CN108996743A - A kind of smelting waste acid deep treatment method and smelt waste acid advanced treatment system - Google Patents
A kind of smelting waste acid deep treatment method and smelt waste acid advanced treatment system Download PDFInfo
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- CN108996743A CN108996743A CN201810835583.8A CN201810835583A CN108996743A CN 108996743 A CN108996743 A CN 108996743A CN 201810835583 A CN201810835583 A CN 201810835583A CN 108996743 A CN108996743 A CN 108996743A
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- electric flocculation
- waste acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of smelting waste acid deep treatment methods, including vulcanisation step, electric flocculation step, membrane filtration step and tail gas absorption step.The invention also discloses a kind of smelting waste acid advanced treatment systems for smelting waste acid deep treatment method.The present invention smelts the standard that the waste acid deep treatment method clear water that ensure that treated reaches industrial reuse water, realizes waste water fully recovering production system, achievees the purpose that waste water zero emission.
Description
Technical field
The present invention relates to industrial sewage treatment technology and apparatus field more particularly to a kind of smelting waste acid deep treatment methods
And the smelting waste acid advanced treatment system using the smelting waste acid deep treatment method.
Background technique
The high-concentration sulfur dioxide flue gas generated in nonferrous metallurgical process is sent again after needing to first pass through dedusting to relieving haperacidity
Sulfur dioxide flue gas is converted sulfuric acid or sulfurous acid by system, to reach thoroughly remove in non-ferrous metal metallurgy exhaust gas two
Sulfur oxide flue gas composition.Need to wash flue gas before relieving haperacidity, purify, in the process of washing the arsenic in flue gas and flue dust, cadmium,
The pollutants such as copper, fluorine enter diluted acid, to prevent the pollutants such as arsenic, cadmium, copper, fluorine from accumulating in diluted acid, needing in production process periodically
A certain amount of diluted acid of discharge be referred to as waste acid to achieve the purpose that remove pollutants, this part diluted acid such as arsenic, cadmium, copper, fluorine.
Major part smelting enterprise handles waste acid using vulcanization-lime iron salt method, lime-iron salt method at present.Due to waste acid
Acidity is high, heavy metal concentration is higher, a large amount of hazardous wastes can be generated in waste acid treatment process, easily cause serious secondary dirt
Dye.In addition, since a large amount of milk of lime is added, so that the excessive high hardness of water outlet, the serious reuse for influencing waste water, cause enterprise
A large amount of wastes of water resource, are unfavorable for the sustainable development of enterprise.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of smelting waste acid deep treatment method,
To overcome in existing waste acid treatment process because acidity is high, heavy metal concentration is higher, a large amount of toxic, danger are generated during processing
Dangerous waste easily causes serious secondary pollution problems, and the excessive high hardness that a large amount of milk of lime makes water outlet again is added, serious
The reuse for influencing waste water, the problems such as causing a large amount of wastes of enterprise's water resource, be unfavorable for the sustainable development of enterprise
The second object of the present invention is to provide a kind of smelting waste acid advanced treatment system, and the system is by carrying out waste acid
Processing, both can guarantee that toxic, the hazardous waste in waste acid were separated, convenient individually to be handled, moreover it is possible to guarantee processing
Clear water afterwards reaches the rank of industrial reuse water, avoids a large amount of wastes of enterprise's water resource, is conducive to the sustainable development of enterprise.
An object of the present invention adopts the following technical scheme that realization:
A kind of smelting waste acid deep treatment method, comprising the following steps:
Vulcanization: vulcanizing agent is that 1~50:1000 mixes and react 5~40min, reaction temperature according to mass percent with waste acid
Degree is no more than 30 DEG C, and after reaction, reaction solution is separated by solid-liquid separation, and obtains clear liquid and solid slag；
Electric flocculation: being delivered to electric flocculation system for clear liquid, adjusts the current density of electric flocculation system to 150~250A/m2,
Aeration intensity is to 10~30m3/m2.h, the pH range that setting electric flocculation is discharged is 8~9, and liquid is filtered to get filtrate and solid slag out；
Film filtering: filtrate is delivered to membrane filtration system, and setting membrane filtration system osmotic pressure is that water purification is made in 20~100bar
And concentrated water, wherein concentrated water returns to vulcanisation step and continues with；
Tail gas absorption: escaping gas is introduced into lye and is absorbed in vulcanisation step, and the lye reuse after absorption is made
Vulcanizing agent；
The vulcanizing agent is the mixed solution of sodium sulfide solution, sodium hydrosulfide or both, the quality hundred of vulcanizing agent
Dividing content is 5~40%, and the lye is potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide solution, ammonium hydroxide or four
Any mixed solution.
