JP7152635B1 - Treatment system and process for waste acid-containing wastewater in copper smelting - Google Patents

Abstract

A system and process for efficiently treating waste acid-containing wastewater in copper smelting. A treatment system includes a primary treatment system and a secondary treatment system for sequentially treating waste acid-containing wastewater, the process comprising a dearsenication step S1 and a defluoridation-neutralization step S2. and step S3 of electrolytic advanced treatment. [Selection drawing] Fig. 1

Description

TECHNICAL FIELD The present invention relates to the technical field of waste acid-containing wastewater treatment, and in particular to an efficient treatment system and process for waste acid-containing wastewater in copper smelting.

The waste acid stock solution from copper smelting is mainly generated in the sulfuric acid flue gas purification process. , and the components in the liquid are complex. The conventional treatment method not only has high operating cost and low overall recovery rate, but also has insufficient treatment effect.

Conventionally, in the treatment system of waste acid-containing wastewater in copper smelting, the arsenic sulfide precipitation process is used to precipitate arsenic in the waste acid solution, which can eliminate the pollution caused by a large amount of arsenic, but the removal effect on other heavy metal elements In the conventional technology, the treatment efficiency of the waste acid-containing wastewater treatment equipment is low, so the treatment amount in a unit time is small, and the needs of production cannot be met. Since the acid solution cannot be treated at a high level, the treatment quality of the waste acid solution is inferior.

In response to the problems described in the background art above, the present invention provides
including a primary treatment system, a secondary treatment system for the sequential treatment of waste acid-containing wastewater,
The primary treatment system comprises a circulation reactor and a precipitation reactor provided below the circulation reactor and in communication with an outlet of the circulation reactor,
The circulation reactor comprises two circulation reaction chambers arranged side by side, a first stirrer movably provided inside the circulation reaction chamber, and two circulation reaction chambers provided above the circulation reaction chamber. upper communication means for communicating with the circulation reaction chamber; lower communication means provided in the lower part of the circulation reaction chamber and communicating the two circulation reaction chambers;
an exhaust turbofan and a hydrogen sulfide gas recovery device in communication with the exhaust turbofan via a negative pressure pipe,
The upper communication means is provided with a negative pressure device for circulating the waste acid-containing wastewater between two circulation reaction chambers, the upper communication means and the lower communication means, and the lower communication means communicates with the precipitation reactor. ,
said secondary treatment system comprising a cyclone flocculation device in communication with a precipitation reactor and a flocculation tank in communication with said cyclone flocculation device;
The cyclone electrolysis flocculation device comprises a cyclone electrolytic cell having water inlets at both ends communicating with the precipitation reaction device, a central rotating shaft provided at the center of the cyclone electrolytic cell, and a cyclone electrolyzing device provided on the central rotating shaft. Two sets of hydrovortex fans close to the water inlet of the tank, a dynamic electrolysis device mounted on the central rotating shaft and positioned between the two hydrovortex fans, and a cyclone electrolysis tank horizontally mounted on the side wall and a drainage unit in communication with the coagulation basin;
The dynamic electrolysis device includes an anode core and a cathode core movably mounted on a central rotating shaft,
The anode core is close to the central rotating shaft (41), and the cathode core is movably mounted around the outside of the anode core, providing an efficient treatment system for waste acid-containing wastewater in copper smelting.

According to one aspect of the present invention, the anode core includes a connection shaft mounted on the central rotating shaft, first connection frames provided at both ends of the connection shaft, and attached to the first connection frames. and a plurality of sets of electrode plate mounts arranged evenly in the radial direction of the central rotation shaft, and a plurality of sets of crescent-shaped electrode plates attached to the electrode plate mounts and arranged evenly in the axial direction of the central rotation shaft. and
The crescent-shaped electrode plate includes an iron electrode plate and an aluminum electrode plate, and the iron electrode plate and the aluminum electrode plate are spaced apart,
The cathode core includes a second connection frame provided on the central rotating shaft, and a plurality of sets of cathode electrode plates attached to the second connecting frame and evenly arranged in a radial direction of the central rotating shaft. ,
The cathode electrode plate is located between the crescent electrode plate and the inner wall of the cyclone electrolytic cell.
By providing a plurality of crescent-shaped iron electrode plates and aluminum electrode plates, the area of the electrode plates with the waste acid solution is effectively increased, the consumption of iron and aluminum increases, and the ferric hydroxide, water Aluminum oxide colloids are produced more and act as micro-flocculants, suspended granules and colloidal contaminants in water are adsorbed and coated by the micro-flocculants, resulting in loss of stability and finally formation of sediment. be.

