CN110194492B - Preparation method of basic nickel carbonate - Google Patents
Preparation method of basic nickel carbonate Download PDFInfo
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- CN110194492B CN110194492B CN201810162277.2A CN201810162277A CN110194492B CN 110194492 B CN110194492 B CN 110194492B CN 201810162277 A CN201810162277 A CN 201810162277A CN 110194492 B CN110194492 B CN 110194492B
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Abstract
The invention discloses a preparation method of basic nickel carbonate, which comprises the steps of mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution; in the synthesis process, first mother liquor is recycled to prepare sodium sulfate crystals, liquid generated by freezing crystallization is used for washing basic nickel carbonate crude products, meanwhile, the first mother liquor is subjected to membrane separation treatment, the treated liquid is returned to be used for preparing sodium carbonate solution and washing the basic nickel carbonate crude products, and finally, washing water generated after washing is recycled and used for preparing the sodium carbonate solution and the nickel sulfate solution again; therefore, the waste liquid in the basic nickel carbonate synthesis process is recycled for multiple times, no waste water is generated in the whole process, the nickel yield is high, the water consumption is low, the sodium sulfate byproduct is recycled, the pollution to the environment is reduced, and the green synthesis is realized.
Description
Technical Field
The invention belongs to an industrial preparation method of basic carbonate, and particularly relates to a preparation method of basic nickel carbonate.
Background
The basic nickel carbonate is an important inorganic fine chemical, is mainly used for preparing various nickel salts and high-quality basic nickel carbonate, and can be applied to the electronic industry and the catalyst industry; in addition, basic nickel carbonate is widely used for electroplating, electroforming, enamel pigments, and the like.
In the prior art, two common basic nickel carbonate synthesis methods are available, one synthesis process is that ammonium carbonate or ammonium bicarbonate and nickel salt are adopted for precipitation reaction, during synthesis, a large amount of ammonia and nickel form soluble complex compounds to cause incomplete nickel precipitation, in the production process of basic nickel carbonate, about 4.5 liters of waste liquid is generated per kilogram of products, the waste liquid is alkalescent, the pH value is about 8-9, the waste liquid contains a large amount of sodium sulfate and also contains residual impurities such as nickel ions, phosphate, carbonate, ammonia salt and the like, and if the waste liquid is directly discharged, not only water sources are polluted, the ecological environment is broken, but also resource waste is caused; the other synthesis process is characterized in that soda ash and a nickel salt solution are adopted for precipitation reaction, when the process is synthesized, the pH value needs to be adjusted to be more than 8.5, nickel can be basically and completely precipitated, the needed soda ash amount is more than 35% more than the theoretical amount, the excessive base cannot be recycled, the Na content in a product obtained by washing and drying materials is more than 300ppm (the product is basic nickel carbonate with the Ni content of 40%), and the pH value of waste water generated by washing is difficult to adjust when the waste water is recycled.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of basic nickel carbonate.
The invention also provides a preparation method of the basic nickel carbonate, which is implemented by the following steps:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
step 2, freezing and crystallizing a part of the first mother liquor obtained in the step 1 to obtain a first mother liquor from which sodium sulfate is removed, and washing the crude basic nickel carbonate product in the step 2 for the first time by using the first mother liquor from which sodium sulfate is removed to obtain a primary nickel carbonate washing product;
step 3, carrying out membrane separation on the first mother liquor obtained in the step 1 to obtain pure water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using the pure water to obtain a secondary nickel carbonate washing product;
and 4, drying and screening the secondary nickel carbonate washing product obtained in the step 3 to obtain basic nickel carbonate.
In the above scheme, the step 1 specifically comprises: adding a sodium carbonate solution and a nickel sulfate solution into a reactor simultaneously by using a peristaltic pump, adjusting the pH value of a flow control system of the sodium carbonate solution and the nickel sulfate solution to be 8.0-8.3 in the feeding process, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and carrying out centrifugal separation on the nickel carbonate mixed solution to obtain a basic nickel carbonate crude product and a first mother solution.
In the scheme, the carbonate ion concentration of the sodium carbonate solution in the step 1 is 180-300 g/L, and the nickel ion concentration of the nickel sulfate solution in the step 1 is 0.5-2 moL/L.