Further, in vulcanisation step, the mass percentage of the vulcanizing agent is 10~20%, the vulcanizing agent with
Waste acid is 2~5:1000 mixing according to mass percent.
Further, in vulcanisation step, the reaction time is 10~20min, and the reaction temperature is 25~28 DEG C.
Further, in electric flocculation step, clear liquid is delivered to the first electric flocculation system first, adjust current density to
180~280A/m2, the pH value for controlling out liquid is 2~3, and acid liquid out is made；Acidity is gone out into liquid again and is delivered to the second electric flocculation system
System adjusts current density to 150~220A/m2, the pH value for controlling out liquid is 8~9.2, and alkalinity is made and goes out liquid.
Further, in electric flocculation step, clear liquid is delivered to the first electric flocculation system first, adjusts its current density
To 200~250A/m2, the pH value for controlling out liquid is 2.5；Acidity is gone out into liquid again and is delivered to the second electric flocculation system, adjusts electric current
Density is to 180~200A/m2, the pH value for controlling out liquid is 8.4~8.9.
Further, the first electric flocculation system uses graphite electrode plate, and the second electric flocculation system uses iron pole plate.
Further, in vulcanisation step, the reaction solution is delivered to filter press and carries out filters pressing, and clear liquid obtained enters electricity
Flocculation step；In electric flocculation step, alkalinity goes out liquid and is delivered to filter press progress filters pressing, and filtrate is made.
Further, in membrane filtration step, the membrane filtration system is reverse osmosis membrane system, and reverse osmosis membrane system is arranged
Osmotic pressure be 75~90bar.
The second object of the present invention adopts the following technical scheme that realization:
A kind of smelting waste acid advanced treatment system using smelting waste acid deep treatment method described in any of the above embodiments, packet
Include vulcanization plant, electric flocculation device, film filter and device for absorbing tail gas；
The vulcanization plant includes vulcanization reaction kettle and the first filter press, and the vulcanization reaction kettle is for receiving waste acid, institute
The outlet at bottom for stating vulcanization reaction kettle is connected to the entrance of the first filter press；
The electric flocculation device include the first electric flocculation equipment, the second electric flocculation equipment and the second filter press, described first
The outlet of the entrance of electric flocculation equipment and the first filter press, outlet and the second electric flocculation of the first electric flocculation equipment are set
Standby entrance connection, the outlet of the second electric flocculation equipment is connected to the entrance of the second filter press；
The outlet of the entrance of the film filter and the second filter press, the outlet and vulcanization of the film filter
The entrance of device is connected to；
The entrance of the device for absorbing tail gas is connected to the top exit of vulcanization reaction kettle, and the outlet of device for absorbing tail gas connects
Logical atmosphere.
Further, the electric flocculation device includes the first elevator pump and the second elevator pump, the first elevator pump difference
Be connected to the entrance of the outlet of the first filter press and the first electric flocculation equipment, second elevator pump respectively with the second filter press
The connection of the entrance of outlet and film filter；
The device for absorbing tail gas further includes air-introduced machine, and the outlet of the air inlet and device for absorbing tail gas of the air-introduced machine connects
It is logical.
Compared with prior art, the beneficial effects of the present invention are:
(1) a kind of waste acid deep treatment method of smelting of the present invention is by passing through the coagulations such as heavy metal in waste acid, filtering
Solid slag is separated with clear liquid, is realized and is largely reduced the generation of waste residue amount in waste acid treatment process, while after guaranteeing processing
Clear water reach the standard of industrial reuse water, realize waste water fully recovering production system, achieve the purpose that waste water zero emission.Together
When, the exhaust gas that waste acid coagulation generates in the process carries out tail gas absorption by device for absorbing tail gas, guarantees to produce in waste acid treatment process
Raw tail gas can reach the rank being directly discharged in atmosphere.
(2) it includes vulcanization plant, electric flocculation device, film filter and tail that the present invention, which smelts waste acid advanced treatment system,
Aspiration receiving apparatus, by vulcanization plant and waste acid and promoting arsenic, cadmium, copper etc. and occur coagulation, then by electric flocculation device into one
Step promotes the foreign-matter contamination in waste acid that complexing, coagulation occurs, and realizes and is separated by solid-liquid separation finally by membrane filtration system, after separation
Clear liquid can fully recovering production system, achieve the purpose that waste water zero emission.
Detailed description of the invention
Fig. 1 is that one embodiment of the present invention smelts waste acid advanced treatment system.
