CN104909507A - Contaminated acid concentrating and recycling method - Google Patents
Contaminated acid concentrating and recycling method Download PDFInfo
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- CN104909507A CN104909507A CN201510294711.9A CN201510294711A CN104909507A CN 104909507 A CN104909507 A CN 104909507A CN 201510294711 A CN201510294711 A CN 201510294711A CN 104909507 A CN104909507 A CN 104909507A
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Abstract
The invention discloses a contaminated acid concentrating and recycling method. The method comprises the following steps: adding a contaminated acid solution and a vulcanizing agent solution into a negative pressure reaction kettle according to an amount ratio of 1L:(10-30)g, reacting under the condition of 60-70 DEG C for 25-40 minutes, performing filter pressing on the reacted materials by using a filter press, and treating the filtrate in the next step; adding the filtrate and the vulcanizing agent solution into another negative pressure reaction kettle according to an amount ratio of 1L:(20-48)g, reacting at room temperature for 80-100 minutes, precipitating by using a thickener, performing filter pressing by using the filter press, treating the obtained contaminated acid filtrate by virtue of a dynamic wave scrubbing tower to remove lots of ions F<-1> and Cl<-1>, thereby obtaining the 50-60% industrial sulfuric acid. The contaminated acid is treated by combining two-stage vulcanization and evaporation and concentration, the heavy metals and arsenic are effectively removed by controlling the time and temperature during two-stage vulcanization, the sulfur and metal elements are comprehensively recycled, the cost is low, and the economic benefits are high.
Description
Technical field
The invention belongs to the dirty acid treatment field of Metal smelting relieving haperacidity, be specifically related to the method that the sour concentration and recovery of a kind of dirt utilizes.
Background technology
In nonferrous metallurgical process, usually containing As in a large amount of acid waters that relieving haperacidity operation produces
3+, As
5+, Cu
2+, Pb
2+, Zn
2+etc. heavy metal ion and F
-, Cl
-, because the concentration of dirty acid is high, heavy metal concentration is higher, in treating processes, valuable metal is all transferred in waste residue and is difficult to recycle, and produces a large amount of Hazardous wastess simultaneously, easily causes serious secondary pollution.
Current most of smelting enterprise adopts the dirty acid of sulfuration-lime iron salt method, lime-iron salt method process, sulfuration removal of impurities neutralization of lime milk, these techniques can consume a large amount of lime resources and produce a large amount of gypsum tailings, cause serious pollution to environment, the wasting of resources, production cost is high; The dirty acid treatment process of existing sulfuration removal of impurities now, but low to the removal efficiency of the toxic metal arsenic in dirty acid, do not reach environmental requirement; And seldom by the recovery comprehensive treating process of sulfuration removal of impurities with acid, economic benefit is lower.
Summary of the invention
The object of the present invention is to provide the production method of the concentrated reuse of a kind of dirty acid, the method achieve the comprehensive reutilization of dirty sour resource, in dirty acid, effective separation of heavy metal and arsenic, reaches the object of energy-saving and emission-reduction, zero release, reduces production cost.
