CN106430709B - Method and device for treating copper-containing wastewater - Google Patents
Method and device for treating copper-containing wastewater Download PDFInfo
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- CN106430709B CN106430709B CN201610911165.3A CN201610911165A CN106430709B CN 106430709 B CN106430709 B CN 106430709B CN 201610911165 A CN201610911165 A CN 201610911165A CN 106430709 B CN106430709 B CN 106430709B
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- copper
- mechanical stirring
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
Abstract
The invention relates to a method and a device for treating copper-containing wastewater; the radioactive copper-containing wastewater in the mechanical stirring reactor is subjected to chemical reaction with basic copper carbonate seed crystals and sodium carbonate through mechanical stirring, so that precipitates are deposited on the surface of the basic copper carbonate seed crystals to form large-grain-size compact crystal particles which are rapidly precipitated to the bottom of the mechanical stirring reactor to remove most of copper ions; the small-particle precipitate and the seed crystal enter a membrane separator along with the supernatant, and the copper ions are further removed after the particles are separated by the hollow fiber membrane, so that the copper concentration of the effluent is greatly reduced. The particle size of the particles formed by the method is large, the structure is compact, the sedimentation performance is good, the defects of large mud production amount and poor sedimentation performance of precipitates in a chemical precipitation method are effectively overcome, the concentration multiple of copper treatment is improved, and meanwhile, serious membrane pollution is not caused, so that the method is an economical and practical method for treating the copper-containing wastewater.
Description
Technical Field
The invention relates to a treatment technology of copper-containing wastewater, in particular to a method for removing copper ions from the wastewater.
Background
copper resources are widely distributed on earth, and copper metal is used in many industries. In recent years, with the development of industries such as copper mine exploitation, metal processing, mechanical manufacturing and the like, pollution of heavy metal copper in the environment is aggravated due to the explosive industrial activities and the large amount of discharged industrial wastewater. Copper can enter water and soil to cause harm to ecological environment and human body. Excessive copper intake in humans can lead to severe mucosal irritation and erosion, stomach discomfort and ulceration, liver and kidney damage, chronic copper poisoning and brain damage. Copper is a hazardous heavy metal, both from the standpoint of ecological safety and human health. Therefore, copper needs to be removed from source wastewater to protect the ecological safety and human health.
The chemical precipitation method is a method for separating precipitate from water by introducing proper anions into water to form precipitate with Cu2+ and then utilizing a solid-liquid separation means. The common precipitant is lime, sulfide, sodium carbonate, etc. The chemical precipitation method has simple process flow, convenient operation and low operating cost, and is suitable for treating the general copper-containing wastewater; however, the CuS precipitate formed by the chemical precipitation method has fine particle size and is difficult to separate from the water body; cu (OH)2 is floccule, has poor settling property, and Cu (OH)2 sludge has high yield and low concentration multiple (the ratio of the total volume of treated wastewater to the volume of generated sludge).
The separation of the precipitate and the water body is difficult in the two precipitation methods, and the liquid-solid separation characteristics of the precipitate formed in the two processes can be improved by introducing the seed crystal by the induced crystallization method. The induced crystallization precipitation method is to add mineral particles into a water body as seed crystals to crystallize and separate out Cu2+ precipitates on the surface of the water body so as to achieve the purposes of increasing the size of the precipitated particles and improving the precipitation performance. Usually, quartz sand is added as a seed crystal, sodium carbonate is added as a precipitator, however, the adding amount of sodium carbonate determines the copper removal rate to a certain extent, the adding amount of sodium carbonate is too low, sufficient carbonate and copper do not react, the copper removal effect is poor, the adding amount is too high, the pH value is increased, and then flocculent precipitate copper hydroxide is generated.
most of the current researches can control the molar ratio of sodium carbonate to copper (the ratio of the concentration of sodium carbonate to the concentration of copper ions in the reaction) to a certain value so as to completely generate crystals in the induced crystallization reaction and improve the performance of precipitates, but the effluent cannot reach the drinking water standard of China, namely 1.0mg/L (GB 5749-2006).
disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for removing copper ions in wastewater by combining mechanical stirring and hollow fiber membrane separation. The method adopts the combination of mechanical stirring and membrane separation, has simple and convenient operation and high automation degree, and is suitable for large-scale engineering application. According to the invention, through mechanical stirring pretreatment, copper ions in the wastewater, sodium carbonate and basic copper carbonate crystal seeds can form particles with large particle size, compact structure and good settling property, the pollution rate of the hollow fiber membrane component is effectively slowed down, the service life of the membrane is prolonged, the copper removal effect and the sludge concentration multiple are obviously improved, and the sludge amount is reduced.
the technical scheme of the invention is as follows:
A method for treating copper-containing wastewater comprises the following steps:
1) Seed crystal feeding: adding basic copper carbonate seed crystals into a mechanical stirring reactor at one time, and adding no seed crystals before emptying the reactor;
2) Mechanical stirring pretreatment: adding excessive sodium carbonate into a mechanical stirring reactor, reacting copper ions in the wastewater with basic copper carbonate crystal seeds and the sodium carbonate to generate large-particle-size dense particles through mechanical stirring, and then precipitating to enable the particles to be deposited at the bottom of the mechanical stirring reactor; CO 32-excess after the reaction is completed;
3) Membrane separation treatment: and (3) the supernatant of the copper-containing wastewater after the mechanical stirring pretreatment enters a membrane separator, continuously reacts under the action of aeration stirring to generate particles, and water is discharged after the separation of the particles by a hollow fiber membrane.
The amount of the one-time added basic copper carbonate seed crystal is 0.5-1.0 g/L.
After the copper-containing wastewater in the step 2) is pretreated by mechanical stirring, excessive CO 32-not less than 50mg/L in the mechanical stirring reactor.
The retention time of the copper-containing wastewater in the step 2) in the mechanical stirring reactor is 15-30min, wherein the stirring time is not less than 5min, and the precipitation time is not less than 10 min.
The residence time of the copper-containing wastewater in the membrane separator is 30-45 minutes.
The invention relates to a copper-containing wastewater treatment device, wherein wastewater is connected with an inlet at the upper part of a mechanical stirring reactor 2 through a water inlet pump 1, a supernatant pipeline of the mechanical stirring reactor 2 is connected with an inlet at the upper part of a membrane separator 4 through a lift pump 3, and a hollow fiber membrane 5 in the membrane separator 4 is connected with an electric valve 6 and a water outlet pump 7 through a water outlet pipe; the medicine storage barrel 8 is connected to a medicine inlet at the upper part of the mechanical stirring reactor 2 through a medicine adding pump 9, the mechanical stirrer 10 and the liquid level meter 11 are installed in the mechanical stirrer 2, the blower 12 is connected to an air inlet at the bottom of the membrane separator 4, and the liquid level meter 13 is installed in the membrane separator 4.
the hollow fiber membrane is a microfiltration membrane or an ultrafiltration membrane which is commonly used in water treatment.
Adding a certain amount of basic copper carbonate seed crystals into a reactor, then adding a certain amount of sodium carbonate into raw water as a precipitator, and mechanically stirring the raw water to uniformly mix the raw water and the basic copper carbonate seed crystals and carry out chemical reaction, namely copper ions and the sodium carbonate form basic copper carbonate in the water and deposit on the surface of the basic copper carbonate seed crystals to form crystal particles with compact large particle size and quickly deposit on the bottom of a mechanical stirrer to remove most of copper ions; the small-particle basic copper carbonate crystal enters a membrane separator along with supernatant, and copper ions are further removed after the particles are separated by a hollow fiber membrane, so that the copper concentration of the effluent is greatly reduced.
the copper-containing wastewater treatment device provided by the invention operates by adopting automatic control.
