CN113149245B - Method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors - Google Patents

Method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors Download PDF

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CN113149245B
CN113149245B CN202110410780.7A CN202110410780A CN113149245B CN 113149245 B CN113149245 B CN 113149245B CN 202110410780 A CN202110410780 A CN 202110410780A CN 113149245 B CN113149245 B CN 113149245B
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stirring
limestone
rotating shaft
dissolution
mine wastewater
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CN113149245A (en
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蒲迅赤
赵高磊
郭佳雯
刘兵
杨永安
梁瑞峰
王远铭
李克锋
李然
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Suining Ecological Environment Security Emergency Center
Sichuan University
China West Normal University
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Suining Ecological Environment Security Emergency Center
Sichuan University
China West Normal University
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
    • G05B19/00—Programme-control systems
    • G05B19/02—Programme-control systems electric
    • G05B19/04—Programme control other than numerical control, i.e. in sequence controllers or logic controllers
    • G05B19/05—Programmable logic controllers, e.g. simulating logic interconnections of signals according to ladder diagrams or function charts
    • 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
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • 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]

Abstract

The invention discloses a method for improving the treatment efficiency of acid mine wastewater based on hydrodynamic factors, which adopts a simulation system to simulate the passive treatment stage of the acid mine wastewater; the simulation system comprises a detection device and a stirring device; the detection device comprises a detection sensor and a detection controller; the stirring device comprises a stirring rotating shaft, a stirring motor and a stirring shell; a stirring rotating shaft is rotatably connected in the stirring shell, the stirring motor is rotatably connected with the stirring shell through the stirring rotating shaft, and a stirring drum is arranged between the stirring rotating shaft and the stirring shell; the detection sensor is arranged between the stirring drum and the stirring rotating shaft; an accommodating layer for accommodating limestone is arranged below the mixing drum; the accommodating layer is arranged on the inner wall of the bottom end of the stirring shell; the invention has the beneficial effects that: through detection device, agitating unit, transmit the lime stone in the stirring shell with the velocity of flow in the churn, rethread detection sensor and detection control ware realize accurate simulation lime stone and dissolve.

Description

Method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for improving the treatment efficiency of acid mine wastewater based on hydrodynamic factors.
Background
Mineral resources are used as basic resources for human development, the environment pollution cannot be avoided while the social and economic development is guaranteed, a large number of tailing dam break accidents cause numerous social disasters and environmental problems, the attention of mine wastes (water) worldwide is caused, and particularly the attention of people is increasingly paid to the environmental problems caused by mine wastewater. In various waste ores, a large amount of sulfur-containing minerals (such as coal gangue, hematite, etc.) are generally contained, and these sulfur-containing minerals are oxidized in the air to produce Acid mine wastewater (AMD). The acid mine wastewater has the characteristics of low pH value, high heavy metal ion concentration and the like, and is a type of mine wastewater which is large in production amount, wide in production range and most serious in environmental hazard. On one hand, the acidity of the receiving water body is increased due to the acidic mine wastewater, and the growth of organisms in the water is adversely affected; on the other hand, heavy metal ions in the acid mine wastewater can damage the environment of the receiving water body, harm fishery and agricultural production and pollute drinking water sources and soil. Therefore, the key problem in the treatment of the acid mine wastewater is to neutralize the acidity of the acid mine wastewater and remove heavy metal ions.
At present, methods for treating acid mine wastewater can be divided into two main categories: active processing and passive processing. The active treatment is to directly put alkaline substances into the mine water or the water body polluted by the mine water by adopting a manual putting method so as to neutralize the acidity of the acidic mine wastewater. The application cost of the method is expensive, and because chemicals are required to be added artificially in the active treatment process, the requirements on daily operation and maintenance are high, the treatment and maintenance cost is high, and the supervision of an environmental protection department is not facilitated. The passive treatment method is to make the acid mine waste water flow through the alkaline ore, and utilize the dissolution of the alkaline ore to achieve the purposes of neutralizing acidity and reducing the concentration of metal ions. The passive treatment method does not need to artificially add chemicals, only needs to consider one-time investment and basically does not need operation and maintenance cost, and is an acid mine wastewater treatment method with high economic benefit, thereby being widely applied in various countries in the world at present.
