CN113881966A - Electrodeposition cobalt circulation system capable of balancing acidity value of electrolyte and circulation process thereof - Google Patents
Electrodeposition cobalt circulation system capable of balancing acidity value of electrolyte and circulation process thereof Download PDFInfo
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- CN113881966A CN113881966A CN202010627609.7A CN202010627609A CN113881966A CN 113881966 A CN113881966 A CN 113881966A CN 202010627609 A CN202010627609 A CN 202010627609A CN 113881966 A CN113881966 A CN 113881966A
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Abstract
The invention discloses an electrodeposition cobalt circulating system capable of balancing acidity value of electrolyte and a circulating process thereof. According to the invention, the electrodeposition circulating mechanism, the tubular reactor, the gas-liquid separation mechanism and the concentration adjusting mechanism are sequentially connected to form a loop, the tubular reactor promotes most of chlorine and hydrogen in the electrolytic barren solution electrolyzed by the electrodeposition circulating mechanism to be synthesized into hydrochloric acid, the acidity value of the electrolytic barren solution is balanced, the hydrochloric acid supplement is reduced, and the cost is effectively reduced; meanwhile, the invention synthesizes partial hydrogen and chlorine in the electrolytic barren solution into hydrochloric acid through the tubular reactor, thereby reducing the solution variable quantity in the electrolyte circulation process, reducing the release of hydrogen and chlorine, and reducing the potential risk degree, thereby effectively improving the safety of industrial production.
Description
Technical Field
The invention belongs to the field of new energy materials, relates to a strategic metal cobalt electrodeposition technology, and particularly relates to an electrodeposition cobalt circulation system capable of balancing acidity value of an electrolyte and a circulation process thereof.
Background
In the process of electrodepositing cobalt in a hydrochloric acid system, the main reaction of the electrolysis process is as follows: losing electrons at the anode chloride ions to generate chlorine, and obtaining electrons at the cathode cobalt ions to generate cobalt; however, in the current industry, the electrolysis process generates side reactions including the decomposition of hydrochloric acid, i.e., the decomposition of hydrochloric acid into chlorine and hydrogen.
In the process of electrodepositing cobalt, the electrolyte can stabilize the electrolysis effect only by keeping a certain acidity, and the decomposition of side reaction hydrochloric acid causes the acidity value of the electrolyte to be continuously reduced; the current practice in the industry is to supplement new hydrochloric acid, so that the acidity of the electrolyte is stabilized in a certain range, the electrolysis effect is ensured, and the consumption of hydrochloric acid in the later period is caused. In addition, the decomposition of the side reaction hydrochloric acid results in the release of hydrogen and chlorine, wherein the hydrogen, whether alone or mixed with chlorine or air, may risk explosion, thereby potentially leading to explosion in industrial production.
Disclosure of Invention
In order to solve the problems, the invention provides an electrodeposition cobalt circulating system capable of balancing the acidity value of an electrolyte, wherein a tubular reactor is used for promoting part of chlorine and hydrogen in an electrolysis barren solution electrolyzed by an electrodeposition circulating mechanism to be synthesized into hydrochloric acid, and the acidity value of the electrolysis barren solution is adjusted, so that the safety problems caused by the need of later-stage hydrochloric acid supplement and hydrogen release in the electrodeposition cobalt process are solved.
Another object of the present invention is to provide an electrodeposited cobalt cycle process capable of balancing acidity values of electrolytes, partially replacing the acid supplementing link, based on the above cycle system.
The technical scheme adopted by the invention is as follows:
an electrodeposition cobalt circulating system capable of balancing acidity value of electrolyte comprises an electrodeposition circulating mechanism, a tubular reactor, a gas-liquid separation mechanism and a concentration adjusting mechanism which are sequentially communicated through pipelines, and a loop is formed to form an electrodeposition core production facility.
Preferably, the electrolytic barren solution treatment device further comprises a component adjusting mechanism, wherein the component adjusting mechanism is arranged between the gas-liquid separating mechanism and the concentration adjusting mechanism, and is used for adjusting the components of the electrolytic barren solution with changed components after multiple times of electrolysis and conveying the electrolytic barren solution into the concentration adjusting mechanism.
In specific implementation, the component adjusting mechanism can also convey the electrolytic barren solution with changed components after multiple times of electrolysis into a front-end production project process after the component adjusting mechanism adjusts the components of the electrolytic barren solution, and the liquid in the component adjusting mechanism flows through a pipeline to form a matched production facility.
Preferably, the component adjusting mechanism comprises a concentration tank, a deep dechlorination reaction tank, an acid control and iron removal reaction tank and a cobalt chloride intermediate tank, the concentration tank, the deep dechlorination reaction tank and the acid control and iron removal reaction tank are not connected with each other, and are respectively used for receiving the electrolysis barren solution separated by the gas-liquid separation mechanism, carrying out component adjustment on the electrolysis barren solution and then conveying the electrolysis barren solution to the cobalt chloride intermediate tank, and the cobalt chloride intermediate tank is communicated with the concentration adjusting mechanism through a pipeline.
Preferably, the device further comprises a waste gas treatment assembly which is arranged in a matched manner, wherein the waste gas treatment assembly comprises a chlorine absorption mechanism and a tail gas treatment mechanism, and the chlorine absorption mechanism is communicated with the rear side of the gas-liquid separation mechanism and is used for absorbing and treating the generated chlorine; the tail gas treatment mechanism is communicated with the rear side of the chlorine absorption mechanism, is communicated with the component adjusting mechanism through a pipeline, and is used for retreating the chlorine which is not completely treated by the chlorine absorption mechanism and absorbing the tail gas generated by the component adjusting mechanism.