In the scheme, the flow rate of the sodium carbonate solution in the feeding process in the step 1 is 5-1000L/h, and the flow rate of the nickel sulfate solution is 50-1000L/h.
In the above scheme, in the step 2, the crude basic nickel carbonate in the step 1 is subjected to primary washing to obtain primary washing water.
In the above scheme, the first mother liquor obtained in step 1 in step 3 is subjected to membrane separation to further obtain concentrated water.
In the above scheme, in the step 3, the pure water is used for carrying out secondary washing on the primary nickel carbonate washing product in the step 2, and secondary washing water is also obtained.
In the foregoing solution, after the step 3, the method further includes: mixing the primary washing water obtained in the step 2 and/or the concentrated water obtained in the step 3 with a sodium carbonate raw material and performing ultrafiltration to obtain the sodium carbonate solution in the step 1.
In the above scheme, the step 3 further includes: and (3) adjusting the pH value of the primary washing water obtained in the step (2) and/or the secondary washing water obtained in the step (3) to 6.0-8.0 by adopting a sulfuric acid solution, mixing the adjusted primary washing water and/or secondary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain the nickel sulfate solution in the step (1).
In the scheme, the drying temperature in the step 4 is 95-105 ℃, and the drying time is 2-3 h; and 4, screening in the step 4 by adopting a 200-400-mesh screen.
Compared with the prior art, the invention provides a preparation method of basic nickel carbonate, which comprises the steps of mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution; in the synthesis process, first mother liquor is recycled to prepare sodium sulfate crystals, liquid generated by freezing crystallization is used for washing basic nickel carbonate crude products, meanwhile, the first mother liquor is subjected to membrane separation treatment, the treated liquid is returned to be used for preparing sodium carbonate solution and washing the basic nickel carbonate crude products, and finally, washing water generated after washing is recycled and used for preparing the sodium carbonate solution and the nickel sulfate solution again; therefore, the waste liquid in the basic nickel carbonate synthesis process is recycled for multiple times, no waste water is generated in the whole process, the nickel yield is high, the water consumption is low, the sodium sulfate byproduct is recycled, the pollution to the environment is reduced, and the green synthesis is realized.
Drawings
Fig. 1 is a process flow diagram of a method for preparing basic nickel carbonate according to embodiment 1 of the present invention;
FIG. 2 is a process flow diagram of a method for preparing basic nickel carbonate according to example 2 of the present invention;
FIG. 3 is a process flow diagram of a method for preparing basic nickel carbonate according to example 3 of the present invention;
FIG. 4 is a process flow diagram of a method for preparing basic nickel carbonate according to example 4 of the present invention;
FIG. 5 is a process flow diagram of a method for preparing basic nickel carbonate according to example 5 of the present invention;
FIG. 6 is a process flow diagram of a method for preparing basic nickel carbonate according to example 6 of the present invention;
fig. 7 is a process flow chart of a method for preparing basic nickel carbonate according to embodiment 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Embodiment 1 of the present invention provides a method for preparing basic nickel carbonate, which has a process flow diagram, as shown in fig. 1, and is implemented by the following steps:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
returning the primary washing water to the step 1 for preparing the sodium carbonate solution, specifically: mixing the primary washing water obtained in the step 2 with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step 1;
the primary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the pH value of the primary washing water needs to be adjusted due to trace carbonate ions contained in the primary washing water, and the method specifically comprises the following steps: adjusting the pH value of the primary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted primary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
when the sodium sulfate in the first mother liquor is removed in the step 2, a sodium sulfate crystal byproduct can be directly obtained through freezing crystallization, and certain economic benefit is achieved.
