CN101633532A - Nitrogen removal processing method and nitrogen removal processing apparatus - Google Patents

Nitrogen removal processing method and nitrogen removal processing apparatus Download PDF

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Publication number
CN101633532A
CN101633532A CN200910151475A CN200910151475A CN101633532A CN 101633532 A CN101633532 A CN 101633532A CN 200910151475 A CN200910151475 A CN 200910151475A CN 200910151475 A CN200910151475 A CN 200910151475A CN 101633532 A CN101633532 A CN 101633532A
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China
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denitrogenation
hydrogen donor
supplied
water
processed water
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CN101633532B (en
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长谷部吉昭
江口正浩
目黑裕章
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PRGANO CORP
Organo Corp
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PRGANO CORP
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention relates to a nitrogen removal processing method and a nitrogen removal processing apparatus which are a water processing method and a water processing apparatus, makes the processed water flow into a fully mixed type nitrogen removal groove during the processing of the water containing nitrate ions and nitrite ions and makes the nitrification removal bacteria granulate. The nitrogen removal processing method comprises: supplying the processed water to the fully mixed type nitrogen removal groove; supplying a hydrogen donor; and reducing the nitrate ions and nitrite ions contained in the processed water into nitrogen through the nitrification removal bacteria. The nitrogen removal groove is provided with a first nitrogen removal part and a second nitrogen removal part on the rear section of the first nitrogen removal part. At least the hydrogen donor is supplied to the first nitrogen removal part in a way of forming the hydrogen donor concentration difference between the first nitrogen removal part and the second nitrogen removal part.

Description

Denitrifying method and denitrification processing device
Technical field
The present invention relates to by denitrifier the nitrate ion that is contained in the processed water, denitrifying method and the denitrification processing device that nitrite ion is reduced into nitrogen.
Background technology
In recent years, in the field of water treatment, particularly in the field that draining is handled, use mostly and the fouling product qualitative change in the draining is turned to the biochemical water treatment that innoxious substance is handled by the physiologically active that utilizes microorganism.As general biological treatment, though activated sludge process is a main flow, but in common activated sludge process, because the high densityization of the microorganism concn in groove difficulty and can not obtain load than the highland, therefore exist need bigger floor space, biological difficult management and be easy to generate handling property deterioration that expansions (パ Le キ Application グ) wait, need large-scale settling apparatus, problem such as the generation of waste materials amount of excess sludge etc. is more.As the technology that addresses these problems, developed by film carry out the method for the solid-liquid separation of active sludge, the method for handling by the microorganism that adheres to sponge or polymer carrier etc., the higher piece of proportion that utilizes microorganism oneself to be a granulated into, promptly utilize method that particle handles etc.Wherein, use the particulate method owing to the microorganism that can keep volume in groove, the speed of response of per unit volume is fast, and solid-liquid separation is also easy, is therefore paid close attention to.
In the draining that contains nitrogen is handled, be suitable for biochemical water treatment equally.For example, have as the draining processing that contains ammonium-nitrogen, under the aerobic condition, by ammonia oxidizing bacteria and nitrite-oxidizing bacteria etc. with ammonium ion nitrated be after nitrite ion, the nitrate ion, in the anaerobism condition and exist under the condition of hydrogen donor, nitrite ion, nitrate ion are reduced to the method for nitrogen by denitrifier.At this moment, as hydrogen donor,, under the insufficient situation of hydrogen donor, need supply from the outside though can utilize organism that contains in the draining etc.At this moment, hydrogen donor is that supply is decided on the basis with the nitrogen concentration in the draining, and adds hydrogen donor continuously based on this supply.
Wherein, nitrite ion, nitrate ion are being reduced in the denitrogenation processing of nitrogen by denitrifier, except activated sludge process, also have for the concentration that improves denitrifier and make solid-liquid separation add sponge or gelatinous carrier easily, carry out the method for denitrogenation processing.And, also have by denitrifier itself and form the higher piece of proportion by own granulation, promptly form particle, significantly improve the concentration of denitrifier in the groove, carry out the method for denitrogenation processing.In using the treatment process of granular denitrifier, owing to the denitrifier of high density can be remained in the groove, the processing speed of the groove speed of comparing with the treatment process of having added carrier is very fast, owing to not needing carrier, and can cost degradation.In addition, because particulate proportion is higher and sedimentation velocity is very fast, therefore have advantages such as solid-liquid separation is easy.Such particulate forms, with anaerobism methane fermentation, upflow sludge bed reactor (upflow sludge blanket reactor) (USB), sequencing batch reactor (sequencing batch reactor) (SBR) confirms (for example, with reference to patent documentation 1 to 3).
Patent documentation 1: Japanese kokai publication sho 63-258695 communique
Patent documentation 2: Japanese kokai publication hei 1-262996 communique
Patent documentation 3: TOHKEMY 2000-51893 communique
Summary of the invention
(problem that invention will solve)
In sequencing batch reactor, denitrifying tank is complete mixed type, in a denitrifying tank, handles through the contacting of inflow, oxygen supply and the processed water of processed water and denitrifier, the deposition of denitrifier, these four operations of discharge for the treatment of water.But because the inflow of processed water and the discharge for the treatment of water are all carried out with the short period of time, the change of therefore handling flow becomes big, needs big flow to adjust groove in the device.Therefore, though in small-scale device because easy and become favourable device, in being difficult to be applicable to～install on a large scale.And under the situation of streaming sludge bed reactor, though obtain very high processing speed, owing to the denitrifying tank that uses special shape, so equipment cost uprises in the use.And, on the formation of device, owing to can not fully carry out the stirring of denitrifying tank inside, so the pH of the processed water control difficulty that becomes, in containing the processed water of calcium etc., have in the incrustation scale of generation or the particle problems such as savings inorganics.
In order to solve such problem, expectation utilizes the denitrifying tank of the complete mixed type of using at present in most devices, and the device that makes processed water continuously flow into (and discharging continuously) constitutes, but up to the present, the granuloplastic report of the denitrifier in not constituting about such device.
Therefore, the objective of the invention is to, in the nitrate ion that contains in processed water by denitrifier, denitrogenation processing that nitrite ion is reduced into nitrogen, when making processed water flow into denitrifying tank, make the denitrifier granulating.
(technical scheme of technical solution problem)
(1) the invention provides a kind of denitrifying method, when processed water was supplied to denitrifying tank, the supply hydrogen donor was reduced into nitrogen by denitrifier with nitrate ion, the nitrite ion that is contained in the processed water; As described denitrifying tank, the second denitrogenation portion of the first denitrogenation portion and the described first denitrogenation portion back segment is set; Be supplied to the described first denitrogenation portion to major general's hydrogen donor, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
(2) and, in the denitrifying method of described (1), preferably, be supplied to the described first denitrogenation portion to major general's hydrogen donor, making the difference of the Cmin of the peak concentration of the hydrogen donor in the described first denitrogenation portion and the hydrogen donor in the described second denitrogenation portion is more than the 50mgTOC/L.
(3) and, in the denitrifying method of described (2), preferably, the volume of the described second denitrogenation portion of the volumetric ratio of the described first denitrogenation portion is little.
(4) and, in the denitrifying method of described (1) or (2), preferably, hydrogen donor is supplied to the described first denitrogenation portion off and on.
(5) and, in the denitrifying method of described (1) or (2), preferably, concentration with respect to nitrate ion, nitrite ion, supply with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of described benchmark value is supplied to the first supply operation of the described first denitrogenation portion and will be supplied to the second supply operation of the described second denitrogenation portion more than the hydrogen donor of the amount of described benchmark value, and hydrogen donor is supplied to the described first denitrogenation portion.
(6) and, in the denitrifying method of described (1), preferably, the described first denitrogenation portion is a plurality of grooves.
(7) and, in the denitrifying method of described (1), preferably, the described second denitrogenation portion is a plurality of grooves.
(8) and, the invention provides a kind of denitrification processing device, comprising: denitrifying tank, processed water is supplied to the processed water feeding mechanism of described denitrifying tank and the hydrogen donor feeding mechanism that hydrogen donor is supplied to described denitrifying tank; In described denitrifying tank, nitrate ion, the nitrite ion that contains in the processed water is reduced into nitrogen by denitrifier; The second denitrogenation portion that described denitrifying tank has the first denitrogenation portion and is arranged on the back segment of the described first denitrogenation portion; Described hydrogen donor feeding mechanism to major general's hydrogen donor is supplied to the described first denitrogenation portion, makes in the described first denitrogenation portion and formation hydrogen donor concentration difference between in the described second denitrogenation portion.
(9) the invention provides a kind of denitrifying method, when processed water is supplied to denitrogenation portion, the supply hydrogen donor, by denitrifier with the nitrate ion that is contained in the processed water, nitrite ion is reduced into nitrogen, described denitrifying method is characterised in that, as described denitrogenation portion, the first denitrogenation portion and the second denitrogenation portion are set, the part of the reaction solution in the described second denitrogenation portion is supplied to the described first denitrogenation portion, and be supplied to the described first denitrogenation portion to major general's hydrogen donor, and return to the described second denitrogenation portion, make in the described first denitrogenation portion and formation hydrogen donor concentration difference between in the described second denitrogenation portion.
(10) and, in the denitrifying method of described (9), preferably, the difference of the Cmin of the hydrogen donor in the peak concentration of the hydrogen donor in the described first denitrogenation portion and the described second denitrogenation portion is more than the 50mgTOC/L.
(11) and, in the denitrifying method of described (9), preferably, when described processed water being supplied to the described second denitrogenation portion and hydrogen donor is supplied to the described first denitrogenation portion, supply contains the water of nitrate ion, nitrite ion.
(12) and, in the denitrifying method of described (11), preferably, the described water that contains nitrate ion, nitrite ion is to be supplied to the processed water ramose water of the described second denitrogenation portion.
(13) and, in the denitrifying method of described (9) or (10), preferably, the supply hydrogen donor is off and on to the described first denitrogenation portion.
(14) and, in the denitrifying method of described (9) or (10), preferably, concentration with respect to nitrate ion, nitrite ion, supply with the needed hydrogen donor of denitrogenation processing is a benchmark, to described first denitrogenation portion supply hydrogen donor, supply the first supply operation and the supply of the hydrogen donor of the amount that is less than described benchmark value by combination and carry out more than the second supply operation of the hydrogen donor of the amount of described benchmark value.
(15) and, the invention provides a kind of denitrification processing device, comprising: denitrogenation portion, processed water is supplied to the processed water feeding mechanism of described denitrogenation portion and the hydrogen donor feeding mechanism that hydrogen donor is supplied to described denitrogenation portion; The nitrate ion, the nitrite ion that contain in processed water by denitrifier in described denitrogenation portion are reduced into nitrogen; Described denitrification processing device is characterised in that, described denitrogenation portion has the first denitrogenation portion and the second denitrogenation portion, has a part with the reaction solution in the described second denitrogenation portion and is supplied to the reaction solution feeding mechanism of the described first denitrogenation portion and the reaction solution that the reaction solution in the described first denitrogenation portion sends back to the described second denitrogenation portion is returned device; By described reaction solution feeding mechanism the part of the reaction solution in the described second denitrogenation portion is supplied to the described first denitrogenation portion, and be supplied to the described first denitrogenation portion by described hydrogen donor feeding mechanism to major general's hydrogen donor, and return device by described reaction solution the reaction solution in the described first denitrogenation portion is sent back to the described second denitrogenation portion, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
(16) and, the invention provides a kind of treatment process of nitrogenous water, it comprises: nitrated operation is oxidized to nitric acid or nitrous acid with the ammonium ion in the processed water; And the denitrogenation operation, when processed water is supplied to denitrifying tank, supply hydrogen donor, and nitrate ion or the nitrite ion that contains in the processed water is reduced into nitrogen by denitrifier; In described denitrogenation operation, hydrogen donor is supplied to described denitrifying tank, make the concentration changes with time of the hydrogen donor in the described denitrifying tank.
(17) and, in the treatment process of the nitrogenous water of described (16), preferably, the peak concentration of the hydrogen donor in the described denitrifying tank and the difference of Cmin are more than the 50mgTOC/L.
(18) and, in the treatment process of the nitrogenous water of described (16) or (17), preferably, hydrogen donor is supplied to described denitrifying tank off and on.
(19) and, in the treatment process of the nitrogenous water of described (16) or (17), preferably, concentration with respect to nitrate ion, nitrite ion, supply with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of described benchmark value is supplied to the first supply operation of described denitrifying tank and will be supplied to the second supply operation of described denitrifying tank more than the hydrogen donor of the amount of described benchmark value, and hydrogen donor is supplied to described denitrifying tank.
(20) and, the invention provides a kind of treatment process of nitrogenous water, comprising: nitrated operation is oxidized to nitric acid or nitrous acid with the ammonium ion in the processed water; And the denitrogenation operation, when processed water is supplied to denitrifying tank, supply hydrogen donor, and nitrate ion or the nitrite ion that contains in the processed water is reduced into nitrogen by denitrifier; As described denitrifying tank, the first denitrogenation portion with at least more than one groove is set and at the back segment of the described first denitrogenation portion and have the second denitrogenation portion of at least more than one groove; Be supplied to the described first denitrogenation portion to major general's hydrogen donor, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
(21) and, in the treatment process of nitrogenous water described (20), preferably be supplied to the described first denitrogenation portion to major general's hydrogen donor, making the difference of the Cmin of the peak concentration of the hydrogen donor in the described first denitrogenation portion and the hydrogen donor in the described second denitrogenation portion is more than the 50mgTOC/L.
(22) and, in the treatment process of the nitrogenous water described (20), preferably, the volume of the described second denitrogenation portion of the volumetric ratio of the described first denitrogenation portion is little.
(23) and, described (20) or the treatment process of the nitrogenous water of (21) in, preferably, hydrogen donor is supplied to the described first denitrogenation portion off and on.
(24) and, described (16) or the treatment process of the nitrogenous water of (20) in, preferably, the mud after the described denitrogenation operation is sent back to described nitrated operation.
(25) and, in the treatment process of nitrogenous water described (24), preferably, before being included in described nitrated operation, the organism that carries out processed water is handled or the treatment process of denitrogenation processing, and the mud after the described denitrogenation operation is sent back in described nitrated operation, the described treatment process at least one.
