CN113493245B - Method for culturing anaerobic ammonia oxidation granular sludge with vivianite core - Google Patents
Method for culturing anaerobic ammonia oxidation granular sludge with vivianite core Download PDFInfo
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
- C02F3/307—Nitrification and denitrification treatment characterised by direct conversion of nitrite to molecular nitrogen, e.g. by using the Anammox process
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- 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
- C02F3/30—Aerobic and anaerobic processes
- C02F3/308—Biological phosphorus removal
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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
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- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
Abstract
The invention belongs to the technical field of sewage treatment, and particularly relates to a culture method of anaerobic ammonium oxidation granular sludge with a vivianite core. The characteristics of an anaerobic ammonium oxidation system are fully utilized, and on one hand, the characteristic that anaerobic ammonium oxidation bacteria can generate nitrate by themselves can strengthen in-situ oxidation of zero-valent iron and increase Fe 2+ And PO 4 3‑ The affinity of the compound promotes nucleation and enhances denitrification; on the other hand, the characteristic that the anaerobic ammonium oxidation bacteria secrete more extracellular polymers than common bacteria is fully utilized, more ions are adsorbed on cell walls, local supersaturation is achieved more quickly, and nucleation is promoted; the invention reduces the Fe generated in situ by nitrate by zero-valent iron through the adjustment of pH and the concentration of phosphate radical in inlet water in different stages 2+ Has stronger phosphate affinity than that of directly added iron salt, and the extracellular polymer of the anaerobic ammonia oxidizing bacteria has stronger Fe 2+ The strong adsorption characteristic ensures the formation of the vivianite core, and effectively improves the problems of nitrate byproduct accumulation and sludge floating.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a culture method of anaerobic ammonium oxidation granular sludge with a vivianite core.
Background
Nitrogen and phosphorus are essential elements of all life forms and are indispensable important components of animals and plants. With the rapid improvement of national economic level, excessive nitrogen and phosphorus discharge causes water eutrophication, and the sustainable development of social economy is seriously influenced. Therefore, before sewage is discharged into a receiving water body, nitrogen and phosphorus elements in the sewage need to be effectively removed, the concentration of the nitrogen and phosphorus elements discharged into the water body needs to be controlled, and the risk of water body pollution and eutrophication is reduced. In recent years, the anaerobic ammonia oxidation process has been recognized by the environmental community as the most sustainable wastewater denitrification technology because of its advantages of no need of additional organic carbon source, low sludge yield, low operation cost, high denitrification efficiency, etc.
When the anaerobic ammonia oxidation process is adopted to treat the nitrogen-containing wastewater, a large amount of N is generated by anaerobic ammonia oxidation bacteria 2 Can not be released, air bags are formed in the granular sludge or are attached to the surface of the granular sludge, so that the density of the granular sludge is reduced, the granular sludge floats upwards, and then the granular sludge runs off along with the effluent, thereby not only increasing the mass concentration of the suspended matters in the effluent, influencing the treatment effect, and even causing the collapse of the system. In addition, the anammox process can produce about 11% nitrate by-products that affect the process' emissions to meet standards. These all severely restrict the large-scale popularization and application of the anaerobic ammonia oxidation process.
For example, patent documents disclose a method for culturing an anammox granular sludge having a hydroxyapatite core, which can culture a granular sludge having a hydroxyapatite core, a good sedimentation property, a high mechanical strength, a large particle diameter and a high bacteria load by adding calcium ions and phosphate ions at a high concentration to influent water, and can realize efficient retention of anammox bacteria at a high flow rate. However, it requires the addition of calcium chloride and high concentrations of phosphate during the cultivation, too high a phosphate concentration is liable to cause inhibition of anammox bacteria, and the process does not involve deep removal of nitrate by-products. In addition, there is a disclosure in the prior patent literature of a treatment method for removing nitrate by-products by adding zero-valent iron powder in an anaerobic ammonia oxidation process. However, the improvement of the sedimentation performance of the anaerobic ammonia oxidation granular sludge is not concerned, and the long-term stable and efficient removal of the total nitrogen is difficult to realize.
In summary, in order to realize the popularization and application of the anaerobic ammonia oxidation process, the problems that the anaerobic ammonia oxidation granular sludge is easy to run off and nitrate byproducts are accumulated need to be solved at the same time.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the sludge is easy to lose due to poor settling performance of the anaerobic ammonium oxidation granular sludge, the standard discharge of the process is influenced by the generated nitrate by-products and the like in the prior art, and provides the culture method of the anaerobic ammonium oxidation granular sludge with the vivianite core.
Therefore, the invention provides the following technical scheme:
the invention provides a method for culturing anaerobic ammonium oxidation granular sludge with a vivianite core, which comprises the following steps:
s1, inoculating active granular sludge in a reactor, and introducing inlet water with phosphate radical concentration of 5-15mg/L to finish starting;
s2, adjusting the pH value of inlet water to be 6.8-7.1, adjusting the concentration of phosphate radicals in the inlet water to be 15-25mg/L, and adding zero-valent iron into the reactor until the average removal rate of phosphorus in the system reaches more than 80%;
and S3, adjusting the pH of the inlet water to 5.9-6.3, adjusting the concentration of phosphate in the inlet water to 35-50mg/L, and increasing the addition of zero-valent iron until solid particles are observed in the anaerobic ammonium oxidation granular sludge.