Step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water and concentrated water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product and secondary washing water;
when the amount of the primary washing water is small, the concentrated water can be returned to the step 1 for preparing sodium carbonate; the method specifically comprises the following steps: mixing the concentrated water obtained in the step (3) with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step (1);
the concentrated water after the water membrane separation is directly used for preparing a sodium carbonate solution because the content of Ca and Mg in the concentrated water is high, Ca and Mg in the concentrated water react with sodium carbonate to generate calcium carbonate and magnesium carbonate impurities, and the Ca and Mg impurities are removed after ultrafiltration;
the secondary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the secondary washing water contains trace carbonate ions, so that the pH value of the secondary washing water needs to be adjusted, and the method specifically comprises the following steps: adjusting the pH value of the secondary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted secondary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
and 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; meanwhile, mother liquor for recovering sodium sulfate can be returned to prepare a sodium carbonate solution, when the amount of the mother liquor is insufficient, wastewater generated by plate-type heat exchange can be used for preparing the sodium carbonate solution after membrane separation, and because impurities exist in concentrated water obtained after membrane separation, an ultrafiltration process is added in the process of preparing the sodium carbonate solution, the impurities in the concentrated water can be removed, so that the purity of the sodium carbonate solution and the purity of a nickel sulfate solution are higher, and the quality of the synthesized basic nickel carbonate is ensured; in addition, the pure water after membrane separation can also be directly used for washing the basic sodium carbonate; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
Example 2
Embodiment 2 of the present invention provides a method for preparing basic nickel carbonate, which is implemented by the following steps, as shown in fig. 2, in a process flow diagram of the method:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
returning the primary washing water to the step 1 for preparing the sodium carbonate solution, specifically: mixing the primary washing water obtained in the step 2 with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step 1;
when the sodium sulfate in the first mother liquor is removed in the step 2, a sodium sulfate crystal byproduct can be directly obtained through freezing crystallization, and certain economic benefit is achieved.
Step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water and concentrated water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product and secondary washing water;
when the amount of the primary washing water is small, the concentrated water can be returned to the step 1 for preparing sodium carbonate; the method specifically comprises the following steps: mixing the concentrated water obtained in the step (3) with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step (1);
the concentrated water after the water membrane separation is directly used for preparing a sodium carbonate solution because the content of Ca and Mg in the concentrated water is high, Ca and Mg in the concentrated water react with sodium carbonate to generate calcium carbonate and magnesium carbonate impurities, and the Ca and Mg impurities are removed after ultrafiltration;
the secondary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the secondary washing water contains trace carbonate ions, so that the pH value of the secondary washing water needs to be adjusted, and the method specifically comprises the following steps: adjusting the pH value of the secondary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted secondary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
and 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; meanwhile, mother liquor for recovering sodium sulfate can be returned to prepare a sodium carbonate solution, when the amount of the mother liquor is insufficient, wastewater generated by plate-type heat exchange can be used for preparing the sodium carbonate solution after membrane separation, and because impurities exist in concentrated water obtained after membrane separation, an ultrafiltration process is added in the process of preparing the sodium carbonate solution, the impurities in the concentrated water can be removed, so that the purity of the sodium carbonate solution and the purity of a nickel sulfate solution are higher, and the quality of the synthesized basic nickel carbonate is ensured; in addition, the pure water after membrane separation can also be directly used for washing the basic sodium carbonate; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
Example 3
Embodiment 3 of the present invention provides a method for preparing basic nickel carbonate, which is implemented by the following steps, as shown in fig. 3, in a process flow diagram of the method:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
the primary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the pH value of the primary washing water needs to be adjusted due to trace carbonate ions contained in the primary washing water, and the method specifically comprises the following steps: adjusting the pH value of the primary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted primary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
when the sodium sulfate in the first mother liquor is removed in the step 2, a sodium sulfate crystal byproduct can be directly obtained through freezing crystallization, and certain economic benefit is achieved.
Step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water and concentrated water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product and secondary washing water;
when the amount of the primary washing water is small, the concentrated water can be returned to the step 1 for preparing sodium carbonate; the method specifically comprises the following steps: mixing the concentrated water obtained in the step (3) with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step (1);
the concentrated water after the water membrane separation is directly used for preparing a sodium carbonate solution because the content of Ca and Mg in the concentrated water is high, Ca and Mg in the concentrated water react with sodium carbonate to generate calcium carbonate and magnesium carbonate impurities, and the Ca and Mg impurities are removed after ultrafiltration;
the secondary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the secondary washing water contains trace carbonate ions, so that the pH value of the secondary washing water needs to be adjusted, and the method specifically comprises the following steps: adjusting the pH value of the secondary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted secondary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
and 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; the waste water generated by plate heat exchange can be used for preparing a sodium carbonate solution after membrane separation, and because impurities exist in the concentrated water obtained after membrane separation, an ultrafiltration process is added in the process of preparing the sodium carbonate solution, so that the impurities in the concentrated water can be removed, the purity of the sodium carbonate solution and the purity of the nickel sulfate solution are higher, and the quality of the synthesized basic nickel carbonate is ensured; in addition, the pure water after membrane separation can also be directly used for washing the basic sodium carbonate; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
Example 4
Embodiment 4 of the present invention provides a method for preparing basic nickel carbonate, which is implemented by the following steps, as shown in fig. 4, in a process flow diagram of the method:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
returning the primary washing water to the step 1 for preparing the sodium carbonate solution, specifically: mixing the primary washing water obtained in the step 2 with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step 1;
the primary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the pH value of the primary washing water needs to be adjusted due to trace carbonate ions contained in the primary washing water, and the method specifically comprises the following steps: adjusting the pH value of the primary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted primary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
when the sodium sulfate in the first mother liquor is removed in the step 2, a sodium sulfate crystal byproduct can be directly obtained through freezing crystallization, and certain economic benefit is achieved.
