Anaerobic ammonia oxidation rapid enhanced starting method based on inactivated sludge
Technical Field
The invention relates to an anaerobic ammonia oxidation rapid enhanced starting method based on inactivated sludge, and belongs to the field of biological wastewater treatment.
Background
The traditional sewage treatment process (nitrification-denitrification process) is not enough to meet the high-standard sewage denitrification requirement due to high energy consumption, large occupied area, low denitrification efficiency, the need of additionally adding an organic carbon source and the like, and the development and research of the novel sewage denitrification process become research hotspots in the field of water environment protection of various countries. The anaerobic ammonia oxidation process is a novel denitrification process which is developed vigorously in recent years. The process is characterized in that under the anaerobic or anoxic condition, ammonia nitrogen is directly converted into nitrogen by anaerobic ammonia oxidation microorganisms by taking nitrite nitrogen as an electron acceptor without adding a carbon source, without aeration, and the process flow is short and has no N2O is generated, so that the denitrification cost is greatly reduced and is only 1/10 of the traditional technical method. Therefore, anaerobic ammonia oxidation technology is gaining increasing favor of researchers by virtue of its excellent treatment effect and low operation cost.
However, the growth of anammox bacteria is slow, the generation time is usually as long as 11 days, and the environmental conditions required for survival are very harsh, enrichment and difficult, so that the start cycle of the anammox process is long, the engineering application of the anammox process is restricted, and the technology is basically in the laboratory theoretical research stage at present and has less industrial application. In addition, currently, the enrichment of the anammox bacteria generally adopts the form of inoculating activated sludge for culture, and in the enrichment culture process, the competitive action of coexisting bacteria hinders the conversion speed of the anammox bacteria to dominant bacteria, so that the starting speed of the anammox process is reduced to a great extent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an anaerobic ammonia oxidation rapid strengthening starting method based on inactivated sludge.
Description of terms:
high-pressure steam inactivation: also called high-pressure steam sterilization, and the high-pressure steam sterilization is carried out for 20-40min at the pressure of 0.1-0.5MPa and the temperature of 120-; it can kill common bacteria, fungi and other microbes, and spore, and is widely used in medical and food industry.
The technical scheme of the invention is as follows:
an anaerobic ammonia oxidation rapid reinforced starting method based on inactivated sludge comprises the following steps:
(1) performing high-pressure steam inactivation on the activated sludge for 20-40min under the conditions that the pressure is 0.1-0.5MPa and the temperature is 120-125 ℃ to obtain inactivated sludge, wherein the water content of the activated sludge is more than or equal to 99 wt%;
(2) uniformly mixing the inactivated sludge obtained in the step (1) and the activated anaerobic ammonium oxidation sludge, and then adding the mixture into a reaction zone of an upflow anaerobic reactor, wherein the water content of the mixed sludge obtained after uniform mixing is more than or equal to 99 wt%;
(3) introducing wastewater to be treated from the bottom of an upflow anaerobic reactor by using a peristaltic pump, adjusting the rotating speed of the peristaltic pump according to the volume of the upflow anaerobic reactor to control the inflow velocity, leading the wastewater to be treated to have hydraulic retention time of 10-48 hours in the upflow anaerobic reactor, keeping the concentration of mixed sludge after introducing the wastewater to be treated at 3000-5000 mg/L, simultaneously adopting a heating rod or a constant-temperature circulating water bath device to keep the internal temperature of the upflow anaerobic reactor at 32-38 ℃, introducing high-purity nitrogen to maintain the anaerobic environment, and introducing carbon dioxide to keep the pH at 7.1-7.7;
(4) keeping the water outlet flow velocity of the upflow anaerobic reactor the same as the water inlet flow velocity, successfully starting the anaerobic ammoxidation reaction of the sludge after the upflow anaerobic reactor operates for 40-70 days, realizing the high-efficiency removal of nitrogen in the sewage, and then entering the next anaerobic ammoxidation reaction.
According to the invention, the activated sludge is preferably activated anaerobic granular sludge or activated aerobic granular sludge, and the activated anaerobic granular sludge or activated aerobic granular sludge is prepared by filtering, washing and culturing sludge discharged by an anaerobic reactor or an aerobic reactor respectively, and specifically comprises the following steps: removing leaves, waste paper and waste plastic impurities in sludge through filtering and flushing, then adding the sludge into a reaction zone of an up-flow anaerobic reactor or an up-flow aerobic reactor, introducing wastewater to be treated from the bottom of the up-flow anaerobic reactor or the up-flow aerobic reactor by using a peristaltic pump, keeping the hydraulic retention time of the wastewater to be treated at 24-96 hours, keeping the water outlet flow rate the same as the water inlet flow rate, removing the floating and expanded sludge, and collecting bottom precipitated sludge after running for 3-7 days to obtain activated sludge; the particle size of the granular sludge is 0.5-4 mm, and the water content of the sludge is more than or equal to 98 wt%.
