CN114506973A - Alkalinity regulation and control method based on deep denitrification of sulfur autotrophic denitrification filter - Google Patents
Alkalinity regulation and control method based on deep denitrification of sulfur autotrophic denitrification filter Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 154
- 239000011593 sulfur Substances 0.000 title claims abstract description 154
- 230000001651 autotrophic effect Effects 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000033228 biological regulation Effects 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 30
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 25
- 230000002829 reductive effect Effects 0.000 claims abstract description 21
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 241000894006 Bacteria Species 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000011081 inoculation Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 abstract description 18
- 230000001276 controlling effect Effects 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 14
- 235000019738 Limestone Nutrition 0.000 description 10
- 239000006028 limestone Substances 0.000 description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
-
- 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 provides an alkalinity regulation and control method based on deep denitrification of a sulfur autotrophic denitrification filter, belonging to the technical field of deep denitrification treatment of wastewater. Aiming at nitrate wastewater with higher requirements on nitrate removal, such as tail water upgrading of a sewage treatment plant or ecological water environment restoration, the invention adopts bicarbonate/carbonate as an alkalinity regulator to regulate and control the sulfur autotrophic denitrification filter. Compared with the traditional sulfur-calcium mixed type sulfur autotrophic denitrification filter, the Total Dissolved Solids (TDS) increment and the sulfate concentration of the outlet water of the pure sulfur type sulfur autotrophic denitrification filter adopted by the invention are reduced by about one third, the sulfur autotrophic denitrification technology has the advantage of regulating and controlling the sulfur autotrophic denitrification process, the process can better cope with the nitrate change of the inlet water quality, the operation mode is more flexible, and the process has good environmental benefit.
Description
Technical Field
The invention belongs to the technical field of advanced nitrogen removal treatment of wastewater, and particularly relates to an alkalinity regulating and controlling method based on advanced nitrogen removal of a sulfur autotrophic denitrification filter.
Background
Denitrification is one of the major problems in wastewater treatment processes. Excessive discharge of nitrogen elements into natural water may cause serious environmental problems such as water eutrophication. Ammonia nitrogen can be well converted into nitrite and nitrate in the aquatic biological treatment process of wastewater, so that the nitrite and the nitrate are main components of nitrogen pollution in tail water of a sewage treatment plant, and the problem of effectively removing the nitrite and the nitrate nitrogen in the factory tail water of the sewage treatment plant is not easy to solve.
At present, the methods for removing nitrate are more, and mainly comprise a physicochemical method and a biological method. The physical and chemical aspects mainly relate to the application of resin adsorption technology. Although resin adsorption has good nitrate removal efficiency, the regeneration treatment of resin eluents poses challenges. In the biological aspect, the traditional nitrification and denitrification nitrogen removal technology needs to supplement an organic carbon source, and has the problems of high cost, easy secondary pollution and the like. Therefore, the autotrophic denitrification filter, especially the sulfur autotrophic denitrification filter, is gradually and widely applied because no organic carbon source needs to be added, and the filter has the advantages of high effluent quality, safe operation, low cost and the like.
The sulfur autotrophic denitrification process is a process for reducing nitrate nitrogen and nitrite nitrogen into nitrogen by using reductive sulfide as an electron donor under the anoxic or anaerobic condition. The denitrification process using elemental sulfur as an electron donor produces acid, sulfate and an inorganic carbon source. Aiming at acid production and the need of inorganic carbon sources, the existing method generally adopts the addition of fillers such as limestone, egg shells and the like to relieve the problem, which inevitably causes higher hardness of effluent (overhigh calcium ions in the effluent). Aiming at sulfate production, the prior application is to control the N/S molar ratio and relieve the problem by sulfur autotrophic denitrification coupling process. The N/S is controlled to be relatively fixed due to the addition of sulfur simple substances, so that the fluctuation condition of nitrate nitrogen of inlet water is difficult to deal with, and in addition, the poor stability of the coupling process caused by different proliferation rates of autotrophic bacteria and heterotrophic bacteria in the sulfur autotrophic denitrification coupling process provides a challenge for large-scale application. Chenyuhao et al (patent application No. CN202110358935.7) provide a sulfur autotrophic denitrification for denitrification filter material with high nitrate concentration. The adding amount of the alkalinity regulator is still fixed, and the filter material is difficult to deal with the water quality fluctuation and the competition problems of autotrophic bacteria and heterotrophic bacteria. Yue Dongmei et al (patent application No. CN202110289081.1), provided a denitrification material based on sulfur autotrophic denitrification, but its alkalinity material can not be regulated and controlled, and bicarbonate mainly acts as a foaming agent in the denitrification material, so it is difficult to realize the regulation and control of the sulfur autotrophic denitrification process, and there is an obvious disadvantage to the change of water quality and water quantity.