In specific implementation, the waste gas treatment assembly is a matched environment-friendly facility; the chlorine absorption mechanism is used for absorbing and treating the waste gas-chlorine generated in the production process of the electrodeposition core production facility; the tail gas treatment mechanism is used for retreating residual chlorine which may be incompletely treated by the chlorine absorption mechanism and is also used for absorbing tail gas generated by matched production facilities; the chlorine absorption mechanism and the tail gas treatment mechanism are communicated with each mechanism through pipelines to form the matched environment-friendly facility.
Preferably, the chlorine gas absorption mechanism comprises a chlorine gas primary absorption groove and a chlorine gas secondary absorption groove, the chlorine gas primary absorption groove is communicated with the gas-liquid separation mechanism through a pipeline, the chlorine gas secondary absorption groove is respectively communicated with the gas-liquid separation mechanism, the concentration regulation mechanism and the electrodeposition circulation mechanism through pipelines, and the chlorine gas primary absorption groove and the chlorine gas secondary absorption groove are communicated with the tail gas treatment mechanism;
in specific implementation, chlorine generated by the electrodeposition circulating mechanism is fully absorbed by the chlorine absorbing mechanism, and a very small amount of migratory chlorine which is possibly not fully absorbed is completely treated by the tail gas treatment mechanism and finally discharged through the exhaust funnel.
Preferably, the electrodeposition circulating mechanism comprises an electrolyte circulating tank and at least one closed electrolytic tank which are communicated through a pipeline, the electrolyte circulating tank is further connected with the concentration regulating mechanism through a pipeline, and the closed electrolytic tank is connected with the tubular reactor through a pipeline.
Preferably, the concentration adjusting mechanism comprises an electrolyte concentration adjusting tank and a hydrochloric acid storage tank, the electrolyte concentration adjusting tank is communicated with the gas-liquid separation mechanism and the component adjusting mechanism through pipelines respectively, and the electrolyte concentration adjusting tank is connected with the electrolyte circulation tank through a pipeline.
Preferably, a flow meter and a metering pump are arranged on a pipeline between the hydrochloric acid storage tank and the electrolyte concentration adjusting tank, and the flow meter and the metering pump can be connected into a DCS production operation system and can realize automatic control.
Preferably, the gas-liquid separation mechanism comprises a first gas-liquid separation tank and a second gas-liquid separation tank which are connected through a pipeline, the first gas-liquid separation tank is connected with the tubular reactor through a pipeline, the second gas-liquid separation tank is connected with the concentration adjustment mechanism through a pipeline, and exhaust ports of the first gas-liquid separation tank and the second gas-liquid separation tank are respectively connected with the chlorine absorption mechanism through pipelines.
The invention also provides an electrodeposition cobalt circulation process capable of balancing acidity value of electrolyte based on the circulation system, which comprises the following steps:
s1, electrodepositing cobalt in the electrodeposition circulating mechanism by the cobalt chloride electrolyte to generate an electrolysis barren solution;
s2, the electrolytic barren solution enters a tubular reactor, and partial hydrogen and chlorine in the electrolytic barren solution are promoted to be synthesized into hydrochloric acid under the action of electrodeposition, so that the electrolytic barren solution with the acidity primarily adjusted is obtained;
s3, feeding the electrolytic barren solution with the preliminarily adjusted acidity value into a gas-liquid separation mechanism to obtain the electrolytic barren solution after gas-liquid separation;
and S4, enabling the gas-liquid separated electrolytic barren solution to enter a concentration adjusting mechanism, adjusting the concentration and acidity value of cobalt chloride to obtain cobalt chloride electrolyte meeting the electrodeposition condition after adjustment, and conveying the cobalt chloride electrolyte to the electrodeposition circulating mechanism for electrodeposition again.
In a specific implementation, depending on the composition of the electrolytic lean solution, the step S4 may further include:
s4, the gas-liquid separated electrolytic barren solution enters a component adjusting mechanism 5 according to the component change, namely enters a concentration tank 51, a deep dechlorination reaction tank 52 and an acid-controlling and iron-removing reaction tank 53 respectively according to the requirement, the electrolytic barren solution adjusted by the components enters a cobalt chloride intermediate tank 54 and then enters a concentration adjusting mechanism to adjust the concentration and acidity of the cobalt chloride to obtain an adjusted cobalt chloride electrolyte, and the adjusted cobalt chloride electrolyte is conveyed to the electrodeposition circulating mechanism for electrodeposition again.
Preferably, the electrodeposition conditions of the electrodeposition cycle mechanism in S1 are: the cobalt ion concentration is 60-100 g/L, and the current density is 400-500A/m2The pH value of the cobalt chloride electrolyte is 1-2, the cell voltage is 2.5-3.0V, and the circulation volume of the electrolyte is 3-4 m3The electrolysis temperature is 50-55 ℃;
the reaction temperature in the tubular reactor in the S2 is 50-55 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. when the device is used, the electrodeposition circulating mechanism, the tubular reactor, the gas-liquid separation mechanism and the concentration adjusting mechanism are sequentially connected to form a loop, the tubular reactor promotes chlorine and hydrogen in the electrolytic barren solution electrolyzed by the electrodeposition circulating mechanism to be synthesized into hydrochloric acid, and the hydrochloric acid enters the electrolytic barren solution to adjust the acidity value of the electrolytic barren solution, so that the acidity adjustment of the electrolytic barren solution is realized, and the variable amount of the solution in the electrolyte circulating process is effectively reduced;
2. the method has the advantages that part of hydrogen and chlorine in the electrolytic barren solution is promoted to be synthesized into hydrochloric acid through the tubular reactor, and the hydrochloric acid enters the electrolytic barren solution to adjust the acidity, so that the amount of hydrochloric acid required to be added when the acidity value of the electrolytic barren solution is adjusted in the concentration adjusting mechanism is within 30% of the consumption amount of hydrochloric acid in the conventional process, the consumption of the hydrochloric acid in the later period is greatly reduced, and the cost is effectively reduced;
3. according to the invention, a part of hydrogen and chlorine in the electrolysis barren solution are promoted to be synthesized into hydrochloric acid through the tubular reactor, so that the release amount of hydrogen and chlorine is reduced, the potential risk degree is reduced, and the safety of industrial production is effectively improved finally.