(effect of invention)
According to the present invention, can when being flowed into denitrifying tank, processed water make the denitrifier granulating, miniaturization and cost degradation that can implement device.
Description of drawings
Fig. 1 is the summary pie graph of an example that the water treatment device of present embodiment is shown.
Fig. 2 is the mode chart of an example of formation that the nitrogen rejection facility of present embodiment is shown.
Fig. 3 is the mode chart of an example that the formation of the nitrogen rejection facility that other embodiments of the present invention relate to is shown.
Fig. 4 is the mode chart of an example that the formation of the nitrogen rejection facility that other embodiments of the present invention relate to is shown.
Fig. 5 is the mode chart of an example that the formation of the nitrogen rejection facility that other embodiments of the present invention relate to is shown.
Fig. 6 is the mode chart of an example that the formation of the nitrogen rejection facility that other embodiments of the present invention relate to is shown.
Fig. 7 is the mode chart of an example that the formation of the nitrogen rejection facility that other embodiments of the present invention relate to is shown.
Fig. 8 is the mode chart of an example that the formation of the nitrogen rejection facility that other embodiments of the present invention relate to is shown.
Fig. 9 is the summary pie graph of an example that the treatment process of nitrogenous water is shown.
Figure 10 is the summary pie graph of an example that the treatment process of nitrogenous water is shown.
Figure 11 is the summary pie graph of an example that the treatment process of nitrogenous water is shown.
Figure 12 is the summary pie graph of an example that the treatment process of nitrogenous water is shown.
Figure 13 is the summary pie graph of an example that the treatment process of nitrogenous water is shown.
Figure 14 is the summary pie graph of an example that the treatment process of nitrogenous water is shown.
Figure 15 is the figure that illustrates in the test of embodiment 1 with respect to through the MLSS change in concentration of fate.
Figure 16 illustrates in the test of embodiment 1 figure that changes with respect to the processing speed through the denitrogenation processing of fate.
Figure 17 illustrates in the test of embodiment 1 figure that passes with respect to through the nitrate ion concentration of the treating water of fate.
Figure 18 illustrates the figure that changes with respect to the SVI through fate in the test of embodiment 1.
Figure 19 is the figure that illustrates in the test of embodiment 3 with respect to through the MLSS change in concentration of fate.
Figure 20 illustrates in the test of embodiment 3 figure that changes with respect to the processing speed through the denitrogenation processing of fate.
Figure 21 illustrates in the test of embodiment 3 figure that passes with respect to through the nitrate ion concentration of the treating water of fate.
Figure 22 illustrates the figure that changes with respect to the SVI through fate in the test of embodiment 3.
Figure 23 is the figure that illustrates in the test of embodiment 4 with respect to through the MLSS change in concentration of fate.
Figure 24 illustrates in the test of embodiment 4 figure that changes with respect to the processing speed through the denitrogenation processing of fate.
Figure 25 illustrates in the test of embodiment 4 figure that passes with respect to through the nitrate ion concentration of the treating water of fate.
Figure 26 illustrates the figure that changes with respect to the SVI through fate in the test of embodiment 4.
Figure 27 is the figure that the TOC change in concentration of the methyl alcohol in the first denitrogenation portion and the second denitrogenation portion is shown.
Figure 28 is the figure that illustrates in the test of embodiment 5 and comparative example 4 with respect to through the nitrated velocity variations of fate.
Figure 29 is the figure that illustrates in the test of embodiment 5 and comparative example 4 with respect to through the denitrogenation velocity variations of fate.
Figure 30 is the figure that illustrates in the test of embodiment 5 and comparative example 4 with respect to through the MLSS change in concentration of fate.
Figure 31 illustrates the figure of the change of water quality in the first denitrogenation portion of embodiment 5.
Figure 32 illustrates the figure of the change of water quality in the second denitrogenation portion of embodiment 5.
Nomenclature
1 water treatment device
10 fluorine treatment unit
12 nitrated devices
14 nitrogen rejection facilitys
The 16a first denitrogenation portion
The 16b second denitrogenation portion
18 oxidation troughs
20 settling baths
22 processed waters, first inflow pipe
23 processed waters, second inflow pipe
24 mud are returned pipe
25,36,44a, 44b pump
26a, 26b, 26c treating water take-off pipe
28 hydrogen donor feeding mechanisms
The 30pH setting device
32a, 32b whipping appts
34 hydrogen donor jars
38 hydrogen donor inflow pipes
40,50a, 50b control device
42pH adjusts the agent jar
46a, 46b pH adjust the agent inflow pipe
48a, 48b pH transmitter
52 partitions
Denitrogenation chambers 54
56 settling chambers
Embodiment
Below, embodiments of the present invention are described.Present embodiment is to implement an example of the present invention, and the present invention is not restricted to present embodiment.
Embodiment 1
Fig. 1 shows the summary pie graph of an example of the water treatment device of present embodiment.As shown in Figure 1, water treatment device 1 comprises: fluorine treatment unit 10, nitrated device 12 and nitrogen rejection facility 14.Though present embodiment relates to contain the denitrifying method and the denitrification processing device of the processed water of nitrate ion, nitrite ion; but; for example in electronic industry draining of semiconductor factory's draining etc. etc.; regular meeting discharges contains fluorine and ammonium-nitrogen draining; in this case; need to remove fluorine by described fluorine treatment unit 10, and by nitrated device 12 with ammonium-nitrogen nitrated be nitric acid or nitrous acid.
Ammonium-nitrogen comes from organic property nitrogen compound of ammonia, ammonium compound or amine compound, for example Tetramethylammonium hydroxide, thanomin, other amino acids etc.Fluorine is to come from hydrofluoric acid, fluorine cpd etc.And about the formation and the nitrifying method of the formation of fluorine treatment unit 10 and fluorine removal method, nitrated device 12, though following an one example is described, device constitutes and method is not limited in this.
Fluorine treatment unit 10 comprises: processed tank, reactive tank and settling bath.The outlet of the outlet of processed tank and the inlet of reactive tank, reactive tank and the inlet of settling bath pass through pipe connection.
Nitrated device 12 comprises processed tank and nitrifying groove.The outlet of the processed tank of the inlet of the processed tank of the outlet of the settling bath of fluorine treatment unit 10 and nitrated device 12, nitrated device 12 and the inlet of nitrifying groove pass through pipe connection.
Fig. 2 shows the mode chart of an example of formation of the nitrogen rejection facility of present embodiment.As shown in Figure 2, nitrogen rejection facility 14 comprises: denitrifying tank (first 16a of denitrogenation portion, second 16b of denitrogenation portion), oxidation trough 18, settling bath 20, processed water first inflow pipe 22, processed water second inflow pipe 23, mud are returned pipe 24, treating water take-off pipe 26a, 26b, 26c, hydrogen donor feeding mechanism 28 and pH setting device 30.Second 16b of denitrogenation portion that denitrifying tank has first 16a of denitrogenation portion and is arranged on the back segment of first 16a of denitrogenation portion.The processed water supply opening of first 16a of denitrogenation portion shown in the outlet of the nitrifying groove of the nitrated device 12 shown in Fig. 1 and Fig. 2 connects by processed water first inflow pipe 22.The processed water supply opening of the processed water relief outlet of first 16a of denitrogenation portion and second 16b of denitrogenation portion connects by processed water second inflow pipe 23.The treating water outlet of second 16b of denitrogenation portion and the inlet of oxidation trough 18, connect by treating water take-off pipe 26a, the inlet of the outlet of oxidation trough 18 and settling bath 20 connects by treating water take-off pipe 26b, and the treating water outlet of settling bath 20 is connected with treating water take-off pipe 26c.The sludge stream inlet of the mud relief outlet of settling bath 20 and first 16a of denitrogenation portion via pump 25, is returned pipe 24 by mud and is connected.In first 16a of denitrogenation portion and second 16b of denitrogenation portion, be provided with whipping appts 32a, 32b that the water in the groove is stirred.
Hydrogen donor feeding mechanism 28, be supplied to first 16a of denitrogenation portion to major general's hydrogen donor, and comprise: accommodate the hydrogen donor jar 34 of hydrogen donor, hydrogen donor delivered to the control device 40 of the supply of the driving of the pump 36 of first 16a of denitrogenation portion, the hydrogen donor inflow pipe 38 of forming the stream of hydrogen donor, control pump 36 and control hydrogen donor.The hydrogen donor supply opening of the outlet of hydrogen donor jar 34 and first 16a of denitrogenation portion via pump 36, connects by hydrogen donor inflow pipe 38.Pump 36 electrically connects with control device 40.And, under the situation of second 16b of denitrogenation portion supply hydrogen donor, also can be provided with in addition the pump that hydrogen donor is transported to second 16b of denitrogenation portion, the hydrogen donor inflow pipe of stream of forming hydrogen donor and the driving of control pump, and the control device of the supply of control hydrogen donor.
PH setting device 30 is used to adjust the pH of the processed water in first 16a of denitrogenation portion and second 16b of denitrogenation portion, and comprises: pH adjusts agent jar 42, and the pH that is used to accommodate alkali such as acid such as hydrochloric acid or sodium hydroxide adjusts agent; Pump 44a and 44b are used for that pH is adjusted agent and deliver to first 16a of denitrogenation portion and second 16b of denitrogenation portion; PH adjusts agent inflow pipe 46a and 46b, forms the stream that pH adjusts agent; PH transmitter 48a and 48b are used to measure the pH value of the processed water in first 16a of denitrogenation portion and second 16b of denitrogenation portion; Control device 50a is used for the driving of control pump 44a, and control is fed to the supply of the pH adjustment agent of first 16a of denitrogenation portion; And control device 50b, be used for the driving of control pump 44b, and control is fed to the supply of the pH adjustment agent of second 16b of denitrogenation portion.PH adjusts first outlet of agent jar 42 and the pH adjustment agent supply opening of first 16a of denitrogenation portion, via pump 44a, adjusts agent inflow pipe 46a by pH and connects.And pH adjusts second outlet of agent jar 42 and the pH adjustment agent supply opening of second 16b of denitrogenation portion, via pump 44b, adjusts agent inflow pipe 46b by pH and connects.PH transmitter 48a and control device 50a, control device 50a and pump 44a, pH transmitter 48b and control device 50b, control device 50b and pump 44b electrically connect.
Then, the water treatment method of present embodiment and the action of water treatment device 1 are described.At first, the processed water that will contain fluorine and ammonium-nitrogen is delivered to the processed tank of the fluorine treatment unit 10 shown in Fig. 1.In this processed tank, in flow and concentration equalization, and adjust after the pH processed water, processed water is delivered to the reactive tank of fluorine treatment unit 10.And, calcium cpd is fed in the reactive tank.And, in the reactive tank of fluorine treatment unit 10, make fluorine and calcium cpd reaction in the processed water, generate Calcium Fluoride (Fluorspan) (CaF 2).Here,, also flocculation agent and calcium cpd can be fed in the reactive tank of fluorine treatment unit 10 simultaneously, make the Calcium Fluoride (Fluorspan) gatheringization of described generation in order to improve the processing efficiency of the fluorine in the processed water.And, in the settling bath of fluorine treatment unit 10, the processed water that contains (gatheringization) Calcium Fluoride (Fluorspan) is carried out solid-liquid separation, from processed water, remove fluorine (and Calcium Fluoride (Fluorspan)).
And fluorine treatment unit 10 also can comprise a plurality of reactive tanks.For example, also can comprise first reactive tank and second reactive tank,, make the treating water and the calcium cpd reaction that contain fluorine and ammonium-nitrogen, generate Calcium Fluoride (Fluorspan),, add flocculation agent, make the Calcium Fluoride (Fluorspan) gatheringization at second reactive tank at first reactive tank.And, in reactive tank, also the stirring mechanism that the water in the groove is stirred can be set.
Be supplied to the calcium cpd of the reactive tank of fluorine treatment unit 10,, do not limited especially, for example also have calcium hydroxide (Ca (OH) so long as the compound that fluorine is separated out as Calcium Fluoride (Fluorspan) can be got final product 2), calcium chloride (CaCl 2), calcium sulfate (CaSO 4) etc.And,, for example can use organic polymer flocculation agent such as inorganic flocculants such as POLY ALUMINIUM CHLORIDE or Tai-Ace S 150 or anionic property polymer etc. as flocculation agent.
Then, will remove the processed water that contains ammonium-nitrogen of fluorine, delivered in the processed tank of the nitrated device 12 shown in Fig. 1.In this processed tank, in flow and concentration equalization, and adjust after the pH processed water, processed water is delivered to nitrifying groove.In nitrifying groove, fill the microorganism maintenance carrier that forms on the carrier by the microbial film that contains nitrifier is remained on.And, in nitrifying groove, being configured to, formation can connect air leading-in conduit (not shown), and supplies air in the interior processed water of nitrifying groove.And, at nitrifying groove, keep the effect of the nitrifier of carrier by microorganism, make the nitrated one-tenth nitrate ammonia of ammonium-nitrogen, nitrite nitrogen in the processed water.Here, nitrifier is for the ammonia oxidizing bacteria of bacterium that the independent battalion of the nitrated one-tenth nitrite nitrogen of the ammonium-nitrogen that contains in the processed water is nourished one's nature, with the nourish one's nature nitrite-oxidizing bacteria etc. of bacterium of the independent battalion of the nitrated one-tenth nitrate ammonia of nitrite nitrogen.
Keep the carrier of nitrifier,, can utilize for example sponge, gel, plastic molded article etc. though have no particular limits.Specifically, preferably utilize hydrophilic polyurethane(s) sponge, polyvinyl alcohol gel etc.And, as described later, returning under the denitrogenation particulate situation, keep the carrier of nitrifier optional.
Then,, promptly contain the processed water of nitrate ammonia, nitrite nitrogen, deliver to by processed water first inflow pipe 22 among first 16a of denitrogenation portion of nitrogen rejection facility 14 the nitration treatment liquid after the described nitration treatment.Here, first 16a of denitrogenation portion is the groove of complete mixed type, when denitrogenation processing, processed water (continuously) is supplied to first 16a of denitrogenation portion.And, make pump 36 work, the hydrogen donor in the hydrogen donor jar 34 is supplied to first 16a of denitrogenation portion by hydrogen donor inflow pipe 38.In first 16a of denitrogenation portion (and in second 16b of denitrogenation portion), under swimming state in water, the mud that contains denitrifier accommodates.At first 16a of denitrogenation portion, make nitrate ion, the nitrite ion in the processed water and after denitrifier contacted, processed water, denitrifier and hydrogen donor were delivered among second 16b of denitrogenation portion by processed water second inflow pipe 23.And second 16b of denitrogenation portion is the groove of complete mixed type, will be supplied to second 16b of denitrogenation portion from the processed water (continuously) that first 16a of denitrogenation portion discharges.