In figure: 1, vulcanization reaction kettle；2, the first filter press；3, the first elevator pump；4, the first electric flocculation equipment；5, the second electricity
Flocculation apparatus；6, the second filter press 7, the second elevator pump；8, membrane filtration system；9, tail gas absorber；10, air-introduced machine.
Specific embodiment
In the following, being described further in conjunction with attached drawing and specific embodiment to the present invention, it should be noted that not
Under the premise of conflicting, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
Embodiment 1
As shown in Figure 1, smelting waste acid advanced treatment system, the smelting waste acid advanced treating for one embodiment of the present invention
System includes vulcanization plant, electric flocculation device, film filter and device for absorbing tail gas.Vulcanization plant includes vulcanization reaction kettle
1 and first filter press 2, the left side of vulcanization reaction kettle 1 be provided with waste acid inlet port and water purification recovery port, waste acid passes through waste acid and enters
Mouth continuously enters the 1 receiving processing of vulcanization reaction kettle.The bottom of vulcanization reaction kettle 1 is provided with outlet at bottom, outlet at bottom
The first filter press 2 is flowed to from outlet at bottom for waste acid；The top of vulcanization reaction kettle 1 is provided with top exit, and top exit is used
The hydrogen sulfide gas or sulfur dioxide gas generated in waste acid sulfidation flows to device for absorbing tail gas from top exit.The
One filter press 2 can tentatively separate the solid slag in the waste acid after neutralization or vulcanization with clear liquid, and solid slag can be used for selling
Or higher valuable metal is sampled in recycling.Electric flocculation device includes the first electric flocculation equipment 4, the second electric flocculation equipment 5 and the
Two filter presses 6.First electric flocculation equipment 4 be preferably graphite electrode plate, after 2 filters pressing of the first filter press it is obtained primary filtrate be delivered to
First electric flocculation equipment 4, under the electrolysis of the first electric flocculation equipment 4, part ion is acidified or is oxidized.Via first
The electrolysis of electric flocculation equipment 4, the electrolyte of discharge are further delivered to the second electric flocculation equipment 5, the second electric flocculation equipment 5
Preferably iron pole plate is made via the reduction of iron pole plate, Iron pick up effect, metal salt precipitate effect or hydroxyl complexing
Separation of solid and liquid is realized with, metal ion or colloidal state impurity or suspended impurity coagulative precipitation.Further by the second electric flocculation
The electrolyte that equipment 5 is discharged is delivered to the second filter press 6, realizes that solid-liquid thoroughly divides via the pressure-filtering process of the second filter press 6
From.With above-mentioned, the second filter press 6 can further be separated the solid slag in the clear liquid after electric flocculation with clear liquid, and solid slag can
For selling or recycling the higher valuable metal of taste.The clear liquid flowed out from the second filter press 6 is further delivered to film mistake
Filter system 8 realizes the other impurity thoroughly removed in clear liquid by the film filtration of membrane filtration system, so that filtering from film
The water purification flowed out in system can reach the rank for being back to production system.The smelting waste acid advanced treatment system further includes tail gas
Absorption plant, device for absorbing tail gas are connected to the top exit of vulcanization reaction kettle 1, are generated in 1 sulfidation of vulcanization reaction kettle
The gases such as hydrogen sulfide, sulfur dioxide can be acted on by the absorption cleaning of device for absorbing tail gas, realize direct emission in air and
The purpose of atmosphere is not polluted.
The present invention smelt waste acid advanced treatment system by by waste acid successively through over cure, filtering, electric flocculation, filtering, film
After filtering, the pollutants such as arsenic, cadmium, copper, fluorine in waste acid are removed by coagulation step by step, filtering, solid slag and clear liquid are realized thorough
Separation, solid slag can be used for recycling and purification part samples higher metal, and clear liquid can also reach the grade for being back to production system
Not, it realizes waste water fully recovering production system, achievees the purpose that waste water zero emission.Meanwhile it being produced during waste acid vulcanization coagulation
Raw exhaust gas carries out tail gas absorption by device for absorbing tail gas, guarantees that the tail gas generated in waste acid treatment process can reach direct
The rank being discharged into atmosphere.
As preferred embodiment, electric flocculation device further includes the first elevator pump 3 and the second elevator pump 7, and first is promoted
Pump 3 is set between the first filter press 2 and the first electric flocculation equipment 4, the clear liquid in the exit of the first filter press 2 to be pumped into
First electric flocculation equipment 4；Second elevator pump 7 is set between the second filter press 6 and membrane filtration system 8, to by the second filters pressing
Machine 6 is considered clear liquid out and is pumped into membrane filtration system 8.By the first elevator pump 3 and the second elevator pump 7 of setting, can effectively promote
The clear liquid that the clear liquid smooth delivery of power that the first filter press 2 is discharged is considered out to the first electric flocculation equipment 4 and the second filter press 6 is suitable
Benefit is transported to membrane filtration system 8, is provided by the circulatory system that the first elevator pump 3 and the second elevator pump 7 are handled for entire waste acid
Hydraulic pressure guarantees that the entire liquid smelted in waste acid advanced treatment system can be circulated persistently.
