CN106830116B - Early warning and predicting device and method for exceeding ferrous ions in acidic wastewater - Google Patents
Early warning and predicting device and method for exceeding ferrous ions in acidic wastewater Download PDFInfo
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- CN106830116B CN106830116B CN201710082321.4A CN201710082321A CN106830116B CN 106830116 B CN106830116 B CN 106830116B CN 201710082321 A CN201710082321 A CN 201710082321A CN 106830116 B CN106830116 B CN 106830116B
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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
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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
- 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
- C02F2209/005—Processes using a programmable logic controller [PLC]
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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
- C02F2209/04—Oxidation reduction potential [ORP]
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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
Abstract
The invention discloses an early warning and predicting device for excessive ferrous ions in acidic wastewater, which comprises a grid advancing water tank, a computer and a NaOH solution tank, wherein a pH probe, an ORP probe and a dosing diffuser are arranged in the grid advancing water tank, the dosing diffuser is connected with the NaOH solution tank through a dosing pipeline, and a NaOH dosing pump is arranged on the dosing pipeline; and transmission lines are connected between the pH probe and the ORP probe and the computer, and an alarm and an electromagnetic valve are connected between the NaOH dosing pump and the computer in series. And a data analysis system is arranged in the computer, the pH value and the ORP value before the sewage plant water inlet grid is received by the pH probe and the ORP probe are analyzed, a pH-ORP fitting regression curve is used for prediction, and the concentration ratio of ferric ions to ferrous ions in a water pool before the grid reaches a set requirement by adding NaOH solution. The invention can realize accurate early warning of excessive concentration of ferrous ions in inlet water of a sewage plant, can process in time and avoid operation faults of subsequent processing equipment.
Description
Technical Field
The invention belongs to the field of water treatment, particularly relates to the field of early warning and emergency treatment of excessive ferrous ions in steel and related water treatment, and relates to a method and a device for early warning and emergency treatment of excessive ferrous ions based on ORP (oxidation-reduction potential) and pH (hydrogen ion concentration index).
Background
The steel industry is water consumers and wastewater discharge consumers, and the treatment condition of steel wastewater is more and more widely concerned by various social circles. The steel original blank is generally pickled before surface electroplating and spraying to remove surface oxides, so that pickling waste liquid and pickling waste water are generated, and nitric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid and the like are common acids in actual industrial production. Wherein the acid-washing waste liquid has higher acid concentration and can recycle the regenerated acid. And a large amount of washing water, namely pickling wastewater, has low acid content, so that the washing water is uneconomical to recycle and is discharged as wastewater. The waste liquid often contains sulfuric acid, nitric acid, iron ions, ferrous ions, oil stains and the like. In the process of treating the steel wastewater by the sewage treatment plant, if the inlet water contains a large amount of ferrous ions, the ferrous ions are oxidized into ferric ions, the pH value of the water quality is reduced, the equipment such as pipelines of the sewage treatment plant and subsequent treatment structures is seriously damaged, the quantity and activity of microorganisms in biochemical treatment of the sewage treatment plant are seriously inhibited, the normal operation of the whole process of the sewage treatment plant is influenced, and the stable standard discharge of the outlet water is difficult to realize.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the early warning and prediction device and the early warning and prediction method for the excessive ferrous ions in the acidic wastewater.
In order to solve the technical problems, the early warning and predicting device for the excessive ferrous ions in the acidic wastewater comprises a grid advancing water tank and a computer, and is characterized by further comprising a NaOH solution tank, wherein a pH probe, an ORP probe and a dosing diffuser are arranged in the grid advancing water tank, the dosing diffuser is connected with the NaOH solution tank through a dosing pipeline, and a NaOH dosing pump is arranged on the dosing pipeline; and transmission lines are connected between the pH probe and the computer and between the ORP probe and the computer, and an alarm and an electromagnetic valve are connected between the NaOH dosing pump and the computer in series.
