CN115611424B - Method for treating stainless steel pickling high nitrate nitrogen wastewater - Google Patents
Method for treating stainless steel pickling high nitrate nitrogen wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 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 title claims abstract description 53
- 238000005554 pickling Methods 0.000 title claims abstract description 46
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 46
- 239000010935 stainless steel Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000010802 sludge Substances 0.000 claims abstract description 102
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 21
- 238000011081 inoculation Methods 0.000 claims abstract description 14
- 238000012258 culturing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 238000005273 aeration Methods 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 18
- 238000005191 phase separation Methods 0.000 claims description 12
- 241000894006 Bacteria Species 0.000 claims description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 230000001174 ascending effect Effects 0.000 claims description 5
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011575 calcium Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 244000005700 microbiome Species 0.000 description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000000844 transformation Methods 0.000 description 1
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
- C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
-
- 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
- C02F3/286—Anaerobic digestion processes including two or more steps
-
- 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
- C02F3/2866—Particular arrangements for anaerobic reactors
-
- 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
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a method for treating stainless steel pickling high nitrate nitrogen wastewater, which comprises the following steps: anaerobic flocculent sludge is selected as inoculation sludge, stainless steel pickling high nitrate nitrogen wastewater is introduced into an up-flow denitrification device to acclimate the inoculation sludge, and sludge resistant to the stainless steel pickling high nitrate nitrogen wastewater is obtained; adjusting the operation condition of the up-flow denitrification device, and culturing flocculent sludge into granular sludge; after the granular sludge is formed, the water inflow of the stainless steel pickling high-nitrate nitrogen wastewater is increased, so that the treatment load is increased; maintaining the upflow denitrification device to operate under high load conditions; the scheme has the characteristics of high efficiency, stable denitrification, less process flow and good purifying effect.
Description
Technical Field
The invention relates to the field of environmental protection wastewater treatment, in particular to a method for treating stainless steel pickling high nitrate nitrogen wastewater.
Background
In recent years, with the continuous upgrading of wastewater discharge standards, many industrial enterprises are urgent to upgrade and reform wastewater treatment stations, and because stainless steel pickling high-nitrate nitrogen wastewater has higher nitrogen content and high-content nitrogen pollutants, the wastewater cannot meet the new discharge standard requirements only by original treatment facilities and processes, so that more efficient denitrification treatment facilities and processes need to be rebuilt in limited sites to meet the latest discharge standard requirements of the wastewater.
In the process of implementing the present invention, the inventor finds that the following problems exist in the prior art: stainless steel pickling high nitrate nitrogen wastewater with low pH and NO 3 - The characteristics of high N concentration and low C/N ratio are that the traditional biological method is difficult to denitrify, and the increasingly strict emission standard requirements cannot be met. And the traditional biological denitrification method has the limitations of large occupied area, low denitrification efficiency, poor impact resistance, relatively complicated process flow, high operation cost and the like. And the stainless steel pickling high-nitrate nitrogen wastewater is high in salt content and calcium ion content, and high in nitrogen content, calcium content and salt content are easy to impact a conventional biochemical process system. How to scientifically guide the normal production and the standard improvement of the waste water of enterprises generating the stainless steel pickling high-nitrate nitrogen waste water, so that the stainless steel pickling high-nitrate nitrogen waste water treatment engineering is safe, reliable, economical, applicable and advanced in technology, and is an urgent environmental protection technical requirement of the enterprises.
Chinese patent CN114506967a discloses a "method for treating high-salt and high-nitrate nitrogen wastewater by biological enhancement", which utilizes a short-cut denitrification tank, a high-efficiency denitrification tank, a biological selection tank, a sedimentation tank and carbon source and denitrifying bacteria to degrade nitrate nitrogen in the high-salt and high-nitrate nitrogen wastewater. Although the method can realize the removal of nitrate nitrogen in the high-salt high-nitrate nitrogen wastewater, the method has the advantages of relatively longer process flow, larger occupied area, more complex operation, higher running cost, and capability of removing only nitrogen pollutants and not Ca in the stainless steel pickling high-nitrate nitrogen wastewater 2+ The substances such as the waste water are removed, and the long-term discharge of the high-hardness waste water can cause adverse effects on the environment。
At present, the treatment technology of the stainless steel pickling high nitrate nitrogen wastewater has little research, so that a method capable of efficiently treating the stainless steel pickling high nitrate nitrogen wastewater is needed to solve the problems.
