CN116022974A - Thallium removal process and device for copper smelting acid-polluted wastewater - Google Patents
Thallium removal process and device for copper smelting acid-polluted wastewater Download PDFInfo
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- CN116022974A CN116022974A CN202310198469.XA CN202310198469A CN116022974A CN 116022974 A CN116022974 A CN 116022974A CN 202310198469 A CN202310198469 A CN 202310198469A CN 116022974 A CN116022974 A CN 116022974A
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Abstract
The invention belongs to the technical field of wastewater treatment, in particular to a thallium removal process and a thallium removal device for copper smelting waste acid wastewater, which select proper medicament adding points under the condition of not changing the existing wastewater treatment process and equipment, and under the condition that the pH value is 8.0-10.5, the thallium content index of the effluent meets the requirements, so that the lime adding amount in the thallium removal process can be reduced, and the wastewater treatment cost is reduced; the added thallium remover and the deep purifying agent combined medicament has no adverse effect on the raw medicaments used in the system, does not influence water and other effluent indexes, and greatly reduces the medicament cost compared with other precipitation methods.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a thallium removal process and device for copper smelting waste acid wastewater.
Background
Thallium is a highly toxic rare dispersed metal, has strong accumulation, and can enter human bodies through drinking water and food chains. The potassium element can be replaced in the enzymatic reaction process of the human body, and has strong affinity with enzyme, toxic action on liver, kidney and the like, serious fatal effect, and far greater thallium toxicity than lead, mercury and other heavy metals under the same dosage. Thallium is put into a blacklist of preferential control pollutants in China, copper smelting waste acid wastewater often contains thallium, the existing treatment technology of thallium-containing wastewater mainly comprises a precipitation method, an adsorption method, an ion exchange method and the like, the precipitation method comprises a sodium sulfide precipitation method, an oxidation precipitation method, an electrochemical precipitation method and a biological agent precipitation method, and the processes are applied to certain industrialization, but have the problems of large hazardous waste production amount, higher operation cost, difficult control of technological parameters, poor impact resistance, unstable treatment effect and the like.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide a thallium removal process and a thallium removal device for copper smelting waste acid and wastewater, which have the advantages of no need of large capital investment, low production and operation cost only by properly adding medicaments.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
the thallium removal process for the copper smelting acid-polluted wastewater comprises the following steps:
s1, regulating the pH value of the sewage and acid wastewater to 8.0-10.5;
s2, adding a certain amount of thallium remover into the wastewater in the duplex reaction tank for reaction;
s3, adding a certain amount of deep purifying agent into the wastewater in a flocculation tank for reaction;
s4, adding flocculating agent PAM into the wastewater at the outlet of the flocculation tank to perform flocculation reaction, and then performing precipitation separation through a precipitation tank to complete thallium removal of the wastewater.
As a preferable scheme of the thallium removal process for the copper smelting waste acid wastewater, the invention comprises the following steps: in the step S1, the pH value is regulated by lime.
As a preferable scheme of the thallium removal process for the copper smelting waste acid wastewater, the invention comprises the following steps: in the step S1, if the pH value of the wastewater is between 8.0 and 10.5, the pH value does not need to be adjusted.
As a preferable scheme of the thallium removal process for the copper smelting waste acid wastewater, the invention comprises the following steps: in the step S2, the thallium removing agent is an agent containing a large number of thiol, hydroxyl, and carboxyl coordinating groups, which is a liquid.
As a preferable scheme of the thallium removal process for the copper smelting waste acid wastewater, the invention comprises the following steps: in the step S2, the addition amount of the thallium removing agent is 0.5 to 1.0L/m 3 And (5) waste water.
As a preferable scheme of the thallium removal process for the copper smelting waste acid wastewater, the invention comprises the following steps: in the step S3, the deep purifying agent is a flocculating copolymer assembly, which is a liquid.
As a preferable scheme of the thallium removal process for the copper smelting waste acid wastewater, the invention comprises the following steps: in the step S3, the adding amount of the deep purifying agent is 0.5-1.0L/m 3 And (5) waste water.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
a thallium removal device for copper smelting acid wastewater, comprising:
a duplex reaction tank, a flocculation tank, a No. 1 thickening tank and a sedimentation tank;
the duplex reaction tank, the flocculation tank and the No. 1 thickening tank are connected in sequence.
As a preferable scheme of the thallium removal device for copper smelting waste acid wastewater, the invention comprises the following steps: and a hardness removal reaction tank is arranged between the No. 1 thickening tank and the sedimentation tank.
As a preferable scheme of the thallium removal device for copper smelting waste acid wastewater, the invention comprises the following steps: and a water outlet tank is also connected behind the sedimentation tank.