Disclosure of Invention
In view of the problems in the related technologies, the method separates bicarbonate from elemental sulfur and/or reduced sulfide, replaces fillers such as limestone and eggshell with the bicarbonate, provides alkalinity and a carbon source by controlling the adding amount of the bicarbonate, and establishes a connection between the adding amount of the alkalinity regulator and the denitrification effect to reduce Total Dissolved Solids (TDS) of effluent and sulfate of the effluent, so that the sulfur autotrophic denitrification process can better cope with the nitrate change of the effluent, and the operation mode is more flexible.
The method has the advantages that the adding amount of bicarbonate is explored according to the condition of nitrate nitrogen in the inlet water, the problem of high hardness of the outlet water can be solved, the aspects of high acid production and sulfate concentration in the sulfur autotrophic denitrification process, inorganic carbon source requirement and the like are synchronously optimized, so that the sulfur autotrophic denitrification process can better cope with the change of nitrate in the inlet water quality, the operation mode is more flexible, the utilization rate of the reactor to sulfur is increased, and more water can be treated under the same scale.
In order to achieve the aim, the invention provides a method for regulating and controlling alkalinity based on deep denitrification of a sulfur autotrophic denitrification filter, which comprises the following specific steps:
s1: constructing a sulfur autotrophic denitrification filter taking sulfur simple substances and/or reduced sulfides as fillers, and not adding any other filling materials;
s2: calculating the adding amount of a theoretical alkalinity regulator required by the denitrification process according to the nitrate concentration of the wastewater;
s3: inoculating sulfur autotrophic denitrification bacteria to the sulfur autotrophic denitrification filter tank until the film formation is successful;
s4: bicarbonate or carbonate solution is used as an alkalinity regulator and a carbon source in the sulfur autotrophic denitrification process, and is pumped into the sulfur autotrophic denitrification filter tank together with the wastewater by a peristaltic pump to perform the sulfur autotrophic denitrification process;
s5: and controlling the flow rate of the peristaltic pump to regulate the adding amount of the alkalinity regulator.
In an alternative embodiment, the reduced sulfide includes iron sulfide, ferrous sulfide.
In an alternative embodiment, the height-diameter ratio of the sulfur autotrophic denitrification filter is 6:1, and the effective volume is 1.28L.
In an alternative embodiment, the nitrogen element in the wastewater is mainly present in the form of nitrate, and can be surface water slightly polluted by nitrate, such as tail water upgrading of a sewage treatment plant, ecological environment water restoration and the like, and wastewater with high requirements for nitrate removal is provided.
In an alternative embodiment, the alkalinity regulator is added in an amount of 150 to 25 wt% of the theoretical alkalinity regulator addition.
Further, the controlling the flow rate of the peristaltic pump to regulate the adding amount of the alkalinity regulator specifically comprises:
pumping the bicarbonate or carbonate solution into the sulfur autotrophic denitrification filter according to 125 wt%, 100 wt%, 75 wt%, 50 wt% and 25% of the adding amount of the theoretical alkalinity regulator required by the denitrification process, and stably operating for 3 hours at each adding amount;
and measuring nitrate, total soluble solid and sulfate in the effluent, and performing linear fitting to obtain the actual adding amount of the alkalinity regulator.