In first 16a of denitrogenation portion and second 16b of denitrogenation portion, by the effect of denitrifier, nitrate ion, nitrite ion in the processed water are reduced into nitrogen.Using under the situation of methyl alcohol as hydrogen donor, the nitrate ion in the processed water, nitrite ion are reduced into nitrogen by the reaction shown in the following reaction formula.
2NO 2 -+CH 3OH→N 2+CO 2+H 2O+2OH -
6NO 3 -+5CH 3OH→3N 2+5CO 2+7H 2O+6OH -
Then, via treating water take-off pipe 26a, will deliver to oxidation trough 18 by the treating water that denitrogenation processing has been removed nitrate ion, nitrite ion, and, make oxidation operations such as hydrogen donor residual in the treating water at oxidation trough 18.Then, via treating water take-off pipe 26b, the treating water of having removed hydrogen donor is delivered to settling bath 20.And in the bottom of settling bath 20, (in the present embodiment for the own granulationization) denitrifier that contains in the processed water is piled up as mud, and the last clarification of water on the top of settling bath 20 is taken out from treating water take-off pipe 26c.And, make pump 25 work, the mud that is deposited in the bottom of settling bath 20 is returned pipe 24 from mud return once more in first 16a of denitrogenation portion.And, also be under the situation of carrying out of the mud with the formula of swimming in the nitration treatment that nitrated device 12 carries out, also mud can be returned nitrifying groove.
Fig. 3 shows the mode chart of an example of formation of the nitrogen rejection facility of other embodiments of the present invention.In nitrogen rejection facility 14, will independently not be provided with denitrifying tank by settling bath 20, as shown in Figure 3, the partition 52 of lower openings can be set in second 16b of denitrogenation portion also, form denitrogenation chamber 54 and settling chamber 56.And solid-liquid separation also can not used the settling bath 20 shown in Fig. 2, reach the settling chamber 56 shown in Fig. 3, but carries out with any device such as gas-solid separator (GSS), membrane separation units.
Oxidation trough 18 is used for the organism such as hydrogen donor that processed water contains are carried out oxygenolysis by action of microorganisms.As shown in Figure 2, oxidation trough 18 also can be arranged on the upstream side of settling bath 20, also can be arranged on the downstream side of settling bath 20.
Then, the Supply Method to hydrogen donor is described in detail.Usually, calculate the supply of the needed hydrogen donor of denitrogenation processing from the nitrate ion of the processed water that is fed to denitrifying tank, the concentration of nitrite ion, and this supply is not changed, continuously hydrogen donor is supplied to denitrifying tank.Therefore, the concentration of the hydrogen donor in the denitrifying tank is low roughly certain.And, in order to carry out denitrogenation processing effectively, (theoretical amount of the hydrogen donor that needs) about 1.2 times of the needed hydrogen donor supply of the denitrogenation processing of nitrate ion in the denitrifying tank and nitrite ion is supplied to denitrifying tank.
But, in the present embodiment, at least to described first denitrogenation portion supply hydrogen donor, make in described first 16a of denitrogenation portion with described second 16b of denitrogenation portion between the concentration difference of formation hydrogen donor.And; for example; also can be at least to first 16a of denitrogenation portion supply hydrogen donor; make the hydrogen donor in first 16a of denitrogenation portion in hydraulic residence time (HRT) of the processed water in second 16b of denitrogenation portion concentration, with second 16b of denitrogenation portion in hydraulic residence time of processed water in concentration poor of hydrogen donor in second 16b of denitrogenation portion, become the concentration difference of the own granulationization (granulating) of inducing denitrifier.An example as the concentration difference that forms hydrogen donor; in control device 40; store the calculating formula of the hydrogen donor addition corresponding in advance (when carrying out adding intermittence with former water nitrogen concentration measurement result; be interpolation and the calculating formula of the time of interpolation); based on this calculating formula, the work of control pump 36, the supply of regulating hydrogen donor; the concentration of the hydrogen donor that the concentration of the hydrogen donor in first 16a of denitrogenation portion and second 16b of denitrogenation portion are interior poor becomes the concentration difference of the own granulationization of inducing denitrifier.
The volume of first 16a of denitrogenation portion is preferably littler than the volume of second 16b of denitrogenation portion, more preferably in the scope of the volumetrical 1/30～1/3 of second 16b of denitrogenation portion; More preferably in the scope of the volumetrical 1/20～1/5 of second 16b of denitrogenation portion.When the volume of first 16a of denitrogenation portion surpasses the volumetrical 1/3 of second 16b of denitrogenation portion; the concentration of the hydrogen donor that the concentration that has a hydrogen donor in first 16a of denitrogenation portion and second 16b of denitrogenation portion are interior poor is difficult to become the situation of the concentration difference of the own granulationization of inducing denitrifier.And, when the volume of first 16a of denitrogenation portion does not reach the volumetrical 1/30 of second 16b of denitrogenation portion, because the HRT in first 16a of denitrogenation portion becomes too short, therefore the molten consumption of depositing oxygen in the processed water of being unable to catch up with flowing into, first 16a of denitrogenation portion becomes the aerobism condition, and existence can not be carried out the situation of denitrogenation processing effectively.Though utilize nitrate ion, nitrite ion concentration, the molten oxygen concentration of depositing in the processed water, first 16a of denitrogenation portion preferably can guarantee the volume size (volumetrical of second 16b of denitrogenation portion is more than 1/30) of the above HRT of several minutes.
Here, preferably, (for example, in the hydraulic residence time (HRT) of the processed water in second 16b of denitrogenation portion) peak concentration of hydrogen donor in first 16a of denitrogenation portion, with (for example, in the hydraulic residence time of the processed water in second 16b of denitrogenation portion) difference of the Cmin of hydrogen donor in second 16b of denitrogenation portion is more than 50mgTOC/L, and be fed in first 16a of denitrogenation portion with this mode to major general's hydrogen donor, more preferably, be fed in first 16a of denitrogenation portion with the mode of concentration difference more than 100mgTOC/L to major general's hydrogen donor.When the difference of the Cmin of the peak concentration of the hydrogen donor in first 16a of denitrogenation portion and the hydrogen donor in second 16b of denitrogenation portion during less than 50mgTOC/L, the situation of the own granulationization of denitrifier can not be fully induced in existence.
In the present embodiment, though also hydrogen donor can be supplied to continuously first 16a of denitrogenation portion (also can be supplied to second 16b of denitrogenation portion), but under the lower situation of the concentration of the nitrate ion in processed water, nitrite ion, because the concentration of the needed hydrogen donor of denitrogenation processing is also lower, therefore between first 16a of denitrogenation portion and second 16b of denitrogenation portion, it is difficult that the formation of the concentration difference of hydrogen donor becomes.So, be preferably hydrogen donor be supplied to first 16a of denitrogenation portion off and on.Promptly, because when the supply of hydrogen donor, the concentration of the hydrogen donor in first 16a of denitrogenation portion is increased, and when the supply of hydrogen donor stops, the concentration of the hydrogen donor in second 16b of denitrogenation portion of back segment is reduced (because hydrogen donor is consumed by denitrogenation processing), therefore the concentration difference of formation hydrogen donor easily between first 16a of denitrogenation portion and second 16b of denitrogenation portion.But the supply of the supply of hydrogen donor and stand-by time, hydrogen donor preferably is configured to, and the difference of the peak concentration of the hydrogen donor in first 16a of denitrogenation portion and the Cmin of the hydrogen donor in second 16b of denitrogenation portion is for example more than the 50mgTOC/L.
Because this point of concentration of the hydrogen donor in can second 16b of denitrogenation portion of equalization back segment when the supply of the hydrogen donor of first 16a of denitrogenation portion and the circulation that stops are carried out repeatedly, so preferably, once the circulation (supplying-stop) time, 50% weak point of the hydraulic residence time of the processed water interior than second 16b of denitrogenation portion promptly carries out more than twice circulation with respect to the hydraulic residence time of the processed water in second 16b of denitrogenation portion.
And, in the present embodiment, with respect to being fed to the nitrate ion in the denitrifying tank and the concentration of nitrite ion, supply (theoretical amount of the hydrogen donor that needs) with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of benchmark value is supplied to first of first 16a of denitrogenation portion to supply operation, and the second supply operation that will be supplied to first 16a of denitrogenation portion more than the hydrogen donor of the amount of described benchmark value, by hydrogen donor being supplied to first 16a of denitrogenation portion, can between first 16a of denitrogenation portion and second 16b of denitrogenation portion, form the concentration difference of hydrogen donor easily.But the supply of the supply of hydrogen donor and stand-by time and hydrogen donor preferably is configured to, and the difference of the peak concentration of the hydrogen donor in first 16a of denitrogenation portion and the Cmin of the hydrogen donor in second 16b of denitrogenation portion is for example more than the 50mgTOC/L.
Because this point of concentration of the hydrogen donor in the circulation of the first supply operation of first 16a of denitrogenation portion and the second supply operation can second 16b of denitrogenation portion of equalization back segment when carrying out repeatedly, so preferably, the time of once circulation (the first supply operation-second supply operation), 50% weak point of the hydraulic residence time of the processed water interior than second 16b of denitrogenation portion promptly carries out more than twice circulation with respect to the hydraulic residence time of the processed water in second 16b of denitrogenation portion.
In the present embodiment, though be supplied to first 16a of denitrogenation portion just passable to major general's hydrogen donor, but also hydrogen donor can be supplied to second 16b of denitrogenation portion (comprising the intermittence supply of supplying-stopping, volume supply-a small amount of supply etc.), form the hydrogen donor concentration difference in described first 16a of denitrogenation portion and between in described second 16b of denitrogenation portion.And; for example; if the concentration of the hydrogen donor in the hydraulic residence time of the processed water in second 16b of denitrogenation portion in first 16a of denitrogenation portion, with second 16b of denitrogenation portion in hydraulic residence time of processed water in concentration poor of hydrogen donor in second 16b of denitrogenation portion; become the concentration difference of the own granulationization (granulating) of inducing denitrifier, also hydrogen donor can be supplied to second 16b of denitrogenation portion (comprising the intermittence supply of supplying-stopping, volume supply-a small amount of supply etc.).But, when becoming when hydrogen donor is supplied to second 16b of denitrogenation portion,, need to increase the supply of the hydrogen donor of first 16a of denitrogenation portion in order to ensure described concentration difference, therefore exist the usage quantity of hydrogen donor to increase the situation that the operating cost of device uprises.Therefore, preferably only hydrogen donor is supplied to first 16a of denitrogenation portion.
In the present embodiment, though be that example shows first 16a of denitrogenation portion and the secondth 16b of denitrogenation portion, be not limited in this with single groove.That is, if between first 16a of denitrogenation portion and second 16b of denitrogenation portion, can form the concentration difference of the hydrogen donor of the own granulationization (granulating) of inducing denitrifier, first 16a of denitrogenation portion also can be a plurality of grooves, and second 16b of denitrogenation portion also can be a plurality of grooves.For example, first 16a of denitrogenation portion can have sulculus A, B, and second 16b of denitrogenation portion can have sulculus C, D.In this case; for example; the concentration of the concentration of the sulculus A of first 16a of denitrogenation portion and sulculus B is poor in the hydraulic residence time of the processed water in second 16b of denitrogenation portion; it or not the concentration difference of inducing the hydrogen donor of own granulationization (granulating); the concentration of the sulculus C of the concentration of the sulculus A of first 16a of denitrogenation portion and second 16b of denitrogenation portion is poor in the hydraulic residence time of the processed water in second 16b of denitrogenation portion; the perhaps concentration of the sulculus C of the concentration of the sulculus B of first 16a of denitrogenation portion and second 16b of denitrogenation portion poor in the hydraulic residence time of the processed water in second 16b of denitrogenation portion, for the concentration difference of the hydrogen donor of the own granulationization (granulating) of inducing denitrifier just passable.At this moment, it is just passable that hydrogen donor is supplied to sulculus A and the sulculus B of the sulculus A of first 16a of denitrogenation portion or first 16a of denitrogenation portion at least.And, in denitrogenation portion is under the situation of a plurality of grooves, for example, has under the situation of sulculus C, D at second 16b of denitrogenation portion, the hydraulic residence time of the processed water in second 16b of denitrogenation portion, for hydraulic residence time of the processed water in sulculus C, the D and.The volume of the volume of first 16a of denitrogenation portion, second 16b of denitrogenation portion too, for example, have sulculus A, B at first 16a of denitrogenation portion, second 16b of denitrogenation portion has under the situation of sulculus C, D, the volumetrical of sulculus A, B and (volume of first 16a of denitrogenation portion), be preferably littler than volume and (volume of second 16b of denitrogenation portion) of sulculus C, D, more preferably in 1/30～1/3 scope of the volumetrical of sulculus C, D and (volume of second 16b of denitrogenation portion), more preferably in 1/20～1/5 scope of the volumetrical of sulculus C, D and (volume of second 16b of denitrogenation portion).
In the present embodiment, though processed water all flow into first 16a of denitrogenation portion, be not limited in this.For example, the situation of the hydraulic residence time of the processed water in control first 16a of denitrogenation portion is inferior, processed water also can flow into first 16a of denitrogenation portion and the second 16b both sides of denitrogenation portion, also can switch processed water to the inflow of first 16a of denitrogenation portion with to the inflow of second 16b of denitrogenation portion according to the time.
And, when making the denitrifier granulating, have the situation of adding the part metals class and obtaining good result.In general, these are promoted material as granulating, as ionic species, for example calcium ion, iron ion, as compounds, for example flyash, ferric oxide, lime carbonate etc.About ionic species wherein, preferably, during denitrogenation processing is whole or between the starting period of device, add continuously or off and on.And, about compounds, preferably, when device starts and the interpolation of mud add simultaneously.
The hydrogen donor that uses in the present embodiment for example is methyl alcohol, ethanol, Virahol, acetic acid, hydrogen, acetone, glucose, methylethylketone, Tetramethylammonium hydroxide (TMAH) etc., but is not restricted to this, as hydrogen donor, can use existing known whole.
