CN107074591A - Ammonia-containing water processing equipment and processing method - Google Patents
Ammonia-containing water processing equipment and processing method Download PDFInfo
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- CN107074591A CN107074591A CN201580057627.3A CN201580057627A CN107074591A CN 107074591 A CN107074591 A CN 107074591A CN 201580057627 A CN201580057627 A CN 201580057627A CN 107074591 A CN107074591 A CN 107074591A
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- ammonia
- containing water
- sulfuric acid
- ammonium sulfate
- acid solution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/30—Accessories; Auxiliary operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/32—Controlling or regulating
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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
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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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
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- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Sorption (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention solves the problem of removing deammoniation from ammonia-containing water using gas-liquid separation membrane, so as to obtain the ammonium sulfate of high concentration in the processing that ammonia is reclaimed with ammonium sulfate.The processing equipment 1 of ammonia-containing water is provided with：Ammonia removing device 16, the ammonia removing device 16 has gas-liquid separation membrane 26, the first liquid room 24a with the surface contiguous setting of gas-liquid separation membrane 26 and the second liquid room 24b set with another surface contiguous, the ammonia removing device 16 removes deammoniation from the ammonia-containing water for flowing through the first liquid room 24a, and make to contact with the ammonia removed with the sulfuric acid solution that ammonia-containing water counterflows through the second liquid room 24b, so as to reclaim as ammonium sulfate；For the entrance side valve 56 for the sulfuric acid solution entrance side for opening and closing the second liquid room 24b, and control device, the control device is used to close entrance side valve 56 and outlet side valve 58 when flowing of the stopping sulfuric acid solution by the second liquid room 24b.
Description
Technical field
The present invention relates to for handle from the facilities such as electronic industry factory, chemical plant discharge ammonia-containing water and with sulphur
Sour ammonium reclaims the ammonia-containing water processing equipment and processing method of the ammonia included in waste water.
Background technology
There is containing for rather high concentration from discharges such as the electronic industry such as such as semiconductor factory factory, chemical plant, steam power plants
Ammonia waste water, for example, passing through ammonia vaporizing extract process (ammonia stripping) (for example, with reference to patent document 1), evaporation concentration method (example
Such as, referring to patent document 2), the method such as catalytic wet air oxidation (for example, with reference to patent document 3) handles.With relatively low dense
The ammonia-containing water of degree is handled such as by biological treatment.
In ammonia vaporizing extract process, after alkaline solution is added in ammonia-containing water, heats ammonia-containing water and flow it
Cross filled with filler stripper and with steam and air contact, the ammonia in waste water is shifted to gas side.This method is relative
The simple but large-scale stripper of needs.This method such as heat energy such as heating or steam it is further desirable that using gas side is had moved towards
Ammonia is handled by catalysis oxidation at high temperature, generates the problem of processing cost is improved.In addition, can be produced during catalysis oxidation
Raw NOxOr N2O etc..
In the case of evaporation concentration method, heat and make ammonia-containing water evaporation to produce steam containing ammonia, then experience condensation
And reclaimed with ammoniacal liquor.This method has the heating cost of energy and incrustation scale that include generation steam to the heating surface of evaporator
The shortcomings of attachment.
Catalytic wet air oxidation in the presence of a catalyst, at a temperature of 100 to 370 DEG C, under stress processing contain
The method of ammonia waste water.The processing method carried out at high temperature under high pressure triggers safety and Cost Problems.
Have been proposed using allow ammonia by but prevent the hydrophobic porous gas-liquid separation membrane that passes through of liquid from useless containing ammonia
The gas-liquid separation embrane method of deammoniation is removed in water (for example, with reference to patent document 4).According to this method, make ammonia-containing water alkalization so that pH
For the ammonia in more than 10 and waste water, and by the downstream of vacuum pumping gas-liquid separation membrane, so that from useless containing ammonia
Deammoniation is removed in water.However, this method needs to set the washer of single ammonium sulfate.
Also proposed make the hydrophobic hollow fiber film as gas-liquid separation membrane downstream flowing sulfuric acid solution with
Ammonia-containing water counter current contacting, so as to reclaim the further gas-liquid separation embrane method of ammonia with ammonium sulfate (for example, with reference to patent
Document 5).The technology makes pH adjust to more than 10 ammonia-containing water the outside for flowing to hollow-fibre membrane, while making pH be less than 2
The adverse current of sulfuric acid solution flows to the inner side of hollow-fibre membrane, so as to remove and reclaim the ammonia in waste water.The ammonia of gasification and hollow fibre
The sulfuric acid contact of flowing on the inside of film is tieed up, and is reclaimed with ammonium sulfate.
Using gas-liquid separation membrane method can with simple equipment economy Ammonia-Containing Wastewater Treatment to produce with sulfuric acid
The recycling ammonia of ammonium salt solution.However, these methods the disadvantage is that, when the concentration of ammonium sulfate in ammonium sulfate is low,
In order to recycle or reclaim as valuable commodity, the further concentration of ammonium sulfate is necessary.Particularly, concentration is small
Valuable commodity are cannot function as in 25 mass % ammonium sulfate to handle and can be as offal treatment.Therefore, it is such
Ammonium sulfate needs further to concentrate by processing methods such as reverse osmosis membrane (RO films) processing and ion exchange resin treatments.
