CN104909507B - Contaminated acid concentrating and recycling method - Google Patents

Contaminated acid concentrating and recycling method Download PDF

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Publication number
CN104909507B
CN104909507B CN201510294711.9A CN201510294711A CN104909507B CN 104909507 B CN104909507 B CN 104909507B CN 201510294711 A CN201510294711 A CN 201510294711A CN 104909507 B CN104909507 B CN 104909507B
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waste acid
filtrate
reaction kettle
delivered
air
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CN104909507A (en
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王胜利
王东亮
侯明旺
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Henan Feiditai Environmental Technology Co. Ltd.
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He'nan Shuangyu New Material Technology Co Ltd
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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

A kind of method that waste acid concentration and recovery is utilized
Technical field
The invention belongs to metal smelt relieving haperacidity waste acid process field, and in particular to the side that a kind of waste acid concentration and recovery is utilized Method.
Background technology
In nonferrous metallurgical process, As is usually contained in a large amount of acid waters that relieving haperacidity operation is produced3+、As5+、Cu2 +、Pb2+、Zn2+Etc. heavy metal ion and F、Cl, because the concentration of waste acid is high, heavy metal concentration is higher, have in processing procedure Valency metal is transferred to be difficult to recycle in waste residue, while producing substantial amounts of hazardous waste, easily causes serious secondary pollution.
Major part smelting enterprise is using vulcanization-lime iron salt method, lime-iron salt method treatment waste acid, vulcanization removal of impurities at present Neutralization of lime milk, these techniques can consume substantial amounts of lime resource and produce substantial amounts of gypsum tailings, cause serious to environment Pollution, the wasting of resources, production cost is high;Vulcanized the waste acid handling process of removal of impurities now, but to waste acid in poisonous gold The removal efficiency for belonging to arsenic is low, does not reach environmental requirement;And seldom will vulcanize removal of impurities with acid recovery integrated treatment, economic benefit compared with It is low.
The content of the invention
It is an object of the invention to provide the production method that a kind of waste acid concentrates reuse, waste acid resource is the method achieve Comprehensive reutilization, heavy metal and arsenic are efficiently separated in waste acid, have reached the purpose of energy-saving and emission-reduction, zero-emission, reduce life Produce cost.
The present invention is achieved by the following technical solutions
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:(10~30)The waste acid solution and sulfur agent solution of g, are added to Pressure under the conditions of 60 ~ 70 DEG C, reacts 25 ~ 40min to be well mixed in the negative reaction kettle of -250 ~ -350Pa;It is low in temperature Under the conditions of 70 DEG C, in closed container, a small amount of H is produced2S gases, a small amount of hydrogen sulfide gas by air-introduced machine by negative pressure for- The pressure of 900 ~ -1000Pa is drawn into supporting alkali liquid washing tower, by the control of pH value, the vulcanization obtained after washing Sodium solution can be used for the preparation of vulcanizing agent;The material that reaction is finished in negative reaction kettle is delivered to filter press mistake by filter pressing pump Filter, the filter residue sulfide after filtering returns to feed proportioning system and recycles;Filtrate enters into next negative reaction kettle and carries out Post-cure;
During primary vulcanization, temperature is 60 ~ 70 DEG C, and excessive H will not be made at this temperature2S is escaped, it is ensured that sulfide The effective of precipitation is carried out;Be conducive to the formation of heavy metal ion sulfide precipitation at this temperature simultaneously, be also beneficial to heavy metal from Son and As in solution2S3The carrying out of reaction, therefore it is unfavorable for the formation of arsenic sulfide precipitation;Reaction time is shorter, is also unfavorable for arsenic The formation of sulfide precipitation;The rate of deposition of the heavy metals in process ion reaches 99.2%, and the rate of deposition of arsenic only has 3 ~ 4.5%; Key reaction is as follows:
Na2S + H2SO4 = Na2SO4 + H2S
H2S = 2H+ + S2-
Na2S = Na+ + S2-
Cu2+ + S2- = CuS
Pb2+ + S2- = PbS
Zn2+ + S2- = ZnS
Step(2):Vulcanize for second:It is 1L by amount ratio:(20~48)The step of g(1)In the filtrate that obtains and vulcanizing agent Solution, is added to well mixed, 80 ~ 100min of reaction stoppings, the process at room temperature in the reactor that negative pressure is -450 ~ -600Pa It is middle to produce minimal amount of H2S gases, the hydrogen sulfide gas of generation are the suction of -900 ~ -1000Pa pressure by negative pressure by air-introduced machine Into in supporting alkali liquid washing tower, after the material that reaction is finished in negative reaction kettle is fully precipitated through concentrator, the ore deposit of bottom Slurry is drawn off by thickener underflow mouthful, and Filter Press is delivered to by filter pressing pump, obtains filter residue arsenones, and arsenones carry out specialty Propose arsenic treatment;The waste acid filtrate obtained after filtering is sent to waste acid concentration systems with pipeline.