As a preferable scheme of the thallium removal device for copper smelting waste acid wastewater, the invention comprises the following steps: the device also comprises a pre-neutralization tank, a 3# thickening tank, a first-stage neutralization tank A, a first-stage neutralization tank B and a 2# thickening tank which are arranged in sequence before the duplex reaction tank.
As a preferable scheme of the thallium removal device for copper smelting waste acid wastewater, the invention comprises the following steps: an adjusting tank and a mixing tank are sequentially arranged between the 3# thickening tank and the first section neutralization tank A.
As a preferable scheme of the thallium removal device for copper smelting waste acid wastewater, the invention comprises the following steps: a section of reaction tank is also arranged between the No. 2 dense tank and the duplex reaction tank.
The beneficial effects of the invention are as follows:
the invention provides a thallium removal process and a thallium removal device for copper smelting waste acid wastewater, which select proper reagent adding points under the condition of not changing the existing sewage treatment process and equipment, and under the condition that the pH value is 8.0-10.5, the thallium content index of the effluent meets the requirement of modification list of GB 25466-2010 lead and zinc industrial pollutant emission standard (before the thallium emission limit value is regulated by the new standard of copper smelting wastewater, the thallium removal process is executed by referring to the total thallium emission limit value regulated by the lead-zinc standard), so that the lime adding amount in the thallium removal process can be reduced, and the wastewater treatment cost is reduced; the added thallium remover and deep purifying agent combination agent has no adverse effect on the original use of the agent in the system, and no influence on water and other effluent indexes, and the process cost of other precipitation methods is generally 5-6 yuan/m 3 Waste water, compared with the method, has high costThe amplitude decreases.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a thallium removal device for copper smelting waste acid and wastewater.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications (such as up, down, left, right, front, and rear … …) are included in the embodiments of the present invention, the directional indications are merely used to explain the relative positional relationship, movement conditions, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indications are correspondingly changed.
In addition, if there is a description of "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention provides a thallium removal process and a thallium removal device for copper smelting waste acid wastewater, which select proper reagent adding points under the condition of not changing the existing sewage treatment process and equipment, and under the condition that the pH value is 8.0-10.5, the thallium content index of the effluent meets the requirement of modification list of GB 25466-2010 lead and zinc industrial pollutant emission standard (before the thallium emission limit value is regulated by the new standard of copper smelting wastewater, the thallium removal process and the thallium removal device are executed by referring to the total thallium emission limit value regulated by the lead-zinc standard), and the thallium removal process and the thallium removal device can remove thallium in the wastewater under the condition of relatively lower pH value, can directly reduce lime adding amount in the existing process flow, and further reduce the production cost of enterprises; according to the invention, proper addition amount can be adjusted according to different thallium content ranges in the wastewater, and the thallium deslagging and deslagging can be combined into the original system for the treatment of the filter-pressing mud; the added combined medicament has no adverse effect on the original medicament used in the system and no influence on other water outlet indexes.
According to one aspect of the invention, the invention provides the following technical scheme:
as shown in fig. 1, a thallium removal device for lead-zinc smelting wastewater according to an embodiment of the invention includes:
a duplex reaction tank, a flocculation tank, a No. 1 thickening tank and a sedimentation tank;
the duplex reaction tank, the flocculation tank and the No. 1 thickening tank are connected in sequence.
Preferably, a hardness removal reaction tank is arranged between the No. 1 thickening tank and the sedimentation tank; and a water outlet tank is also connected behind the sedimentation tank. The device also comprises an adjusting tank, a pre-neutralization tank, a 3# thickening tank, a first-stage neutralization tank A, a first-stage neutralization tank B and a 2# thickening tank which are arranged in sequence in front of the duplex reaction tank; further preferably, an adjusting tank and a mixing tank are sequentially arranged between the 3# thickening tank and the first section neutralization tank A; a section of reaction tank is also arranged between the No. 2 dense tank and the duplex reaction tank.
The invention does not change the existing sewage treatment process and equipment and facilities, and realizes the low-cost treatment of the copper smelting acid wastewater by selecting proper medicament adding points.
According to another aspect of the invention, the invention further provides the following technical scheme:
the thallium removal process for the copper smelting acid-polluted wastewater comprises the following steps:
s1, regulating the pH value of the sewage and acid wastewater to 8.0-10.5;
s2, adding a certain amount of thallium remover into the wastewater in the duplex reaction tank for reaction;
s3, adding a certain amount of deep purifying agent into the wastewater in a flocculation tank for reaction;
s4, adding flocculating agent PAM into the wastewater at the outlet of the flocculation tank to perform flocculation reaction, and then performing precipitation separation through a precipitation tank to complete thallium removal of the wastewater.