Optionally, in the step S2, the adding amount of the zero-valent iron is gradually increased, and each concentration is operated until the nitrogen and phosphorus removal efficiency is reduced to a level without adding the zero-valent iron;
in the step S3, the adding amount of the zero-valent iron is gradually increased, and each concentration is operated until the nitrogen and phosphorus removal efficiency is reduced to the level of the zero-valent iron which is not added.
Optionally, the passivated zero valent iron in the reactor is replaced with fresh zero valent iron.
Optionally, the inoculation amount of the activated granular sludge accounts for 5-8% of the total volume of the reactor.
Optionally, the particle size of the activated granular sludge is 0.3-1.5mm.
Optionally, the reactor is filled with activated carbon;
optionally, the activated carbon has a length of 0.1-2cm and a diameter of 1-2mm.
Optionally, the adding amount of the activated carbon is 150-250g/L based on the total volume of the reactor;
optionally, the activated carbon and the activated granular sludge account for 30-40% of the total volume of the reactor.
Optionally, the operating temperature of the reactor is 34-36 ℃, and the hydraulic retention time is 4-6h.
Optionally, the zero-valent iron is at least one of iron powder, iron filings or iron-carbon materials.
Optionally, in step S1, NH is added to the feed water at a rate of 10-20mg/L 4 + -N and NO 2 - The concentration of N is increased to 200-300mg/L respectively.
In particular, the method for culturing the anaerobic ammonium oxidation granular sludge with the vivianite core preferably comprises the following steps of adopting an up-flow anaerobic sludge bed reactor, adding granular activated carbon as an internal filler, inoculating anaerobic ammonium oxidation granular sludge, taking simulated wastewater containing ammonia nitrogen, nitrite nitrogen, inorganic salt and trace elements as inflow water, and under the anaerobic condition that the temperature is 35 +/-1 ℃ and the hydraulic retention time is set to be 4-6 hours:
(1) Adjusting the pH value of the inlet water to 7.5 +/-0.1, adding phosphate into the inlet water to enable the phosphorus concentration to reach 5-15mg/L, and gradually increasing the substrate concentration in the inlet water by a concentration gradient of 10-20mg/L until the ammonia nitrogen concentration and the nitrite concentration reach 200-230mg/L;
(2) Reducing the pH value of inlet water to 7.0 +/-0.1, increasing the concentration of phosphate added into the inlet water to 15-25mg/L, increasing the adding amount of zero-valent iron in the anaerobic ammoxidation reactor in a multiplied increase range, operating each adding amount until the nitrogen and phosphorus removal efficiency of the anaerobic ammoxidation reactor is reduced to the level of zero-valent iron which is not added, moving the passivated zero-valent iron out of the reactor, adding multiplied fresh zero-valent iron, and operating until the average phosphorus removal rate under the zero-valent iron amount reaches over 80%;
(3) The pH value is reduced to 6.0 +/-0.1, the concentration of the phosphate in the inlet water is increased to 35-50mg/L, the adding amount of zero-valent iron in the anaerobic ammonia oxidation reactor is increased in a multiplying manner in the stage (2), each adding amount is operated until the nitrogen and phosphorus removal efficiency of the anaerobic ammonia oxidation reactor is reduced to the level of zero-valent iron which is not added, the passivated zero-valent iron is removed from the reactor, and multiple times of fresh zero-valent iron is added, and the operation is performed until the anaerobic ammonia oxidation granular sludge contains solid particles.
Optionally, the step (1) of gradually increasing the substrate concentration in the inlet water by a concentration gradient of 10-20mg/L until the ammonia nitrogen and nitrite concentration reaches 200-230mg/L means that when the nitrite concentration in the outlet water is lower than 10mg/L, the ammonia nitrogen and nitrite concentration in the inlet water is synchronously increased by 10-20 mg/L.
Optionally, the pH value of the inlet water is 1 mol.L -1 Hydrochloric acid is used for regulation.
Optionally, the added zero-valent iron is iron powder, scrap iron or iron-carbon material and other iron-based materials taking zero-valent iron as main reducing substances, and before use, the iron-based materials are pickled by 5% hydrochloric acid, and then washed by water to remove oil stains and rust on the surface, and the obtained zero-valent iron is dried for later use.
Optionally, the phosphate of the inlet water is formed by KH 2 PO 4 Provided is a method.
Optionally, the zero-valent iron is added into the reactor, the addition is started from 1g/L, each dosage is maintained until the nitrate nitrogen removal rate and the phosphorus removal rate of the reactor are raised back to the state before the zero-valent iron is not added, the "passivated" zero-valent iron in the reactor is taken out, fresh zero-valent iron is added into the reactor again, and the addition dosage of the zero-valent iron is increased in a multiplied amplitude, namely 2g/L,4g/L,8g/L, 16g/L and the like, and the like.