In passive processing methods, the most commonly used alkaline mineral is limestone. The rate of dissolution of limestone is one of the major factors that limit the efficiency of passive treatment systems. Because the dissolution speed of the limestone is very slow, the hydraulic retention time for the acid mine wastewater to flow through the limestone is long. If the flow of the acid mine wastewater is large, the required occupied area is large, so that the investment cost is increased, and the advantages of the method cannot be embodied. The quantitative relation between the hydrodynamic force condition and the dissolution rate of the acid mine wastewater in the limestone is established, and theoretical support can be provided for solving the problem of low dissolution rate of the limestone. However, most of the existing experimental systems for simulating the dissolution rate of wastewater in limestone adopt a slow reaction mode, and specific dissolution models and specific data of hydrodynamic parameters are not given for the dissolution rate of limestone in acid mine wastewater under different hydrodynamic conditions.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for improving the treatment efficiency of acid mine wastewater based on hydrodynamic factors so as to at least achieve the aims of accurately simulating a limestone dissolution process and determining hydrodynamic parameters.
The purpose of the invention is realized by the following technical scheme:
a method for improving the treatment efficiency of acid mine wastewater based on hydrodynamic factors adopts a simulation system to simulate a passive treatment stage of acid mine wastewater; the simulation system comprises a detection device and a stirring device; the detection device comprises a detection sensor and a detection controller; the stirring device comprises a stirring rotating shaft, a stirring motor and a stirring shell;
the stirring motor is rotatably connected with the stirring shell through the stirring rotating shaft, and a stirring drum is arranged between the stirring rotating shaft and the stirring shell; the bottom end of the mixing drum is provided with a filter screen;
the detection sensor is arranged between the stirring drum and the stirring rotating shaft and is connected with the detection controller through an electric signal; the detection controller is also connected with the stirring motor through an electric signal; an accommodating layer for accommodating limestone is arranged below the stirring cylinder; the accommodating layer is arranged on the inner wall of the bottom end of the stirring shell.
Preferably, in order to further realize the purpose of accurately simulating the limestone dissolution process, the top end of the stirring shell is provided with a sampling port, a rotating shaft port and a lead inlet; the rotating shaft opening is arranged at the center of a circle at the top end of the stirring shell; the sampling port and the lead wire inlet are symmetrically arranged relative to the vertical plane where the axial lead of the rotating shaft port is located; the stirring rotating shaft penetrates through the rotating shaft port; through setting up including the sample connection, the stirring shell top of pivot mouth and wire entry, through the sample connection that adopts evenly distributed, pivot mouth and wire entry to can monitor the pH data in the acid waste water in real time through the sample connection, cooperate the detection sensor again, thereby detect out the real-time data of the lime stone dissolution rate under the different hydrodynamic force conditions, and then found out the dissolution model of accurate lime stone in acid mine waste water.
Preferably, in order to further achieve the purpose of determining hydrodynamic parameters, the accommodating layer sequentially comprises, from inside to outside, an accommodating first region, an accommodating second region, an accommodating third region, an accommodating fourth region and an accommodating fifth region; the connecting line of the axis of the containing area and the circle center of the stirring shell is in the same straight line; the five accommodating areas are abutted to the stirring shell; the accommodating layer is partitioned, and the surface of the limestone reacted in the lower layer is presented in different partitions, so that the dissolution condition of the limestone in the wastewater in different partitions can be inspected, and the purpose of accurately simulating wastewater dissolution is achieved.
Preferably, in order to further achieve the purpose of determining hydrodynamic parameters, a stirring rod is arranged on the side wall of the stirring rotating shaft; the stirring rod is designed in a triangular shape; the stirring rod with the triangular design can accurately transmit the power of the stirring motor 22 to the mine wastewater, and the turbulent power in the stirring stage is transmitted to the stirring shell because the stirring occurs in the stirring cylinder, so that the turbulent power is received by the detection sensor, the flow velocity data on the limestone is accurately measured, and the purpose of determining hydrodynamic parameters is realized.