Drawings
FIG. 1 is a schematic structural diagram of an electrodeposited cobalt circulation system capable of balancing acidity of an electrolyte according to example 1 of the present invention;
FIG. 2 is a schematic flow chart of an electrodeposited cobalt circulation system capable of balancing acidity of an electrolyte according to example 1 of the present invention;
in fig. 2, the solid line represents the flow path of the liquid, and the dotted line represents the movement path of the gas;
FIG. 3 is a schematic diagram of electrochemical reaction of an electrodeposition circulating mechanism in an electrodeposition cobalt circulating system capable of balancing acidity value of an electrolyte provided in example 1 of the present invention;
FIG. 4 is a schematic diagram of the reaction in the tubular reactor of the system for recycling electrodeposited cobalt, which is capable of balancing the acidity of the electrolyte, according to example 1 of the present invention;
FIG. 5 is a flow chart of an electrodeposition cobalt cycle process capable of balancing acidity of an electrolyte according to example 2 of the present invention.
In the figure: 1. an electrodeposition circulation mechanism; 11. an electrolyte circulation tank; 12. a closed electrolytic cell; 2. a tubular reactor; 3. a gas-liquid separation mechanism; 31. a first gas-liquid separation tank; 32. a second gas-liquid separation tank; 4. a concentration adjusting mechanism; 41. an electrolyte concentration adjusting tank; 42. a hydrochloric acid storage tank; 5. a component adjusting mechanism; 51. a concentration tank; 52. a deep dechlorination reaction tank; 53. controlling acid and removing iron in the reaction tank; 54. a cobalt chloride intermediate tank; 6. a tail gas treatment mechanism; 7. a chlorine absorption mechanism; 71. a chlorine primary absorption tank; 72. chlorine secondary absorption groove.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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
The embodiment provides an electrodeposition cobalt circulation system capable of balancing acidity value of electrolyte, as shown in fig. 1 and fig. 2, the system comprises an electrodeposition circulation mechanism 1, a tubular reactor 2, a gas-liquid separation mechanism 3 and a concentration regulation mechanism 4 which are sequentially communicated through a pipeline, and a loop is formed to form an electrodeposition core production facility;
the electrowinning device comprises an electrowinning circulating mechanism 1, a tubular reactor 2, a gas-liquid separation mechanism 3, a concentration adjusting mechanism 4 and a gas-liquid separation mechanism, wherein the electrowinning circulating mechanism 1 is used for electrolyzing a cobalt chloride electrolyte to form cobalt, the tubular reactor 2 is used for receiving an electrolysis barren solution electrolyzed by the electrowinning circulating mechanism 1, promoting hydrogen and chlorine in the electrolysis barren solution to synthesize hydrochloric acid, and returning the hydrochloric acid to the electrolysis barren solution so as to preliminarily adjust the acidity of the electrolysis barren solution, the gas-liquid separation mechanism 3 is used for carrying out gas-liquid separation on the electrolysis barren solution with preliminarily balanced acidity, and the concentration adjusting mechanism 4 is used for carrying out concentration adjustment on the electrolysis barren solution subjected to gas-liquid separation, including adjustment on the concentration of cobalt chloride in the electrolyte and adjustment on the acidity of the electrolyte.
Thus, the electrodeposition circulating mechanism 1, the tubular reactor 2, the gas-liquid separating mechanism 3 and the concentration adjusting mechanism 4 are sequentially connected to form a loop, cobalt chloride electrolyte enters the electrodeposition circulating mechanism 1 to electrolyze to produce cobalt and generate electrolytic barren solution containing chlorine and hydrogen, the electrolytic barren solution containing chlorine and hydrogen enters the tubular reactor 2, the tubular reactor 2 promotes hydrogen and chlorine generated in the electrodeposition circulating mechanism 1 to be synthesized into hydrochloric acid, so that the acidity value of the electrolytic barren solution is preliminarily balanced, the electrolytic barren solution with the preliminarily balanced acidity value enters the gas-liquid separating mechanism 3 to be subjected to gas-liquid separation and then enters the concentration adjusting mechanism 4, the cobalt chloride concentration and the acidity value of the electrolytic barren solution are adjusted by adding high-concentration cobalt chloride and hydrochloric acid, so that electrolytic front liquid capable of being directly electrolyzed is obtained and can be conveyed to the electrodeposition circulating mechanism 1 again to be electrolyzed, the circulation of the electrolyte is completed.
As shown in fig. 4, the tubular reactor 2 provided in this example promotes most of the hydrogen and chlorine to be synthesized into hydrochloric acid, and the acidity value of the electrolytic lean solution is preliminarily balanced, so that a small amount of hydrochloric acid needs to be added when the acidity value of the electrolytic lean solution is adjusted at a later stage. Compared with the traditional process, the hydrochloric acid consumption of the embodiment is greatly reduced, and the hydrochloric acid consumption can be controlled within 30% of the hydrochloric acid consumption of the traditional process. Therefore, the hydrochloric acid consumption of the embodiment is not more than 30% of that of the traditional process, and the cost is effectively saved while the production risk is reduced.
