CN109384359A - A kind of manganese slag extraction wastewater recovery processing equipment and process - Google Patents
A kind of manganese slag extraction wastewater recovery processing equipment and process Download PDFInfo
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- CN109384359A CN109384359A CN201811581241.4A CN201811581241A CN109384359A CN 109384359 A CN109384359 A CN 109384359A CN 201811581241 A CN201811581241 A CN 201811581241A CN 109384359 A CN109384359 A CN 109384359A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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Abstract
The present invention relates to manganese slag waste water recycling device technical fields, and more particularly to a kind of manganese slag extraction wastewater recovery processing equipment and process, the equipment includes membrane bioreactor, cationic switch, ammonia nitrogen recyclable device and tail gas absorber, the process step are as follows: (1) adjust and filter；(2) pretreatment and manganese sulfate recycling；(3) ammonia stripping；(4) ammonium sulfate recycles；(5) tail gas clean-up；Fine suspension in extraction waste water is filtered, while playing the role of throttling；It is collected in concentrate storage tank after the manganese ion in waste water is concentrated into the concentration of electrolytic manganese needs under alkaline environment, achieve the purpose that remove the harmful substance manganese ion in waste water and recycles manganese ion to put into electrolytic manganese process again；It can be with the ammonium sulfate of reuse by generation after dilute sulfuric acid is added into ammonia absorption tower；It realizes the recycling and reusing to manganese and ammonia nitrogen in extraction waste water, and reaches wastewater zero discharge, to the purpose of zero environmental.
Description
Technical field
The present invention relates to manganese slag waste water recycling device technical fields, and extract waste water recycling device more particularly to a kind of manganese slag
Equipment and process.
Background technique
In modern industry, the compound of manganese and manganese has wide range of applications, and the manganese in the whole world about 95% is used for metallurgical industry,
About 5% for chemistry, construction material, medicine, electronics, environmental protection and farming and animal husbandry etc., Chinese electrolytic manganese metal is (referred to as electric for remaining
The 98% of the world production capacity Yi Zhan production capacity Xie Meng), in electrolytic manganese production process, the waste residue amount that different manganese ores generates is different,
So that domestic manganese carbonate ore produces 1 ton of electrolytic manganese and about generates 8 tons of manganese slags, and manganese ore quality is lower, and the manganese quantity of slag is bigger.Manganese
Slag not only has the great wasting of resources, while having biggish harm to human body and environment.
Generally filling after manganese slag and lime mixed processing, China mainly send manganese slag to stockyard for developed country, carries out
Wet process of building a dam stockpiling or landfill, and the manganese slag for accumulating landfill can generate appropriation of land farmland, destroy soil texture, keep soil sour
Change, destroy the problems such as surrounding biologic diversity, the manganese slag after landfill not only generates adverse effect to the plant in soil, through rainwater
The percolate generated after washing away is directly entered river water, together with all kinds of Mn-bearing waste waters generated in electrolytic manganese production process at
For the important pollution entering the water of electrolytic manganese industry；And the landfill of manganese slag also indirectly can have an adverse effect to the mankind.Chronic Mn Poisoning
It can cause psychiatric system lesion, the various diseases such as endocrine system disorder seriously endanger the health of the mankind.
Vulcanize purification in the ore tailings and liquid making technique that manganese ore acidleach liquid making technique generates to be recycled to derive from
The manganese slag in various heavy metal sulfides precipitating generated, the prior art mainly use extracting technology and diaphragm to be pressurized filters pressing work
Skill is separated by solid-liquid separation, and the such as water-soluble manganese sulfate of the water-soluble substances in manganese slag, ammonium sulfate are extracted, but extracted
The extraction waste water generated in journey contains higher manganese ion and ammonia nitrogen, does not still meet discharge standard, and pollution environment causes simultaneously
The waste of a large amount of manganese and ammonia nitrogen resource, processing method recovery efficiency in the prior art is low, and technical process still can generate waste water
Environmental pollution is caused, there is no the manganese fundamentally solved the problems, such as in manganese slag extraction waste water and ammonia-nitrogen content are higher.
Summary of the invention
The present invention is in view of the deficienciess of the prior art, provide a kind of manganese slag extraction wastewater recovery processing equipment and technique side
Method solves the problems, such as that manganese and ammonia-nitrogen content in manganese slag extraction waste water are higher and pollute environment and the wasting of resources.
The technical scheme to solve the above technical problems is that a kind of manganese slag extraction wastewater recovery processing equipment and work
Process, including to remove oil removal and there is the membrane bioreactor of throttling function, to recycle Manganese in Waste Water ion
Cationic switch, the ammonia nitrogen recyclable device to recycle ammonia nitrogen and the tail gas absorption to absorb remaining ammonia nitrogen in tail gas
Tower, the membrane bioreactor are connect with cationic switch, and the cation switch is also connected with medicine system, described
Medicine system includes acid storage tank and alkali storage tank, and the cation switch is connect with alkali storage tank, cationic switch it is dense
Contracting liquid storage tank is connect with acid storage tank, loads manganese ion private exchange resin in the cation switch, the ammonia nitrogen returns
Receiving apparatus includes ammonia-nitrogen stripping tower and ammonia nitrogen absorption tower, and the cation switch is connect with ammonia-nitrogen stripping tower, the ammonia nitrogen
Stripping tower passes through the air-introduced machine being arranged between with ammonia nitrogen absorption tower and connect, and the ammonia-nitrogen stripping tower is connect with sandfiltration pot,
The ammonia nitrogen absorption tower is connect with tail gas absorber, and the ammonia nitrogen absorption tower is also connected with dilute sulfuric acid storage tank.