As preferred embodiment, device for absorbing tail gas includes tail gas absorber 9, and the middle part of tail gas absorber 9 is equipped with
Lye spray system, the bottom of tail gas absorber 9 are equipped with exhaust gas entrance, and the top of tail gas absorber 9 is equipped with gas vent, waste acid
The gases such as the hydrogen sulfide, the sulfur dioxide that generate in sulfidation are discharged into tail gas absorption from the top exit of vulcanization reaction kettle 1
Tower 9 sponges the sour gas such as hydrogen sulfide, the sulfur dioxide in exhaust gas by means of the lye spray system in tail gas absorber 9,
Clean air can be directly discharged into atmosphere.
As preferred embodiment, device for absorbing tail gas further includes air-introduced machine 10, air-introduced machine 10 and 9 phase of tail gas absorber
Connection, is made to keep negative pressure state in tail gas absorber 9 and in vulcanization reaction kettle 1 by air-introduced machine 10, facilitates tail gas absorption
Exhaust gas or pure air in tower 9 and in vulcanization reaction kettle 1 are smoothly discharged.
As preferred embodiment, above-mentioned vulcanization plant, electric flocculation device, film filter and device for absorbing tail gas
Between connecting pipe be all made of pvc pipe connection.
A kind of smelting waste acid deep treatment method of the present invention is discussed in detail in 2-6 by the following examples.The present invention smelts dirty
Sour deep treatment method includes: vulcanisation step, electric flocculation step, membrane filtration step and tail gas absorption step.
Embodiment 2
The sodium sulfide solution that mass percent is 10%: being placed in holding vessel by vulcanisation step in advance, when handling waste acid,
Sodium sulfide solution and waste acid are pumped into vulcanization reaction kettle according to the ratio that flow-rate ratio is 5:100,650r/min is at the uniform velocity stirred instead
10min is answered, reaction temperature is 28 DEG C.In reaction process, the sour gas such as hydrogen sulfide, sulfur dioxide for being generated in vulcanization reaction kettle
Device for absorbing tail gas, which is delivered to, by the outlet in vulcanization reaction kettle top portion carries out vent gas treatment.After reaction, reaction solution is defeated
Send to the first filter press carry out filters pressing processing, collect filters pressing generate solid slag for recycle or purify in solid slag sample it is higher
Metal, the clear liquid of the first filter press discharge are delivered to electric flocculation device and carry out electric flocculation step.
Electric flocculation step: the clear liquid that the first filter press is discharged is delivered to the first electric flocculation device, the first electric flocculation device
Pole plate be graphite electrode plate, adjust the first electric flocculation device current density be 200A/m2, the pH value for controlling outlet solution is
2.5, acid liquid out is made.Acidity is gone out into liquid and is delivered to the second electric flocculation device, the pole plate of the second electric flocculation device is iron pole plate,
The current density for adjusting the second electric flocculation device is 180A/m2, aeration intensity 20m3/m2.h, the pH value for controlling outlet solution is
8.6, alkalinity is made and goes out liquid.After reaction, alkalinity is gone out into liquid and is delivered to the progress filters pressing processing of the second filter press, it is raw to collect filters pressing
At solid slag sample higher metal for recycling or purifying in solid slag, the clear liquid of the second filter press discharge is delivered to film filtering
Device carries out membrane filtration step.
Membrane filtration step: the clear liquid that the second filter press is discharged is delivered to film filter and carries out film filtration treatment, herein
Film filter be reverse osmosis membrane, the osmotic pressure for controlling film filter is 80bar, and filtered clear water can be back to production
System, concentrated water, which is fed back in vulcanization reaction kettle, carries out vulcanizing treatment, continues cycling through and carries out vulcanisation step, electric flocculation step and film mistake
Step is filtered, until thoroughly removing the foreign-matter contamination in waste acid.
Tail gas absorption step: in vulcanisation step, the sour gas quilt such as hydrogen sulfide, sulfur dioxide for being escaped in vulcanization reaction kettle
Introduce tail gas absorber, sponged by means of the sodium hydroxide solution spray system in tail gas absorber hydrogen sulfide in exhaust gas,
The sour gas such as sulfur dioxide, clean air can be directly discharged into atmosphere.