Quotation list
Patent document
Patent document 1：JP 3987896 B
Patent document 2：JP 2011-153043 A
Patent document 3：JP 3272859 B
Patent document 4：JP 3240694 B
Patent document 5：JP 2013-202475 A
The content of the invention
Problems to be solved by the invention
The purpose of the present invention is except deammoniation and to make sulfuric acid solution with removing from ammonia-containing water using gas-liquid separation membrane
The ammonia gone is contacted using in the processing of the ammonia-containing water reclaimed as ammonium sulfate, for example, obtaining has more than 25 mass %
High concentration ammonium sulfate.
The solution used to solve the problem
According to an aspect of the present invention, ammonia-containing water processing equipment is included with gas-liquid separation membrane, with gas-liquid separation membrane
The first liquid room and removed with the ammonia of the second liquid room of another surface contiguous setting of gas-liquid separation membrane that one surface contiguous is set
Unit；It is configured to open and close the entrance side valve of the sulfuric acid solution entrance side of the second liquid room liquid room, and is configured to beat on and off
Close the outlet side valve of the sulfuric acid solution outlet side of the second liquid room；Stop flowing of the sulfuric acid solution by the second liquid room with being configured to work as
When close entrance side valve and outlet side valve controller.Ammonia removing unit removes deammoniation simultaneously from the ammonia-containing water for flowing through the first liquid room
And make to contact with the ammonia removed with the sulfuric acid solution that ammonia-containing water counterflows through the second liquid room, so as to be reclaimed with ammonium sulfate
Ammonia.
Preferably, ammonia-containing water processing equipment further comprises being configured to remove entrance side valve and exports the pressure between side valve
The pressure relief unit of power, and controller is configured to close entrance side when stopping sulfuric acid solution by the flowing of the second liquid room
Valve and outlet side valve and starting pressure releasing unit.
Preferably, ammonia-containing water processing equipment include being configured to when stopping sulfuric acid solution by the flowing of the second liquid room from
The processing water circulation unit of the lateral entrance side circulation in outlet of the processing water that ammonia removing unit is obtained from the first liquid room.
Preferably, ammonia-containing water processing equipment includes the sulfuric acid for being configured to adjust the sulfuric acid solution that supply to the second liquid room
The sulfuric acid adding device of concentration, the sulfuric acid concentration for the sulfuric acid solution to be added from sulfuric acid adding device is more than 50 mass %.
Preferably, the outlet of ammonium sulfate from second liquid room of the ammonia-containing water processing equipment including being configured to reclaim is lateral
The ammonium sulfate cycling element of entrance side circulation；With the sulphur for being configured to measure the concentration of ammonium sulfate in the ammonium sulfate of recovery
Sour ammonium concentration measuring unit, when the ammonium sulfate concentrations of measurement is more than predetermined values, takes out the ammonium sulfate reclaimed.
Preferably, in ammonia-containing water processing equipment, the temperature of the ammonia-containing water in ammonia removing unit is at 30 to 55 DEG C
In the range of.
Preferably, in ammonia-containing water processing equipment, the pH of the ammonia-containing water in ammonia removing unit is more than 11.
Preferably, ammonia-containing water processing equipment further comprises being configured to removing before ammonia-containing water flows through the first liquid room
The oxidant removing unit of the oxidant included in ammonia-containing water.
According to another aspect of the present invention, the processing method of ammonia-containing water includes following ammonia removing step：From flow through including
Gas-liquid separation membrane, the first liquid room with the surface contiguous setting of gas-liquid separation membrane and another surface neighbour with gas-liquid separation membrane
Deammoniation is removed in the ammonia-containing water for the first liquid room for connecing the ammonia removing unit of the second liquid room of setting, and is made and ammonia-containing water adverse current
The sulfuric acid solution for flowing through the second liquid room is contacted with the ammonia removed, so as to reclaim ammonia as ammonium sulfate.When stopping, sulfuric acid is molten
When liquid is by the flowing of the second liquid room, closed configuration is opens and closes the entrance side valve of the sulfuric acid solution entrance side of the second liquid room
With the outlet side valve for the sulfuric acid solution outlet side for being configured to open and close the second liquid room.
Preferably, in the processing method of ammonia-containing water, when flowing of the stopping sulfuric acid solution by the second liquid room, close
It is configured to open and close the entrance side valve of the sulfuric acid solution entrance side of the second liquid room and is configured to open and close the second liquid room
Sulfuric acid solution outlet side outlet side valve, and start be configured to remove entrance side valve and export side valve between pressure pressure
Power releasing unit.
Preferably, the processing method of ammonia-containing water includes following processing water circulation step：When stopping sulfuric acid solution by the
During the flowing of two liquid rooms, circulate the lateral entrance side in outlet of the processing water from the first liquid room that are obtained by ammonia removing step.
Preferably, in the processing method of ammonia-containing water, to be supplied into the sulfuric acid solution of the second liquid room for adjusting
Sulfuric acid concentration and the sulfuric acid concentration in the sulfuric acid solution that adds is more than 50 mass %.