As shown in fig. 1, the electrolytic cell further comprises a composition adjusting mechanism 5, when the electrolytic solution is electrolyzed for a plurality of times, the electrolytic reaction is continuously carried out in the process, the material composition of the solution is changed, so that the composition adjusting mechanism 5 for adjusting the composition of the electrolytic barren solution is arranged between the gas-liquid separating mechanism 3 and the concentration adjusting mechanism 4, and the composition adjusting mechanism 5 is used for adjusting the composition of the electrolytic barren solution with changed composition after the electrolysis for a plurality of times and conveying the electrolytic barren solution to the concentration adjusting mechanism 4.
In specific implementation, the component adjusting mechanism 5 can also convey the electrolytic barren solution with changed components after multiple times of electrolysis into the front-end production project process after the component adjusting mechanism 5 adjusts the components of the electrolytic barren solution, and the liquid in the component adjusting mechanism 5 flows through a pipeline to form a matched production facility
As shown in fig. 2, the component adjusting mechanism 5 includes a concentration tank 51, a deep dechlorination reaction tank 52, an acid-controlling and iron-removing reaction tank 53 and a cobalt chloride intermediate tank 54, the concentration tank 51, the deep dechlorination reaction tank 52 and the acid-controlling and iron-removing reaction tank 53 are not connected to each other, and are respectively used for receiving the lean electrolyte separated by the gas-liquid separating mechanism 3, adjusting the components of the lean electrolyte, and then conveying the lean electrolyte to the cobalt chloride intermediate tank 54, and the cobalt chloride intermediate tank 54 is communicated with the concentration adjusting mechanism 4, that is, the electrolyte concentration adjusting tank 41 through a pipeline.
The specific process is that the electrolyte is continuously electrolyzed, the material components of the electrolyte are changed, and three different directions are respectively adopted according to the component changes: firstly, transferring one part of the solution into an acid-controlling iron-removing reaction tank 53, removing accumulated iron content, controlling acidity to reach a better range, performing filter pressing to remove impurities to obtain a relatively pure solution, and then continuing to participate in electrolysis circulation; secondly, transferring one part of the solution into a deep dechlorination reaction tank 52, continuously removing the chlorine in the solution, and then continuously participating in electrolytic circulation; and thirdly, transferring one part of the electrolyte into a concentration tank 51, carrying out micro-negative pressure heating concentration, improving the content of the electrolyte (cobalt chloride), and continuing to participate in electrolysis circulation after the content is improved. If the impurities in the solution after the three-part process treatment are increased, the solution continuously participates in electrolysis circulation after being subjected to impurity removal by methods such as filter pressing and the like.
Thus, the components in the electrolyte are adjusted and the adjusted lean electrolyte is fed to the cobalt chloride intermediate tank 54, and the cobalt chloride intermediate tank 54 can also receive an external cobalt chloride solution.
In specific implementation, the electrolytic lean solution separated by the gas-liquid separation mechanism 3 is periodically detected, and the change trend of components in the electrolytic lean solution is found, so that the arrangement can be performed in advance.
As shown in fig. 1, the system further comprises a waste gas treatment assembly which is arranged in a matched manner, wherein the waste gas treatment assembly comprises a chlorine absorption mechanism 7 and a tail gas treatment mechanism 6, and the chlorine absorption mechanism 7 is communicated with and arranged at the rear side of the gas-liquid separation mechanism 3 and is used for absorbing and treating the generated chlorine; the tail gas treatment mechanism 6 is communicated with the rear side of the chlorine absorption mechanism 7, is communicated with the component adjusting mechanism 5 through a pipeline, and is used for retreating the chlorine which is not completely treated by the chlorine absorption mechanism 7 and absorbing the tail gas generated by the component adjusting mechanism 5.
In specific implementation, the waste gas treatment assembly is a matched environment-friendly facility; the chlorine absorption mechanism 7 is used for absorbing and treating the waste gas-chlorine generated in the production process of the electrodeposition core production facility; the tail gas treatment mechanism 6 is used for retreating residual chlorine which may be incompletely treated by the chlorine absorption mechanism and is also used for absorbing tail gas generated by a matched production facility; the chlorine absorption mechanism 7 and the tail gas treatment mechanism 6 are communicated with the mechanisms through pipelines to form the matched environment-friendly facility.
The chlorine gas absorption mechanism 7 comprises a chlorine gas primary absorption groove 71 and a chlorine gas secondary absorption groove 72, the chlorine gas primary absorption groove 71 is communicated with the gas-liquid separation mechanism 3, namely the first gas-liquid separation groove 31, through a pipeline, the chlorine gas secondary absorption groove 72 is respectively communicated with the second gas-liquid separation groove 32, the concentration regulation mechanism 4 and the electrodeposition circulation mechanism 1 in the gas-liquid separation mechanism 3 through pipelines, and the chlorine gas primary absorption groove 71 and the chlorine gas secondary absorption groove 72 are communicated with the tail gas treatment mechanism 6. Chlorine generated by the electrodeposition circulating mechanism 1 passes through the tubular reactor and is separated in the gas-liquid separation mechanism, the separated gas enters the chlorine absorption mechanism 7 through a pipeline, the chlorine is generally fully absorbed, and a small amount of migratory chlorine which is not completely absorbed is not eliminated, and the chlorine is treated again through the tail gas treatment mechanism 6.
