Real-time monitoring system and method for copper electrolyte purification and copper arsenic sulfide separation process

Abstract

The present invention relates to a real-time monitoring system and method for a copper electrolyte purification copper arsenic sulfide separation process, including a PLC reaction control module, a primary sulfide real-time monitoring module, a secondary sulfide real-time monitoring module, a tertiary sulfide real-time monitoring module, a hydrogen sulfide intake valve and a sulfide liquid drain valve. The present invention uses PLC to first obtain the copper arsenic concentration change of the primary sulfide process monitoring module in real time, analyze and judge the critical point of arsenic slight drop, and interlock the intake valve to close the drain valve and open, so as to achieve copper more precipitation and arsenic slight precipitation; secondly, obtain the copper arsenic concentration change of the secondary sulfide process monitoring module in real time, analyze and judge the critical point of copper dropping to near zero, and interlock the intake valve to close the drain valve and open, so as to achieve copper full precipitation and arsenic less precipitation; finally, obtain the arsenic concentration change of the tertiary sulfide process monitoring module in real time, analyze and judge the critical point of arsenic dropping to the limit value, and interlock the intake valve to close the drain valve and open, so as to achieve stable arsenic concentration up to standard. It is beneficial to improve sulfide production efficiency, increase copper resource recycling rate, and reduce the amount of arsenic-containing hazardous waste.

Description

Technical Field

[0001] The present invention belongs to an electrolytic refining purification system in the copper smelting industry, relates to the technical field of clean production of copper-arsenic sulfide separation process, and specifically relates to a real-time monitoring system and method for copper electrolyte purification of copper-arsenic sulfide separation process. Background Art

[0002] Since the birth of the copper smelting industry, the copper arsenic cannot be effectively separated in the electrolytic refining and purification system of the copper smelting industry, and copper is mixed with arsenic slag and arsenic is mixed with copper slag, resulting in excessive arsenic-containing hazardous waste. 200,000 tons of arsenic-containing hazardous waste are added each year, which has become the most prominent major problem in the industry. The copper electrolytic refining purification system mainly includes two methods: electrolytic de-arsenication and sulfide de-arsenication. Electrolytic de-arsenication is the most traditional electrolyte purification method in the industry. However, due to the similar potential of copper and arsenic electrodes, co-deposition is very likely to occur and cannot be effectively separated. In addition, the production process is prone to produce toxic and harmful gas arsenic hydrogen, which endangers safe production. Therefore, many manufacturers and research institutions are actively seeking new copper electrolyte purification methods to replace electrolytic de-arsenication. As a new purification process, sulfide dearsenicization has gradually emerged in the copper smelting industry and has been widely used. However, both the secondary copper sulfide arsenic separation process and the more advanced tertiary copper sulfide arsenic separation process have not yet solved the problems of high arsenic content in the primary and secondary sulfide slags, high copper content in the tertiary sulfide slag, low copper resource recovery rate, and excessive arsenic hazardous waste generation.

[0003] The copper-arsenic sulfidation reaction is rapid (measured in seconds), and the current mainstream equipment has a long detection time (2-4 hours), and the amount of hydrogen sulfide added cannot be adjusted in real time according to the concentration of each species. Excessive addition of hydrogen sulfide causes copper-arsenic co-precipitation with arsenic in copper slag and copper in arsenic slag. Enterprises are in urgent need of real-time monitoring of the copper-arsenic concentration in the liquid phase of the sulfidation reaction process and accurate control of the technology and method of the reaction endpoint. Therefore, the invention of a real-time monitoring system and method for the copper electrolyte purification copper-arsenic sulfidation separation process is an urgent need for enterprises to achieve effective separation of copper and arsenic in electrolyte purification, improve the reuse rate of copper resources, reduce the amount of arsenic hazardous waste, reduce toxic gas emissions, and save energy, reduce consumption, reduce pollution, and increase efficiency. Summary of the invention

[0004] The present invention aims at the problems that the electrolytic refining and purification system in the current copper smelting industry, whether adopting electrolytic dearsenication or sulfide dearsenication, has low copper resource recovery rate, excessive arsenic hazardous waste generation, and the copper arsenic concentration in the liquid phase of the sulfide reaction process cannot be monitored in real time and the reaction end point cannot be accurately controlled. A real-time monitoring system and method for the copper arsenic sulfide separation process of copper electrolyte purification is proposed. Through a reasonably designed three-stage sulfide reaction process and precise control of the reaction process by PLC, scientific guidance of precise addition of hydrogen sulfide is achieved, the utilization efficiency of copper resources is improved, and the generation of arsenic-containing hazardous waste is reduced.

[0005] To achieve the above object, the present invention adopts the following technical solution:

[0006] In the first aspect, the present invention provides a real-time monitoring method for the separation process of copper electrolyte purification of copper arsenic sulfide:

[0007] The method is based on a set three-stage copper-arsenic sulfidation reaction process;

[0008] In the first-stage copper-arsenic sulfidation reaction process, the concentration change of copper-arsenic ions in the first-stage copper-arsenic sulfidation reaction process is monitored in real time, and the critical point of slight drop of arsenic is determined by PLC calculation, and the air intake valve is closed and the discharge valve is opened, so that the copper is mostly precipitated and the arsenic is slightly precipitated in the sulfidation liquid discharged from the first-stage copper-arsenic sulfidation reaction process;

[0009] In the secondary copper-arsenic sulfidation process, the concentration of copper-arsenic ions is monitored in real time, and the critical point where copper drops to near zero is determined by PLC calculation, and the air intake valve is closed and the discharge valve is opened, so that the copper is fully precipitated and the arsenic is less precipitated in the sulfidation liquid discharged from the secondary copper-arsenic sulfidation process.