Disclosure of Invention
To achieve the above object, the present inventors have provided a method for treating stainless steel pickling high nitrate nitrogen wastewater, comprising the steps of:
anaerobic flocculent sludge is selected as inoculation sludge, stainless steel pickling high nitrate nitrogen wastewater is introduced into an up-flow denitrification device to acclimate the inoculation sludge, and sludge resistant to the stainless steel pickling high nitrate nitrogen wastewater is obtained;
adjusting the operation condition of the up-flow denitrification device, and culturing flocculent sludge into granular sludge;
after the granular sludge is formed, the water inflow of the stainless steel pickling high-nitrate nitrogen wastewater is increased, so that the treatment load is increased;
maintaining the upflow denitrification device operating under high load conditions.
As a preferable mode of the invention, the formed granular sludge is gray, the surface is attached with rod-shaped bacteria and smooth and regular, the diameter of the particle size is 1-6mm, and the sedimentation speed of single sludge is 198-273m/h.
As a preferred mode of the present invention, the upflow denitrification device maintains the granular sludge SV in the reaction system during operation under high load conditions 30 The volume of the catalyst is 10-30% of the volume of the reaction system.
As a preferable mode of the invention, the up-flow denitrification device comprises a water inlet system, a carbon source adding system connected with a water inlet system pipeline, a reaction system, a three-phase separation system, a water outlet system, a heat preservation system wrapped outside the reaction system, an internal circulation system respectively connected with the three-phase separation system and the water inlet system, an aeration system connected with the water inlet system and a sludge discharge system connected with the reaction system.
As a preferable mode of the invention, the operation condition of the upflow denitrification device takes methanol as a carbon source, the adding amount of the carbon source is C/N=2.0-3.5, the temperature in the heat preservation system is 28-38 ℃, the pH value in the reaction system is 7-9, the HRT is 10-13h, and the hydraulic ascending flow rate in the upflow denitrification device is 1-2.75m/h.
As a preferable mode of the invention, the nitrate nitrogen concentration in the stainless steel pickling high nitrate nitrogen wastewater which is introduced into the up-flow denitrification device is 700-1200mg/L, the ammonia nitrogen concentration is 15-30mg/L, the nitrite nitrogen concentration is 10-30mg/L, and the total nitrogen concentration is 800-1300mg/L.
As a preferable mode of the invention, the up-flow denitrification device is started in an internal circulation continuous low water inflow mode, aeration is carried out for 1-2 times per day at regular time, 30-60s each time, and the temperature of the denitrification area of the up-flow denitrification device is controlled.
As a preferable mode of the invention, the inoculation sludge is anaerobic flocculent sludge which is subjected to preliminary precipitation for 30 minutes to remove supernatant, the MLSS of the inoculation sludge is 6-10g/L, and the MLVSS is 4-6g/L.