The invention has the beneficial effects that: the implementation of the invention can obviously improve the sedimentation performance and the concentration multiple of the copper sludge in the copper-containing wastewater, simultaneously improve the removal effect of copper ions in water and reduce the potential harm of copper to the environment and the public. The reactor based on the method can be designed into a fixed or movable device according to the needs, the design scale can be flexibly selected, and the method is suitable for treating general copper-containing wastewater, and has wide application prospect and remarkable environmental benefit.
Drawings
FIG. 1: is a device diagram of the invention.
In the figure: 1-a lift pump; 2-mechanically stirring the reactor; 3-a lift pump; 4-a membrane separation reactor; 5-hollow fiber membranes; 6, electrically operated valve; 7-water outlet pump; 8, a medicine storage barrel; 9-a dosing pump; 10-a mechanical stirrer; 11-a liquid level meter; 12-a blower; 13-liquid level meter.
Detailed Description
Embodiments of the present invention will be described below with reference to the drawings. It should be noted that the present embodiment is illustrative and not restrictive, and the scope of the invention is not limited by the embodiment.
The device of the invention is shown in the attached drawings. The size phi of the waste water storage tank is 1100 multiplied by 2150 mm; the mechanical stirring reactor is a cylinder, and phi is multiplied by H which is 240 multiplied by 347 mm; the membrane separator phi x H is 120 x 1500mm, is provided with 1 hollow fiber microfiltration membrane component, the nominal aperture is 0.22 μm, the effective area is 0.5m2, the water inlet pump and the water outlet pump are lift pumps, the drug feeding pump and the membrane water outlet pump are peristaltic pumps, and the water outlet flow meter is a rotameter. The device adopts PLC (programmable logic controller) control and full-automatic operation, and the PLC adopts general technique programming. The device continuously operates 24 hours a day, wherein the mechanical stirring reactor adopts sequencing batch water inlet and outlet, the membrane separator adopts intermittent water outlet, and the water outlet lasts for 9 minutes and the air aeration lasts for 1 minute in each 10-minute cycle.
The specific operation process is as follows: when the device is started, basic copper carbonate seed crystals are added into the mechanical stirring reactor 2 at one time. Under PLC control, when 11 low liquid levels in liquid level, intake pump 1 pumps copper-containing waste water, rivers get into mechanical stirring reactor 2 by upper portion, intake pump 1 is closed during 11 high liquid levels in level gauge, start agitator 10, start simultaneously with medicine pump 9 will store up the sodium carbonate in medicine bucket 7 and add mechanical stirring reactor 2 by upper portion, copper-containing waste water, seed crystal and sodium carbonate collide each other, react under mechanical agitator effect 10, form the granule of big particle diameter, closely knit, that settling properties is good, deposit gradually to the bottom of mechanical stirring reactor 2. When the liquid level meter 13 is at a low liquid level, the supernatant in the mechanical stirrer 2 enters the membrane separator 4 through the lift pump 3; when the liquid level meter 13 is at a high liquid level, the lifting pump 4 is closed, and the water outlet pump 7 is opened; to mitigate fouling of the hollow fiber micro-membranes 5, the blower 12 aerates the membrane separator 4 to provide air agitation; under the suction action of the water outlet pump 7, water is discharged after passing through the hollow fiber micro-membrane 5 and the electric valve 6, the water outlet pump 7 is closed when the liquid level meter 13 is at a low liquid level, water discharging is stopped, then the lifting pump 3 is started to feed water into the membrane separator 4, and circulation is performed in sequence.
