CN103304059A - System and method for treating acidic wastewater in metallurgical off-gas acid-making process - Google Patents

System and method for treating acidic wastewater in metallurgical off-gas acid-making process Download PDF

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Publication number
CN103304059A
CN103304059A CN2013102674803A CN201310267480A CN103304059A CN 103304059 A CN103304059 A CN 103304059A CN 2013102674803 A CN2013102674803 A CN 2013102674803A CN 201310267480 A CN201310267480 A CN 201310267480A CN 103304059 A CN103304059 A CN 103304059A
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China
Prior art keywords
reaction still
order reaction
pump
communicating pipe
waste water
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CN2013102674803A
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Chinese (zh)
Inventor
常全忠
刘玉强
赵千里
冯拥军
甘宪福
贾小军
曹伟
张述荣
刘元戎
黄海丽
杨振杰
马岩
林振
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Jinchuan Group Co Ltd
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Jinchuan Group Co Ltd
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Priority to CN2013102674803A priority Critical patent/CN103304059A/en
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Abstract

The invention provides a system for treating acidic wastewater in a sulfuric acid making process and a method for treating the acidic wastewater in the sulfuric acid making process by utilizing the system. The system comprises a first-stage reaction kettle, a second-stage reaction kettle, a third-stage reaction kettle, a slag pot and a slurry pump which are connected in sequence, wherein stirring paddles are arranged in the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle; the lower part of the first-stage reaction kettle is connected with the lower part of the second-stage reaction kettle through a first communication pipe; the upper part of the second-stage reaction kettle is connected with the upper part of the third-stage reaction kettle through a second communication pipe; the upper part of the third-stage reaction kettle is connected with the slag pot through an overflow pipe; the first communication pipe is connected with a sodium sulfide pump and a sodium sulfide storage tank; and the second communication pipe is connected with a ferrous sulfate pump and a ferrous sulfate storage tank. According to the system and the method, arsenic and heavy metal ions of copper, lead, cadmium and the like in the acidic wastewater can be effectively removed.