As a preferable mode of the invention, the denitrification granular sludge is domesticated and cultured by adopting an up-flow denitrification device under the continuous flow operation condition, the initial hydraulic retention time is 63.7h, the water inlet is stainless steel pickling high nitrate nitrogen wastewater, the nitrate nitrogen concentration is 700-1200mg/L, and the corresponding nitrate nitrogen volume load is 0.43-0.45 kg.m -3 ·d -1 。
As a preferable mode of the invention, the MLSS of the denitrified granular sludge after the successful culture is 134.2g/L, the MLVSS is 15.7g/L, and the denitrification rate is 2-3gNO 3 - -N/(gVSS·d)。
Compared with the prior art, the beneficial effects achieved by the technical scheme are as follows:
(1) The method provides a process starting and efficient operation scheme for treating stainless steel pickling high-nitrate nitrogen wastewater by using denitrifying granular sludge, wherein the denitrifying granular sludge is combined with an up-flow denitrification device, the stainless steel pickling high-nitrate nitrogen wastewater is adopted to domesticate and culture the denitrifying granular sludge under continuous flow operation conditions, the denitrifying granular sludge successfully domesticated and cultured has excellent sedimentation performance, functional bacteria such as denitrifying bacteria are enriched, and the system can efficiently and stably denitrify;
(2) The method combines denitrification granular sludge with an up-flow denitrification device to treat stainless steel pickling high nitrate nitrogen wastewater, can reduce the adding amount of an organic carbon source by about 40%, can reduce the running energy consumption of sewage, simultaneously enables high-efficiency denitrification of low carbon nitrogen ratio wastewater to be possible, can shorten the hydraulic retention time, reduces the effective volume and occupied area of the up-flow denitrification device, reduces the treatment cost and the capital investment, reduces the adding amount of acid-base regulating agents, shortens the process flow, and is simpler to run and manage;
(3) The denitrification particle sludge denitrification treatment process provided by the method can utilize the denitrification principle, realize the rapid and efficient removal of nitrate nitrogen in the stainless steel pickling high-nitrate nitrogen wastewater under the condition that the pH environment of the reaction is not controlled by externally adding acid, and simultaneously has a certain removal effect on calcium ions and ammonia nitrogen in the wastewater, thereby achieving the purposes of purifying water quality and reducing the effluent index;
(4) The method combines the denitrification granular sludge with the up-flow denitrification device, can treat the nitrogen pollutants in the stainless steel pickling high-nitrate nitrogen wastewater in one step to reach the C-level discharge standard (TN) of wastewater discharge into town sewer quality standard (GB/T31962-2015)<45mg/L、NH 3 -N<25 mg/L) for discharge.
Drawings
FIG. 1 is a block diagram of an upflow denitrification device system according to an embodiment;
FIG. 2 is a schematic diagram of an upflow denitrification device according to an embodiment;
FIG. 3 is a graph showing the trend of nitrate nitrogen removal effect according to an embodiment;
FIG. 4 is a graph showing total nitrogen removal trend according to an embodiment;
FIG. 5 is a trend graph of ammonia nitrogen removal effect according to an embodiment;
FIG. 6 is a graph showing the pH change trend according to the embodiment;
FIG. 7 is a graph showing the trend of COD remaining amount according to the embodiment;
FIG. 8 shows the Ca according to the embodiment 2+ Removing an effect trend graph;
FIG. 9 is a graph comparing granular sludge and inoculated sludge according to an embodiment.
Reference numerals illustrate:
1. a water inlet system; 101. a water inlet pipe; 102. a water inlet pump; 103. a water inlet; 2. a carbon source adding system; 3. a reaction system; 301. a reactor; 4. a three-phase separation system; 5. a water outlet system; 501. a water outlet; 6. a thermal insulation system; 601. a water bath heat preservation layer; 602. a water bath heat preservation pump; 603. a constant temperature water bath kettle; 7. an internal circulation system; 701. an internal circulation pump; 8. an aeration system; 801. an aeration pump; 9. a mud discharging system; 901. a mud discharging port; 110. and a sampling port.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the technical solution in detail, the following description is made in connection with the specific embodiments in conjunction with the accompanying drawings.
The embodiment provides a method for treating stainless steel pickling high nitrate nitrogen wastewater, which comprises the following steps:
anaerobic flocculent sludge is selected as inoculation sludge, stainless steel pickling high nitrate nitrogen wastewater is introduced into an up-flow denitrification device to acclimate the inoculation sludge, and sludge resistant to the stainless steel pickling high nitrate nitrogen wastewater is obtained;
adjusting the operation condition of the up-flow denitrification device, and culturing flocculent sludge into granular sludge;
after the granular sludge is formed, the water inflow of the stainless steel pickling high-nitrate nitrogen wastewater is increased, so that the treatment load is increased;
the upflow denitrification device is kept to operate under the high-load condition, and the effluent reaches the discharge standard to be discharged.
In the embodiment, as shown in c and d in fig. 9, the denitrified granular sludge after successful culture is grey white, the surface is attached with rod-shaped bacteria and smooth and regular, the diameter of the particle diameter is 1-6mm, the sedimentation speed of single sludge is 198-273m/h, and the surface microorganisms are mainly rod-shaped bacteria with shorter forms and are distributed densely; as shown in a and b in fig. 9, the surface microorganisms are mainly bacteria with longer forms and are distributed relatively sparsely, and the surface microorganisms are inoculated sludge from the beginning; the surface microorganisms of the denitrified granular sludge after successful culture are more and denser, and the sedimentation effect is better, so that the sewage treatment is effectively promoted.