The beneficial effects of the present invention are: being carried out by setting membrane bioreactor to the fine suspension in extraction waste water
Filtering, while playing the role of throttling, be conducive to improve filter efficiency；Manganese ion private exchange resin is loaded by the way that setting is internal
Cationic switch, under alkaline environment by the manganese ion in waste water be concentrated into electrolytic manganese needs concentration after be collected in it is dense
Contracting liquid storage tank generates the manganese sulfate that can be back to electrolytic manganese process by being added into concentrate storage tank, reaches after sulfuric acid
To the harmful substance manganese ion in removal waste water and manganese ion is recycled to put into the purpose of electrolytic manganese process again, is advantageously reduced
The pollution level of waste water and the production cost for reducing electrolytic manganese；By the way that ammonia-nitrogen stripping tower is arranged, extremely by the ammonia stripping in waste water
Ammonia absorption tower generates by being added after dilute sulfuric acid into ammonia absorption tower and can pass through sandfiltration pot with the ammonium sulfate of reuse
Being formed after being filtered to the waste water that ammonia stripping finishes can recycle-water；By the way that tail gas absorber is arranged, in ammonia absorption tower
The ammonia not being completely absorbed carries out absorbing to make tail gas qualified discharge；Realize the recycling to manganese and ammonia nitrogen in extraction waste water
It recycles, and reaches wastewater zero discharge, to the purpose of zero environmental.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the cationic switch includes that the first cation exchange tower being connected in parallel and the second cation are handed over
Change tower, the inlet of first cation exchange tower and the second cation exchange tower is respectively set the first regulating valve and second and adjusts
Save valve.
Beneficial effect using above-mentioned further scheme is, by the way that the first cation exchange tower being connected in parallel and the is arranged
Two cation exchange towers can select the quantity of the cation exchange tower of access wastewater recycling process route according to demand, or
Only use a cation exchange tower, another cation exchange tower as spare, with cope with wastewater flow rate to be treated it is big or
Person's equipment fault influences the problem of wastewater treatment is normally carried out.
Further, the air blower to accelerate ammonia stripping is installed in the bottom of ammonia-nitrogen stripping tower.
Beneficial effect using above-mentioned further scheme is, by the way that air blower is arranged, to accelerate the stripping effect of ammonia in wastewater
Rate, to improve the recovery efficiency of ammonia in wastewater.
Further, the import connection steam generator or heat blower of air blower.
Beneficial effect using above-mentioned further scheme is, by setting steam generator or heat blower, to improve drum
The temperature of blower air blast to accelerate the stripping speed of ammonia, and then improves the recovery efficiency of ammonia.
Further, the tail gas absorber is connected with the absorbing liquid circulating box to accommodate circulating absorption solution.
Beneficial effect using above-mentioned further scheme is, by the way that absorbing liquid circulating box is arranged, to fill tail gas with absorbing liquid
Tap touching, while realizing the recycling of absorbing liquid, reduce production cost and reducing environmental pollution.
Further, the inlet of the membrane bioreactor connects the conditioning tank extraction waste water to be adjusted.
Beneficial effect using above-mentioned further scheme is, by the way that conditioning tank is arranged, to the water and water quality of extraction waste water
It is adjusted, to achieve the purpose that water homogeneous is balanced, stable waste water source is provided for membrane bioreactor, is reduced due to useless
The change dramatically of water water and water quality is impacted caused by membrane bioreactor, to extend the use longevity of membrane bioreactor
Life.
Further, the pretreatment water tank to buffer is set between the membrane bioreactor and cationic switch.
Beneficial effect using above-mentioned further scheme is, by the way that pretreatment water tank is arranged, to through membrane bioreactor mistake
Waste water after filter is buffered and is staticly settled, to provide stable waste water source for cationic switch, prevent because
Water it is excessive it is too urgent cause manganese ion thickening efficiency reduce or manganese ion private exchange resin block the case where, extend manganese ion it is special
With the service life of exchanger resin.
Further, buffer tank is set between the cationic switch and ammonia-nitrogen stripping tower.
Beneficial effect using above-mentioned further scheme is the efficiency for being conducive to improve ammonia stripping, to improve ammonia
Recovery efficiency.