Step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water and concentrated water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product;
when the amount of the primary washing water is small, the concentrated water can be returned to the step 1 for preparing sodium carbonate; the method specifically comprises the following steps: mixing the concentrated water obtained in the step (3) with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step (1);
the concentrated water after the water membrane separation has high Ca and Mg content and is directly used for preparing sodium carbonate solution, Ca and Mg in the concentrated water react with sodium carbonate to generate calcium carbonate and magnesium carbonate impurities, and the impurities of Ca and Mg are removed after ultrafiltration.
And 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; meanwhile, mother liquor for recovering sodium sulfate can be returned to prepare a sodium carbonate solution, when the amount of the mother liquor is insufficient, wastewater generated by plate-type heat exchange can be used for preparing the sodium carbonate solution after membrane separation, and because impurities exist in concentrated water obtained after membrane separation, an ultrafiltration process is added in the process of preparing the sodium carbonate solution, the impurities in the concentrated water can be removed, so that the purity of the sodium carbonate solution and the purity of a nickel sulfate solution are higher, and the quality of the synthesized basic nickel carbonate is ensured; in addition, the pure water after membrane separation can also be directly used for washing the basic sodium carbonate; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
Example 5
Embodiment 5 of the present invention provides a method for preparing basic nickel carbonate, which has a process flow diagram, as shown in fig. 5, and is implemented by the following steps:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
returning the primary washing water to the step 1 for preparing the sodium carbonate solution, specifically: mixing the primary washing water obtained in the step 2 with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step 1;
the primary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the pH value of the primary washing water needs to be adjusted due to trace carbonate ions contained in the primary washing water, and the method specifically comprises the following steps: adjusting the pH value of the primary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted primary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
when the sodium sulfate in the first mother liquor is removed in the step 2, a sodium sulfate crystal byproduct can be directly obtained through freezing crystallization, and certain economic benefit is achieved.
Step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product and secondary washing water;
the secondary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the secondary washing water contains trace carbonate ions, so that the pH value of the secondary washing water needs to be adjusted, and the method specifically comprises the following steps: adjusting the pH value of the secondary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted secondary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
and 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; meanwhile, mother liquor for recovering sodium sulfate can be returned to prepare sodium carbonate solution; in addition, the pure water after membrane separation can be directly used for washing the basic sodium carbonate, and can be used for preparing a nickel sulfate solution after the pH is adjusted; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
Example 6
Embodiment 6 of the present invention provides a method for preparing basic nickel carbonate, which is implemented by the following steps, as shown in fig. 6, in a process flow diagram of the method:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
returning the primary washing water to the step 1 for preparing the sodium carbonate solution, specifically: mixing the primary washing water obtained in the step 2 with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step 1;
when the sodium sulfate in the first mother liquor is removed in the step 2, a sodium sulfate crystal byproduct can be directly obtained through freezing crystallization, and certain economic benefit is achieved.