Preferably, according to the invention, in the step (1), the high-pressure steam inactivation pressure is 0.103-0.203MPa, the temperature is 121-122 ℃, and the inactivation time is 30 min.
According to the optimization of the invention, the activated anaerobic ammonium oxidation sludge is prepared by carrying out enrichment culture on sludge discharged by an anaerobic reactor, the sludge is added into a reaction zone of an up-flow anaerobic ammonium oxidation reactor, wastewater to be treated is introduced from the bottom of the up-flow anaerobic ammonium oxidation reactor by using a peristaltic pump, the hydraulic retention time of the wastewater to be treated in the up-flow anaerobic reactor is 24-96 hours, the effluent flow rate of the up-flow anaerobic ammonium oxidation reactor is kept to be the same as the influent flow rate, the floating and swelling sludge is removed, and after the up-flow anaerobic ammonium oxidation reactor runs for 3-7 days, bottom precipitated sludge is collected, namely the activated anaerobic ammonium oxidation sludge; the color of the anaerobic ammonia oxidation sludge is red or brownish red, and the water content of the sludge is more than or equal to 98 wt%.
Preferably, in the invention, the mass ratio of the activated anaerobic ammonium oxidation sludge to the inactivated sludge in the step (2) is: 0.5-1.8:1, unit: g/kg.
Further preferably, the mass ratio of the activated anaerobic ammonium oxidation sludge to the inactivated sludge in the step (2) is: 0.8-1.2:1, unit: g/kg.
Preferably, the concentration of the mixed sludge after the wastewater to be treated is introduced in the step (3) is kept at 3200 mg/L.
Preferably, in the step (3), the introduction amount of the high-purity nitrogen is as follows: and introducing nitrogen into the upflow anaerobic reactor every 6 hours for 20-30 minutes to maintain the anaerobic environment, wherein the aeration intensity is 2-5 ml/(L.min).
Preferably, in order to enable the reactor to uniformly distribute water and inlet water and to fully contact with sludge, an upper gravel layer and a lower gravel layer are arranged at the bottom of the upflow anaerobic reactor, the thickness of the upper gravel layer is 2-3 cm, the average diameter of gravels is 2-5 mm, the thickness of the lower gravel layer is 3-5 cm, the average diameter of gravels is 5-7 mm, and the water inlet pipe is laid below the lower gravel layer.
Preferably, the reactor of the upflow anaerobic reactor is vertical cylindrical, the height is 75cm, the inner diameter is 9cm, the effective volume is 6L, the side wall is provided with a sampling port, the water inflow velocity of the reactor is 0.125-0.60L/h, and the hydraulic retention time of the sewage to be treated in the upflow anaerobic reactor is 10-48 hours.
The method inactivates coexisting bacteria in the anaerobic granular sludge, which have a competitive relationship with the anaerobic ammonium oxidation bacteria, by high-pressure steam, so that an environment which is more beneficial to the growth of the anaerobic ammonium oxidation bacteria is created, the enrichment of the anaerobic ammonium oxidation bacteria is accelerated, and the starting of an anaerobic ammonium oxidation process is enhanced; the inactivated sludge provides a carrier for the propagation and growth of the anaerobic ammonium oxidation bacteria, elements in the inactivated sludge promote the propagation of the anaerobic ammonium oxidation bacteria and accelerate the enrichment of the anaerobic ammonium oxidation bacteria, so that the starting time of an anaerobic ammonium oxidation process can be shortened, the impact load resistance of the reactor is enhanced due to the high concentration of the anaerobic ammonium oxidation bacteria, the stable removal efficiency can be kept in the face of the change of hydraulic retention time and nitrogen load, the inactivated sludge is suitable for removing ammonia nitrogen in pharmaceutical, coking wastewater and petrochemical wastewater, and is particularly suitable for wastewater with high ammonia nitrogen concentration and large ammonia nitrogen concentration fluctuation.
