CN115178084A - Synchronous denitrification and desulfurization system and method - Google Patents
Synchronous denitrification and desulfurization system and method Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01D53/8625—Nitrogen oxides
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- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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Abstract
The invention belongs to the field of sewage treatment, and particularly relates to a synchronous denitrification and desulfurization system and a synchronous denitrification and desulfurization method. The specific technical scheme is as follows: the bio-trickling filter is characterized in that a filler of the bio-trickling filter is polyurethane foam. The invention combines the denitrification process with H 2 The S oxidation processes are organically coupled, so that a new technical approach of treating waste by waste is provided, and important theoretical basis and technical support can be provided for biogas slurry, biogas desulfurization and anaerobic digestive juice denitrification in China.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a synchronous denitrification and desulfurization system and a synchronous denitrification and desulfurization method.
Background
The biogas is a biogas generated by anaerobic biological fermentation of biomass raw materials. At present, the main raw materials for biogas fermentation in China are livestock and poultry farm manure, straws and sewage, and because the livestock and poultry manure and the sewage contain a large amount of protein and other sulfur-containing compounds, biogas generated by anaerobic fermentation contains H 2 And S. H in the marsh gas 2 The volume concentration of S is 1-12 g/m 3 。H 2 S is a very corrosive compound and has very strong acute toxicity. At the same time, mixed with H 2 After combustion of S' S biogas, H 2 S can be converted into sulfur oxides to be released into the air, so that the air pollution is caused. Therefore, the biogas must be desulfurized before use.
At present, thousands of large and medium-sized biogas projects of large-scale farms are available in China, and the biogas projects play an extremely important role in the treatment process of non-point source pollution of agricultural livestock and poultry in China. But because anaerobic fermentation mainly decomposes and converts C, H and O element, and finally uses CH 4 And CO 2 The release in gaseous form contributes greatly to the COD reduction, but has little effect on the reduction of the nutrient element N. The protein in the livestock and poultry manure is subjected to ammoniation reaction in the anaerobic fermentation process, and the N element is more than NH 4+ -N、NH 3- the-N form exists in digestive liquid, and the digestive liquid is organic waste water rich in high ammonia nitrogen. Therefore, the problem of ammonia nitrogen pollution of digestive liquid in biogas engineering becomes one of the bottlenecks restricting sustainable development of the biogas energy industry in China. The traditional nitrification and denitrification processes such as A/O, SBR and the like are carried out on the raw materialsThe effect of denitrification is not ideal. The reasons are mainly that ammonia nitrogen is oxidized into nitrate nitrogen or nitrite nitrogen in the digestive liquid in the aerobic treatment process, and a small amount of residual organic matters are also degraded into carbon dioxide and water, so that the supply of organic carbon sources (electron donors) in the digestive liquid is seriously insufficient, C/N is seriously disordered, and the denitrification process lacks the organic electron donors. Therefore, the search for inexpensive, adaptive electron donors is one of the key to addressing digestive denitrification.
If the denitrification process is combined with H 2 Organic coupling is carried out in the S oxidation process, and NO can be simultaneously realized 3 - 、NO 2 - And H 2 The removal of S forms a technical approach of treating wastes with wastes. However, the technology is not completely mature, and the structures of the microbial populations with key functions, key speed-limiting steps, reaction kinetics processes, sulfur conversion forms and denitrification coupling H 2 The relationship and efficiency of chemical oxidation and biological oxidation in S oxidation process need to be studied intensively.
Disclosure of Invention
The invention aims to provide a synchronous denitrification and desulfurization system and a synchronous denitrification and desulfurization method.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows: the bio-trickling filter is characterized in that a filler of the bio-trickling filter is polyurethane foam.
Correspondingly, the application of the biological trickling filter in the synchronous denitrification and desulfurization of biogas slurry and/or biogas is provided.
Preferably, in said application, the S/N molar ratio of the feed water is between 5/3 and 5/2.
Preferably, before the synchronous denitrification and desulfurization, the filler is subjected to biofilm formation treatment by using biogas slurry/biogas to be treated, and then the filler is used for denitrification and desulfurization, wherein the S/N molar ratio of inlet water is 5/3-5/2 during the biofilm formation treatment.
Preferably, the biofilm formation treatment comprises the following steps:
(1) Pre-filming: placing the filler into an anaerobic container mixed with biogas slurry to be treated and a basic culture medium, keeping the temperature at 28 ℃, and treating until NO is contained in the culture medium 3 - When the N is removed to 80 percent, replacing the basic culture medium with new one, and culturing until the N is removedO 3 - The N removal rate is stable, and pre-film forming is completed;
(2) Strengthening film hanging: irregularly placing the filler subjected to pre-biofilm formation into the biological trickling filter reactor, adding a basic culture medium to strengthen biofilm formation, wherein the strengthening biofilm formation period is 15-20 days.
Preferably, the basic culture medium is: na (Na) 2 S 2 O 3 ·5H 2 O 5g/L，KNO 3 4g/L，KH 2 PO 4 2g/L，NaHCO 3 1g/L，MgCl 2 ·6H 2 O 0.5g/L，FeSO 4 ·7H 2 0.01g/L of O and 1mL of trace elements, and adjusting the pH value to 7.5;
the trace elements are: EDTA 0.5g/L, feSO 4 ·7H 2 O0.2 g/L and SL-6100mL of trace elements;
the trace elements SL-6 are: znSO 4 ·7H 2 O 0.1g/L，MnCl 2 ·4H 2 O 0.03g/L， H 3 BO 3 0.3g/L，CoCl 2 ·6H 2 O 0.2g/L，CuCl 2 ·2H 2 O 0.01g/L，NiCl 2 ·6H 2 O 0.02g/L，Na 2 MoO 4 ·H 2 O 0.03g/L。
Preferably, after the film forming treatment is finished, the filler is subjected to reinforced film forming treatment again, and then the synchronous denitrification and desulfurization are carried out; the reinforced re-filming treatment comprises the following steps:
(1) The first stage is as follows: adjusting the pH value of a system in the biological trickling filtration tower to 6.8-7.2, adding sodium thiosulfide into the system, wherein the adding mass of the sodium thiosulfide is gradually increased according to 5g/L, 8g/L, 10g/L and 15g/L, and the first stage is maintained for 8-12 days;
(2) After the first stage is completed, H is introduced into the system 2 S, the air inlet flow rate is gradually increased at 0.4L/min, 0.8L/min and 1.0L/min, and the second stage is maintained for 12-17 days.
