CN113998767B - Electrocatalytic pH value treatment system based on automatic control - Google Patents
Electrocatalytic pH value treatment system based on automatic control Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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Abstract
The invention provides an electrocatalytic pH value treatment system based on automatic control, which comprises a pH sensor (2) for detecting the pH value of electroplating waste liquid in real time, a pH regulator (3) for adding compound alkali dropwise according to the instruction of the controller (4), and a controller (4) for receiving the signal of the pH sensor (2) in real time, calculating and outputting the instruction to the pH regulator (3); the controller (4) calculates and obtains PID control feedback quantity and control system regulating quantity through error variable, then obtains pH value regulating quantity through PID control feedback quantity and control system regulating quantity, and realizes further regulation of error feedback quantity through introduction of error second derivative, matching with error value and error first derivative, so as to ensure that an automatic system is further regulated stably, and the pH value in the electrocatalytic process is stabilized at a target value.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to an electrocatalytic pH value treatment system based on automatic control.
Background
Industrial pollution refers to pollution of waste gas, waste water and solid emissions formed in industrial production processes to the environment; industrial pollution not only damages living environment of living beings, but also directly endangers physical health of human beings. In industrial pollution, industrial wastewater is a common type, and the most main pollution source in the industrial wastewater is electroplating wastewater; the source of the electroplating wastewater is generally plating part cleaning water, waste electroplating liquid, other wastewater (such as scouring workshop floor, scrubbing polar plate washing water, ventilation equipment condensed water, various bath liquids and drainage caused by 'running, overflowing, dripping and leaking' due to seepage or improper operation management of a plating tank), equipment cooling water and the like; the electroplating wastewater has complex water quality and difficult control of components, and pollutants comprise heavy metals (nickel, chromium, copper, zinc and the like) and complexing agents, wherein the existing forms of the heavy metal complexes, heavy metal ions, organic matters and the like are heavy metal complexes, heavy metal ions, organic matters and the like, and some of the heavy metal complexes are carcinogenic, teratogenic and mutagenic highly toxic substances; currently, the concentration of contaminants in electroplating wastewater composed of these substances is as high as several thousand milligrams per liter, far exceeding the discharge standard of electroplating wastewater.
In the prior art, aiming at electroplating wastewater treatment, more treatment methods are mainly an air floatation method, an ion exchange method, an electrocatalytic method and an extraction method. The electrocatalytic method mainly generates active groups such as superoxide radicals, hydrogen peroxide, hydroxyl radicals and the like to act on organic matters in water through the action of electrodes and catalytic materials, and the organic matters undergo rapid oxidation reaction and only radical chain reaction under the action of the active groups, so that the purpose of removal is achieved; the electrocatalytic treatment process mainly comprises electrons, does not need to add an oxidant, does not produce secondary pollution, has mild reaction conditions and high energy efficiency, and has the effects of interval air floatation, flocculation and sterilization, and the method has the advantages of simple reaction device, flexible process, strong controllability and easy automation, and is one of the sewage purification methods widely focused in the industry in recent years. However, in the electrocatalytic treatment process of electroplating wastewater, various parameters are as follows: the reaction time and efficiency of the electrocatalytic waste liquid can be influenced by the current, the pH value of the waste liquid, the electrode material, the distance between the electrode plates, the initial concentration of pollutants and the like, wherein the pH value range has great influence on the treatment efficiency and the running cost in the waste liquid treatment process, so that a control system is generally adopted in the prior art to monitor and regulate the pH in real time; for example: chinese patent CN210367090U, entitled "a photovoltaic-driven electrocatalytic degradation ignition wastewater treatment device", which adopts a pH meter, a pH controller and the like to adjust the pH value in an electrolytic cell so as to ensure that the degradation of wastewater reaches the optimal condition, but the pH adjusting system of the patent can only adjust the interior of the electrolytic cell between 2 and 5, has a large fluctuation range (the pH value fluctuates in a section of 3), leads to low treatment efficiency of an electrocatalytic process, and can cause unstable whole reaction process and neglect and slow of the electrocatalytic process due to the large fluctuation range of the pH value of the electrolytic cell. Since the pH value dynamically changes with the reaction time (i.e., the longer the operation time and the smaller the pH value in the wastewater treatment process), it relates to various factors such as the addition time of the regulator, the addition amount, the pH change amount in the wastewater treatment process, etc., so if the pH value is to be controlled in a region with a smaller range, the cost involved in the control is increased (the smaller the region is, the higher the control cost is), and the treatment process is complicated and the fluctuation amount of the adjustment is increased (i.e., the smaller the maintained region is and the lower the stability in the adjustment process is); therefore, how to always maintain and stabilize the pH value in a small range is one of the difficulties faced in the current electrocatalytic electroplating wastewater treatment technology.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an electrocatalytic pH value treatment system based on automatic control, which can effectively stabilize the pH value in the electrocatalytic process at a target value, and has the advantages of small oscillation, high stability and high degree of automation.