In an optional embodiment, the alkalinity regulating method based on deep denitrification of the sulfur autotrophic denitrification filter further includes: s6: and (3) measuring the denitrification, total dissolved solids and sulfate of the sulfur autotrophic denitrification filter.
In alternative embodiments, the sulfur autotrophic denitrifying bacteria may be harvested by medium enrichment or inoculation from a successfully operated sulfur autotrophic denitrifying device.
In an alternative embodiment, the operation mode of the sulfur autotrophic denitrification filter is a lower-inlet and upper-outlet operation mode.
Compared with the prior art, the invention has at least the following beneficial effects:
1. the pure sulfur type sulfur autotrophic denitrification filter provided by the invention realizes the separation of elemental sulfur and/or reduced sulfide and alkalinity regulator, and can control the adding amount of the alkalinity regulator, thereby providing a feasible method for regulating and controlling the sulfur autotrophic denitrification filter in practical application.
2. Although the cost of providing alkalinity by replacing limestone with bicarbonate/carbonate is higher, the pure sulfur type sulfur autotrophic denitrification filter tank improves the sulfur filling rate of the filter tank and reduces the consumption of sulfur, can relatively prolong the sulfur filling period, and can reduce the cost by using waste alkali resources in practical application.
3. The alkalinity control method for deep denitrification of the sulfur autotrophic denitrification filter tank can effectively reduce the discharge of total dissolved solids (especially calcium ions) into a water body, can effectively relieve the hardness of the water body, and can relieve the possibility of converting the sulfate into harmful substances such as hydrogen sulfide and the like in the water body.
Drawings
FIG. 1 is a schematic diagram of the operation of a pure sulfur type sulfur autotrophic denitrification filter;
FIG. 2 shows the denitrification effect of a sulfur-only autotrophic denitrification filter under different alkalinity regulations, with sodium bicarbonate as alkalinity regulator and carbon source;
FIG. 3 shows the Total Dissolved Solids (TDS) and sulfate in the effluent of the sulfur-only autotrophic denitrification filter under different alkalinity controls, and sodium bicarbonate is used as an alkalinity regulator and a carbon source;
FIG. 4 is a linear fitting of Total Dissolved Solids (TDS) and sulfate in the effluent of the pure sulfur autotrophic denitrification filter under different alkalinity control;
FIG. 5 shows the denitrification effect of a sulfur-only autotrophic denitrification filter under different alkalinity regulations, wherein sodium carbonate is used as an alkalinity regulator and a carbon source;
FIG. 6 shows the Total Dissolved Solids (TDS) and sulfate in the effluent of the sulfur-only autotrophic denitrification filter under different alkalinity controls, and sodium carbonate is used as an alkalinity regulator and a carbon source;
FIG. 7 shows two SAD denitrification operation effects, wherein FIG. 7(a) shows a sulfur-calcium mixed type sulfur autotrophic denitrification filter, and FIG. 7(b) shows a pure sulfur type sulfur autotrophic denitrification filter;
FIG. 8 is a diagram showing the analysis of the operation conditions of two filters under the condition of fluctuating influent nitrate concentration, wherein SL-SAD is a sulfur-calcium mixed type sulfur autotrophic denitrification filter; S-SAD is a pure sulfur type sulfur autotrophic denitrification filter, the SL-SAD nitrate removal situation is shown in figure 8(a), the S-SAD nitrate removal situation is shown in figure 8(b), the TDS situation of the effluent of the two filters is shown in figure 8(c), and the sulfate situation of the effluent of the two filters is shown in figure 8 (d).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all embodiments, and do not limit the claims of the present invention at all.
In the embodiment of the invention, the operation mode of the sulfur autotrophic denitrification filter is a lower-in and upper-out or upper-in and lower-out operation mode, and the lower-in and upper-out operation mode is preferably adopted, referring to fig. 1.