[0010] During the tertiary copper-arsenic sulfidation reaction, the changes in copper-arsenic ion concentration during the tertiary copper-arsenic sulfidation reaction are monitored in real time, and the PLC calculation is used to determine the critical point where the arsenic drops to the limit value, and the intake valve is closed and the discharge valve is opened, so that the arsenic concentration in the sulfide liquid discharged from the tertiary copper-arsenic sulfidation reaction process meets the standard.

[0011] In a specific implementation scheme, during the primary copper-arsenic sulfidation reaction, the change of copper-arsenic ion concentration in the primary sulfidation reaction tank over time is monitored in real time, including the change of copper ions from entering the liquid to leaving the liquid with the sulfidation time, and the change of arsenic ions from entering the liquid to leaving the liquid with the sulfidation time, and the data is transmitted to the PLC in real time; when the PLC determines the critical point of the slight decrease in the arsenic ion concentration during the primary copper-arsenic sulfidation reaction through analysis, the PLC is used to control the closing of the air inlet valve and the opening of the drain valve of the primary sulfidation reaction tank to terminate the reaction, ensuring that the discharged primary sulfidation liquid has more copper and less arsenic. And the critical point of slight decrease is arsenic content ≤ 2.5%

[0012] In a specific implementation scheme, during the secondary copper-arsenic sulfidation reaction, the change of the copper-arsenic ion concentration in the secondary sulfidation reaction tank over time is monitored in real time, including the change of the copper ion from the inlet to the outlet with the sulfidation time, and the change of the arsenic ion from the inlet to the outlet with the sulfidation time, and the data is transmitted to the PLC in real time; when the PLC determines that the copper ion concentration in the secondary copper-arsenic sulfidation reaction process drops to a critical point close to zero, the PLC is used to control the air inlet valve of the secondary sulfidation reaction tank to close and the drain valve to open, and the reaction is terminated to ensure that the copper is fully precipitated and the arsenic is less precipitated in the discharged secondary sulfidation liquid. And the critical point is that the copper concentration is 0 mg / L.

[0013] In a specific implementation scheme, during the three-stage copper-arsenic sulfidation reaction, the change of the copper-arsenic ion concentration in the three-stage sulfidation reaction tank over time is monitored in real time, including the change of the copper ion from the inlet to the outlet with the sulfidation time, and the change of the arsenic ion from the inlet to the outlet with the sulfidation time, and the data is transmitted to the PLC in real time; when the PLC determines that the arsenic ion concentration in the three-stage copper-arsenic sulfidation reaction process drops to the critical point of the limit value, the PLC is used to control the air inlet valve of the three-stage sulfidation reaction tank to close and the drain valve to open, and the reaction is terminated to ensure that the arsenic concentration in the discharged three-stage sulfidation liquid meets the standard. And the critical point is that the arsenic concentration is 1 000 mg / L.

[0014] In a second aspect, the present invention provides a real-time monitoring system for the copper electrolyte purification copper arsenic sulfide separation process:

[0015] The system consists of a primary vulcanization reaction tank, a secondary vulcanization reaction tank, and a tertiary vulcanization reaction tank, and on this basis, it also includes a PLC reaction control module, a primary vulcanization real-time monitoring module, a secondary vulcanization real-time monitoring module, a tertiary vulcanization real-time monitoring module, a hydrogen sulfide intake valve, and a sulfide liquid discharge valve;

[0016] The PLC reaction control module includes a primary copper sulfide arsenic reaction closed-loop control module, a secondary copper sulfide arsenic reaction closed-loop control module, and a tertiary copper sulfide arsenic reaction closed-loop control module;

[0017] The primary copper arsenic sulfide reaction closed-loop control module is in communication and electrical connection with the primary sulfidation real-time monitoring module, the hydrogen sulfide intake valve and the sulfide liquid discharge valve, and is used to retrieve the copper arsenic ion concentration of the primary sulfidation real-time monitoring module in real time, and when the critical point of a slight decrease in the arsenic ion concentration in the primary sulfidation process is determined by analysis, the primary sulfidation reaction tank hydrogen sulfide intake solenoid valve in the hydrogen sulfide intake valve and the sulfide liquid discharge valve are closed, and the primary sulfidation reaction tank sulfide liquid discharge ball valve is opened to terminate the reaction;

[0018] The secondary copper arsenic sulfide reaction closed-loop control module is in communication and electrical connection with the secondary sulfidation real-time monitoring module, the hydrogen sulfide intake valve and the sulfide liquid discharge valve, and is used to retrieve the copper arsenic ion concentration of the secondary sulfidation real-time monitoring module in real time, and when it is determined by analysis that the copper ion concentration in the secondary sulfidation process drops to a critical point close to zero, the hydrogen sulfide intake solenoid valve of the secondary sulfidation reaction tank in the hydrogen sulfide intake valve and the sulfide liquid discharge valve are closed, and the sulfide liquid discharge ball valve of the secondary sulfidation reaction tank is opened to terminate the reaction;