Preferably, for the purpose of further accurately simulating the limestone dissolution process, the method for improving the acid mine wastewater treatment efficiency based on hydrodynamic factors comprises the following steps:
s1, selecting limestone ore, grinding the limestone ore into a shape matched with the accommodating layer, fixing the limestone ore in the accommodating layer, and abutting against the stirring shell to obtain a fixed accommodating layer;
s2, preparing acidic mine wastewater, pouring the acidic mine wastewater into a stirring drum, simultaneously penetrating a stirring shaft with a stirring motor in a rotating shaft port at the top end of a stirring shell, inserting a lead of a detection sensor into a lead inlet, then covering the top end of the stirring shell, starting the stirring motor, controlling the rotating speed, and starting timing;
s3, after timing, taking out the sample from the sampling port according to the set time, detecting the pH and ion concentration data, and simultaneously recording the data of the detection sensor received by the detection controller;
s4, after the reaction is finished, taking out limestone, and collecting and storing the limestone;
s5 setting the rotating speeds of different stirring motors, and returning to S2 to obtain data of different rotating speeds and pH values;
s6, carrying out dissolution model construction on the obtained data, and screening out the determined rotation speed and the optimal area for limestone dissolution, namely the method;
through the steps, the stirring flow rate data, the detected pH data and the like are subjected to comprehensive statistics, and a dissolution model is constructed, so that the optimal dissolution area and the optimal flow rate during dissolution are determined, the optimal hydrodynamic parameters of the dissolution process are further determined, and the purpose of accurately simulating the limestone dissolution process is achieved.
Preferably, for the purpose of further determining the hydrodynamic parameters, the rotation speeds of the different stirring motors are 10rpm, 30rpm, 60rpm and 90 rpm; different rotating speeds of the stirring motor are adopted, hydrodynamic conditions of different rotating speeds are utilized, so that the rotating speed interval is limited, and the optimal rotating speed is determined by comparing different dissolution rate constants.
Preferably, for the purpose of further accurately simulating the dissolution process of limestone, the dissolution model construction includes constructing a model of pH and dissolution rate to model the dissolution processFlow rate models of different areas of limestone; the model of pH and dissolution rate is specifically as follows: calcium ions are generated by dissolution of limestone, a part of which exists in solution in a free state and a part of which is in contact with SO4 2-In combination with the generation of calcium sulfate precipitates and the inclusion of magnesium carbonate impurities in the limestone, the corrected dissolution rate of the limestone is calculated by the formula:
Figure BDA0003020994570000031
for a uniform water body, the reaction in the water body conforms to a first order kinetic reaction rate equation, so that the dissolution rate constant and the pH of the water body have the following relation:
Figure BDA0003020994570000032
wherein K is a dissolution rate constant; pH valueeThe pH at which the reaction reaches equilibrium,
solving the differential equation to obtain
ln(pHe-pH)＝-Kt+C
Will ln (pH)e-pH) is fitted to the timed time t relationship, i.e. the specific dissolution rate constant is obtained;
the dissolution models of the limestone in different areas are specifically as follows: the first containing area, the second containing area, the third containing area, the fourth containing area and the fifth containing area are arranged from inside to outside of the containing layer, the flow speeds at the same radius position are the same according to the similar principle, and the area proportion occupied by each area is counted according to the distribution curve of the flow speeds along the radial direction to obtain the weighted value alpha of the influence of the area proportion on the limestone dissolution ratei：
Figure BDA0003020994570000041
In the formula, AiThe area of the ith zone is expressed, and since K is influenced by hydrodynamic factors, there is an expression for a certain partition:
Figure BDA0003020994570000042
in the formula, viRepresents the flow rate of the ith zone; f (v)i) The influence rule relation of a certain flow rate on the dissolution rate K is shown; s is a constant and is only influenced by the temperature, limestone and chemical components of acid mine wastewater,
when v isiThe dissolution rate constant K of limestone is numerically equal to S when it is 0;
fitting the quantitative relation between the flow rate and the dissolution rate constant of the limestone by applying the principle of a least square method, wherein the relation between the obtained flow rate and the dissolution rate constant K is as follows:
Figure BDA0003020994570000043
the dissolving model is formed by constructing a model of pH and dissolving rate and flow rate models of different areas of limestone, the relation between the pH and the dissolving rate constant K is utilized, so that the relation between the pH and the dissolving rate constant K is obtained by measuring the pH in a plurality of time periods, then a plurality of subareas are carried out on the accommodating layer, the radial flow rate in each subarea is controlled to be the same, the mathematical model construction of the flow rate and the dissolving rate constant K is realized, the relation between hydrodynamic factors such as the pH and the flow rate and the dissolving rate constant K is further realized, and the aim of accurately simulating the limestone dissolving process is fulfilled.