Embodiment 3
The sodium sulfide solution that mass percent is 10%: being placed in holding vessel by vulcanisation step in advance, when handling waste acid,
Sodium sulfide solution and waste acid are pumped into vulcanization reaction kettle according to the ratio that flow-rate ratio is 6:100,650r/min is at the uniform velocity stirred instead
10min is answered, reaction temperature is 25 DEG C.In reaction process, the sour gas such as hydrogen sulfide, sulfur dioxide for being generated in vulcanization reaction kettle
Device for absorbing tail gas, which is delivered to, by the outlet in vulcanization reaction kettle top portion carries out vent gas treatment.After reaction, reaction solution is defeated
Send to the first filter press carry out filters pressing processing, collect filters pressing generate solid slag for recycle or purify in solid slag sample it is higher
Metal, the clear liquid of the first filter press discharge are delivered to electric flocculation device and carry out electric flocculation step.
Electric flocculation step: the clear liquid that the first filter press is discharged is delivered to the first electric flocculation device, the first electric flocculation device
Pole plate be graphite electrode plate, adjust the first electric flocculation device current density be 250A/m2, the pH value for controlling outlet solution is
3.0, acid liquid out is made.Acidity is gone out into liquid and is delivered to the second electric flocculation device, the pole plate of the second electric flocculation device is iron pole plate,
The current density for adjusting the second electric flocculation device is 200A/m2, aeration intensity 20m3/m2.h, the pH value for controlling outlet solution is
8.9, alkalinity is made and goes out liquid.After reaction, alkalinity is gone out into liquid and is delivered to the progress filters pressing processing of the second filter press, it is raw to collect filters pressing
At solid slag sample higher metal for recycling or purifying in solid slag, the clear liquid of the second filter press discharge is delivered to film filtering
Device carries out membrane filtration step.
Membrane filtration step: the clear liquid that the second filter press is discharged is delivered to film filter and carries out film filtration treatment, herein
Film filter be reverse osmosis membrane, the osmotic pressure for controlling film filter is 75bar, and filtered clear water can be back to production
System, concentrated water, which is fed back in vulcanization reaction kettle, carries out vulcanizing treatment, continues cycling through and carries out vulcanisation step, electric flocculation step and film mistake
Step is filtered, until thoroughly removing the foreign-matter contamination in waste acid.
Tail gas absorption step: in vulcanisation step, the sour gas quilt such as hydrogen sulfide, sulfur dioxide for being escaped in vulcanization reaction kettle
Introduce tail gas absorber, sponged by means of the potassium hydroxide solution spray system in tail gas absorber hydrogen sulfide in exhaust gas,
The sour gas such as sulfur dioxide, clean air can be directly discharged into atmosphere.
Embodiment 4
The sodium sulfide solution that mass percent is 10%: being placed in holding vessel by vulcanisation step in advance, when handling waste acid,
Sodium sulfide solution and waste acid are pumped into vulcanization reaction kettle according to the ratio that flow-rate ratio is 5.5:100,650r/min is at the uniform velocity stirred
20min is reacted, reaction temperature is 27 DEG C.In reaction process, the sour gas such as hydrogen sulfide, sulfur dioxide for being generated in vulcanization reaction kettle
Body is delivered to device for absorbing tail gas by the outlet in vulcanization reaction kettle top portion and carries out vent gas treatment.After reaction, by reaction solution
Be delivered to the first filter press carry out filters pressing processing, collect filters pressing generate solid slag for recycle or purify in solid slag sample it is higher
Metal, the first filter press discharge clear liquid be delivered to electric flocculation device carry out electric flocculation step.
Electric flocculation step: the clear liquid that the first filter press is discharged is delivered to the first electric flocculation device, the first electric flocculation device
Pole plate be graphite electrode plate, adjust the first electric flocculation device current density be 200A/m2, the pH value for controlling outlet solution is
2.0, acid liquid out is made.Acidity is gone out into liquid and is delivered to the second electric flocculation device, the pole plate of the second electric flocculation device is iron pole plate,
The current density for adjusting the second electric flocculation device is 200A/m2, aeration intensity 20m3/m2.h, the pH value for controlling outlet solution is
8.4, alkalinity is made and goes out liquid.After reaction, alkalinity is gone out into liquid and is delivered to the progress filters pressing processing of the second filter press, it is raw to collect filters pressing
At solid slag sample higher metal for recycling or purifying in solid slag, the clear liquid of the second filter press discharge is delivered to film filtering
Device carries out membrane filtration step.