According to one aspect of the present invention, a plurality of sets of annular ducts are evenly arranged in the axial direction on the side wall of the cyclone electrolytic bath, and jet nozzles communicating with the cyclone electrolytic bath are evenly distributed in the annular ducts. are placed.
By providing the annular duct, the internal pressure of the cyclone electrolytic cell increases, and in combination with the microbubbles, air levitation is realized, further improving the treatment effect.
According to one aspect of the present invention, the lower communication means includes a communication cavity provided in the lower part of the circulation reaction chamber, a connection cover provided in the upper central portion of the communication cavity, and a connection cover provided inside the communication cavity. , and a filtration blocking unit located below the connection cover,
The filtration blocking unit divides the communication cavity into a drain chamber and a cake storage chamber, and the connecting cover is provided with a first filtrate spiral conveyer communicating with the cake storage chamber at an angle.
By installing a filter blocking unit in the circulation reactor, the sediment in the circulating water stream is filtered, and the sediment is removed by the first filtrate spiral conveyer, so that the reaction progresses more fully. , the quality of dearsenicing is effectively improved.

According to one aspect of the present invention, the precipitation reactor comprises a mixing reaction chamber provided directly below a communicating cavity and communicating with a drain chamber, and a second stirrer provided inside the mixing reaction chamber. ,
a limestone slurry inlet provided in the side wall of the mixing reaction chamber; a gypsum settling chamber provided in the lower portion of the mixing reaction chamber; and a filter press provided in the gypsum settling chamber;
The filter press includes two gypsum filter press plates that are vertically movable with respect to the interior of the gypsum settling chamber, a power module that is provided in the gypsum settling chamber and drives the gypsum filter press plates, and an inclined gypsum filter press plate. and a second filtrate helical transporter in communication with the central space of the gypsum settling chamber.

The filter press efficiently separates the sediment from the filtrate, which is advantageous for improving treatment efficiency.
According to one aspect of the present invention, the hydrogen sulfide gas recovery device comprises a closed reaction vessel, an atomized alkaline solution spray disk provided in the upper part of the closed reaction vessel, and an outer wall of the closed reaction vessel. A hydrogen sulfide gas jet ring, a connection port that connects the hydrogen sulfide gas jet ring and the exhaust turbofan via a high-pressure pipe, and a sodium sulfide solution replenishment provided at the bottom of the closed reaction vessel and communicating with the circulation reaction chamber. including plumbing.
The generated hydrogen sulfide gas can generate sodium hydroxide and sodium sulfide, thus reducing the amount of sodium sulfide used while the harmful gas is recovered and reused,
Therefore, it is advantageous for cost reduction.

A process for efficient treatment of waste acid-containing wastewater in copper smelting, comprising:
First, waste acid-containing wastewater and a sodium sulfide solution with a concentration of 35 to 45% are mixed at a ratio of 1:0.08 to 0.3.
into the circulation reaction chamber at a volume ratio of , continuously stirred at a rotation speed of 600-2000 r/min using the first stirrer, and the waste acid-containing wastewater and the sodium sulfide solution are subjected to two circulation reactions by a negative pressure device. circulating in the chamber, the upper communication means and the lower communication means, then separating and filtering out the produced precipitate, and efficiently exhausting the produced hydrogen sulfide waste gas by means of an exhaust turbofan;
Step S1 of the arsenic removal treatment to send to the hydrogen sulfide gas recovery device;
Next, the waste acid-containing waste water in the circulation reaction chamber is put into the precipitation reactor, and the limestone slurry is added to 1500
Add up to 2800 g/L, react while stirring, react waste acid-containing wastewater and limestone to produce gypsum and calcium fluoride precipitates, filter and press, remove precipitates, and separate the primary filtrate. Next, sodium hydroxide is added to the primary filtrate until the pH reaches 6 to 7, reacted with stirring, and then subjected to a secondary filtration press to remove precipitates and separate the secondary filtrate. Then, step S2 of the defluorination-neutralization treatment,
The secondary filtrate is charged from both ends of the cyclone electrolytic cell, the secondary filtrate is turned into a vortex by high-speed rotation of the hydrovortex fan, the anode core and cathode core are rotated, and the secondary filtrate is brought to a current density of 3.
Electrolyze at 30-600 A/m ² for 30-60 minutes to form hydroxide colloids, adsorb remaining heavy metal contaminants, and finally send the secondary filtrate with hydroxide colloids to the coagulation sedimentation tank. , and step S3 of electrolysis high-level processing in which air flotation/sedimentation separation is performed.
Beneficial effects of the present invention are as follows. In the efficient treatment system of waste acid-containing wastewater in copper smelting provided by the present invention, waste acid-containing wastewater circulates in a circulation reactor, reacts with sodium sulfide, and precipitates generated during circulation is filtered and discharged, and the exhaust turbofan installed above the upper liquid level of the waste acid quickly discharges the hydrogen sulfide gas and circulates it repeatedly, not only improving the reaction rate but also improving the processing quality. can improve.