The invention has the beneficial effects that:
1. through the detection device including detecting sensor and detection control ware, including the stirring pivot, agitator motor and stirring shell's agitating unit, through the stirring pivot of stirring in the churn with the bottom area filter screen, thereby in the lime stone in stirring shell is transmitted to the stirring stream with in the churn, the rethread is including detecting sensor and detection control ware, utilize the velocity of flow data that detects sensor detection churn and stirring shell, thereby can be accurate simulate out lime stone dissolution rate model under the different hydrodynamic force conditions in acid mine waste water, realize accurate simulation lime stone dissolution process.
2. Through setting up including the sample connection, the stirring shell top of pivot mouth and wire entry, through the sample connection 231 that adopts evenly distributed, pivot mouth 232 and wire entry 233 to can be through the pH data in the sample connection 231 real-time supervision acid waste water, the detection sensor that deuterogamies, thereby detect out the real-time data of the lime stone dissolution rate under the different hydrodynamic force conditions, and then found out the dissolution model of accurate lime stone in acid mine waste water.
3. The accommodating layer is partitioned, and the surface of the limestone reacted in the lower layer is presented in different partitions, so that the dissolution condition of the limestone in the wastewater in different partitions can be inspected, and the purpose of accurately simulating wastewater dissolution is achieved.
4. The stirring rod with the triangular design can accurately transmit the power of the stirring motor 22 to the mine wastewater, and the turbulent power in the stirring stage is transmitted to the stirring shell because the stirring occurs in the stirring cylinder, so that the turbulent power is received by the detection sensor, the flow velocity data on the limestone is accurately measured, and the purpose of determining hydrodynamic parameters is realized.
5. Through the steps, the stirring flow rate data, the detected pH data and the like are subjected to comprehensive statistics, and a dissolution model is constructed, so that the optimal dissolution area and the optimal flow rate during dissolution are determined, the optimal hydrodynamic parameters of the dissolution process are further determined, and the purpose of accurately simulating the limestone dissolution process is achieved.
6. The dissolving model is formed by constructing a model of pH and dissolving rate and flow rate models of different areas of limestone, the relation between the pH and the dissolving rate constant K is utilized, so that the relation between the pH and the dissolving rate constant K is obtained by measuring the pH in a plurality of time periods, then a plurality of subareas are carried out on the accommodating layer, the radial flow rate in each subarea is controlled to be the same, the mathematical model construction of the flow rate and the dissolving rate constant K is realized, the relation between hydrodynamic factors such as the pH and the flow rate and the dissolving rate constant K is further realized, and the aim of accurately simulating the limestone dissolving process is fulfilled.
Drawings
FIG. 1 is a schematic diagram of the system of the present invention;
FIG. 2 is a top view of the agitator housing of the present invention;
FIG. 3 is a parametric illustration of a dissolution model of the present invention;
FIG. 4 is a graph of flow speed results for different speeds of the present invention;
FIG. 5 is a graph showing the distribution of turbulent kinetic energy at different rotational speeds according to the present invention;
in the figure, 1-detection device, 11-detection sensor, 12-detection controller, 2-stirring device, 21-stirring rotating shaft, 22-stirring motor, 23-stirring shell, 231-sampling port, 232-rotating shaft port, 233-lead inlet, 24-stirring cylinder, 25-filter screen, 26-containing layer, 261-containing one zone, 262-containing two zone, 263-containing three zone, 264-containing four zone and 265-containing five zone.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
The detection device 1 used comprises an acoustic doppler flow velocity meter ADV manufactured by Nortek corporation with a detection sensor 11 and a detection controller 12, and has a measurement range of ± 4m/s and a measurement accuracy of ± 0.5% of the measurement value;
the pH value is measured by a PHS-10 precision pH meter produced by the Chengdu Fangzhou science and technology limited company, the measuring range of the instrument is 0.00-14.00, and the measuring precision is +/-0.01.
The metal ions are measured by using a TAS-990 atomic absorption spectrophotometer manufactured by Beijing general analytical instruments, Inc., and the wavelength range is 190-900 nm.
And SO4 2-The measuring method uses a TU-1950 ultraviolet-visible spectrophotometer produced by Beijing general analysis general instruments, Inc., and the wavelength range is 400-900 nm.
The specific parameters of the limestone are as follows: calcium carbonate content of 98% or more, average particle diameter of 5mm, and density of 2.9g/cm3The Mohs hardness was 3.5.