The course of reaction is carried out at room temperature, and the reaction time is more long, is conducive to the formation of arsenic sulfide precipitation;And can remove Remaining a small amount of other heavy metal ion during primary vulcanization;After by second vulcanizing treatment, arsenic goes in waste acid Except rate reaches more than 99.5%;Key reaction is as follows during being somebody's turn to do:
Na2S + H2SO4 = Na2SO4 + H2S
H2S = 2H+ + S2-
Na2S = Na+ + S2-
As3+ + S2- = As2S3
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing column overhead by delivery pump, from Tower top is sprayed downwards;Air is converted into hot-air by the waste heat produced in production system, into dynamic wave scrubbing tower bottom, with oneself Waste acid filtrate under above is inversely contacted, and high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while improving acid concentration, by steaming Vapour has taken away substantial amounts of F, Cl ion, takes away the tail gas of F, Cl ion and is passed through from the escaping pipe discharge in dynamic wave scrubber overhead portion and matches somebody with somebody The alkali liquid washing tower forming salt of set, recycling.Obtain the industrial sulphuric acid that concentration is 50% ~ 60% and enter storage acid tank.By waste acid Concentration, the clearance of F, Cl ion reaches more than 80%.
The method that described waste acid concentration and recovery is utilized, metal smelt technique, the difference of raw material, what its acid making system was produced Waste acid composition is also different, and waste acid composition is mainly in the present invention:H2SO4:20000 ~ 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 waste acid concentration and recovery is utilized, step(1), step(2)Described in vulcanizing agent be vulcanized sodium, sulphur The weight/mass percentage composition for changing sodium solution is 10 ~ 15%;
The method that described waste acid concentration and recovery is utilized, step(1)Described in filter residue be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)Described in filter residue be mainly:Arsenones.
The method that described waste acid concentration and recovery is utilized, step(3)The temperature of the hot-air is 200 ~ 280 DEG C;It is hot empty The speed that is passed through of gas is 0.5 ~ 1.2m/s.
Compared with prior art, the present invention has the positive effect that
(1)The present invention processes acid water using two-step cure with the mode that waste acid concentration is combined, and realizes Sulphur ressource Comprehensive reutilization, with improving the characteristics of Sulphur ressource utilization rate, environmental protection and energy saving;The synthesis for realizing valuable metal element is returned Receipts, recycling, reduce pollutant emission and the consumption of raw material, reduce production cost.
(2)Present invention process has a wide range of application, to all F、Cl、As3+Waste water of the ion concentration less than 10g/L can be made It is the raw material of the technique, the waste acid that such as various vulcanization mineral aggregate flue gas during smeltings are produced during wet cleaning, and potroom Sour water produced during ANODE SLIME TREATMENT etc..
(3)" vulcanization removal of impurities neutralization of lime milk " neutralisation handling process can produce substantial amounts of gypsum tailings, and stacking both took Secondary pollution is caused in space to soil and water body again, and the difficulty of these gypsum tailings landfill is big, costly;In processing method of the present invention The Sulphur ressource in waste acid is reclaimed in industrial sulphuric acid form, the utilization rate of sulphur is improve, it is to avoid is produced substantial amounts of gypsum tailings, is eliminated The environmental protection pressure of enterprise's production run.
(4)Thermogenetic hot blast concentrates waste acid more than present invention utilization production system, by " waste recycling ", with industrial sulphur Sour form reclaims the Sulphur ressource in waste acid, improves the utilization rate of sulphur.