From nitrate ion, nitrite ion reduction reaction to nitrogen, though some difference owing to the kind of hydrogen donor, but anyly all be, since generation and nitrate ion, the equimolar oxyhydroxide ion of nitrite ion, the processed water pH rising in the groove.In general, be fit to the pH of the processed water in the denitrogenation processing is adjusted to 8～9 scope.But, uprise and the calcium ion worrying to contain in the processed water etc. causes under the situation that scale produces in the carbonic acid ionic concentration of hydrogen donor origin, preferably, the processed water pH in the groove is adjusted to 6～7.5 scope, more preferably, be adjusted to 6.3～7.0 scope.Specifically, detect the pH of the processed water of first 16a of denitrogenation portion and second 16b of denitrogenation portion by pH transmitter 48a, the 48b of pH setting device 30, based on detected pH, make pump 44a, 44b work by control device 50a, 50b, pH is adjusted agent be supplied to first 16a of denitrogenation portion and second 16b of denitrogenation portion from pH adjustment agent jar 42, come the pH of the processed water in the regulating tank, make the processed water pH in the 16a of denitrogenation portion that wins, second 16b of denitrogenation portion become described pH scope.
MLSS concentration in the denitrifying tank (first 16a of denitrogenation portion and second 16b of denitrogenation portion) has no particular limits, but in order to reach sufficient denitrogenation processing speed, is preferably the degree of 5000～100000mgMLSS/L.
As mentioned above; with in described first 16a of denitrogenation portion and between in described second 16b of denitrogenation portion; form the mode of hydrogen donor concentration difference; preferably; the mode of difference more than 50mgTOC/L with the peak concentration and the Cmin in second 16b of denitrogenation portion of the hydrogen donor in first 16a of denitrogenation portion; be supplied to first 16a of denitrogenation portion to major general's hydrogen donor, thereby can make the denitrifier granulating.And; for example with the concentration of the hydrogen donor in first 16a of denitrogenation portion in the hydraulic residence time (HRT) of the processed water in second 16b of denitrogenation portion, with second 16b of denitrogenation portion in hydraulic residence time of processed water in concentration poor of hydrogen donor in second 16b of denitrogenation portion; mode for the concentration difference (granulating) of the own granulationization of inducing denitrifier; be supplied to first 16a of denitrogenation portion to major general's hydrogen donor, thereby can make the denitrifier granulating.By making the denitrifier granulating,, therefore can improve the processing speed of denitrogenation processing, and can make equipment miniaturization or cost degradation owing to can increase the microorganism concn (sludge concentration) in the denitrifying tank.
Embodiment 2
Fig. 4 is the mode chart of an example of formation that the nitrogen rejection facility of other embodiments of the present invention is shown.As shown in Figure 4, nitrogen rejection facility 14 comprises: denitrogenation portion (first 16a of denitrogenation portion, second 16b of denitrogenation portion), oxidation trough 18, settling bath 20, processed water inflow pipe 22, reaction solution return pipe 23, mud return pipe 24, treating water take-off pipe 26a, 26b, 26c, as reaction solution supply pipe 27 and pump 29, hydrogen donor feeding mechanism 28 and the pH setting device 30 of reaction solution feeding mechanism.Denitrogenation portion is complete mixed type, and has first 16a of denitrogenation portion and second 16b of denitrogenation portion.The processed water supply opening of second 16b of denitrogenation portion shown in the outlet of the nitrifying groove of the nitrated device 12 shown in Fig. 1 and Fig. 4 connects by processed water inflow pipe 22.The reaction solution supply opening of the reaction solution relief outlet of first 16a of denitrogenation portion and second 16b of denitrogenation portion is returned pipe 23 by reaction solution and is connected.The treating water outlet of second 16b of denitrogenation portion and the inlet of oxidation trough 18, connect by treating water take-off pipe 26a, the inlet of the outlet of oxidation trough 18 and settling bath 20 connects by treating water take-off pipe 26b, and the treating water outlet of settling bath 20 is connected with treating water take-off pipe 26c.The sludge stream inlet of the mud relief outlet of settling bath 20 and second 16b of denitrogenation portion via pump 25, is returned pipe 24 by mud and is connected.In first 16a of denitrogenation portion and second 16b of denitrogenation portion, be provided with whipping appts 32a, 32b that the water in the groove is stirred.
The reaction solution feeding mechanism is used to extract the reaction solution in second 16b of denitrogenation portion, is supplied to first 16a of denitrogenation portion, and an end of reaction solution supply pipe 27 is inserted in second 16b of denitrogenation portion, and the other end is connected in the reaction solution supply opening of first 16a of denitrogenation portion.And pump 29 is arranged at reaction solution supply pipe 27.
Hydrogen donor feeding mechanism 28, be supplied to first 16a of denitrogenation portion to major general's hydrogen donor, and comprise: accommodate the hydrogen donor jar 34 of hydrogen donor, hydrogen donor delivered to the control device 40 of the supply of the driving of the pump 36 of first 16a of denitrogenation portion, the hydrogen donor inflow pipe 38 of forming the stream of hydrogen donor, control pump 36 and control hydrogen donor.The hydrogen donor supply opening of the outlet of hydrogen donor jar 34 and first 16a of denitrogenation portion via pump 36, connects by hydrogen donor inflow pipe 38.Pump 36 electrically connects with control device 40.And, under the situation of second 16b of denitrogenation portion supply hydrogen donor, also can be provided with in addition the pump that hydrogen donor is transported to second 16b of denitrogenation portion, the hydrogen donor inflow pipe of stream of forming hydrogen donor and the driving of pump are controlled, and the control device of the supply of control hydrogen donor.
PH setting device 30 is used to adjust the pH of the processed water in first 16a of denitrogenation portion and second 16b of denitrogenation portion, and comprises: pH adjusts agent jar 42, and the pH that is used to accommodate alkali such as acid such as hydrochloric acid or sodium hydroxide adjusts agent etc.; Pump 44a and 44b are used for that pH is adjusted agent and deliver to first 16a of denitrogenation portion and second 16b of denitrogenation portion; PH adjusts agent inflow pipe 46a and 46b, forms the stream that pH adjusts agent; PH transmitter 48a and 48b are used to measure the pH value of the processed water in first 16a of denitrogenation portion and second 16b of denitrogenation portion; Control device 50a is used for the driving of control pump 44a, and control is fed to the supply of the pH adjustment agent of first 16a of denitrogenation portion; And control device 50b, be used for the driving of control pump 44b, and control is fed to the supply of the pH adjustment agent of second 16b of denitrogenation portion.PH adjusts first outlet of agent jar 42 and the pH adjustment agent supply opening of first 16a of denitrogenation portion, via pump 44a, adjusts agent inflow pipe 46a by pH and connects.And pH adjusts second outlet of agent jar 42 and the pH adjustment agent supply opening of second 16b of denitrogenation portion, via pump 44b, adjusts agent inflow pipe 46b by pH and connects.PH transmitter 48a and control device 50a, control device 50a and pump 44a, pH transmitter 48b and control device 50b, control device 50b and pump 44b electrically connect.
Then, the water treatment method that present embodiment is related to and the action of water treatment device 1 describe.At first, the processed water that will contain fluorine and ammonium-nitrogen is delivered to the processed tank of the fluorine treatment unit 10 shown in Fig. 1.In this processed tank, in flow and concentration equalization, and adjust after the pH processed water, processed water is delivered to the reactive tank of fluorine treatment unit 10.And, calcium cpd is fed in the reactive tank.And, in the reactive tank of fluorine treatment unit 10, make fluorine and calcium cpd reaction in the processed water, generate Calcium Fluoride (Fluorspan) (CaF 2).Here,, also flocculation agent and calcium cpd can be fed in the reactive tank of fluorine treatment unit 10 simultaneously, make the Calcium Fluoride (Fluorspan) gatheringization of described generation in order to improve the processing efficiency of the fluorine in the processed water.And, in the settling bath of fluorine treatment unit 10, the processed water that contains (gatheringization) Calcium Fluoride (Fluorspan) is carried out solid-liquid separation, from processed water, remove fluorine (and Calcium Fluoride (Fluorspan)).
And fluorine treatment unit 10 also can comprise a plurality of reactive tanks.For example, also can comprise first reactive tank and second reactive tank,, make the treating water and the calcium cpd reaction that contain fluorine and ammonium-nitrogen, generate Calcium Fluoride (Fluorspan),, add flocculation agent, make the Calcium Fluoride (Fluorspan) gatheringization at second reactive tank at first reactive tank.And, in reactive tank, also the stirring mechanism that the water in the groove is stirred can be set.
Be supplied to the calcium cpd of the reactive tank of fluorine treatment unit 10,, do not limited especially, for example also have calcium hydroxide (Ca (OH) so long as the compound that fluorine is separated out as Calcium Fluoride (Fluorspan) can be got final product 2), calcium chloride (CaCl 2), calcium sulfate (CaSO 4) etc.And,, for example can use organic polymer flocculation agent such as inorganic flocculants such as POLY ALUMINIUM CHLORIDE or Tai-Ace S 150 or anionic property polymer etc. as flocculation agent.
Then, will remove the processed water that contains ammonium-nitrogen of fluorine, delivered in the processed tank of the nitrated device 12 shown in Fig. 1.In this processed tank, in flow and concentration equalization, and adjust after the pH processed water, processed water is delivered to nitrifying groove.In nitrifying groove, fill the microorganism maintenance carrier that forms on the carrier by the microbial film that contains nitrifier is remained on.And, being configured in the nitrifying groove, formation can connect air leading-in conduit (not shown), and supplies air in the interior processed water of nitrifying groove.And, at nitrifying groove, keep the effect of the nitrifier of carrier by microorganism, make the nitrated one-tenth nitrate ammonia of ammonium-nitrogen, nitrite nitrogen in the processed water.Here, nitrifier is for the ammonia oxidizing bacteria of bacterium that the independent battalion of the nitrated one-tenth nitrite nitrogen of the ammonium-nitrogen that contains in the processed water is nourished one's nature, with the nourish one's nature nitrite-oxidizing bacteria etc. of bacterium of the independent battalion of the nitrated one-tenth nitrate ammonia of nitrite nitrogen.
Keep the carrier of nitrifier,, can utilize for example sponge, gel, plastic molded article etc. though have no particular limits.Specifically, preferably utilize hydrophilic polyurethane(s) sponge, polyvinyl alcohol gel etc.And, as described later, returning under the denitrogenation particulate situation, keep the carrier of nitrifier optional.
Then,, promptly contain the processed water of nitrate ammonia, nitrite nitrogen, be fed to by processed water inflow pipe 22 (continuously) among second 16b of denitrogenation portion of the nitrogen rejection facility 14 shown in Fig. 4 the nitration treatment liquid after the described nitration treatment.And, make pump 29 work of reaction solution feeding mechanism, the part with the reaction solution in second 16b of denitrogenation portion (processed water in second 16b of denitrogenation portion and denitrifier etc.) is fed to first 16a of denitrogenation portion from reaction solution supply pipe 27 when, make pump 36 work of hydrogen donor feeding mechanism 28, the hydrogen donor in the hydrogen donor jar 34 is fed to first 16a of denitrogenation portion via hydrogen donor inflow pipe 38.Afterwards, the reaction solution in first 16a of denitrogenation portion being returned pipe 23 via reaction solution supplies to second 16b of denitrogenation portion.Like this, the denitrifier in the reaction solution in first 16a of denitrogenation portion is exposed to the hydrogen donor of high density temporarily.And because the reaction solution in first 16a of denitrogenation portion is supplied to second 16b of denitrogenation portion, therefore, the denitrifier in the reaction solution in second 16b of denitrogenation portion is exposed under the lower environment of hydrogen donor concentration.Therefore, by making of the variation of hydrogen donor concentration, can induce the denitrifier granulating with respect to denitrifier.And, the pump 29 of reaction solution feeding mechanism is worked on, the part of the reaction solution in second 16b of denitrogenation portion is supplied in first 16a of denitrogenation portion, and also can make pump 29 discontinuous operations of reaction solution feeding mechanism, the part of the reaction solution in second 16b of denitrogenation portion intermittently is fed in first 16a of denitrogenation portion.
In first 16a of denitrogenation portion and second 16b of denitrogenation portion, by the effect of denitrifier, nitrate ion, nitrite ion in the processed water are reduced into nitrogen.Using under the situation of methyl alcohol as hydrogen donor, the nitrate ion in the processed water, nitrite ion are reduced into nitrogen by the reaction shown in the following reaction formula.
2NO 2 -+CH 3OH→N 2+CO 2+H 2O+2OH -
6NO 3 -+5CH 3OH→3N 2+5CO 2+7H 2O+6OH -
Then, via treating water take-off pipe 26a, will deliver to oxidation trough 18 by the treating water that denitrogenation processing has been removed nitrate ion, nitrite ion, and, make oxidation operations such as hydrogen donor residual in the treating water at oxidation trough 18.Then, via treating water take-off pipe 26b, the treating water of having removed hydrogen donor is delivered to settling bath 20.And in the bottom of settling bath 20, (in the present embodiment for the own granulationization) denitrifier that contains in the processed water is piled up as mud, and the last clarification of water on the top of settling bath 20 is taken out from treating water take-off pipe 26c.And, make pump 25 work, the mud that is deposited in the bottom of settling bath 20 is returned pipe 24 from mud return (or in first 16a of denitrogenation portion) in second 16b of denitrogenation portion once more.And, under the situation that nitration treatment that nitrated device 12 carries out is carried out with the mud of the formula of swimming, also mud can be returned nitrifying groove.
Fig. 5 shows the mode chart of an example of formation of the nitrogen rejection facility of other embodiments of the present invention.In nitrogen rejection facility 14, will independently not be provided with denitrogenation portion by settling bath 20, as shown in Figure 5, the partition 52 of lower openings can be set in second 16b of denitrogenation portion also, form denitrogenation chamber 54 and settling chamber 56.And solid-liquid separation also can not used the settling bath 20 shown in Fig. 4, reach the settling chamber 56 shown in Fig. 5, but carries out with any device such as gas-solid separator (GSS), membrane separation units.
Oxidation trough 18 is used for the organism such as hydrogen donor that processed water contains are carried out oxygenolysis by action of microorganisms.As shown in Figure 4, oxidation trough 18 also can be arranged on the upstream side of settling bath 20, also can be arranged on the downstream side of settling bath 20.