Preferably, in the processing method of ammonia-containing water, make the outlet of ammonium sulfate from the second liquid room of recovery lateral
Entrance side is circulated, and measures the ammonium sulfate concentrations in the ammonium sulfate reclaimed, and when the ammonium sulfate concentrations of measurement are predetermined value
During the above, the ammonium sulfate reclaimed is taken out.
Preferably, in the processing method of ammonia-containing water, the temperature of the ammonia-containing water in ammonia removing step is at 30 to 55 DEG C
In the range of.
Preferably, in the processing method of ammonia-containing water, the pH of the ammonia-containing water in ammonia removing step is more than 11.
Preferably, the processing method of ammonia-containing water, which further comprises removing before ammonia-containing water flows through the first liquid room, contains ammonia
The oxidant removing step of the oxidant included in waste water.
The effect of invention
According to the present invention, except deammoniation and make sulfuric acid solution and the ammonia removed from ammonia-containing water using gas-liquid separation membrane
Contact can obtain the ammonium sulfate of such as more than 25 mass % high concentration using in the method for reclaiming ammonia as ammonium sulfate
Solution.
Brief description of the drawings
[Fig. 1] Fig. 1 is the knot for the example for schematically showing the ammonia-containing water processing equipment according to embodiment of the present invention
The figure of structure.
[Fig. 2] Fig. 2 is another example for schematically showing the ammonia-containing water processing equipment according to embodiment of the present invention
Structure figure.
Embodiment
Embodiment of the present invention will be described.The present embodiment is only to implement the example of the present invention, and the present invention is not limited
In these embodiments.
Fig. 1 schematically shows the example of the ammonia-containing water processing equipment according to embodiment of the present invention, will describe its knot
Structure.Ammonia-containing water processing equipment 1 includes the ammonia removing device 16 as ammonia removing unit, and as ammonium sulfate circulator
Circulating slot 18.Ammonia-containing water processing equipment 1 may further include raw water groove 10, the heat exchanger 12 as heater, pH and adjust
Save groove 14, sulfuric acid storage tank 20 and pH adjusting agent storage tank 22 as sulfuric acid adding device.
Ammonia removing device 16 includes gas-liquid separation membrane 26 and the first liquid room 24a and the second liquid that are divided by gas-liquid separation membrane 26
Room 24b.Gas-liquid separation membrane 26 be for example, do not allow liquid by but allow the hollow-fibre membrane that passes through of gaseous ammonia.First liquid room
24a and a surface contiguous of gas-liquid separation membrane 26 are set and the second liquid room 24b and another surface contiguous of gas-liquid separation membrane 26
Set.Ammonia-containing water is supplied to the first liquid room 24a and sulfuric acid solution and supplied to the second liquid room 24b.
In the ammonia-containing water processing equipment 1 shown in Fig. 1, raw water pipe arrangement 30 is connected with the raw water entrance of raw water groove 10.It is former
The outlet of tank 10 and the raw water entrance of heat exchanger 12 are connected to each other by raw water supplying tubing 32, and heat exchanger 12
Raw water outlet and the entrances of pH regulating tanks 14 be connected to each other by raw water supplying tubing 34.The outlet of pH regulating tanks 14 is with setting
The entrance put in the first liquid room 24a of the first side of ammonia removing device 16 adjusts water pipe arrangement 36 by pH and connected.It is arranged on ammonia
First liquid room 24a of the second side of removing device 16 outlet is with the processing water inlet of heat exchanger 12 by handling water circulation
Pipe arrangement 38 is connected, and processing water out and the raw water groove 10 of heat exchanger 12 processing water inlet via valve 62 by handling water
Circulation pipe arrangement 40 is connected.Between the processing water out and valve 62 of heat exchanger 12, processing water discharge pipe arrangement 54 is via processing water
Valve 64 is taken out to connect.Second liquid room 24b of second side of the outlet of circulating slot 18 with being arranged on ammonia removing device 16 entrance
Pipe arrangement 42 is circulated via entrance side valve 56 by ammonium sulfate to connect, and the second liquid room 24b outlet is removed with being arranged on ammonia
Go the entrance of the circulating slot 18 of the first side of device 16 to circulate pipe arrangement 44 by ammonium sulfate via outlet side valve 58 to connect.
Reclaim the conveying end that ammonium sulfate pipe arrangement 50 is connected to circulating slot 18.The outlet of sulfuric acid storage tank 20 is connected by sulfuric acid pipe arrangement 46
To circulating slot 18.The outlet of pH adjusting agent storage tank 22 is connected to pH regulating tanks 14 by pH adjusting agent pipe arrangement 48.Ammonium sulfate concentrations
Measurement apparatus 66 can be attached to circulating slot 18.
By operation of the description according to the processing method and ammonia-containing water processing equipment 1 of the ammonia-containing water of the present embodiment.
It is stored in as needed in raw water groove 10 by raw water pipe arrangement 30 as the ammonia-containing water of raw water, then passes through raw water
Supplying tubing 32 is transported to heat exchanger 12 as needed.As raw water ammonia-containing water as needed in the heat exchanger 12 with
The processing water for being fed through handling water pipe arrangement 38 occurs heat exchange and heated (heating process).If the temperature of ammonia-containing water is pre-
Definite value, then need not carry out heating stepses.