Optionally, the simulated wastewater comprises the following components: ammonia nitrogen 50-250 mg.L -1 Nitrite nitrogen 50-250 mg.L -1 Phosphate 5-50 mg. L -1 ，KHCO 3 120-130mg·L -1 ,EDTA 5-10mg·L -1 And trace elements I1-2 mL. L -1 1-2 mL/L of trace elements -1 The solvent is water.
The trace elements I comprise: naCl 500-600 mg.L -1 ,KCl 700-800mg·L -1 ,CaCl 2 ·2H 2 O 700-800mg·L -1 ,MgSO 4 ·7H 2 O 400-600mg·L -1 。
And the trace element II comprises: cuSO 4 ·5H 2 O 0.2-0.3mg·L -1 ,ZnSO 4 ·7H 2 O 0.4-0.5mg·L -1 , CoCl 2 ·6H 2 0 0.2-0.3mg·L -1 ,MnCl 2 ·4H 2 O 0.9-1.2mg·L -1 ,NaMoO 4 ·2H 2 O 0.2-0.3mg·L -1 ,NiCl 2 ·6H 2 O 0.1-0.2mg·L -1 ,NaSeO 4 0.1-0.21mg·L -1 ,H 3 BO 3 0.01-0.02mg·L -1
Optionally, the suspended solid concentration of the inoculated mixed liquid of the anaerobic ammonia oxidation granular sludge is 1-3 g.L -1 The grain diameter is 0.3-1.5mm, and the inoculation volume accounts for 5% -8% of the total volume of the reactor.
Optionally, the added biological filler granular activated carbon has a length of 0.1-2cm and a diameter of 1-2mm, and the addition amount of the biological filler granular activated carbon relative to the reactor is 150-250 g.L -1 And after the addition, the mixed volume of the granular activated carbon and the sludge accounts for 30 to 40 percent of the total volume of the reactor.
The technical scheme of the invention has the following advantages:
the invention provides a method for culturing anaerobic ammonium oxidation granular sludge with a vivianite core, which comprises the following steps: s1, inoculating active granular sludge into a reactor, and introducing inlet water with phosphate radical concentration of 5-15mg/L to finish starting; s2, adjusting the pH value of inlet water to be 6.8-7.1, wherein the concentration of phosphate radicals in the inlet water is 15-25mg/L, and adding zero-valent iron into the reactor until the average removal rate of phosphorus in the system reaches more than 80%; and S3, adjusting the pH of the inlet water to 5.9-6.3, adjusting the concentration of phosphate in the inlet water to 35-50mg/L, and increasing the addition of zero-valent iron until solid particles are observed in the anaerobic ammonium oxidation granular sludge. The invention makes full use of the characteristics of the anaerobic ammonia oxidation system, on one hand, the anaerobic ammonia oxidation bacteria can generate nitrate through the unique physiological characteristics of the anaerobic ammonia oxidation bacteria, so that the aim of oxidizing zero-valent iron in situ can be strengthened, and Fe is increased 2+ And PO 4 3- The affinity of the compound promotes nucleation and enhances denitrification; on the other hand, the characteristics that the anaerobic ammonium oxidation bacteria secrete more extracellular polymers than common bacteria are fully utilized, more ions are adsorbed on cell walls, local supersaturation is achieved more quickly, and nucleation is promoted; the invention adopts the zero-valent iron as the medicament for forming the granular sludge kernel, has smaller influence on the environment compared with other chemical reagents, and does not influence the subsequent treatment of the wastewater. The zero-valent iron has strong reduction characteristic, nitrate by-products in the anaerobic ammonia oxidation reactor can be reduced into ammonia nitrogen, and the newly generated ammonia nitrogen and nitrite nitrogen are subjected to anaerobic ammonia oxidation reaction again, so that the total nitrogen removal rate is improved. While reducing nitrate, the zero-valent iron is oxidized to generate Fe 2+， Fe generated by these in situ oxidations 2+ Can be bonded with PO in water with higher bonding energy 4 3- And (4) combining. On the other hand, anammox bacteria can secrete a large amount of extracellular polymeric substances which are rich in functional groups such as hydroxyl, carboxyl and amino groups and can promote Fe by electrostatic attraction or other actions 2+ And PO 4 3- The ion concentration is locally supersaturated, so that the generation of the vivianite on the surface of the anaerobic ammonia oxidation bacteria is induced, the vivianite grows into the kernel of the anaerobic ammonia oxidation granular sludge, the sedimentation performance of the anaerobic ammonia oxidation granular sludge is improved, the sludge loss is effectively prevented, a large amount of enrichment of the anaerobic ammonia oxidation sludge is realized, and the long-term stable and efficient denitrification performance of the anaerobic ammonia oxidation process is realized. The formula for reducing nitrate by zero-valent iron and generating vivianite is as follows:
4Fe 0 +NO 3 - +10H + →NH 4 + +3H 2 O+4Fe 2+ (1)
2PO 4 3- +3Fe 2+ +8H 2 O→Fe 3 (PO 4 )2.8H 2 O (2)
in order to promote the removal of the anaerobic ammonium oxidation nitrate by-product and the formation of vivianite, the pH of the system is gradually reduced, and the inhibition of anaerobic ammonium oxidation bacteria by lower pH is avoided; excess Fe 2+ And PO 4 3- Is an important prerequisite for the formation of vivianite, while a lower pH accelerates the reduction of zero-valent iron to nitrate and produces more Fe 2+ . Specifically, in order to promote the formation of vivianite and avoid the inhibition of lower pH on anaerobic ammonium oxidation bacteria, the pH of the inlet water is firstly reduced to 6.8-7.1, so that the anaerobic ammonium oxidation bacteria have certain tolerance to the lower pH, and then the pH is reduced to 5.9-6.3, so that the formation of the sludge with vivianite core anaerobic ammonium oxidation particles is effectively promoted. According to the invention, through adjustment of culture conditions, especially adjustment of pH values at different stages and adjustment of concentration of phosphate radicals in inlet water, removal of anaerobic ammonium oxidation nitrate byproducts is effectively promoted, and the sludge floating problem is improved. Experimental results show that the anaerobic ammonia oxidation reactor effectively promotes the reduction and transformation of nitrate in the process of running under the condition of the method, and the nuclear-containing granular sludge cultured by the method has the advantages of good sedimentation performance, high mechanical strength, large particle size, dense bacteria carrier and the like; in addition, the economic value of the vivianite per unit mass is the highest in all recoverable phosphate products, the vivianite can be used as a phosphate fertilizer raw material and a lithium battery synthesis raw material, and the large-particle high-purity vivianite crystal also has high collection value.