As shown in fig. 1, in order to achieve the environmental protection purpose of reaching the emission standard, the tail gas treatment mechanism 6 is communicated with the component adjustment mechanism 4 and the chlorine gas absorption mechanism 7 through pipelines, and is used for absorbing and treating residual waste gas which may not be completely absorbed in the chlorine gas absorption mechanism 7 and tail gas of the component adjustment mechanism, and finally performing organized centralized treatment, and the reddest is discharged through a centralized exhaust funnel in a qualified manner. The exhaust funnel is provided with an online monitoring and alarming assembly, a data signal of the online monitoring and alarming assembly is connected to a production safety and environmental protection control center, an enterprise is intensively supervised through an information platform, and waste gas detection information is networked with a government environmental protection supervision organization to receive real-time supervision.
As shown in fig. 1 and fig. 3, the electrodeposition circulating mechanism 1 includes an electrolyte circulating tank 11 and at least one closed electrolytic tank 12 which are communicated with each other through a pipeline, the electrolyte circulating tank 11 is further connected with the concentration regulating mechanism 4 through a pipeline, and the closed electrolytic tank 12 is connected with the tubular reactor 2 through a pipeline.
The electrolytic solution in the electrolytic circulation tank 11 is introduced into a closed electrolytic tank 12 to be electrolyzed, and an electrolytic lean solution containing chlorine and hydrogen is produced.
As shown in fig. 1 and 2, the gas-liquid separation mechanism 3 includes a first gas-liquid separation tank 31 and a second gas-liquid separation tank 32 connected by a pipeline, the first gas-liquid separation tank 31 is connected to the tubular reactor 2 by a pipeline, the second gas-liquid separation tank 32 is connected to the electrolyte concentration adjusting tank 41, the concentration tank 51, the deep dechlorination reaction tank 52 and the acid and iron removal reaction tank 53 by pipelines, and exhaust ports of the first gas-liquid separation tank 31 and the second gas-liquid separation tank 32 are respectively connected to the chlorine gas absorption mechanism 7 by pipelines.
After the electrolytic barren solution containing chlorine and hydrogen enters the tubular reactor 2, the tubular reactor 2 promotes partial hydrogen and chlorine to synthesize hydrochloric acid under the action of electrodeposition, so as to carry out primary balance on the acidity of the electrolytic barren solution, the electrolytic barren solution with the primary balance acidity enters the gas-liquid separation mechanism 3, harmful gas mainly containing chlorine is absorbed by the chlorine absorption mechanism 7, and the residual chlorine is absorbed by the tail gas treatment mechanism 6 and finally reaches the standard to be discharged. The initial absorption liquid in the chlorine absorption mechanism 7 and the tail gas treatment mechanism 6 is 10% sodium hydroxide solution, and the initial absorption liquid becomes ammonium hypochlorite solution after absorbing tail gas, so that the ammonium hypochlorite solution can be used as a wastewater treatment agent, can be prepared into 84 disinfectant for life disinfection and sterilization, and can also be sold as a product.
As shown in fig. 1 and 2, the concentration adjusting mechanism 4 includes an electrolyte concentration adjusting tank 41 and a hydrochloric acid storage tank 42 which are communicated with each other through a pipeline, the electrolyte concentration adjusting tank 41 is respectively communicated with the gas-liquid separating mechanism 3 and the component adjusting mechanism 5 through pipelines, and a liquid outlet of the electrolyte concentration adjusting tank 41 is connected with the electrolyte circulation tank 11 through a pipeline.
Specifically, the electrolyte concentration adjusting tank 41 is communicated with the second gas-liquid separation tank 32 and the cobalt chloride intermediate tank 54 through pipelines, the electrolyte separated by the second gas-liquid separation tank 32 directly enters the electrolyte concentration adjusting tank 41 for concentration adjustment, or when the components of the electrolyte change, the electrolyte in the second gas-liquid separation tank 32 respectively enters the concentration tank 51, the deep dechlorination reaction tank 52 and the acid-controlling and iron-removing reaction tank 53 correspondingly according to the change, and after the components are adjusted, the electrolyte enters the cobalt chloride intermediate tank 54 and then is conveyed to the electrolyte concentration adjusting tank 41.
In order to control the addition of hydrochloric acid, a metering pump and a flow meter are arranged on a pipeline between the hydrochloric acid storage tank 42 and the electrolyte concentration adjusting tank 41, and the metering pump and the flow meter can be connected to a DCS production operation system as required, so that automatic control can be realized.
Thus, the lean electrolyte after gas-liquid separation enters the electrolyte concentration adjusting tank 41 according to actual conditions, or enters the concentration tank 51, the deep dechlorination reaction tank 52 and the acid-controlling iron-removing reaction tank 53 when the components of the lean electrolyte change, the components of the lean electrolyte are adjusted, the lean electrolyte enters the cobalt chloride intermediate tank 54, the lean electrolyte is conveyed to the electrolyte concentration adjusting tank 41, and the concentration of the lean electrolyte is adjusted by testing the acidity and the concentration of the cobalt chloride; concentration regulation includes two aspects: firstly, the concentration of cobalt chloride in the electrolysis barren solution is adjusted, because part of the cobalt chloride is decomposed into metal cobalt and chlorine gas in the electrolysis process, the concentration of the cobalt chloride is reduced, and at the moment, a cobalt chloride solution with higher concentration is required to be added, so that the concentration of the cobalt chloride is balanced; secondly, the acidity of the electrolysis barren solution is adjusted, because part of the hydrochloric acid is decomposed into hydrogen and chlorine in the electrodeposition circulating mechanism 1, namely the closed electrolytic bath 12, the acidity value is reduced, although the acidity value is initially balanced by the tubular reactor 2, a small amount of hydrochloric acid is still required to be added to balance the acidity value.