A kind of process of manganese slag extraction waste water recycling device, this method step are as follows:
(1) it adjusts and filters: manganese slag extraction waste water being come together in into conditioning tank, then the waste water of conditioning tank is via membrane bioreaction
Device is answered to be filtered；
(2) pre-process and manganese sulfate recycling: the waste water of (1) step by membrane bioreactor processing by pump be pumped into it is pre-
Water tank is handled, after being buffered and precipitated via pretreatment water tank, opens the first regulating valve, the waste water in pretreatment water tank enters
First cation exchange tower, temperature and pH value in adjusting tower, by the manganese ion private exchange resin in tower by manganese under acidic environment
Ionic adsorption is concentrated into concentrate storage tank, and then sulfuric acid is added into concentrate storage tank and reacts with manganese ion for opening acid storage tank
It generates manganese sulfate and enters manganese sulfate recycling bins, so that manganese ion be recycled；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffered water by cationic switch
Case is entered in tower after being buffered by the top of ammonia-nitrogen stripping tower, and PH in ammonia-nitrogen stripping tower is adjusted, and opens air blower to ammonia nitrogen
The bottom of stripping tower is passed through steam or hot wind, adjusts the temperature in ammonia-nitrogen stripping tower, will be in waste water under the action of air blower
Exported after ammonia stripping by the top of ammonia-nitrogen stripping tower, in tower remaining waste water by tower bottom flow to sandfiltration pot it is for re-filtering after
As recycle-water in electrolytic manganese production；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower via air-introduced machine by the ammonia of ammonia-nitrogen stripping tower output, opens dilute sulphur
Acid storage tank be added into ammonia nitrogen absorption tower Solute mass fraction≤70% dilute sulfuric acid aqueous solution and ammonia formed ammonium sulfate it is laggard
Enter ammonium sulfate recycling bins, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower to ammonia enters tail gas absorber, absorbing liquid by tower top
Absorbing liquid in circulating box is flowed by the tower top of tail gas absorber, absorbing liquid circulating box is flowed out to by tower bottom, to form circulation
Flowing, in tail gas absorber inner exhaust gas remaining ammonia by absorbing liquid absorb it is up to standard after through being discharged by the exhaust tube of tower top.
Beneficial effect using above-mentioned further scheme is adjusted by water and water quality of the conditioning tank to extraction waste water
Section provides stable waste water source for membrane bioreactor to achieve the purpose that water homogeneous is balanced, reduces due to waste water water
It is impacted caused by membrane bioreactor with the change dramatically of water quality, to extend the service life of membrane bioreactor；Pass through
Membrane bioreactor is filtered the fine suspension in extraction waste water, while playing the role of throttling, is conducive to improve
Filter efficiency；
Further, in (1) step membrane bioreactor membrane flux be 15-25L/ ㎡ ﹒ h, membrane bioreactor it is effective
Area be 0.6-1.0 ㎡/.
Beneficial effect using above-mentioned further scheme is, by membrane flux and significant surface that membrane bioreactor is arranged
Product, improves the filter efficiency of waste water.
Further, in (2) step, the second regulating valve is opened while opening the first regulating valve, it is useless in pretreatment water tank
Water enters the first cation exchange tower and the second cation exchange tower simultaneously, adjusts temperature and pH value in two towers, carries out manganese
Ionic adsorption concentration.
Beneficial effect using above-mentioned further scheme is to pass through the first cation exchange tower and the second cation exchange tower
It uses simultaneously, is conducive to improve the flow in the waste water unit time, to improve the recovery efficiency of manganese ion.
Further, temperature is 298k-313k in adjusting tower in (2) step, and adjusting pH value is 4-7.
Beneficial effect using above-mentioned further scheme is handed over by the first cation exchange tower of setting and the second cation
The temperature and pH value in tower are changed, improves the absorption displacement efficiency of manganese ion, and then improve the recovery efficiency of manganese ion.
Further, the waste water in (2) step in pretreatment water tank also passes through pump blowback membrane bioreactor progress mistake again
Filter the suspended particulate in the turbidity and water to reduce waste water.
Beneficial effect using above-mentioned further scheme is, by by the return of waste water in pretreatment water tank to membrane bioreaction
It answers device to be refiltered, reduces the turbidity of waste water, reduce the probability that membrane bioreactor blocks, and then extend membrane bioreaction
Answer the service life of device.
Further, PH >=11 in ammonia-nitrogen stripping tower are adjusted in (3) step, the temperature adjusted in ammonia-nitrogen stripping tower is more than or equal to
40℃。
Beneficial effect using above-mentioned further scheme is, by the pH value and temperature in setting ammonia-nitrogen stripping tower, favorably
In the stripping efficiency for improving ammonia, steam or hot wind are blasted into tower by air blower, the temperature in tower is improved, further increases
The stripping efficiency of ammonia, improves the rate of recovery of ammonia.
Further, the tail gas in (5) step in tail gas absorber is not thorough through absorbing liquid purification, is passed through membrane biological reaction
Device purification for re-filtering.
Beneficial effect using above-mentioned further scheme is that it is raw to be passed through film by the tail gas that tail gas absorption top of tower is discharged
Object reactor is refiltered, and realizes waste water and gas zero-emission, prevents the pollution row during manganese slag extraction waste water recycling device
It puts.
Detailed description of the invention
Fig. 1 is the process route view of the embodiment of the present invention 1, embodiment 3 and embodiment 5；
Fig. 2 is the process route view of the embodiment of the present invention 2；
Fig. 3 is the process route view of the embodiment of the present invention 4.