The upflow denitrification device maintains the granular sludge SV in the reaction system during operation under high load conditions 30 The volume of the catalyst is 10-30% of the volume of the reaction system.
As shown in fig. 1 and 2, the up-flow denitrification device comprises a water inlet system 1, a carbon source adding system 2 connected with a water inlet system pipeline, a reaction system 3, a three-phase separation system 4, a water outlet system 5, a heat preservation system 6 wrapped outside the reaction system, an internal circulation system 7 respectively connected with the three-phase separation system and the water inlet system, an aeration system 8 connected with the water inlet system, and a sludge discharge system 9 connected with the reaction system. In the embodiment, a water inlet pipe 101 of a water inlet system is communicated with a water inlet 103 at the bottom of a reactor 301 of a reaction system through a water inlet pump 102; the carbon source adding system 2 can be directly communicated with a water source or a water inlet pipe of the water inlet system; the three-phase separation system is arranged at the top of the reactor and is used for separating water, gas and solids in the reactor, the gas in the reactor is discharged through an inverted funnel-shaped exhaust pipe, overflowed liquid is discharged through a water outlet 501, and the solids are left in the reactor 301; the water bath heat preservation layer 601 of the heat preservation system 6 is wrapped on the outer side wall of the reactor 301 and is used for preserving heat of the reactor, the water outlet end of the water bath heat preservation layer 601 is communicated with the constant-temperature water bath 603, the heat preservation circulating water is heated through the constant-temperature water bath 603, and the heated circulating water is pumped into the water bath heat preservation layer through the water bath heat preservation pump 602; the water outlet of the internal circulation system is arranged at the upper part of the reactor, the water inlet is arranged at the bottom of the reactor, and the internal circulation pump 701 is used for circulating to fully mix the granular sludge in the reactor with the stainless steel pickling high nitrate nitrogen wastewater; the aeration system comprises an aeration pump 801, the reactor is aerated through the aeration pump 801, and an air inlet end of the aeration is arranged at the bottom of the reactor; a mud discharging port 901 of the mud discharging system is arranged at the bottom of the reactor and is used for discharging mud; in this embodiment, the reactor is provided with a plurality of sampling ports 110 from top to bottom.
In the embodiment, the operation condition of the upflow denitrification device uses methanol as a carbon source, the carbon source adding amount C/N is 2.0-3.5, and the carbon nitrogen ratio C/N in the carbon source adding amount in the embodiment refers to the carbon nitrogen ratio in the inlet water, namely, the nitrogen of the wastewater in the inlet water is taken as a reference; the temperature in the heat preservation system is 28-38 ℃, the pH value in the reaction system is 7-9, the HRT is 10-13h, and the hydraulic ascending flow rate in the reaction system of the upflow denitrification device is 1-2.75m/h. The concentration of nitrate nitrogen in the stainless steel pickling high nitrate nitrogen wastewater introduced into the up-flow denitrification device is 700-1200mg/L, the concentration of ammonia nitrogen is 15-30mg/L, the concentration of nitrite nitrogen is 10-30mg/L, and the total nitrogen concentration is 800-1300mg/L.