The concentration-adjusted lean electrolyte enters the electrolyte circulation tank 11 and is conveyed to the closed type electrolytic tank 12 again for electrolysis.
The working principle is as follows: starting the tail gas treatment mechanism 6 and the chlorine absorption mechanism 7, starting the circulating system, and allowing the cobalt chloride electrolyte to enter a closed electrolytic cell 12 for electrolysis to generate an electrolysis barren solution containing chlorine and hydrogen; after the electrolytic lean solution containing chlorine and hydrogen enters the tubular reactor 2, the tubular reactor 2 promotes part of the hydrogen and chlorine to be synthesized into hydrochloric acid, so as to carry out primary balance on the acidity of the electrolytic lean solution;
the electrolytic barren solution with the primary balance acidity enters a first gas-liquid separation tank 31, gas mainly containing chlorine is absorbed by a chlorine absorption mechanism 7, the rest chlorine is absorbed and treated by a tail gas treatment mechanism 6, and finally reaches the standard to be discharged, wherein the initial absorption solution in the chlorine absorption mechanism 7 and the tail gas treatment mechanism 6 is a 10% sodium hydroxide solution, and after waste gas is absorbed, the solution becomes an ammonium hypochlorite solution which can be used as a wastewater treatment agent and can be sold as a byproduct, and 84 disinfectant can also be prepared for life disinfection and sterilization.
The barren solution after the second gas-liquid separation enters the electrolyte concentration adjusting tank 41 according to the actual situation, or when the components of the barren solution change to a certain degree, the barren solution enters the concentration tank 51, the deep dechlorination reaction tank 52 and the acid-controlling iron-removing reaction tank 53, the components of the barren solution are adjusted, the barren solution is adjusted to the cobalt chloride intermediate tank 54 (or the front-end production project), then the barren solution is conveyed to the electrolyte concentration adjusting tank 41, and the concentration of the barren solution is adjusted by testing the acidity and the cobalt chloride concentration of the barren solution; the concentration adjustment comprises adjustment of the concentration of cobalt chloride in the electrolysis barren solution and adjustment of the acidity of the electrolysis barren solution, and the electrolysis barren solution with the adjusted concentration enters the electrolyte circulation tank 11 and is conveyed to the closed type electrolytic tank 12 again for electrolysis.
When the device is used, the electrodeposition circulating mechanism, the tubular reactor, the gas-liquid separation mechanism and the concentration adjusting mechanism are sequentially connected to form a loop, the tubular reactor promotes part of chlorine and hydrogen in the electrolytic barren solution electrolyzed by the electrodeposition circulating mechanism to be synthesized into hydrochloric acid, and the hydrochloric acid enters the electrolytic barren solution to adjust the acidity value of the electrolytic barren solution, so that the acidity adjustment of the electrolytic barren solution is realized; compared with the traditional process, the hydrochloric acid consumption of the embodiment is greatly reduced, and the hydrochloric acid consumption can be controlled within 30% of the hydrochloric acid consumption of the traditional process. Namely, the consumption of the hydrochloric acid in the embodiment is not more than 30% of that in the traditional process, so that the cost is effectively saved;
moreover, the invention can adaptively adjust the components of the electrolyte after multiple electrolytic reactions through the component adjusting mechanism, thereby being beneficial to the continuous operation of the electrolytic reactions.
Meanwhile, the invention synthesizes partial hydrogen and chlorine in the electrolytic barren solution into hydrochloric acid through the tubular reactor, thereby reducing the solution variable quantity in the electrolyte circulation process, reducing the release of hydrogen and chlorine, and reducing the potential risk degree, thereby effectively improving the safety of industrial production and ensuring that the industrial production is more stable.
Example 2
This example provides a recycling process based on the recycling system of example 1, that is, an electrodeposited cobalt recycling process capable of balancing acidity values of electrolytes, as shown in fig. 5, which includes the following steps:
s1, electrodepositing cobalt in the electrodeposition circulating mechanism by the cobalt chloride electrolyte to generate an electrolysis barren solution;
s2, the electrolytic barren solution enters a tubular reactor, and partial hydrogen and chlorine in the electrolytic barren solution are promoted to be synthesized into hydrochloric acid under the action of electrodeposition, so that the electrolytic barren solution with the acidity primarily adjusted is obtained;
s3, feeding the electrolytic barren solution with the preliminarily adjusted acidity value into a gas-liquid separation mechanism to obtain the electrolytic barren solution after gas-liquid separation;
and S4, enabling the gas-liquid separated electrolytic barren solution to enter a concentration adjusting mechanism, adjusting the concentration and acidity value of cobalt chloride to obtain cobalt chloride electrolytic front solution meeting the electrodeposition conditions after adjustment, and conveying the cobalt chloride electrolytic front solution to the electrodeposition circulating mechanism for electrodeposition again.
Wherein the electrodeposition conditions of the electrodeposition circulation mechanism in S1 are as follows: the cobalt ion concentration is 60-100 g/L, and the current density is 400-500A/m2The pH value of the cobalt chloride electrolyte is 1-2, the cell voltage is 2.5-3.0V, and the circulation volume of the electrolyte is 3-4 m3The electrolysis temperature is 50-55 ℃; the electrodeposition conditions in S4 were the same.
In order to ensure the generation of the synthesis reaction of the hydrogen and the chlorine in the tubular reactor 2, the reaction temperature in the tubular reactor 2 in the S2 is 50-55 ℃.