Example 1: the water treatment amount of the device is 15L/h, the residence time of the mechanical stirring reactor is 15 minutes (stirring for 5 minutes and settling for 10 minutes), and the hydraulic residence time of the membrane separator is 30 minutes. The device is used for treating simulated wastewater with the pH value of 6.1-6.2 and the copper-containing concentration of 20 mg/L. When the experiment is started, 0.5g/L of basic copper carbonate seed crystal is added into the mechanical stirring reactor; when the adding amount of sodium carbonate is controlled to be 104mg/L in an experiment, the mass concentration of the copper in the effluent is stabilized to be below 1mg/L, and is gradually reduced to 0.4mg/L along with the increase of the treated water amount, so that the removal efficiency reaches 98%; the concentration of the carbonate ion in the effluent is 50-55 mg/L. The concentration factor for the process under this condition was 7982. The specific flux of the membrane is reduced from the initial 57L/(m2 h m) to 33L/(m2 h m), and can be restored to 51L/(m2 h m) after chemical cleaning.
Example 2: the water treatment amount of the device is 15L/h, the residence time of the mechanical stirring reactor is 15 minutes (stirring for 5 minutes and settling for 10 minutes), and the hydraulic residence time of the membrane separator is 45 minutes. The device is used for treating simulated wastewater with the pH value of 6.2-6.4 and the copper-containing concentration of 20 mg/L. When the experiment is started, 0.5g/L of basic copper carbonate seed crystal is added into the mechanical stirring reactor; in the experiment, when the adding amount of sodium carbonate is controlled to be 104mg/L, the mass concentration of the copper in the effluent is stabilized to be below 2mg/L, the copper concentration in the effluent is stabilized to be 0.07mg/L after the treated water amount reaches 800L, and the removal rate reaches 99%; the concentration of the carbonate ion in the effluent is 50-55 mg/L. The concentration factor of the process under this condition was 3175. The specific flux of the membrane is reduced from the initial 62.2L/(m2 h m) to 34.7L/(m2 h m), and the specific flux can be restored to 57L/(m2 h m) after chemical cleaning.
Example 3: the water treatment capacity of the apparatus was 20L/h, the residence time of the mechanically stirred reactor was 30 minutes (5 minutes of stirring, 16 minutes of settling) and the hydraulic residence time of the membrane separator was 30 minutes. The device is used for treating simulated wastewater with the pH value of 6.1-6.2 and the copper-containing concentration of 50 mg/L. When the experiment is started, 1g/L of basic copper carbonate seed crystal is added into the mechanical stirring reactor; in the experiment, when the adding amount of sodium carbonate is controlled to be 180mg/L, the mass concentration of the copper in the effluent is stabilized to be about 0.5mg/L, and the removal rate reaches 99 percent; the concentration of the carbonate ion in the effluent is 50-60 mg/L. The specific flux of the membrane is reduced from the initial 46.9L/(m2 h m) to 29.6L/(m2 h m), and can be restored to 46.2L/(m2 h m) after chemical cleaning.
Example 4: the water treatment capacity of the apparatus was 20L/h, the residence time of the mechanically stirred reactor was 30 minutes (5 minutes of stirring, 16 minutes of settling) and the hydraulic residence time of the membrane separator was 45 minutes. The device is used for treating simulated wastewater with the pH value of 6.0-6.1 and the copper-containing concentration of 50 mg/L. When the experiment is started, 1g/L of basic copper carbonate seed crystal is added into the mechanical stirring reactor; when the adding amount of sodium carbonate is controlled at 140mg/L in the experiment, the mass concentration of the copper in the effluent is stabilized at about 1mg/L, and the removal rate reaches 98%; the concentration of the carbonate ion in the effluent is 50-60 mg/L. The concentration factor for this process under this condition was 2032. The specific flux of the membrane is reduced from 47.5L/(m2 h m) to 39.3L/(m2 h m), and can be recovered to 47.6L/(m2 h m) after chemical cleaning.