The sulfur autotrophic denitrifying bacteria used in the embodiment of the invention are obtained by culture medium enrichment, and the culture medium is as follows: adding Na into 1L of water2S2O3·5H2O 5g，KH2PO4 2g，KNO3 2g，NaHCO3 1g，NH4Cl 0.5g，MgCl2·6H2O 0.5g，FeSO4·7H2O 0.01g。
Or inoculated from a successfully operated sulfur autotrophic denitrification facility.
The wastewater related in the embodiment of the invention can be surface water slightly polluted by nitrate, such as tail water upgrading of a sewage treatment plant, ecological environment water restoration and the like, and the wastewater has higher requirements on nitrate removal, in particular to the wastewater containing 1-30mg/L nitrate.
Example 1
This example is intended to investigate the relationship between the amount of the alkalinity regulator added and the denitrification effect. In the embodiment, sodium bicarbonate solution is used as alkalinity regulator of a pure sulfur type sulfur autotrophic denitrification filter, sulfur is used as filler, the dosage of the alkalinity regulator is respectively 125 wt%, 100 wt%, 75 wt%, 50 wt% and 25 wt% of the dosage of the theoretical alkalinity regulator, and wastewater comes from sewageWater treatment plant tailwater, NO therein3 -N is 10mg/L, and the NO of effluent is researched under the condition that the Hydraulic Retention Time (HRT) is 3h3 --trend of variation of N.
As can be seen from FIG. 2, under the conditions that the dosage of the alkalinity regulator is 125 wt% and 100 wt% of the theoretical value, the denitrification effect of the filter is good, and the nitrate nitrogen of effluent is about 0.2mg/L, so that the nitrogen removal rate can reach 98%; when the dosage of the alkalinity regulator is 75 wt% of the theoretical value, the nitrogen concentration of the effluent is greatly improved, the total nitrogen of the effluent is improved from 0.5mg/L to 5mg/L, and the nitrogen removal rate is about 50%; in the next stage, namely the adding amount of the alkalinity regulator is 50 wt% and 25 wt% of the theoretical value, the effluent nitrate nitrogen is lifted from 5mg/L to 7mg/L, and the nitrogen removal rate is stabilized at about 30%.
The adding amount of the alkalinity regulator can achieve better denitrification effect at 125 wt% and 100 wt% of a theoretical value, which shows that the alkalinity under the two conditions is sufficient, but the denitrification effect is obviously reduced along with the further reduction of the adding amount of the alkalinity regulator, namely, the adding amount is only 75 wt% of the theoretical value, and the sulfur autotrophic denitrification process is limited due to insufficient alkalinity. As the alkalinity regulator dosage is reduced to 50 wt% of the theoretical dosage again, the sulfur autotrophic denitrification process is further limited; as the adding amount of the alkalinity regulator is reduced to 25 wt% of the theoretical value, the sulfur autotrophic denitrification process is limited to reach a stable state, and the concentration of effluent nitrate nitrogen is not fluctuated any more.
And (3) measuring the Total Dissolved Solids (TDS) and sulfate in the effluent of the pure sulfur autotrophic denitrification filter tank under the regulation and control of different alkalinity. FIG. 3 shows the variation of Total Dissolved Solids (TDS) and sulfate in the effluent of the alkalinity adjustment experiment of the sulfur-only autotrophic denitrification filter. As the dosage of the alkalinity regulator is reduced, the concentration of Total Dissolved Solids (TDS) in the effluent shows a trend of continuously decreasing from 290 +/-10 mg/L to 245 +/-5 mg/L. Furthermore, the concentration of the effluent sulfate is reduced from 103 plus or minus 2mg/L to about 56 plus or minus 4 mg/L. The mode that combines Total Dissolved Solids (TDS) of play water, sulfate concentration to know this kind of regulation alkalinity regulator input can regulate and control sulphur autotrophy denitrification process to alkalinity regulator input is linear correlation rather than Total Dissolved Solids (TDS) of play water, sulfate concentration, thereby reaches the effect of an accurate control to Total Dissolved Solids (TDS), sulfate concentration of play water. FIG. 4 linear fit of sodium bicarbonate as alkalinity regulator dosing with effluent TDS and sulfate.