the present invention is achieved by the following technical solutions
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: be 1L:(10 ~ 30 by amount ratio) the dirty acid solution of g and sulfur agent solution, joining pressure is mix in the negative reaction still of-250 ~-350Pa, under 60 ~ 70 DEG C of conditions, reaction 25 ~ 40min; In temperature lower than under 70 DEG C of conditions, in encloses container, produce a small amount of H
2s gas, a small amount of hydrogen sulfide is aspirated by the pressure that induced draft fan is-900 ~-1000Pa by negative pressure and enters in supporting alkali liquid washing tower, and by the control of pH value, the sodium sulfide solution obtained after washing may be used for the preparation of vulcanizing agent; In negative reaction still, the complete material of reaction is delivered to Filter Press by filter pressing pump, and the filter residue sulfide after filtration returns feed proportioning system and recycles; Filtrate enters into next negative reaction still and carries out second time sulfuration;
In primary vulcanization process, temperature is 60 ~ 70 DEG C, can not make too much H at this temperature
2s overflows, and ensure that effectively carrying out of sulfide precipitation; Be conducive to the formation of heavy metal ion sulfide precipitation simultaneously at this temperature, be also conducive to As in heavy metal ion and solution
2s
3the carrying out of reaction, is therefore unfavorable for the formation of arsenic sulfide precipitation; Reaction times is shorter, is also unfavorable for the formation of arsenic sulfide precipitation; The deposition rate of this heavy metals in process ion reaches 99.2%, and the deposition rate of arsenic only has 3 ~ 4.5%; Principal reaction is as follows:
Na
2S + H
2SO
4 = Na
2SO
4 + H
2S
H
2S = 2H
+ + S
2-
Na
2S = Na
+ + S
2-
Cu
2+ + S
2-= CuS
Pb
2+ + S
2- = PbS
Zn
2+ + S
2-= ZnS
Step (2): second time sulfuration: be 1L:(20 ~ 48 by amount ratio) g step (1) in the filtrate that obtains and sulfur agent solution, joining negative pressure is mix in the reactor of-450 ~-600Pa, react 80 ~ 100min under room temperature to stop, in this process, producing the H of seldom amount
2s gas, produce hydrogen sulfide by induced draft fan by negative pressure be-900 ~-1000Pa pressure suction enter in supporting alkali liquid washing tower, the material that in negative reaction still, reaction is complete is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, Filter Press is delivered to by filter pressing pump, obtain filter residue red arsenic, red arsenic carry out specialty and propose arsenic process; The dirty acidleach liquid pipeline obtained after filtration is sent to dirty sour concentration systems.
This reaction process is at room temperature carried out, and the reaction times is longer, is conducive to the formation of arsenic sulfide precipitation; And remaining other heavy metal ion a small amount of in primary vulcanization process can be removed; After second time sulfidizing, in dirty acid, the clearance of arsenic reaches more than 99.5%; In this process, principal reaction is as follows:
Na
2S + H
2SO
4= Na
2SO
4+ H
2S
H
2S = 2H
++ S
2-
Na
2S = Na
++ S
2-
As
3++ S
2-= As
2S
3
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in production system, enter dynamic wave scrubbing tower bottom, contact with top-down dirty acidleach liquid is reverse, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while improving acid concentration, taken away a large amount of F, Cl ions by steam, the tail gas taking away F, Cl ion passes into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50% ~ 60% industrial sulphuric acid enter storage acid tank.Through dirty sour concentration, the clearance of F, Cl ion reaches more than 80%.
The method that described dirt acid concentration and recovery utilizes, the difference of Metal smelting technique, raw material, the dirt acid composition that its acid making system produces is also different, and in the present invention, dirty sour composition is mainly: H
2sO
4: 20000 ~ 30000mg/L, As:800 ~ 1500mg/L, Cu:600 ~ 800mg/L, Zn:300 ~ 600mg/L, Pb:100 ~ 400mg/L, F:500 ~ 1500mg/L, Cl:500 ~ 1500mg/L.
The method that described dirt acid concentration and recovery utilizes, step (1), the vulcanizing agent described in step (2) they are sodium sulphite, and the mass percentage of sodium sulfide solution is 10 ~ 15%;
The method that described dirt acid concentration and recovery utilizes, the filter residue described in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue described in step (2) is mainly: red arsenic.
The method that described dirt acid concentration and recovery utilizes, the temperature of step (3) described warm air is 200 ~ 280 DEG C; The speed that passes into of warm air is 0.5 ~ 1.2m/s.
compared with prior art, the present invention has following positively effect
(1) the present invention utilizes the two-step cure mode process acid water that combine concentrated with dirt acid, achieves the comprehensive reutilization of Sulphur ressource, has the advantages that to improve Sulphur ressource utilization ratio, environmental protection and energy saving; Achieve the synthetical recovery of valuable metal element, recycling, decrease pollutant emission and raw-material consumption, reduce production cost.