In the present invention, a cyclone electrolyzer, a hydrovortex fan, and a dynamic electrolyzer are provided to efficiently and dynamically electrolyze the waste water containing waste acid, and the iron electrode provided because sodium hydroxide is excessively added. Ferric hydroxide and colloidal aluminum hydroxide are generated by the plates and aluminum electrode plates, and function as micro-flocculants. The processing quality is further improved, Cu, As,
Advanced treatment to harmful substances such as Zn, Pb, F is achieved.

1 is a schematic diagram of the overall structure of Embodiment 1 of the present invention; FIG. 1 is a structural schematic diagram of a hydrogen sulfide gas recovery apparatus according to Example 1 of the present invention; FIG. FIG. 4 is a structural schematic diagram of the lower communication means of Embodiment 1 of the present invention; 1 is a structural schematic diagram of a precipitation reactor of Example 1 of the present invention; FIG. FIG. 2 is a structural schematic diagram of a cyclone electrocoagulation apparatus according to Example 2 of the present invention; FIG. 4 is a structural schematic diagram of an anode electrode plate according to Example 2 of the present invention; FIG. 4 is a structural schematic diagram of the cathode electrode plate of Example 2 of the present invention; FIG. 4 is a structural schematic diagram of an annular duct according to Embodiment 3 of the present invention;

Example 1
An efficient treatment system for waste acid-containing wastewater in copper smelting includes a primary treatment system for treating waste acid-containing wastewater,
As shown in FIG. 1, the primary treatment system includes a circulation reactor 1 and a precipitation reactor 2 provided below the circulation reactor 1 and communicating with the outlet of the circulation reactor 1,
The circulation reaction apparatus 1 includes two circulation reaction chambers 10 arranged in parallel, a first stirrer 14 movably provided inside the circulation reaction chamber 10, and a upper communication means 11 for communicating the reaction chambers 10; lower communication means 12 provided in the lower part of the circulation reaction chamber 10 and communicating the two circulation reaction chambers 10; and upper communication means 11 provided in the circulation reaction chambers. including two exhaust turbofans 13 corresponding to 10 and a hydrogen sulfide gas recovery device 3 communicating with the exhaust turbofans 13 via negative pressure piping,
As shown in FIG. 2, the hydrogen sulfide gas recovery device 3 includes a closed reaction tank 30, an atomized alkaline liquid spray disk 31 provided in the upper part of the closed reaction tank 30, and an outer wall of the closed reaction tank 30. A hydrogen sulfide gas jet ring 32, a connection port 33 that connects the hydrogen sulfide gas jet ring 32 and the exhaust turbofan 13 via a high-pressure pipe, and a connection port 33 that is provided at the bottom of the closed reaction tank 30 and communicates with the circulation reaction chamber 10. and a sodium sulfide solution replenishment line 34.
The upper communication means 11 includes two circulation reaction chambers 10, an upper communication means 11 and a lower communication means 12.
A negative pressure device 110 is provided for circulating the waste acid-containing waste water between, and the lower communication means 12 communicates with the precipitation reactor 2,
As shown in FIG. 3, the lower communication means 12 includes a communication cavity 120 provided in the lower part of the circulation reaction chamber 10, a connection cover 121 provided in the upper central part of the communication cavity 120,
a filtration blocking unit 122 provided inside the communication cavity 120 and positioned below the connection cover 121;
The filter blocking unit 122 partitions the communication cavity 120 into a drain chamber 123 and a filter cake storage chamber 124 , and the connection cover 121 includes the first filtrate spiral conveying machine 1 communicating with the filter cake storage chamber 124 .
25 are slanted.
As shown in FIG. 4, the precipitation reactor 2 includes a mixing reaction chamber 20 provided directly below a communicating cavity 120 and communicating with a drain chamber 123, and a second stirrer provided inside the mixing reaction chamber 20. 21, a limestone slurry inlet 22 provided in the side wall of the mixing reaction chamber 20, a gypsum settling chamber 23 provided in the lower portion of the mixing reaction chamber 20, and a filter press 24 provided in the gypsum settling chamber 23.
The filter press 24 includes two gypsum filter press plates 240 vertically movable inside the gypsum settling chamber 23, a power module 241 provided in the gypsum settling chamber 23 for driving the gypsum filter press plates 240, and an inclined gypsum filter press plate 241. and a second filtrate spiral conveyer 242 provided at the end of the gypsum settling chamber 23 and communicating with the central space of the gypsum settling chamber 23 .
Among these, the second filtrate spiral conveying machine 242, the power module 241, the second agitator 21, the first filtrate spiral conveying machine 125, the negative pressure device 110, the exhaust turbofan 13, and the first agitator 14 are all conventional Products are adopted by technology, and specific product numbers may be determined by those skilled in the art according to their needs.