Starting the up-flow denitrification device in an internal circulation continuous low water inlet mode, carrying out aeration for 1-2 times per day at regular time for 30-60s each time, and controlling the temperature of a denitrification area of the up-flow denitrification device, wherein the denitrification area is a reaction system area. The inoculated sludge is anaerobic flocculent sludge from which supernatant liquid is removed through preliminary precipitation for 30min, the MLSS is 6-10g/L, and the MLVSS is 4-6g/L. Under the continuous flow running condition, the denitrification granular sludge is domesticated and cultured by adopting an up-flow denitrification device, the initial hydraulic retention time is 63.7h, the inlet water is stainless steel pickling high nitrate nitrogen wastewater, the nitrate nitrogen concentration is 700-1200mg/L, and the corresponding nitrate nitrogen volume load is 0.43-0.45 kg.m -3 ·d -1 。
The MLSS of the denitrified granular sludge after successful culture is 134.2g/L, the MLVSS is 15.7g/L, and the denitrification rate is 2-3gNO 3 - -N/(gVSS·d)。
The specific experimental process is as follows:
an up-flow denitrification device with the effective volume of 18.57L of a reaction system is adopted, the inoculated sludge of the up-flow denitrification device is anaerobic flocculent sludge of a sewage treatment station of a certain enterprise for removing supernatant through preliminary precipitation for 30min, the inoculated sludge accounts for 21.4% of the effective volume of the reaction system, the MLSS of the inoculated sludge is 8.82g/L, MLVSS and 5.04g/L, the up-flow denitrification device is adopted for domestication culture of denitrification granular sludge under the continuous flow operation condition, and the initial hydraulic retention time is 63.7h. The nitrate nitrogen concentration of the inlet water of the up-flow denitrification device is 700-1200mg/L, the ammonia nitrogen concentration is within 30mg/L, and the nitrite nitrogen concentration is withinThe concentration is within 30mg/L, the total nitrogen concentration is 800-1300mg/L, and the corresponding nitrate nitrogen volume load is 0.43-0.45 kg.m -3 ·d -1 The carbon source adding system selects methanol as a carbon source, the adding amount is C/N=3.5, when the internal circulation flow of the internal circulation system is higher than the boundary between the reaction system and the three-phase separation system, the height of a sludge layer in the reaction system is not higher than the boundary between the reaction system and the three-phase separation system, on one hand, the higher hydraulic ascending flow rate in the reaction system can wash out the sludge with poorer sedimentation performance so as to promote the rapid formation of granular sludge, on the other hand, the full mixing of the sludge and the water can be promoted so as to improve the denitrification efficiency, the aeration system selects air for aeration, the aeration frequency is 2 times per day, the temperature maintained by the heat preservation system is 33+/-1 ℃, and the sludge discharge system is basically not used for discharging sludge during the starting of the up-flow type denitrification device.
After 9d of operation, the removal efficiency of nitrate nitrogen in the effluent of the upflow denitrification device is improved from 42.79% to 99.93%, which indicates that the inoculation sludge is successfully domesticated, the water inflow rate is improved to ensure that the hydraulic retention time is 44.6h, and the corresponding nitrate nitrogen volume load is 0.42-0.63 kg.m -3 ·d -1 The carbon source adding system selects methanol as a carbon source, the adding amount is C/N=3.5, the height of a sludge layer in the reaction system is not higher than the boundary between the reaction system and the three-phase separation system when the internal circulation flow of the internal circulation system is higher than that of the flow type denitrification device, the aeration system selects air for aeration, the aeration frequency is 2 times per day, each time is 30-60s, the temperature maintained by the heat preservation system is 33+/-1 ℃, and the volume of granular sludge in the sludge discharge system is 21.4% of the volume of the reaction system when the sludge discharge system discharges sludge in SV 30.
After 35d of operation, the average removal efficiency of nitrate nitrogen in the effluent of the upflow denitrification device is 99.96% in the 10 th-35 d period, and the shape of the sludge in the macroscopic reaction system is converted from black flocculent sludge in inoculation into black flocculent mixed dark gray granular mixed sludge, which indicates that denitrification granular sludge is formed preliminarily, the water inflow rate is increased to ensure that the hydraulic retention time is 16.5h, and the corresponding nitrate nitrogen load is 1.25-1.40 kg.m -3 ·d -1 The carbon source adding system selects methanol as a carbon source, the adding amount is C/N=3.5, and the internal circulation of the internal circulation systemWhen the flow rate is higher than that of the flow-up denitrification device, the height of sludge in the reaction system is not higher than the boundary between the reaction system and the three-phase separation system, the aeration system selects air for aeration, the aeration frequency is 2 times per day, each time is 30-60s, the temperature maintained by the heat preservation system is 33+/-1 ℃, and the sludge discharge amount of the sludge discharge system is SV 30 The volume of the granular sludge accounts for 21.4 percent of the volume of the reaction system.