(2) present invention process applied range, to all F
-, Cl
-, As
3+the waste water that ionic concn is less than 10g/L all can be used as the raw material of this technique, as the dirt acid that various sulfuration mineral aggregate flue gas during smelting produces in wet purification process, and the sour water etc. produced in electrolytic workshop anode mud treating processes.
(3) " sulfuration removal of impurities neutralization of lime milk " neutralisation treatment process can produce a large amount of gypsum tailings, and stack and not only take up room but also cause secondary pollution to soil and water body, the difficulty of these gypsum tailings landfills greatly, costly; Reclaim the Sulphur ressource in dirty acid with industrial sulphuric acid form in treatment process of the present invention, improve the utilization ratio of sulphur, avoid producing a large amount of gypsum tailings, eliminate the environmental protection pressure of enterprise's production run.
(4) the present invention utilizes thermogenetic hot blast more than production system by concentrated for dirt acid, by " waste recycling ", reclaim the Sulphur ressource in dirty acid with industrial sulphuric acid form, improve the utilization ratio of sulphur.
(5) the application adopts the method for twice sulfuration, and by the control of time and temperature, primary vulcanization effectively eliminates the heavy metal ion in dirty acid solution, and the metallic sulfide obtained returns feed circuit as the raw material smelted; Second time sulfuration effectively eliminates the arsenic in dirty acid solution, and red arsenic is carried out the refining arsenic process of specialty.Therefore, when carrying out removal of impurities process to dirty acid, effectively remove and be separated the larger arsenic of toxicity, the metal in dirty acid obtains good recycling, improves economic benefit.The dirty acid solution of the present invention after twice sulfuration, not only effectively eliminates F, Cl ion in solution in high temperature concentration process, and F, Cl absorb formation salt through corresponding alkali liquor absorption tower, and recycle, removal effect is good, high financial profit.
(6) treatment process cost provided by the invention is low, remarkable in economical benefits: for Copper making industry, and copper per ton about produces 0.3 ~ 0.7m according to statistics
3the dirt acid of left and right, adopts traditional neutralisation process 1m
3dirty sour average cost about 150 yuan (not limy slag landfill expense), adopts disposal methods 1m of the present invention
3the cost of dirty acid can reduce about 50 yuan than original technique.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the present invention is described in further detail, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
embodiment 1
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: the dirty acid solution and the sodium sulfide solution that by amount ratio are 1L:25g, joining pressure is mix in the negative reaction still of-350Pa, 40min is reacted at 60 DEG C, after reaction stops, the material of negative reaction still is delivered to Filter Press by filter pressing pump, filter residue after filtration is delivered to feed proportioning system and recycles, and filtrate is delivered to next reactor and carries out second time sulfidizing.The a small amount of H produced in this process
2s gas, the pressure being-950 ~-1000Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (2): second time sulfuration: be the filtrate that obtains of the step (1) of 1L:44g and sodium sulfide solution by amount ratio, joining negative pressure is in the negative reaction still of-600Pa, 80min is reacted under room temperature, material after reaction stops in negative reaction still is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, be delivered to pressure filter by filter pressing pump, in the filter residue after filtration, be mainly red arsenic, be sent to specialized factory and carry out proposing arsenic process; Dirty acidleach liquid and the supernatant liquor of being discharged by thickener top annular groove by Cemented filling to dirty sour concentration systems.A small amount of H is produced in this process
2s gas, the pressure being-900 ~-950Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in production system, and the temperature of warm air is 200 DEG C, enters dynamic wave scrubbing tower bottom, and the speed that passes into of warm air is 1.2m/s.Warm air upwards fully contacts with dirty acidleach liquid is reverse at the bottom of tower, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while raising acid concentration, a large amount of F, Cl ions has been taken away by steam, take away F, Cl ion and pass into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50 ~ 60% industrial sulphuric acid enter storage acid tank.