Membrane filtration step: the clear liquid that the second filter press is discharged is delivered to film filter and carries out film filtration treatment, herein
Film filter be reverse osmosis membrane, the osmotic pressure for controlling film filter is 90bar, and filtered clear water can be back to production
System, concentrated water, which is fed back in vulcanization reaction kettle, carries out vulcanizing treatment, continues cycling through and carries out vulcanisation step, electric flocculation step and film mistake
Step is filtered, until thoroughly removing the foreign-matter contamination in waste acid.
Tail gas absorption step: in vulcanisation step, the sour gas quilt such as hydrogen sulfide, sulfur dioxide for being escaped in vulcanization reaction kettle
Introduce tail gas absorber, sponged by means of the potassium hydroxide solution spray system in tail gas absorber hydrogen sulfide in exhaust gas,
The sour gas such as sulfur dioxide, clean air can be directly discharged into atmosphere.
Tail gas absorption step: in vulcanisation step, the sour gas quilt such as hydrogen sulfide, sulfur dioxide for being escaped in vulcanization reaction kettle
Tail gas absorber is introduced, hydrogen sulfide, the sulfur dioxide in exhaust gas are sponged by means of the lye spray system in tail gas absorber
Equal sour gas, clean air can be directly discharged into atmosphere.Wherein, lye be potassium hydroxide solution, sodium hydroxide solution,
The mixed solution of calcium hydroxide solution and ammonium hydroxide, potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide solution and ammonium hydroxide rub
You are than being 3:1:3:1.
Embodiment 5
The sodium sulfide solution that mass percent is 20%: being placed in holding vessel by vulcanisation step in advance, when handling waste acid,
Sodium sulfide solution and waste acid are pumped into vulcanization reaction kettle according to the ratio that flow-rate ratio is 1:100,550r/min is at the uniform velocity stirred instead
40min is answered, reaction temperature is 24 DEG C.In reaction process, the sour gas such as hydrogen sulfide, sulfur dioxide for being generated in vulcanization reaction kettle
Device for absorbing tail gas, which is delivered to, by the outlet in vulcanization reaction kettle top portion carries out vent gas treatment.After reaction, reaction solution is defeated
Send to the first filter press carry out filters pressing processing, collect filters pressing generate solid slag for recycle or purify in solid slag sample it is higher
Metal, the clear liquid of the first filter press discharge are delivered to electric flocculation device and carry out electric flocculation step.
Electric flocculation step: the clear liquid that the first filter press is discharged is delivered to the first electric flocculation device, the first electric flocculation device
Pole plate be graphite electrode plate, adjust the first electric flocculation device current density be 150A/m2, the pH value for controlling outlet solution is
2.5, acid liquid out is made.Acidity is gone out into liquid and is delivered to the second electric flocculation device, the pole plate of the second electric flocculation device is iron pole plate,
The current density for adjusting the second electric flocculation device is 280A/m2, aeration intensity 30m3/m2.h, the pH value for controlling outlet solution is
9.2, alkalinity is made and goes out liquid.After reaction, alkalinity is gone out into liquid and is delivered to the progress filters pressing processing of the second filter press, it is raw to collect filters pressing
At solid slag sample higher metal for recycling or purifying in solid slag, the clear liquid of the second filter press discharge is delivered to film filtering
Device carries out membrane filtration step.
Membrane filtration step: the clear liquid that the second filter press is discharged is delivered to film filter and carries out film filtration treatment, herein
Film filter be reverse osmosis membrane, the osmotic pressure for controlling film filter is 50bar, and filtered clear water can be back to production
System, concentrated water, which is fed back in vulcanization reaction kettle, carries out vulcanizing treatment, continues cycling through and carries out vulcanisation step, electric flocculation step and film mistake
Step is filtered, until thoroughly removing the foreign-matter contamination in waste acid.
Tail gas absorption step: in vulcanisation step, the sour gas quilt such as hydrogen sulfide, sulfur dioxide for being escaped in vulcanization reaction kettle
Tail gas absorber is introduced, hydrogen sulfide, the dioxy in exhaust gas are sponged by means of the ammonia spirit spray system in tail gas absorber
Changing sour gas, the clean air such as sulphur can be directly discharged into atmosphere.