According to the method for culturing the anaerobic ammonia oxidation granular sludge with the vivianite core, provided by the invention, the problems that vivianite cannot be formed and the activity of anaerobic ammonia oxidizing bacteria is inhibited due to too little or too much zero-valent iron can be solved by specifically limiting the zero-valent iron adding mode, and the effect of culturing the anaerobic ammonia oxidation granular sludge with the vivianite core can be quickly realized by using a small amount of zero-valent iron on the premise of maintaining higher anaerobic ammonia oxidizing activity.
The culture method of the anaerobic ammonia oxidation granular sludge with the vivianite core, provided by the invention, has the effects of accelerating the starting of the anaerobic ammonia oxidation process and promoting the granulation of the sludge by specifically limiting the activated granular sludge and the inoculation amount.
According to the method for culturing the anaerobic ammonia oxidation granular sludge with the vivianite core, the reactor is also filled with the activated carbon carrier, and zero-valent iron and iron are simultaneously present in the reactor1.2V electrode potential difference exists between the active carbon and the iron and the carbon, an iron-carbon microelectrode is formed between the active carbon and the carbon, and the release of Fe from zero-valent iron is accelerated 2+ . Meanwhile, the activated carbon has a large specific surface area and can adsorb Fe generated in the solution 2+ High Fe is produced with continuous adsorption 2+ 、PO 4 3- Thereby effectively promoting the formation of vivianite. In addition, the activated carbon can be used as a biological carrier, and provides a suitable environment for the growth of the anaerobic ammonia oxidation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of the structure of an upflow anaerobic sludge blanket reactor used in the example of the present invention;
FIG. 2 is a graph of nitrogen removal performance during operation of an anammox reactor in accordance with example 1 of the present invention, wherein: NLR represents nitrogen loading rate; NRR represents nitrogen removal load; NRE represents nitrogen removal efficiency;
FIG. 3 is a graph of phosphorus removal performance during operation of an anammox reactor in accordance with example 1 of the present invention, wherein: PLR represents phosphorus loading rate; PRR stands for phosphorus removal load; PRE represents phosphorus removal efficiency;
FIG. 4 is a kernel XRD pattern of anammox granular sludge prepared in example 1 of the present invention;
reference numerals:
1. a water inlet barrel; 2, a water pump; 3. a water inlet; 4. heating in water bath; 5. a multi-parameter water quality analyzer; 6. a reactor main body; 7. a water outlet; 8, discharging the water bucket.
Detailed Description
The following examples are provided to better understand the invention optionally, not to limit the invention to the best mode, and not to limit the content and scope of the invention, and any product similar or similar to the invention, which is obtained by combining the invention with other prior art features, with the teaching of the invention, falls within the scope of the invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1
The embodiment provides a method for culturing anaerobic ammonium oxidation granular sludge with a vivianite core, which comprises the following specific steps:
taking an upflow anaerobic sludge blanket reactor with effective volume of 2.5L, the structure is shown in figure 1, adding 180 g.L into a reactor main body 6 -1 The granular activated carbon is used as a biological carrier, the anaerobic ammonia oxidation granular sludge is inoculated, and the suspended solid concentration of the mixed solution of the anaerobic ammonia oxidation granular sludge is 2 g.L -1 The simulated wastewater is used as inflow water, the reactor is operated under the conditions of anaerobism, light resistance, 35 +/-1 ℃ and 5.4h of hydraulic retention time, and the water bath heating 4 is used for heating the reactor main body 6.
The simulated wastewater comprises ammonia nitrogen 50-210 mg.L -1 Nitrite nitrogen 50-210 mg.L -1 Phosphate 8-44 mg. L -1 ，KHCO 3 125mg·L -1 ,EDTA 5mg·L -1 And trace elements I2 mL. L -1 1 mL. L of trace elements II -1 The solvent is water.