(5)Method of the application using vulcanizing twice, by the control of time and temperature, primary vulcanization is effectively removed Heavy metal ion in waste acid solution, the metal sulfide for obtaining returns to raw material system as the raw material smelted;Second sulphur Change the effective arsenic eliminated in waste acid solution, and arsenones are carried out the refining arsenic treatment of specialty.Therefore removed to waste acid When living together reason, the larger arsenic of toxicity is effectively removed and has separated, the metal in waste acid has obtained preferable recycling, improve Economic benefit.The present invention by vulcanizing twice after waste acid solution, not only effectively eliminate solution in high temperature concentration process Middle F, Cl ion, and F, Cl absorb forming salt by corresponding alkali liquor absorption tower, recycle, and removal effect is good, economy effect It is beneficial high.
(6)The processing method low cost that the present invention is provided, remarkable in economical benefits:By taking Copper making industry as an example, according to statistics often Ton copper about produces 0.3 ~ 0.7m3The waste acid of left and right, 1m is processed using traditional neutralisation3About 150 yuan of waste acid average unit cost(Be free of Lime mud fills expense), using disposal methods 1m of the present invention3The cost of waste acid can reduce by 50 yuan or so than original technique.
Specific embodiment
In order to deepen the understanding of the present invention, with reference to embodiment, the present invention is described in further detail, the embodiment It is only used for explaining the present invention, is not intended to limit the scope of the present invention..
Embodiment 1
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:The waste acid solution and sodium sulfide solution of 25g, are added to pressure To be well mixed in the negative reaction kettle of -350Pa, 40min is reacted at 60 DEG C, the material of negative reaction kettle leads to after reaction stopping Cross filter pressing pump and be delivered to Filter Press, the filter residue after filtering is delivered to feed proportioning system recycling, and filtrate is delivered to next Individual reactor carries out second vulcanizing treatment.The a small amount of H produced during this2S gases, by air-introduced machine by negative pressure be -950 ~ - The pressure of 1000Pa is drawn into supporting alkali liquid washing tower.
Step(2):Vulcanize for second:It is 1L by amount ratio:The step of 44g(1)The filtrate for obtaining and sodium sulfide solution, plus Enter in the negative reaction kettle that negative pressure is -600Pa, 80min is reacted at room temperature, the material warp after reaction stopping in negative reaction kettle After concentrator is fully precipitated, the ore pulp of bottom is drawn off by thickener underflow mouthful, filter press is delivered to by filter pressing pump, after filtering Filter residue in predominantly arsenones, being sent to specialized factory propose arsenic treatment;Waste acid filtrate and by concentrator top annular groove The supernatant of discharge is by pipeline to waste acid concentration systems.A small amount of H is produced during this2S gases, by air-introduced machine by Negative pressure is drawn into supporting alkali liquid washing tower for the pressure of -900 ~ -950Pa.
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing tower tower by waste acid delivery pump Top, sprays downwards from tower top;Air is converted into hot-air by the waste heat produced in production system, and the temperature of hot-air is 200 DEG C, Into dynamic wave scrubbing tower bottom, the speed that is passed through of hot-air is 1.2m/s.Hot-air is reverse with waste acid filtrate upwards from bottom of towe It is fully contacted, high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while acid concentration is improved, has been taken away by steam substantial amounts of F, Cl ion, take away F, Cl ion and are passed through supporting alkali liquid washing tower from the discharge of the escaping pipe in dynamic wave scrubber overhead portion and formed Salt, recycling.Obtain the industrial sulphuric acid that concentration is 50 ~ 60% and enter storage acid tank.
The method that described waste acid concentration and recovery is utilized, step(1)Described waste acid composition is mainly:H2SO4: 30000mg/L, As:1500mg/L, Cu:800mg/L, Zn:600mg/L, Pb:400mg/L, F:1500mg/L, Cl:1500mg/ L。
The method that described waste acid concentration and recovery is utilized, the weight/mass percentage composition of vulcanized sodium is:10%.
The method that described waste acid concentration and recovery is utilized, step(1)In filter residue composition be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)In filter residue composition be mainly:Arsenones.