Ammonia-containing water heated as needed is defeated as needed by raw water supplying tubing 34 in heat exchanger 12
Deliver to pH regulating tanks 14.In pH regulating tanks 14, supplied as needed from pH adjusting agent storage tank 22 by pH adjusting agent pipe arrangement 48
To pH adjusting agent, the pH of ammonia-containing water is adjusted to predetermined value (pH adjusts process).The pH adjusting agent of process is adjusted for pH
For for example, such as sodium hydroxide solution alkali or such as hydrochloric acid acid.During pH regulation processes, ammonia-containing water is preferably by making to contain
Ammonium ion acid dissociation in ammonia waste water is adjusted pH to more than 11 to improve the ammonia in aftermentioned ammonia removal step with forming ammonia
Removal rate.In view of the influence to film and piping material, for example, more preferably ammonia-containing water is adjusted to pH11-12 scope.
If the pH of ammonia-containing water is predetermined value, pH regulation processes need not be carried out.
The pH regulation water that experienced pH regulations as needed removes dress by pH regulation water pipe arrangement 36 from ammonia is arranged on
The entrance for putting 16 the first side is delivered to the first liquid room 24a.In ammonia removing device 16, prevent liquid by and allow ammonia
The gas-liquid separation membrane 26 passed through is used to from ammonia-containing water remove deammoniation.Therefrom except the processing water of deammoniation is removed from ammonia is arranged on
The first liquid room 24a of the second side of device 16 outlet is gone to be delivered to heat exchanger 12 by handling water pipe arrangement 38.The opposing party
Face, in the case where entrance side valve 56 and outlet side valve 58 are opened, supplies and stores from sulfuric acid storage tank 20 by sulfuric acid pipe arrangement 46
The sulfuric acid solution existed in circulating slot 18 circulates pipe arrangement 42 from the second end for being arranged on ammonia removing device 16 by ammonium sulfate
The entrance of side is supplied to the second liquid room 24b.In the second liquid room 24b, make the ammonia-containing water in sulfuric acid solution and the first liquid room 24a
Counter-current flow.For example, making ammonia-containing water be flowed in the outside (the first liquid room 24a) of hollow-fibre membrane and make sulfuric acid solution in
Inner side (the second liquid room 24b) flowing of hollow fiber film.Ammonia and the second liquid room of ammonia removing device 16 by gas-liquid separation membrane 26
The sulfuric acid solution contact of flowing in 24b is so as to generate ammonium sulfate (ammonia removal step).
Be delivered to the processing water of heat exchanger 12 as needed in the heat exchanger 12 with it is defeated by raw water supplying tubing 32
Deliver to ammonia-containing water experience heat exchange therein and cool down (refrigerating work procedure).It is cold in the case where valve 62 is closed and valve 64 is opened
But processing water is discharged by handling water discharge pipe arrangement 54.
By the ammonium sulfate generated in the second liquid room 24b of ammonia removing device 16 in the state of being dissolved in sulfuric acid solution,
Pipe arrangement 44 is circulated from the second liquid room 24b of the first side for being arranged on ammonia removing device 16 outlet by ammonium sulfate to convey
To circulating slot 18.Sulfuric acid solution circulates the circulation of pipe arrangement 42 and 44 until the concentration of ammonium sulfate by circulating slot 18 and ammonium sulfate
Reach predetermined value (ammonium sulfate circulating process).Now, sulfuric acid solution is supplied from sulfuric acid storage tank 20 by sulfuric acid pipe arrangement 46
To circulating slot 18, the pH of recycle sulfuric acid solution is adjusted to predetermined value.Once the ammonium sulfate of the recovery in recycle sulfuric acid solution
Concentration reach more than predetermined value, just from circulating slot 18 by reclaim ammonium sulfate pipe arrangement 50 discharge ammonium sulfate be used as recovery sulphur
Acid ammonium solution.
Present inventor has performed studying and find, when using gas-liquid separation membrane Ammonia-Containing Wastewater Treatment, not only ammonia but also
Vapor movement passes through gas-liquid separation membrane.The vapor can dilute recovery ammonium sulfate, make the ammonium sulfate in ammonium sulfate
Concentration decreases below the level of predetermined value, and it is less than the value predicted.Especially it is clear that there is relative lower concentration example in processing
When such as from about 3, below 000mg/L ammonia-containing water, in order to obtain ammonium sulfates more than 25 mass %, it is impossible to ignore such water
The movement of steam.
The present inventor further study vapor moving and indicating through gas-liquid separation membrane, contain ammonia even in stopping
During the flowing that waste water passes through gas-liquid separation membrane, vapor still moves through gas-liquid separation membrane and reduces the dense of ammonium sulfate
Degree.Specifically, in the equipment shown in Fig. 1, for example, flowing and the shape when stopping ammonia-containing water by gas-liquid separation membrane 26
When state maintains about half a day, or when the water level of raw water groove 10 is reduced and stops the flowing of ammonia-containing water, vapor passes through gas
Liquid seperation film 26 and the water level for continuously improving the ammonium sulfate in the circulating slot 18 for storing ammonium sulfate, so as to reduce sulphur
The concentration of sour ammonium.