Step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product and secondary washing water;
the secondary washing water can also be returned to the step 1 for preparing the nickel sulfate solution, and the secondary washing water contains trace carbonate ions, so that the pH value of the secondary washing water needs to be adjusted, and the method specifically comprises the following steps: adjusting the pH value of the secondary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted secondary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
and 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; meanwhile, mother liquor for recovering sodium sulfate can be returned to prepare sodium carbonate solution; in addition, the pure water after membrane separation can be directly used for washing the basic sodium carbonate, and can be used for preparing a nickel sulfate solution after the pH is adjusted; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
Example 7
Embodiment 7 of the present invention provides a method for preparing basic nickel carbonate, which has a process flow diagram, as shown in fig. 1, and is implemented by the following steps:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
the method specifically comprises the following steps: preparing a sodium carbonate solution with a carbonate ion concentration of 180-300 g/L by using a sodium carbonate raw material, preparing a nickel sulfate solution with a nickel ion concentration of 0.5-2 moL/L by using a nickel sulfate raw material, simultaneously adding the sodium carbonate solution and the nickel sulfate solution into a reactor by using a peristaltic pump, adjusting the flow rate of the sodium carbonate solution to be 5-1000L/h and the flow rate of the nickel sulfate solution to be 50-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.0-8.3, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and (3) carrying out centrifugal separation on the nickel carbonate mixed solution obtained in the step (1.3) to obtain a basic nickel carbonate crude product and a first mother liquor.
Step 2, introducing the first mother liquor obtained in the step 1 and tap water into a plate heat exchanger for heat exchange, freezing and crystallizing a part of the heat-exchanged first mother liquor to obtain a first mother liquor without sodium sulfate, and washing the basic nickel carbonate crude product in the step 2 by adopting the first mother liquor without sodium sulfate to obtain a nickel carbonate primary washing product and primary washing water;
the primary washing water can be returned to the step 1 for preparing the nickel sulfate solution, and the pH value of the primary washing water needs to be adjusted due to the fact that the primary washing water contains trace carbonate ions, and the method specifically comprises the following steps: adjusting the pH value of the primary washing water to 6.0-8.0 by using a sulfuric acid solution, mixing the adjusted primary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain a nickel sulfate solution with the nickel ion concentration of 0.5-2 moL/L in the step 1;
step 3, performing membrane separation treatment on the remaining heat-exchanged first mother liquor to obtain pure water and concentrated water; carrying out secondary washing on the primary nickel carbonate washing product in the step 2 by using pure water to obtain a secondary nickel carbonate washing product;
the concentrated water can be returned to the step 1 for preparing sodium carbonate; the method specifically comprises the following steps: mixing the concentrated water obtained in the step (3) with a sodium carbonate raw material and carrying out ultrafiltration to obtain a sodium carbonate solution with the carbonate ion concentration of 180-300 g/L in the step (1);
the concentrated water after the water membrane separation is directly used for preparing a sodium carbonate solution because the content of Ca and Mg in the concentrated water is high, Ca and Mg in the concentrated water react with sodium carbonate to generate calcium carbonate and magnesium carbonate impurities, and the Ca and Mg impurities are removed after ultrafiltration;
and 4, drying the secondary nickel carbonate washing product obtained in the step 3 at 95-105 ℃ for 2-3 h, and screening by adopting a 200-400-mesh sieve to obtain the basic nickel carbonate.
Compared with the prior art, the nickel content of the basic nickel carbonate obtained by the synthesis process is 40-49%, and the nickel content in the basic nickel carbonate can be controlled.
According to the invention, the basic nickel carbonate is synthesized by adopting the sodium carbonate solution and the nickel sulfate solution, and the mother liquor of the reaction of the sodium carbonate and the nickel sulfate is basically the sodium sulfate solution, so that the sodium sulfate is recovered by adopting the plate heat exchange and freeze crystallization processes, the pollution to waste water is reduced, and the sodium sulfate crystal byproduct can be recovered, thereby having certain economic benefit; the waste water generated by plate heat exchange is used for preparing a sodium carbonate solution after membrane separation, and because impurities exist in the concentrated water obtained after membrane separation, an ultrafiltration process is added in the process of preparing the sodium carbonate solution, so that the impurities in the concentrated water can be removed, the purity of the sodium carbonate solution and the nickel sulfate solution is higher, and the quality of the synthesized basic nickel carbonate is ensured; in addition, the pure water after membrane separation can also be directly used for washing the basic sodium carbonate; therefore, no wastewater is generated in the whole process, and meanwhile, the process has high nickel yield and low water consumption, and the sodium sulfate byproduct is recovered, so that the pollution to the environment is reduced, and the process is green and environment-friendly.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (7)
1. A preparation method of basic nickel carbonate is characterized by comprising the following steps:
step 1, mixing a sodium carbonate solution and a nickel sulfate solution, and carrying out solid-liquid separation to obtain a basic nickel carbonate crude product and a first mother solution;
step 2, freezing and crystallizing a part of the first mother liquor to obtain sodium sulfate crystals and the first mother liquor from which sodium sulfate is removed, and washing the crude basic nickel carbonate product in the step 1 for the first time by using the first mother liquor from which sodium sulfate is removed to obtain a primary basic nickel carbonate washing product and primary washing water; so that the primary washing water is returned to the step 1 for preparing the sodium carbonate solution or/and the nickel sulfate solution;
step 3, performing membrane separation on the remaining first mother liquor to obtain pure water and concentrated water; carrying out secondary washing on the primary basic nickel carbonate washing product in the step 2 by using the pure water to obtain a secondary basic nickel carbonate washing product and secondary washing water; the concentrated water is returned to the step 1 for preparing sodium carbonate, and the secondary washing water is also returned to the step 1 for preparing a sodium carbonate solution or/and a nickel sulfate solution;
and 4, drying and screening the secondary washing product of the basic nickel carbonate obtained in the step 3 to obtain the basic nickel carbonate.