The trace elements I comprise: naCl 500 mg. L -1 ,KCl 700mg·L -1 ,CaCl 2 ·2H 2 O 700mg·L -1 ,MgSO 4 ·7H 2 O 500mg·L -1 。
The trace element II comprises: cuSO 4 ·5H 2 O 0.25mg·L -1 ,ZnSO 4 ·7H 2 O 0.43mg·L -1 ,CoCl 2 ·6H 2 0 0.24mg·L -1 ,MnCl 2 ·4H 2 O 0.99mg·L -1 ,NaMoO 4 ·2H 2 O 0.22mg·L -1 ,NiCl 2 ·6H 2 O 0.19mg·L -1 ,NaSeO 4 0.11mg·L -1 ,H 3 BO 3 0.014mg·L -1 。
Firstly, the starting stage of the anaerobic ammonia oxidation reactor is carried out, the pH of inlet water in a water inlet barrel 1 is adjusted to 7.5 +/-0.1, the pH is monitored by a multi-parameter water quality analyzer 5 at any time, and KH is added into the inlet water 2 PO 4 The phosphorus concentration reaches 10 +/-2 mg/L, and the initial substrate concentration is NH 4 + -N and NO 2 - The content of-N is 50 mg.L each -1 The reactor body is supplied with feed water through a water pump 2 and a water inlet 3, and NH in the feed water is gradually increased 4 + -N and NO 2 - N concentration (i.e. whenever NO is present) 2 - N effluent concentration is lower than 10mg/L, NH in the water is synchronously increased by steps of 10mg/L 4 + -N and NO 2 - Concentration of N) until NH in the feed water 4 + -N and NO 2 - The N concentration reaches 210mg/L, and the effluent is discharged into an effluent barrel 8 through a water outlet 7. After 16 days of stable operation, the reactor is successfully started, the total nitrogen removal rate reaches 83.92%, and the average concentration of the effluent nitrate reaches 51.53mg/L.
Then the pH value of the inlet water is reduced to 7.0 +/-0.1, and the KH of the inlet water is increased 2 PO 4 The content of the phosphorus is such that the phosphorus concentration reaches 20 +/-2 mg/L. Maintaining the phosphorus concentration, beginning to add zero-valent iron (325-mesh zero-valent iron powder) into the anaerobic ammoxidation reactor and increasing the adding amount of the zero-valent iron in a multiplied growth mode, wherein the adding amount of the zero-valent iron in the embodiment is 1g/L,2g/L and 4g/L respectively, and when the adding amount of the zero-valent iron in the anaerobic ammoxidation reactor is 4g/L, the average phosphorus removal rate under the adding amount reaches 80.35 percent and the total nitrogen removal rate reaches 86.09 percent. The concentration of the nitrate in the effluent is reduced, the reduction degree is in direct proportion to the addition amount of zero-valent iron, the average removal rate of the nitrate under the dosage reaches 23.24 percent, and the addition amount of the zero-valent iron is stopped to be increased.
Finally, the pH of the inlet water is reduced to 6.0 +/-0.1, and the KH of the inlet water is increased 2 PO 4 The content of phosphorus can reach 40 + -4 mgAnd L. Maintaining the phosphorus concentration, adding 4g/L,8g/L and 16g/L of zero-valent iron into the anaerobic ammonia oxidation reactor on the basis of the previous step, wherein when the adding amount of the zero-valent iron reaches 16g/L, the generation of the nuclear-containing anaerobic ammonia oxidation granular sludge can be obviously observed, the bacterial load is dense, the concentration of nitrate in effluent is obviously reduced, the average removal rate reaches 51.39%, and the total nitrogen removal rate reaches 91.57%.
FIG. 2 is a graph of nitrogen removal performance during operation of an anammox reactor in accordance with example 1 of the present invention, wherein: NLR represents nitrogen loading rate; NRR represents nitrogen removal duty; NRE represents nitrogen removal efficiency; as can be seen from the figure, the addition of zero-valent iron can significantly improve the denitrification performance of the anammox process by reducing the effluent nitrate concentration, but the nitrogen removal efficiency shows a periodically fluctuating trend due to the passivation of zero-valent iron.
FIG. 3 is a graph of phosphorus removal performance during operation of an anammox reactor in accordance with example 1 of the present invention, wherein: PLR represents phosphorus loading rate; PRR represents phosphorus removal load; PRE represents phosphorus removal efficiency; as can be seen from the figure, the addition of zero-valent iron can effectively promote the phosphorus removal efficiency of the system, and the improvement of the phosphorus removal efficiency has a certain relation with the addition dosage and pH of the zero-valent iron.
Fig. 4 is a kernel XRD pattern of the anammox granular sludge prepared in example 1 of the present invention, from which it can be seen that the anammox granular sludge kernel is identified as vivianite.