Embodiment 6
The sodium sulfide solution that mass percent is 1.5%: being placed in holding vessel by vulcanisation step in advance, handles waste acid
When, sodium sulfide solution and waste acid are pumped into vulcanization reaction kettle according to the ratio that flow-rate ratio is 30:100,600r/min is at the uniform velocity stirred
Reaction 50min is mixed, reaction temperature is 29 DEG C.In reaction process, the acidity such as hydrogen sulfide, sulfur dioxide for being generated in vulcanization reaction kettle
Gas is delivered to device for absorbing tail gas by the outlet in vulcanization reaction kettle top portion and carries out vent gas treatment.After reaction, it will react
Liquid is delivered to the first filter press and carries out filters pressing processing, collect solid slag that filters pressing generates for recycle or purify in solid slag taste compared with
High metal, the clear liquid of the first filter press discharge are delivered to electric flocculation device and carry out electric flocculation step.
Electric flocculation step: the clear liquid that the first filter press is discharged is delivered to the first electric flocculation device, the first electric flocculation device
Pole plate be graphite electrode plate, adjust the first electric flocculation device current density be 250A/m2, the pH value for controlling outlet solution is
2.2, acid liquid out is made.Acidity is gone out into liquid and is delivered to the second electric flocculation device, the pole plate of the second electric flocculation device is iron pole plate,
The current density for adjusting the second electric flocculation device is 180A/m2, aeration intensity 10m3/m2.h, the pH value for controlling outlet solution is
8.0, alkalinity is made and goes out liquid.After reaction, alkalinity is gone out into liquid and is delivered to the progress filters pressing processing of the second filter press, it is raw to collect filters pressing
At solid slag sample higher metal for recycling or purifying in solid slag, the clear liquid of the second filter press discharge is delivered to film filtering
Device carries out membrane filtration step.
Membrane filtration step: the clear liquid that the second filter press is discharged is delivered to film filter and carries out film filtration treatment, herein
Film filter be reverse osmosis membrane, the osmotic pressure for controlling film filter is 100bar, and filtered clear water can be back to life
Production system, concentrated water, which is fed back in vulcanization reaction kettle, carries out vulcanizing treatment, continues cycling through and carries out vulcanisation step, electric flocculation step and film
Filtration step, until thoroughly removing the foreign-matter contamination in waste acid.
Tail gas absorption step: in vulcanisation step, the sour gas quilt such as hydrogen sulfide, sulfur dioxide for being escaped in vulcanization reaction kettle
Introduce tail gas absorber, sponged by means of the calcium hydroxide solution spray system in tail gas absorber hydrogen sulfide in exhaust gas,
The sour gas such as sulfur dioxide, clean air can be directly discharged into atmosphere.
From taking five parts of waste acids to pass through the smelting waste acid deep treatment method in embodiment 2-6 in the smelting enterprise of Gansu Province various regions
It is handled, is implemented referring to related inductively coupled plasma atomic emission spectrometry (ICP) measurement of GB/T 17593.2-2007
Smelting waste acid deep treatment method in example 2-6 handles the content of forward and backward waste acid and heavy metal in waste liquid.Measurement result is shown in Table
1。
Table 1
By table 1 the results show that the smelting waste acid deep treatment method in embodiment 2-6 can effectively remove the weight in waste acid
Metal pollutant guarantees that treated clear water reaches the standard of industrial reuse water, realizes waste water fully recovering production system, reach
The purpose of waste water zero emission.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of smelting waste acid deep treatment method, which comprises the following steps:
Vulcanization: vulcanizing agent is that 1~50:1000 mixes and react 5~40min according to mass percent with waste acid, and reaction temperature is not
More than 30 DEG C, after reaction, reaction solution is separated by solid-liquid separation, and obtains clear liquid and solid slag；
Electric flocculation: being delivered to electric flocculation system for clear liquid, adjusts the current density of electric flocculation system to 150~250A/m2, aeration
Intensity is to 10~30m3/m2.h, the pH range that setting electric flocculation is discharged is 8~9, and liquid is filtered to get filtrate and solid slag out；
Film filtering: filtrate is delivered to membrane filtration system, and setting membrane filtration system osmotic pressure is that water purification and dense is made in 20~100bar
Water, wherein concentrated water returns to vulcanisation step and continues with；
Tail gas absorption: escaping gas is introduced into lye and is absorbed in vulcanisation step, and the lye reuse work after absorption vulcanizes
Agent；
The vulcanizing agent is the mixed solution of sodium sulfide solution, sodium hydrosulfide or both, and the quality percentage of vulcanizing agent contains
Amount be 5~40%, the lye be potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide solution, ammonium hydroxide or four appoint
Meaning mixed solution.
2. smelting waste acid deep treatment method as described in claim 1, which is characterized in that in vulcanisation step, the vulcanization
The mass percentage of agent is 10~20%, and the vulcanizing agent is that 2~5:1000 is mixed according to mass percent with waste acid.