The early warning and forecasting method for the excessive ferrous ion in the acidic wastewater is realized by utilizing the early warning and forecasting device for the excessive ferrous ion in the acidic wastewater, wherein a data analysis system is installed in the computer, and the pH probe is used for monitoring the pH value of the sewage plant before the water inlet grille; the ORP probe is used for monitoring an ORP value before a water inlet grid of a sewage plant; the data analysis system analyzes the pH value and the ORP value of the inlet water of the sewage plant, which are received by the pH probe and the ORP probe, before the inlet water grid of the sewage plant, so as to obtain the concentration ratio of ferric ions to ferrous ions of the inlet water of the sewage plant; when in useWhen the concentration ratio of ferric ions to ferrous ions of inlet water of a sewage plant obtained by a data analysis system exceeds a set value, an alarm alarms, a NaOH dosing pump is started to dose NaOH solution in a NaOH solution pool from a dosing diffuser to a grid advancing water pool through a dosing pipeline, the data analysis system utilizes the pH value and the ORP value detected by a pH probe and an ORP probe, and the ORP value is measured under different pH value conditions according to a regression equation y aebxFitting a regression curve to obtain the concentration ratio of ferric ions to ferrous ions in the water tank 3 before the grating; the above regression equation y ═ aebxIn the method, x is an ORP value of inlet water, y is a concentration ratio of ferric ions to ferrous ions in the inlet water, e is a natural constant, and e is approximately equal to 2.71828; a and b are constants, and the values of a and b are as follows according to the pH value of inlet water:
and predicting whether the concentration ratio of the ferric ions to the ferrous ions meets a set value or not according to the obtained concentration ratio of the ferric ions to the ferrous ions in the water tank 3 before the grating.
Furthermore, the method is used for the early warning and prediction method of the overproof ferrous ions in the acidic wastewater, and the set value of the concentration ratio of the ferric ions to the ferrous ions of the inlet water of the sewage plant is Fe3+:Fe2+And (2) adding NaOH solution into the grid water forwarding tank to enable the pH value in the grid water forwarding tank to be 6-7.
Compared with the prior art, the invention has the advantages that:
according to the invention, the concentration ratio of ferric ions and ferrous ions is predicted by using an ORP-pH fitting regression curve through the online monitoring of the combination of an ORP probe and a pH probe according to a mathematical regression idea, and when the concentration of the ferrous ions is higher than the early warning concentration, a sewage plant can receive alarm information in time so that the sewage plant can take emergency measures (NaOH is added in front of a grid in time) to prevent the ferrous ions from causing corrosion to a subsequent treatment structure. The early warning precision of the invention can reach 0.702-0.998, can realize the accurate early warning of the excessive concentration of the ferrous ions in the inlet water of the sewage plant, and can process in time to avoid the operation fault of the subsequent processing equipment.
Drawings
FIG. 1 is a pH-ORP fitted regression curve in accordance with the present invention, reflecting ORP simulated regression curves for different proportions of ferric and ferrous ions at different pH conditions;
fig. 2 is a schematic structural diagram of the early warning prediction device of the present invention:
fig. 3 is a flow chart of the early warning prediction method of the present invention.
In the figure: 1-pH probe, 2-ORP probe, 3-grid water-feeding tank, 4-chemical-feeding diffuser, 5-NaOH solution tank, 6-NaOH chemical-feeding pump, 7-computer, 8-alarm and 9-electromagnetic valve.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention.
As shown in fig. 2, the early warning and predicting device for excessive ferrous ions in acidic wastewater provided by the present invention comprises a grid forward water tank 3, a computer 7 and a NaOH solution tank 5, wherein a pH probe 1, an ORP probe 2 and a dosing diffuser 4 are arranged in the grid forward water tank 3, the dosing diffuser 4 is connected to the NaOH solution tank 5 through a dosing pipeline 10, and the dosing pipeline 10 is provided with a NaOH dosing pump 6; transmission lines are connected between the pH probe 1 and the computer 7 and between the ORP probe 2 and the computer 7, and an alarm 8 and an electromagnetic valve 9 are connected in series between the NaOH dosing pump 6 and the computer 7.
