Real-time monitoring system and method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning

Abstract

A real-time monitoring system and method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning is provided. The system includes a PLC control module, a primary mother liquor real-time monitoring module, an de-arsenication circulating solution real-time monitoring module, a de-arsenicated solution real-time monitoring module, and an accurate regulation module. The present invention utilizes copper-arsenic electrowinning and concentration competition differences, with the difference and limit of copper arsenic concentration in the de-arsenication circulating liquid as the constraint indexs, and the PLC control module is configured to control monitoring modules to acquire copper and arsenic concentrations in a primary mother liquor, an de-arsenication circulating solution and a de-arsenicated solution in real time, to calculate and analyze required copper and arsenic ion concentrations in the de-arsenication circulating solution, and to accurately regulate dosage volume of the primary mother liquor with high copper and arsenic concentrations.

Description

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of and priority to Chinese Patent Application No. 202411638567.1, filed Nov. 18, 2024, which is hereby incorporated by reference herein in its entirety.TECHNICAL FIELD

[0002] The present disclosure belongs to the technical field of clean production of electrolyte purification systems in the copper smelting industry, and particularly relates to a real-time monitoring system and method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning.BACKGROUND

[0003] Electrowinning de-arsenication of copper electrolytic refining is a widely used electrolyte purification method in the industry. Due to close electrode potentials of copper and arsenic, it is prone to co-deposition. When a copper ion concentration is too low, it is highly prone to generating a highly toxic arsine gas during electrodeposition of arsenic, making safe production impossible. When the copper ion concentration is too high, it is highly prone to causing co-deposition of copper during electrodeposition of arsenic, leading to resource loss. To maintain a certain concentration of copper ion and concentration of arsenic ion in the system in the production of enterprises, it is necessary to detect and analyze a primary mother liquor, a de-arsenication circulating solution and a de-arsenicated solution. By regulating dosage volume of high-concentration primary mother liquor, it is ensured that the copper ion concentration and the arsenic ion concentration in the process of de-arsenic by electrowinning are within the optimal de-arsenic range (the arsenic ion concentration is always greater than the copper ion concentration, the copper ion can fluctuate in the range of 2-5 g / L, and the arsenic ion can fluctuate in the range of 3-10 g / L), the copper ion concentration of the de-arsenicated solution is controlled to be approximately less than or equal to 0.5 g / L, and the arsenic ion concentration of the de-arsenicated solution is controlled to be approximately less than or equal to 2.0 g / L. However, the time for detecting and analyzing the primary mother liquor, the de-arsenication circulating solution and de-arsenicated solution for electrowinning-based de-arsenic unit in the enterprise laboratory is as long as 2-4 hours at present, the copper and arsenic ion concentrations of the solution in the electrolytic process are constantly changing, and the existing detection and analysis frequency cannot meet the requirements of dynamic regulation of electrolytic process. This leads to the arsine evolution when the copper concentration is too low and the co-deposition of copper when the copper concentration is too high during electrowinning. Arsenic hazardous waste increases the loss of copper resources, which not only increases the production cost of enterprises, but also produces a series of safety and environmental protection hazards.

[0004] The copper smelting industry urgently needs to invent a real-time monitoring system and method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning. By monitoring target ion concentrations in the primary mother liquor, de-arsenication circulating solution and de-arsenicated solution in real time, the dosage volume of high-concentration primary mother liquor can be accurately regulated to ensure that the copper ion concentration and the arsenic ion concentration are in the optimal de-arsenic range during de-arsenic by electrowinning. The evolution of arsine during deposition is suppressed, the deposition efficiency of de-arsenic residue is improved, and the residual copper concentration in the de-arsenicated solution is reduced, and thus both safety and production requirements of the enterprise are satisfied.SUMMARY

[0005] The present disclosure provides a real-time monitoring system and method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning, aiming at the problems that an electrolytic process of electrowinning de-arsenication in copper electrolytic refining cannot be dynamically regulated, arsenide is evolved when the copper concentration is too low, copper is co-deposited when the copper concentration is too high, and arsenic hazardous waste increases the loss of copper resources, thereby achieving rapid regulation of the optimal copper concentration and arsenic concentration, ensuring that copper ion concentration and arsenic ion concentration in the electrowinning de-arsenic process are in the optimal de-arsenic range, suppressing the arsine evolution in the deposition process, improving the deposition efficiency of de-arsenication residues, and reducing residual copper concentration in a de-arsenicated solution.