3. smelting waste acid deep treatment method as claimed in claim 2, which is characterized in that in vulcanisation step, the reaction
Time is 10~20min, and the reaction temperature is 25~28 DEG C.
4. smelting waste acid deep treatment method as described in claim 1, which is characterized in that in electric flocculation step, first will
Clear liquid is delivered to the first electric flocculation system, adjusts current density to 180~280A/m2, the pH value for controlling out liquid is 2~3, is made
Acidity goes out liquid；Acidity is gone out into liquid again and is delivered to the second electric flocculation system, adjusts current density to 150~220A/m2, control out liquid
PH value be 8~9.2, be made alkalinity go out liquid.
5. smelting waste acid deep treatment method as claimed in claim 4, which is characterized in that in electric flocculation step, first will
Clear liquid is delivered to the first electric flocculation system, adjusts its current density to 200~250A/m2, the pH value for controlling out liquid is 2.5；Again
Acidity is gone out into liquid and is delivered to the second electric flocculation system, adjusts current density to 180~200A/m2, the pH value for controlling out liquid is 8.4
~8.9.
6. smelting waste acid deep treatment method as claimed in claim 5, which is characterized in that the first electric flocculation system uses
Graphite electrode plate, the second electric flocculation system use iron pole plate.
7. smelting waste acid deep treatment method as claimed in claim 6, which is characterized in that in vulcanisation step, the reaction
Liquid is delivered to filter press and carries out filters pressing, and clear liquid obtained enters electric flocculation step；In electric flocculation step, alkalinity goes out liquid and is delivered to
Filter press carries out filters pressing, and filtrate is made.
8. smelting waste acid deep treatment method as described in claim 1, which is characterized in that in membrane filtration step, the film
Filtration system is reverse osmosis membrane system, and the osmotic pressure that reverse osmosis membrane system is arranged is 75~90bar.
9. a kind of using the described in any item smelting waste acid advanced treating systems for smelting waste acid deep treatment method of claim 1-8
System, which is characterized in that including vulcanization plant, electric flocculation device, film filter and device for absorbing tail gas；
The vulcanization plant includes vulcanization reaction kettle and the first filter press, and the vulcanization reaction kettle is for receiving waste acid, the sulphur
The outlet at bottom for changing reaction kettle is connected to the entrance of the first filter press；
The electric flocculation device includes the first electric flocculation equipment, the second electric flocculation equipment and the second filter press, the first electricity wadding
The entrance of solidifying equipment and the outlet of the first filter press, outlet and the second electric flocculation equipment of the first electric flocculation equipment
Entrance connection, the outlet of the second electric flocculation equipment is connected to the entrance of the second filter press；
The outlet of the entrance of the film filter and the second filter press, the outlet of the film filter and vulcanization plant
Entrance connection；
The entrance of the device for absorbing tail gas is connected to the top exit of vulcanization reaction kettle, and the outlet of device for absorbing tail gas is big
Gas.
10. smelting waste acid advanced treatment system as claimed in claim 9, which is characterized in that the electric flocculation device includes the
One elevator pump and the second elevator pump, first elevator pump enter with the outlet of the first filter press and the first electric flocculation equipment respectively
Mouth connection, second elevator pump are connected to the entrance of the outlet of the second filter press and film filter respectively；
The device for absorbing tail gas further includes air-introduced machine, the air inlet of the air-introduced machine and the outlet of device for absorbing tail gas.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909507A (en) * | 2015-06-02 | 2015-09-16 | 河南双屿新材料科技有限公司 | Contaminated acid concentrating and recycling method |
| CN107162281A (en) * | 2017-07-21 | 2017-09-15 | 甘肃中顺石化工程装备有限公司 | The processing method and Waste Water Treatment of heavy metal ion in a kind of removal smelting wastewater |
| CN108285229A (en) * | 2018-02-09 | 2018-07-17 | 武汉飞博乐环保工程有限公司 | The waste acid processing method of nonferrous smelting |
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2018
- 2018-07-26 CN CN201810835583.8A patent/CN108996743A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909507A (en) * | 2015-06-02 | 2015-09-16 | 河南双屿新材料科技有限公司 | Contaminated acid concentrating and recycling method |
| CN107162281A (en) * | 2017-07-21 | 2017-09-15 | 甘肃中顺石化工程装备有限公司 | The processing method and Waste Water Treatment of heavy metal ion in a kind of removal smelting wastewater |
| CN108285229A (en) * | 2018-02-09 | 2018-07-17 | 武汉飞博乐环保工程有限公司 | The waste acid processing method of nonferrous smelting |
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Application publication date: 20181214 |