Embodiment 2
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:The waste acid solution and sodium sulfide solution of 10.5g, are added to pressure Power be -250Pa negative reaction kettle in be well mixed, react 25min at 70 DEG C, reaction stop after negative reaction kettle material Filter Press is delivered to by filter pressing pump, the filter residue after filtering is delivered to feed proportioning system recycling, filtrate is delivered to down One reactor carries out second vulcanizing treatment.The a small amount of H produced during this2S gases are -950 by negative pressure by air-introduced machine The pressure of ~ -1000Pa is drawn into supporting alkali liquid washing tower.
Step(2):Vulcanize for second:It is 1L by amount ratio:The step of 29g(1)The filtrate for obtaining and sodium sulfide solution, plus Enter in the negative reaction kettle that negative pressure is -450Pa, 100min, the material after reaction stopping in negative reaction kettle are reacted at room temperature After fully being precipitated through concentrator, the ore pulp of bottom is drawn off by thickener underflow mouthful, and filter press is delivered to by filter pressing pump, filters it Arsenones are mainly in filter residue afterwards, being sent to specialized factory carries out proposing arsenic treatment;Waste acid filtrate and by concentrator top annular The supernatant of groove discharge is by pipeline to waste acid concentration systems.A small amount of H is produced during this2S gases, by air-introduced machine By negative pressure for the pressure of -900 ~ -950Pa is drawn into supporting alkali liquid washing tower.
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing tower tower by waste acid delivery pump Top, sprays downwards from tower top;Air is converted into hot-air by the waste heat produced in production system, and the temperature of hot-air is 280 DEG C, Into dynamic wave scrubbing tower bottom, the speed that is passed through of hot-air is 0.5m/s.Hot-air is reverse with waste acid filtrate upwards from bottom of towe It is fully contacted, high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while acid concentration is improved, has been taken away by steam substantial amounts of F, Cl ion, the tail gas for taking away F, Cl ion are passed through supporting alkali liquid washing tower from the escaping pipe discharge in dynamic wave scrubber overhead portion Forming salt, recycling.Obtain the industrial sulphuric acid that concentration is 50 ~ 60% and enter storage acid tank.
The method that described waste acid concentration and recovery is utilized, step(1)Described waste acid composition is mainly:H2SO4: 20000mg/L, As:800mg/L, Cu:600mg/L, Zn:300mg/L, Pb:100mg/L, F:500mg/L, Cl:500mg/L.
The method that described waste acid concentration and recovery is utilized, the weight/mass percentage composition of vulcanized sodium is:15%.
The method that described waste acid concentration and recovery is utilized, step(1)In filter residue composition be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)In filter residue composition be mainly:Arsenones.
Embodiment 3
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:The waste acid solution and sodium sulfide solution of 17g, are added to pressure To be well mixed in the negative reaction kettle of -300Pa, 32min is reacted at 65 DEG C, the material of negative reaction kettle leads to after reaction stopping Cross filter pressing pump and be delivered to Filter Press, the filter residue after filtering is delivered to feed proportioning system recycling, and filtrate is delivered to next Individual reactor carries out second vulcanizing treatment.The a small amount of H produced during this2S gases by air-introduced machine by negative pressure be -950 ~ - The pressure of 1000Pa is drawn into supporting alkali liquid washing tower.
Step(2):Vulcanize for second:It is 1L by amount ratio:The step of 29g(1)The filtrate for obtaining and sodium sulfide solution, plus Enter in the negative reaction kettle that negative pressure is -520Pa, 90min is reacted at room temperature, the material warp after reaction stopping in negative reaction kettle After concentrator is fully precipitated, the ore pulp of bottom is drawn off by thickener underflow mouthful, filter press is delivered to by filter pressing pump, after filtering Filter residue in predominantly arsenones, being sent to specialized factory propose arsenic treatment;Waste acid filtrate and by concentrator top annular groove The supernatant of discharge is by pipeline to waste acid concentration systems.A small amount of H is produced during this2S gases, by air-introduced machine by Negative pressure is drawn into supporting alkali liquid washing tower for the pressure of -900 ~ -950Pa.