[0006] To achieve the above objectives, the present disclosure employs the technical solution as follows:

[0007] in a first aspect, the present disclosure provides a real-time monitoring method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning:

[0008] based on a configured copper electrowinning-based de-arsenic reaction process includes a primary mother liquor tank, a de-arsenication circulating solution tank, an electrowinning de-arsenication reactor and a de-arsenicated solution tank, the method includes the following steps:

[0009] first: monitoring a copper ion concentration Ct1 and an arsenic ion concentration Cs1 in the primary mother liquor tank, a copper ion concentration Ct2 and an arsenic ion concentration Cs2 in the de-arsenication circulating solution tank, and a copper ion concentration Ct3 and an arsenic ion concentration Cs3 in the de-arsenicated solution tank in real time;

[0010] second: acquiring allowable variation ranges of the copper ion concentration Ct2 and the arsenic ion concentration Cs2 for a de-arsenication circulating solution: 2 g / L≤Ct2≤5 g / L, and 3 g / L≤Cs2≤10 g / L, as well as an effluent constraint index of the de-arsenication circulating solution entering the electrowinning de-arsenication reactor: Cs2>Ct2≥2 g / L;

[0011] third: establishing a copper concentration equation set and an arsenic concentration equation set based on monitored copper ion concentration data and arsenic ion concentration data and actual volume of the de-arsenication circulating solution tank:2⁢ g / L≤Ct⁢1×V1+Ct⁢2×V2V1+V2≤5⁢ g / L3⁢ g / L≤Cs⁢1×V1+Cs⁢2×V2V1+V2≤10⁢ g / Lwhere, V1 denotes inflow volume of primary mother liquor, and V2 denotes the actual volume of the de-arsenication circulating solution tank;fourth: solving foregoing simultaneous equation set to obtain the inflow volume V1 of the primary mother liquor which simultaneously meets the allowable variation ranges of the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution, thereby ensuring that the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution maintains in the allowable variation ranges of electrowinning arsenic removal after the primary mother liquor is added into the de-arsenication circulating solution and a de-arsenicated solution returns to the de-arsenication circulating solution periodically; andfifth: regulating a diversion direction of effluent of the de-arsenicated solution, and in a case that the effluent meets process index requirements of Cs3≤2 g / L and Ct3≤0.5 g / L, entering the effluent into an electrolytic refining system in a next procedure; and in a case that the effluent fails to meet the process index requirements of Cs3>2 g / L and Ct3>0.5 g / L, returning the effluent to the primary mother liquor tank for reuse.

[0014] In a second aspect, the present disclosure provides a real-time monitoring system for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning:

[0015] the system includes a primary mother liquor tank, a de-arsenication circulating solution tank, an electrowinning de-arsenication reactor, a de-arsenicated solution tank, a programmable logic controller (PLC) control module, a primary mother liquor real-time monitoring module, a de-arsenication circulating solution real-time monitoring module, a de-arsenicated solution real-time monitoring module, and an accurate regulation module;

[0016] an input pipeline of the primary mother liquor tank is connected to a concentrated crystallized copper solution, an output pipeline of the primary mother liquor tank is connected to the de-arsenication circulating solution tank, an output pipeline of the de-arsenication circulating solution tank is connected to the de-arsenicated solution tank via the electrowinning de-arsenication reactor, an output pipeline of the de-arsenicated solution tank is connected to an electrolytic refining system in a next procedure. A return pipeline is connected between the de-arsenicated solution tank and the de-arsenication circulating solution tank, and a return pipeline is connected between the de-arsenicated solution tank and the primary mother liquor tank;