The aim of the invention is achieved by the following technical scheme:
an electrocatalytic pH value treatment system based on automatic control, which is characterized in that: comprising the following steps:
the pH sensor is used for detecting the pH value of the electroplating waste liquid in real time;
the pH regulator adopts a compound alkali automatic adder, and performs dropwise addition of compound alkali according to the instruction of the controller;
the controller is used for receiving the pH value fed back by the pH sensor in real time, calculating the pH value regulating quantity according to the feedback value and then outputting a command to the pH regulator;
the controller is electrically connected with the pH sensor and the pH regulator respectively;
the step of the controller calculating the pH value adjustment amount specifically comprises the following steps:
firstly, obtaining an error variable e (t) by comparing the difference value of a measured value and a target value fed back by a pH sensor;
and then calculating to obtain PID control feedback quantity through an error variable e (t):
wherein, p (t) is PID control feedback quantity; k (K) p 、K i 、K d The coefficient values of the proportional coefficient, the integral coefficient and the differential coefficient are obtained according to the setting method of the PID control module;
in the electroplating wastewater treatment process, in order to ensure that the fluctuation range of the pH value is in an optimal range, the adjustment quantity f (t) of the control system is calculated through an error variable e (t);
wherein sign (x) is a function symbol, and when x > 0, sign (x) =1; when x < 0, sign (x) = -1;
finally, the feedback quantity p (t) and the control system regulating quantity f (t) are controlled through PID to obtain the pH value regulating quantity mu (t):
μ(t)＝p(t)·[1+0.5f(t)]。
and further optimizing, wherein the compound alkali adopts a mixture of sodium carbonate and sodium hydroxide in a mass ratio of 1:1.
Preferably, the target value is between 2.7 and 2.9.
And further optimizing, wherein the controller comprises a comparison module, a calculation module, a PID control module, an input module, an output module and a power supply module.
And the controller is further optimized and comprises a display module and a display screen, and is used for displaying the calculated amount of the compound alkali to be added dropwise and the current pH value detected by the pH sensor.
Considering that a waste liquid treatment pool is enlarged, a pH regulator is added with mixed alkali to regulate the pH value for a certain time difference, so that the pH value of a local area is too high and the pH value of the local area is too low, and meanwhile, in the electrocatalytic effect, the distance from an electrode to the electrode is not communicated, and the contents of various substances in the waste water are inconsistent with each other in a local high and local low way (the diffusion speed of molecular substances in the water is related to the temperature, concentration difference and the like); thereby affecting the efficiency of electrocatalytic treatment of the waste liquid and failing to obtain optimal running cost.
And further optimizing, the electrocatalytic pH value treatment system further comprises a spoiler, and the spoiler is reasonably arranged in the electrocatalytic cell according to the position of the electrode plate.
Preferably, the turbulence generator adopts a turbulence submersible pump for forming convection in the electric catalytic pool and accelerating the exchange speed of substances in water, so as to avoid the substances in water from forming local high and local low distribution.
Further preferably, the pH regulator is installed near the electrode plate of the electrocatalytic cell, and the pH sensor is installed between the pH regulator and the electrode plate.
The invention has the following technical effects:
according to the invention, the PID control system is introduced to comprehensively consider the change conditions of the current error, the past error and the future error, and the control variable can be well regulated to a stable value, so that the pH value is ensured to be kept within the target value (namely, within the range of 2.7-2.9); meanwhile, the adjustment quantity of the control system is introduced, namely, the second derivative of the error (namely, whether the process of expanding or shrinking the error is in acceleration or deceleration is judged), and the error value and the first derivative of the error (namely, whether the error is expanding or shrinking) are matched, so that the adjustment of the error feedback quantity is further realized, the oscillation is slowed down, and the further stable adjustment of the whole automatic system is ensured.
The system can effectively keep the pH value in the electrocatalytic process in the range of 2.7-2.9 (the pH value range is 0.2 and is far smaller than the pH value range of the prior art in the range of 3; the area section of the system is reduced to 60 times of the prior art), meanwhile, the system controls the pH value to keep the pH value in the range of the cells and simultaneously has small oscillation and high stability (namely, the pH value of electroplating wastewater is always kept in the small range of 2.7-2.9 to fluctuate in the electrocatalytic process), and the automation degree is high; in addition, the invention can realize the purposes of keeping the pH value within a small range of 0.2, small fluctuation and small vibration by only adopting the pH sensor, the pH regulator and the controller, has simple structure (no need of adding other auxiliary equipment), easy operation of process steps (automatic identification and operation, no need of adding other process steps) and low cost, and can greatly improve the treatment efficiency of treating the electroplating waste liquid by the electrocatalytic method, thereby reducing the operation cost of the electrocatalytic process.