1. membrane bioreactor in figure, 2. pretreatment water tanks, 3. first regulating valves, 4. first cation exchange towers, 5. is slow
Waste preventer, 6. acid storage tanks, 7. alkali storage tanks, 8. ammonia-nitrogen stripping towers, 9. air-introduced machines, 10. ammonia nitrogen absorption towers, 11. dilute sulfuric acid storage tanks,
12. exhaust tube, 13. tail gas absorbers, 14. absorbing liquid circulating boxes, 15. ammonium sulfate recycling bins, 16. reuse water tanks, 17. sand filtrations
Tank, 18. air blowers, 19. manganese sulfate recycling bins, 20. second cation exchange towers, 21. second regulating valves, 22. conditioning tanks.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
A kind of manganese slag extraction wastewater recovery processing equipment, the equipment include to remove oil removal and have throttling function
Membrane bioreactor 1, the cationic switch to recycle Manganese in Waste Water ion, the ammonia nitrogen recyclable device to recycle ammonia nitrogen
It connects with the inlet of the tail gas absorber to absorb remaining ammonia nitrogen in tail gas, the membrane bioreactor 1 to extraction
The conditioning tank 22 that waste water is adjusted, the membrane bioreactor 1 are connect with cationic switch, the cation exchange dress
It sets and is also connected with medicine system, the medicine system includes acid storage tank 6 and alkali storage tank 7, the cation switch and alkali storage tank 7
Connection, the concentrate storage tank of cationic switch are connect with acid storage tank 6, load manganese ion in the cation switch
Private exchange resin, the ammonia nitrogen recyclable device include ammonia-nitrogen stripping tower 8 and ammonia nitrogen absorption tower 10, the cation switch
It is connect with ammonia-nitrogen stripping tower 8, the air blower 18 to accelerate ammonia stripping is installed in the bottom of ammonia-nitrogen stripping tower 8, air blower 18
Import connects heat blower, and the ammonia-nitrogen stripping tower 8 passes through the air-introduced machine 9 being arranged between with ammonia nitrogen absorption tower 10 and connects
It connects, the ammonia-nitrogen stripping tower 8 is connect with sandfiltration pot 17, and the ammonia nitrogen absorption tower 10 is connect with tail gas absorber 13, the tail gas
Absorption tower 13 is connected with the absorbing liquid circulating box 14 to accommodate circulating absorption solution, and the ammonia nitrogen absorption tower 10 is also connected with dilute sulfuric acid
Storage tank 11.
Pretreatment water tank 2 to buffer, the sun are set between the membrane bioreactor 1 and cationic switch
Buffer tank 5 is set between ion interchange unit and ammonia-nitrogen stripping tower 8, and the cation switch includes the be connected in parallel
One cation exchange tower 4 and the second cation exchange tower 20, first cation exchange tower 4 and the second cation exchange tower 20
Inlet the first regulating valve 3 and the second regulating valve 21 is respectively set.
By the way that membrane bioreactor 1 is arranged, the fine suspension in extraction waste water is filtered, while playing throttling
Effect is conducive to improve filter efficiency；The cationic switch that manganese ion private exchange resin is loaded by setting inside,
It is collected in concentrate storage tank after the manganese ion in waste water is concentrated into the concentration of electrolytic manganese needs under alkaline environment, by dense
The manganese sulfate that can be back to electrolytic manganese process is generated after sulfuric acid is added in contracting liquid storage tank, reaches the nuisance in removal waste water
Matter manganese ion puts into the purpose of electrolytic manganese process with recycling manganese ion again, advantageously reduces the pollution level and reduction of waste water
The production cost of electrolytic manganese；By the way that ammonia-nitrogen stripping tower 8 is arranged, by the ammonia stripping in waste water to ammonia absorption tower, by ammonia
It generates and ammonia stripping can be finished by sandfiltration pot 17 with the ammonium sulfate of reuse after dilute sulfuric acid is added in aspiration tower 10
Waste water is formed after being filtered can recycle-water；By the way that tail gas absorber 13 is arranged, to what is be not completely absorbed in ammonia absorption tower
Ammonia carries out absorbing to make tail gas qualified discharge；Realize the recycling and reusing to manganese and ammonia nitrogen in extraction waste water, Yi Jida
To wastewater zero discharge, to the purpose of zero environmental.
Embodiment 1
A kind of process of manganese slag extraction waste water recycling device, it is characterised in that: this method step are as follows:
(1) adjust and filter: by manganese slag extraction waste water 100L come together in conditioning tank 22, then the waste water of conditioning tank 22 via
Membrane bioreactor 1 is filtered, and the membrane flux of membrane bioreactor 1 is 20L/ ㎡ ﹒ h, the effective area of membrane bioreactor 1
For 0.8 ㎡/；
(2) pre-process and manganese sulfate recycles: the waste water of (1) step is pumped by the processing of membrane bioreactor 1 by pumping
Pretreatment water tank 2 after being buffered and precipitated via pretreatment water tank 2, is opened second while opening the first regulating valve 3 and is adjusted
Valve 21, the waste water in pretreatment water tank 2 enter the first cation exchange tower 4 and the second cation exchange tower 20 simultaneously, adjust two
Temperature and pH value in a tower, temperature is 300k in adjusting tower, and adjusting pH value is 6, carries out manganese ion Adsorption Concentration, acidic environment
Under by the manganese ion private exchange resin in tower by manganese ion Adsorption Concentration to concentrate storage tank, then open acid storage tank 6 to
The interior addition sulfuric acid of concentrate storage tank reacts generation manganese sulfate with manganese ion and enters manganese sulfate recycling bins 19, so that manganese ion be returned
It receives；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffer tank by cationic switch
5, entered in tower after being buffered by the top of ammonia-nitrogen stripping tower 8, adjusting PH in ammonia-nitrogen stripping tower 8 is 11, opens air blower
18 are passed through steam or hot wind to the bottom of ammonia-nitrogen stripping tower 8, and adjusting the temperature in ammonia-nitrogen stripping tower 8 is 40 DEG C, in air blower 18
Under the action of will be exported after the ammonia stripping in waste water by the top of ammonia-nitrogen stripping tower 8, remaining waste water is flow to by tower bottom in tower
Enter reuse water tank 16 in electrolytic manganese production as recycle-water after sandfiltration pot 17 is for re-filtering；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower 10 via air-introduced machine 9 by the ammonia that ammonia-nitrogen stripping tower 8 exports, opens
The dilute sulfuric acid aqueous solution of Solute mass fraction≤70% is added into ammonia nitrogen absorption tower 10 for dilute sulfuric acid storage tank 11 and ammonia forms sulphur
Enter ammonium sulfate recycling bins 15 after sour ammonium, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower 10 to ammonia enters tail gas absorber 13 by tower top, inhales
The absorbing liquid received in liquid circulating box 14 is flowed by the tower top of tail gas absorber 13, flows out to absorbing liquid circulating box 14 by tower bottom, from
And formed circulate, in 13 inner exhaust gas of tail gas absorber remaining ammonia by absorbing liquid absorb it is up to standard after through by tower top exhaust
Cylinder 12 discharges, and the tail gas in tail gas absorber 13 is not thorough through absorbing liquid purification, is passed through membrane bioreactor 1 and carries out mistake again
Filter purification.