Example 2
This example is intended to investigate the relationship between the amount of the alkalinity regulator added and the denitrification effect. In the embodiment, a sodium carbonate solution is used as an alkalinity regulator of a pure sulfur type sulfur autotrophic denitrification filter, ferric sulfide or ferrous sulfide is used as a filler, the adding amount of the alkalinity regulator is respectively 125 wt%, 100 wt%, 75 wt%, 50 wt% and 25 wt% of the adding amount of a theoretical alkalinity regulator, and NO 3-N in inlet water is 10mg/L, the operation is stable for 3 hours, namely, the Hydraulic Retention Time (HRT) is 3 hours, and the NO of the inlet water is explored3 --N trend of change. As can be seen from FIG. 5, under the conditions that the dosage of the alkalinity regulator is 125 wt% and 100 wt% of the theoretical value, the denitrification effect of the filter is good, and the nitrate nitrogen of the effluent is about 0.5mg/L and can reach 97% of nitrogen removal rate; when the adding amount of the alkalinity regulator is 75 wt% of a theoretical value, the nitrogen concentration of effluent is greatly improved, the nitrate nitrogen of the effluent is improved from 0.5mg/L to 5mg/L, and the nitrogen removal rate is about 50%; in the next stage, namely the adding amount of the alkalinity regulator is 50 wt% and 25 wt% of the theoretical value, the effluent nitrate nitrogen is lifted from 5mg/L to 7mg/L, and the nitrogen removal rate is stabilized at about 30%.
The adding amount of the alkalinity regulator can achieve better denitrification effect at 125 wt% and 100 wt% of a theoretical value, which shows that the alkalinity under the two conditions is sufficient, but the denitrification effect is obviously reduced along with the further reduction of the adding amount of the alkalinity regulator, namely, the adding amount is only 75 wt% of the theoretical value, and the sulfur autotrophic denitrification process is limited due to insufficient alkalinity. As the alkalinity regulator dosage is reduced to 50 wt% of the theoretical dosage again, the sulfur autotrophic denitrification process is further limited; as the adding amount of the alkalinity regulator is reduced to 25 wt% of the theoretical value, the sulfur autotrophic denitrification process is limited to reach a stable state, and the concentration of effluent nitrate nitrogen is not fluctuated any more.
And (3) measuring the Total Dissolved Solids (TDS) and sulfate in the effluent of the pure sulfur autotrophic denitrification filter tank under the regulation and control of different alkalinity. FIG. 6 shows the variation of Total Dissolved Solids (TDS) and sulfate in the effluent of the alkalinity adjustment experiment of the sulfur-only autotrophic denitrification filter. As the dosage of the alkalinity regulator is reduced, the concentration of Total Dissolved Solids (TDS) in the effluent shows a trend of continuously decreasing from 345 +/-12 mg/L to 255 +/-5 mg/L. Furthermore, the concentration of the sulfate in the effluent is reduced from 140 plus or minus 4mg/L to about 62 plus or minus 3 mg/L. The mode that combines Total Dissolved Solids (TDS) of play water, sulfate concentration to know this kind of regulation alkalinity regulator input can regulate and control sulphur autotrophy denitrification process to alkalinity regulator input is linear correlation rather than Total Dissolved Solids (TDS) of play water, sulfate concentration, thereby reaches the effect of an accurate control to Total Dissolved Solids (TDS), sulfate concentration of play water.
Comparative example 1
In this example, two sulfur autotrophic denitrification filters of sulfur-calcium mixed type (sulfur and limestone mixed filler, sulfur: limestone 3:1, sufficient alkalinity) and pure sulfur autotrophic denitrification filter (sulfur and inert filler mixed filler, sulfur: inert filler 3:1, alkalinity regulator addition 125 wt% of theoretical value) were operated, and NO in the inlet water3 -And (3) shortening the hydraulic retention time under the condition that the N concentration is 10mg/L, and evaluating whether the pure sulfur type sulfur autotrophic denitrification filter provided by the invention has equivalent denitrification efficiency compared with the traditional sulfur-calcium mixed type sulfur autotrophic denitrification filter.