The invention has the following advantages:
1. the method of the invention can effectively shorten the starting time of the anaerobic ammonia oxidation process, and can greatly improve the enrichment speed of anaerobic ammonia oxidation bacteria: the reactor for inoculating the high-pressure steam inactivated sludge can shorten the starting time from 90-120 days to 40-70 days, and when the volume load of total nitrogen of inlet water is 1040N mg/m3When the nitrogen removal rate is about d, the total nitrogen removal rate of the reactor inoculated with the high-pressure steam inactivated sludge can be improved by 9.4 percent, as shown in figures 1 and 2;
2. on one hand, the method kills coexisting bacteria having a competitive action with the anammox bacteria by utilizing high-pressure steam inactivation, and accelerates the enrichment of the anammox bacteria; on the other hand, the anaerobic ammonia oxidizing bacteria with higher enrichment degree increase the load impact resistance of the reactor, so that the anaerobic ammonia oxidizing bacteria are more suitable for the nitrogen-containing sewage treatment task with complicated and variable water quality in practical application; meanwhile, the method is simple to operate, free of additional product generation, economical and efficient.
3. The method has mild operation conditions, can be carried out at normal temperature and normal pressure, and does not need specific conditions; and no toxic and harmful substances are generated, and the method is safe and harmless to the environment.
Drawings
FIG. 1 is a graph showing the variation of ammonia nitrogen concentration in inlet and outlet water in a reactor fed with inactivated sludge and a reactor fed with inactivated sludge in an application experimental example.
FIG. 2 is a bar graph showing the change in the copy number of anammox bacteria in the reactor fed with non-inactivated sludge and the reactor fed with inactivated sludge in the experimental examples.
Detailed Description
The present invention will now be described in detail by way of examples with reference to the accompanying drawings. It should be noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
In the examples, all the chemicals used were purchased from chemical reagents of national drug group, ltd, and were all analytical grade. The peristaltic pump is purchased from Zenglang constant flow pump, Inc., and has the model number of BT 100-2J.
The upflow anaerobic reactor is made of polymethyl methacrylate material.
The high-purity nitrogen used for aeration is purchased from special gas of Jinan De Yangtze province, Co., Ltd, and the specification is 99.999%.
The submersible pump, the heating rod, the water inlet and outlet pipe and the gas guide pipe are all conventional commercial equipment.
Example 1
An anaerobic ammonia oxidation rapid reinforced starting method based on inactivated sludge comprises the following steps:
(1) putting the activated anaerobic granular sludge into a reactor with the pressure of 0.13MPa and the temperature of 120 ℃ for high-pressure steam inactivation for 30min to obtain inactivated sludge, then adding the inactivated sludge into a reaction zone of an upflow anaerobic reactor, simultaneously adding activated anaerobic ammonium oxidation sludge into the reactor, and uniformly mixing the activated anaerobic ammonium oxidation sludge and the inactivated sludge, wherein the mass ratio of the activated anaerobic ammonium oxidation sludge to the inactivated sludge is as follows: 0.5:1, unit: g/kg. The water content of the mixed sludge is more than or equal to 99 wt%, the height range of the upflow anaerobic reactor is 75cm, the inner diameter range is 9cm, the effective volume is 6L, the top is provided with a three-phase separator, the side wall is provided with sampling ports with different heights, the bottom is paved with a gravel layer, and a water inlet pipe is paved in the gravel layer;
the active anaerobic granular sludge is prepared by filtering, washing and culturing sludge discharged by an anaerobic reactor, and specifically comprises the following steps: removing leaves, waste paper and waste plastic impurities in sludge through filtering and flushing, then adding the sludge into a reaction zone of an upflow anaerobic reactor, introducing wastewater to be treated from the bottom of the upflow anaerobic reactor by using a peristaltic pump, leading the hydraulic retention time of the wastewater to be treated to be 24-96 hours, keeping the effluent flow rate the same as the influent flow rate, removing the floating and expanded sludge, and collecting bottom precipitated sludge after running for 3-7 days, namely activated sludge; the particle size of the granular sludge is 0.5-4 mm, and the water content of the sludge is more than or equal to 98 wt%.