Thus the present inventor is removing equipment of the deammoniation to reclaim ammonium sulfate using gas-liquid separation membrane from ammonia-containing water
In, flowing through the downstream of gas-liquid separation membrane 26, i.e. the entrance side and outlet side of the second liquid room 24b sulfuric acid solution are set respectively
Entrance side valve 56 and outlet side valve 58 are put.Then the inventors discovered that, by when stop sulfuric acid solution passing through the second liquid room 24b
Flowing when inlet porting side valve 56 and outlet both side valves 58 be closed, even if vapor movement passes through gas-liquid separation
Film 26, also suppresses vapor and circulates movement of the pipe arrangement 42 and 44 to circulating slot 18 by ammonium sulfate.Thus, it is possible to obtain such as
The ammonium sulfate of more than 25 mass % high concentration.Entrance side valve 56 and outlet side valve 58 can pass through unshowned controller
To open or close.When the water level of raw water groove 10 is low or the water level of circulating slot 18 is high, " standby " state can be set as.That is,
Sulfuric acid solution can be stopped by the second liquid room 24b flowing and entrance side valve 56 and outlet both side valves 58 can be closed,
So as to prevent vapor from flowing into ammonium sulfate so as to reduce the concentration of ammonium sulfate.
Preferably, ammonia-containing water processing equipment 1 is set to " standby " state and blows out the before restarting operation
The sulfuric acid solution accumulated in two liquid room 24b.This also suppresses the reduction of the concentration of ammonium sulfate after operation restarting.
Even if the research of the present inventor is demonstrated that when closing entrance side valve 56 and outlet side valve 58, in sulfuric acid solution
In the case of being stopped by the second liquid room 24b flowing, in the downstream of gas-liquid separation membrane 26, i.e. remaining in the second liquid room 24b
Ammonium sulfate concentration, for example, significantly reducing after several days and the pressure between entrance side valve 56 and outlet side valve 58
Power rises 0.05-0.4MPa.Therefore, shown in ammonia-containing water processing equipment 3 as shown in Figure 2, for example, entrance side valve 56 with
It is used as between second liquid room 24b entrance via the pressure release connection of pipe arrangement 52 between release entrance side valve 56 and outlet side valve 58
Pressure pressure relief unit pressure relief valve 60.Then when flowing of the stopping sulfuric acid solution by the second liquid room 24b
Control device is to close entrance side valve 56 and outlet side valve 58 and open pressure relief valve 60.Even if when operation stops for a long time
When, the structure can also suppress the rising of the downstream lateral pressure of gas-liquid separation membrane 26, so as to prevent from applying to gas-liquid separation membrane 26
Overvoltage.Pressure, which discharges pipe arrangement 52 and pressure relief valve 60, can be arranged between the second liquid room 24b outlet and outlet side valve 58.
Entrance side valve 56, outlet side valve 58 and pressure relief valve 60 can be opened or closed by unshowned controller.
When flowing of the stopping sulfuric acid solution by the second liquid room 24b, in the case where valve 62 is opened and valve 64 is closed, place
Managing water can be from the first liquid room 24a outlet side by using the processing water circulation pipe arrangement 38 and 40 and original for dealing with water circulation unit
Tank 10 is circulated (processing water circulation process) to the first liquid room 24a entrance side.Water is handled from the upstream side of gas-liquid separation membrane 26,
That is, the operation circulated from the first liquid room 24a to raw water groove 10 makes to give up containing ammonia as raw water by being incubated or heating ammonia-containing water
The temperature of water is maintained within a predetermined range, so as to so that the processing of operation after rebooting is stable.
Ammonia-containing water to be processed includes, for example, from the electronic industry such as such as semiconductor factory factory, chemical plant and steam power plant
The ammonia-containing water discharged Deng factory.
Such as in the ammonia-containing water discharged from such as semiconductor factory's electronic industry factory, when ammonia-containing water includes such as peroxide
When changing the oxidants such as hydrogen, it can be handled in the leading portion of ammonia removing device 16 for example, by the activated carbon as oxidant removing unit
Equipment removes oxidant (oxidant removal step).The process can prevent as caused by the oxidants such as hydrogen peroxide in ammonia
The reduction of ammonia removal rate and the deterioration of gas-liquid separation membrane during removal step.
Ammonia density in ammonia-containing water as raw water is not particularly limited.Preferably, it is dense in order to obtain ammonium sulfate
Degree is adjusted to more than 25 mass % recovery ammonium sulfate, while the ammonia in the precipitation in order to prevent ammonium sulfate, ammonia-containing water
Concentration is preferably controlled between 900mg/L and 2,200mg/L.
, can be for example, ammonia removing device 16 when the ammonia density in ammonia-containing water low (for example, less than 900mg/L)
Leading portion concentrates ammonia by reverse osmosis membrane processing etc..Further, for concentrated vitriol ammonium, for example, making to contain by handling low concentration
The ammonium sulfate of ammonia waste water generation returns to raw water groove 10 from circulating slot 18, further to carry out ammonia treatment.