Preferably, in the step S1, the pH is adjusted by lime; if the pH value of the wastewater is between 8.0 and 10.5, the pH value does not need to be regulated. In particular, the pH of the wastewater may be, for example, but not limited to, any one or a combination of any two of 8.0, 8.5, 9.0, 9.5, 10.0, 10.5.
Preferably, in the step S2, the thallium removing agent is an autonomously developed sewage treatment agent capable of rapidly capturing thallium element from heavy colored wastewater. The medicament is a general chemical, contains a large number of coordination groups such as sulfhydryl, hydroxyl, carboxyl and the like, can form chelate with polycyclic coordination bonds with Tl (I/III), is insoluble in water, and can be rapidly precipitated under the action of a flocculating agent, so that thallium is effectively removed. The medicament is a liquid, colorless or light yellow product, and the stock solution is directly added and used in the range of pH value of copper smelting waste acid and water being 8.0-10.5; the addition amount of the thallium removing agent is 0.5 to 1.0L/m 3 And (5) waste water. Specifically, the thallium removing agent may be added in an amount of, for example, but not limited to, 0.5L/m 3 Waste water, 0.6L/m 3 Waste water, 0.7L/m 3 Waste water, 0.8L/m 3 Waste water, 0.9L/m 3 Waste water, 1.0L/m 3 Any one or the combination of any two of the waste water.
Preferably, in the step S3The deep purifying agent is a deep removing agent for thallium and other heavy metals, can efficiently remove trace thallium heavy metal ions remained in the water body, and can deeply purify other pollution factors in the water body. The flocculant is mainly a flocculation copolymer combination, can form stable polycyclic chelate precipitate with thallium and other substances, and rapidly subsides under the action of a flocculant, thereby realizing the deep removal of thallium. The medicament is a liquid product, and the stock solution is directly added and is used in the range of pH value of 8.0-10.5 of copper smelting acid-polluted wastewater; the adding amount of the deep purifying agent is 0.5-1.0L/m 3 And (5) waste water. Specifically, the thallium removing agent may be added in an amount of, for example, but not limited to, 0.5L/m 3 Waste water, 0.6L/m 3 Waste water, 0.7L/m 3 Waste water, 0.8L/m 3 Waste water, 0.9L/m 3 Waste water, 1.0L/m 3 Any one or the combination of any two of the waste water.
The technical scheme of the invention is further described below by combining specific embodiments.
Selecting a certain copper smelting plant waste acid wastewater (hereinafter referred to as wastewater) as a treatment object, comprising the following steps:
(1) The positions of the dosing points of inventive example 1 and comparative examples 1-2 were determined as follows:
the thallium remover adding position of the embodiment 1 of the invention is arranged in the duplex reaction tank, the deep purifying agent adding position is arranged in the flocculation tank, and the water quality analysis sampling point is arranged at the outlet of the No. 1 thickening tank;
the thallium remover of comparative example 1 is added in the mixing tank before the rear section of the preneutralization tank enters the 3# thickening tank, the deep purifying agent is added in the inlet chute of the 3# thickening tank, and the water quality analysis sampling point is arranged at the outlet of the 3# thickening tank;
the thallium remover addition position of comparative example 2 is respectively arranged at the mixing tank before the rear section of the pre-neutralization tank enters the 3# thickening tank and at the neutralization tank A of the first section, the deep purifying agent addition position is arranged at the neutralization tank B of the first section, and the water quality analysis sampling point is arranged at the outlet of the 2# thickening tank.
The dosing line was laid out at the position of the dosing point selected according to example 1 and comparative examples 1-2 above;
(2) Starting a waste acid and waste water lifting pump to enable waste water to continuously enter a waste acid and waste water treatment system, wherein the water inflow is 50m 3 /h。
(3) Starting the stirrer, the lime feeder and other devices, and controlling the lime feeding amount according to the pH value indicated by the pH meter of the primary secondary neutralization tank to maintain the pH value at 9+/-0.5.
(4) In example 1 and comparative examples 1-2, the corresponding thallium remover and deep-purifier dosing pumps were started to start dosing, respectively.
(5) When the effluent enters the flocculation tank, a flocculant dosing pump is started, and flocculant is started to be added.
(6) After the system is normally operated for 2 hours, sampling the 1 st time of water sample at a sampling point, and then sampling each time at intervals. The process parameters and test results of inventive example 1 and comparative examples 1-2 are shown in table 1.