[0019] The three-stage copper arsenic sulfide reaction closed-loop control module communicates and is electrically connected with the three-stage sulfidation real-time monitoring module, the hydrogen sulfide intake valve, and the sulfide liquid discharge valve, and is used to retrieve the copper arsenic ion concentration of the three-stage sulfidation real-time monitoring module in real time, and when the arsenic ion concentration of the three-stage sulfidation process drops to the critical point of the limit value through analysis and judgment, the three-stage sulfidation reaction tank hydrogen sulfide intake solenoid valve in the hydrogen sulfide intake valve and the sulfide liquid discharge valve are linked to close the three-stage sulfidation reaction tank sulfide liquid discharge ball valve, and open to terminate the reaction;

[0020] The primary sulfidation real-time monitoring module is installed at the primary sulfidation reaction tank, and is used to monitor the change of copper arsenic ion concentration over time during the primary sulfidation process, focusing on monitoring the critical point where the arsenic ion concentration begins to slightly decrease, and the corresponding reaction time is the reaction end point discharge time; real-time monitoring of the change of copper ions from liquid entry to liquid exit with the sulfidation time, and the change of arsenic ions from liquid entry to liquid exit with the sulfidation time, and transmitting the data in real time to the primary copper sulfide arsenic reaction closed-loop control module in the PLC reaction control module;

[0021] The secondary sulfidation real-time monitoring module is installed at the secondary sulfidation reaction tank, and is used to monitor the change of copper arsenic ion concentration over time during the secondary sulfidation process, focusing on monitoring the critical point where the copper ion concentration drops to near zero, and the corresponding reaction time is the reaction end point discharge time; real-time monitoring of the change of copper ions from liquid entry to liquid exit as the sulfidation time changes, and the change of arsenic ions from liquid entry to liquid exit as the sulfidation time changes, and transmits the data in real time to the secondary copper sulfide arsenic reaction closed-loop control module in the PLC reaction control module;

[0022] The three-stage sulfidation real-time monitoring module is installed at the three-stage sulfidation reaction tank, and is used to monitor the change of copper arsenic ion concentration over time during the three-stage sulfidation process, focusing on monitoring the critical point where the arsenic ion concentration drops to the limit value, and the corresponding reaction time is the reaction end point discharge time; real-time monitoring of the change of copper ions from liquid entry to liquid exit with the sulfidation time, and the change of arsenic ions from liquid entry to liquid exit with the sulfidation time, and transmitting the data in real time to the three-stage copper arsenic sulfide reaction closed-loop control module in the PLC reaction control module;

[0023] The hydrogen sulfide intake valve and the sulfide liquid discharge valve include a primary sulfide reaction tank hydrogen sulfide intake solenoid valve and a primary sulfide reaction tank sulfide liquid discharge ball valve, a secondary sulfide reaction tank hydrogen sulfide intake solenoid valve and a secondary sulfide reaction tank sulfide liquid discharge ball valve, a tertiary sulfide reaction tank hydrogen sulfide intake solenoid valve and a tertiary sulfide reaction tank sulfide liquid discharge ball valve;

[0024] The primary sulfide reaction tank hydrogen sulfide intake solenoid valve and the primary sulfide reaction tank sulfide liquid discharge ball valve are installed at the primary sulfide reaction tank and can be opened and closed accordingly according to the instructions of the primary copper sulfide arsenic reaction closed-loop control module in the PLC reaction control module;

[0025] The secondary sulfide reaction tank hydrogen sulfide intake solenoid valve and the secondary sulfide reaction tank sulfide liquid discharge ball valve are installed at the secondary sulfide reaction tank and can be opened and closed accordingly according to the instructions of the secondary copper sulfide arsenic reaction closed-loop control module in the PLC reaction control module;

[0026] The three-stage sulfide reaction tank hydrogen sulfide intake solenoid valve and the three-stage sulfide reaction tank sulfide liquid discharge ball valve are installed at the three-stage sulfide reaction tank and can be opened and closed accordingly according to the instructions of the three-stage copper sulfide arsenic reaction closed-loop control module in the PLC reaction control module.

[0027] The remarkable effects of the present invention are:

[0028] The present invention discloses a real-time monitoring system and method for the copper electrolyte purification copper arsenic sulfide separation process, including a PLC reaction control module, a primary sulfidation real-time monitoring module, a secondary sulfidation real-time monitoring module, a tertiary sulfidation real-time monitoring module, a hydrogen sulfide intake valve and a sulfide liquid drain valve. Based on the basic characteristics that copper precipitates before arsenic in the copper arsenic sulfidation process, the present invention monitors the critical point of arsenic slightly decreasing in the primary copper arsenic sulfidation process, uses the PLC interlocking intake valve to close the drain valve to open, and ensures that the primary sulfidation liquid copper is more precipitated and the arsenic is slightly precipitated; monitors the critical point of copper dropping to near zero in the secondary copper arsenic sulfidation process, uses the PLC interlocking intake valve to close the drain valve to close, and ensures that the secondary sulfidation liquid copper is fully precipitated and the arsenic is less precipitated; monitors the critical point of arsenic dropping to 1000 mg / L in the tertiary sulfidation process, uses the PLC interlocking intake valve to close the drain valve to close, and ensures that the arsenic concentration in the tertiary sulfidation liquid is stable and meets the standard. The present invention realizes scientific guidance of hydrogen sulfide precise addition, improves the utilization efficiency of copper resources, and reduces the generation of arsenic-containing hazardous waste. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is the system block diagram and control route diagram of the present invention.