The activated anaerobic ammonium oxidation sludge is prepared by carrying out enrichment culture on sludge discharged by an anaerobic reactor, the sludge is added into a reaction zone of an up-flow anaerobic ammonium oxidation reactor, wastewater to be treated is introduced from the bottom of the up-flow anaerobic ammonium oxidation reactor by using a peristaltic pump, the hydraulic retention time of the wastewater to be treated in the up-flow anaerobic reactor is 24-96 hours, the effluent flow rate of the up-flow anaerobic ammonium oxidation reactor is kept to be the same as the influent flow rate, the floating and swelling sludge is removed, and after the up-flow anaerobic ammonium oxidation reactor operates for 3-7 days, bottom precipitated sludge is collected, namely the activated anaerobic ammonium oxidation sludge; the color of the anaerobic ammonia oxidation sludge is red or brownish red, and the water content of the sludge is more than or equal to 98 wt%.
(2) Introducing wastewater to be treated from the bottom of an upflow anaerobic reactor by using a peristaltic pump, adjusting the rotating speed of the peristaltic pump according to the volume of the upflow anaerobic reactor to control the inflow velocity, controlling the inflow velocity to be 0.125L/h, leading the wastewater to be treated to hydraulically stay in the upflow anaerobic reactor for 48 hours, simultaneously maintaining the internal temperature of the upflow anaerobic reactor at 35 ℃ by using a heating rod, introducing nitrogen into the upflow anaerobic reactor for aeration for 20 minutes every 6 hours, wherein the aeration intensity is 5 mL/(L.min), preferably, the nitrogen aeration is also carried out for 30 minutes before the wastewater to be treated is introduced, the aeration intensity is 5 mL/(L.min) to maintain the anaerobic environment, and introducing carbon dioxide to keep the pH value at 7.5.
(3) Keeping the water outlet flow velocity of the upflow anaerobic reactor the same as the water inlet flow velocity, successfully starting the anaerobic ammonia oxidation reaction of the sludge after the upflow anaerobic reactor operates for 63 days, realizing the high-efficiency removal of nitrogen in the sewage, and then entering the anaerobic ammonia oxidation stabilization stage. During stable operation, the total nitrogen load of inlet water is improved by adjusting the hydraulic retention time and the inlet water flow rate, and meanwhile, the load impact resistance is tested. The total nitrogen removal load during stable operation reached 1150mg N/L/d, and in the face of increasing total nitrogen load, the reactor maintained stable operation effect, and no large fluctuation in nitrogen removal effect occurred.
Comparative example 1
A method for efficiently treating nitrogen-containing wastewater by anaerobic ammonia oxidation comprises the following steps:
(1) adding activated anaerobic granular sludge and activated anaerobic ammonium oxidation sludge into a reaction zone of an upflow anaerobic reactor, wherein the water content of the mixed sludge is more than or equal to 99 wt%, the height range of the upflow anaerobic reactor is 75cm, the inner diameter range is 9cm, the effective volume is 6L, the top is provided with a three-phase separator, the side wall is provided with sampling ports with different heights, the bottom is paved with a gravel layer, and a water inlet pipe is paved in the gravel layer; the active anaerobic granular sludge is prepared by filtering and washing sludge discharged from an anaerobic sewage treatment device of a paper mill; the active anaerobic ammonium oxidation sludge is prepared by enrichment culture of an anaerobic ammonium oxidation reactor.
(2) Introducing wastewater to be treated from the bottom of an upflow anaerobic reactor by using a peristaltic pump, adjusting the rotating speed of the peristaltic pump according to the volume of the upflow anaerobic reactor to control the inflow velocity, controlling the inflow velocity to be 0.125L/h, keeping the wastewater to be treated in the upflow anaerobic reactor for 48 hours, controlling the sludge concentration after introducing the wastewater to be treated to be 3200mg/L, simultaneously maintaining the internal temperature of the upflow anaerobic reactor at 35 ℃ by using a heating rod, introducing nitrogen into the upflow anaerobic reactor every 6 hours for aeration for 20 minutes, wherein the aeration intensity is 5 mL/(L.min), preferably, also performing nitrogen aeration for 30 minutes before introducing the wastewater to be treated, and keeping the aeration intensity to be 5 mL/(L.min) to maintain the anaerobic environment, and introducing carbon dioxide to keep the pH value to be 7.5.
(3) Keeping the water outlet flow velocity of the upflow anaerobic reactor the same as the water inlet flow velocity, successfully starting the anaerobic ammonia oxidation reaction of the sludge after the upflow anaerobic reactor operates for 101 days, realizing the high-efficiency removal of nitrogen in the sewage, and then entering the anaerobic ammonia oxidation stabilization stage. The total nitrogen removal load during steady operation reached 1100mg N/L/d, which exhibited relatively poor stability in the face of excessive fluctuations in nitrogen load concentration.