Example 2
The embodiment provides a method for culturing anaerobic ammonium oxidation granular sludge with a vivianite core, which comprises the following specific steps:
taking an up-flow anaerobic sludge bed reactor with an effective volume of 2.5L, inoculating anaerobic ammonia oxidation granular sludge in a reactor main body 6, wherein the suspended solid concentration of the mixed liquid of the anaerobic ammonia oxidation granular sludge is 2 g.L -1 The simulated wastewater is used as inflow water, the reactor is operated under the conditions of anaerobism, light resistance, 35 +/-1 ℃ and 5.4h of hydraulic retention time, and the water bath heating 4 is used for heating the reactor main body 6.
The simulated wastewater comprises 50-230mg of ammonia nitrogen·L -1 Nitrite nitrogen 50-230 mg.L -1 6-49 mg.L of phosphate -1 ，KHCO 3 125mg·L -1 ,EDTA 5mg·L -1 And trace elements I2 mL. L -1 1 mL. L of trace elements II -1 The solvent is water, and the composition of trace elements is the same as that in example 1.
Firstly, the anaerobic ammoxidation reactor is started, the pH value of inlet water in an inlet water barrel 1 is adjusted to 7.5 +/-0.1, the pH value is constantly monitored by a multi-parameter water quality analyzer 5, and KH is added into the inlet water 2 PO 4 The phosphorus concentration reaches 8 +/-2 mg/L, and the initial substrate concentration is NH 4 + -N and NO 2 - The contents of-N are each 50 mg.L -1 The reactor body is supplied with feed water through a water pump 2 and a water inlet 3, and NH in the feed water is gradually increased 4 + -N and NO 2 - N concentration (i.e. whenever NO is present) 2 - N effluent concentration is lower than 10mg/L, NH in the water is synchronously increased by steps of 10mg/L 4 + -N and NO 2 - Concentration of N) up to NH in the feed water 4 + -N and NO 2 - The concentration of N reaches 230mg/L, and the effluent is discharged into an effluent bucket 8 through a water outlet 7. After 20 days of stable operation, the reactor is successfully started, the total nitrogen removal rate reaches 82.08%, and the average concentration of effluent nitrate reaches 55.03mg/L.
Then the pH value of the inlet water is reduced to 6.9 +/-0.1, and the KH of the inlet water is increased 2 PO4 content was such that the phosphorus concentration reached 17. + -.2 mg/L. While maintaining the phosphorus concentration, zero-valent iron (325 mesh of zero-valent iron powder) was initially charged into the anammox reactor and the amount of zero-valent iron charged was increased in a multiplied manner, in this example, the amount of zero-valent iron charged was 1g/L,2g/L, and 4g/L, respectively. When the addition amount of zero-valent iron in the anaerobic ammonium oxidation reactor is 4g/L, the average removal rate of phosphorus reaches 82.06%, the total nitrogen removal rate reaches 84.34%, the average removal rate of nitrate reaches 20.98%, and the increase of the addition amount of zero-valent iron is stopped.
Finally, the pH of the inlet water is reduced to 6.1 +/-0.1, and the KH of the inlet water is increased 2 PO 4 The content of the phosphorus in the solution is 45 +/-4 mg/L. Maintaining the phosphorus concentration in the preceding stepOn the basis, zero-valent iron is added into the anaerobic ammonia oxidation reactor, the adding amount is respectively 4g/L,8g/L and 16g/L, when the adding amount of the zero-valent iron reaches 16g/L, the generation of the anaerobic ammonia oxidation granular sludge containing nuclei can be obviously observed, the bacterial load is dense, the average removal rate of nitrate reaches 46.09%, and the total nitrogen removal rate reaches 88.95%.
Comparative example 1
The comparative example provides a culture method of anaerobic ammonia oxidation granular sludge with a vivianite core, which comprises the following specific steps:
taking an upflow anaerobic sludge blanket reactor with effective volume of 2.5L, the structure is shown in figure 1, adding 180 g.L into a reactor main body 6 -1 The granular activated carbon is used as a biological carrier, the anaerobic ammonia oxidation granular sludge is inoculated, and the suspended solid concentration of the mixed solution of the anaerobic ammonia oxidation granular sludge is 2 g.L -1 The simulated wastewater is used as inflow water, the reactor is operated under the conditions of anaerobism, light resistance, 35 +/-1 ℃ and 5.4h of hydraulic retention time, and the water bath heating 4 is used for heating the reactor main body 6. The simulated wastewater composition was the same as in example 1.
Firstly, the starting stage of the anaerobic ammonia oxidation reactor is carried out, the pH of inlet water in a water inlet barrel 1 is adjusted to 7.5 +/-0.1, the pH is monitored by a multi-parameter water quality analyzer 5 at any time, and KH is added into the inlet water 2 PO 4 The phosphorus concentration is 10 +/-2 mg/L, and the initial substrate concentration is NH 4 + -N and NO 2 - The content of-N is 50 mg.L each -1 The reactor body is supplied with feed water through a water pump 2 and a water inlet 3, and NH in the feed water is gradually increased 4 + -N and NO 2 - N concentration (i.e. whenever NO is present) 2 - N effluent concentration is lower than 10mg/L, NH in the water is synchronously increased by steps of 10mg/L 4 + -N and NO 2 - Concentration of N) up to NH in the feed water 4 + -N and NO 2 - The N concentration reaches 210mg/L, and the effluent is discharged into an effluent barrel 8 through a water outlet 7. After 16 days of stable operation, the reactor is successfully started, the total nitrogen removal rate reaches 82.56%, and the average concentration of effluent nitrate reaches 52.98mg/L.