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing tower tower by waste acid delivery pump Top, sprays downwards from tower top;Air is converted into hot-air by the waste heat produced in production system, and the temperature of hot-air is 240 DEG C, Into dynamic wave scrubbing tower bottom, the speed that is passed through of hot-air is 0.8m/s.Hot-air is reverse with waste acid filtrate upwards from bottom of towe It is fully contacted, high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while acid concentration is improved, has been taken away by steam substantial amounts of F, Cl ion, the tail gas for taking away F, Cl ion are passed through supporting alkali liquid washing tower from the escaping pipe discharge in dynamic wave scrubber overhead portion Forming salt, recycling.Obtain the industrial sulphuric acid that concentration is 50 ~ 60% and enter storage acid tank.
The method that described waste acid concentration and recovery is utilized, step(1)Described waste acid composition is mainly:H2SO4: 25000mg/L, As:1150mg/L, Cu:700mg/L, Zn:450mg/L, Pb:250mg/L, F:1000mg/L, Cl:1000mg/ L。
The method that described waste acid concentration and recovery is utilized, the weight/mass percentage composition of vulcanized sodium is:12%.
The method that described waste acid concentration and recovery is utilized, step(1)In filter residue composition be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)In filter residue composition be mainly:Arsenones.
Embodiment 4
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:The waste acid solution and sodium sulfide solution of 16.5g, are added to pressure Power be -320Pa negative reaction kettle in be well mixed, react 36min at 62 DEG C, reaction stop after negative reaction kettle material Filter Press is delivered to by filter pressing pump, the filter residue after filtering is delivered to feed proportioning system recycling, filtrate is delivered to down One reactor carries out second vulcanizing treatment.The a small amount of H produced during this2S gases are -950 by negative pressure by air-introduced machine The pressure of ~ -1000Pa is drawn into supporting alkali liquid washing tower.
Step(2):Vulcanize for second:It is 1L by amount ratio:The step of 31.5g(1)The filtrate for obtaining and sodium sulfide solution, It is added in the negative reaction kettle that negative pressure is -560Pa, 85min, the material after reaction stopping in negative reaction kettle is reacted at room temperature After fully being precipitated through concentrator, the ore pulp of bottom is drawn off by thickener underflow mouthful, and filter press is delivered to by filter pressing pump, filters it Arsenones are mainly in filter residue afterwards, being sent to specialized factory carries out proposing arsenic treatment;Waste acid filtrate and by concentrator top annular The supernatant of groove discharge is by pipeline to waste acid concentration systems.A small amount of H is produced during this2S gases, by air-introduced machine By negative pressure for the pressure of -900 ~ -950Pa is drawn into supporting alkali liquid washing tower.
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing tower tower by waste acid delivery pump Top, sprays downwards from tower top;Air is converted into hot-air by the waste heat produced in production system, and the temperature of hot-air is 220 DEG C, Into dynamic wave scrubbing tower bottom, the speed that is passed through of hot-air is 1.0m/s.Hot-air is reverse with waste acid filtrate upwards from bottom of towe It is fully contacted, high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while acid concentration is improved, has been taken away by steam substantial amounts of F, Cl ion, the tail gas for taking away F, Cl ion are passed through supporting alkali liquid washing tower from the escaping pipe discharge in dynamic wave scrubber overhead portion Forming salt, recycling.Obtain the industrial sulphuric acid that concentration is 50 ~ 60% and enter storage acid tank.
The method that described waste acid concentration and recovery is utilized, step(1)Described waste acid composition is mainly:H2SO4: 27500mg/L, As:1320mg/L, Cu:750mg/L, Zn:520mg/L, Pb:320mg/L, F:1250mg/L, Cl:1250mg/ L。
The method that described waste acid concentration and recovery is utilized, the weight/mass percentage composition of vulcanized sodium is:13%.
The method that described waste acid concentration and recovery is utilized, step(1)In filter residue composition be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)In filter residue composition be mainly:Arsenones.
Embodiment 5
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:The waste acid solution and sodium sulfide solution of 12g, are added to pressure To be well mixed in the negative reaction kettle of -280Pa, 30min is reacted at 68 DEG C, the material of negative reaction kettle leads to after reaction stopping Cross filter pressing pump and be delivered to Filter Press, the filter residue after filtering is delivered to feed proportioning system recycling, and filtrate is delivered to next Individual reactor carries out second vulcanizing treatment.The a small amount of H produced during this2S gases by air-introduced machine by negative pressure be -950 ~ - The pressure of 1000Pa is drawn into supporting alkali liquid washing tower.