Embodiment 2
A kind of process of manganese slag extraction waste water recycling device, it is characterised in that: this method step are as follows:
(1) adjust and filter: by manganese slag extraction waste water 100L come together in conditioning tank 22, then the waste water of conditioning tank 22 via
Membrane bioreactor 1 is filtered, and the membrane flux of membrane bioreactor 1 is 20L/ ㎡ ﹒ h, the effective area of membrane bioreactor 1
For 0.8 ㎡/；
(2) pre-process and manganese sulfate recycles: the waste water of (1) step is pumped by the processing of membrane bioreactor 1 by pumping
Pretreatment water tank 2 after being buffered and precipitated via pretreatment water tank 2, opens the first regulating valve 3, useless in pretreatment water tank 2
Water enters the first cation exchange tower 4 simultaneously, temperature and pH value in adjusting tower, and temperature is 300k in adjusting tower, adjusts pH value
Be 6, carry out manganese ion Adsorption Concentration, under acidic environment by the manganese ion private exchange resin in tower by manganese ion Adsorption Concentration extremely
Concentrate storage tank, then open acid storage tank 6 is added into concentrate storage tank sulfuric acid reacted with manganese ion generation manganese sulfate into
Enter manganese sulfate recycling bins 19, so that manganese ion be recycled；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffer tank by cationic switch
5, entered in tower after being buffered by the top of ammonia-nitrogen stripping tower 8, adjusting PH in ammonia-nitrogen stripping tower 8 is 11, opens air blower
18 are passed through steam or hot wind to the bottom of ammonia-nitrogen stripping tower 8, and adjusting the temperature in ammonia-nitrogen stripping tower 8 is 40 DEG C, in air blower 18
Under the action of will be exported after the ammonia stripping in waste water by the top of ammonia-nitrogen stripping tower 8, remaining waste water is flow to by tower bottom in tower
Enter reuse water tank 16 in electrolytic manganese production as recycle-water after sandfiltration pot 17 is for re-filtering；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower 10 via air-introduced machine 9 by the ammonia that ammonia-nitrogen stripping tower 8 exports, opens
The dilute sulfuric acid aqueous solution of Solute mass fraction≤70% is added into ammonia nitrogen absorption tower 10 for dilute sulfuric acid storage tank 11 and ammonia forms sulphur
Enter ammonium sulfate recycling bins 15 after sour ammonium, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower 10 to ammonia enters tail gas absorber 13 by tower top, inhales
The absorbing liquid received in liquid circulating box 14 is flowed by the tower top of tail gas absorber 13, flows out to absorbing liquid circulating box 14 by tower bottom, from
And formed circulate, in 13 inner exhaust gas of tail gas absorber remaining ammonia by absorbing liquid absorb it is up to standard after through by tower top exhaust
Cylinder 12 discharges, and the tail gas in tail gas absorber 13 is not thorough through absorbing liquid purification, is passed through membrane bioreactor 1 and carries out mistake again
Filter purification.
