated solution. The method has the advantages of fast crystallization, more stable crystallization compared with the traditional concentration crystallization mode, difficult agglomeration, stable crystal form, uniform particle size, easy separation of crystals from mother liquor and the like. The method is suitable for crystallizing the nickel sulfate solution obtained by recovering nickel from chemical nickel plating waste liquid or other nickel-containing industrial waste liquid.
Description
Technical Field
The invention belongs to the technical field of crystallization, and relates to a crystallization method of a nickel sulfate solution. This application claims priority from patent application No. 2017113437903, filed on 12/4/2017.
Background
The industrial production fields of nickel electroplating, chemical nickel plating and the like can generate a large amount of nickel-containing waste liquid, and because the recovery value of nickel is high and nickel has great harm to the environment and human bodies, the necessity of recovering nickel in the nickel-containing waste liquid is caused.
At present, there are many recovery methods for nickel, including precipitation, electrolysis, ion exchange, solvent extraction, etc., except for direct conversion into nickel simple substance or direct preparation of new material, many final recovery methods for nickel are in the form of nickel sulfate, such as precipitation, after precipitating nickel with precipitant, dissolving precipitate with sulfuric acid to obtain nickel sulfate solution; after the ion exchange method is used for exchange, sulfuric acid is also used as a desorbent to obtain a nickel sulfate desorption solution; in the same way, in the back extraction process, many of the nickel sulfate is desorbed by acid, and the back extraction solution of the nickel sulfate can also be obtained. A common feature of the nickel sulfate solutions described above is that the nickel sulfate solution obtained from sulfuric acid contains a portion of the acid. The method commonly used in the industry for treating such nickel sulfate solutions is crystallization by heating for concentration and cooling. However, this method has several disadvantages: if the concentration is not enough, the crystallization is slow or not, and if the concentration is excessive, a large amount of fine crystals can be rapidly separated out and are not formed; direct cooling crystallization may lead to inconsistent crystal forms; in addition, too high a concentration of acid in the solution after concentration may also affect the crystallization effect.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a nickel sulfate crystallization method which has the advantages of rapid crystallization, stable and uniform crystal form, high yield and easy separation of mother liquor and crystallization.
The technical scheme is as follows: in order to achieve the technical purpose, the invention provides a crystallization method of a nickel sulfate solution, which comprises the following steps:
(1) heating, evaporating and concentrating the nickel sulfate solution until the density is 1.01g/cm3～5.0g/cm3；
(2) Stirring the concentrated nickel sulfate solution at normal temperature and cooling to 30-65 ℃;
(3) adding a load to the solution;
(4) cooling and crystallizing at normal temperature;
(5) and directly taking out the load after crystallization, separating mother liquor from the crystal, tapping the load to enable the crystal to fall and collect, and drying the crystal to obtain the nickel sulfate crystal.
Wherein, the nickel sulfate solution in the step (1) is a nickel sulfate solution obtained by recovering nickel from chemical nickel plating waste liquid or other nickel-containing industrial waste liquid, and the pH range is 0.1-5.
Preferably, the density in step (1) is 1.4g/cm3～1.5g/cm3；
The load used in the step (3) has the external part in a cylindrical shape, a spherical shape or other shapes and the internal part in a honeycomb hollow structure.
Preferably, the internal void size of the load used is in the range of 1 to 10mm, preferably in the range of 3 to 10 mm.
Preferably, the loading is added in an amount such that the loading is submerged in the solution after the loading is added. Preferably, the load used is completely immersed in the solution after addition to the solution, the volume of the added load being slightly less than the volume of the solution. For example, the amount of the load added can be controlled to be less than 25cm per 25ml of the mother liquor3The load of (2).
Preferably, in the step (4), the cooling rate is 0.5 ℃/min to 5 ℃/min, preferably 2 ℃/min to 5 ℃/min, and the crystallization time is 2h to 48 h.
In one embodiment, the carrier is any one of ceramic, hollow plastic, solid plastic, charcoal, volcanic rock, glass, wood and rubber, and the addition amount of the carrier is 0.01-9.9 g/mL of the solution.