Claims (3)
1. A method for treating copper-containing wastewater is characterized by comprising the following steps:
1) Seed crystal feeding: adding basic copper carbonate seed crystals into a mechanical stirring reactor at one time, and adding no seed crystals before emptying the reactor;
2) Mechanical stirring pretreatment: adding excessive sodium carbonate into a mechanical stirring reactor, reacting copper ions in the wastewater with basic copper carbonate seed crystals and the sodium carbonate to generate large-particle-size dense particles through mechanical stirring for a certain time, and then standing and precipitating for a period of time to enable the particles to be deposited at the bottom of the mechanical stirring reactor;
3) membrane separation treatment: the supernatant fluid of the copper-containing wastewater after the mechanical stirring pretreatment enters a membrane separator, continues to react under the action of aeration stirring to generate particles, and then is separated by a hollow fiber membrane to obtain water;
The amount of the one-time added basic copper carbonate seed crystal in the step 1) is 0.5-1.0 g/L;
after the copper-containing wastewater in the step 2) is subjected to mechanical stirring pretreatment, excessive CO 32-not less than 50mg/L in the mechanical stirring reactor; the copper-containing wastewater stays in the mechanical stirring reactor for 15-30min, wherein the stirring time is not less than 5min, and the precipitation time is not less than 10 min;
the residence time of the copper-containing wastewater in the membrane separator is 30-45 minutes.
2. The treatment device for realizing the copper-containing wastewater treatment method of claim 1 is characterized in that wastewater is connected with an inlet at the upper part of a mechanical stirring reactor 2 through a water inlet pump 1, a supernatant pipeline of the mechanical stirring reactor 2 is connected with an inlet at the upper part of a membrane separator 4 through a lift pump 3, and a hollow fiber membrane 5 in the membrane separator 4 is connected with an electric valve 6 and a water outlet pump 7 through a water outlet pipe; the medicine storage barrel 8 is connected to a medicine inlet at the upper part of the mechanical stirring reactor 2 through a medicine adding pump 9, the mechanical stirrer 10 and the liquid level meter 11 are installed in the mechanical stirrer 2, the blower 12 is connected to an air inlet at the bottom of the membrane separator 4, and the liquid level meter 13 is installed in the membrane separator 4.
3. The apparatus of claim 2, wherein the hollow fiber membrane is a microfiltration membrane or an ultrafiltration membrane commonly used in water treatment.
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| CN201610911165.3A CN106430709B (en) | 2016-10-19 | 2016-10-19 | Method and device for treating copper-containing wastewater |
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| CN109205829A (en) * | 2018-09-08 | 2019-01-15 | 天津大学 | The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water |
| CN111170354A (en) * | 2019-12-31 | 2020-05-19 | 东莞市广华化工有限公司 | Purification device for recovering basic copper carbonate from acidic etching waste liquid and use method thereof |
| CN115784408B (en) * | 2022-08-31 | 2023-09-12 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by utilizing modified seed crystal induced crystallization |
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| CN101024533A (en) * | 2007-02-01 | 2007-08-29 | 天津大学 | Method of diaphragm separation electrolyzing integrated treatment of wate, water containing heavy metal copper |
| WO2015014546A1 (en) * | 2013-07-31 | 2015-02-05 | Krones Ag | Method and device for material-oriented water treatment for mines |
| CN105948366A (en) * | 2016-07-15 | 2016-09-21 | 武汉尚远环保股份有限公司 | Treatment method for copper-containing wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024533A (en) * | 2007-02-01 | 2007-08-29 | 天津大学 | Method of diaphragm separation electrolyzing integrated treatment of wate, water containing heavy metal copper |
| WO2015014546A1 (en) * | 2013-07-31 | 2015-02-05 | Krones Ag | Method and device for material-oriented water treatment for mines |
| CN105948366A (en) * | 2016-07-15 | 2016-09-21 | 武汉尚远环保股份有限公司 | Treatment method for copper-containing wastewater |
Non-Patent Citations (1)
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| 诱导结晶工艺处理含铜废水;阎中等;《化工学报》;20091031;第60卷(第10期);正文第2604页左栏第1行至第2608页左栏第16行、图1 * |
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