The method for realizing the early warning prediction by using the early warning prediction device for the excessive ferrous ions in the acidic wastewater comprises the following steps of installing a data analysis system in the computer 7 as shown in figure 2, wherein the pH probe 1 is used for monitoring the pH value of the sewage plant before the water inlet grid; the ORP probe 2 is used for monitoring an ORP value before a water inlet grid of a sewage plant; the data analysis system analyzes the pH value and the ORP value of the inlet water of the sewage plant, which are received by the pH probe 1 and the ORP probe 2, before the inlet water grid of the sewage plant, so as to obtain the concentration ratio of ferric ions to ferrous ions of the inlet water of the sewage plant; iron ions and iron ions of inlet water of sewage plantThe set value of the concentration ratio of iron ions is Fe3+:Fe2+When the concentration ratio of ferric ions to ferrous ions of inlet water of a sewage plant obtained by a data analysis system exceeds a set value, an alarm 8 gives an alarm, and a NaOH dosing pump 6 is started to feed NaOH solution in a NaOH solution tank 5 from a dosing diffuser 4 into a grating forwarding water tank 3 through a dosing pipeline 10, because the pH value of ferric ions is about 2-3 and the pH value of ferrous ions is about 7-8, the pH value can be increased by adding the NaOH solution, so that the precipitation amount of ferrous ions can be increased, the pH value in the grating forwarding water tank 3 is 6-7, and subsequent sewage treatment structures are prevented from being corroded. Meanwhile, the data analysis system utilizes the pH value and the ORP value detected by the pH probe 1 and the ORP probe 2 to measure the ORP value under different pH values according to the regression equation y aebxFitting a regression curve, such as the pH-ORP fitting regression curve shown in FIG. 1, to obtain the concentration ratio of ferric ions and ferrous ions in the grid forwarding water pool 3; the above regression equation y ═ aebxIn the method, x is an ORP value of inlet water, y is a concentration ratio of ferric ions to ferrous ions in the inlet water, e is a natural constant, and e is approximately equal to 2.71828; a and b are constants, and the values of a and b are as follows according to the pH value of inlet water:
and finally, predicting whether the concentration ratio of the ferric ions to the ferrous ions meets a set value or not according to the obtained concentration ratio of the ferric ions to the ferrous ions in the water tank 3 before the grating.
The method is particularly suitable for early warning that the ferrous ions exceed the standard in the process of receiving the steel pickling wastewater by the municipal sewage treatment plant. The acid washing wastewater has a low pH value, and ferric ions and ferrous ions can be well dissolved in water under an acidic condition, so that the invention is only directed to the acidic wastewater. Although the prediction alarm device of the invention aims at the total iron concentration of 120mg/L, the design principle of the invention is still applicable to other total iron concentrations.
Example 1: the early warning and predicting device for the excessive ferrous ion of the acidic wastewater is adopted to predict wastewater with excessive ferrous ion, the pH value of the wastewater is 3.0, the ORP value is 480, and the early warning is given out when the concentration ratio of the ferric ion to the ferrous ion is lower than 1: 2. The processing steps for realizing early warning prediction are as follows:
(1) after industrial sewage is discharged into a pipe network and enters a sewage treatment plant, two indexes of pH and ORP of inlet water are monitored through a pH probe 1 and an ORP probe 2 before a coarse grid;
(2) the pH probe 1 and the ORP probe 2 transmit the measured numerical value to a total control system of a sewage treatment plant, namely a computer 7 through a transmission line;
(3) the data analysis system in the computer 7 automatically simulates the concentration ratio of ferric ions and ferrous ions of the current inlet water of the sewage plant by utilizing a pH-ORP fitting regression curve shown in figure 1 through the received pH value and ORP value, and measures that the concentration ratio of the ferric ions and the ferrous ions of the current inlet water is 3.5: 1;
(4) the concentration ratio of the iron ions and the ferrous ions of the current inlet water does not reach the early warning value, the alarm 8 is not started, and a NaOH emergency feeding system consisting of a NaOH solution pool 5, a NaOH feeding pump 6 and a feeding diffuser 4 is not started.
Example 2: the early warning prediction device for the excessive ferrous ion content in the acidic wastewater is used for predicting wastewater with excessive ferrous ion content, the pH of the wastewater is 3.0, the ORP of the wastewater is 430, and the early warning is given out when the concentration ratio of the ferric ion to the ferrous ion is lower than 1: 2. The processing steps for realizing early warning prediction are as follows:
the steps (1) to (3) are the same as the embodiment 1, and the concentration ratio of the iron ions and the ferrous ions of the current inlet water is measured to be 0.25: 1;
(4) the concentration of ferrous ions of the current inflow exceeds the standard, the electromagnetic valve 9 is opened, the alarm 8 is started to send out an alarm, the NaOH emergency feeding system composed of the NaOH solution tank 5, the NaOH feeding pump 6 and the feeding diffuser 4 is started simultaneously, and the NaOH solution is fed in front of the coarse grating to adjust the pH value of water quality to 6-7, so that the subsequent structures are prevented from suffering from acidic corrosion.