Step(2):Vulcanize for second:It is 1L by amount ratio:The step of 20.5g(1)The filtrate for obtaining and sodium sulfide solution, It is added in the negative reaction kettle that negative pressure is -480Pa, 95min, the material after reaction stopping in negative reaction kettle is reacted at room temperature After fully being precipitated through concentrator, the ore pulp of bottom is drawn off by thickener underflow mouthful, and filter press is delivered to by filter pressing pump, filters it Arsenones are mainly in filter residue afterwards, being sent to specialized factory carries out proposing arsenic treatment;Waste acid filtrate and by concentrator top annular The supernatant of groove discharge is by pipeline to waste acid concentration systems.A small amount of H is produced during this2S gases, by air-introduced machine By negative pressure for the pressure of -900 ~ -950Pa is drawn into supporting alkali liquid washing tower.
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing tower tower by waste acid delivery pump Top, sprays downwards from tower top;Air is converted into hot-air by the waste heat produced in production system, and the temperature of hot-air is 260 DEG C, Into dynamic wave scrubbing tower bottom, the speed that is passed through of hot-air is 0.7m/s.Hot-air is reverse with waste acid filtrate upwards from bottom of towe It is fully contacted, high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while acid concentration is improved, has been taken away by steam substantial amounts of F, Cl ion, the tail gas for taking away F, Cl ion are passed through supporting alkali liquid washing tower from the escaping pipe discharge in dynamic wave scrubber overhead portion Forming salt, recycling.Obtain the industrial sulphuric acid that concentration is 50 ~ 60% and enter storage acid tank.
The method that described waste acid concentration and recovery is utilized, step(1)Described waste acid composition is mainly:H2SO4: 22500mg/L, As:980mg/L, Cu:650mg/L, Zn:380mg/L, Pb:180mg/L, F:750mg/L, Cl:750mg/L.
The method that described waste acid concentration and recovery is utilized, the weight/mass percentage composition of vulcanized sodium is:15%.
The method that described waste acid concentration and recovery is utilized, step(1)In filter residue composition be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)In filter residue composition be mainly:Arsenones.
Embodiment 6
A kind of method that waste acid concentration and recovery is utilized, comprises the following steps:
Step(1):Primary vulcanization:It is 1L by amount ratio:The acid solution and sodium sulfide solution of 15g, be added to pressure for- It is well mixed in the negative reaction kettle of 290Pa, 30min is reacted at 67 DEG C, the material of negative reaction kettle passes through after reaction stopping Filter pressing pump is delivered to Filter Press, and the filter residue after filtering is delivered to feed proportioning system recycling, and filtrate is delivered to next Reactor carries out second vulcanizing treatment.The a small amount of H produced during this2S gases by air-introduced machine by negative pressure be -950 ~ - The pressure of 1000Pa is drawn into supporting alkali liquid washing tower.
Step(2):Vulcanize for second:It is 1L by amount ratio:The step of 22.5g(1)The filtrate for obtaining and sodium sulfide solution, It is added in the negative reaction kettle that negative pressure is -500Pa, 93min, the material after reaction stopping in negative reaction kettle is reacted at room temperature After fully being precipitated through concentrator, the ore pulp of bottom is drawn off by thickener underflow mouthful, and filter press is delivered to by filter pressing pump, filters it Arsenones are mainly in filter residue afterwards, being sent to specialized factory carries out proposing arsenic treatment;Waste acid filtrate and by concentrator top annular The supernatant of groove discharge is by pipeline to waste acid concentration systems.A small amount of H is produced during this2S gases, by air-introduced machine By negative pressure for the pressure of -900 ~ -950Pa is drawn into supporting alkali liquid washing tower.