[0017] the PLC control module is in communication and electrical connection with the primary mother liquor real-time monitoring module, the de-arsenication circulating solution real-time monitoring module, the de-arsenicated solution real-time monitoring module and the accurate regulation module. The PLC control module is configured to send operation instructions to the primary mother liquor real-time monitoring module, the de-arsenication circulating solution real-time monitoring module and the de-arsenicated solution real-time monitoring module and to receive real-time monitoring data fed back. The PLC control module is configured to send an instruction to the accurate regulation module based on the real-time monitoring data fed back to regulate valve opening, to acquire appropriate inflow volume from the primary mother liquid tank to the de-arsenication circulating solution tank, and to regulate a diversion direction of effluent from the de-arsenicated solution tank;

[0018] the primary mother liquor real-time monitoring module is installed in the primary mother liquor tank and in communication and electrical connection with the PLC control module, and is configured to monitor a copper ion concentration and an arsenic ion concentration in the primary mother liquor tank in real time according to an operation instruction from the PLC control module, and to transmit the copper ion concentration and the arsenic ion concentration in the primary mother liquor tank to the PLC control module in real time through feedback;

[0019] the de-arsenication circulating solution real-time monitoring module is installed in the de-arsenication circulating solution tank and in communication and electrical connection with the PLC control module, and is configured to monitor a copper ion concentration and an arsenic ion concentration in the de-arsenication circulating solution tank in real time according to an operation instruction from the PLC control module, and to transmit the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution tank to the PLC control module in real time through feedback;

[0020] the de-arsenicated solution real-time monitoring module is installed in the de-arsenicated solution tank and in communication and electrical connection with the PLC control module, and is configured to monitor a copper ion concentration and an arsenic ion concentration in the de-arsenicated solution tank in real time according to an operation instruction from the PLC control module, and to transmit the copper ion concentration and the arsenic ion concentration in the de-arsenicated solution tank to the PLC control module in real time through feedback;

[0021] the accurate regulation module includes a first accurate regulation module and a second accurate regulation module. The first accurate regulation module is installed on a pipeline between the primary mother liquor tank and the de-arsenication circulating solution tank and in communication and electrical connection with the PLC control module. The first accurate regulation module includes a solenoid regulating valve and a volume flowmeter (FM), and is configured to measure parameters by using the volume flowmeter and adjust opening of the solenoid regulating valve according to the instruction from the PLC control module. The second accurate regulation module is installed at an output end of the de-arsenicated solution tank, and is in communication and electrical connection with the PLC control module. The second accurate regulation module includes multiple solenoid regulating valve (RV) sets and a flow diversion pipeline, and is configured to open or close the solenoid regulating valve sets and convey effluent of an de-arsenicated solution to the electrolytic refining system in the next procedure or return the effluent of the de-arsenicated solution to the primary mother liquor tank through the flow diversion pipeline based on the instruction from the PLC control module.

[0022] The present disclosure has beneficial effects as follows:

[0023] the present disclosure provides real-time monitoring system and method for inhibiting arsine evolution in electrodeposition de-arsenic process of copper electrowinning. The system includes a PLC control module, a primary mother liquor real-time monitoring module, a de-arsenication circulating solution real-time monitoring module, an de-arsenicated solution real-time monitoring module, and an accurate regulation module. By using copper-arsenic electrowinning and difference in copper-arsenic concentration competition and taking concentration difference and limit value of copper and arsenic in a de-arsenication circulating solution as constraint indexes, the PLC control module is configured to control the monitoring modules to acquire copper ion concentration and arsenic ion concentration in a primary mother liquor, a de-arsenication circulating solution and an de-arsenicated solution in real time, to calculate and analyze required copper ion concentration and arsenic ion concentration in the de-arsenication circulating solution, and to accurately regulate the dosage volume of the primary mother liquor with high copper ion concentration and arsenic ion concentration to ensure that the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution remain within an optimal range of arsenic removal by electrowinning after a de-arsenicated solution periodically returns, thereby, improving arsenic deposition, reducing copper deposition, suppressing the evolution of highly toxic arsine gas, accurately regulating flow diversion of the de-arsenicated solution, so as to achieve efficient arsenic removal while meeting the requirements of enterprises for safe production.BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG. 1 is a system block diagram and a control route diagram according to the present disclosure.