[0030] Figure 2 This is a graph showing changes in copper arsenic ion concentration during real-time monitoring of a primary sulfidation reaction in an embodiment of the present invention.

[0031] Figure 3 It is a graph showing the change in copper arsenic ion concentration during real-time monitoring of the secondary sulfidation reaction in an embodiment of the present invention.

[0032] Figure 4 It is a graph showing the change in copper arsenic ion concentration during real-time monitoring of the three-stage sulfidation reaction in an embodiment of the present invention. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. The following embodiments are used to illustrate the present invention.

[0034] See also Figure 1 The system structure of the present invention includes: a PLC reaction control module 1, a primary sulfide real-time monitoring module 2, a secondary sulfide real-time monitoring module 3, a tertiary sulfide real-time monitoring module 4, a hydrogen sulfide intake valve and a sulfide liquid discharge valve 5.

[0035] See also Figure 1 , PLC reaction control module 1, including a primary copper sulfide arsenic reaction closed-loop control module 1-1, a secondary copper sulfide arsenic reaction closed-loop control module 1-2, and a secondary copper sulfide arsenic reaction closed-loop control module 1-3. The primary copper sulfide arsenic reaction closed-loop control module 1-1 is used to call the copper arsenic ion concentration of the primary sulfide real-time monitoring module 2 in real time. When the arsenic ion concentration in the primary sulfide process drops slightly (solid phase As≈2.5%) through analysis, the PLC is quickly used to interlock the primary sulfide tank air inlet valve to close the drain valve and open the reaction to ensure that the primary sulfide liquid copper is mostly precipitated and the arsenic is slightly precipitated; the secondary copper sulfide arsenic reaction closed-loop control module 1-2 is used to call the copper arsenic ion concentration of the secondary sulfide real-time monitoring module 2 in real time. When the copper ion concentration in the secondary sulfide process drops to the critical point through analysis, it is determined that the copper ion concentration drops to nearly When the critical point of zero (Cu≈0mg / L) is reached, the PLC is used to quickly interlock the air inlet valve of the secondary sulfide tank and close the drain valve to terminate the reaction, ensuring that the copper in the secondary sulfide liquid is fully precipitated and less arsenic is precipitated; the tertiary copper sulfide arsenic reaction closed-loop control module 1-3 is used to real-time retrieve the copper arsenic ion concentration of the tertiary sulfide real-time monitoring module 3, and through analysis and judgment, the critical point at which the arsenic ion concentration in the tertiary sulfide process drops to the limit value (for example, As≈1000mg / L) is quickly interlocked with the air inlet valve of the tertiary sulfide tank and close the drain valve to terminate the reaction, ensuring that the arsenic concentration in the tertiary sulfide liquid is stable and meets the standard.

[0036] See also Figure 1 The primary sulfidation real-time monitoring module 2 is installed at the primary sulfidation reaction tank to monitor the change of copper arsenic ion concentration over time during the primary sulfidation process, focusing on the critical point where the arsenic concentration begins to drop slightly (solid phase As≈2.5%), and the corresponding reaction time t=x1min, which is the end point of the reaction. Real-time monitoring of the change of copper ions from the inlet liquid C1 to the outlet liquid C2 with the sulfidation time, and the change of arsenic ions from the inlet liquid c1 to the outlet liquid c2 with the sulfidation time, and the data is transmitted to the primary copper sulfide arsenic reaction closed-loop control module 1-1 in real time.

[0037] See also Figure 1The secondary sulfidation real-time monitoring module 3 is installed at the secondary sulfidation reaction tank to monitor the change of copper arsenic ion concentration over time during the secondary sulfidation process, focusing on the critical point where the copper concentration drops to near zero (Cu≈0mg / L), and the corresponding reaction time t=x2min, which is the end point of the reaction. Real-time monitoring of the change of copper ions from the inlet liquid C2 to the outlet liquid C3 with the sulfidation time, and the change of arsenic ions from the inlet liquid c2 to the outlet liquid c3 with the sulfidation time, and the data is transmitted to the secondary copper sulfide arsenic reaction closed-loop control module 1-2 in real time.

[0038] See also Figure 1 The three-stage sulfidation real-time monitoring module 4 is installed at the three-stage sulfidation reaction tank to monitor the change of copper arsenic ion concentration over time during the three-stage sulfidation process, focusing on the critical point where the arsenic concentration drops to the limit value (As≈1000mg / L), and the corresponding reaction time t=x3min, which is the reaction end point discharge time. Real-time monitoring of the change of copper ions from the inlet liquid C3 to the outlet liquid C4 with the sulfidation time, and the change of arsenic ions from the inlet liquid c3 to the outlet liquid c4 with the sulfidation time, and the data is transmitted to the three-stage copper sulfide arsenic reaction closed-loop control module 1-3 in real time.