Has the advantages that: compared with the prior art, the method has the advantages that most of crystals are quickly and stably separated out on the load by adding the load into the nickel sulfate concentrated solution, and the method is more stable than the traditional concentrated crystallization method, is not easy to agglomerate, has stable crystal form and uniform particle size, is easy to separate crystals from mother liquor, and the like. The method is suitable for crystallizing the nickel sulfate solution obtained by recovering nickel from chemical nickel plating waste liquid or other nickel-containing industrial waste liquid.
Drawings
FIG. 1 is a graph of the crystal size distribution obtained without the addition of a support;
FIG. 2 is a graph showing the distribution of the crystal particle size obtained by adding cylindrical porous polypropylene plastic;
FIG. 3 is a comparison of crystals obtained with no addition and with a loading, where the left is no addition and the right is addition;
FIG. 4 is a graph of the crystal size distribution obtained without the addition of a support;
FIG. 5 is a graph showing the distribution of the crystal particle size obtained by adding cylindrical porous polypropylene plastic;
FIG. 6 is a comparison of crystals obtained with no addition and with a loading, where the left is no addition and the right is addition;
FIG. 7 is a graph of the crystal size distribution obtained without the addition of a support;
FIG. 8 is a distribution diagram of crystal grain size obtained by adding a frosted ceramic plate;
fig. 9 is a comparison of crystals obtained with no addition and with the addition of the support, where the left is no addition and the right is addition.
Detailed Description
Example 1
The embodiment of the invention provides a crystallization method of a nickel sulfate solution recovered after chemical nickel plating waste liquid is treated by a solvent extraction method. The concentration of nickel in the nickel sulfate solution obtained after extraction and back extraction by a solvent extraction method is 16.4g/L, and the pH value is 1.634.
The nickel sulfate solution is heated and concentrated, and the density is 1.4259g/cm3Stirring and cooling to 60 ℃, respectively putting 25mL of the mixture into two beakers, namely a beaker A1, and adding a load b (cylindrical porous polypropylene plastic with the diameter of 20mm, the diameter of an inner hole of 3mm and the height of the cylindrical plastic of 30 mm); beaker a2 did not add load. The two beakers were allowed to stand at room temperature for 8 hours. After the supported material was taken out, the crystals were taken out from the above, and after drying, the total mass of the support material weighed out without addition and the total mass of the support material added were 2.778g and 3.8909g, respectively. The particle size distribution of the crystals under the two conditions is shown in FIGS. 1 and 2. The crystal photographs are shown in fig. 3, wherein the left image shows no addition, the right image shows the addition of the load, and the left image shows that the crystal is green and is nickel sulfate heptahydrate, and the right image shows blue and is nickel sulfate hexahydrate.
The particle size distribution of crystals was relatively uniform in both the case of adding and not adding the support, but the actual crystal control chart showed irregular and agglomerated crystals, and nickel sulfate heptahydrate in the case of no addition and nickel sulfate hexahydrate in the case of addition.
Example 2
The embodiment of the invention provides a crystallization method of a nickel sulfate solution recovered after chemical nickel plating waste liquid is treated by a solvent extraction method. The concentration of nickel in the nickel sulfate solution obtained after extraction and back extraction by a solvent extraction method is 14.3g/L, and the pH value is 0.75.
After the nickel sulfate solution is concentrated, the density is 1.4128g/cm3Stirring and cooling to 62 ℃, respectively putting 25mL of the mixture into two beakers, namely a beaker B1, and adding a load B (cylindrical porous polypropylene plastic with the diameter of 20mm, the diameter of an inner hole of 3mm and the height of the cylindrical plastic of 30 mm); beaker B2 was not added and both beakers were allowed to stand at room temperature for 10 h. After the supported material was taken out, the crystals were taken out from the above, and after drying, the total mass of the support material weighed out without addition and the total mass of the support material added were 5.854g and 6.6297g, respectively. The particle size distribution of the crystals under the two conditions are shown in FIGS. 4 and 5. The crystal photographs are shown in fig. 6, wherein the left image shows no addition, the right image shows the addition of the load, and the left image shows that the crystal is green and is nickel sulfate heptahydrate, and the right image shows blue and is nickel sulfate hexahydrate.