[0025] FIG. 2 is a diagram showing variations of copper and arsenic ion concentrations in primary mother liquor from a sample in actual plant operating conditions.

[0026] FIG. 3 is a diagram showing variations of copper and arsenic ion concentrations in a de-arsenication circulating solution from a sample in actual plant operating conditions.

[0027] FIG. 4 is a diagram showing variations of copper and arsenic ion concentrations in a de-arsenicated solution from a sample in actual plant operating conditions.DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] To make the objectives, technical solutions and advantages of embodiments of the present disclosure more clearly, the technical solutions in the embodiments are described clearly and completely below with reference to the accompanying drawings in the embodiments of the present disclosure. The following embodiments are used for the description of the present disclosure.

[0029] Refer to FIG. 1, a system provided by the present disclosure includes a primary mother liquor tank, a de-arsenication circulating solution tank, an electrowinning de-arsenication reactor, a de-arsenicated solution tank, a PLC control module 1, a primary mother liquor real-time monitoring module 2, a de-arsenication circulating solution real-time monitoring module 3, a de-arsenicated solution real-time monitoring module 4, and an accurate regulation module 5.

[0030] Refer to FIG. 1, a connection mode of the primary mother liquor tank, the de-arsenication circulating solution tank, the electrowinning de-arsenication reactor and the de-arsenicated solution tank is as follows: an input pipeline of the primary mother liquor tank is connected to a concentrated crystallized copper solution, an output pipeline of the primary mother liquor tank is connected to the de-arsenication circulating solution tank, an output pipeline of the de-arsenication circulating solution tank is connected to the de-arsenicated solution tank via the electrowinning de-arsenic removal, an output pipeline of the de-arsenicated solution tank is connected to an electrolytic refining system in a next procedure. A return pipeline is connected between the de-arsenicated solution tank and the de-arsenication circulating solution tank, and a return pipeline is connected between the de-arsenicated solution tank and the primary mother liquor tank.

[0031] Refer to FIG. 1, the PLC control module 1 is in communication and electrical connection with the primary mother liquor real-time monitoring module 2, the de-arsenication circulating solution real-time monitoring module 3, the de-arsenicated solution real-time monitoring module 4 and the accurate regulation module 5, and can achieve the following functions.

[0032] control monitoring: the PLC control module 1 can send operation instructions A-1, A-2 and A-3 to the primary mother liquor real-time monitoring module 2, the de-arsenication circulating solution real-time monitoring module 3 and the de-arsenicated solution real-time monitoring module 4 simultaneously, and is responsible for receiving A-1 feedback information, A-2 feedback information and A-3 feedback information, thereby acquiring a copper ion concentration Ct1 and an arsenic ion concentration Cs1 in a primary mother liquor through the A-1 feedback, a copper ion concentration Ct2 and an arsenic ion concentration Cs2 in an de-arsenication circulating solution through the A-2 feedback, and a copper ion concentration Ct3 and an arsenic ion concentration Cs3 in the de-arsenicated solution through the A-3 feedback.

[0033] Refer to FIG. 2, FIG. 3 and FIG. 4, copper ion concentrations and arsenic ion concentrations in the primary mother liquor, the de-arsenication circulating solution and the de-arsenicated solution in a sample from actual plant operating conditions are shown, respectively.