Step(3):By step(2)The waste acid filtrate for obtaining is delivered to dynamic wave scrubbing tower tower by waste acid delivery pump Top, sprays downwards from tower top;Air is converted into hot-air by the waste heat produced in sour production system, and the temperature of hot-air is 250 DEG C, into dynamic wave scrubbing tower bottom, the speed that is passed through of hot-air is 0.8m/s.Hot-air is inverse with waste acid filtrate upwards from bottom of towe To being fully contacted, high-temperature heat insulation evaporation and concentration is carried out to waste acid filtrate, while acid concentration is improved, taken away largely by steam F, Cl ion, take away the tail gas of F, Cl ion and be passed through supporting alkali liquid washing from the escaping pipe discharge in dynamic wave scrubber overhead portion Tower forming salt, recycling.Obtain the industrial sulphuric acid that concentration is 50 ~ 60% and enter storage acid tank.
The method that described waste acid concentration and recovery is utilized, step(1)Described waste acid composition is mainly:H2SO4: 24000mg/L, As:1000mg/L, Cu:690mg/L, Zn:530mg/L, Pb:240mg/L, F:900mg/L, Cl:900mg/L.
The method that described waste acid concentration and recovery is utilized, the weight/mass percentage composition of vulcanized sodium is:14%.
The method that described waste acid concentration and recovery is utilized, step(1)In filter residue composition be mainly:Copper sulfide, vulcanized lead, Zinc sulphide.
The method that described waste acid concentration and recovery is utilized, step(2)In filter residue composition be mainly:Arsenones.

Claims (2)

1. a kind of method that waste acid concentration and recovery is utilized, it is characterised in that comprise the following steps:
Step(1):Waste acid solution, sulfur agent solution are taken, is added to after being well mixed in negative reaction kettle and is reacted, after reaction stops Material in negative reaction kettle is delivered to Filter Press by filter pressing pump, and filter residue is recycled, and filtrate is processed into next step;
It is 1L with the amount ratio of sulfur agent solution that waste acid solution is added described in the step:(10~30)g;
Waste acid composition described in the step is:H2SO4:20000 ~ 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;
Reaction pressure is -250 ~ -350Pa in negative reaction kettle described in the step, and reaction temperature is 60 ~ 70 DEG C, reaction time It is 25 ~ 40min;
Step(2):Take step(1)Filtrate, the sulfur agent solution for obtaining, are added to after being well mixed in negative reaction kettle and react, After reaction stops, after the material in reactor is delivered to concentrator precipitation, slurry is delivered to Filter Press, filter residue by filter pressing pump Recycled, waste acid filtrate is processed into next step;
The filtrate being added in negative reaction kettle described in the step is with the amount ratio of sulfur agent solution:1L:(20~48)g;
The reaction pressure in reactor described in the step is -450 ~ -600Pa, and 80 ~ 100min is reacted at room temperature;
Above-mentioned steps(1)And step(2)Described in vulcanizing agent be sodium sulfide solution, the weight/mass percentage composition of sodium sulfide solution is 10~15%;
Step(3):By step(2)The waste acid filtrate obtained after vulcanizing treatment is delivered to dynamic wave and washes by waste acid delivery pump Column overhead is washed, is sprayed downwards from tower top;Hot-air enters dynamic wave scrubbing tower bottom, with waste acid filtrate counter current contacting, hot-air Waste acid filtrate high-temperature heat insulation is concentrated by evaporation, with F-、Cl-Tail gas be passed through from the discharge of the escaping pipe in dynamic wave scrubber overhead portion Alkali liquid washing tower, obtains industrial goods sulfuric acid and enters storage acid tank in tower.
2. the method that waste acid concentration and recovery according to claim 1 is utilized, it is characterised in that:Step(3)Described heat is empty The temperature of gas is 200 ~ 280 DEG C, and the speed that is passed through of hot-air is 0.5 ~ 1.2m/s.
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CN105502307B (en) * 2015-12-24 2017-09-01 南通三圣石墨设备科技股份有限公司 The method and special purpose device of waste acid concentration defluorinating chlorine
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
CN108946889A (en) * 2017-06-01 2018-12-07 株洲三特环保节能股份有限公司 A kind of processing method and processing equipment of the spent acid containing heavy metal
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
CN107512813B (en) * 2017-08-25 2020-11-03 金川集团股份有限公司 Multi-way recycling method for acid-making wastewater of smelting flue gas
CN108996743A (en) * 2018-07-26 2018-12-14 甘肃中顺石化工程装备有限公司 A kind of smelting waste acid deep treatment method and smelt waste acid advanced treatment system
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

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