Preferably, raw water is heated between 30 and 55 DEG C using such as grade heater of heat exchanger 12, preferably 35 with
Between 55 DEG C, and ammonia-containing water is set to be delivered to ammonia removing device 16.When the temperature of raw water is less than 30 DEG C, containing ammonia
Ammonia in waste water is difficult to gasify, and the removal rate of ammonia tends to reduction in ammonia removing device 16., can be by such as instead of heat exchanger 12
The device that heater etc. can be heated is arranged at least one of raw water groove 10, raw water pipe arrangement 30 and raw water supplying tubing 32,
So as to heat raw water.
During ammonia removal step, from the viewpoint of ammonia removal rate, the pH of ammonia-containing water to be processed is preferably more than 11.
If the ammonia that the pH of ammonia-containing water to be processed is less than in 11, ammonia-containing water is difficult to gasify, so that the removal rate tendency of ammonia
In reduction.
Gas-liquid separation membrane 26 is not particularly limited, if its do not allow liquid by and allow gaseous ammonia pass through i.e.
Can.Gas-liquid separation membrane 26 is for example, hydrophobic porous hollow-fibre membrane.Can use a diameter of about 300 μm of such as doughnut,
It is the hollow-fibre membrane of about 40 to about 50% with (average) porosity that emptying aperture size, which is about 0.03 μm,.The gas included in ammonia-containing water
State ammonia is removed by the gas-liquid separation membrane 26 with said structure and from ammonia-containing water.
It is preferred that causing the pH of recycle sulfuric acid solution to maintain less than 2 from the injection sulfuric acid solution of sulfuric acid storage tank 20, for example, in 1-
In the range of 2, and preferably in the range of 1.5-2.The pH of recycle sulfuric acid solution can reduce ammonia removal rate for more than 2.
The sulfuric acid solution to be added from sulfuric acid storage tank 20 preferably has concentration as high as possible., be from sulphur in terms of processing
The sulfuric acid concentration for the sulfuric acid solution that sour storage tank 20 is added is preferably more than 50 mass %.
As described above, for example, when the concentration of the recovery ammonium sulfate in recycle sulfuric acid solution reaches more than predetermined value, such as 25 matter
When measuring more than %, ammonium sulfate is reclaimed as ammonium sulfate is reclaimed and is discharged from circulating slot 18 by ammonium sulfate pipe arrangement 50.
The concentration of ammonium sulfate in recycle sulfuric acid solution can use such as densimeter and densimeter to be used as ammonium sulfate concentrations
The ammonium sulfate concentrations measurement apparatus 66 of measuring unit is measured.When the concentration of the ammonium sulfate of measurement reaches more than predetermined concentration, such as
During more than 25 mass % (for example, when densimeter measured value indicate 25 mass % ammonium sulfate proportion be about 1.14 with
When upper), it can be used as recovery ammonium sulfate to collect ammonium sulfate from circulating slot 18 by ammonium sulfate pipe arrangement 50 automatically.And
In the example shown in Fig. 1 and 2, ammonium sulfate concentrations measurement apparatus 66 is arranged in circulating slot 18, ammonium sulfate concentrations measurement apparatus
66 can be arranged in ammonium sulfate circulation pipe arrangement 42.In addition, making ammonium sulfate be not easy the concentration (example separated out to obtain
Such as, below 40 mass %), the device that can further set the measurement concentration based on ammonium sulfate to automatically feed water to dilute.
For example, when gas-liquid separation membrane 26 is by the pollution such as metallic salt and the reduction of ammonia removal rate, or in order to anti-
The only reduction of ammonia removal rate, can implement acid cleaning (acid cleaning process) in the predetermined time to gas-liquid separation membrane 26.For example, entering
One step sets sour storage tank so that acid solution adjusts water pipe arrangement 36 by pH supplies the first liquid room 24a to ammonia removing device 16 with clear
Clean gas-liquid separation membrane 26.Selectively, the sulfuric acid solution from sulfuric acid storage tank 20 can be partly fed to the first liquid room 24a.
Such as sulfuric acid, hydrochloric acid and citric acid acid solution can be used for acid cleaning process.
The present invention will more specifically be described by embodiment and comparative example below.However, implementing the invention is not restricted to following
Example.
The Ammonia-Containing Wastewater Treatment under the conditions of tests below.
[experimental condition]
The gas-liquid separation membrane used：Polypropylene porous hollow fiber membrane component
Membrane area：1.4m2
Water-flowing amount：0.0145m3/h
Water temperature：30℃
Ammonia-containing water pH：More than 12
Sour side pH：Less than 2
The ammonia-containing water for making ammonia density be 1796mg/L flows through the upstream side (the first liquid room) 6 hours of gas-liquid separation membrane.On
The flow of trip side (the first liquid room) and downstream (the second liquid room) is respectively set as 14.5L/h and 19.0L/h.Make to flow through the first liquid
The ammonia-containing water of room by adding sodium hydroxide solution with more than 12 pH, and by by 50 mass % sulfuric acid solution
The pH for flowing through the solution of the second liquid room is set to maintain less than 2 added to the 14 mass % at initial stage ammonium sulfate.
Embodiment 1
After ammonia-containing water is flowed 6 hours with processing, the flowing of ammonia-containing water and the flowing of sulfuric acid solution is set to stop 17
Hour, and control the entrance side valve of entrance side for opening or closing sulfuric acid solution and for opening and closing outlet side
Side valve is exported to close.