When the load is added, the crystal distribution with the grain diameter of 1-2.5 mm is more; when no addition is made, the particle size is distributed in a large amount of 3 to 4 mm. When a load is added, crystals are in a uniform spherical shape, and when the load is not added, the crystal particle size is larger because crystal lumps are together, so that the particle size is increased, but the crystal form is extremely irregular and is mostly in a strip shape.
Example 3
The embodiment of the invention provides a crystallization method of a nickel sulfate solution recovered after chemical nickel plating waste liquid is treated by a solvent extraction method. The concentration of nickel in the nickel sulfate solution obtained after extraction and back extraction by a solvent extraction method is 18.5g/L, and the pH value is 0.56.
After the nickel sulfate solution is concentrated, the density is 1.4256g/cm3Stirring and cooling to 55 deg.C, adding 25mL of the mixture into two beakers, beaker C1, and adding a load a (ground ceramic plate, about 2500mm in area)2Thickness 4mm), beaker C2 was unloaded. The two beakers were allowed to stand at room temperature for 11 hours. After the supported material was taken out, the crystals were taken out from the above, and after drying, the total mass of the support material weighed out without addition and the total mass of the support material added were 2.5688g and 3.2023g, respectively. The particle size distribution of the crystals under the two conditions are shown in FIGS. 7 and 8. The crystal photograph is shown in FIG. 9.
When no load was added, crystals having a particle size of 5mm or more appeared, but the crystal form was irregular. The crystal grain size after adding the loading material is uniform.
Example 4
The embodiment of the invention provides a crystallization method of a nickel sulfate solution recovered after chemical nickel plating waste liquid is treated by a solvent extraction method. The concentration of nickel in the nickel sulfate solution obtained after extraction and back extraction by a solvent extraction method is 16.4g/L, and the pH value is 1.634.
The nickel sulfate solution is heated and concentrated, and the density is 1.4259g/cm3Stirring and cooling to 60 ℃, respectively putting 25mL into 6 beakers, respectively adding 6 types of materials with the volume of 20cm3Left and right loads. Beaker D1 was filled with a load a (ground ceramic sheet, approximately 2500mm in area)2And the thickness is 8 mm); load b (cylindrical porous polypropylene plastic, 30mm in diameter, 3mm in diameter of internal pore, 30mm in height of cylindrical plastic) was added to beaker D2, load c (cylindrical solid polypropylene plastic, 30mm in diameter, 30mm in height of cylindrical plastic) was added to beaker D3, and load D (elongated charcoal flakes, approximately 2000mm in cross-sectional area) was added to beaker D42Thickness 10mm), a load e (volcanic rock sheet, area about 2000 mm) was added to the beaker D5210mm thick with prismatic apertures 3mm in diameter), a load f (glass sheet, about 2500mm in area) was added to beaker D62And 8mm in thickness). The 6 beakers were allowed to stand at room temperature for 8 hours. After the supported material was taken out, the crystals were taken off from the above, and after drying, the total mass of the support material weighed out without addition and the total mass of the support material added were 4.226g, 5.556g, 3.752g, 6.134g, 6.592g and 3.154g, respectively.
The particle size of the crystals was relatively uniform and uniform spherical with the addition of 6 supports. Comparing the quality of crystallization on 6 supports, volcanic rock, charcoal, porous plastic are superior to solid plastic, ceramic flakes, glass flakes. I.e., the rougher the surface, the greater the surface area in the same volume, and the more favorable the formation of crystals.
It was found from the above examples that the crystallization with and without added support was very different, and the main advantage of the added support crystallization compared to the crystallization without added support was:
(1) greater total mass of crystals: adding a load to obtain the total mass of the crystals which is always larger than the total mass of the crystals obtained without adding the load;
(2) more stable and uniform crystal form and particle size: the obtained crystals are easy to agglomerate without addition, and large irregular strip-shaped crystals are formed; spherical crystals with moderate and uniform particle size can be more easily obtained after the loading substance is added;
(3) more stable nickel sulfate hexahydrate is formed: the green color is nickel sulfate heptahydrate, and the blue color is nickel sulfate hexahydrate. Compared with nickel sulfate heptahydrate, nickel sulfate hexahydrate is more stable and valuable. Under the condition of no addition, the nickel sulfate hexahydrate and the nickel sulfate heptahydrate both have crystals, and the nickel sulfate heptahydrate has more crystals. Nickel sulfate hexahydrate was used in the presence of the additive.