Example 1
A method for improving the treatment efficiency of acid mine wastewater based on hydrodynamic factors adopts a simulation system to simulate a passive treatment stage of acid mine wastewater; the simulation system is shown in figure 1 and comprises a detection device 1 and an agitating device 2; the detection device 1 comprises a detection sensor 11 and a detection controller 12; the stirring device 2 comprises a stirring rotating shaft 21, a stirring motor 22 and a stirring shell 23;
the stirring shell 23 is rotatably connected with the stirring rotating shaft 21, the stirring motor 22 is rotatably connected with the stirring shell 23 through the stirring rotating shaft 21, and a stirring drum 24 is arranged between the stirring rotating shaft 21 and the stirring shell 23; a filter screen 25 is arranged at the bottom end of the mixing drum 24;
the detection sensor 11 is arranged between the mixing drum 24 and the mixing rotating shaft 21, and the detection sensor 12 is connected with the detection controller 12 through an electric signal; the detection controller 12 is also connected with the stirring motor 22 through an electric signal; an accommodating layer 26 for accommodating limestone is arranged below the stirring cylinder 24; the accommodating layer 26 is arranged on the inner wall of the bottom end of the stirring shell 23.
In order to further achieve the purpose of accurately simulating the limestone dissolution process, the top end of the stirring shell 23 is provided with a sampling port 231, a rotating shaft port 232 and a wire inlet 233 as shown in fig. 2; the rotating shaft port 232 is arranged at the center of the top circle of the stirring shell 23; the sampling port 231 and the lead wire inlet 233 are symmetrically arranged relative to the vertical plane where the axial lead of the rotating shaft port 232 is located; the stirring rotating shaft 21 penetrates through the rotating shaft port 232; including sample connection 231, pivot mouth 232 and wire entry 233's stirring shell 23 top through the setting, through sample connection 231 who adopts evenly distributed, pivot mouth 232 and wire entry 233 to can be through the pH data in the sample connection 231 real-time supervision acid waste water, the detection sensor that deuterogamies, thereby detect out the real-time data of the lime stone dissolution rate under the different hydrodynamic force condition, and then found out the dissolution model of accurate lime stone in acid mine waste water.
For the purpose of further determining hydrodynamic parameters, the accommodating layer 26 sequentially comprises, from inside to outside, an accommodating first region 261, an accommodating second region 262, an accommodating third region 263, an accommodating fourth region 264 and an accommodating fifth region 265; the connecting line of the axis where the containing zone 261 is located and the circle center of the stirring shell 23 is in the same straight line; the five accommodating areas 265 are arranged against the stirring shell 23; by dividing the accommodating layer 26 into different areas, the surface of the limestone reacted in the lower layer presents different areas, so that the dissolution condition of the limestone in the wastewater in different areas can be inspected, and the purpose of accurately simulating wastewater dissolution is achieved.
For the purpose of further determining hydrodynamic parameters, a stirring rod 211 is disposed on a side wall of the stirring rotating shaft 21; the stirring rod 211 is designed in a triangular shape; the stirring rod 211 with a triangular design can accurately transmit the power of the stirring motor 22 to the mine wastewater, and the turbulent power in the stirring stage is transmitted to the stirring shell 23 due to the stirring in the stirring cylinder 24, so that the turbulent power is received by the detection sensor 11, the flow velocity data of the limestone is accurately measured, and the purpose of determining hydrodynamic parameters is achieved.
In order to further achieve the purpose of accurately simulating the limestone dissolution process, the method for improving the acid mine wastewater treatment efficiency based on hydrodynamic factors comprises the following steps:
s1, selecting limestone ore, grinding the limestone ore into a shape matched with the accommodating layer 26, wherein the specific data is that the diameter is 280mm and the thickness is 20mm, then fixing the limestone ore in the accommodating layer 26 and abutting against the stirring shell 23 to obtain the well-fixed accommodating layer 26;
s2, preparing acid mine wastewater, wherein the specific parameters are as follows: initial pH 2.2, Fe3+Concentration of 50mg/L, SO4 2-Pouring the mixture with the concentration of 180mg/L into the stirring drum 24, simultaneously penetrating a stirring shaft 21 with a stirring motor 22 into a rotating shaft port 232 at the top end of the stirring shell 23, inserting a lead of the detection sensor 11 into a lead inlet 233, then covering the top end of the stirring shell 23, starting the stirring motor 22, controlling the rotating speed and starting timing;
after timing in S3, taking out the sample from the sampling port 231 according to the set time, detecting the pH and the ion concentration data, and recording the data received by the detection sensor 11 by the detection controller 12;
s4, after the reaction is finished, taking out limestone, and collecting and storing the limestone;
s5 setting the rotating speed of the stirring motor 22 and returning to S2 to obtain the data of different rotating speeds and pH values;
s6, carrying out dissolution model construction on the obtained data, and screening out the determined rotation speed and the optimal area for limestone dissolution, namely the method;
through the steps, the stirring flow rate data, the detected pH data and the like are subjected to comprehensive statistics, and a dissolution model is constructed, so that the optimal dissolution area and the optimal flow rate during dissolution are determined, the optimal hydrodynamic parameters of the dissolution process are further determined, and the purpose of accurately simulating the limestone dissolution process is achieved.