Example 2
Compared with Example 1, the following points are different.
An efficient treatment system for waste acid-containing wastewater in copper smelting includes a primary treatment system, a secondary treatment system for sequentially treating waste acid-containing wastewater,
The secondary treatment system includes a cyclone flocculation device 4 in communication with the precipitation reactor 2 and a flocculation tank 5 in communication with the cyclone flocculation device 4,
As shown in FIG. 5, the cyclone electrolytic flocculation device 4 includes a cyclone electrolytic bath 40 having water inlets at both ends communicating with the precipitation reactor 2, a central rotary shaft 41 provided at the center of the cyclone electrolytic bath 40, and a central Two sets of hydrovortex fans 42 provided on the rotating shaft 41 and close to the water inlet of the cyclone electrolyzer 40, and a dynamic electrolysis device attached to the central rotating shaft 41 and positioned between the two hydrovortex fans 42. 43, and a drainage unit 44 horizontally mounted on the side wall of the cyclone electrolyzer 40 and in communication with the coagulating sedimentation tank 5,
The dynamic electrolysis device 43 includes an anode core 430 and a cathode core 43 which are movably provided on the central rotating shaft 41.
including 1
Anode core 430 is close to central rotating shaft 41 , and cathode core 431 is provided around anode core 430 .
As shown in FIG. 6, the anode core 430 includes a connection shaft 432 installed on the central rotating shaft 41, first connection frames 433 provided at both ends of the connection shaft 432, and attached to the first connection frames 433,
and a plurality of sets of electrode plate mounts 434 arranged evenly in the radial direction of the central rotating shaft 41;
a plurality of sets of crescent-shaped electrode plates 437 attached to the electrode plate mount 434 and evenly spaced in the axial direction of the central rotating shaft 41;
The crescent-shaped electrode plate 437 includes an iron electrode plate and an aluminum electrode plate, and the iron electrode plate and the aluminum electrode plate are spaced apart.
As shown in FIG. 7, the cathode cores 431 are attached to a second connection frame 435 provided on the central rotating shaft 41 and the second connecting frame 435 and arranged evenly in the radial direction of the central rotating shaft 41. a plurality of sets of cathode electrode plates 436;
Cathode electrode plate 436 is located between crescent electrode plate 437 and the inner wall of cyclone electrolytic cell 40 .
Among these, the hydrovortex fan 42 adopts products according to the prior art, and specific product numbers may be determined by those skilled in the art according to their needs.

Example 3
Compared with Example 2, the following points are different.
As shown in FIG. 8 , six groups of annular ducts 45 are evenly arranged in the axial direction on the side wall of the cyclone electrolytic bath 40 , and the jet nozzles 46 communicating with the cyclone electrolytic bath 40 are evenly spaced in the annular ducts 45 . are placed.