Comparative example 1
After ammonia-containing water is flowed 6 hours with processing, the flowing of ammonia-containing water and the flowing of sulfuric acid solution is set to stop 17
Hour, and open entrance side valve and outlet both side valves.
(experimental result)
Experimental result is shown in table 1.
[table 1]
| Raw water | Embodiment 1 | Comparative example 1 | |
| NH4 +[mg/L] | 1,796 | 403 | 403 |
| Ammonium sulfate [quality %] | 14.4 | 29.7 | 22.5 |
In embodiment 1, ammonium sulfate can stably be reclaimed with concentration more than 25 mass %；And in comparative example 1
In, the concentration of final ammonium sulfate is less than 25 mass % (22.5 mass %).Think in comparative example 1, due at 17 hours
Entrance side valve and outlet both side valves are opened during stopping so that vapor is through gas-liquid separation membrane so as to dilute in circulating slot
Ammonium sulfate, thus reduces the concentration of ammonium sulfate.
Description of reference numerals
1st, 3 ammonia-containing water processing equipment, 10 raw water grooves, 12 heat exchangers, 14 pH regulating tanks, 16 ammonia removing devices,
18 circulating slots, 20 sulfuric acid storage tanks, 22 pH adjusting agent storage tanks, the first liquid of 24a room, the second liquid of 24b room, 26 gas-liquid separations
Film, 30 raw water pipe arrangements, 32,34 raw water supplying tubings, 36 pH regulation water pipe arrangements, 38,40 processing water circulation pipe arrangements, 42,44
Ammonium sulfate circulates pipe arrangement, 46 sulfuric acid pipe arrangements, 48 pH adjusting agent pipe arrangements, 50 recovery ammonium sulfate pipe arrangements, 52 pressure
Discharge pipe arrangement, 54 processing water discharge pipe arrangements, 56 entrance side valves, 58 outlet side valves, 60 pressure relief valves, 62 valves, 64 processing
Water takes out valve, 66 ammonium sulfate concentrations measurement apparatus.
Claims (10)
1. a kind of ammonia-containing water processing equipment, it includes：
Ammonia removing unit, the ammonia removing unit includes gas-liquid separation membrane, set with a surface contiguous of the gas-liquid separation membrane
The first liquid room for putting and the second liquid room set with another surface contiguous of the gas-liquid separation membrane, the ammonia removing unit is from stream
The sulphur for removing deammoniation and making to counterflow through the second liquid room with the ammonia-containing water is crossed in the ammonia-containing water of the first liquid room
Acid solution is contacted with the ammonia removed, so as to reclaim the ammonia with ammonium sulfate；
Entrance side valve, the entrance side valve is configured to open and close the sulfuric acid solution entrance side of the second liquid room, and outlet
Side valve, the outlet side valve is configured to open and close the sulfuric acid solution outlet side of the second liquid room；With
Controller, it is described that the controller is configured to the closing when flowing of the stopping sulfuric acid solution by the second liquid room
Entrance side valve and the outlet side valve.
2. ammonia-containing water processing equipment according to claim 1, it further comprises：
Pressure relief unit, the pressure relief unit is configured to remove the pressure between the entrance side valve and the outlet side valve
Power,
Wherein described controller is configured to described in closing enter when flowing of the stopping sulfuric acid solution by the second liquid room
Mouthful side valve and the outlet side valve and start the pressure relief unit.
3. ammonia-containing water processing equipment according to claim 1 or 2, it includes：
Water circulation unit is handled, the processing water circulation unit is configured to when the stopping sulfuric acid solution passing through the second liquid room
Flowing when make the outlet lateral entrance side circulation of processing water from the first liquid room that is obtained from the ammonia removing unit.
4. the ammonia-containing water processing equipment according to claim any one of 1-3, it includes：
Sulfuric acid adding device, the sulfuric acid adding device, which is configured to regulation, will supply into the sulfuric acid solution of the second liquid room
Sulfuric acid concentration, wherein
Sulfuric acid concentration in the sulfuric acid solution to be added from the sulfuric acid adding device is more than 50 mass %.
5. the ammonia-containing water processing equipment according to claim any one of 1-4, it includes：
Ammonium sulfate cycling element, the ammonium sulfate cycling element is configured to make the ammonium sulfate of recovery from institute
State the lateral entrance side circulation in outlet of the second liquid room；With
Ammonium sulfate concentrations measuring unit, the ammonium sulfate concentrations measuring unit is configured to measure in the ammonium sulfate of recovery
Ammonium sulfate concentrations, wherein
When the ammonium sulfate concentrations of measurement is more than predetermined values, the ammonium sulfate reclaimed is taken out.
6. the ammonia-containing water processing equipment according to claim any one of 1-5, wherein
The temperature of the ammonia-containing water in the ammonia removing unit is in the range of 30 to 55 DEG C.
7. the ammonia-containing water processing equipment according to claim any one of 1-6, wherein
The pH of the ammonia-containing water in the ammonia removing unit is more than 11.
8. the ammonia-containing water processing equipment according to claim any one of 1-7, it contains oxidant in the ammonia-containing water
In the case of further comprise：
Oxidant removing unit, the oxidant removing unit is configured to before the ammonia-containing water flows through the first liquid room
Remove the oxidant included in the ammonia-containing water.