The method that described dirt acid concentration and recovery utilizes, the dirt acid composition described in step (1) is mainly: H
2sO
4: 30000mg/L, As:1500mg/L, Cu:800mg/L, Zn:600mg/L, Pb:400mg/L, F:1500mg/L, Cl:1500mg/L.
The method that described dirt acid concentration and recovery utilizes, the mass percentage of sodium sulphite is: 10%.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (2) is mainly: red arsenic.
embodiment 2
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: the dirty acid solution and the sodium sulfide solution that by amount ratio are 1L:10.5g, joining pressure is mix in the negative reaction still of-250Pa, 25min is reacted at 70 DEG C, after reaction stops, the material of negative reaction still is delivered to Filter Press by filter pressing pump, filter residue after filtration is delivered to feed proportioning system and recycles, and filtrate is delivered to next reactor and carries out second time sulfidizing.The a small amount of H produced in this process
2s gas is aspirated by the pressure that induced draft fan is-950 ~-1000Pa by negative pressure and enters in supporting alkali liquid washing tower.
Step (2): second time sulfuration: be the filtrate that obtains of the step (1) of 1L:29g and sodium sulfide solution by amount ratio, joining negative pressure is in the negative reaction still of-450Pa, 100min is reacted under room temperature, material after reaction stops in negative reaction still is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, be delivered to pressure filter by filter pressing pump, in the filter residue after filtration, be mainly red arsenic, be sent to specialized factory and carry out proposing arsenic process; Dirty acidleach liquid and the supernatant liquor of being discharged by thickener top annular groove by Cemented filling to dirty sour concentration systems.A small amount of H is produced in this process
2s gas, the pressure being-900 ~-950Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in production system, and the temperature of warm air is 280 DEG C, enters dynamic wave scrubbing tower bottom, and the speed that passes into of warm air is 0.5m/s.Warm air upwards fully contacts with dirty acidleach liquid is reverse at the bottom of tower, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while raising acid concentration, a large amount of F, Cl ions has been taken away by steam, the tail gas taking away F, Cl ion passes into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50 ~ 60% industrial sulphuric acid enter storage acid tank.
The method that described dirt acid concentration and recovery utilizes, the dirt acid composition described in step (1) is mainly: H
2sO
4: 20000mg/L, As:800mg/L, Cu:600mg/L, Zn:300mg/L, Pb:100mg/L, F:500mg/L, Cl:500mg/L.
The method that described dirt acid concentration and recovery utilizes, the mass percentage of sodium sulphite is: 15%.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (2) is mainly: red arsenic.
embodiment 3
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: the dirty acid solution and the sodium sulfide solution that by amount ratio are 1L:17g, joining pressure is mix in the negative reaction still of-300Pa, 32min is reacted at 65 DEG C, after reaction stops, the material of negative reaction still is delivered to Filter Press by filter pressing pump, filter residue after filtration is delivered to feed proportioning system and recycles, and filtrate is delivered to next reactor and carries out second time sulfidizing.The a small amount of H produced in this process
2s gas is aspirated by the pressure that induced draft fan is-950 ~-1000Pa by negative pressure and enters in supporting alkali liquid washing tower.
Step (2): second time sulfuration: be the filtrate that obtains of the step (1) of 1L:29g and sodium sulfide solution by amount ratio, joining negative pressure is in the negative reaction still of-520Pa, 90min is reacted under room temperature, material after reaction stops in negative reaction still is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, be delivered to pressure filter by filter pressing pump, in the filter residue after filtration, be mainly red arsenic, be sent to specialized factory and carry out proposing arsenic process; Dirty acidleach liquid and the supernatant liquor of being discharged by thickener top annular groove by Cemented filling to dirty sour concentration systems.A small amount of H is produced in this process
2s gas, the pressure being-900 ~-950Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in production system, and the temperature of warm air is 240 DEG C, enters dynamic wave scrubbing tower bottom, and the speed that passes into of warm air is 0.8m/s.Warm air upwards fully contacts with dirty acidleach liquid is reverse at the bottom of tower, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while raising acid concentration, a large amount of F, Cl ions has been taken away by steam, the tail gas taking away F, Cl ion passes into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50 ~ 60% industrial sulphuric acid enter storage acid tank.