Drawings
FIG. 1 is a schematic diagram of the overall structure of an electrocatalytic waste liquid pH treatment system according to an embodiment of the present invention.
Wherein, 1, an electrocatalytic cell; 11. a power supply; 12. an anode electrode plate; 13. a cathode electrode plate; 14. a water inlet; 15. a photoelectrocatalyst addition port; 16. a water outlet; 2. a pH sensor; 3. a pH adjustor; 4. a controller; 5. a spoiler.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples:
as shown in fig. 1, an electrocatalytic pH value processing system based on automation control is characterized in that: comprising the following steps:
the pH sensor 2 is used for detecting the pH value of the electroplating waste liquid in real time;
the controller 4 receives the pH value fed back by the pH sensor 2 in real time through the input module, calculates the pH value adjustment amount according to the feedback value, and then outputs an instruction to the pH regulator 3 through the output module; the controller 4 comprises a comparison module, a calculation module, a PID control module, an input module, an output module and a power supply module; the controller 4 also comprises a display module and a display screen, and is used for displaying the calculated amount of the compound alkali to be added dropwise and the current pH value detected by the pH sensor 2;
the pH regulator 3 adopts an automatic compound alkali adder and performs dropwise addition of compound alkali according to the instruction of the controller 4;
the controller 4 is electrically connected with the pH sensor 2 and the pH regulator 3 respectively.
The step of the controller 4 calculating the pH adjustment amount is specifically:
firstly, the controller 4 obtains the current real-time collected pH value fed back by the pH sensor 2 through an input module, then compares the difference value between the measured value fed back by the pH sensor 2 and the target value (namely, the value required to be kept by the pH value is between 2.7 and 2.9) through a comparison module, and obtains an error variable e (t) through a calculation module;
and then calculating by using a calculation module and a PID control module through an error variable e (t) to obtain a PID control feedback quantity:
wherein, p (t) is PID control feedback quantity; k (K) p 、K i 、K d The coefficient values of the proportional coefficient, the integral coefficient and the differential coefficient are obtained according to the setting method of the PID control module;
in the electroplating wastewater treatment process, in order to ensure that the fluctuation range of the pH value is in an optimal range, the adjustment quantity f (t) of a control system is calculated by utilizing a calculation module and a PID control module through an error variable e (t);
wherein sign (x) is a function symbol, and when x > 0, sign (x) =1; when x < 0, sign (x) = -1;
finally, the feedback quantity p (t) and the control system regulating quantity f (t) are controlled by a computing module through PID, and the pH value regulating quantity mu (t) is obtained:
μ(t)＝p(t)·[1+0.5f(t)]。
wherein, the compound alkali adopts a mixture of sodium carbonate and sodium hydroxide with the mass ratio of 1:1.
Considering that the waste liquid treatment pool is enlarged, the pH value of the pH regulator 3 is regulated by adding mixed alkali to have a certain time difference, so that the pH value of a local area is too high and the pH value of the local area is too low, meanwhile, in the electrocatalytic effect, the distance from the electrode to the electrode is not communicated, and the contents of various substances in the waste water are inconsistent with local high and local low (the diffusion speed of molecular substances in the water is related to the temperature, concentration difference and the like); thereby affecting the efficiency of electrocatalytic treatment of the waste liquid and failing to obtain optimal running cost.
The electrocatalytic pH value processing system further includes a spoiler 5, where the spoiler 5 is reasonably disposed in the electrocatalytic cell 1 according to the positions of the electrode plates (i.e. the anode electrode plate 12 and the cathode electrode plate 13) (the optimum setting mode is selected according to the conventional setting mode in the art and the setting mode for achieving the purpose of the present invention, which is a conventional technology in the art, so the present invention will not be discussed too much). Preferably, the turbulence generator 5 adopts a turbulence submersible pump for forming convection in the electrocatalytic tank 1 and accelerating the exchange speed of the substances in water, so as to avoid the formation of local high and local low distribution of the substances in water.