For the purpose of further determining the hydrodynamic parameters, the rotation speeds of the different stirring motors 22 are 10rpm, 30rpm, 60rpm and 90 rpm; by using different rotation speeds of the stirring motor 22, hydrodynamic conditions of the different rotation speeds are utilized to define the interval of the rotation speed, and then by comparing different dissolution rate constants, the optimal rotation speed is determined.
In order to further realize the purpose of accurately simulating the limestone dissolution process, the dissolution model construction comprises the steps of constructing a model of pH and dissolution rate and flow rate models of different areas of limestone; the model of pH and dissolution rate is specifically as follows: calcium ions are generated by dissolution of limestone, a part of which exists in solution in a free state and a part of which is in contact with SO4 2-In combination with the generation of additional magnesium carbonate impurities in the limestone, the rate is calculated as:
Figure BDA0003020994570000071
for a uniform water body, the reaction in the water body conforms to a first order kinetic reaction rate equation, so that the dissolution rate constant and the pH of the water body have the following relation:
Figure BDA0003020994570000081
wherein K is a dissolution rate constant; pH valueeThe pH at which the reaction reaches equilibrium,
solving the differential equation to obtain
ln(pHe-pH)＝-Kt+C
Will ln (pH)e-pH) and the timed time t, and obtaining the specific dissolution rate constants as shown in figure 3, wherein the dissolution rate constants K of the limestone are respectively 0.109, 0.1461, 0.164 and 0.1628 at the rotating speeds of 10rpm, 30rpm, 60rpm and 90rpm, and the fitted correlation coefficient R20.9291, 0.9906, 0.9846 and 0.9773, respectively, are all strongly related;
the dissolution models of the limestone in different areas are specifically as follows: the first containing area 261, the second containing area 262, the third containing area 263, the fourth containing area 264 and the fifth containing area 265 of the containing layer 26 are arranged from inside to outside, the flow rates at the same radius are the same according to the similar principle, and the area proportion occupied by each area is counted according to the distribution curve of the flow rates along the radial direction to obtain the weighted value alpha of the influence of the area proportion on the dissolution rate of the limestonei：
Figure BDA0003020994570000082
In the formula, AiThe area of the ith zone is expressed, and since K is influenced by hydrodynamic factors, there is an expression for a certain partition:
Figure BDA0003020994570000083
in the formula, viRepresents the flow rate of the ith zone; f (v)i) The influence rule relation of a certain flow rate on the dissolution rate K is shown; s is a constant and is only influenced by the temperature, limestone and chemical components of acid mine wastewater,
when v isiWhen the solution is at rest, limeThe dissolution rate constant K of the stone is numerically equal to S;
fitting the quantitative relation between the flow rate and the dissolution rate constant of the limestone by applying the principle of a least square method, wherein the relation between the obtained flow rate and the dissolution rate constant K is as follows:
Figure BDA0003020994570000084
based on the rate constant, taking the rotation speed of the limestone in different areas as an example, the flow rotation speed of the limestone surface at different rotation speeds of the stirring rotating shaft 22 is measured, as shown in fig. 4, the flow speeds at different areas and different flow speeds are symmetrically distributed about the Z-axis, the flow speeds at the same radius distance are equal, the flow speed increases and then decreases from the rotation center to the edge, and the flow speed is almost 0 near the wall surface.