In a specific implementation, depending on the composition of the electrolytic lean solution, the step S4 may further include:
s4, the gas-liquid separated electrolytic barren solution enters a component adjusting mechanism 5 according to the component change, namely enters a concentration tank 51, a deep dechlorination reaction tank 52 and an acid-controlling and iron-removing reaction tank 53 respectively according to the requirement, the electrolytic barren solution adjusted by the components enters a cobalt chloride intermediate tank 54 and then enters a concentration adjusting mechanism to adjust the concentration and acidity of the cobalt chloride to obtain an adjusted cobalt chloride electrolyte, and the adjusted cobalt chloride electrolyte is conveyed to the electrodeposition circulating mechanism for electrodeposition again.
The working process is as follows: firstly, preparing a refined and purified cobalt chloride solution as an electrolysis stock solution, wherein the content of cobalt chloride in the electrolysis stock solution is 60-100 g/L, the content of metal impurities such as copper, lead, iron, manganese, zinc and the like is respectively less than or equal to 0.001g/L, and the content of oil is less than or equal to 0.001 g/L; then starting a tail gas treatment mechanism 6, conveying the electrolysis stock solution into a closed electrolytic tank 12, and controlling the flow of the electrolysis stock solution entering the closed electrolytic tank 12 to be 3-4 m3The conditions for controlling the electrolysis process are as follows: the current density is 400-500A/m2Chlorine (C)The pH value of the cobalt electrolyte is 1-2, the cell voltage is 2.5-3.0V, and the circulation volume of the electrolyte is 3-4 m3The electrolysis temperature is 50-55 ℃, as shown in figure 3, metal cobalt is deposited on the cathode plate, a metal cobalt plate is grown, and meanwhile, an electrolysis barren solution containing hydrogen and chlorine is obtained;
the electrolytic lean solution containing hydrogen and chlorine is circulated to the tubular reactor 2, and as shown in fig. 4, the tubular reactor 2 promotes most of hydrogen and chlorine to be synthesized into hydrochloric acid, and the acidity of the electrolytic lean solution is preliminarily balanced; then the electrolytic barren solution is circulated continuously and enters the gas-liquid separation mechanism 3, the gas mainly containing chlorine is absorbed by the chlorine absorption mechanism 7, and the residual chlorine is absorbed and treated by the tail gas treatment mechanism 6 and finally discharged after reaching the standard. Wherein the initial absorption liquid in the chlorine absorption mechanism 7 and the tail gas treatment mechanism 6 is 10 percent sodium hydroxide solution, and the initial absorption liquid becomes ammonium hypochlorite solution after absorbing the waste gas, can be used as a wastewater treatment medicament, can be sold as a byproduct, and can also be prepared into 84 disinfectant for life disinfection and sterilization.
The barren electrolyte after the secondary gas-liquid separation enters the electrolyte concentration regulating tank 41 respectively according to actual conditions, or when the components of the barren electrolyte change, the barren electrolyte correspondingly enters the concentration tank 51, the deep dechlorination reaction tank 52 and the acid-controlling iron-removing reaction tank 53 respectively, the components of the barren electrolyte are regulated, then the barren electrolyte enters the cobalt chloride intermediate tank 54, then the barren electrolyte is conveyed to the electrolyte concentration regulating tank 41, and the concentration of the barren electrolyte is regulated by testing the acidity and the concentration of the cobalt chloride; the concentration adjustment comprises adjustment of the concentration of cobalt chloride in the electrolysis barren solution and adjustment of the acidity of the electrolysis barren solution, and the electrolysis barren solution with the adjusted concentration enters the electrolyte circulation tank 11 and is conveyed to the closed type electrolytic tank 12 again for electrolysis.
When the device is used, the electrodeposition circulating mechanism, the tubular reactor, the gas-liquid separation mechanism and the concentration adjusting mechanism are sequentially connected to form a loop, the tubular reactor promotes part of chlorine and hydrogen in the electrolytic barren solution electrolyzed by the electrodeposition circulating mechanism to be synthesized into hydrochloric acid, and the hydrochloric acid enters the electrolytic barren solution to adjust the acidity value of the electrolytic barren solution, so that the acidity adjustment of the electrolytic barren solution is realized; compared with the traditional process, the hydrochloric acid consumption of the embodiment is greatly reduced, and the hydrochloric acid consumption can be controlled within 25% of the hydrochloric acid consumption of the traditional process. Namely, the consumption of the hydrochloric acid in the embodiment is not more than 30% of that in the traditional process, so that the cost is effectively saved;
meanwhile, the invention synthesizes partial hydrogen and chlorine in the electrolytic barren solution into hydrochloric acid through the tubular reactor, thereby reducing the solution variable quantity in the electrolyte circulation process, reducing the release of hydrogen and chlorine, and reducing the potential danger degree, thereby effectively improving the safety of industrial production.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The utility model provides a can balance electrodeposition cobalt circulation system of electrolyte acidity value which characterized in that, includes electrodeposition circulation mechanism (1), tubular reactor (2), gas-liquid separation mechanism (3) and concentration adjustment mechanism (4) that communicate in proper order through the pipeline, and forms the return circuit.
2. The system of claim 1, further comprising a component adjusting mechanism (5), wherein the component adjusting mechanism (5) is disposed between the gas-liquid separating mechanism (3) and the concentration adjusting mechanism (4), and is configured to adjust the component of the electrolytic barren solution with changed component after multiple electrolyzations, and convey the electrolytic barren solution to the concentration adjusting mechanism (4).