After 42d operation, in the 35-42d period, the average removal efficiency of nitrate nitrogen in the effluent of the upflow denitrification device is 99.96%, and at the moment, the shape of the sludge in the macroscopic reaction system is converted from black flocculent mixed sludge doped with dark gray particles into gray granular sludge, which indicates that the denitrifying granular sludge is completely formed, the particle size of the mature denitrifying granular sludge is 1-6mm, the MLSS is 134.2g/L, the MLVSS is 15.7g/L, the sedimentation speed of single sludge is 198-273m/h, the water inflow rate is increased again to ensure that the hydraulic retention time is 11.1h, and the corresponding volume load of nitrate nitrogen is 1.85-2.44 kg.m -3 ·d -1 The carbon source adding system selects methanol as a carbon source, the adding amount is C/N=3.5, the internal circulation flow of the internal circulation system is set to enable the hydraulic ascending flow velocity in the reaction system to be 1.4m/h, the aeration system selects air for aeration, the aeration frequency is 2 times per day, each time is 30-60s, the temperature maintained by the heat preservation system is 33+/-1 ℃, and the mud discharge amount of the mud discharge system is SV 30 The volume of the granular sludge accounts for 21.4 percent of the volume of the reaction system.
The water quality of the stainless steel pickling high nitrate nitrogen wastewater used in the test is shown in the following table:
the process start-up and high-efficiency operation test data of the up-flow denitrification device combined with denitrification granular sludge for treating stainless steel pickling high-nitrate nitrogen wastewater are shown in fig. 3 to 8.
As the nitrogen content in the stainless steel pickling high-nitrate nitrogen wastewater is mainly nitrate nitrogen, the method utilizes an up-flow denitrification device to combine denitrification granular sludge and utilizes the principle of denitrification to treat the stainless steel pickling high-nitrate nitrogen wastewaterMeanwhile, ca in the stainless steel pickling wastewater treated by denitrification, alkali production, neutralization and defluorination by lime and removal of heavy metal ions is utilized 2+ The content is higher, so that the pH environment in the reaction system can be maintained stable, and Ca in the stainless steel pickling high nitrate nitrogen wastewater can be maintained 2+ The method can promote the rapid formation of denitrification granular sludge, and rapidly start the up-flow denitrification device so as to enable the up-flow denitrification device to efficiently and stably denitrify.
As can be seen from the test data in FIGS. 3 to 8, the up-flow denitrification device can realize stable and high-efficiency denitrification after 9 days of starting and sludge acclimation, and the volume load of nitrate nitrogen is 0.42-2.0 kg/(m) 3 In d), the average removal rate of nitrate nitrogen is 99.94%, the effluent is stably maintained within 4mg/L, the average removal rate of total nitrogen is 99.31%, the effluent is stably maintained within 10mg/L, the average removal rate of ammonia nitrogen is 70.62%, and the effluent is stably maintained within 8 mg/L; the volume load of nitrate nitrogen is 2.0-2.44 kg/(m) 3 And d) the average removal rate of nitrate nitrogen is 98.03%, the effluent is stably maintained within 31mg/L, the average removal rate of total nitrogen is 97.81%, the effluent is stably maintained within 35mg/L, the average removal rate of ammonia nitrogen is 89.76%, and the effluent is stably maintained within 5 mg/L. Meets the C-level discharge standard (TN) of the wastewater quality standard of wastewater discharged into towns (GB/T31962-2015)<45mg/L、NH 3 -N<25 mg/L). Meanwhile, the pH value in the reaction system is kept between 7.5 and 9 stably during the operation without adding an external medicament to adjust the pH environment, and in addition, the reaction system is used for Ca 2+ Has high removal efficiency and high Ca removal efficiency during the 9-76d high-efficiency operation 2+ The average removal efficiency is 91.91 percent, and the hardness of the stainless steel pickling high nitrate wastewater is greatly reduced.
It should be noted that, although the foregoing embodiments have been described herein, the scope of the present invention is not limited thereby. Therefore, based on the innovative concepts of the present invention, alterations and modifications to the embodiments described herein, or equivalent structures or equivalent flow transformations made by the present description and drawings, apply the above technical solution, directly or indirectly, to other relevant technical fields, all of which are included in the scope of the invention.