Then the pH value of the inlet water is reduced to 7.0 +/-0.1, and the KH of the inlet water is increased 2 PO 4 The content of the phosphorus in the solution is 20 +/-2 mg/L. The stable operation of the phosphorus concentration is maintained for 49 days, the average phosphorus removal rate is 35.67 percent, the total nitrogen removal rate is 80.97 percent, the concentration of nitrate in effluent is not obviously changed, and the average concentration is 53.05mg/L.
Finally, the pH of the inlet water is reduced to 6.0 +/-0.1, and the KH of the inlet water is increased 2 The PO4 content was such that the phosphorus concentration reached 40. + -.4 mg/L. The operation is carried out for 53 days while maintaining the phosphorus concentration, the average phosphorus removal rate is 33.12 percent, the generation of the anaerobic ammonium oxidation granular sludge containing the nuclei is not observed all the time, the bacterial load is sparse, the concentration of nitrate in effluent is not obviously changed, the average concentration is 51.24mg/L, and the total nitrogen removal rate is 81.33 percent.
Comparative example 2
The comparative example provides a culture method of anaerobic ammonia oxidation granular sludge with a vivianite core, which comprises the following specific steps:
taking an upflow anaerobic sludge blanket reactor with effective volume of 2.5L, adding 180 g.L into a reactor main body 6 as shown in figure 1 -1 The granular activated carbon (2) is used as a biological carrier, and is inoculated with anaerobic ammonium oxidation granular sludge, and the suspended solid concentration of the mixed solution of the anaerobic ammonium oxidation granular sludge is 2 g.L -1 The simulated wastewater is taken as inflow water, the reactor is operated under the conditions of anaerobism, light shielding, 35 +/-1 ℃ and 5.4h of hydraulic retention time, and the reactor body 6 is heated by the water bath heating 4. The simulated wastewater composition was the same as in example 1.
Firstly, the starting stage of the anaerobic ammonia oxidation reactor is carried out, the pH of inlet water in a water inlet barrel 1 is adjusted to 7.5 +/-0.1, the pH is monitored by a multi-parameter water quality analyzer 5 at any time, and KH is added into the inlet water 2 PO 4 The phosphorus concentration is 10 +/-2 mg/L, and the initial substrate concentration is NH 4 + -N and NO 2 - The content of-N is 50 mg.L each -1 The reactor body is supplied with feed water through a water pump 2 and a water inlet 3, and NH in the feed water is gradually increased 4 + -N and NO 2 - N concentration (i.e. whenever NO is present) 2 - N effluent concentration is lower than 10mg/L, NH in the influent water is synchronously increased in steps of 10mg/L 4 + -N and NO 2 - Concentration of N) until NH in the feed water 4 + -N and NO 2 - The N concentration reaches 210mg/L, and the effluent is discharged into an effluent barrel 8 through a water outlet 7. After 16 days of stable operation, the reactor is successfully started, the total nitrogen removal rate reaches 80.85%, and the average accumulated amount of effluent nitrate reaches 52.56mg/L.
Then, the pH value of the inlet water is maintained at 7.5 +/-0.1, and the KH of the inlet water is increased 2 PO4 content was such that the phosphorus concentration reached 20. + -.2 mg/L. Maintaining the phosphorus concentration, adding zero-valent iron (325-mesh zero-valent iron powder) into the anaerobic ammoxidation reactor, and increasing the adding amount of the zero-valent iron in a multiple increasing manner, wherein the adding amount of the zero-valent iron in the embodiment is respectively 1g/L,2g/L,4g/L and 8g/L, when the adding amount of the zero-valent iron in the anaerobic ammoxidation reactor is 8g/L, the average phosphorus removal rate under the adding amount reaches 81.47%, the total nitrogen removal rate reaches 84.03%, the average water nitrate removal rate is 22.09%, and stopping increasing the adding amount of the zero-valent iron. Compared with the zero-valent iron adding amount of example 4g/L, the zero-valent iron adding amount of 8g/L reaches over 80 percent of phosphorus removal rate and corresponding nitrate removal rate, but the required zero-valent iron is more, the operation cost is increased, and the time is relatively long.
Finally, the pH value of the inlet water is kept to be 7.5 +/-0.1, and the KH in the inlet water is increased 2 The PO4 content was such that the phosphorus concentration reached 40. + -.4 mg/L. The phosphorus concentration is maintained, zero-valent iron is added into the anaerobic ammonia oxidation reactor on the basis of the previous step, the adding amount is respectively 8g/L,16g/L and 32g/L, when the adding amount of the zero-valent iron reaches 32g/L, the generation of anaerobic ammonia oxidation granular sludge with smaller nuclei can be observed, the bacteria-carrying density degree is not as high as that of the anaerobic ammonia oxidation granular sludge in the above example 2, the effluent nitrate removal rate is 25.74%, the total nitrogen removal rate is 84.68%, and the removal rate is not obviously reduced along with the increase of the adding amount of the zero-valent iron.