[0039] See also Figure 1 , the hydrogen sulfide intake valve and the sulfide liquid discharge valve 5, including a primary sulfide reaction tank hydrogen sulfide intake solenoid valve 5-1-1 and a primary sulfide reaction tank sulfide liquid discharge ball valve 5-1-2 installed at the primary sulfide reaction tank, a secondary sulfide reaction tank hydrogen sulfide intake solenoid valve 5-2-1 and a secondary sulfide reaction tank sulfide liquid discharge ball valve 5-2-2 installed at the secondary sulfide reaction tank, and a tertiary sulfide reaction tank hydrogen sulfide intake solenoid valve 5-3-1 and a tertiary sulfide reaction tank sulfide liquid discharge ball valve 5-3-2 installed at the tertiary sulfide reaction tank. The above valve groups can be opened and closed accordingly according to the instructions of the primary copper sulfide arsenic reaction closed-loop control module 1-1, the secondary copper sulfide arsenic reaction closed-loop control module 1-2, and the tertiary copper sulfide arsenic reaction closed-loop control module 1-3 in the PLC reaction control module 1.

[0040] In summary, the three-stage sulfidation reaction process configured in the present invention is closely related to the on-site process conditions. It can be understood that the primary sulfidation reaction removes high copper, the secondary sulfidation reaction removes low copper, and the tertiary sulfidation reaction removes high arsenic. The primary sulfidation reaction can reduce copper by about 80-90%, and the secondary sulfidation reaction will precipitate the remaining 10-20% of copper. Since there is no copper but only arsenic in the tertiary sulfidation reaction, the tertiary sulfidation reaction only removes arsenic. The purpose of the three-stage sulfidation reaction adopted in the present invention is to effectively separate the high-concentration copper ions and arsenic ions in the electrolyte into copper slag and arsenic slag through step-by-step sulfidation precipitation.

[0041] [Example]

[0042] According to the sulfide solubility product principle, in the presence of appropriate amount of H2 Cu under S condition 2+ As 5+ Preferential sulfidation precipitation, using this characteristic to add H 2 S makes S 2- First with Cu 2+ The precipitate is then reacted with As 5+ A precipitate is generated, which is the theoretical basis of sulfide decoppering and dearsenicing.

[0043] The specific copper sulfidation reaction is shown in equation (1), and the arsenic sulfidation reaction is shown in equation (2):

[0044] Cu 2+ +S 2- →CuS↓ (1)

[0045] 2As 5+ +5S 2- →As 2 S 3 ↓+2S↓ (2)

[0046] Note: The relative atomic mass of Cu is 64; the relative atomic mass of As is 75; the relative atomic mass of S is 32.

[0047] 1. Primary sulfidation reaction process

[0048] Copper electrolytic refining enters the purification system, and the copper ion Cu in the electrolyte before the primary sulfidation reaction 2+ The concentration is about 10000mg / L, arsenic ion As 5+ The concentration is about 9000 mg / L. See Table 1.

[0049] Table 1 Copper arsenic ion concentration before primary sulfidation

[0050]

[0051] First, the electrolyte containing high concentration of copper arsenic is pumped into the primary sulfidation reaction tank, and hydrogen sulfide gas is slowly added while vigorously stirring to carry out the sulfidation reaction.

[0052] The primary sulfidation reaction process requires real-time monitoring of the change in copper arsenic ion concentration, and the data is fed back to the PLC reaction control module in real time. By quickly calculating and analyzing the arsenic content in the slag, it is determined whether the sulfidation reaction has reached the end point (limit requirement: solid phase arsenic content: As <2.5%), ensuring that the primary sulfidation liquid has more copper and less arsenic. The real-time monitoring of the change in copper arsenic ion concentration in the primary sulfidation reaction is shown in Figure 2 .

[0053] from Figure 2 Several representative time points (see Table 2) are selected to calculate whether the primary vulcanization reaction has reached the end point:

[0054] Table 2 Changes in copper arsenic ion concentrations during real-time monitoring of primary sulfidation reaction

[0055]

[0056] From the above formula, it can be seen that the slag phase obtained by the sulfidation reaction is mainly composed of CuS, As 2 S 3 , S composition, the primary sulfidation reaction limit requirement is that the arsenic As content in the slag phase is ≤2.5%.

[0057] Right now:

[0058] ① When t = 15min, the Cu consumed by the reaction precipitation 2 +=(10000-5000)mg / L=5000mg / L; As 5+ =(9000-8900)mg / L=100mg / L.

[0059] Substituting the concentrations of Cu and As consumed during the reaction into formula 3, we can obtain:

[0060]

[0061] Since 1.30%<2.5% (limit value), the vulcanization endpoint has not been reached and the vulcanization reaction continues.

[0062] ② When t = 25min, the Cu consumed by the reaction precipitation 2 +=(10000-2500)mg / L=7500mg / L; As 5 +=(9000-8800)mg / L=200mg / L.

[0063] Substituting the concentrations of Cu and As consumed during the reaction into formula 3, we can obtain:

[0064]

[0065] Since 1.72%<2.5% (limit value), the sulfurization endpoint has not been reached and the reaction continues.

[0066] ③When t=30min, the Cu consumed by the reaction precipitation 2 +=(10000-2400)mg / L=7600mg / L; As 5 +=(9000-8700)mg / L=300mg / L.