Example 4
An efficient treatment process for waste acid-containing wastewater in copper smelting using the treatment system of Example 1 includes the following steps.
S1, arsenic removal treatment First, waste acid-containing waste water and a sodium sulfide solution having a concentration of 35% are introduced into the circulation reaction chamber 10 at a volume ratio of 1:0.08, and the first stirrer 14 is used to rotate the mixture at 600 r/min. The waste acid-containing waste water and the sodium sulfide solution are passed through two circulation reaction chambers 10 by a negative pressure device 110 while being continuously stirred at a rotational speed.
, the upper communication means 11 and the lower communication means 12 are circulated, then the produced precipitate is separated, filtered and discharged, and the produced hydrogen sulfide waste gas is efficiently discharged by the exhaust turbo fan 13. , to the hydrogen sulfide gas recovery unit 3 .
S2, defluorination-neutralization treatment Next, the waste acid-containing waste water in the circulation reaction chamber is put into the precipitation reactor 2, and 150% limestone slurry is added.
Add 0 g/L, react while stirring, react waste acid-containing wastewater and limestone to produce gypsum and calcium fluoride precipitates, filter press, remove precipitates, separate primary filtrate,
Next, sodium hydroxide is added to the primary filtrate until the pH reaches 6, and the mixture is reacted with stirring, followed by a secondary filtration press to remove precipitates and separate the secondary filtrate.

Example 5
An efficient treatment process for waste acid-containing wastewater in copper smelting by the treatment system of Example 2 described in this example includes the following steps.
S1, arsenic removal treatment First, waste acid-containing waste water and a sodium sulfide solution having a concentration of 35% are introduced into the circulation reaction chamber 10 at a volume ratio of 1:0.08, and the first stirrer 14 is used to rotate the mixture at 600 r/min. The waste acid-containing waste water and the sodium sulfide solution are passed through two circulation reaction chambers 1 by a negative pressure device 110 while being continuously stirred at a rotational speed.
0, circulating in the upper communication means 11 and the lower communication means 12, then separating and filtering the generated sediment and discharging the generated hydrogen sulfide waste gas efficiently by the exhaust turbo fan 13; and sent to the hydrogen sulfide gas recovery device 3.
S2, defluorination-neutralization treatment Next, the waste acid-containing waste water in the circulation reaction chamber is put into the precipitation reactor 2, and 150% limestone slurry is added.
Add 0 g/L, react while stirring, react waste acid-containing waste water with limestone to produce gypsum and calcium fluoride precipitates, filter and press, remove precipitates, and separate the primary filtrate. Next, sodium hydroxide is added to the primary filtrate until the pH reaches 6, reacted with stirring, and then subjected to a secondary filtration press to remove precipitates and separate the secondary filtrate.
S3, the secondary filtrate is charged from both ends of the advanced electrolytic treatment cyclone electrolytic tank 40, the hydrovortex fan 42 is rotated at high speed of 2000 r/min to make the secondary filtrate vortex, and the anode core 430 and the cathode core 4
31 was rotated to electrolyze the secondary filtrate at a current density of 330 A/m ² for 30 minutes to form hydroxide colloids, adsorb the remaining contaminants such as heavy metals, and finally generate hydroxide colloids. The secondary filtrate is sent to the coagulation-sedimentation tank 5 for air flotation and sedimentation separation.

Example 6
Compared with Example 5, the following points are different.
S1, in the arsenic removal treatment, the first stirrer 14 continuously stirs at a rotation speed of 2000 r/min,
S2, adding 1800 g/L of limestone slurry, adding sodium hydroxide to the primary filtrate so that the pH becomes 6 in the defluorination-neutralization treatment,
In S3, electrolysis advanced treatment, the hydrovortex fan 42 rotates at a high speed of 4000 r/min, the current density is 500 A/m ² , and the electrolysis time is 40 min.

Example 7
Compared with Example 5, the following points are different.
S1, in the arsenic removal treatment, the first stirrer 14 continuously stirs at a rotation speed of 2000 r/min,
S2, adding 1800 g/L of limestone slurry, adding sodium hydroxide to the primary filtrate so that the pH becomes 6 in the defluorination-neutralization treatment,
In S3, electrolysis advanced treatment, the hydrovortex fan 42 rotates at a high speed of 4000 r/min, the current density is 600 A/m ² , and the electrolysis time is 60 min.

Example 8
Compared with Example 7, the following points are different.
S2, adding sodium hydroxide to the primary filtrate to bring the pH to 7 in the defluorination-neutralization process.

Example 9
Compared with Example 7, the following points are different.
S1, in the arsenic removal treatment, waste acid-containing waste water and sodium sulfide solution with a concentration of 45% were mixed in a ratio of 1:0.
. put into the circulation reaction chamber 10 at a volume ratio of 3,
S2, add 2800 g/L of limestone slurry.