Description

Treatment system and the method for acid waste water in a kind of metallurgical off-gas acid-making technology
Technical field
The invention belongs to chemical technology field, relate to the treatment system of acid waste water in a kind of metallurgical off-gas acid-making technology and utilize the treatment process of acid waste water in the metallurgical off-gas acid-making technology that this system carries out.
Background technology
Can produce a large amount of SO in the metal sulfide smelting process 2Flue gas, this part SO 2Flue gas prepares sulfuric acid by metallurgical off-gas acid-making technology usually, and fume purifying processes extensively adopts the wet scrubbing flue gases purification to carry out SO in the metallurgical off-gas acid-making technology 2Gas cleaning.Because SO 2Contain a large amount of detrimental impurity in the flue gas, comprising heavy metal ion such as arsenic and copper, lead, cadmiums.This part detrimental impurity is deposited in washing process in the circulation cleaning water, and this circulation cleaning water is again because the SO in the absorption flue gas 2Form acid waste water.In order to reduce harmful ion to the infringement of cleaning section, this part acid waste water needs regularly discharge from acid making system, owing to contain more detrimental impurity, causes this acid waste water can't recycling, directly efflux and can cause environmental pollution, therefore need its improvement that neutralizes.At present, it is the lime neutralisation that the neutralization of this acid waste water is administered what extensively adopt, produces but this technology has a large amount of waste residues, and has increased solid dust and particulate matter can damage environment.
Summary of the invention
The objective of the invention is to the problem at the prior art existence, the treatment system of acid waste water in a kind of metallurgical off-gas acid-making technology is provided, carries out effective neutralizing treatment and remove heavy metal ion and other detrimental impurity in the acid waste water with the acid waste water that metallurgical off-gas acid-making technology is produced.
Another object of the present invention is to provide a kind for the treatment of process of utilizing acid waste water in the metallurgical off-gas acid-making technology that said system carries out.
For this reason, the present invention adopts following technical scheme:
The treatment system of acid waste water in a kind of metallurgical off-gas acid-making technology comprises the first order reaction still, second order reaction still, third order reaction still, slag ladle and the slag stock pump that connect successively, all has stirring rake in described first order reaction still, second order reaction still, the third order reaction still; Between described first order reaction still bottom and the second order reaction still bottom, between second order reaction still top and the third order reaction still top, be connected by first communicating pipe, second communicating pipe and upflow tube respectively between third order reaction still top and the slag ladle, also be connected with sulfuration sodium pump and sodium sulphite storage tank described first communicating pipe, also be connected with ferrous sulfate pump and ferrous sulfate storage tank on described second communicating pipe.
Further, also be provided with the fourth-order reaction still between described third order reaction still and the slag ladle, have stirring rake in the described fourth-order reaction still, be connected by the third connecting pipe between the bottom of the bottom of described third order reaction still and fourth-order reaction still, be connected by upflow tube between described fourth-order reaction still top and the slag ladle, also be connected with flocculation agent pump and flocculation agent storage tank on the described third connecting pipe.
A kind for the treatment of process of utilizing acid waste water in the metallurgical off-gas acid-making technology that above-mentioned acid waste water treatment system carries out comprises following processing step:
Adopt the acid waste water treatment system, this system comprises mine distributor, first order reaction still, second order reaction still, third order reaction still, slag ladle and the slag stock pump that connects successively, all has stirring rake in described first order reaction still, second order reaction still, the third order reaction still; Between described first order reaction still bottom and the second order reaction still bottom, between second order reaction still top and the third order reaction still top, be connected by first communicating pipe, second communicating pipe and upflow tube respectively between third order reaction still top and the slag ladle, also be connected with sulfuration sodium pump and sodium sulphite storage tank described first communicating pipe, also be connected with ferrous sulfate pump and ferrous sulfate storage tank on described second communicating pipe;