9. a kind of processing method of ammonia-containing water, it includes：
Ammonia removing step：From the first of the surface contiguous setting flowed through including gas-liquid separation membrane and the gas-liquid separation membrane
First liquid in the ammonia removing unit of liquid room and the second liquid room set with another surface contiguous of the gas-liquid separation membrane
Deammoniation is removed in the ammonia-containing water of room, and makes sulfuric acid solution and removing that the second liquid room is counterflowed through with the ammonia-containing water
The ammonia contact, so as to reclaim ammonia with ammonium sulfate；
Wherein when stopping the sulfuric acid solution by the flowing of the second liquid room, closed configuration is opens and closes described the
The entrance side valve of the sulfuric acid solution entrance side of two liquid rooms and the sulfuric acid solution outlet for being configured to open and close the second liquid room
The outlet side valve of side.
10. the processing method of ammonia-containing water according to claim 9, wherein,
When flowing of the stopping sulfuric acid solution by the second liquid room, closed configuration is opening and closing second liquid
The entrance side valve of the sulfuric acid solution entrance side of room and the sulfuric acid solution for being configured to open and close the second liquid room
The outlet side valve of outlet side, and start the pressure for being configured to remove the pressure between the entrance side valve and the outlet side valve
Releasing unit.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014217268A JP6386338B2 (en) | 2014-10-24 | 2014-10-24 | Ammonia-containing wastewater treatment apparatus and treatment method |
| JP2014-217268 | 2014-10-24 | ||
| PCT/JP2015/069130 WO2016063578A1 (en) | 2014-10-24 | 2015-07-02 | Ammonia-containing wastewater treatment apparatus and treatment method |
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| CN107074591A true CN107074591A (en) | 2017-08-18 |
| CN107074591B CN107074591B (en) | 2020-08-21 |
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| CN201580057627.3A Active CN107074591B (en) | 2014-10-24 | 2015-07-02 | Ammonia-containing wastewater treatment equipment and treatment method |
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| JP (1) | JP6386338B2 (en) |
| CN (1) | CN107074591B (en) |
| SG (1) | SG11201703055XA (en) |
| TW (1) | TWI646056B (en) |
| WO (1) | WO2016063578A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112543803A (en) * | 2018-08-24 | 2021-03-23 | 南沼气技术有限责任公司 | Apparatus and method for neutralizing ammonium sulfate solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6592386B2 (en) * | 2016-03-09 | 2019-10-16 | オルガノ株式会社 | Method and apparatus for treating ammonia-containing wastewater |
| JP6653626B2 (en) * | 2016-06-07 | 2020-02-26 | オルガノ株式会社 | Water treatment method and apparatus, water treatment apparatus modification method, and water treatment apparatus modification kit |
| JP7198394B2 (en) * | 2018-04-24 | 2023-01-04 | 国立大学法人豊橋技術科学大学 | How to remove ammonia |
| KR101997846B1 (en) * | 2018-10-08 | 2019-07-08 | 웅진코웨이엔텍 주식회사 | Ammonia removal system and method using membrane contactor |
| KR102108512B1 (en) * | 2019-09-25 | 2020-05-08 | 코웨이엔텍 주식회사 | Ammonia removal system and method using membrane contactor |
| KR102155238B1 (en) | 2019-09-25 | 2020-09-11 | 코웨이엔텍 주식회사 | Ammonia removal system and method using membrane contactor for sewage reuse |
| CN110697814B (en) * | 2019-09-29 | 2021-09-03 | 赣州腾远钴业新材料股份有限公司 | Ammonia-containing sulfate wastewater treatment system and process |
| KR102325892B1 (en) * | 2021-03-03 | 2021-11-12 | 한수테크니칼서비스(주) | Method for treating waste water containing ammonia |
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| JP5928070B2 (en) * | 2012-03-28 | 2016-06-01 | 住友金属鉱山株式会社 | Method for removing ammonia from wastewater containing ammonia |
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2015
- 2015-07-02 WO PCT/JP2015/069130 patent/WO2016063578A1/en active Application Filing
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| US20100218573A1 (en) * | 2009-02-27 | 2010-09-02 | Victor Van Slyke | System and method for producing an organic based fertilizer and usable water from animal waste |
| US20120315209A1 (en) * | 2011-04-20 | 2012-12-13 | Thermoenergy Corporation | Methods and systems for treating water streams |
| CN102951745A (en) * | 2011-08-19 | 2013-03-06 | 天津荣翔正达环保科技有限责任公司 | Landfill leachate treatment process based on novel ammonia nitrogen removal technology |
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| CN112543803A (en) * | 2018-08-24 | 2021-03-23 | 南沼气技术有限责任公司 | Apparatus and method for neutralizing ammonium sulfate solution |
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| JP2016083609A (en) | 2016-05-19 |
| CN107074591B (en) | 2020-08-21 |
| SG11201703055XA (en) | 2017-05-30 |
| TWI646056B (en) | 2019-01-01 |
| JP6386338B2 (en) | 2018-09-05 |
| WO2016063578A1 (en) | 2016-04-28 |
| TW201619064A (en) | 2016-06-01 |
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