[0067] Substituting the concentrations of Cu and As consumed during the reaction into formula 3, we can obtain:

[0068]

[0069] Since 2.49%≈2.5% (limit value), it is close to the end point of vulcanization, so it is necessary to terminate the reaction and perform fluid filtration.

[0070] 2. Secondary sulfidation reaction process

[0071] The electrolyte after the primary sulfidation is the liquid before the secondary sulfidation reaction, and the copper arsenic ion concentration is shown in Table 3.

[0072] Table 3 Copper arsenic ion concentration in electrolyte before secondary sulfidation

[0073]

[0074] Then the primary sulfided liquid containing a certain copper arsenic ion concentration is pumped into the secondary sulfidation reaction tank, and hydrogen sulfide gas is slowly added while vigorously stirring to carry out the sulfidation reaction.

[0075] The secondary sulfidation reaction process requires real-time monitoring of the concentration of copper arsenic ions and real-time feedback of the data to the PLC reaction control module to quickly calculate and analyze whether the sulfidation reaction endpoint has been reached (limit requirement: liquid phase copper concentration Cu 2+ ≈0mg / L), ensuring that the copper in the secondary sulfidation solution is fully precipitated and the arsenic is less precipitated. The change of copper and arsenic ion concentration in the real-time monitoring of the secondary sulfidation reaction is shown in Figure 3 .

[0076] from Figure 3 Several representative time points (see Table 4) are selected to calculate whether the secondary vulcanization reaction has reached the end point:

[0077] Table 4 Changes in copper arsenic ion concentrations during real-time monitoring of the secondary sulfidation reaction

[0078]

[0079] ①When t=10min, Cu 2+ =1341mg / L>0mg / L (limit value), the sulfidation end point has not been reached, so the reaction continues.

[0080] ②When t=20min, Cu 2+ =750mg / L>0mg / L (limit value), the sulfidation end point has not been reached, so the reaction continues.

[0081] ③When t=30min, Cu 2+ =0mg / L, the sulfidation endpoint has been reached, the reaction is terminated, and drainage and filtration are performed.

[0082] At this time, the Cu consumed by the reaction precipitation 2+=(2400-0)mg / L=2400mg / L; As 5+ =(8700-6800)mg / L=1900mg / L.

[0083] Substituting the concentrations of Cu and As consumed in the reaction into Formula 3, we can obtain the arsenic content in the slag:

[0084]

[0085] Substituting the concentrations of Cu and As consumed in the reaction into Formula 4, we can obtain the copper content in the slag:

[0086] The proportion of Cu in the filter residue:

[0087]

[0088] In summary, Cu accounts for 31.86% and As accounts for 25.22% in the slag phase.

[0089] 3. Three-stage vulcanization reaction process

[0090] The electrolyte after the secondary sulfidation is the liquid before the tertiary sulfidation reaction, and the copper arsenic ion concentration is shown in Table 5.

[0091] Table 5 Copper arsenic ion concentration in electrolyte before tertiary sulfidation

[0092]

[0093]

[0094] Finally, the electrolyte after secondary sulfidation is pumped into the tertiary sulfidation reaction tank, and hydrogen sulfide gas is slowly added while vigorously stirring to carry out the sulfidation reaction.

[0095] The three-stage sulfidation reaction process requires real-time monitoring of the copper arsenic ion concentration change, and the data is fed back to the PLC reaction control module in real time. Through rapid calculation and analysis, it is determined whether the sulfidation reaction end point has been reached (limit requirement: liquid phase arsenic concentration: As 5+ ≈1000mg / L), ensuring that the arsenic concentration in the third-stage sulfidation liquid is stable and meets the standard. The change of arsenic ion concentration in the third-stage sulfidation reaction is monitored in real time. Figure 4 .

[0096] from Figure 4 Several representative time points (see Table 6) are selected to calculate whether the tertiary vulcanization reaction has reached the end point:

[0097] Table 6 Changes in copper arsenic ion concentrations during real-time monitoring of the three-stage sulfidation reaction

[0098]

[0099] ①When t=10min, As 5 +=3600mg / L>1000mg / L (limit), the sulfidation end point has not yet been reached, so the reaction continues. ② When t=20min, As 5 +=1800mg / L>1000mg / L (limit), the sulfidation end point has not been reached, so the reaction continues. ③ When t=30min, As 5 + = 1000mg / L, the sulfidation end point has been reached, and the filtrate is discharged and filtered, and the filtrate is returned to the system. At this time, the As consumed by the reaction precipitation 5+ =6800mg / L-1000mg / L=5800mg / L,

[0100] Substituting the concentrations of Cu and As consumed in the reaction into Formula 3, we can obtain the arsenic content in the slag:

[0101]

[0102] The above description of the embodiments is to facilitate the understanding and application of the present invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims

1. A real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process, characterized in that: A three-stage copper-arsenic sulfidation reaction process based on the setup; In the first-stage copper-arsenic sulfidation reaction process, the concentration change of copper-arsenic ions in the first-stage copper-arsenic sulfidation reaction process is monitored in real time, and the critical point of slight drop of arsenic is determined by PLC calculation, and the air intake valve is closed and the discharge valve is opened, so that the copper is mostly precipitated and the arsenic is slightly precipitated in the sulfidation liquid discharged from the first-stage copper-arsenic sulfidation reaction process; In the secondary copper-arsenic sulfidation process, the concentration of copper-arsenic ions is monitored in real time, and the critical point where copper drops to near zero is determined by PLC calculation, and the air intake valve is closed and the discharge valve is opened, so that the copper is fully precipitated and the arsenic is less precipitated in the sulfidation liquid discharged from the secondary copper-arsenic sulfidation process. During the tertiary copper-arsenic sulfidation reaction, the changes in copper-arsenic ion concentration during the tertiary copper-arsenic sulfidation reaction are monitored in real time, and the PLC calculation is used to determine the critical point where the arsenic drops to the limit value, and the intake valve is closed and the discharge valve is opened, so that the arsenic concentration in the sulfide liquid discharged from the tertiary copper-arsenic sulfidation reaction process meets the standard.

2. The real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process according to claim 1, characterized in that: During the primary copper-arsenic sulfidation reaction, the change of the copper-arsenic ion concentration in the primary sulfidation reaction tank over time is monitored in real time, including the change of the copper ion from entering the liquid to leaving the liquid with the sulfidation time, and the change of the arsenic ion from entering the liquid to leaving the liquid with the sulfidation time, and the data is transmitted to the PLC in real time; when the PLC determines through analysis that the critical point of the arsenic ion concentration slightly decreases during the primary copper-arsenic sulfidation reaction, the PLC is used to control the closing of the air inlet valve and the opening of the drain valve of the primary sulfidation reaction tank to terminate the reaction, thereby ensuring that the discharged primary sulfidation liquid contains more copper and less arsenic.

3. The real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process according to claim 1 is characterized in that: During the secondary copper-arsenic sulfidation reaction, the change of the copper-arsenic ion concentration in the secondary sulfidation reaction tank over time is monitored in real time, including the change of the copper ion from entering the liquid to leaving the liquid with the sulfidation time, and the change of the arsenic ion from entering the liquid to leaving the liquid with the sulfidation time, and the data is transmitted to the PLC in real time; when the PLC determines through analysis that the copper ion concentration in the secondary copper-arsenic sulfidation reaction process drops to a critical point close to zero, the PLC is used to control the air inlet valve of the secondary sulfidation reaction tank to close and the drain valve to open, so as to terminate the reaction and ensure that the copper in the discharged secondary sulfidation liquid is fully precipitated and the arsenic is less precipitated.

4. The real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process according to claim 1, characterized in that: During the three-stage copper-arsenic sulfidation reaction, the change of the copper-arsenic ion concentration in the three-stage sulfidation reaction tank over time is monitored in real time, including the change of the copper ion from entering the liquid to leaving the liquid with the sulfidation time, and the change of the arsenic ion from entering the liquid to leaving the liquid with the sulfidation time, and the data is transmitted to the PLC in real time; when the PLC determines through analysis that the arsenic ion concentration in the three-stage copper-arsenic sulfidation reaction process drops to the critical point of the limit value, the PLC is used to control the air inlet valve of the three-stage sulfidation reaction tank to close and the drain valve to open, so as to terminate the reaction and ensure that the arsenic concentration in the discharged three-stage sulfidation liquid meets the standard.

5. The real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process according to claim 2, characterized in that: The critical point at which the arsenic ion concentration slightly decreases during the primary copper arsenic sulfidation reaction is: arsenic content ≤ 2.5%.

6. The real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process according to claim 3, characterized in that: The critical point at which the copper ion concentration drops to the limit value during the secondary copper-arsenic sulfidation reaction is: 0 mg / L.

7. The real-time monitoring method for the copper electrolyte purification copper arsenic sulfide separation process according to claim 4, characterized in that: The critical point at which the arsenic ion concentration drops to the limit value during the three-stage copper-arsenic sulfidation reaction is: 1000 mg / L.