The method that described dirt acid concentration and recovery utilizes, the dirt acid composition described in step (1) is mainly: H
2sO
4: 25000mg/L, As:1150mg/L, Cu:700mg/L, Zn:450mg/L, Pb:250mg/L, F:1000mg/L, Cl:1000mg/L.
The method that described dirt acid concentration and recovery utilizes, the mass percentage of sodium sulphite is: 12%.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (2) is mainly: red arsenic.
embodiment 4
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: the dirty acid solution and the sodium sulfide solution that by amount ratio are 1L:16.5g, joining pressure is mix in the negative reaction still of-320Pa, 36min is reacted at 62 DEG C, after reaction stops, the material of negative reaction still is delivered to Filter Press by filter pressing pump, filter residue after filtration is delivered to feed proportioning system and recycles, and filtrate is delivered to next reactor and carries out second time sulfidizing.The a small amount of H produced in this process
2s gas is aspirated by the pressure that induced draft fan is-950 ~-1000Pa by negative pressure and enters in supporting alkali liquid washing tower.
Step (2): second time sulfuration: be the filtrate that obtains of the step (1) of 1L:31.5g and sodium sulfide solution by amount ratio, joining negative pressure is in the negative reaction still of-560Pa, 85min is reacted under room temperature, material after reaction stops in negative reaction still is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, be delivered to pressure filter by filter pressing pump, in the filter residue after filtration, be mainly red arsenic, be sent to specialized factory and carry out proposing arsenic process; Dirty acidleach liquid and the supernatant liquor of being discharged by thickener top annular groove by Cemented filling to dirty sour concentration systems.A small amount of H is produced in this process
2s gas, the pressure being-900 ~-950Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in production system, and the temperature of warm air is 220 DEG C, enters dynamic wave scrubbing tower bottom, and the speed that passes into of warm air is 1.0m/s.Warm air upwards fully contacts with dirty acidleach liquid is reverse at the bottom of tower, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while raising acid concentration, a large amount of F, Cl ions has been taken away by steam, the tail gas taking away F, Cl ion passes into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50 ~ 60% industrial sulphuric acid enter storage acid tank.
The method that described dirt acid concentration and recovery utilizes, the dirt acid composition described in step (1) is mainly: H
2sO
4: 27500mg/L, As:1320mg/L, Cu:750mg/L, Zn:520mg/L, Pb:320mg/L, F:1250mg/L, Cl:1250mg/L.
The method that described dirt acid concentration and recovery utilizes, the mass percentage of sodium sulphite is: 13%.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (2) is mainly: red arsenic.
embodiment 5
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: the dirty acid solution and the sodium sulfide solution that by amount ratio are 1L:12g, joining pressure is mix in the negative reaction still of-280Pa, 30min is reacted at 68 DEG C, after reaction stops, the material of negative reaction still is delivered to Filter Press by filter pressing pump, filter residue after filtration is delivered to feed proportioning system and recycles, and filtrate is delivered to next reactor and carries out second time sulfidizing.The a small amount of H produced in this process
2s gas is aspirated by the pressure that induced draft fan is-950 ~-1000Pa by negative pressure and enters in supporting alkali liquid washing tower.
Step (2): second time sulfuration: be the filtrate that obtains of the step (1) of 1L:20.5g and sodium sulfide solution by amount ratio, joining negative pressure is in the negative reaction still of-480Pa, 95min is reacted under room temperature, material after reaction stops in negative reaction still is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, be delivered to pressure filter by filter pressing pump, in the filter residue after filtration, be mainly red arsenic, be sent to specialized factory and carry out proposing arsenic process; Dirty acidleach liquid and the supernatant liquor of being discharged by thickener top annular groove by Cemented filling to dirty sour concentration systems.A small amount of H is produced in this process
2s gas, the pressure being-900 ~-950Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in production system, and the temperature of warm air is 260 DEG C, enters dynamic wave scrubbing tower bottom, and the speed that passes into of warm air is 0.7m/s.Warm air upwards fully contacts with dirty acidleach liquid is reverse at the bottom of tower, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while raising acid concentration, a large amount of F, Cl ions has been taken away by steam, the tail gas taking away F, Cl ion passes into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50 ~ 60% industrial sulphuric acid enter storage acid tank.