Then, the Supply Method to hydrogen donor is described in detail.Usually, calculate the supply of the needed hydrogen donor of denitrogenation processing from the nitrate ion of the processed water that is fed to denitrogenation portion, the concentration of nitrite ion, and this supply is not changed, continuously hydrogen donor is supplied to denitrogenation portion.Therefore, the concentration of the hydrogen donor in the denitrogenation portion is low roughly certain.And, in order to carry out denitrogenation processing effectively, (theoretical amount of the hydrogen donor that needs) about 1.2 times of the needed hydrogen donor supply of the denitrogenation processing of nitrate ion in the denitrifying tank and nitrite ion is supplied to denitrogenation portion.
But, in the present embodiment, reaction solution in second 16b of denitrogenation portion is fed to first 16a of denitrogenation portion, and at least to described first 16a of denitrogenation portion supply hydrogen donor, and return second 16b of denitrogenation portion, make in described first 16a of denitrogenation portion with described second 16b of denitrogenation portion between the concentration difference of formation hydrogen donor.And; for example; also can be at least to first 16a of denitrogenation portion supply hydrogen donor; and return second 16b of denitrogenation portion; make the hydrogen donor in first 16a of denitrogenation portion in hydraulic residence time (HRT) of the processed water in second 16b of denitrogenation portion concentration, with second 16b of denitrogenation portion in hydraulic residence time of processed water in concentration poor of hydrogen donor in second 16b of denitrogenation portion, become the concentration difference of the own granulationization (granulating) of inducing denitrifier.An example as the concentration difference that forms hydrogen donor; in control device 40; store the calculating formula of the hydrogen donor addition corresponding in advance (when carrying out adding intermittence with former water nitrogen concentration measurement result; be interpolation and the calculating formula of the time of interpolation); based on this calculating formula, the work of control pump 36, the supply of regulating hydrogen donor; the concentration of the hydrogen donor that the concentration that makes the hydrogen donor in first 16a of denitrogenation portion and second 16b of denitrogenation portion are interior poor becomes the concentration difference of the own granulationization of inducing denitrifier.And, reaction solution is returned pipe 23 from reaction solution returns second 16b of denitrogenation portion.
Here, preferably, (for example, in the hydraulic residence time (HRT) of the processed water in second 16b of denitrogenation portion) peak concentration of hydrogen donor in first 16a of denitrogenation portion, with the difference of the Cmin of hydrogen donor in (for example, in the hydraulic residence time of the processed water in second 16b of denitrogenation portion) second 16b of denitrogenation portion more than 50mgTOC/L; More preferably, concentration difference is more than 100mgTOC/L.When the difference of the Cmin of the peak concentration of the hydrogen donor in first 16a of denitrogenation portion and the hydrogen donor in second 16b of denitrogenation portion during less than 50mgTOC/L, the situation of the own granulationization of denitrifier can not be fully induced in existence.And the Cmin of the hydrogen donor in second 16b of denitrogenation portion is with respect to the peak concentration of the hydrogen donor in first 16a of denitrogenation portion, preferably in (, the scope 1/2 below of peak concentration bigger than 0) below 1/2.When described Cmin surpass peak concentration 1/2 the time, exist denitrifier own granulationization induce the change situation of difficult.
In the present embodiment, under the situation lower from the concentration of the nitrate ion in the reaction solution that passes through reaction solution supply pipe 27 of second 16b of denitrogenation portion, nitrite ion, in order to improve the denitrification activity in first 16a of denitrogenation portion after hydrogen donor is supplied, the water that preferably will contain nitrate ion, nitrite ion is supplied to first 16a of denitrogenation portion.Specifically, be provided with the jar of accommodating the water that contains nitrate ion, nitrite ion, be used for this water is transported to pump and the liquid pushing tube of first 16a of denitrogenation portion from jar, this water is fed to first 16a of denitrogenation portion.But this point of formation for simplification device preferably, makes processed water inflow pipe 22 branches, by making the ramose pipe coupling in first 16a of denitrogenation portion, processed water as the water that contains nitrate ion, nitrite ion, is fed to first 16a of denitrogenation portion.
In the present embodiment, though also hydrogen donor can be supplied to continuously first 16a of denitrogenation portion (also can be supplied to second 16b of denitrogenation portion), but under the lower situation of the concentration of the nitrate ion in processed water, nitrite ion, between first 16a of denitrogenation portion and second 16b of denitrogenation portion, it is difficult that the formation of the concentration difference of hydrogen donor becomes.Here,, can form this point of concentration difference of hydrogen donor easily, preferably hydrogen donor is supplied to off and on first 16a of denitrogenation portion between first 16a of denitrogenation portion and second 16b of denitrogenation portion.But the supply of the supply of hydrogen donor and stand-by time, hydrogen donor preferably is configured to, and the difference of the peak concentration of the hydrogen donor in first 16a of denitrogenation portion and the Cmin of the hydrogen donor in second 16b of denitrogenation portion is for example more than the 50mgTOC/L.
Because this point of concentration of the hydrogen donor in can second 16b of denitrogenation portion of equalization back segment when the supply of the hydrogen donor of first 16a of denitrogenation portion and the circulation that stops are carried out repeatedly, so preferably, once the circulation (supplying-stop) time, 50% weak point of the hydraulic residence time of the processed water interior than second 16b of denitrogenation portion promptly carries out more than twice circulation with respect to the hydraulic residence time of the processed water in second 16b of denitrogenation portion.
And, in the present embodiment, with respect to being fed to the nitrate ion in the denitrifying tank and the concentration of nitrite ion, supply (theoretical amount of the hydrogen donor that needs) with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of benchmark value is supplied to first of first 16a of denitrogenation portion to supply operation, and the second supply operation that will be supplied to first 16a of denitrogenation portion more than the hydrogen donor of the amount of described benchmark value, by hydrogen donor being supplied to first 16a of denitrogenation portion, can between first 16a of denitrogenation portion and second 16b of denitrogenation portion, form the concentration difference of hydrogen donor easily.But the supply of the supply of hydrogen donor and stand-by time and hydrogen donor preferably is configured to, and the difference of the peak concentration of the hydrogen donor in first 16a of denitrogenation portion and the Cmin of the hydrogen donor in second 16b of denitrogenation portion is for example more than the 50mgTOC/L.
Because this point of concentration of the hydrogen donor in the circulation of the first supply operation of first 16a of denitrogenation portion and the second supply operation can second 16b of denitrogenation portion of equalization back segment when carrying out repeatedly, so preferably, the time of once circulation (the first supply operation-second supply operation), 50% weak point of the hydraulic residence time of the processed water interior than second 16b of denitrogenation portion promptly carries out more than twice circulation with respect to the hydraulic residence time of the processed water in second 16b of denitrogenation portion.
In the present embodiment, though be supplied to first 16a of denitrogenation portion just passable to major general's hydrogen donor, but also hydrogen donor can be supplied to second 16b of denitrogenation portion (comprising the intermittence supply of supplying-stopping, volume supply-a small amount of supply etc.), form the hydrogen donor concentration difference in described first 16a of denitrogenation portion and between in described second 16b of denitrogenation portion.And; for example; if the concentration of the hydrogen donor in the hydraulic residence time of the processed water in second 16b of denitrogenation portion in first 16a of denitrogenation portion; poor with the concentration of hydrogen donor in second 16b of denitrogenation portion in hydraulic residence time of processed water in second 16b of denitrogenation portion; become the concentration difference of the own granulationization (granulating) of inducing denitrifier, also hydrogen donor can be supplied to second 16b of denitrogenation portion (comprising the intermittence supply of supplying-stopping, volume supply-a small amount of supply etc.).But, when becoming when hydrogen donor is supplied to second 16b of denitrogenation portion,, need to increase the supply of the hydrogen donor of first 16a of denitrogenation portion in order to ensure described concentration difference, therefore exist the usage quantity of hydrogen donor to increase the situation that the operating cost of device uprises.Therefore, preferably only hydrogen donor is supplied to first 16a of denitrogenation portion.
In the present embodiment, though be that example shows first 16a of denitrogenation portion and the secondth 16b of denitrogenation portion with single groove, be not limited in this, first 16a of denitrogenation portion also can be a plurality of grooves, and second 16b of denitrogenation portion also can be a plurality of grooves.And first 16a of denitrogenation portion there is no need to be groove.Fig. 6 shows the mode chart of an example of formation of the nitrogen rejection facility of other embodiments of the present invention.As shown in Figure 6, first 16a of denitrogenation portion also can be for having both pipes of measured length.That is, return the pipeline that pipe 23 forms one by the 16a of denitrogenation portion, the reaction solution of reaction solution supply pipe 27, cast.And, be under the situation of cast at first 16a of denitrogenation portion as present embodiment, there is no need to possess the liquid of responding and return pipe 23.
And, hydrogen donor is fed in the 16a of denitrogenation portion of cast from hydrogen donor feeding mechanism 28, in the 16a of denitrogenation portion of cast, the reaction solution of extracting out from second 16b of denitrogenation portion contacts with hydrogen donor, flowing through both has first 16a of denitrogenation portion, the reaction solution of measured length and returns pipe 23, returns second 16b of denitrogenation portion.Here, the set length of first 16a of denitrogenation portion is because flow of reaction solution etc. and different, but as long as just passable can guarantee fully that the reaction solution and the mode that contacts of hydrogen donor are carried out suitable setting.
And, when making the denitrifier granulating, have the situation of adding the part metals class and obtaining good result.In general, these are promoted material as granulating, as ionic species, for example calcium ion, iron ion, as compounds, for example flyash, ferric oxide, lime carbonate etc.About ionic species wherein, preferably, during denitrogenation processing is whole or between the starting period of device, add continuously or off and on.And, about compounds, preferably, when starting and the interpolation of mud add simultaneously.
The hydrogen donor that uses in the present embodiment for example is methyl alcohol, ethanol, Virahol, acetic acid, hydrogen, acetone, glucose, methylethylketone, Tetramethylammonium hydroxide (TMAH) etc., but is not restricted to this, as hydrogen donor, can use existing known whole.
From nitrate ion, nitrite ion reduction reaction to nitrogen, though some difference owing to the kind of hydrogen donor, but anyly all be, since generation and nitrate ion, the equimolar oxyhydroxide ion of nitrite ion, the processed water pH rising in the groove.In general, be fit to the pH of the processed water in the denitrogenation processing is adjusted to 8～9 scope.But, uprise and the calcium ion worrying to contain in the processed water etc. causes under the situation that scale produces in the carbonic acid ionic concentration of hydrogen donor origin, preferably, the processed water pH in the groove is adjusted to 6～7.5 scope, more preferably, be adjusted to 6.3～7.0 scope.Specifically, detect the pH of the processed water of first 16a of denitrogenation portion and second 16b of denitrogenation portion by pH transmitter 48a, the 48b of pH setting device 30, based on detected pH, make pump 44a, 44b work by control device 50a, 50b, pH is adjusted agent be supplied to first 16a of denitrogenation portion and second 16b of denitrogenation portion from pH adjustment agent jar 42, come the pH of the processed water in the regulating tank, make the interior processed water pH of the 16a of denitrogenation portion that wins, second 16b of denitrogenation portion in described pH scope.
MLSS concentration in the denitrogenation portion (first 16a of denitrogenation portion and second 16b of denitrogenation portion) has no particular limits, but in order to reach sufficient denitrogenation processing speed, is preferably the degree of 5000～100000mgMLSS/L.
Embodiment 3
Fig. 7 shows the mode chart of an example of formation of the nitrogen rejection facility of other embodiments of the present invention.As shown in Figure 7, nitrogen rejection facility 14 comprises: denitrifying tank 16, oxidation trough 18, settling bath 20, processed water inflow pipe 22, mud are returned pipe 24, treating water take-off pipe 26a, 26b, 26c, hydrogen donor feeding mechanism 28 and pH setting device 30.Processed water inflow pipe 22 is the streams that are used for processed water is fed to denitrifying tank 16.The outlet of the nitrifying groove of the nitrated device 12 shown in Fig. 1 and the processed water supply opening of the denitrifying tank shown in Fig. 7 16 connect by processed water inflow pipe 22.The treating water outlet of denitrifying tank 16 and the inlet of oxidation trough 18 connect by treating water take-off pipe 26a, and the inlet of the outlet of oxidation trough 18 and settling bath 20 connects by treating water take-off pipe 26b, and the treating water outlet of settling bath 20 is connected with treating water take-off pipe 26c.The mud relief outlet of settling bath 20 and the sludge stream of denitrifying tank 16 inlet via pump 23, are returned pipe 24 by mud and are connected.In denitrifying tank 16, be provided with the whipping appts 32 that the water in the groove is stirred.
Hydrogen donor feeding mechanism 28, be used for hydrogen donor is supplied to denitrifying tank 16, and comprise: accommodate the hydrogen donor jar 34 of hydrogen donor, hydrogen donor delivered to the control device 40 of the supply of the driving of the pump 36 of denitrifying tank 16, the hydrogen donor inflow pipe 38 of forming the stream of hydrogen donor, control pump 36 and control hydrogen donor.The hydrogen donor supply opening of the outlet of hydrogen donor jar 34 and denitrifying tank 16 via pump 36, connects by hydrogen donor inflow pipe 38.Pump 36 electrically connects with control device 40.
PH setting device 30 is used to adjust the pH of the processed water in the denitrifying tank 16, and comprises: pH adjusts agent jar 42, and the pH that is used to accommodate alkali such as acid such as hydrochloric acid or sodium hydroxide adjusts agent etc.; Pump 44 is used for that pH is adjusted agent and delivers to denitrifying tank 16; PH adjusts agent inflow pipe 46, forms the stream that pH adjusts agent; PH transmitter 48 is used to measure the pH value of the processed water in the denitrifying tank 16; And control device 50, be used for the driving of control pump 44, and control pH adjusts the supply of agent.PH adjusts the outlet of agent jar 42 and the pH of denitrifying tank 16 adjusts the agent supply opening, via pump 44, adjusts agent inflow pipe 46 by pH and connects.PH transmitter 48 electrically connects with pump 44 with control device 50, control device 50.