8. A real-time monitoring system for the copper electrolyte purification copper arsenic sulfidation separation process, comprising a primary sulfidation reaction tank, a secondary sulfidation reaction tank, and a tertiary sulfidation reaction tank, characterized in that: It also includes a PLC reaction control module (1), a primary sulfide real-time monitoring module (2), a secondary sulfide real-time monitoring module (3), a tertiary sulfide real-time monitoring module (4), a hydrogen sulfide intake valve and a sulfide liquid discharge valve (5); The PLC reaction control module (1) comprises a primary copper sulfide arsenic reaction closed-loop control module (1-1), a secondary copper sulfide arsenic reaction closed-loop control module (1-2), and a tertiary copper sulfide arsenic reaction closed-loop control module (1-3); The primary copper arsenic sulfide reaction closed-loop control module (1-1) is in communication and electrical connection with the primary sulfidation real-time monitoring module (2) and the hydrogen sulfide intake valve and the sulfide liquid discharge valve (5), and is used to retrieve the copper arsenic ion concentration of the primary sulfidation real-time monitoring module (2) in real time, and when the critical point of the arsenic ion concentration slightly decreasing in the primary sulfidation process is determined by analysis, the primary sulfidation reaction tank hydrogen sulfide intake solenoid valve (5-1-1) in the hydrogen sulfide intake valve and the sulfide liquid discharge valve (5) is closed, and the primary sulfidation reaction tank sulfide liquid discharge ball valve (5-1-2) is opened to terminate the reaction; The secondary copper arsenic sulfide reaction closed-loop control module (1-2) is in communication and electrical connection with the secondary sulfidation real-time monitoring module (3) and the hydrogen sulfide intake valve and the sulfide liquid discharge valve (5), and is used to retrieve the copper arsenic ion concentration of the secondary sulfidation real-time monitoring module (3) in real time, and when it is determined by analysis that the copper ion concentration in the secondary sulfidation process drops to a critical point close to zero, the secondary sulfidation reaction tank hydrogen sulfide intake solenoid valve (5-2-1) in the hydrogen sulfide intake valve and the sulfide liquid discharge valve (5) is closed, and the secondary sulfidation reaction tank sulfide liquid discharge ball valve (5-2-2) is opened to terminate the reaction; The three-stage copper arsenic sulfide reaction closed-loop control module (1-3) is in communication and electrical connection with the three-stage sulfidation real-time monitoring module (4) and the hydrogen sulfide intake valve and the sulfide liquid discharge valve (5), and is used to retrieve the copper arsenic ion concentration of the three-stage sulfidation real-time monitoring module (4) in real time, and when the arsenic ion concentration in the three-stage sulfidation process drops to a critical point of a limit value through analysis and judgment, the three-stage sulfidation reaction tank hydrogen sulfide intake solenoid valve (5-3-1) in the interlocked hydrogen sulfide intake valve and the sulfide liquid discharge valve (5) is closed, and the three-stage sulfidation reaction tank sulfide liquid discharge ball valve (5-3-2) is opened to terminate the reaction; The primary sulfidation real-time monitoring module (2) is installed at the primary sulfidation reaction tank, and is used to monitor the change of copper arsenic ion concentration over time during the primary sulfidation process, with a focus on monitoring the critical point where the arsenic ion concentration begins to slightly decrease, and the corresponding reaction time is the reaction end point liquid discharge time; real-time monitoring of the change of copper ions from liquid entry to liquid exit as the sulfidation time changes, and the change of arsenic ions from liquid entry to liquid exit as the sulfidation time changes, and transmits the data in real time to the primary copper arsenic sulfide reaction closed-loop control module (1-1) in the PLC reaction control module (1); The secondary sulfidation real-time monitoring module (3) is installed at the secondary sulfidation reaction tank and is used to monitor the change of copper arsenic ion concentration over time during the secondary sulfidation process, with a focus on monitoring the critical point where the copper ion concentration drops to near zero, and the corresponding reaction time is the reaction endpoint discharge time; Real-time monitoring of the change of copper ions from entering the liquid to exiting the liquid as the sulfidation time progresses, and the change of arsenic ions from entering the liquid to exiting the liquid as the sulfidation time progresses, and transmitting the data in real time to the secondary copper sulfide arsenic reaction closed-loop control module (1-2) in the PLC reaction control module (1); The three-stage sulfidation real-time monitoring module (4) is installed at the three-stage sulfidation reaction tank, and is used to monitor the change of copper arsenic ion concentration over time during the three-stage sulfidation process, focusing on monitoring the critical point at which the arsenic ion concentration drops to the limit value, and the corresponding reaction time is the reaction end point liquid discharge time; real-time monitoring of the change of copper ions from liquid entry to liquid exit as the sulfidation time changes, and the change of arsenic ions from liquid entry to liquid exit as the sulfidation time changes, and transmitting the data in real time to the three-stage copper arsenic sulfide reaction closed-loop control module (1-3) in the PLC reaction control module (1); The hydrogen sulfide intake valve and sulfide liquid discharge valve (5) comprise a primary sulfide reaction tank hydrogen sulfide intake solenoid valve (5-1-1) and a primary sulfide reaction tank sulfide liquid discharge ball valve (5-1-2), a secondary sulfide reaction tank hydrogen sulfide intake solenoid valve (5-2-1) and a secondary sulfide reaction tank sulfide liquid discharge ball valve (5-2-2), a tertiary sulfide reaction tank hydrogen sulfide intake solenoid valve (5-3-1) and a tertiary sulfide reaction tank sulfide liquid discharge ball valve (5-3-2); The primary sulfide reaction tank hydrogen sulfide intake solenoid valve (5-1-1) and the primary sulfide reaction tank sulfide liquid discharge ball valve (5-1-2) are installed at the primary sulfide reaction tank and can be opened and closed accordingly according to the instructions of the primary copper sulfide arsenic reaction closed-loop control module (1-1) in the PLC reaction control module (1); The secondary sulfidation reaction tank hydrogen sulfide intake solenoid valve (5-2-1) and the secondary sulfidation reaction tank sulfide liquid discharge ball valve (5-2-2) are installed at the secondary sulfidation reaction tank and can be opened and closed accordingly according to the instructions of the secondary copper sulfide arsenic reaction closed-loop control module (1-2) in the PLC reaction control module (1); The three-stage sulfidation reaction tank hydrogen sulfide intake solenoid valve (5-3-1) and the three-stage sulfidation reaction tank sulfide liquid discharge ball valve (5-3-2) are installed at the three-stage sulfidation reaction tank and can be opened and closed accordingly according to the instructions of the three-stage copper sulfide arsenic reaction closed-loop control module (1-3) in the PLC reaction control module (1).

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