[0034] Data analysis: allowable variation ranges of the copper ion concentration Ct2 and arsenic ion concentration Cs2 for a de-arsenication circulating process are: 2 g / L≤Ct2≤5 g / L, 3 g / L≤Cs2≤10 g / L, and an effluent constraint index of an de-arsenication circulating solution entering electrowinning de-arsenication reactor is Cs2>Ct2≥2 g / L, that is, the copper ion concentration and the arsenic ion concentration may be both high or both low, but the arsenic ion concentration is required to be greater than the copper ion concentration (to suppress copper electrodeposition), and the copper ion concentration is required to be greater than or equal to 2 g / L (to suppress arsine evolution). Firstly, copper concentration equation set (1) and an arsenic concentration equation set (2) are listed.2⁢ g / L≤Ct⁢1×V1+Ct⁢2×V2V1+V2≤5⁢ g / L(1)3⁢ g / L≤Cs⁢1×V1+Cs⁢2×V2V1+V2≤10⁢ g / L(2)where, V1 denotes inflow volume of primary mother liquor, and V2 denotes actual volume of the de-arsenication circulating solution tank.According to the copper concentration data and arsenic concentration data fed back by the monitoring modules in real time and the actual volume of the de-arsenication circulating solution tank, the simultaneous equations (1) and (2) are solved to acquire the inflow volume V1 of high-concentration primary mother liquor which meets copper ion concentration and arsenic ion concentration in the de-arsenication circulating solution at the same time.

[0036] Accurate regulation: based on the analysis data results, the PLC control module 1 can send an instruction B to a first accurate regulation module 5-1 to regulate valve opening to obtain appropriate inflow volume V1 of the primary mother liquor. Based on the real-time monitoring data, the PLC control module 1 can send an instruction C to a second accurate regulation module 5-2 to control a diversion direction of effluent of a de-arsenicated solution. If the effluent meets process index requirements of Cs3≤2 g / L, Ct3≤0.5 g / L, the effluent enters an electrolytic refining system in a next procedure. If the effluent does not meet the process index requirements of Cs3>2 g / L, Ct3>0.5 g / L, the effluent is returned to the primary mother liquor for reuse.

[0037] Refer to FIG. 1, the primary mother liquor real-time monitoring module 2 is installed in the primary mother liquor tank and in communication and electrical connection with the PLC control module 1, and is configured to monitor a copper ion concentration Ct1 and an arsenic ion concentration Cs1 in the primary mother liquor tank in real time according to the instruction A-1 from the PLC control module 1, and to transmit the copper ion concentration Ct1 and the arsenic ion concentration Cs1 to the PLC control module 1 in real time through the A-1 feedback.

[0038] Refer to FIG. 1, the de-arsenication circulating solution real-time monitoring module 3 is installed in the de-arsenication circulating solution tank and in communication and electrical connection with the PLC control module 1, and is configured to monitor a copper ion concentration Ct2 and an arsenic ion concentration Cs2 in the de-arsenication circulating solution tank in real time according to the instruction A-2 from the PLC control module 1, and to transmit the copper ion concentration Ct2 and an arsenic ion concentration Cs2 to the PLC control module 1 in real time through the A-2 feedback.

[0039] Refer to FIG. 1, the de-arsenicated solution real-time monitoring module 4 is installed in the de-arsenicated solution tank and in communication and electrical connection with the PLC control module 1, and is configured to monitor a copper ion concentration Ct3 and an arsenic ion concentration Cs3 in the de-arsenicated solution tank in real time according to the instruction A-3 from the PLC control module 1, and to transmit the copper ion concentration Ct3 and the arsenic ion concentration Cs3 to the PLC control module 1 in real time through the A-3 feedback.

[0040] Refer to FIG. 1, the accurate regulation module 5 includes a first accurate regulation module 5-1 mounted on a pipeline between the primary mother liquor tank and the de-arsenication circulating solution tank and a second accurate regulation module 5-2 mounted at an output end of the de-arsenicated solution tank. The first accurate regulation module 5-1 and the second accurate regulation module 5-2 are both in communication and electrical connection with the PLC control module 1. The first accurate regulation module 5-1 includes a solenoid regulating valve and a volume flowmeter, and can measure parameters by using the volume flowmeter and dynamically regulate opening of the solenoid regulating valve according to the instruction B from the PLC control module 1, thereby accurately controlling inflow volume V1 of the primary mother liquor, ensuring that the total copper entering the de-arsenication circulating solution tank, expressed as Ttotal copper=Ct1*V1 meets a data analysis requirement of the PLC control module 1. The second accurate regulation module 5-2 includes plurality of solenoid regulating valve sets and a flow diversion pipeline and is configured to open or close the solenoid regulating valve sets according to the instruction C from the PLC control module 1 to allow qualified liquid to enter the next procedure and unqualified liquid to be returned to the primary mother liquor tank.