Then, the water treatment method that present embodiment is related to and the action of water treatment device 1 describe.At first, the processed water that will contain fluorine and ammonium-nitrogen is delivered to the processed tank of the fluorine treatment unit 10 shown in Fig. 1.In this processed tank, in flow and concentration equalization, and adjust after the pH processed water, processed water is delivered to the reactive tank of fluorine treatment unit 10.And, calcium cpd is fed in the reactive tank.And, in the reactive tank of fluorine treatment unit 10, make fluorine and calcium cpd reaction in the processed water, generate Calcium Fluoride (Fluorspan) (CaF 2).Here,, also flocculation agent and calcium cpd can be fed in the reactive tank of fluorine treatment unit 10 simultaneously, make the Calcium Fluoride (Fluorspan) gatheringization of described generation in order to improve the processing efficiency of the fluorine in the processed water.And, in the settling bath of fluorine treatment unit 10, the processed water that contains (gatheringization) Calcium Fluoride (Fluorspan) is carried out solid-liquid separation, from processed water, remove fluorine (and Calcium Fluoride (Fluorspan)).
And fluorine treatment unit 10 also can comprise a plurality of reactive tanks.For example, also can comprise first reactive tank and second reactive tank,, make the treating water and the calcium cpd reaction that contain fluorine and ammonium-nitrogen, generate Calcium Fluoride (Fluorspan),, add flocculation agent, make the Calcium Fluoride (Fluorspan) gatheringization at second reactive tank at first reactive tank.And, also the stirring mechanism that the water in the groove is stirred can be set at reactive tank.
Be supplied to the calcium cpd of the reactive tank of fluorine treatment unit 10,, do not limited especially, for example also have calcium hydroxide (Ca (OH) so long as the compound that fluorine is separated out as Calcium Fluoride (Fluorspan) can be got final product 2), calcium chloride (CaCl 2), calcium sulfate (CaSO 4) etc.And,, for example can use organic polymer flocculation agent such as inorganic flocculants such as POLY ALUMINIUM CHLORIDE or Tai-Ace S 150 or anionic property polymer etc. as flocculation agent.
Then, will remove the processed water that contains ammonium-nitrogen of fluorine, delivered in the processed tank of the nitrated device 12 shown in Fig. 1.In this processed tank, in flow and concentration equalization, and adjust after the pH processed water, processed water is delivered to nitrifying groove.In nitrifying groove, fill the microorganism maintenance carrier that forms on the carrier by the microbial film that contains nitrifier is remained on.And, being configured in the nitrifying groove, formation can connect air leading-in conduit (not shown), and supplies air in the interior processed water of nitrifying groove.And, at nitrifying groove, keep the effect of the nitrifier of carrier by microorganism, make the nitrated one-tenth nitrate ammonia of ammonium-nitrogen, nitrite nitrogen in the processed water.Here, nitrifier is for the ammonia oxidizing bacteria of bacterium that the independent battalion of the nitrated one-tenth nitrite nitrogen of the ammonium-nitrogen that contains in the processed water is nourished one's nature, with the nourish one's nature nitrite-oxidizing bacteria etc. of bacterium of the independent battalion of the nitrated one-tenth nitrate ammonia of nitrite nitrogen.
Keep the carrier of nitrifier,, can utilize for example sponge, gel, plastic molded article etc. though have no particular limits.Specifically, preferably utilize hydrophilic polyurethane(s) sponge, polyvinyl alcohol gel etc.And, as described later, to return under the denitrogenation particulate situation, the carrier of maintenance nitrifier is not necessarily.
Then,, promptly contain the processed water of nitrate ammonia, nitrite nitrogen, deliver to by processed water inflow pipe 22 in the denitrifying tank 16 of nitrogen rejection facility 14 the nitration treatment liquid after the described nitration treatment.Here, denitrifying tank 16 is denitrifying tanks 16 of complete mixed type, when denitrogenation processing, processed water (continuously) is supplied to denitrifying tank 16.And, make pump 36 work, the hydrogen donor in the hydrogen donor jar 34 of hydrogen donor feeding mechanism 28 is supplied to denitrifying tank 16 by hydrogen donor inflow pipe 38.In denitrifying tank 16, under swimming state in water, the mud that contains denitrifier accommodates, and by the effect of this denitrifier, nitrate ion, nitrite ion in the processed water are reduced into nitrogen.Using under the situation of methyl alcohol as hydrogen donor, the nitrate ion in the processed water, nitrite ion are reduced into nitrogen by the reaction shown in the following reaction formula.
2NO 2-+CH 3OH→N 2+CO 2+H 2O+2OH
6NO 3 -+5CH 3OH→3N 2+5CO 2+7H 2O+6OH -
Then, via treating water take-off pipe 26a, will deliver to oxidation trough 18 by the treating water that denitrogenation processing has been removed nitrate ion, nitrite ion, and, make oxidation operations such as hydrogen donor residual in the treating water at oxidation trough 18.Then, via treating water take-off pipe 26b, the treating water of having removed hydrogen donor is delivered to settling bath 20.And in the bottom of settling bath 20, (in the present embodiment for the own granulationization) denitrifier that contains in the processed water is piled up as mud, and the last clarification of water on the top of settling bath 20 is taken out from treating water take-off pipe 26c.And, make pump 23 work, the mud that is deposited in the bottom of settling bath 20 is returned pipe 24 from mud return once more in the denitrifying tank 16.And, under the situation that nitration treatment that nitrated device 12 carries out is carried out with the mud of the formula of swimming, also mud can be returned nitrifying groove.
Fig. 8 shows the mode chart of an example of formation of the nitrogen rejection facility of other embodiments of the present invention.In nitrogen rejection facility 14, will independently not be provided with denitrifying tank 16 by settling bath 20, as shown in Figure 8, the partition 52 of lower openings can be set in denitrifying tank 16 also, form denitrogenation chamber 54 and settling chamber 56.And solid-liquid separation also can not used the settling bath 20 shown in Fig. 2, reach the settling chamber 56 shown in Fig. 8, but carries out with any device such as gas-solid separator (GSS), membrane separation units.
Oxidation trough 18 is used for the organism such as hydrogen donor that processed water contains are carried out oxygenolysis by action of microorganisms.As shown in Figure 7, oxidation trough 18 also can be arranged on the upstream side of settling bath 20, also can be arranged on the downstream side of settling bath 20.
Then, the Supply Method to hydrogen donor is described in detail.Usually, calculate the supply of the needed hydrogen donor of denitrogenation processing from the nitrate ion of the processed water that is fed to denitrifying tank 16, the concentration of nitrite ion, and this supply is not changed, continuously hydrogen donor is supplied to denitrifying tank 16.Therefore, the concentration of the hydrogen donor in the denitrifying tank 16 is low roughly certain.And, in order to carry out denitrogenation processing effectively, (theoretical amount of the hydrogen donor that needs) about 1.2 times of the needed hydrogen donor supply of denitrogenation processing of nitrate ion in the denitrifying tank 16 and nitrite ion is supplied to denitrifying tank 16.
But, in the present embodiment, hydrogen donor is supplied to denitrifying tank 16 in the mode of the concentration changes with time of the hydrogen donor in the denitrifying tank 16.As an example; at control device 40; the calculating formula of the hydrogen donor addition that record is corresponding with former water nitrogen concentration measurement result is (when carrying out adding intermittence in advance; be interpolation and the calculating formula of the time of interpolation); based on this calculating formula, the work of control pump 36, and the supply of regulating hydrogen donor; make the poor of the peak concentration of hydrogen donor and Cmin, become the concentration difference of the own granulationization of inducing denitrifier.That is, carry out volume supply-a small amount of supply of the supply of hydrogen donor described later-stop, hydrogen donor.
Here, preferably, (for example, in the hydraulic residence time of the processed water in the denitrifying tank 16) peak concentration of hydrogen donor in the denitrifying tank 16 and the difference of Cmin be more than the 50mgTOC/L, hydrogen donor is fed in the denitrifying tank 16, more preferably, concentration difference is more than the 100mgTOC/L, and hydrogen donor is fed in the denitrifying tank 16.When the difference of the peak concentration of the hydrogen donor in the denitrifying tank 16 and Cmin during less than 50mgTOC/L, the situation of the own granulationization of denitrifier can not be fully induced in existence.
Here, preferably, the Cmin of the hydrogen donor in the denitrifying tank is (greater than 0, smaller or equal to 1/2 scope of peak concentration) in below 1/2 of peak concentration.When described Cmin surpass peak concentration 1/2 the time, exist denitrifier own granulationization induce the change situation of difficult.
In the present embodiment, by hydrogen donor is supplied to denitrifying tank 16 off and on, can make the concentration changes with time of the hydrogen donor in the denitrifying tank 16.Promptly, because when the supply of hydrogen donor, the concentration of the hydrogen donor in the denitrifying tank 16 is increased, and when the supply of hydrogen donor stops, can make the concentration of the hydrogen donor in the denitrifying tank 16 reduce (hydrogen donor is owing to denitrogenation processing is consumed), therefore can make the concentration changes with time of the hydrogen donor in the denitrifying tank 16.But, the supply of the supply of hydrogen donor and stand-by time, hydrogen donor need be configured to, the peak concentration of the hydrogen donor in (for example, in the hydraulic residence time (HRT) of the processed water in the denitrifying tank 16) denitrifying tank 16 and the difference of Cmin are for example more than the 50mgTOC/L.
Preferably, the supply stand-by time of hydrogen donor is than 50% length of the supply time of hydrogen donor.When the supply stand-by time of hydrogen donor at 50% when following of the supply time of hydrogen donor, even the difference of the peak concentration of hydrogen donor and Cmin for example more than the 50mgTOC/L, also can exist denitrifier own granulationization induce the change situation of difficult.
Under repeatedly situation was carried out in the supply of hydrogen donor and the circulation that stops, preferably, once 50% of the hydraulic residence time of time ratio of circulation (supplying-stop) is short, promptly carries out more than twice circulation with respect to the hydraulic residence time.When only carrying out circulation time one time with respect to the hydraulic residence time, the difference of the peak concentration of hydrogen donor and Cmin becomes big, but, because the high treating water of concentration of hydrogen donor is discharged outside denitrifying tank 16, therefore when the load that is used for removing from treating water the oxidation trough 18 of hydrogen donor uprises, there is the situation of the water quality deterioration for the treatment of water.And because in denitrogenation processing, it is many that the hydrogen donor that is not effectively used becomes, and therefore needing increases the hydrogen donor supply, the situation that exists the cost of denitrogenation processing to uprise.
And, in the present embodiment, with respect to the nitrate ion in the denitrifying tank 16 and the concentration of nitrite ion, supply (theoretical amount of the hydrogen donor that needs) with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of benchmark value is supplied to the first supply operation of denitrifying tank 16 and will be supplied to the second supply operation of denitrifying tank 16 more than the hydrogen donor of the amount of described benchmark value, by hydrogen donor being supplied to denitrifying tank 16, can make the concentration changes with time of the hydrogen donor in the denitrifying tank 16.But, need be configured in the first supply operation and time of supply hydrogen donor of the second supply operation and the supply of in this time, supplying, the peak concentration of the hydrogen donor in the denitrifying tank 16 and the difference of Cmin are for example more than the 50mgTOC/L.
Preferably, the supply time of the hydrogen donor in the first supply operation is than 50% length of the supply time of the hydrogen donor in the second supply operation.When 50% when following of the supply time of the hydrogen donor of supply time in the second supply operation of the hydrogen donor of first supply in the operation; even the difference of the peak concentration of hydrogen donor and Cmin for example more than the 50mgTOC/L, also can exist denitrifier own granulationization fully induce the change situation of difficult.
Circulation in the first supply operation and the second supply operation is carried out under repeatedly the situation, preferably, 50% weak point of the hydraulic residence time of time ratio of once circulation (the first supply operation-second supply operation) promptly carries out more than twice circulation with respect to the hydraulic residence time.When only carrying out circulation time one time with respect to the hydraulic residence time, the difference of the peak concentration of hydrogen donor and Cmin becomes big, but, because the high treating water of concentration of hydrogen donor is discharged outside denitrifying tank 16, therefore when the load that is used for removing from treating water the oxidation trough 18 of hydrogen donor uprises, there is the situation of the water quality deterioration for the treatment of water.And because in denitrogenation processing, it is many that the hydrogen donor that is not effectively used becomes, and therefore needs to increase the supply of hydrogen donor, the situation that exists the cost of denitrogenation processing to uprise.
And, in the present embodiment, preferably, the Cmin of the hydrogen donor in the denitrifying tank 16 below 100mgTOC/L, more preferably, in the scope of 10mgTOC/L～100mgTOC/L.When the Cmin of hydrogen donor during greater than 100mgTOC/L, exist denitrifier own granulationization fully induce the change situation of difficult.And, when the Cmin of hydrogen donor during, can not carry out denitrogenation processing effectively less than 10mgTOC/L, there is the situation of the water quality deterioration for the treatment of water.
And, when making the denitrifier granulating, have the situation of adding the part metals class and obtaining good result.In general, these are promoted material as granulating, as ionic species, for example calcium ion, iron ion, as compounds, for example flyash, ferric oxide, lime carbonate etc.About ionic species wherein, preferably, during denitrogenation processing is whole or between the starting period of device, add continuously or off and on.And, about compounds, preferably, when device starts and the interpolation of mud add simultaneously.
The hydrogen donor that uses in the present embodiment for example is methyl alcohol, ethanol, Virahol, acetic acid, hydrogen, acetone, glucose, methylethylketone, Tetramethylammonium hydroxide (TMAH) etc., but is not restricted to this, as hydrogen donor, can use existing known whole.
From nitrate ion, nitrite ion reduction reaction to nitrogen, though some difference owing to the kind of hydrogen donor, but anyly all be, since generation and nitrate ion, the equimolar oxyhydroxide ion of nitrite ion, floating processed water pH rising of going up in the groove.In general, be fit to the pH of the processed water in the denitrogenation processing is adjusted to 8～9 scope.But, uprise and the calcium ion worrying to contain in the processed water etc. causes under the situation that scale produces in the carbonic acid ionic concentration of hydrogen donor origin, preferably, the floating processed water pH that goes up in the groove is adjusted to 6～7.5 scope, more preferably, be adjusted to 6.3～7.0 scope.Specifically, detect the pH of processed water by the pH transmitter 48 of pH setting device 30, based on the pH that detects, make pump 44 work by control device 50, pH is adjusted agent be supplied to denitrifying tank 16 from pH adjustment agent jar 42, regulate the pH of the processed water in the denitrifying tank 16, make processed water pH in the denitrifying tank 16 in described pH scope.