The method that described dirt acid concentration and recovery utilizes, the dirt acid composition described in step (1) is mainly: H
2sO
4: 22500mg/L, As:980mg/L, Cu:650mg/L, Zn:380mg/L, Pb:180mg/L, F:750mg/L, Cl:750mg/L.
The method that described dirt acid concentration and recovery utilizes, the mass percentage of sodium sulphite is: 15%.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (2) is mainly: red arsenic.
embodiment 6
The method that the sour concentration and recovery of dirt utilizes, comprises the following steps:
Step (1): primary vulcanization: the acid solution and the sodium sulfide solution that by amount ratio are 1L:15g, joining pressure is mix in the negative reaction still of-290Pa, 30min is reacted at 67 DEG C, after reaction stops, the material of negative reaction still is delivered to Filter Press by filter pressing pump, filter residue after filtration is delivered to feed proportioning system and recycles, and filtrate is delivered to next reactor and carries out second time sulfidizing.The a small amount of H produced in this process
2s gas is aspirated by the pressure that induced draft fan is-950 ~-1000Pa by negative pressure and enters in supporting alkali liquid washing tower.
Step (2): second time sulfuration: be the filtrate that obtains of the step (1) of 1L:22.5g and sodium sulfide solution by amount ratio, joining negative pressure is in the negative reaction still of-500Pa, 93min is reacted under room temperature, material after reaction stops in negative reaction still is after thickener fully precipitates, the ore pulp of bottom is drawn off by thickener underflow mouth, be delivered to pressure filter by filter pressing pump, in the filter residue after filtration, be mainly red arsenic, be sent to specialized factory and carry out proposing arsenic process; Dirty acidleach liquid and the supernatant liquor of being discharged by thickener top annular groove by Cemented filling to dirty sour concentration systems.A small amount of H is produced in this process
2s gas, the pressure being-900 ~-950Pa by negative pressure by induced draft fan aspirates and enters in supporting alkali liquid washing tower.
Step (3): the dirty acidleach liquid obtained through step (2) is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Air is converted into warm air by the waste heat produced in acid production system, and the temperature of warm air is 250 DEG C, enters dynamic wave scrubbing tower bottom, and the speed that passes into of warm air is 0.8m/s.Warm air upwards fully contacts with dirty acidleach liquid is reverse at the bottom of tower, high-temperature heat insulation evaporation concentration is carried out to dirty acidleach liquid, while raising acid concentration, a large amount of F, Cl ions has been taken away by steam, the tail gas taking away F, Cl ion passes into supporting alkali liquid washing turriform salify, recycling from the escape pipe discharge in dynamic wave scrubber overhead portion.Obtain concentration be 50 ~ 60% industrial sulphuric acid enter storage acid tank.
The method that described dirt acid concentration and recovery utilizes, the dirt acid composition described in step (1) is mainly: H
2sO
4: 24000mg/L, As:1000mg/L, Cu:690mg/L, Zn:530mg/L, Pb:240mg/L, F:900mg/L, Cl:900mg/L.
The method that described dirt acid concentration and recovery utilizes, the mass percentage of sodium sulphite is: 14%.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (1) is mainly: cupric sulfide, lead sulfide, zinc sulphide.
The method that described dirt acid concentration and recovery utilizes, the filter residue composition in step (2) is mainly: red arsenic.