The acid waste water that the alkaline mine tailing slurry that produces in the ore dressing process and metallurgical off-gas acid-making technology are produced is sent into and is carried out neutralization reaction in the first order reaction still, and control to make the pH value of reaction back slip be 6-8; Reaction back slip enters the second order reaction still through first communicating pipe, and simultaneously, the sodium sulfide solution in the sodium sulphite storage tank reacts with slip by the sulfuration sodium pump and through entering first communicating pipe in the second order reaction still; Reacted slip enters the third order reaction still through second communicating pipe, and simultaneously, the copperas solution in the ferrous sulfate storage tank reacts with slip by the ferrous sulfate pump and through entering second communicating pipe in the third order reaction still; Reacted slip, is discharged by the slag stock pump to slag ladle then by the overflow of third order reaction still.
Further, the acid waste water treatment system that adopts also comprises the fourth-order reaction still, described fourth-order reaction still is located between third order reaction still and the slag ladle, have stirring rake in the described fourth-order reaction still, be connected by the third connecting pipe between the bottom of the bottom of described third order reaction still and fourth-order reaction still, be connected by upflow tube between described fourth-order reaction still top and the slag ladle, also be connected with flocculation agent pump and flocculation agent storage tank on the described third connecting pipe;
Slip behind the third order reaction still internal reaction is sent into the fourth-order reaction still through the third connecting pipe, and simultaneously, the flocculation agent in the flocculation agent storage tank reacts with slip by the flocculation agent pump and in the third connecting pipe enters the fourth-order reaction still; Reacted supernatant slip, is discharged by the slag stock pump to slag ladle then by the overflow of fourth-order reaction still.
Further, described flocculation agent is polyacrylamide.
One, the reaction principle in the second order reaction still of the present invention is as follows:
Na 2S + CuSO 4 ==== CuS + Na 2SO 4
2HAsO 2 + 3Na 2S ==== As 2S 3 + H 20
Sodium sulfide solution precipitates the sulfide that the part heavy metal ion is converted into insoluble or indissoluble (be example with copper, arsenic); And according to the size of metallic sulfide solubleness, the order that its precipitation is separated out is: As 3+>Cu 2+>Pb 2+>Cd 2+>Ni 2+, the metallic sulfide that the position is more forward, its solubleness is more little, more easy separating out.
Two, the reaction principle in the third order reaction still of the present invention is as follows:
12 FeSO 4 + 6H 2O + 3O 2 ==== 4 Fe 2(SO 43 + 4Fe (OH) 3
Fe 2(SO 43 + 6NaOH ==== 2Fe (OH) 3 + 3Na 2SO 4
AsO 3 3- + Fe (OH) 3 ==== FeAsO 3 + 3OH -
AsO 4 3- + Fe (OH) 3 ==== FeAsO 4 + 3OH -
At first, ferrous sulfate generates ferric sulfate and ironic hydroxide through oxidizing reaction; Ironic hydroxide is gelatinoid, can adsorb the impurity suspended substance in the slip, and settling velocity is fast, floc particle is big, and sludge volume is little and closely knit, can play the water purification effect; The part ironic hydroxide also generates ferric arsenate and iron arsenite precipitation, Fe (OH) with arsenate ion and arsenous anion ionic reaction 3Colloid adsorbs the ferric arsenate of generation and iron arsenite simultaneously and coprecipitated, and effect of removing arsenic is remarkable.
Three, after flocculating settling is handled, in the fourth-order reaction still, add certain density polyacrylamide solution again as coagulant aids, can accelerate the sedimentation of flco, to slag ladle, the throw out that containing assorted and heavy metal ion is deposited on fourth-order reaction still bottom through neutralizing treatment and the supernatant slip overflow of removing detrimental impurity on fourth-order reaction still top.
Beneficial effect of the present invention is: the present invention can effectively remove heavy metal ion such as arsenic in the acid waste water and copper, lead, cadmium; The mine tailing slurry that the inventive method has effectively utilized ore dressing to produce, cost is low and efficient, has reduced environmental pollution.
Description of drawings
Fig. 1 is the structural representation of acid waste water treatment system in the metallurgical off-gas acid-making technology of the present invention.
Among the figure, 1-first order reaction still; 2-second order reaction still, 3-third order reaction still, 4-fourth-order reaction still, the 5-slag ladle, 6-slag stock pump, 7-sodium sulphite storage tank, 8-vulcanizes sodium pump, 9-ferrous sulfate storage tank, 10-ferrous sulfate pump, 11-flocculation agent storage tank, 12-flocculation agent pump, first communicating pipe of 13-, second communicating pipe of 14-, 15-third connecting pipe, the 16-upflow tube.
Embodiment
Embodiment 1
As shown in Figure 1, the treatment system of acid waste water in a kind of metallurgical off-gas acid-making technology, comprise the first order reaction still 1, second order reaction still 2, third order reaction still 3, fourth-order reaction still 4, slag ladle 5 and the slag stock pump 6 that connect successively, all have stirring rake in first order reaction still 1, second order reaction still 2, third order reaction still 3 and the fourth-order reaction still 4; Between first order reaction still 1 bottom and second order reaction still 2 bottoms, between second order reaction still 2 tops and third order reaction still 3 tops, between third order reaction still 3 bottoms and fourth-order reaction still 4 bottoms, be connected by first communicating pipe 13, second communicating pipe 14, third connecting pipe 15 and upflow tube 16 respectively between fourth-order reaction still 4 tops and the slag ladle 5, also be