[0041] Refer to FIG. 1, there is a “periodic circulation” arrow pointing to the de-arsenication circulating solution tank in the de-arsenicated solution tank, that is, a low-concentration solution in the de-arsenicated solution tank will be periodically circulated to the de-arsenication solution circulating tank. This is because the solution in the de-arsenication circulating solution tank is required to be replenished in real time as it is consumed. The replenishment primarily consists of de-arsenicated solution, with a small amount of primary mother liquor.

[0042] It should be noted that the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution should be adjusted to within a specific range before entering the electrowinning arsenic removal procedure. The de-arsenicated solution, which has low copper ion concentration and low arsenic ion concentration, is preferentially and periodically returned to the de-arsenication circulating solution tank for mixing to maintain water balance. Only when the continuous addition of primary mother liquor may cause excessive volume of the de-arsenication circulating solution, the surplus de-arsenicated solution can enter the subsequent electrolytic refining system. The continuous return of the de-arsenicated solution to the de-arsenication circulating solution for mixing leads to continuous decrease of the copper ion concentration and arsenic ion concentration, so that the dosage volume of the primary mother liquor, which contains high concentrations of copper and arsenic, needs to be precisely regulated based on the copper ion concentration and arsenic ion concentration requirements in the de-arsenication circulating solution, thereby ensuring that the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution remain within the optimal range for the electrowinning process after each periodic return of the de-arsenicated solution.EMBODIMENTTABLE 1Basic informationPrimary motherDe-arsenicationDe-arsenicatedSpecies andliquorcirculating solutionsolutionconcentration (g / L)Ct1Cs1Ct2Cs2Ct3Cs3Concentration of20-402-50.1-1.0copper ion Cu2+Concentration of18-253-100.5-5.0arsenic ion As5+1) Data of monitoring module: the copper ion concentration and the arsenic ion concentration in the primary mother liquor, the de-arsenication circulating solution and the de-arsenicated solution are always in dynamic variation, it is assumed that the measured values before regulation are as follows: in the primary mother liquor, Ct1=25 g / L and Cs1=22 g / L; in the de-arsenication circulating solution, Ct2=3 g / L and Cs2=8 g / L; and in the de-arsenicated solution, Ct1=0.3 g / L and Cs1=3 g / L;

[0044] 2) based on the known structural data of the enterprise facilities: the volume of the de-arsenication circulating solution tank is set as follows: V2=200 m3;

[0045] 3) because the copper concentration Ct2 and the arsenic concentration Cs2 in the de-arsenication circulating solution tank are always kept as Ct2≥2 g / L and Cs2≥3 g / L (the de-arsenicated solution periodically returns to the de-arsenication circulating solution tank), it is only required to determine the dosage volume V1 of the primary mother liquor under the condition that the copper concentration Ct2≤5 g / L and the arsenic concentration Cs2≤10 g / L;