Embodiment 3
A kind of process of manganese slag extraction waste water recycling device, it is characterised in that: this method step are as follows:
(1) adjust and filter: by manganese slag extraction waste water 100L come together in conditioning tank 22, then the waste water of conditioning tank 22 via
Membrane bioreactor 1 is filtered, and the membrane flux of membrane bioreactor 1 is 15L/ ㎡ ﹒ h, the effective area of membrane bioreactor 1
For 0.6 ㎡/；
(2) pre-process and manganese sulfate recycles: the waste water of (1) step is pumped by the processing of membrane bioreactor 1 by pumping
Pretreatment water tank 2 after being buffered and precipitated via pretreatment water tank 2, is opened second while opening the first regulating valve 3 and is adjusted
Valve 21, the waste water in pretreatment water tank 2 enter the first cation exchange tower 4 and the second cation exchange tower 20 simultaneously, adjust two
Temperature and pH value in a tower, temperature is 310k in adjusting tower, and adjusting pH value is 6, carries out manganese ion Adsorption Concentration, alkaline environment
Under by the manganese ion private exchange resin in tower by manganese ion Adsorption Concentration to concentrate storage tank, then open acid storage tank 6 to
The interior addition sulfuric acid of concentrate storage tank reacts generation manganese sulfate with manganese ion and enters manganese sulfate recycling bins 19, so that manganese ion be returned
It receives；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffer tank by cationic switch
5, entered in tower after being buffered by the top of ammonia-nitrogen stripping tower 8, adjusting PH in ammonia-nitrogen stripping tower 8 is 11, opens air blower
18 are passed through steam or hot wind to the bottom of ammonia-nitrogen stripping tower 8, and adjusting the temperature in ammonia-nitrogen stripping tower 8 is 40 DEG C, in air blower 18
Under the action of will be exported after the ammonia stripping in waste water by the top of ammonia-nitrogen stripping tower 8, remaining waste water is flow to by tower bottom in tower
Enter reuse water tank 16 in electrolytic manganese production as recycle-water after sandfiltration pot 17 is for re-filtering；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower 10 via air-introduced machine 9 by the ammonia that ammonia-nitrogen stripping tower 8 exports, opens
The dilute sulfuric acid aqueous solution of Solute mass fraction≤70% is added into ammonia nitrogen absorption tower 10 for dilute sulfuric acid storage tank 11 and ammonia forms sulphur
Enter ammonium sulfate recycling bins 15 after sour ammonium, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower 10 to ammonia enters tail gas absorber 13 by tower top, inhales
The absorbing liquid received in liquid circulating box 14 is flowed by the tower top of tail gas absorber 13, flows out to absorbing liquid circulating box 14 by tower bottom, from
And formed circulate, in 13 inner exhaust gas of tail gas absorber remaining ammonia by absorbing liquid absorb it is up to standard after through by tower top exhaust
Cylinder 12 discharges, and the tail gas in tail gas absorber 13 is not thorough through absorbing liquid purification, is passed through membrane bioreactor 1 and carries out mistake again
Filter purification.
Embodiment 4
A kind of process of manganese slag extraction waste water recycling device, it is characterised in that: this method step are as follows:
(1) adjust and filter: by manganese slag extraction waste water 100L come together in conditioning tank 22, then the waste water of conditioning tank 22 via
Membrane bioreactor 1 is filtered, and the membrane flux of membrane bioreactor 1 is 20L/ ㎡ ﹒ h, the effective area of membrane bioreactor 1
For 0.8 ㎡/；
(2) pre-process and manganese sulfate recycles: the waste water of (1) step is pumped by the processing of membrane bioreactor 1 by pumping
Pretreatment water tank 2, the waste water in pretreatment water tank 2 are for re-filtering to reduce waste water by pump blowback membrane bioreactor 1
Turbidity and water in suspended particulate, after being buffered and precipitated via pretreatment water tank 2, open the first regulating valve 3 while
The second regulating valve 21 is opened, the waste water in pretreatment water tank 2 enters the first cation exchange tower 4 and the second cation exchange simultaneously
Tower 20 adjusts temperature and pH value in two towers, and temperature is 300k in adjusting tower, and adjusting pH value is 6, and it is dense to carry out manganese ion absorption
Contracting, under acidic environment by the manganese ion private exchange resin in tower by manganese ion Adsorption Concentration to concentrate storage tank, then beat
Open acid storage tank 6 be added into concentrate storage tank sulfuric acid reacted with manganese ion generate manganese sulfate enter manganese sulfate recycling bins 19, from
And manganese ion is recycled；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffer tank by cationic switch
5, entered in tower after being buffered by the top of ammonia-nitrogen stripping tower 8, adjusting PH in ammonia-nitrogen stripping tower 8 is 11, opens air blower
18 are passed through steam or hot wind to the bottom of ammonia-nitrogen stripping tower 8, and adjusting the temperature in ammonia-nitrogen stripping tower 8 is 40 DEG C, in air blower 18
Under the action of will be exported after the ammonia stripping in waste water by the top of ammonia-nitrogen stripping tower 8, remaining waste water is flow to by tower bottom in tower
Enter reuse water tank 16 in electrolytic manganese production as recycle-water after sandfiltration pot 17 is for re-filtering；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower 10 via air-introduced machine 9 by the ammonia that ammonia-nitrogen stripping tower 8 exports, opens
The dilute sulfuric acid aqueous solution of Solute mass fraction≤70% is added into ammonia nitrogen absorption tower 10 for dilute sulfuric acid storage tank 11 and ammonia forms sulphur
Enter ammonium sulfate recycling bins 15 after sour ammonium, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower 10 to ammonia enters tail gas absorber 13 by tower top, inhales
The absorbing liquid received in liquid circulating box 14 is flowed by the tower top of tail gas absorber 13, flows out to absorbing liquid circulating box 14 by tower bottom, from
And formed circulate, in 13 inner exhaust gas of tail gas absorber remaining ammonia by absorbing liquid absorb it is up to standard after through by tower top exhaust
Cylinder 12 discharges, and the tail gas in tail gas absorber 13 is not thorough through absorbing liquid purification, is passed through membrane bioreactor 1 and carries out mistake again
Filter purification.