connected with sulfuration sodium pump 8 and sodium sulphite storage tank 7 first communicating pipe 13, also be connected with ferrous sulfate pump 10 and ferrous sulfate storage tank 9 on second communicating pipe 14, third connecting pipe 15 also is connected with flocculation agent pump 12 and flocculation agent storage tank 11; First order reaction still 1, second order reaction still 2, third order reaction still 3, fourth-order reaction still 4 and slag ladle 5 exits all are equipped with pH meter (not marking among the figure) with on-line monitoring slip pH value; In addition, the height of first order reaction still 1, second order reaction still 2, third order reaction still 3, fourth-order reaction still 4 and slag ladle 5 can reduce (not shown) in turn, so that keep difference of altitude between above-mentioned conversion unit, thus the slip of thickness in the system can be flowed smoothly.
A kind for the treatment of process of utilizing acid waste water in the metallurgical off-gas acid-making technology that above-mentioned acid waste water treatment system carries out comprises following processing step:
A. adopt acid waste water treatment system shown in Figure 1, this system comprises first order reaction still 1, second order reaction still 2, third order reaction still 3, fourth-order reaction still 4, slag ladle 5 and the slag stock pump 6 that connects successively, all has stirring rake in first order reaction still 1, second order reaction still 2, third order reaction still 3 and the fourth-order reaction still 4; Between first order reaction still 1 bottom and second order reaction still 2 bottoms, between second order reaction still 2 tops and third order reaction still 3 tops, between third order reaction still 3 bottoms and fourth-order reaction still 4 bottoms, be connected by first communicating pipe 13, second communicating pipe 14, third connecting pipe 15 and upflow tube 16 respectively between fourth-order reaction still 4 tops and the slag ladle 5, also be connected with sulfuration sodium pump 8 and sodium sulphite storage tank 7 first communicating pipe 13, also be connected with ferrous sulfate pump 10 and ferrous sulfate storage tank 9 on second communicating pipe 14, third connecting pipe 15 also is connected with flocculation agent pump 12 and flocculation agent storage tank 11;
The acid waste water that the alkaline mine tailing slurry that produces in the ore dressing process and metallurgical off-gas acid-making technology are produced is sent into and is carried out neutralization reaction in the first order reaction still 1, and wherein, the chemical ingredients (weight ratio) of mine tailing slurry is: Al 2O 330.2%, Fe 2O 311%, MgO 1.9%, and surplus is water and impurity, and density is 1.47t/m 3The mass percent concentration of sulfuric acid is 5% in the acid waste water, and solid content is 2%; The volume ratio that ore pulp and acid waste water are pressed 8:2 adds; Reaction back slip pH value is 6;
B. reaction back slip enters second order reaction still 2 through first communicating pipe 13, and simultaneously, the sodium sulfide solution in the sodium sulphite storage tank 7 enters in the second order reaction still 2 by sulfuration sodium pump 8 and through first communicating pipe 13, reacts with slip; Wherein, the mass percent concentration of sodium sulfide solution is 5%, and add-on is 0.3 times of acid waste water volume;
C. reacted slip enters third order reaction still 3 through second communicating pipe 14; Second communicating pipe 14 was located at second order reaction still 2 tops, namely adopted the input and output material mode of low in and high out, can make slip fully reaction in the second order reaction still; Simultaneously, the copperas solution in the ferrous sulfate storage tank 9 enters in the third order reaction still 3 by ferrous sulfate pump 10 and through second communicating pipe 14, reacts with slip; The mass percent concentration of copperas solution is 5%, and add-on is 0.05 times of acid waste water volume;
D. reacted slip enters fourth-order reaction still 4 through third connecting pipe 15, and simultaneously, the flocculation agent in the flocculation agent storage tank 11, reacts with slip in third connecting pipe 15 enters fourth-order reaction still 4 by flocculation agent pump 12; Flocculation agent selects for use polypropylene to mill amine, and mass percent concentration is 1%, and add-on is 15L/m 3, namely every cubic metre of slip adds the 15L flocculation agent;
E. reacted supernatant slip by fourth-order reaction still 4 through upflow tube 16 overflows to slag ladle 5, discharge by slag stock pump 6 then.
Embodiment 2
The treatment process of acid waste water in a kind of sulfuric acid acid-making process, the difference of itself and embodiment 1 is:
Among the step a, the volume ratio that ore pulp and acid waste water are pressed 8:1.5 adds; Reaction back slip pH value is 7;
Among the step b, the add-on of sodium sulfide solution is 0.25 times of acid waste water volume;
Among the step c, the add-on of copperas solution is 0.04 times of acid waste water volume.
Embodiment 3
The treatment process of acid waste water in a kind of sulfuric acid acid-making process, the difference of itself and embodiment 1 is:
Among the step a, the volume ratio that ore pulp and acid waste water are pressed 8:1 adds; Reaction back slip pH value is 8;
Among the step b, the add-on of sodium sulfide solution is 0.2 times of acid waste water volume;
Among the step c, the add-on of copperas solution is 0.035 times of acid waste water volume.