Examples of the experiments
The granular sludge obtained in the embodiment and the comparative example of the invention is subjected to performance tests, including the tests of sedimentation performance, mechanical strength, particle size, bacterial load density and the like, and the specific test method and test results are as follows:
1. settling property: the sedimentation performance index of the sludge is characterized by a Sludge Volume Index (SVI). Firstly, the concentration of Mixed Liquor Suspended Solids (MLSS) is measured by adopting a standard weight method, namely, a certain volume of complete muddy water mixed liquor is dried at 105 ℃ to constant weight, the MLSS is obtained by dividing a weighed value by the volume of the mixed liquor, and then a sludge sedimentation ratio (SV) is measured by adopting a 30-minute sedimentation method, namely the volume of activated sludge settled in a 1000-milliliter measuring cylinder for 30 minutes is SV30. The SVI value is the ratio of SV30 to MLSS.
2. Mechanical strength: the mechanical strength of the sludge is characterized by using an integral coefficient IC, and the specific method is that a plurality of representative mature granular sludge are selected and placed in a conical flask, the speed of a flat-plate shaking table is set to be 200r/min, and the percentage of the number of granules with complete structures in the total number of granules is measured after shaking for 5 min.
3. Particle size of the particles: the particle size distribution of the particles was measured using a laser particle size analyzer (Microtrac S3550, usa).
TABLE 1
The data in the table show that the settling property, the mechanical strength and the particle size of the granular sludge in the examples 1 and 2 are obviously superior to those of the granular sludge in the comparative examples 1 and 2, namely the granular sludge containing nuclei cultured by the method has the advantages of good settling property, high mechanical strength, large particle size, dense bacteria load and the like, and meanwhile, in the process of running under the condition of the method, the generation of the granular sludge containing nuclei can be obviously observed, the performance of the sludge granules is obviously improved, the phenomenon of sludge loss is avoided, the sludge enrichment is promoted, and the overall denitrification performance of the anaerobic ammonia oxidation reactor is greatly improved. On the other hand, the addition of the zero-valent iron effectively promotes the reduction and conversion of the nitrate, reduces the concentration of the nitrate in the effluent, and further improves the denitrification efficiency of the anaerobic ammonia oxidation process.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A method for culturing anaerobic ammonium oxidation granular sludge with a vivianite core is characterized by comprising the following steps:
s1, inoculating active granular sludge in a reactor, and introducing inlet water with phosphate radical concentration of 5-15mg/L to finish starting;
s2, adjusting the pH value of inlet water to be 6.8-7.1, wherein the concentration of phosphate radicals in the inlet water is 15-25mg/L, and adding zero-valent iron into the reactor until the average removal rate of phosphorus in the system reaches more than 80%;
and S3, adjusting the pH value of the inlet water to 5.9-6.3, adjusting the concentration of phosphate radicals in the inlet water to 35-50mg/L, and increasing the adding amount of zero-valent iron until the anaerobic ammonium oxidation granular sludge is observed to contain solid particles.
2. The method for culturing the anaerobic ammonium oxidation granular sludge with the vivianite core as claimed in claim 1, wherein in the step S2, the addition amount of the zero-valent iron is gradually increased, and each concentration is operated until the denitrification and dephosphorization efficiency is reduced to the level of the zero-valent iron which is not added;
in the step S3, the adding amount of the zero-valent iron is gradually increased, and each concentration is operated until the nitrogen and phosphorus removal efficiency is reduced to the level of the zero-valent iron which is not added.
3. The method of cultivating anammox granular sludge having a vivianite core according to claim 2, wherein the passivated zero valent iron in the reactor is replaced with fresh zero valent iron.
4. The method for cultivating anammox granular sludge having a vivianite core according to any one of claims 1 to 3, wherein the amount of the inoculated active granular sludge is 5 to 8% of the total volume of the reactor.
5. The method for cultivating anammox granular sludge having a vivianite core according to claim 4, wherein the activated granular sludge has a particle size of 0.3-1.5mm.
6. The method for culturing anammox granular sludge having a vivianite core according to any one of claims 1 to 3 or 5, wherein the reactor is filled with activated carbon;
the length of the active carbon is 0.1-2cm, and the diameter is 1-2mm.
7. The method for culturing the anaerobic ammonium oxidation granular sludge with the vivianite core according to claim 6, wherein the addition amount of the activated carbon is 150-250g/L based on the total volume of the reactor;
the active carbon and the active granular sludge account for 30-40% of the total volume of the reactor.
8. The method for cultivating anammox granular sludge having a vivianite core according to any one of claims 1 to 3,5 or 7, characterized in that the operating temperature of the reactor is 34-36 ℃ and the hydraulic retention time is 4-6h.
9. The method for culturing anammox granular sludge having a vivianite core according to any one of claims 1 to 3,5 or 7, wherein the zero valent iron is at least one of iron powder, iron filings or iron-carbon material.
10. The method for cultivating anammox granular sludge having a vivianite core according to claim 9, wherein in step S1, NH is fed into water at a rate of 10-20mg/L 4 + -N and NO 2 - The concentration of the N is increased to 200-300mg/L respectively.
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