FIG. 7(a) and FIG. 7(b) show the load increase of the sulfur-calcium mixed type sulfur autotrophic denitrification filter and the pure sulfur type sulfur autotrophic denitrification filter, respectively. After a load lifting period of 80 days, the sulfur-calcium mixed type sulfur autotrophic denitrification filter and the pure sulfur type sulfur autotrophic denitrification filter can achieve the performance of well removing nitrate nitrogen. Fig. 7(a) shows the operation of the sulfur-calcium mixed type sulfur autotrophic denitrification filter, and it can be seen from fig. 7(a) that the reactor can be quickly adjusted after undergoing a short-term unstable process in the process of shortening the hydraulic retention time from 24 hours to 3 hours, and the removal rate of nitrate nitrogen is gradually increased from about 75% to about 98%. As the HRT is reduced, the reactor effluent can reach 98% nitrogen removal faster. FIG. 7(b) shows a pure sulfur type sulfur compoundAs can be seen from FIG. 7(b), the operation of the denitrification filter (alkalinity is provided by sodium bicarbonate, and the amount of the alkalinity regulator is 125% of the theoretical value) can achieve the same denitrification effect by adding sodium bicarbonate. And the comparison shows that the pure sulfur type sulfur autotrophic denitrification filter tank can achieve good denitrification effect more easily in a short time. The analysis reason is that sodium bicarbonate is directly dissolved in the reactor, sulfur autotrophic denitrifying bacteria can more easily obtain the alkalinity provided by the sodium bicarbonate, limestone has the problem of slow dissolution rate, and the solid slow-release alkalinity can achieve a stable denitrification effect within a relatively long time. The alkalinity provided by the limestone and the sodium bicarbonate can achieve a better effect of removing nitrate nitrogen, and the alkalinity provided by the sodium bicarbonate can more quickly enable the reactor to reach the alkalinityToAnd (4) stabilizing. The feasibility of providing alkalinity by sodium bicarbonate in sulfur autotrophic denitrification is proved, and a foundation is laid for adjusting the alkalinity of the sulfur autotrophic denitrification filter.
Comparative example 2
This comparative example was carried out on the basis of example 1 and comparative example 1. Through the previous embodiment and the comparative example, the pure sulfur type sulfur autotrophic denitrification filter can achieve equivalent denitrification effect with the traditional sulfur-calcium mixed type sulfur autotrophic denitrification filter, and the adjustment and control of the sulfur autotrophic denitrification process can be achieved by adjusting the adding amount of the alkalinity regulator of the pure sulfur type sulfur autotrophic denitrification filter. Based on the above, under the condition that the hydraulic retention time is 3h, the sulfur-calcium mixed type sulfur autotrophic denitrification filter (the mixed filler of sulfur and limestone, the sulfur: limestone is 3:1, and the alkalinity is sufficient) and the pure sulfur type sulfur autotrophic denitrification filter (the mixed filler of sulfur and inert flavoring, the sulfur: inert filler is 3:1, and the adding amount of the alkalinity regulator is a theoretical value) are operated by changing the concentration of the nitrate in the inlet water, and the performance of the two sulfur autotrophic denitrification filters is evaluated.