As mentioned above; when processed water (continuously) is supplied to the denitrifying tank of complete mixed type; hydrogen donor is supplied to denitrifying tank 16; make the concentration changes with time of the hydrogen donor in the denitrifying tank 16; and the peak concentration of the hydrogen donor in the denitrifying tank 16 and the difference of Cmin be preferably for example more than the 50mgTOC/L, thereby can make the denitrifier granulating.By making the denitrifier granulating,, therefore can improve the processing speed of denitrogenation processing, and can make equipment miniaturization or cost degradation owing to can increase the microorganism concn (sludge concentration) in the denitrifying tank.
As the treatment process of nitrogenous water, be not defined as and use the water treatment device shown in Fig. 1.Fig. 9 to Figure 14 is the summary pie graph that an one example is shown.(A) of Fig. 9 and (B) show the treatment process of the nitrogenous water of handling with the order of the denitrogenation operation A of nitrated operation, present embodiment or B, precipitation process operation.Nitrated operation illustrates as described, for (there is under the condition of oxygen) operation that is oxidized to nitric acid or nitrous acid in ammonium-nitrogen under the aerobic condition.The denitrogenation operation A of present embodiment for hydrogen donor off and on or the volume supply-be supplied to denitrifying tank 16 (that is, using the nitrogen rejection facility of Fig. 7, Fig. 8) on a small quantity, and under oxygen free condition, nitric acid or nitrite nitrogen are reduced into the operation of nitrogen.And, the denitrogenation process B of present embodiment is for to supply hydrogen donor (promptly in the mode that forms set concentration difference between first 16a of denitrogenation portion and second 16b of denitrogenation portion, use the nitrogen rejection facility of Fig. 2 to Fig. 6), and under oxygen free condition, nitric acid or nitrite nitrogen are reduced into the operation of nitrogen.The precipitation process operation illustrates as described, is the separation circuit of mud in the treating water and treating water.And,, have and will return the pipeline of nitrated operation with the isolating mud for the treatment of water at (A) of Fig. 9 with (B).Like this, the granule sludge circulation that denitrogenation operation A or B by present embodiment are obtained.In this case, owing to form the particle that contains nitrifier, therefore nitrated operation also can be handled by same particle.
(A) of Figure 10 and (B) show the treatment process of the nitrogenous water of handling with the order of the denitrogenation operation A of organism treatment process, nitrated operation, present embodiment or B, precipitation process operation.The organism treatment process is for to handle the organism nitrogen in the processed water or other organism under aerobic or anaerobic condition, and removing the organic operation that simultaneously organism nitrogen is transformed to ammonium-nitrogen.The treatment process of (A) of Figure 10 and the nitrogenous water that (B) illustrates too, the granule sludge circulation that denitrogenation operation A or B by present embodiment are obtained.In this case, owing to form the particle that contains nitrifier, therefore nitrated operation also can be handled by same particle.
(A) of Figure 11 and (B) show the treatment process of the nitrogenous water of handling with the order of the denitrogenation operation A of nitrated operation, present embodiment or B, oxidation operation, precipitation process operation.Oxidation operation illustrates as described, the operation that the remainder of the hydrogen donor that adds after the denitrogenation is carried out aerobic processing.The treatment process of (A) of Figure 11 and the nitrogenous water that (B) illustrates too, the granule sludge circulation that denitrogenation operation A or B by present embodiment are obtained.In this case, owing to form the particle that contains nitrifier, therefore nitrated operation also can be handled by same particle.
(A) of Figure 12 and (B) show the treatment process of the nitrogenous water of handling with the order of the denitrogenation operation A of present embodiment or B, nitrated operation, existing denitrogenation operation, oxidation operation, precipitation process operation.(A) of Figure 13 and (B) show the treatment process of the nitrogenous water of handling with the order of the denitrogenation operation A of existing denitrogenation operation, nitrated operation, present embodiment or B, oxidation operation, precipitation process operation.Existing denitrogenation operation for do not carry out with hydrogen donor off and on or the volume supply-be supplied to denitrifying tank 16 on a small quantity or between first 16a of denitrogenation portion and second 16b of denitrogenation portion, supply hydrogen donor in the mode that forms set concentration difference, and under oxygen free condition, nitric acid or nitrite nitrogen are reduced into the operation of nitrogen.And, at (A) of Figure 12 with (B) or in the treatment process of Figure 13 (A) and nitrogenous water (B), in order to improve handling property, the part of the treating water that will obtain by nitrated engineering is returned denitrogenation operation A, B or the existing denitrogenation operation of the present embodiment that is configured in leading portion.(A) of Figure 12 and (B) and the treatment process of Figure 13 (A) and the nitrogenous water that (B) illustrates too, the granule sludge circulation that denitrogenation operation A or B by present embodiment are obtained.In this case, owing to form the particle that contains nitrifier, therefore nitrated operation also can be handled by same particle.
(A) of Figure 14 and (B) show the treatment process of the nitrogenous water of handling with the order of the denitrogenation operation A of organism treatment process, nitrated operation, present embodiment or B, oxidation operation, precipitation process operation.The treatment process of (A) of Figure 14 and the nitrogenous water that (B) illustrates too, the granule sludge circulation that denitrogenation operation A or B by present embodiment are obtained.In this case, owing to form the particle that contains nitrifier, therefore nitrated operation also can be handled by same particle.
Embodiment
Below, list embodiment and comparative example, more specifically at length the present invention will be described, but the present invention is not limited to following embodiment.
(embodiment 1)
In embodiment 1, use and the identical device shown in Fig. 2, with the continuous water flowing of processed water of the water quality shown in the following table 1 to denitrifying tank.The volume of first 16a of denitrogenation portion is 4L, and the volume of the second denitrogenation portion is 40L.Use methyl alcohol as hydrogen donor, this methyl alcohol is supplied to the first denitrogenation portion continuously, and the difference that makes the Cmin of the methyl alcohol in the second denitrogenation portion among the HRT of the peak concentration of the methyl alcohol in the first denitrogenation portion among the HRT of the processed water in the second denitrogenation portion and the processed water in the second denitrogenation portion is more than 50mgTOC/L.With respect to handling the nitrogen amount, the supply of methyl alcohol is 3kg methyl alcohol/kg nitrogen.And, when on-test, will be supplied to the first denitrogenation portion and the second denitrogenation portion with the active sludge that the mode of about 500mgMLSS/L is carried out denitrogenation.And, use hydrochloric acid that the pH of the processed water of the first denitrogenation portion and the second denitrogenation portion is adjusted into 6.5.And, the mud of staying the settling bath that is arranged at the denitrifying tank back segment is returned to the first denitrogenation portion.Test was carried out 33 days.
Table 1
SODIUMNITRATE ?100mgN
Calcium chloride ?300mgCa
Phosphoric acid ?2mgP
Tap water ?1L
(comparative example 1)
In comparative example 1, the first denitrogenation portion is not set, except the difference with the peak concentration of methyl alcohol among the HRT of the processed water in the second denitrogenation portion and Cmin maintains not enough 50mgTOC/L, test with the condition identical with embodiment 1.
Figure 15 shows in the test of embodiment 1 with respect to through fate, the figure of the variation of MLSS concentration.Figure 16 shows in the test of embodiment 1 with respect to through fate, the figure of the variation of the processing speed of denitrogenation processing.Figure 17 illustrates in the test of embodiment 1 with respect to through fate the figure that the nitrate ion concentration for the treatment of water is passed.Figure 18 illustrates in the test of embodiment 1 with respect to through fate the figure that SVI changes.As shown in figure 15, in embodiment 1, through in the fate, MLSS concentration rises, from on-test at the 33rd day, MLSS concentration reaches 8000mgMLSS/L.And as shown in figure 16, when MLSS concentration rose, the processing speed of denitrogenation processing also rose, from on-test at the 33rd day, reach about 2kgN/m 3/ day, confirm to obtain higher processing speed.And as shown in figure 17, the nitrate ion concentration in the treating water is lower, carries out stable treated during the validation test.And as shown in figure 18, through reducing in the fate, SVI value very little (precipitation threshold is good) is confirmed the formation particle as the SVI of the index of sludge settling.And the SVI of general active sludge is 120～150mL/g.On the other hand, in comparative example 1, from on-test at the 33rd day, MLSS concentration does not reach the degree of 2000mgMLSS/L, the processing speed of denitrogenation processing is 0.4kgN/m 3/ day.
(embodiment 2)
In embodiment 2, except the volume of the first denitrogenation portion is 20L, 12L, 4L, 2L, 1L, test with the condition identical with embodiment 1.And after 25 days on-tests, whether the mud that contains denitrifier with following benchmark evaluation denitrifying tank granulating, and it is summarized in the table 2.
Zero contains the whole granulatings of mud of denitrifier
△ contains the mud part granulating of denitrifier
* the mud that contains denitrifier does not have granulating
Table 2
The first denitrogenation portion capacity Ratio with respect to the second denitrogenation portion What granulating formed has or not
Do not have ??0 ??×
??20L ??1/2 ??△
??12L ??3/10 ??○
??4L ??1/10 ??○
??2L ??1/20 ??○
??1L ??1/40 ??△
Can judge from table 2, under the situation that the first denitrogenation portion (described comparative example) is not set, even from on-test through 33 days, denitrifier does not have granulating yet.And the volume of the volume/second denitrogenation portion by making the first denitrogenation portion is 3/10,1/10,1/20, from on-test through after 33 days, can make the whole granulatings of the mud that contains denitrifier, obtain good result.
(embodiment 3)
In embodiment 3, use and the identical device shown in Fig. 2, with the continuous water flowing of processed water of the water quality shown in the following table 3 to denitrifying tank.Use methyl alcohol as hydrogen donor, this methyl alcohol is supplied to the first denitrogenation portion off and on, and the difference that makes the Cmin of the methyl alcohol in the second denitrogenation portion among the HRT of the peak concentration of the methyl alcohol in the first denitrogenation portion among the HRT of the processed water in the second denitrogenation portion and the processed water in the second denitrogenation portion is more than 50mgTOC/L.The stand-by time of hydrogen donor was fixed as 1: 4 with the ratio of supply time, and the round-robin time of supplying-stopping to change cycling time as 1/5 of HRT by flowing into nitrogen load.In addition, under the condition identical, test with embodiment 1.Test was carried out 50 days.
Table 3
SODIUMNITRATE ?40mgN
Calcium chloride ?300mgCa
Phosphoric acid ?1mgP
Tap water ?1L
(comparative example 2)
In comparative example 2, methyl alcohol is supplied to the first denitrogenation portion continuously.The difference of the Cmin of the methyl alcohol among the HRT of the processed water in the peak concentration of the methyl alcohol among the HRT of the processed water in the second denitrogenation portion in the first denitrogenation portion and the second denitrogenation portion in the second denitrogenation portion maintains not enough 50mgTOC/L.In addition, under the condition identical, test with embodiment 3.
Figure 19 illustrates in the test of embodiment 3 with respect to through fate, the figure of the change in concentration of MLSS.Figure 20 illustrates in the test of embodiment 3 with respect to through fate the figure that the processing speed of denitrogenation processing changes.Figure 21 illustrates in the test of embodiment 3 with respect to through fate the figure that the nitrate ion concentration for the treatment of water is passed.Figure 22 illustrates in the test of embodiment 3 with respect to through fate the figure that SVI changes.As shown in figure 19, in embodiment 3, through in the fate, MLSS concentration rises, from on-test at the 50th day, MLSS concentration reaches 8000mgMLSS/L.And as shown in figure 20, the processing speed of denitrogenation processing also rises, from on-test at the 50th day, reach about 2kgN/m 3/ day, and confirm to obtain higher processing speed.And as shown in figure 21, the nitrate ion concentration in the treating water reduces, and confirms to carry out stable treated at duration of test.And, as shown in figure 22,, through reducing in the fate, confirm to form the particle of the value very little (precipitation threshold is good) of SVI as the SVI of the index of sludge settling.On the other hand, in comparative example 2, from on-test at the 50th day, MLSS concentration only reaches 1000mgMLSS/L, the processing speed of denitrogenation processing also is 0.25kgN/m 3/ day.And the TOC concentration in the first denitrogenation portion of this moment is 30～40mgTOC/L, in the second denitrogenation portion, is value roughly the same below the 15mgTOC/L during whole.
(embodiment 4)
In embodiment 4, use and the identical device shown in Fig. 4, be the second denitrogenation portion of 40L with the continuous water flowing of processed water to the volume of the water quality shown in the following table 4.And, with the reaction solution in the second denitrogenation portion without interruption be the first denitrogenation portion (HRT of the first denitrogenation portion 6 minutes～144 minutes) of 4L to volume.Use methyl alcohol as hydrogen donor, this methyl alcohol is supplied to the first denitrogenation portion off and on, and the difference that makes the Cmin of the methyl alcohol in the second denitrogenation portion among the HRT of the peak concentration of the methyl alcohol in the first denitrogenation portion among the HRT of the processed water in the second denitrogenation portion and the processed water in the second denitrogenation portion is more than 50mgTOC/L.The stand-by time of the hydrogen donor ratio with supply time was fixed as 1: 19, and the round-robin time of adding-stopping to change corresponding to the inflow velocity of processed water, be the second denitrogenation portion HRT 1/5.This moment, the methyl alcohol supply was 2.7kg methyl alcohol/kg nitrogen with respect to handling the nitrogen amount.And, when on-test, will be supplied to the first denitrogenation portion and the second denitrogenation portion with the active sludge that the mode of about 500mgMLSS/L is carried out denitrogenation.And, use hydrochloric acid that the pH of the processed water of the first denitrogenation portion and the second denitrogenation portion is adjusted into 6.5～7.0.And, the mud of staying the settling bath that is arranged at denitrogenation portion back segment is returned to the first denitrogenation portion.Test was carried out 33 days.
Table 4
SODIUMNITRATE ?100mgN
Calcium chloride ?300mgCa
Phosphoric acid ?2mgP
Tap water ?1L
In comparative example 3, the first denitrogenation portion is not set, except the difference with the peak concentration of methyl alcohol among the HRT of the processed water in the second denitrogenation portion and Cmin maintains not enough 50mgTOC/L, test with the condition identical with embodiment 4.