TABLE 1 Process parameters and test results for inventive example 1 and comparative examples 1-2
As can be seen from Table 1, when the wastewater inflow is 50m 3 When the thallium content is 1mg/L or less per hour, the pH value is controlled to be above 8.0, and the thallium concentration in each cubic waste water can be stably reduced to below 17ug/L by using the process of the invention for treating each cubic waste water.
The thallium remover of example 1 of the invention was placed in a duplex reaction tank with a thallium remover addition of 0.6L/m 3 The wastewater and the deep purifying agent adding position is arranged in the flocculation tank, and the adding amount of the deep purifying agent is 0.6L/m 3 Waste water; each sampling result after adding the medicament can reach the standard stably;
the thallium remover of comparative example 1 was added in an amount of 1.0L/m to the mixing tank before the rear section of the preneutralization tank was fed into the 3# thickening tank 3 The wastewater and deep purifying agent adding position is arranged at the inlet chute of the No. 3 thickening tank, and the adding amount of the deep purifying agent is 1.0L/m 3 Waste water; the 7-0# (pre-neutralization of the raw water of the wastewater) has abnormal value, the water quality after 7-1# -7-6# treatment has fluctuation, the section is that the back-stage sludge returns to react with the waste acid to generate dissolution, the water quality is unstable, the treatment effect is not ideal, the thallium content in the filter press residues is relatively high, and the thallium content in the raw water is increased after the back-stage neutralization reaction;
the thallium remover addition positions of comparative example 2 are respectively arranged at the mixing tank before the rear section of the pre-neutralization tank enters the 3# thickening tank and at the neutralization tank A of one section, and the addition amounts of the thallium remover are all 0.5L/m 3 The wastewater and the deep purifying agent are added at the position of the first-stage neutralization tank B, and the adding amount of the deep purifying agent is 1.0L/m 3 The wastewater and the preneutralization pond section are not up to the standard, and the neutralization pond section can be up to the standard stably, but the sample test result of Tl content in the wastewater and the preneutralization pond section is obviously higher than that in the example 1.
The thallium remover of example 1 of the present invention was calculated to have a cost of 1.6 yuan/m 3 The cost of the wastewater and the deep purifying agent is 1.6 yuan/m 3 The process cost of the wastewater and other precipitation methods is generally 5-6 yuan/m 3 The cost of the waste water is greatly reduced compared with the cost of the medicament.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The thallium removal process for the copper smelting acid wastewater is characterized by comprising the following steps of:
s1, regulating the pH value of the sewage and acid wastewater to 8.0-10.5;
s2, adding a certain amount of thallium remover into the wastewater in the duplex reaction tank for reaction;
s3, adding a certain amount of deep purifying agent into the wastewater in a flocculation tank for reaction;
s4, adding flocculating agent PAM into the wastewater at the outlet of the flocculation tank to perform flocculation reaction, and then performing precipitation separation through a precipitation tank to complete thallium removal of the wastewater.
2. The process according to claim 1, wherein in step S1, the pH is adjusted with lime.
3. The process of claim 1 wherein in step S2 the thallium removal agent is a pharmaceutical agent comprising a plurality of thiol, hydroxyl, and carboxyl coordinating groups, which is a liquid.
4. The process according to claim 1, wherein in the step S2, the thallium removing agent is added in an amount of 0.5 to 1.0L/m 3 And (5) waste water.
5. The process of claim 1, wherein in step S3, the depth scavenger is a flocculated copolymer composition that is a liquid.
6. The process according to claim 1, wherein in the step S3, the depth purifying agent is added in an amount of 0.5 to 1.0L/m 3 And (5) waste water.
7. A thallium removal device for copper smelting waste acid wastewater, characterized by being used for implementing the process of any one of claims 1-6, comprising:
a duplex reaction tank, a flocculation tank, a No. 1 thickening tank and a sedimentation tank;
the duplex reaction tank, the flocculation tank and the No. 1 thickening tank are connected in sequence.
8. The apparatus of claim 7, further comprising a pre-neutralization tank, a # 3 thickening tank, a section of neutralization tank a, a section of neutralization tank B, and a # 2 thickening tank arranged in sequence before the duplex reaction tank.
9. The device according to claim 8, wherein an adjusting tank and a mixing tank are arranged between the 3# thickening tank and the first neutralizing tank A in sequence.
10. The apparatus of claim 8, wherein a reaction tank is further provided between the # 2 dense tank and the duplex reaction tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310198469.XA CN116022974A (en) | 2023-03-03 | 2023-03-03 | Thallium removal process and device for copper smelting acid-polluted wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310198469.XA CN116022974A (en) | 2023-03-03 | 2023-03-03 | Thallium removal process and device for copper smelting acid-polluted wastewater |
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