3. The system of claim 2, wherein the component adjusting mechanism (5) comprises a concentration tank (51), a deep dechlorination reaction tank (52), an acid control and iron removal reaction tank (53) and a cobalt chloride intermediate tank (54), the concentration tank (51), the deep dechlorination reaction tank (52) and the acid control and iron removal reaction tank (53) are not connected with each other, and are respectively used for receiving the electrolysis barren solution separated by the gas-liquid separating mechanism (3), adjusting the components of the electrolysis barren solution, and conveying the electrolysis barren solution to the cobalt chloride intermediate tank (54), and the cobalt chloride intermediate tank (54) is communicated with the concentration adjusting mechanism (4) through a pipeline.
4. The system for recycling electrodeposited cobalt capable of balancing acidity of electrolyte according to claim 2 or 3, further comprising a waste gas treatment component disposed in a matching manner, wherein the waste gas treatment component comprises a chlorine gas absorption mechanism (7) and a tail gas treatment mechanism (6), and the chlorine gas absorption mechanism (7) is disposed in communication with the rear side of the gas-liquid separation mechanism (3) for absorbing the generated chlorine gas; the tail gas treatment mechanism (6) is communicated with the rear side of the chlorine absorption mechanism (7), is communicated with the component adjusting mechanism (5) through a pipeline, and is used for retreating the chlorine which is not completely treated by the chlorine absorption mechanism (7) and absorbing the tail gas generated by the component adjusting mechanism (5).
5. The system of claim 4, wherein the chlorine gas absorption mechanism (7) comprises a chlorine gas primary absorption tank (71) and a chlorine gas secondary absorption tank (72), the chlorine gas primary absorption tank (71) is communicated with the gas-liquid separation mechanism (3) through a pipeline, the chlorine gas secondary absorption tank (72) is respectively communicated with the gas-liquid separation mechanism (3), the concentration regulation mechanism (4) and the electrodeposition circulation mechanism (1) through pipelines, and the chlorine gas primary absorption tank (71) and the chlorine gas secondary absorption tank (72) are communicated with the tail gas treatment mechanism (6).
6. An electrodeposition cobalt circulation system capable of balancing acidity values of electrolyte according to claim 5, wherein the electrodeposition circulation mechanism (1) comprises an electrolyte circulation tank (11) and at least one closed electrolytic tank (12) which are communicated through a pipeline, the electrolyte circulation tank (11) is further connected with the concentration regulating mechanism (4) through a pipeline, and the closed electrolytic tank (12) is connected with the tubular reactor (2) through a pipeline.
7. The system of claim 5, wherein the concentration adjusting mechanism (4) comprises an electrolyte concentration adjusting tank (41) and a hydrochloric acid storage tank (42) which are communicated through a pipeline, the electrolyte concentration adjusting tank (41) is respectively communicated with the gas-liquid separation mechanism (3) and the component adjusting mechanism (5) through a pipeline, and the electrolyte concentration adjusting tank (41) is connected with the electrodeposition circulating mechanism (1) through a pipeline.
8. An electrodeposited cobalt circulation system capable of balancing acidity value of electrolyte according to any one of claims 5 to 7, characterized in that the gas-liquid separation means (3) comprises a first gas-liquid separation tank (31) and a second gas-liquid separation tank (32) connected by a pipeline, the first gas-liquid separation tank (31) is connected with the tubular reactor (2) by a pipeline, the second gas-liquid separation tank (32) is connected with the concentration adjusting means (4) by a pipeline, and exhaust ports of the first gas-liquid separation tank (31) and the second gas-liquid separation tank (32) are respectively connected with the chlorine absorbing means (7) by a pipeline.
9. An electrodeposition cobalt circulation process capable of balancing acidity value of electrolyte, which is characterized in that the circulation system of any one of claims 1 to 8 is applied to balance acidity value of electrolyte in the electrodeposition cobalt process, and the process comprises the following steps:
s1, electrodepositing cobalt in the electrodeposition circulating mechanism by the cobalt chloride electrolyte to generate an electrolysis barren solution;
s2, the electrolytic barren solution enters a tubular reactor, and partial hydrogen and chlorine in the electrolytic barren solution are promoted to be synthesized into hydrochloric acid under the action of electrodeposition, so that the electrolytic barren solution with the acidity primarily adjusted is obtained;
s3, feeding the electrolytic barren solution with the preliminarily adjusted acidity value into a gas-liquid separation mechanism to obtain the electrolytic barren solution after gas-liquid separation;
and S4, enabling the gas-liquid separated electrolytic barren solution to enter a concentration adjusting mechanism, adjusting the concentration and acidity value of cobalt chloride to obtain cobalt chloride electrolyte meeting the electrodeposition condition after adjustment, and conveying the cobalt chloride electrolyte to the electrodeposition circulating mechanism for electrodeposition again.
10. The electrowinning cobalt cycle process capable of equilibrating acidity values of the electrolyte of claim 9, wherein the electrowinning conditions of the electrowinning cycle mechanism in S1 are: the cobalt ion concentration is 60-100 g/L, and the current density is 400-500A/m2The pH value of the cobalt chloride electrolyte is 1-2, the cell voltage is 2.5-3.0V, and the circulation volume of the electrolyte is 3-4 m3The electrolysis temperature is 50-55 ℃;
the reaction temperature in the tubular reactor in the S2 is 50-55 ℃.
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| CN202010627609.7A CN113881966A (en) | 2020-07-01 | 2020-07-01 | Electrodeposition cobalt circulation system capable of balancing acidity value of electrolyte and circulation process thereof |
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