2. The method for preparing basic nickel carbonate according to claim 1, wherein the step 1 is specifically as follows: adding a sodium carbonate solution and a nickel sulfate solution into a reactor simultaneously by using a peristaltic pump, adjusting the pH value of a flow control system of the sodium carbonate solution and the nickel sulfate solution to be 8.0-8.3 in the feeding process, and reacting for 5-10 h at 70-100 ℃ to obtain a nickel carbonate mixed solution; and carrying out centrifugal separation on the nickel carbonate mixed solution to obtain a basic nickel carbonate crude product and a first mother solution.
3. The method for preparing basic nickel carbonate according to claim 2, wherein the carbonate ion concentration of the sodium carbonate solution in the step 1 is 180-300 g/L, and the nickel ion concentration of the nickel sulfate solution in the step 1 is 0.5-2 mol/L.
4. The method for preparing basic nickel carbonate according to claim 3, wherein the flow rate of the sodium carbonate solution in the feeding process in the step 1 is 5-1000L/h, and the flow rate of the nickel sulfate solution is 50-1000L/h.
5. The method for preparing basic nickel carbonate according to any one of claims 1 to 4, wherein when the primary washing water is used for preparing the sodium carbonate solution, the method comprises the following steps: mixing the primary washing water with a sodium carbonate raw material and carrying out ultrafiltration to obtain the sodium carbonate solution in the step 1; when the concentrated water is used for preparing a sodium carbonate solution, the method comprises the following steps: mixing the concentrated water with a sodium carbonate raw material and performing ultrafiltration to obtain the sodium carbonate solution in the step 1.
6. The method for preparing basic nickel carbonate according to claim 5, wherein when the primary washing water is used for preparing the nickel sulfate solution, the method comprises the following steps: adjusting the pH value of the primary washing water to 6.0-8.0 by adopting a sulfuric acid solution, mixing the adjusted primary washing water with a nickel sulfate raw material, and performing ultrafiltration to obtain the nickel sulfate solution in the step 1; when the secondary washing water is used for preparing the nickel sulfate solution, the pH value of the secondary washing water is adjusted to 6.0-8.0 by using the sulfuric acid solution, and the adjusted secondary washing water and the nickel sulfate raw material are mixed and subjected to ultrafiltration to obtain the nickel sulfate solution in the step 1.
7. The method for preparing basic nickel carbonate according to claim 1, wherein the drying temperature in the step 4 is 95-105 ℃, and the drying time is 2-3 h; and 4, screening in the step 4 by adopting a 200-400-mesh screen.
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| CN100484882C (en) * | 2006-12-29 | 2009-05-06 | 金川集团有限公司 | Method of preparing electronic grade nickel carbonate by sodium carbonate deposition |
| CN101264943B (en) * | 2008-04-24 | 2010-06-09 | 吉林市金泰化工有限公司 | Water-saving discharge-reducing consume-reducing continuous production device for nickel carbonate |
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| US20120301375A1 (en) * | 2011-05-27 | 2012-11-29 | Jeff Miller | Low energy method of preparing basic metal carbonates and other salts |
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