Claims (10)
1. A method for treating stainless steel pickling high nitrate nitrogen wastewater, which is characterized by comprising the following steps:
anaerobic flocculent sludge is selected as inoculation sludge, stainless steel pickling high nitrate nitrogen wastewater is introduced into an up-flow denitrification device to acclimate the inoculation sludge, and sludge resistant to the stainless steel pickling high nitrate nitrogen wastewater is obtained;
adjusting the operation condition of the up-flow denitrification device, and culturing flocculent sludge into granular sludge;
after the granular sludge is formed, the water inflow of the stainless steel pickling high-nitrate nitrogen wastewater is increased, so that the treatment load is increased;
maintaining the upflow denitrification device to operate under high load conditions;
the up-flow denitrification device comprises a carbon source adding system, wherein the carbon source adding amount of the carbon source adding system is C/N=2.0-3.5.
2. The method according to claim 1, characterized in that: the formed granular sludge is gray, the surface is attached with rod-shaped bacteria and smooth and regular, the diameter of the particle size is 1-6mm, and the sedimentation speed of single sludge is 198-273m/h.
3. The method according to claim 1, characterized in that: the upflow denitrification device maintains the granular sludge SV in the reaction system during operation under high load conditions 30 The volume of the catalyst is 10-30% of the volume of the reaction system.
4. The method according to claim 1, characterized in that: the up-flow denitrification device comprises a water inlet system, a carbon source adding system connected with a pipeline of the water inlet system, a reaction system, a three-phase separation system, a water outlet system, a heat preservation system wrapped outside the reaction system, an internal circulation system respectively connected with the three-phase separation system and the water inlet system, an aeration system connected with the water inlet system and a sludge discharge system connected with the reaction system.
5. The method according to claim 4, wherein: the operation condition of the upflow denitrification device takes methanol as a carbon source, the adding amount of the carbon source is C/N=2.0-3.5, the temperature in the heat preservation system is 28-38 ℃, the pH value in the reaction system is 7-9, the HRT is 10-13h, and the hydraulic ascending flow rate in the upflow denitrification device is 1-2.75m/h.
6. The method according to claim 1, characterized in that: the concentration of nitrate nitrogen in the stainless steel pickling high-nitrate nitrogen wastewater introduced by the up-flow denitrification device is 700-1200mg/L, the concentration of ammonia nitrogen is 15-30mg/L, the concentration of nitrite nitrogen is 10-30mg/L, and the total nitrogen concentration is 800-1300mg/L.
7. The method according to claim 1, characterized in that: starting the up-flow denitrification device in an internal circulation continuous low water inflow mode, carrying out aeration for 1-2 times per day at regular time, each time for 30-60s, and controlling the temperature of a denitrification area of the up-flow denitrification device.
8. The method according to claim 1, characterized in that: the inoculation sludge is anaerobic flocculent sludge with supernatant removed by preliminary precipitation for 30min, the MLSS of the inoculation sludge is 6-10g/L, and the MLVSS is 4-6g/L.
9. The method according to claim 1, characterized in that: under the continuous flow running condition, the denitrification granular sludge is domesticated and cultured by adopting an up-flow denitrification device, the initial hydraulic retention time is 63.7h, the inlet water is stainless steel pickling high nitrate nitrogen wastewater, the nitrate nitrogen concentration is 700-1200mg/L, and the corresponding nitrate nitrogen volume load is 0.43-0.45 kg.m -3 ·d -1 。
10. The method according to claim 9, wherein: the MLSS of the denitrified granular sludge after successful culture is 134.2g/L, the MLVSS is 15.7g/L, and the denitrification rate is 2-3gNO 3 - -N/(gVSS·d)。
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Inventor after: Luo Qian Inventor after: Sun Jianing Inventor after: Yao Jiansong Inventor after: Zhou Guomiao Inventor after: Li Ying Inventor after: Jiang Yanhong Inventor after: Cai Junyun Inventor after: Huang Huimin Inventor after: Zhang Shengjun Inventor after: Wang Yingjie Inventor after: Dong Minfeng Inventor after: Mei Rongwu Inventor before: Luo Qian Inventor before: Jiang Yanhong Inventor before: Sun Jianing Inventor before: Mei Rongwu Inventor before: Zhou Guomiao Inventor before: Cai Junyun Inventor before: Wang Yingjie Inventor before: Yao Jiansong |