Example 10
This example describes an efficient treatment process for waste acid-containing wastewater in copper smelting by the treatment system of Example 3, and differs from Example 5 in the following points.
S3, the secondary filtrate is charged from both ends of the advanced electrolytic treatment cyclone electrolytic tank 40, the hydrovortex fan 42 is rotated at high speed to make the secondary filtrate a whirlpool, and the anode core 430 and the cathode core 431 are rotated to rotate the secondary filtrate. The filtrate is electrolysed to form hydroxide colloids, and at the same time microbubbles are packed into the vortex through jet nozzles 46 by annular duct 45, and the microbubbles combine with the hydroxide colloids to release residual heavy metals, etc. Adsorb pollutants.

EXPERIMENTAL EXAMPLES Example 4, Example 5, Example 6 and the prior art method described above were used to treat waste acid-containing wastewater from a copper smelting plant having a waste acid concentration of 15%, and the results of the tests in each example. The processing quality and time involved are recorded in Table 1 below.
Table 1: Contaminant Removal Rate and Treatment Time for Each Example

(1) Comparing the test results of Examples 4 to 10 provided in the present invention with the test results of the prior art, it is found that, compared with the prior art, the technical solution of the present invention is the impurities such as arsenic. can effectively increase the removal rate of , effectively improve the treatment efficiency, improve the treatment volume per unit time, greatly improve the treatment quality of waste acid-containing wastewater by conventional technology, and contribute to the copper smelting enterprise It was found to meet the required waste acid-containing wastewater discharge requirements.
(2) Comparing the test results of Example 4 and Example 5, it was found that Example 5 can further increase the pollutant removal rate. , the processing quality of the waste acid solution is further improved, and the waste acid-containing wastewater is efficiently and dynamically electrolyzed by installing a cyclone electrolytic cell, a hydrovortex fan, and a dynamic electrolysis device,
Since sodium hydroxide is added, ferric hydroxide and aluminum hydroxide colloids are generated by the iron electrode plate and aluminum electrode plate provided, which function as micro-flocculants and remove suspended granules and colloidal contaminants in water. Adsorbed and coated by the microflocculant, thereby
The treatment quality is further improved, and advanced treatment of harmful substances such as Cu, As, Zn, Pb, and F is achieved.
(3) By comparing Examples 5 and 6, it was found that the treatment quality could be further improved by extending the electrolysis time and increasing the current density. will release more iron ions, aluminum ions, and more hydroxide colloids will be produced in the waste acid solution, thus promoting high adsorption removal.
(4) Comparing Example 5, Example 6 and Example 7, it is found that the electrolysis parameters provided in Example 7 are the optimum electrolysis parameters disclosed in this technical solution;
Here, the current density is 600 A/m ² and the electrolysis time is 60 min.
(6) Comparing Example 7 and Example 8, it was found that the treatment quality was further improved by increasing the electrolysis pH from 6 to 7. There are more hydroxyl radicals in the environment, and the surplus hydroxyl radical ions combine with the iron ions and aluminum ions generated at the electrolytic anode to form more hydroxide colloids, while the hydroxyl radical ions are released from the waste acid solution. A precipitate can be formed with the heavy metal ions in it, which makes the treatment effect better.
(7) Comparing Example 7 and Example 9, it was found that by increasing the amount of sodium sulfide and limestone slurry added, the positive reaction in the circulation reaction in the circulation reaction chamber 10, the upper communication means 11 and the lower communication means 12 was found to be advantageous for accelerating the progress of arsenic and precipitating arsenic more efficiently. Moreover, the test results show that the addition amount of sodium sulfide, limestone slurry in Example 9 is the optimum value, and if the addition amount is too high, it will cause waste.
(8) The annular duct and jet nozzle added in Example 10 fill the cyclone electrolytic bath with microbubbles, thereby performing an air floating treatment on the microflocculant, and combining the microbubbles and the flocculant for an adsorption effect. and improve processing quality.
(9) From the above comparison, Example 10 is the best embodiment disclosed in this technical solution, which greatly improves the treatment quality of waste acid-containing wastewater by the prior art, and is required by copper smelting enterprises. meet waste acid-containing wastewater discharge requirements.