(4) The crystallization is more convenient to separate from the mother liquor: after the loading substance is added, most of the crystals are loaded on the loading substance, the loading substance is directly taken out, and the crystals can be separated from the loading substance by slight external force, which is more convenient than that when the loading substance is not added.
The crystal is divided into two steps in the process of crystallization, firstly, the 'nucleation' is carried out, a supersaturated solution is generated after concentration, crystal nuclei are generated in the process of temperature reduction, and then the crystal nuclei are continuously grown. The solid phase particles on the surface of the load in the invention have the same function as the solid phase particles precipitated from the solution, namely 'nucleation', and then atoms or molecules are covered on the initially formed tiny crystal nucleus layer by layer and continuously 'grow' until certain size of crystal grains are formed. The load provides a larger attachment area for crystal nuclei, so that the crystal nuclei are more dispersed, and the less smooth the surface of the load is, the more favorable the attachment and growth of crystals are.
In addition, in the case of different pH conditions, the crystal particle size is not greatly different. But compared with the condition without adding the load, the crystal obtained by adding the load has spherical blue crystals (namely nickel sulfate hexahydrate) which are more stable and uniform in crystal form and particle size in morphology. The obtained crystal is not easy to agglomerate and has better industrial value. The method is suitable for the nickel sulfate solution obtained by recovering nickel from the acidic chemical nickel plating waste liquid with the pH range of 0.1-5 or other nickel-containing industrial waste liquids.
Claims (8)
1. A method for crystallizing a nickel sulfate solution is characterized by comprising the following steps:
(1) heating, evaporating and concentrating the nickel sulfate solution until the density is 1.01g/cm3～5.0g/cm3；
(2) Stirring the concentrated nickel sulfate solution at normal temperature and cooling to 30-65 ℃;
(3) adding a load to the solution;
(4) cooling and crystallizing at normal temperature;
(5) and (3) directly taking out the load after crystallization is finished, separating the mother liquor from the crystals, tapping the load to enable the crystals on the load to fall and collect, and drying the crystals to obtain the nickel sulfate crystals, wherein the load used in the step (3) is cylindrical, spherical or other in external part and has a honeycomb hollow structure in internal part.
2. The method according to claim 1, wherein the nickel sulfate solution in step (1) is a nickel sulfate solution obtained by recovering nickel from chemical nickel plating waste liquid or other nickel-containing industrial waste liquid, and the pH value is in a range of 0.1-5.
3. The method according to claim 1, wherein the density in step (1) is 1.4g/cm3～1.5g/cm3。
4. The method according to claim 1, wherein the internal void size of the support used in step (3) is in the range of 1 to 10 mm.
5. The method of claim 1, wherein the loading substance used in step (3) is added in an amount such that the loading substance is immersed in the solution.
6. The method as claimed in claim 1, wherein in the step (4), the temperature reduction rate is 0.5 ℃/min to 5 ℃/min, and the crystallization time is 2h to 48 h.
7. The method of claim 1 or 4, wherein the support is any one of ceramic, hollow plastic, solid plastic, charcoal, volcanic rock, glass, wood, and rubber.
8. The method of claim 6, wherein the loading substance is added in an amount of 0.01 to 9.9g/mL of solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017113437903 | 2017-12-14 | ||
| CN201711343790 | 2017-12-14 |
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| CN109487084B true CN109487084B (en) | 2020-10-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190335A (en) * | 2010-03-19 | 2011-09-21 | 上海健达化工有限公司 | Method for improving physical appearance of nickel sulfate crystals |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190335A (en) * | 2010-03-19 | 2011-09-21 | 上海健达化工有限公司 | Method for improving physical appearance of nickel sulfate crystals |
| CN102417987A (en) * | 2011-08-09 | 2012-04-18 | 朱小红 | Method for recovering valuable metal from electroplating sludge |
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