It can be seen from the example 2 that, when the ferrous ion concentration exceeds the early warning value, the early warning prediction device of the invention can timely add the NaOH solution, adjust the pH value of the water quality to meet the requirement of the subsequent treatment, not only enable the subsequent biological treatment to normally operate, but also prevent the subsequent structures from suffering from acidic corrosion.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (2)
1. The early warning and predicting method for the excessive ferrous ions in the acidic wastewater comprises a grid advancing water tank (3), a NaOH solution tank (5) and a computer (7), wherein a pH probe (1), an ORP probe (2) and a dosing diffuser (4) are arranged in the grid advancing water tank (3), the dosing diffuser (4) is connected with the NaOH solution tank (5) through a dosing pipeline (10), and a NaOH dosing pump (6) is arranged on the dosing pipeline (10); transmission lines are connected between the pH probe (1) and the computer (7) and between the ORP probe (2) and the computer (7), and an alarm (8) and an electromagnetic valve (9) are connected in series between the NaOH dosing pump (6) and the computer (7);
the system is characterized in that a data analysis system is installed in the computer (7), and the pH probe (1) is used for monitoring the pH value of the sewage plant before the water inlet grid; the ORP probe (2) is used for monitoring an ORP value before a water inlet grid of a sewage plant; the data analysis system analyzes the pH value and the ORP value of the sewage plant inlet water before the grid is received through the pH probe (1) and the ORP probe (2), so that the concentration ratio of ferric ions to ferrous ions of the sewage plant inlet water is obtained; when the concentration ratio of ferric ions to ferrous ions of inlet water of a sewage plant obtained by a data analysis system exceeds a set value, an alarm (8) gives an alarm, a NaOH dosing pump (6) is started to dose NaOH solution in a NaOH solution pool (5) into the grid forward water pool (3) from the dosing diffuser (4) through a dosing pipeline (10), and the data analysis system utilizes the pH value and the ORP value detected by a pH probe (1) and an ORP probe (2) to perform different pH value conditionsNext, by measuring the ORP value, ae is estimated from the regression equation ybxFitting a regression curve to obtain the concentration ratio of ferric ions to ferrous ions in the water tank (3) before the grating; the above regression equation y ═ aebxIn the method, x is an ORP value of inlet water, y is a concentration ratio of ferric ions to ferrous ions in the inlet water, e is a natural constant, and e is approximately equal to 2.71828; a and b are constants, and the values of a and b are as follows according to the pH value of inlet water:
and predicting whether the concentration ratio of the ferric ions to the ferrous ions meets a set value or not according to the obtained concentration ratio of the ferric ions to the ferrous ions in the water tank (3) in which the grating advances.
2. The method for warning and predicting the overproof of ferrous ions in acidic wastewater as claimed in claim 1, wherein the concentration ratio of ferrous ions to ferrous ions in the inlet water of the sewage plant is set to Fe3+:Fe2+And (2: 1), adding a NaOH solution into the grid water forwarding tank (3) to enable the pH value in the grid water forwarding tank (3) to be 6-7.
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Citations (6)
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| JPS58159896A (en) * | 1982-03-17 | 1983-09-22 | Sintokogio Ltd | Discriminating device of characteristic of activated sludge liquid |
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| CN1563967A (en) * | 2004-04-05 | 2005-01-12 | 建德市环境保护科学研究所 | Monitoring method and device for electroplated waste water |
| CN103399524A (en) * | 2013-08-09 | 2013-11-20 | 桂林理工大学 | Toxicity prewarning and monitoring device for inlet water of urban wastewater treatment plant |
| CN104460577A (en) * | 2014-07-24 | 2015-03-25 | 上海市城市排水有限公司 | Water quality safety early warning decision making system |
| CN106124727A (en) * | 2016-08-31 | 2016-11-16 | 北京太和洁源科技发展有限公司 | Water quality on-line monitoring system |
-
2017
- 2017-02-15 CN CN201710082321.4A patent/CN106830116B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58159896A (en) * | 1982-03-17 | 1983-09-22 | Sintokogio Ltd | Discriminating device of characteristic of activated sludge liquid |
| CN1331054A (en) * | 2000-06-29 | 2002-01-16 | 上海理日申能环境工程有限公司 | Intermittent automatic process and equipment for treating waste water |
| CN1563967A (en) * | 2004-04-05 | 2005-01-12 | 建德市环境保护科学研究所 | Monitoring method and device for electroplated waste water |
| CN103399524A (en) * | 2013-08-09 | 2013-11-20 | 桂林理工大学 | Toxicity prewarning and monitoring device for inlet water of urban wastewater treatment plant |
| CN104460577A (en) * | 2014-07-24 | 2015-03-25 | 上海市城市排水有限公司 | Water quality safety early warning decision making system |
| CN106124727A (en) * | 2016-08-31 | 2016-11-16 | 北京太和洁源科技发展有限公司 | Water quality on-line monitoring system |
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