1-Circulation reactor, 10-Circulation reaction chamber, 11-Upper communication means, 110-Negative pressure device, 12-
Lower communication means, 120 - communication cavity, 121 - connection cover, 122 - filtration blocking unit, 123 - drain chamber, 124 - filter cake storage room, 125 - first filtrate spiral conveyer, 13 - exhaust turbofan, 14 - 1st agitator, 2 - precipitation reactor, 20 - mixing reaction chamber, 21 - 2nd agitator, 22 - limestone slurry inlet, 23 - gypsum precipitation chamber, 24 - filter press, 240 -
Gypsum filter press plate, 241 - power module, 242 - second filtrate spiral conveyer, 3 - hydrogen sulfide gas recovery device, 30 - closed reaction tank, 31 - atomized alkaline liquid spray disc, 32 - hydrogen sulfide gas jet ring , 33-connection port, 34-sodium sulfide solution replenishment pipe, 4-cyclone electrolytic flocculation device, 40-cyclone electrolytic cell, 41-central rotating shaft, 42-hydrovortex fan, 43-dynamic electrolysis device, 430-anode core , 431—cathode core, 432
- connection shaft, 433 - first connection frame, 434 - electrode plate mount, 437 - crescent electrode plate 43
5-, second connecting frame, 436-cathode electrode plate, 44-drainage unit, 45-annular duct, 46
- jet nozzle, 5 - coagulation basin

Claims (7)