The electrocatalytic cell 1 comprises a power supply 11, an anode electrode plate 12, a cathode electrode plate 13, a water inlet 14, a photoelectrocatalyst adding port 15 and a water outlet 16; wherein, the anode electrode plate 12 and the cathode electrode plate 13 are respectively positioned in the electrocatalytic cell 1, one ends of the anode electrode plate 12 and the cathode electrode plate are respectively electrically connected with the power supply 11, the water inlet 14, the photoelectrocatalyst adding port 15 and the water outlet 16 are respectively arranged on the side wall of the electrocatalytic cell 1, the water inlet 14 is positioned at the uppermost end, and the water outlet 16 is positioned at the lowermost end.
The pH adjuster 3 is installed near an electrode plate (one or more of an anode electrode plate 12 or a cathode electrode plate 13) of the electrocatalytic cell 1, and installing a plurality of pH adjusters 2 ensures uniform adjustment of the whole), and the pH sensor 2 is installed between the pH adjuster 3 and the electrode plate.
The basic principles of the present disclosure have been described above in connection with specific embodiments, however, it should be noted that the advantages, benefits, effects, etc. mentioned in the present disclosure are merely examples and not limiting, and these advantages, benefits, effects, etc. are not to be considered as necessarily possessed by the various embodiments of the present disclosure. Furthermore, the specific details disclosed herein are for purposes of illustration and understanding only, and are not intended to be limiting, since the disclosure is not necessarily limited to practice with the specific details described.
The block diagrams of the devices, apparatuses, devices, systems referred to in this disclosure are merely illustrative examples and are not intended to require or imply that the connections, arrangements, configurations must be made in the manner shown in the block diagrams. As will be appreciated by one of skill in the art, the devices, apparatuses, devices, systems may be connected, arranged, configured in any manner. Words such as "including," "comprising," "having," and the like are words of openness and mean "including but not limited to," and are used interchangeably therewith. The terms "or" and "as used herein refer to and are used interchangeably with the term" and/or "unless the context clearly indicates otherwise. The term "such as" as used herein refers to, and is used interchangeably with, the phrase "such as, but not limited to.
In addition, as used herein, the use of "or" in the recitation of items beginning with "at least one" indicates a separate recitation, e.g., "at least one of A, B or C" recitation means a or B or C, or AB or AC or BC, or ABC (i.e., a and B and C). Furthermore, the term "exemplary" does not mean that the described example is preferred or better than other examples.
The foregoing description has been presented for purposes of illustration and description. Furthermore, this description is not intended to limit the embodiments of the disclosure to the form disclosed herein. Although a number of example aspects and embodiments have been discussed above, a person of ordinary skill in the art will recognize certain variations, modifications, alterations, additions, and combinations thereof.
Claims (3)
1. An electrocatalytic pH value treatment system based on automatic control, which is characterized in that: comprising the following steps:
the pH sensor (2) is used for detecting the pH value of the electroplating waste liquid in real time;
a pH regulator (3) which adopts an automatic compound alkali adder and performs dropwise addition of compound alkali according to the instruction of the controller (4);
the controller (4) is used for receiving the pH value fed back by the pH sensor (2) in real time, calculating the pH value regulating quantity according to the feedback value and then outputting a command to the pH regulator (3);
the controller (4) is respectively and electrically connected with the pH sensor (2) and the pH regulator (3);
the step of the controller (4) for calculating the pH value adjustment amount specifically comprises the following steps:
firstly, obtaining an error variable e (t) by comparing the difference value of a measured value and a target value fed back by a pH sensor;
and then calculating to obtain PID control feedback quantity through an error variable e (t):
wherein, p (t) is PID control feedback quantity; k (K) p 、K i 、K d The coefficient values of the proportional coefficient, the integral coefficient and the differential coefficient are obtained according to the setting method of the PID control module;
in the electroplating wastewater treatment process, in order to ensure that the fluctuation range of the pH value is in an optimal range, the adjustment quantity f (t) of the control system is calculated through an error variable e (t);
wherein sign (x) is a function symbol, and when x > 0, sign (x) =1; when x < 0, sign (x) = -1;
finally, the feedback quantity p (t) and the control system regulating quantity f (t) are controlled through PID to obtain the pH value regulating quantity mu (t):
μ(t)＝p(t)·[1+0.5f(t)]；
the target value is between 2.7 and 2.9;
the electrocatalytic pH value treatment system further comprises a spoiler (5), and the spoiler (5) is reasonably arranged in the electrocatalytic cell (1) according to the position of the electrode plate.
2. An electrocatalytic pH value treatment system based on automation control as claimed in claim 1, wherein: the compound alkali adopts a mixture of sodium carbonate and sodium hydroxide in a mass ratio of 1:1.
3. An electrocatalytic pH value treatment system based on automation control according to claim 1 or 2, wherein: the pH regulator (3) is arranged near the electrode plate of the electrocatalytic cell (1), and the pH sensor (2) is arranged between the pH regulator (3) and the electrode plate.
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