Embodiment 5
A kind of process of manganese slag extraction waste water recycling device, it is characterised in that: this method step are as follows:
(1) adjust and filter: by manganese slag extraction waste water 100L come together in conditioning tank 22, then the waste water of conditioning tank 22 via
Membrane bioreactor 1 is filtered, and the membrane flux of membrane bioreactor 1 is 20L/ ㎡ ﹒ h, the effective area of membrane bioreactor 1
For 0.8 ㎡/；
(2) pre-process and manganese sulfate recycles: the waste water of (1) step is pumped by the processing of membrane bioreactor 1 by pumping
Pretreatment water tank 2 after being buffered and precipitated via pretreatment water tank 2, is opened second while opening the first regulating valve 3 and is adjusted
Valve 21, the waste water in pretreatment water tank 2 enter the first cation exchange tower 4 and the second cation exchange tower 20 simultaneously, adjust two
Temperature and pH value in a tower, temperature is 300k in adjusting tower, and adjusting pH value is 6, carries out manganese ion Adsorption Concentration, acidic environment
Under by the manganese ion private exchange resin in tower by manganese ion Adsorption Concentration to concentrate storage tank, then open acid storage tank 6 to
The interior addition sulfuric acid of concentrate storage tank reacts generation manganese sulfate with manganese ion and enters manganese sulfate recycling bins 19, so that manganese ion be returned
It receives；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffer tank by cationic switch
5, entered in tower after being buffered by the top of ammonia-nitrogen stripping tower 8, adjusting PH in ammonia-nitrogen stripping tower 8 is 11, opens air blower
18 are passed through normal temperature air to the bottom of ammonia-nitrogen stripping tower 8, and adjusting the temperature in ammonia-nitrogen stripping tower 8 is 40 DEG C, in air blower 18
It will be exported after the ammonia stripping in waste water by the top of ammonia-nitrogen stripping tower 8 under effect, remaining waste water flow to sand by tower bottom in tower
Enter reuse water tank 16 in electrolytic manganese production as recycle-water after filter tank 17 is for re-filtering；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower 10 via air-introduced machine 9 by the ammonia that ammonia-nitrogen stripping tower 8 exports, opens
The dilute sulfuric acid aqueous solution of Solute mass fraction≤70% is added into ammonia nitrogen absorption tower 10 for dilute sulfuric acid storage tank 11 and ammonia forms sulphur
Enter ammonium sulfate recycling bins 15 after sour ammonium, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower 10 to ammonia enters tail gas absorber 13 by tower top, inhales
The absorbing liquid received in liquid circulating box 14 is flowed by the tower top of tail gas absorber 13, flows out to absorbing liquid circulating box 14 by tower bottom, from
And formed circulate, in 13 inner exhaust gas of tail gas absorber remaining ammonia by absorbing liquid absorb it is up to standard after through by tower top exhaust
Cylinder 12 discharges, and the tail gas in tail gas absorber 13 is not thorough through absorbing liquid purification, is passed through membrane bioreactor 1 and carries out mistake again
Filter purification.
Analysis of experimental data:
Through detecting, 100L manganese slag extracts the pollution parameters in waste water: manganese ion concentration 25g/L, ammonia-nitrogen content 50g/
L。
By embodiment 1-5 processing after and control group (with no treatment) pollution parameters and manganese and ammonia the rate of recovery
Arrange and is as follows:
It is analyzed by above-mentioned data it is found that 1. seeing on the whole, according to recovery process method disclosed herein and respectively
Parameter carries out recycling manganese and ammonia, and the recovery efficiency of manganese and ammonia is all larger than 95%；2. comparative example 1 and embodiment 3, when film is logical
Amount is 20L/ ㎡ ﹒ h, the effective area of membrane bioreactor be 0.8 ㎡/, temperature is 300k in cationic switch, is adjusted
PH value is 6, and PH is 11 in ammonia-nitrogen stripping tower 8, and when the temperature in ammonia-nitrogen stripping tower 8 is 40 DEG C, the recovery efficiency of manganese and ammonia is higher；
3. comparative example 1 and embodiment 5, when air blower is passed through steam or hot wind to 8 bottom of ammonia-nitrogen stripping tower, the rate of recovery of ammonia is more
It is high；4. comparative example 1 and embodiment 4, when the waste water in pretreatment water tank 2 is carried out again by pump blowback membrane bioreactor 1
When secondary filtering, the reaction time is elongated, but the rate of recovery of manganese and ammonia is higher；5. comparative example 1 and embodiment 2, when only using
When one cation exchange tower 4 works, the reaction time is longer, and the rate of recovery of manganese and ammonia reduces.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of manganese slag extracts wastewater recovery processing equipment, it is characterised in that: including to remove oil removal and there is throttle power
Membrane bioreactor, the cationic switch to recycle Manganese in Waste Water ion, the ammonia nitrogen to recycle ammonia nitrogen of energy recycle
Device and the tail gas absorber to absorb remaining ammonia nitrogen in tail gas, the inlet connection of membrane bioreactor is to useless to extraction
The conditioning tank that water is adjusted, the membrane bioreactor are connect with cationic switch, and the cation switch is also
Medicine system is connected, the medicine system includes acid storage tank and alkali storage tank, and the cation switch is connect with alkali storage tank, sun
The concentrate storage tank of ion interchange unit is connect with acid storage tank, loads manganese ion private exchange in the cation switch
Resin, the ammonia nitrogen recyclable device include ammonia-nitrogen stripping tower and ammonia nitrogen absorption tower, the cation switch and ammonia-nitrogen desorption
Tower connection, the ammonia-nitrogen stripping tower pass through the air-introduced machine being arranged between with ammonia nitrogen absorption tower and connect, the ammonia-nitrogen desorption
Tower is connect with sandfiltration pot, and the ammonia nitrogen absorption tower is connect with tail gas absorber, and the tail gas absorber is connected with to follow to accommodate
The absorbing liquid circulating box of ring absorbing liquid, the ammonia nitrogen absorption tower are also connected with dilute sulfuric acid storage tank.