A treatment system for waste acid-containing wastewater in copper smelting, comprising:
comprising a primary treatment system and a secondary treatment system for sequentially treating waste acid-containing wastewater;
The primary treatment system comprises a circulation reactor (1) and a precipitation reactor (2) provided below the circulation reactor (1) and communicating with a drain port of the circulation reactor (1). including
The circulation reactor (1) includes two circulation reaction chambers (10) arranged side by side, and the circulation reaction chamber (
10), a first stirrer (14) movably provided inside the circulation reaction chamber (10), and an upper communication means (11) provided above the circulation reaction chamber (10) and communicating the two circulation reaction chambers (10). , a lower communication means (12) provided in the lower part of the circulation reaction chamber (10) and communicating the two circulation reaction chambers (10); 10
) and a hydrogen sulfide gas recovery device (3) communicating with the exhaust turbofans (13) via negative pressure piping,
The upper communication means (11) includes two circulation reaction chambers (10), upper communication means (11)
and a negative pressure device (110) for circulating the waste acid-containing waste water between the lower communication means (12), the lower communication means (12) communicating with the precipitation reactor (2),
said secondary treatment system comprising a cyclone flocculation device (4) in communication with a precipitation reactor (2) and a flocculation tank (5) in communication with said cyclone flocculation device (4);
The cyclone electrolytic flocculation device (4) comprises a cyclone electrolytic bath (40) having water inlets at both ends communicating with the precipitation reactor (2), and a central rotating shaft (40) provided at the center of the cyclone electrolytic bath (40). 41), two sets of hydrovortex fans (42) attached to the central rotating shaft (41) and close to the water inlet of the cyclone electrolyzer (40), attached to the central rotating shaft (41), and A dynamic electrolysis device (43) located between two hydrovortex fans (42) and a waste water horizontally installed on the side wall of said cyclone electrolyser (40) and communicating with a coagulating sedimentation basin (5). a unit (44);
The dynamic electrolysis device (43) includes an anode core (
430) and a cathode core (431),
Said anode core (430) is close to the central axis of rotation (41) and said cathode core (431)
is movably disposed around the outside of the anode core (430),
A processing system characterized by: The anode core (430) includes a connection shaft (432) installed on the central rotating shaft (41), first connection frames (433) provided at both ends of the connection shaft (432), and the first 1 connection frame (
A plurality of sets of electrode plate mounts (434) attached to the central rotating shaft (41) and evenly distributed in the radial direction of the central rotating shaft (41); a plurality of sets of crescent-shaped electrode plates (437) evenly spaced in the axial direction of
The crescent-shaped electrode plate (437) includes an iron electrode plate and an aluminum electrode plate, and the iron electrode plate and the aluminum electrode plate are spaced apart,
The cathode core (431) has a second connection frame (43) attached to the central rotating shaft (41).
5), and a plurality of sets of cathode electrode plates (436) attached to the second connection frame (435) and evenly arranged in the radial direction of the central rotating shaft (41),
The cathode electrode plate (436) comprises a crescent electrode plate (437) and a cyclone electrolytic bath (40).
located between the inner wall of
The treatment system for waste acid-containing waste water in copper smelting according to claim 1, characterized in that: A plurality of sets of annular ducts (45) are evenly arranged in the axial direction on the sidewall of the cyclone electrolytic bath (40), and the annular ducts (45) are jet nozzles communicating with the cyclone electrolytic bath (40). (46) are evenly distributed,
The treatment system for waste acid-containing waste water in copper smelting according to claim 1, characterized in that: The lower communication means (12) is a communication cavity (
120) and a connection cover (1
21) and a connection cover (121) provided inside the communication cavity (120) and
a filtration block unit (122) located below the
The filtration blocking unit (122) partitions the communication cavity (120) into a drainage chamber (123) and a filter cake storage chamber (124), and the connection cover (121) includes a filter cake storage chamber (124).
A first filtrate spiral conveyer (125) is provided at an angle in communication with
The treatment system for waste acid-containing waste water in copper smelting according to claim 1, characterized in that: Said precipitation reactor (2) is provided directly below the communicating cavity (120) and has a drain chamber (
123), a second agitator (21) provided inside said mixing reaction chamber (20), and a limestone slurry inlet provided on the side wall of said mixing reaction chamber (20). (22), a gypsum settling chamber (23) provided below the mixing reaction chamber (20), and a filter press (24) provided in the gypsum settling chamber (23),
The filter press (24) comprises two gypsum filter press plates (240) that are vertically movable with respect to the interior of the gypsum settling chamber (23), and the gypsum filter press that is installed in the gypsum settling chamber (23). comprising a power module (241) for driving the plate (240) and a second filtrate spiral conveyer (242) provided at an angle and communicating with the central space of the gypsum settling chamber (23);
The treatment system for waste acid-containing waste water in copper smelting according to claim 1, characterized in that: The hydrogen sulfide gas recovery device (3) comprises a closed reaction tank (30), an atomized alkaline liquid spray disk (31) provided in the upper part of the closed reaction tank (30), and the closed reaction tank (30).
a hydrogen sulfide gas jet ring (32) mounted on the outer wall of the, a connection port (33) that connects the hydrogen sulfide gas jet ring (32) and the exhaust turbofan (13) via high-pressure piping;
A sodium sulfide solution replenishment pipe (34) provided at the bottom of the closed reaction vessel (30) and communicating with the circulation reaction chamber (10),
The treatment system for waste acid-containing waste water in copper smelting according to claim 1, characterized in that: First, waste acid-containing wastewater and a sodium sulfide solution with a concentration of 35 to 45% are mixed at a ratio of 1:0.08 to 0.3.
into the circulation reaction chamber (10) at a volume ratio of 600 to 2000 using the first stirrer (14)
Stirring continuously at r/min rotation speed, waste acid-containing wastewater and sodium sulfide solution are passed through two circulation reaction chambers (10), upper communication means (11) and lower communication means (11) by a negative pressure device (110).
12) circulate inside, then separate the produced precipitate, filter and discharge, and the produced hydrogen sulfide waste gas is efficiently discharged by exhaust turbofan (13), hydrogen sulfide gas recovery device (
3), step S1 of the dearsenicing treatment, and
Next, the waste acid-containing waste water in the circulation reaction chamber is put into the precipitation reactor (2), and the limestone slurry is
Add 500 to 2800 g/L, react while stirring, react waste acid-containing wastewater and limestone to produce gypsum and calcium fluoride precipitates, filter press, remove precipitates, and separate primary filtrate. Next, sodium hydroxide is added to the primary filtrate until the pH reaches 6 to 7, reacted with stirring, and then subjected to a secondary filtration press to remove precipitates, and the secondary filtrate is To separate,
Step S2 of the defluorination-neutralization treatment;
A secondary filtrate is introduced from both ends of the cyclone electrolytic cell (40), and a hydrovortex fan (
42) to turn the secondary filtrate into a vortex, rotate the anode core (430) and the cathode core (431) to electrolyze the secondary filtrate at a current density of 330-600 A/m ² for 30-60 minutes, form hydroxide colloids, adsorb remaining heavy metal contaminants, and finally send the secondary filtrate in which hydroxide colloids are produced to a coagulating sedimentation tank (5) for air flotation and sedimentation separation; including advanced processing step S3,
The treatment process of the treatment system for waste acid-containing wastewater in copper smelting according to any one of claims 1 to 5, characterized in that:

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