Figure 23 illustrates in the test of embodiment 4 with respect to through fate, the figure of the change in concentration of MLSS.Figure 24 illustrates in the test of embodiment 4 with respect to through fate the figure that the processing speed of denitrogenation processing changes.Figure 25 illustrates in the test of embodiment 4 with respect to through fate the figure that the nitrate ion concentration for the treatment of water is passed.Figure 26 illustrates in the test of embodiment 4 with respect to through fate the figure that SVI changes.As shown in figure 23, in embodiment 4, through in the fate, MLSS concentration rises, from on-test at the 33rd day, MLSS concentration reaches 5000mgMLSS/L.And as shown in figure 24, when MLSS concentration rose, the processing speed of denitrogenation processing also rose, from on-test at the 33rd day, reach about 2.5kgN/m 3/ day, and confirm to obtain higher processing speed.And as shown in figure 25, the nitrate ion concentration in the treating water reduces, and confirms to carry out stable treated at duration of test.And, as shown in figure 26,, through reducing in the fate, confirm to form the particle of the value very little (settleability is good) of SVI as the SVI of the index of sludge settling.And the SVI of general active sludge is 120～150mL/g.On the other hand, in comparative example 3, from on-test at the 33rd day, MLSS concentration only reaches 2000mgMLSS/L, the processing speed of denitrogenation processing also is 0.4kgN/m 3/ day.
In embodiment 4, contain originally mud for the denitrifier of the shape that swims, from on-test through after about 2 weeks, be varied to granular; After about 3 weeks, roughly all be changed to the granule sludge that diameter is the 0.3mm degree; After 30 days, be changed to the granule sludge that diameter is the 0.5mm degree.
And Figure 27 is the figure that the TOC change in concentration of the methyl alcohol in the first denitrogenation portion and the second denitrogenation portion is shown.As shown in figure 27, though in the first denitrogenation portion, in effluxion, the TOC change in concentration of methyl alcohol, in the second denitrogenation portion, the TOC concentration of methyl alcohol is lower concentration, confirms as roughly certain.And in an embodiment, the TOC concentration of the methyl alcohol in the treating water of acquisition is 0.362gTOC/g methyl alcohol.
In embodiment 5, utilize the treatment process shown in (B) of Figure 11 to test.In nitrated operation, use the nitrifying groove of volume as 36L, in the denitrogenation process B, use volume as the first denitrogenation portion of 4L and volume as the second denitrogenation portion of 36L, in the oxide treatment operation, use the oxidation trough of volume as 20L.And the water area of the settling bath in the precipitation process operation is 0.012m 2
The continuous water flowing of processed water with the water quality shown in the following table 5.And, in nitrifying groove and oxidation trough, expose air to the open air, DO is maintained more than the 2mgO/L.Use methyl alcohol as hydrogen donor, and be added into the first denitrogenation portion off and on.The once circulation of the interpolation of hydrogen donor-stop, 1/4 of second HRT of denitrogenation portion that calculates for the volumometer of the total of returning flow from processed water and mud and the second denitrogenation portion.The stand-by time of hydrogen donor is 1: 19 with the ratio of supply time.In embodiment 5, be mode below the 10mgN/L with the whole nitrogen concentrations from the treating water that settling bath is discharged, stage ground increases the processed water yield, and load is risen.And the addition of methyl alcohol is 3kg methyl alcohol/kgN with respect to flowing into the nitrogen amount.And, when on-test, will be supplied to the first denitrogenation portion and the second denitrogenation portion with the active sludge that the mode of about 500mgMLSS/L is carried out denitrogenation.And, use hydrochloric acid or sodium hydroxide, the pH of the processed water of the nitrifying groove and the second denitrogenation portion is adjusted into 7.0～7.5.And the mud that uses vacuum pump will stay the settling bath that is arranged at denitrogenation portion back segment is returned to nitrifying groove.
Table 5
Ammonium chloride ?33mgN
SODIUMNITRATE ?5mgN
Calcium chloride ?300mgCa
Phosphoric acid ?2mgP
Tap water ?1L
In comparative example 4, except the first denitrogenation portion not being set and adding continuously the hydrogen donor, test with the condition identical with embodiment 5.
Figure 28 illustrates in the test of embodiment 5 and comparative example 4 with respect to through fate, the figure of nitrated velocity variations.Figure 29 illustrates in the test of embodiment 5 and comparative example 4 with respect to through fate, the figure of denitrogenation velocity variations.Figure 30 illustrates in the test of embodiment 5 and comparative example 4 with respect to through fate, the figure of the change in concentration of MLSS.In comparative example 4, though temporary transient nitrated speed rises to 0.3kgN/m 3/ it is neighbouring, denitrogenation speed rises to 0.4kgN/m 3/ day near, but fierce from the outflow of the mud of settling bath, can not keep sufficient sludge concentration.Therefore, MLSS concentration also reduces, and as a result of (94 days), nitrated velocity-stabilization is at 0.15kgN/m 3/ day near, the denitrogenation velocity-stabilization is at 0.18kgN/m 3Near/the sky.And the state of mud does not almost have granulating.In embodiment 5, confirm the increase of MLSS concentration, the nitrated speed and the denitrogenation speed that accompany therewith also rise, and after 2 months, nitrated speed and denitrogenation speed all rise to 0.6kgN/m after on-test 3The degree in/sky, the speed of 3 times of degree of acquisition comparative example 4.And the mud state is realized own granulationization, and the formation diameter is the particle about 200 μ m.
Figure 31 is the figure that the change of water quality in the first denitrogenation portion of embodiment 5 is shown.Figure 32 is the figure that the change of water quality in the second denitrogenation portion of embodiment 5 is shown.In the first denitrogenation portion of embodiment 5,, confirm the change of the hydrogen donor concentration of 0～200mgTOC/L degree (the about 200mgTOC/L of peak concentration) as TOC concentration; In the second denitrogenation portion,, confirm the change of the hydrogen donor concentration of 2～18mgTOC/L degree (the about 2mgTOC/L of Cmin) as TOC concentration.

Claims (25)

1, a kind of denitrifying method, when processed water was supplied to denitrifying tank, the supply hydrogen donor was reduced into nitrogen by denitrifier with nitrate ion, the nitrite ion that is contained in the processed water, and described denitrifying method is characterised in that,
As described denitrifying tank, the second denitrogenation portion of the first denitrogenation portion and the described first denitrogenation portion back segment is set,
Be supplied to the described first denitrogenation portion to major general's hydrogen donor, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
2, denitrifying method according to claim 1 is characterized in that,
Be supplied to the described first denitrogenation portion to major general's hydrogen donor, making the difference of the Cmin of the peak concentration of the hydrogen donor in the described first denitrogenation portion and the hydrogen donor in the described second denitrogenation portion is more than the 50mgTOC/L.
3, denitrifying method according to claim 1 is characterized in that,
The volume of the described second denitrogenation portion of the volumetric ratio of the described first denitrogenation portion is little.
4, denitrifying method according to claim 1 and 2 is characterized in that,
Hydrogen donor is supplied to the described first denitrogenation portion off and on.
5, denitrifying method according to claim 1 and 2 is characterized in that,
Concentration with respect to nitrate ion, nitrite ion, supply with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of described benchmark value is supplied to the first supply operation of the described first denitrogenation portion and will be supplied to the second supply operation of the described first denitrogenation portion more than the hydrogen donor of the amount of described benchmark value, and hydrogen donor is supplied to the described first denitrogenation portion.
6, denitrifying method according to claim 1 is characterized in that,
The described first denitrogenation portion is a plurality of grooves.
7, denitrifying method according to claim 1 is characterized in that,
The described second denitrogenation portion is a plurality of grooves.
8, a kind of denitrification processing device, comprise: denitrifying tank, processed water is supplied to the processed water feeding mechanism of described denitrifying tank and the hydrogen donor feeding mechanism that hydrogen donor is supplied to described denitrifying tank, in described denitrifying tank, by denitrifier nitrate ion, the nitrite ion that contains in the processed water is reduced into nitrogen, described denitrification processing device is characterised in that
The second denitrogenation portion that described denitrifying tank has the first denitrogenation portion and is arranged at the back segment of the described first denitrogenation portion;
Described hydrogen donor feeding mechanism to major general's hydrogen donor is supplied to the described first denitrogenation portion, makes in the described first denitrogenation portion and formation hydrogen donor concentration difference between in the described second denitrogenation portion.
9, a kind of denitrifying method, when processed water was supplied to denitrogenation portion, the supply hydrogen donor was reduced into nitrogen by denitrifier with nitrate ion, the nitrite ion that is contained in the processed water, and described denitrifying method is characterised in that,
As described denitrogenation portion, the first denitrogenation portion and the second denitrogenation portion are set,
The part of the reaction solution in the described second denitrogenation portion is supplied to the described first denitrogenation portion,
And be supplied to the described first denitrogenation portion to major general's hydrogen donor, and and return to the described second denitrogenation portion, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
10, denitrifying method according to claim 9 is characterized in that,
The difference of the Cmin of the hydrogen donor in the peak concentration of the hydrogen donor in the described first denitrogenation portion and the described second denitrogenation portion is more than the 50mgTOC/L.
11, denitrifying method according to claim 9 is characterized in that,
When described processed water being supplied to the described second denitrogenation portion and hydrogen donor is supplied to the described first denitrogenation portion, supply contains the water of nitrate ion, nitrite ion.
12, denitrifying method according to claim 11 is characterized in that,
The water that contains described nitrate ion, nitrite ion is to be supplied to the processed water ramose water of the described second denitrogenation portion.
13, according to claim 9 or 10 described denitrifying methods, it is characterized in that,
The supply hydrogen donor is off and on to the described first denitrogenation portion.
14, according to claim 9 or 10 described denitrifying methods, it is characterized in that,
Concentration with respect to nitrate ion, nitrite ion, supply with the needed hydrogen donor of denitrogenation processing is a benchmark, to described first denitrogenation portion supply hydrogen donor, supply the first supply operation and the supply of the hydrogen donor of the amount that is less than described benchmark value by combination and carry out more than the second supply operation of the hydrogen donor of the amount of described benchmark value.
15, a kind of denitrification processing device, comprise: denitrogenation portion, processed water is supplied to the processed water feeding mechanism of described denitrogenation portion and the hydrogen donor feeding mechanism that hydrogen donor is supplied to described denitrogenation portion, in described denitrogenation portion, by denitrifier nitrate ion, the nitrite ion that contains in the processed water is reduced into nitrogen, described denitrification processing device is characterised in that
Described denitrogenation portion has the first denitrogenation portion and the second denitrogenation portion,
Have a part with the reaction solution in the described second denitrogenation portion and be supplied to the reaction solution feeding mechanism of the described first denitrogenation portion and the reaction solution that the reaction solution in the described first denitrogenation portion sends back to the described second denitrogenation portion is returned device,
By described reaction solution feeding mechanism the part of the reaction solution in the described second denitrogenation portion is supplied to the described first denitrogenation portion,
And be supplied to the described first denitrogenation portion by described hydrogen donor feeding mechanism to major general's hydrogen donor, and return device by described reaction solution the reaction solution in the described first denitrogenation portion is sent back to the described second denitrogenation portion, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
16, a kind of treatment process of nitrogenous draining comprises: nitrated operation is oxidized to nitric acid or nitrous acid with the ammonium ion in the processed water; And the denitrogenation operation, when processed water is supplied to denitrifying tank, supply hydrogen donor, and nitrate ion or the nitrite ion that contains in the processed water is reduced into nitrogen by denitrifier, the treatment process of described nitrogenous draining is characterised in that,
In described denitrogenation operation, hydrogen donor is supplied to described denitrifying tank, make the concentration changes with time of the hydrogen donor in the described denitrifying tank.
17, the treatment process of nitrogenous water according to claim 16 is characterized in that, the peak concentration of the hydrogen donor in the described denitrifying tank and the difference of Cmin are more than the 50mgTOC/L.
18, according to the treatment process of claim 16 or 17 described nitrogenous water, it is characterized in that, hydrogen donor is supplied to described denitrifying tank off and on.
19, according to the treatment process of claim 16 or 17 described nitrogenous water, it is characterized in that, concentration with respect to nitrate ion, nitrite ion, supply with the needed hydrogen donor of denitrogenation processing is a benchmark, the hydrogen donor that combination will be less than the amount of described benchmark value is supplied to the first supply operation of described denitrifying tank and will be supplied to the second supply operation of described denitrifying tank more than the hydrogen donor of the amount of described benchmark value, and hydrogen donor is supplied to described denitrifying tank.
20, a kind of treatment process of nitrogenous water comprises: nitrated operation is oxidized to nitric acid or nitrous acid with the ammonium ion in the processed water; And the denitrogenation operation, when processed water is supplied to denitrifying tank, supply hydrogen donor, and nitrate ion or the nitrite ion that contains in the processed water is reduced into nitrogen by denitrifier, the treatment process of described nitrogenous water is characterised in that,
As described denitrifying tank, the first denitrogenation portion with at least more than one groove is set and at the back segment of the described first denitrogenation portion and have the second denitrogenation portion of at least more than one groove,
Be supplied to the described first denitrogenation portion to major general's hydrogen donor, make in the described first denitrogenation portion and form the hydrogen donor concentration difference between in the described second denitrogenation portion.
21, the treatment process of nitrogenous water according to claim 20, it is characterized in that, be supplied to the described first denitrogenation portion to major general's hydrogen donor, making the difference of the Cmin of the peak concentration of the hydrogen donor in the described first denitrogenation portion and the hydrogen donor in the described second denitrogenation portion is more than the 50mgTOC/L.
22, the treatment process of nitrogenous water according to claim 20 is characterized in that, the volume of the described second denitrogenation portion of the volumetric ratio of the described first denitrogenation portion is little.
23, according to the treatment process of claim 20 or 21 described nitrogenous water, it is characterized in that, hydrogen donor is supplied to the described first denitrogenation portion off and on.
24, according to the treatment process of claim 16 or 20 described nitrogenous water, it is characterized in that, the mud after the described denitrogenation operation is sent back to described nitrated operation.
25, the treatment process of nitrogenous water according to claim 24 is characterized in that,
Before being included in described nitrated operation, the organism that carries out processed water is handled or the treatment process of denitrogenation processing,
Mud after the described denitrogenation operation is sent back in described nitrated operation, the described treatment process at least one.
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