[0046] the simultaneous equationsCt⁢1×V1+Ct⁢2×V2V1+V2≤5⁢ g / L(1)andCs⁢1×V1+Cs⁢2×V2V1+V2≤10⁢ g / L(2)are solved.that is,V1≤5×V2-Ct⁢2×V2Ct⁢1-5(1)andV1≤10×V2-Cs⁢2×V2Cs⁢1-10(2)is obtained.The measured data in 1) is substituted into above expression, then: (1) V1≤5×V2-Ct⁢2×V2Ct⁢1-5=5×2⁢0⁢0-3×2⁢0⁢02⁢5-5=20⁢ m3 / h,(1)V1≤1⁢0×V2-Cs⁢2×V2Cs⁢1-10=1⁢0×2⁢0⁢0-8×2⁢0⁢02⁢2-1⁢0=33⁢ m3 / h;(2)thus, when the requirements of (1) and (2) need to be met at the same time, the value is that V1≤20 m3 / h;it is assumed that a value V1=18 m3 / h, and the data is substituted into the expression to obtain the copper ion concentration and arsenic ion concentration in the de-arsenication circulating solution after the primary mother liquor is added for regulation as follows:the copper concentration is as follows:Ct⁢1×V1+Ct⁢2×V2V1+V2=2⁢5×1⁢8+3×2⁢0⁢01⁢8+2⁢0⁢0=4.8 g / L,(1)which meets the requirement of 2 g / L≤Ct2≤5 g / L; andthe arsenic concentration is as follows:Cs⁢1×V1+Cs⁢2×V2V1+V2=2⁢2×1⁢8+8×2⁢0⁢01⁢8+2⁢0⁢0=9.2 g / L,(2)which meets the requirement of 3 g / L≤Cs2≤10 g / L.The above description of the embodiment is intended to facilitate the understanding and application of the present disclosure by those of ordinary skill in the art. Those skilled in the art will readily appreciate that various modifications can be made to these embodiments and apply the general principles described herein to other embodiments without inventive effort. Therefore, the present disclosure is not limited to the embodiments described here. Any improvements or modifications made by a person skilled in the art based on the disclosure of the present disclosure, without departing from the scope thereof, shall fall within the scope of protection of the present disclosure.

Claims

1. A real-time monitoring method for inhibiting arsine evolution in de-arsenic process of copper electrowinning, comprising:based on a configured copper electrowinning-based arsenic removal reaction process comprising a primary mother liquor tank, a de-arsenication circulating solution tank, an electrowinning de-arsenication reactor and a de-arsenicated solution tank:first: monitoring a copper ion concentration Ct1 and an arsenic ion concentration Cs1 in the primary mother liquor tank, a copper ion concentration Ct2 and an arsenic ion concentration Cs2 in the de-arsenication circulating solution tank, and a copper ion concentration Ct3 and an arsenic ion concentration Cs3 in the de-arsenicated solution tank in real time;second: acquiring allowable variation ranges of the copper ion concentration Ct2 and the arsenic ion concentration Cs2 for a de-arsenication circulating solution: 2 g / L Ct2≤5 g / L, and 3 g / L≤Cs2≤10 g / L, as well as an effluent constraint index of the de-arsenication circulating solution entering the electrowinning de-arsenication reactor: Cs2>C2≥2 g / L;third: establishing a copper concentration equation set and an arsenic concentration equation set based on monitored copper ion concentration data and arsenic ion concentration data and actual volume of the de-arsenication circulating solution tank:2⁢ g / L≤Ct⁢1×V1+Ct⁢2×V2V1+V2≤5⁢ g / L3⁢ g / L≤Cs⁢1×V1+Cs⁢2×V2V1+V2≤10⁢ g / Lwherein V1 denotes inflow volume of primary mother liquor, and V2 denotes the actual volume of the de-arsenication circulating solution tank;fourth: solving foregoing simultaneous equation set to obtain the inflow volume V1 of the primary mother liquor which simultaneously meets the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution, thereby ensuring that the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution maintains in an optimal range of electrowinning de-arsenication after the primary mother liquor is added into the de-arsenication circulating solution and a de-arsenicated solution returns to the de-arsenication circulating solution periodically; andfifth: regulating a diversion direction of effluent of the de-arsenicated solution, and in a case that the effluent meets process index requirements, namely Cs3≤2 g / L and Ct3≤0.5 g / L, entering the effluent into an electrolytic refining system in a next procedure, and in a case that the effluent fails to meet the process index requirements, namely Cs3≥2 g / L and C3≥0.5 g / L, returning the effluent to the primary mother liquor tank for reuse.