Claims (5)

1. the treatment system of acid waste water in the metallurgical off-gas acid-making technology, it is characterized in that, comprise the first order reaction still, second order reaction still, third order reaction still, slag ladle and the slag stock pump that connect successively, all have stirring rake in described first order reaction still, second order reaction still, the third order reaction still; Between described first order reaction still bottom and the second order reaction still bottom, between second order reaction still top and the third order reaction still top, be connected by first communicating pipe, second communicating pipe and upflow tube respectively between third order reaction still top and the slag ladle, also be connected with sulfuration sodium pump and sodium sulphite storage tank described first communicating pipe, also be connected with ferrous sulfate pump and ferrous sulfate storage tank on described second communicating pipe.
2. the treatment system of acid waste water in a kind of metallurgical off-gas acid-making technology according to claim 1, it is characterized in that, also be provided with the fourth-order reaction still between described third order reaction still and the slag ladle, have stirring rake in the described fourth-order reaction still, be connected by the third connecting pipe between the bottom of the bottom of described third order reaction still and fourth-order reaction still, be connected by upflow tube between described fourth-order reaction still top and the slag ladle, also be connected with flocculation agent pump and flocculation agent storage tank on the described third connecting pipe.
3. a treatment process of utilizing acid waste water in the metallurgical off-gas acid-making technology that the described acid waste water treatment system of claim 1 carries out is characterized in that, comprises following processing step:
Adopt the acid waste water treatment system, this system comprises mine distributor, first order reaction still, second order reaction still, third order reaction still, slag ladle and the slag stock pump that connects successively, all has stirring rake in described first order reaction still, second order reaction still, the third order reaction still; Between described first order reaction still bottom and the second order reaction still bottom, between second order reaction still top and the third order reaction still top, be connected by first communicating pipe, second communicating pipe and upflow tube respectively between third order reaction still top and the slag ladle, also be connected with sulfuration sodium pump and sodium sulphite storage tank described first communicating pipe, also be connected with ferrous sulfate pump and ferrous sulfate storage tank on described second communicating pipe;
The acid waste water that the alkaline mine tailing slurry that produces in the ore dressing process and metallurgical off-gas acid-making technology are produced is sent into and is carried out neutralization reaction in the first order reaction still, and control to make the pH value of reaction back slip be 6-8; Reaction back slip enters the second order reaction still through first communicating pipe, and simultaneously, the sodium sulfide solution in the sodium sulphite storage tank reacts with slip by the sulfuration sodium pump and through entering first communicating pipe in the second order reaction still; Reacted slip enters the third order reaction still through second communicating pipe, and simultaneously, the copperas solution in the ferrous sulfate storage tank reacts with slip by the ferrous sulfate pump and through entering second communicating pipe in the third order reaction still; Reacted slip, is discharged by the slag stock pump to slag ladle then by the overflow of third order reaction still.
4. the treatment process of acid waste water in a kind of metallurgical off-gas acid-making technology according to claim 3, it is characterized in that, the acid waste water treatment system that adopts also comprises the fourth-order reaction still, described fourth-order reaction still is located between third order reaction still and the slag ladle, have stirring rake in the described fourth-order reaction still, be connected by the third connecting pipe between the bottom of the bottom of described third order reaction still and fourth-order reaction still, be connected by upflow tube between described fourth-order reaction still top and the slag ladle, also be connected with flocculation agent pump and flocculation agent storage tank on the described third connecting pipe;
Slip behind the third order reaction still internal reaction is sent into the fourth-order reaction still through the third connecting pipe, and simultaneously, the flocculation agent in the flocculation agent storage tank reacts with slip by the flocculation agent pump and in the third connecting pipe enters the fourth-order reaction still; Reacted supernatant slip, is discharged by the slag stock pump to slag ladle then by the overflow of fourth-order reaction still.
5. the treatment process of acid waste water in a kind of metallurgical off-gas acid-making technology according to claim 3 is characterized in that described flocculation agent is polyacrylamide.
CN2013102674803A 2013-06-30 2013-06-30 System and method for treating acidic wastewater in metallurgical off-gas acid-making process Pending CN103304059A (en)

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CN103641227A (en) * 2013-12-10 2014-03-19 杭州立佳环境服务有限公司 Method for eliminating heavy metal in industrial sewage
CN104003554A (en) * 2014-06-04 2014-08-27 武汉飞博乐环保工程有限公司 Waste acid purifying device and process
CN104829014A (en) * 2015-06-03 2015-08-12 南宁市桂润环境工程有限公司 Short-distance membrane separation treatment process for lead-zinc industrial beneficiation and smelting wastewater
CN107008126A (en) * 2017-04-27 2017-08-04 昆明理工大学 It is a kind of while removing the method for reducing atmosphere sulfureous in flue gas hydrogen and heavy metal
CN107399855A (en) * 2017-08-25 2017-11-28 金川集团股份有限公司 A kind of system and method for handling metallurgical off-gas acid-making acid waste water
CN107540074A (en) * 2017-08-25 2018-01-05 金川集团股份有限公司 The magnesia neutralized system and method for a kind of metallurgical off-gas acid-making acid waste water
CN108178367A (en) * 2017-12-14 2018-06-19 金川集团股份有限公司 The processing method of acid waste water in a kind of non-ferrous metal metallurgy flue gas acid preparing
CN109574319A (en) * 2019-01-07 2019-04-05 紫金矿业集团股份有限公司 The solid arsenic technique of the high arsenic waste acid of non-ferrous metal metallurgy
CN109607872A (en) * 2019-01-07 2019-04-12 紫金矿业集团股份有限公司 A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic

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CN107399855A (en) * 2017-08-25 2017-11-28 金川集团股份有限公司 A kind of system and method for handling metallurgical off-gas acid-making acid waste water
CN107540074A (en) * 2017-08-25 2018-01-05 金川集团股份有限公司 The magnesia neutralized system and method for a kind of metallurgical off-gas acid-making acid waste water
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CN108178367A (en) * 2017-12-14 2018-06-19 金川集团股份有限公司 The processing method of acid waste water in a kind of non-ferrous metal metallurgy flue gas acid preparing
CN109574319A (en) * 2019-01-07 2019-04-05 紫金矿业集团股份有限公司 The solid arsenic technique of the high arsenic waste acid of non-ferrous metal metallurgy
CN109607872A (en) * 2019-01-07 2019-04-12 紫金矿业集团股份有限公司 A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic

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Application publication date: 20130918