Application example:
introducing synthetic wastewater into the methods of example 1 and comparative example 1, treating the wastewater, controlling continuous flow inflow by using a peristaltic pump, controlling the hydraulic retention time to be 48 hours, controlling effluent backflow by using the peristaltic pump, and controlling the inflow flow rate of the reactor to be 0.125L/h; the artificial synthetic wastewater comprises the following specific components: 471mg (NH)4)2SO4/L,640mg NaNO2/L,500mg KHCO3/L,27.2mg KH2PO4/L,120mg MgSO4·7H2O/L,180mg CaCl2·2H2O/L,5.6mgFeSO41mL of trace elements/L. The specific components of the trace elements are 20000mg EDTA/L and 430mg ZnSO4·7H2O/L,240mg CoCl2·6H2O/L,990mg MnCl2·4H2O/L,250mg CuSO4·5H2O/L,220mg NaMoO4·2H2O/L,190mg NiCl2·6H2O/L,210mg NaSeO4·6H2O/L,14mg H3BO4/L。
Measuring the nitrogen concentration every 3 days, and evaluating the running state of the reactor and the starting effect of the anaerobic ammonia oxidation according to the nitrogen concentration; and (3) taking a sludge sample every 50 days to perform q-PCR analysis, and evaluating the growth and enrichment speed of the anammox bacteria.
Comparative example 1 adding active anaerobic granular sludge and an active anaerobic ammonium oxidation sludge reactor, running for 72 days to successfully start the anaerobic ammonium oxidation process, and after running for 200 days, the q-PCR result of anaerobic ammonium oxidation bacteria in the sludge of the reactor is 1.37 multiplied by 108copies/ng DNA; in the embodiment 1 of the invention, the anaerobic granular sludge inoculated with inactivation and the activated anaerobic ammonium oxidation sludge reactor successfully starts the anaerobic ammonium oxidation process after running for 63 days, the starting time is shortened by 9.3 percent, and the q-PCR result of anaerobic ammonium oxidation bacteria in the sludge of the reactor after running for 200 days is 1.93 multiplied by 108The number of copies/ng DNA and anammox bacteria is increased by 40.9%.
Example 2
An anaerobic ammonia oxidation rapid reinforced starting method based on inactivated sludge is the same as that in example 1, and is characterized in that:
in the step (1), the activated aerobic granular sludge is subjected to high-pressure steam inactivation for 30min under the conditions that the pressure is 0.3MPa and the temperature is 122 ℃, so that inactivated sludge is obtained, and other treatment steps are carried out according to the example 1.
And the anaerobic ammoxidation reaction of the sludge is successfully started after the upflow anaerobic reactor runs for 60 days.
Example 3
An anaerobic ammonia oxidation rapid reinforced starting method based on inactivated sludge is the same as that in example 1, and is characterized in that:
the mass ratio of the activated anaerobic ammonia oxidation sludge to the inactivated sludge in the step (1) is as follows: 0.8:1, unit: g/kg, the other working-up steps were carried out as in example 1. And the anaerobic ammoxidation reaction of the sludge is successfully started after the upflow anaerobic reactor runs for 54 days.
Comparative example 2
The difference between the method for efficiently treating the nitrogen-containing wastewater by anaerobic ammonia oxidation and the method in the embodiment 1 is that:
in step (1), only the inactivated sludge was added, and the activated anammox sludge was not added, and the other treatment steps were performed as in example 1. The anaerobic ammoxidation reaction of the sludge is successfully started only after the upflow anaerobic reactor runs for 120 days.
Comparative example 3
The difference between the method for efficiently treating the nitrogen-containing wastewater by anaerobic ammonia oxidation and the method in the embodiment 1 is that:
the mass ratio of the activated anaerobic ammonia oxidation sludge to the inactivated sludge in the step (1) is as follows: 3:1, unit: g/kg, the other working-up steps were carried out as in example 1. The upflow anaerobic reactor runs for 86 days to successfully start the anaerobic ammoxidation reaction of the sludge.
Comparative example 4
The difference between the method for efficiently treating the nitrogen-containing wastewater by anaerobic ammonia oxidation and the method in the embodiment 1 is that:
the mass ratio of the activated anaerobic ammonia oxidation sludge to the inactivated sludge in the step (1) is as follows: 5:1, unit: g/kg, the other working-up steps were carried out as in example 1. The upflow anaerobic reactor runs for 105 days to successfully start the anaerobic ammoxidation reaction of the sludge.