2. A real-time monitoring system for inhibiting arsine evolution in de-arsenic process of copper electrowinning, comprising:a primary mother liquor tank, a de-arsenication circulating solution tank, an electrowinning de-arsenication reactor, a de-arsenicated solution tank, a programmable logic controller (PLC) control module (1), a primary mother liquor real-time monitoring module (2), a de-arsenication circulating solution real-time monitoring module (3), a de-arsenicated solution real-time monitoring module (4), and an accurate regulation module (5);an input pipeline of the primary mother liquor tank is connected to a concentrated crystallized copper solution, an output pipeline of the primary mother liquor tank is connected to the de-arsenication circulating solution tank, an output pipeline of the de-arsenication circulating solution tank is connected to the de-arsenicated solution tank via the electrowinning de-arsenication reactor, an output pipeline of the de-arsenicated solution tank is connected to an electrolytic refining system in a next procedure; a return pipeline is connected between the de-arsenicated solution tank and the de-arsenication circulating solution tank, and a return pipeline is connected between the de-arsenicated solution tank and the primary mother liquor tank;the PLC control module (1) is in communication and electrical connection with the primary mother liquor real-time monitoring module (2), the de-arsenication circulating solution real-time monitoring module (3), the de-arsenicated solution real-time monitoring module (4) and the accurate regulation module (5); the PLC control module (1) is configured to send operation instructions to the primary mother liquor real-time monitoring module (2), the de-arsenication circulating solution real-time monitoring module (3) and the de-arsenicated solution real-time monitoring module (4) and to receive real-time monitoring data fed back; and the PLC control module (1) is configured to send an instruction to the accurate regulation module (5) based on the real-time monitoring data fed back to regulate valve opening, to acquire appropriate inflow volume from the primary mother liquid tank to the de-arsenication circulating solution tank, and to regulate a diversion direction of effluent from the de-arsenicated solution tank;the primary mother liquor real-time monitoring module (2) is installed in the primary mother liquor tank and in communication and electrical connection with the PLC control module (1), and is configured to monitor a copper ion concentration and an arsenic ion concentration in the primary mother liquor tank in real time according to an operation instruction from the PLC control module (1), and to transmit the copper ion concentration and the arsenic ion concentration in the primary mother liquor tank to the PLC control module (1) in real time through feedback;the de-arsenication circulating solution real-time monitoring module (3) is installed in the de-arsenication circulating solution tank and in communication and electrical connection with the PLC control module (1), and is configured to monitor a copper ion concentration and an arsenic ion concentration in the de-arsenication circulating solution tank in real time according to an operation instruction from the PLC control module (1), and to transmit the copper ion concentration and the arsenic ion concentration in the de-arsenication circulating solution tank to the PLC control module (1) in real time through feedback;the de-arsenicated solution real-time monitoring module (4) is installed in the de-arsenicated solution tank and in communication and electrical connection with the PLC control module (1), and is configured to monitor a copper ion concentration and an arsenic ion concentration in the de-arsenicated solution tank in real time according to an operation instruction from the PLC control module (1), and to transmit the copper ion concentration and the arsenic ion concentration in the de-arsenicated solution tank to the PLC control module (1) in real time through feedback; andthe accurate regulation module (5) comprises a first accurate regulation module (5-1) and a second accurate regulation module (5-2); the first accurate regulation module (5-1) is installed on a pipeline between the primary mother liquor tank and the de-arsenication circulating solution tank and in communication and electrical connection with the PLC control module (1), comprises a solenoid regulating valve and a volume flowmeter, and is configured to measure parameters by using the volume flowmeter and adjust opening of the solenoid regulating valve according to the instruction from the PLC control module; the second accurate regulation module (5-2) is installed at an output end of the de-arsenicated solution tank and in communication and electrical connection with the PLC control module (1), comprises a plurality of solenoid regulating valve sets and a flow diversion pipeline, and is configured to open or close the solenoid regulating valve sets and convey effluent of an de-arsenicated solution to the electrolytic refining system in the next procedure or return the effluent of the de-arsenicated to the primary mother liquor tank through the flow diversion pipeline based on the instruction from the PLC control module.

Images