Meanwhile, turbulence kinetic energy distribution of the surface of limestone at the rotating speeds of 90rpm, 60rpm, 30rpm, 20rpm and 10rpm is obtained by aiming at turbulence kinetic energy simulation measured by the detection sensor 11 and is shown in figure 5, the turbulence kinetic energy distribution at each rotating speed has the common characteristic that the turbulence kinetic energy distribution at each rotating speed is symmetrical about the Z axis, the turbulence kinetic energy at the same radius distance is equal, the turbulence kinetic energy is increased and then reduced from the rotating center to the edge, the circle center of the plane is minimum, and the turbulence kinetic energy of fluid at the high rotating speed is always greater than that of fluid at the low rotating speed at the same radial distance.
The dissolving model comprises a model for constructing pH and dissolving rate and a flow rate model of limestone in different areas, the relation between the pH and the dissolving rate constant K is utilized, the pH in a plurality of time periods is determined, the relation between the dissolving rate constant K is obtained, then a plurality of partitions are carried out on the accommodating layer 26, the radial flow rate in each partition is controlled to be the same, the mathematical model construction of the flow rate and the dissolving rate constant K is realized, the relation between hydrodynamic factors such as the pH and the flow rate and the dissolving rate constant K is further realized, and the aim of accurately simulating the limestone dissolving process is fulfilled.
Comparative example 1
The stirring rotating shaft 21 and the stirring are directly arranged without adopting the stirring cylinder 24The limestone in the enclosure 23 is directly stirred and the dissolution rate constant K of the limestone in the process is determined, but fitted with a correlation coefficient R2The average value was 0.9164, and the correlation was low as compared with example 1, so that the present system using the agitating drum 24 was superior in that the fitting coefficient of the dissolution rate constant K was high.
Comparative example 2
Without the use of a modified calculation formula for the dissolution rate of limestone, there is mainly the following equilibrium for limestone dissolution in acidic mine wastewater solutions:
Figure BDA0003020994570000091
Figure BDA0003020994570000092
Figure BDA0003020994570000093
Figure BDA0003020994570000094
due to hydrolysis of carbonate and bicarbonate, a large amount of hydroxide is generated in the solution. The generated hydroxide radicals combine with hydrogen ions in the solution to raise the pH value of the solution and are Fe3+Also involved in the reaction of the precipitation of ferric hydroxide during the change of pH:
Figure BDA0003020994570000095
the dissolution rate of limestone cannot be calculated from the measured pH change alone.
Regardless of the deviation, the data model is obtained, and the dissolution rate of limestone in the process is measuredNumber K, but fitting the correlation coefficient R2The average value was 0.8914, and the correlation was lower than that in example 1, and therefore, the fitting coefficient of the dissolution rate constant K obtained by using the dissolution rate calculation formula of limestone after correction was high, and therefore, the method was superior.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. The method for improving the treatment efficiency of the acid mine wastewater based on hydrodynamic factors is characterized by comprising the following steps: a passive treatment stage of simulating acid mine wastewater by adopting a simulation system; the simulation system comprises a detection device (1) and a stirring device (2); the detection device (1) comprises a detection sensor (11) and a detection controller (12); the stirring device (2) comprises a stirring rotating shaft (21), a stirring motor (22) and a stirring shell (23);
the stirring rotating shaft (21) is rotationally connected in the stirring shell (23), the stirring motor (22) is rotationally connected with the stirring shell (23) through the stirring rotating shaft (21), and a stirring drum (24) is arranged between the stirring rotating shaft (21) and the stirring shell (23); a filter screen (25) is arranged at the bottom end of the mixing drum (24);
the detection sensor (11) is arranged between the stirring drum (24) and the stirring rotating shaft (21), and the detection sensor (11) is connected with the detection controller (12) through an electric signal; the detection controller (12) is also connected with the stirring motor (22) through an electric signal; an accommodating layer (26) for accommodating limestone is arranged below the stirring cylinder (24); the accommodating layer (26) is arranged on the inner wall of the bottom end of the stirring shell (23).
2. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors according to claim 1, wherein the method comprises the following steps: the top end of the stirring shell (23) is provided with a sampling port (231), a rotating shaft port (232) and a lead wire inlet (233); the rotating shaft port (232) is arranged at the center of the top circle of the stirring shell (23); the sampling port (231) and the lead wire inlet (233) are symmetrically arranged relative to the vertical plane where the axial lead of the rotating shaft port (232) is located; the stirring rotating shaft (21) penetrates through the rotating shaft opening (232).
3. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors according to claim 1, wherein the method comprises the following steps: the accommodating layer (26) sequentially comprises an accommodating first area (261), an accommodating second area (262), an accommodating third area (263), an accommodating fourth area (264) and an accommodating fifth area (265) from inside to outside; the connecting line of the axis of the containing zone (261) and the circle center of the stirring shell (23) is in the same straight line; the five containing areas (265) are arranged to abut against the stirring shell (23).
4. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors according to claim 1, wherein the method comprises the following steps: the side wall of the stirring rotating shaft (21) is provided with a stirring rod (211); the stirring rod (211) is designed in a triangular shape.
5. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors according to any one of claims 1 to 4, wherein the method comprises the following steps: the simulation comprises the following steps:
s1, selecting limestone ore, grinding the limestone ore into a shape matched with the accommodating layer (26), fixing the limestone ore in the accommodating layer (26), and abutting against the stirring shell (23) to obtain a fixed accommodating layer (26);
s2, preparing acidic mine wastewater, pouring the acidic mine wastewater into a stirring cylinder (24), simultaneously penetrating a stirring rotating shaft (21) with a stirring motor (22) into a rotating shaft port (232) at the top end of a stirring shell (23), inserting a lead of a detection sensor (11) into a lead inlet (233), then covering the top end of the stirring shell (23), starting the stirring motor (22), controlling the rotating speed, and starting timing;
s3, after timing, taking out the sample from the sampling port (231) according to the set time, detecting the pH and the ion concentration data, and simultaneously recording the data received by the detection sensor (11) by the detection controller (12);
s4, after the reaction is finished, taking out limestone, and collecting and storing the limestone;
s5 setting the rotating speed of different stirring motors (22), and returning to S2 to obtain data of different rotating speeds and pH values;
s6, carrying out dissolution model construction on the obtained data, and screening out the determined rotation speed and the optimal area for limestone dissolution, namely the method.
6. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors according to claim 5, wherein the method comprises the following steps: the rotation speeds of the different stirring motors (22) are 10rpm, 30rpm, 60rpm and 90 rpm.
7. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors according to claim 5, wherein the method comprises the following steps: the dissolution model construction comprises the construction of a pH and dissolution rate model and dissolution models of different areas of limestone.
8. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors of claim 7, wherein the method comprises the following steps: the model of pH and dissolution rate is specifically as follows: the dissolution of limestone generates calcium ions, a part of which is present in the solution in the free state and a part of which is associated with SO4 2-Calcium sulfate precipitation is generated in combination, and in addition, the limestone contains magnesium carbonate impurities, so the calculation formula is as follows:
Figure FDA0003020994560000021
for a uniform water body, the reaction in the water body conforms to a first order kinetic reaction rate equation, so that the dissolution rate constant and the pH of the water body have the following relation:
Figure FDA0003020994560000022
wherein K is a dissolution rate constant; pH valueeThe pH at which the reaction reaches equilibrium,
solving the differential equation to obtain
ln(pHe-pH)＝-Kt+C
Will ln (pH)e-pH) is fitted to the timed time t relationship to obtain a specific dissolution rate constant.
9. The method for improving acid mine wastewater treatment efficiency based on hydrodynamic factors of claim 7, wherein the method comprises the following steps: the flow rate models of different areas of the limestone are specifically as follows: the first containing area (261), the second containing area (262), the third containing area (263), the fourth containing area (264) and the fifth containing area (265) of the containing layer (26) are arranged from inside to outside, the flow rates at the same radius are the same according to the similar principle, and the area proportion occupied by each area is counted according to the distribution curve of the flow rates in the radial direction to obtain the weighted value alpha of the influence of the area proportion on the limestone dissolution ratei：
Figure FDA0003020994560000023
In the formula, AiThe area of the ith zone is expressed, and since K is influenced by hydrodynamic factors, there is an expression for a certain partition:
Figure FDA0003020994560000031
in the formula, viRepresents the flow rate of the ith zone; f (v)i) The influence rule relation of a certain flow rate on the dissolution rate K is shown; s is constant and is only formed by temperature, limestone and acid mine wastewaterThe influence of each of the components is divided into,
when v isiWhen 0 (i.e. when the solution is at rest), the dissolution rate constant K of the limestone is numerically equal to S;
fitting the quantitative relation between the flow rate and the dissolution rate constant of the limestone by applying the principle of a least square method, wherein the relation between the obtained flow rate and the dissolution rate constant K is as follows:
Figure FDA0003020994560000032
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