2. a kind of manganese slag according to claim 1 extracts wastewater recovery processing equipment, it is characterised in that: the membrane bioreaction
Answer the pretreatment water tank being arranged between device and cationic switch to buffer, the cation switch and ammonia-nitrogen desorption
Buffer tank is set between tower, the cation switch include the first cation exchange tower being connected in parallel and the second sun from
The inlet of sub- exchange column, the first cation exchange tower and the second cation exchange tower is respectively set the first regulating valve and second and adjusts
Save valve.
3. a kind of manganese slag according to claim 1 or 2 extracts wastewater recovery processing equipment, it is characterised in that: ammonia-nitrogen desorption
The bottom of tower is installed by the air blower to accelerate ammonia stripping, the import connection steam generator or heat blower of air blower.
4. a kind of process of manganese slag extraction waste water recycling device, it is characterised in that: this method step are as follows:
(1) it adjusts and filters: manganese slag extraction waste water being come together in into conditioning tank, then the waste water of conditioning tank is via membrane bioreactor
It is filtered；
(2) pre-process and manganese sulfate recycles: the waste water of (1) step is pumped into pretreatment by pumping by the processing of membrane bioreactor
Water tank after being buffered and precipitated via pretreatment water tank, opens the first regulating valve, and the waste water in pretreatment water tank enters first
Cation exchange tower, temperature and pH value in adjusting tower, by the manganese ion private exchange resin in tower by manganese ion under acidic environment
Then Adsorption Concentration opens acid storage tank sulfuric acid is added into concentrate storage tank and react generation with manganese ion to concentrate storage tank
Manganese sulfate enters manganese sulfate recycling bins, so that manganese ion be recycled；
(3) ammonia stripping: the waste water after recycling manganese ion in (2) step is expelled to buffer tank by cationic switch, into
Entered in tower after row buffering by the top of ammonia-nitrogen stripping tower, adjust PH in ammonia-nitrogen stripping tower, opens air blower to ammonia-nitrogen desorption
The bottom of tower is passed through steam or hot wind, the temperature in ammonia-nitrogen stripping tower is adjusted, by the ammonia in waste water under the action of air blower
It is exported after stripping by the top of ammonia-nitrogen stripping tower, remaining waste water flow to sandfiltration pot rear conduct for re-filtering by tower bottom in tower
Recycle-water is in electrolytic manganese production；
(4) ammonium sulfate recycles: inputting ammonia nitrogen absorption tower via air-introduced machine by the ammonia of ammonia-nitrogen stripping tower output, opens dilute sulfuric acid storage
Tank enters sulphur after the dilute sulfuric acid aqueous solution and ammonia formation ammonium sulfate of Solute mass fraction≤70% are added into ammonia nitrogen absorption tower
Sour ammonium recycling bins, the ammonium sulfate of formation is in electrolytic manganese production；
(5) tail gas clean-up: the tail gas after being absorbed by ammonia nitrogen absorption tower to ammonia enters tail gas absorber, absorbing liquid circulation by tower top
Absorbing liquid in case is flowed by the tower top of tail gas absorber, is flowed out to absorbing liquid circulating box by tower bottom, is circulated to be formed,
In tail gas absorber inner exhaust gas remaining ammonia by absorbing liquid absorb it is up to standard after through by tower top exhaust tube discharge.
5. a kind of process of manganese slag extraction waste water recycling device according to claim 4, it is characterised in that: (1)
The membrane flux of membrane bioreactor is 15-25L/ ㎡ ﹒ h in step, the effective area of membrane bioreactor be 0.6-1.0 ㎡/.
6. a kind of process of manganese slag extraction waste water recycling device according to claim 4, it is characterised in that: (2)
In step, the second regulating valve is opened while opening the first regulating valve, the waste water in pretreatment water tank enters the first cation simultaneously
Exchange column and the second cation exchange tower adjust temperature and pH value in two towers, carry out manganese ion Adsorption Concentration.
7. a kind of process of manganese slag extraction waste water recycling device according to claim 6, it is characterised in that: (2)
Temperature is 298k-313k in adjusting tower in step, and adjusting pH value is 4-7.
8. a kind of process of manganese slag extraction waste water recycling device according to claim 7, it is characterised in that: (2)
Waste water in step in pretreatment water tank also pass through pump blowback membrane bioreactor it is for re-filtering with reduce waste water turbidity and
Suspended particulate in water.
9. according to a kind of process of any manganese slag extraction waste water recycling device of claim 4-8, it is characterised in that:
PH >=11 in ammonia-nitrogen stripping tower are adjusted in (3) step, the temperature adjusted in ammonia-nitrogen stripping tower is more than or equal to 40 DEG C.
10. according to a kind of process of any manganese slag extraction waste water recycling device of claim 4-8, feature exists
In: the tail gas in (5) step in tail gas absorber is not thorough through absorbing liquid purification, is passed through membrane bioreactor and is carried out mistake again
Filter purification.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021093491A1 (en) * | 2019-11-14 | 2021-05-20 | 西南科技大学 | Method for electric field enhanced harmless treatment of electrolytic manganese residue |
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