The denitrification performance of the pure sulfur type sulfur autotrophic denitrification filter and the sulfur-calcium mixed type sulfur autotrophic denitrification filter under the condition of different concentrations of the nitrate of the inlet water is compared. Similar and excellent nitrate removal performance was obtained in both the sulfur-calcium mixed type sulfur autotrophic denitrification filter and the pure sulfur type sulfur autotrophic denitrification filter, see fig. 8(a) and 8 (b). Under the same conditions, the total dissolved solid increment of the pure sulfur type sulfur autotrophic denitrification filter is about 1/3 less than that of the sulfur-calcium mixed type sulfur autotrophic denitrification filter. When the concentration of the nitrate in the inlet water is 10mg/L, the concentration of the sulfate in the outlet water of the pure sulfur type sulfur autotrophic denitrification filter is reduced by about 33.60 percent compared with that of the sulfur-calcium mixed type sulfur autotrophic denitrification filter. The sulfate concentration of the effluent of the sulfur-calcium mixed type sulfur autotrophic denitrification filter and the pure sulfur type sulfur autotrophic denitrification filter is in a linear descending trend along with the reduction of the nitrate concentration of the influent from 10mg/L to 2.5 mg/L. The descending trend of the pure sulfur type sulfur autotrophic denitrification filter is higher than that of the sulfur-calcium mixed type sulfur autotrophic denitrification filter, which shows that the content of sulfate in the outlet water of the pure sulfur type sulfur autotrophic denitrification filter is less than that of the sulfur-calcium mixed type sulfur autotrophic denitrification filter, and the difference is increased under the condition of higher concentration of nitrate in the inlet water.
In summary, the alkalinity regulation and control method provided by the invention uses bicarbonate/carbonate to replace limestone and the like to provide alkalinity for the sulfur autotrophic denitrification filter, so that the sulfur autotrophic denitrification process can be accurately regulated and controlled. When the adding amount of the alkalinity regulator is a theoretical value, compared with the traditional sulfur-calcium mixed type sulfur autotrophic denitrification filter tank, the Total Dissolved Solids (TDS) increment and the sulfate concentration of the outlet water of the provided pure sulfur type sulfur autotrophic denitrification filter tank are reduced by about one third, thereby contributing to water environment protection.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. An alkalinity regulation and control method based on deep denitrification of a sulfur autotrophic denitrification filter is characterized by comprising the following steps:
s1: constructing a sulfur autotrophic denitrification filter taking sulfur simple substances and/or reduced sulfides as fillers, and not adding any other filling materials;
s2: calculating the adding amount of a theoretical alkalinity regulator required by the denitrification process according to the nitrate concentration of the wastewater;
s3: inoculating sulfur autotrophic denitrification bacteria to the sulfur autotrophic denitrification filter tank until the film formation is successful;
s4: bicarbonate or carbonate solution is used as an alkalinity regulator and a carbon source in the sulfur autotrophic denitrification process, and is pumped into the sulfur autotrophic denitrification filter tank together with the wastewater by a peristaltic pump to perform the sulfur autotrophic denitrification process;
s5: and controlling the flow rate of the peristaltic pump to regulate the actual adding amount of the alkalinity regulator.
2. The method of claim 1, wherein the reduced sulfide includes iron sulfide and ferrous sulfide.
3. The method according to claim 1, wherein the height-diameter ratio of the sulfur autotrophic denitrification filter is 6:1, and the effective volume is 1.28L.
4. The method according to claim 1, characterized in that the wastewater is a wastewater treatment plant tail water or eco-remediation water, the nitrogen of which is mainly present as nitrate.
5. The method of claim 1, wherein the alkalinity regulator is added in an amount of 150 to 25 wt% of the theoretical alkalinity regulator addition.
6. The method according to claim 1, wherein the controlling of the flow rate of the peristaltic pump to regulate the dosage of the alkalinity regulator comprises:
pumping the bicarbonate or carbonate solution into the sulfur autotrophic denitrification filter according to 125 wt%, 100 wt%, 75 wt%, 50 wt% and 25 wt% of the adding amount of the theoretical alkalinity regulator required by the denitrification process, and stably operating for 3 hours under each adding amount;
and measuring the nitrate, total soluble solid and sulfate in the effluent, and performing linear fitting to obtain the actual adding amount of the alkalinity regulator.
7. The method of claim 1, further comprising: s6: and (3) measuring the denitrification, total dissolved solids and sulfate of the sulfur autotrophic denitrification filter.
8. The method according to claim 1, wherein the sulfur autotrophic denitrifying bacteria are obtained by medium enrichment or inoculation from a successfully operated sulfur autotrophic denitrifying device.
9. The method according to claim 1, wherein the sulfur autotrophic denitrification filter is operated in a bottom-in-top-out mode.
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