。
Claims (8)
1. a method for the sour concentration and recovery utilization of dirt, is characterized in that, comprise the following steps:
Step (1): get dirty acid solution, sulfur agent solution, joins in negative reaction still and mixes rear reaction, and the material after reaction stops in negative reaction still is delivered to Filter Press by filter pressing pump, and filter residue is recycled, and filtrate enters next step process;
Step (2): get filtrate that step (1) obtains, sulfur agent solution, join in negative reaction still and mix rear reaction, after reaction stops, after mass transport in reactor to thickener precipitation, slurry is delivered to Filter Press by filter pressing pump, filter residue recycles, and dirty acidleach liquid enters next step process;
Step (3): the dirty acidleach liquid obtained after step (2) sulfidizing is delivered to dynamic wave scrubbing column overhead by dirty sour transferpump, sprays downwards from tower top; Warm air enters dynamic wave scrubbing tower bottom, with dirty acidleach liquid counter current contact, warm air to dirty acidleach liquid high-temperature heat insulation evaporation concentration, with F
-, Cl
-tail gas discharge from the escape pipe in dynamic wave scrubber overhead portion and pass into alkali liquid washing tower, obtain industrial goods sulfuric acid in tower and enter storage acid tank.
2. the method for the sour concentration and recovery utilization of dirt according to claim 1, is characterized in that: the dirt acid composition described in step (1) is: H
2sO
4: 20000 ~ 30000mg/L, As:800 ~ 1500mg/L, Cu:600 ~ 800mg/L, Zn:300 ~ 600mg/L, Pb:100 ~ 400mg/L, F:500 ~ 1500mg/L, Cl:500 ~ 1500mg/L.
3. the method for the sour concentration and recovery utilization of dirt according to claim 1, it is characterized in that: step (1), the vulcanizing agent described in step (2) are sodium sulfide solution, the mass percentage of sodium sulfide solution is 10 ~ 15%.
4. the method for the sour concentration and recovery utilization of dirt according to claim 1, is characterized in that: the dirty acid that adds described in step (1) is 1L:(10 ~ 30 with the amount ratio of sulfur agent solution) g.
5. the method for the sour concentration and recovery utilization of dirt according to claim 1, it is characterized in that: the reaction pressure in the negative reaction still described in step (1) is-250 ~-350Pa, and temperature of reaction is 60 ~ 70 DEG C, the reaction times is 25 ~ 40min.
6. the method that utilizes of the sour concentration and recovery of dirt according to claim 1, is characterized in that: the amount ratio joining filtrate in negative reaction still and sulfur agent solution described in step (2) is: 1L:(20 ~ 48) g.
7. the method for the sour concentration and recovery utilization of dirt according to claim 1, is characterized in that: the reaction pressure in the reactor described in step (2) is-450 ~-600Pa, reacts 80 ~ 100min under room temperature.
8. the method for the sour concentration and recovery utilization of dirt according to claim 1, it is characterized in that: the temperature of the warm air described in step (3) is 200 ~ 280 DEG C, the speed that passes into of warm air is 0.5 ~ 1.2m/s.
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| CN105617843A (en) * | 2016-02-14 | 2016-06-01 | 楚雄滇中有色金属有限责任公司 | Contaminated acid treatment water recycling method |
| CN107162306A (en) * | 2017-07-07 | 2017-09-15 | 湖南求是检测科技有限公司 | A kind of recycling processing method of battery spent acid |
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| CN109019530A (en) * | 2018-10-31 | 2018-12-18 | 河南菲迪泰环境科技有限公司 | A kind of waste acid processing recovery system and its processing recovery method |
| CN109354098A (en) * | 2018-12-21 | 2019-02-19 | 萍乡市新安环保工程有限公司 | A kind of processing system and method for desulfurization wastewater |
| CN110923440A (en) * | 2019-11-22 | 2020-03-27 | 西北矿冶研究院 | Method for removing arsenic and recovering heavy metal from copper smelting wastewater |
| CN116062951A (en) * | 2023-03-16 | 2023-05-05 | 天津高能时代水处理科技有限公司 | Zero-emission process system for waste acid and wastewater and waste acid and wastewater treatment method |
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