Preferably, the adding mass of the sodium sulfide at the first stage is gradually increased according to 5g/L, 8g/L, 10g/L and 15g/L, wherein each concentration of the first 3 concentrations is maintained for 1-3 days, and then 15g/L is replaced for 3-5 days; and/or; second stage H 2 The air inlet flow rate of S is gradually increased to 0.4L/min, 0.8L/min and 1.0L/minAt flow rate H 2 And when the S removal rate is stabilized to be more than 95 percent and is stabilized for 3 days, expanding the flow rate to be 0.8L/min, and the like.
Accordingly, a microbial composition for use in said applications comprises the genera Thiobacillus, rhodanobacter, arenimonas and Trueera.
Preferably, the amount of microorganisms of the genus Thiobacillus is 40% or more of the amount of viable bacteria.
The invention has the following beneficial effects: the invention combines the denitrification process with H 2 The S oxidation process is organically coupled, a new technical approach of treating waste by waste is provided, and important theoretical basis and technical support can be provided for biogas slurry, biogas desulfurization and anaerobic digestive fluid denitrification in China.
Drawings
FIG. 1 is a schematic view of a bio-trickling filter according to the present invention;
FIG. 2 is a schematic diagram showing the change in pH and ORP for each set at an S/N ratio of 5/4 in example one;
FIG. 3 is a schematic diagram showing the change in pH and ORP for each set at an S/N ratio of 5/3 in example one;
FIG. 4 is a schematic diagram showing the change in pH and ORP for each set at an S/N ratio of 5/2 in example one;
FIG. 5 is a schematic diagram showing the change in pH and ORP for each set at an S/N ratio of 5/1 in example one;
FIG. 6 shows S in each group at an S/N ratio of 5/4 according to an embodiment 2- And SO 4 2- A schematic diagram of variations;
FIG. 7 shows S in each group at an S/N ratio of 5/3 according to an embodiment 2- And SO 4 2- A schematic variation diagram;
FIG. 8 shows S in each group at an S/N ratio of 5/2 in one embodiment 2- And SO 4 2- A schematic diagram of variations;
FIG. 9 shows S in each group at an S/N ratio of 5/1 in one embodiment 2- And SO 4 2- A schematic diagram of variations;
FIG. 10 shows embodiment S 2- SO at complete removal 4 2- A product relative content diagram;
FIG. 11 shows stages H of a BTF panel B 2 S removal rate and NO X - -a schematic diagram of the N concentration relationship;
FIG. 12 shows the stages H in BTF panel C according to example 2 S removal rate and NO X - -N concentration diagram;
FIG. 13 is a graph illustrating the average removal rates of three groups at different stages according to one embodiment;
FIG. 14 is a schematic representation showing the variation of the relative methane content in the examples;
FIG. 15 shows example II H 2 S is a schematic diagram of the relationship among the removal rate, the intake load and the elimination capacity;
FIG. 16 is a graph showing the change in pH during the operation of example two;
FIG. 17 is a schematic of the change in ORP during operation of example two.
Detailed Description
The invention provides a desulfurization system which is a biological trickling filter which is mature in the prior art, the specific structure of the biological trickling filter is not described in detail, and only the place which is adjusted relative to the prior art is described. In the biological trickling filter, the preferable organic glass of tower body material wholly is cylindrical. In one embodiment, the diameter of the tower body is 120mm, and the total height is 1500mm. A packing layer is arranged in the trickling filtration tower, the preferred height of the packing layer is 1200mm, and the effective volume is 11.4L. The nutrient solution is reversely contacted with the marsh gas from top to bottom, and a marsh gas booster pump (energy-gathered KDO 4) is used as a gas supply power source. The spray liquid is circulated by a peristaltic Pump (ringer Pump BT 300-2J), and the circulating liquid is precisely controlled by a glass rotameter (LZB-10F). An online pH and ORP detection system is arranged in the biological trickling filter. The selectable structure of the biological trickling filter is shown in figure 1, wherein in figure 1, 1 is a biogas slurry discharge port, 2 is a biogas slurry check valve, 3 is a biogas slurry lift pump, 4 is a biogas slurry flow meter, 5 is a filler filter plate, 6 is a biogas discharge port, 7 is a spraying device, 8 is a liquid sampling port, 9 is a detecting instrument, and in one embodiment, the biological trickling filter comprises a pH probe and an ORP probe, and 10 is a drainage device. Due to the use of Na 2 S·9H 2 O replaces H in the marsh gas 2 And S, sealing the biogas slurry discharge port 1 by using a water seal.
The filler used in the bio-trickling filter tower is any one or more of polyurethane foam, polyhedral hollow spheres and pall ring filler, and preferably, the filler is polyurethane foam.
The invention also provides a desulfurization treatment method in combination with the desulfurization system, which specifically comprises the following steps: in the biological trickling filter, the S/N molar ratio of inlet water is controlled to be 5/3-5/2,S 2- The concentration is less than or equal to 16.8mM (538 mgL) -1 )。
The invention further provides a microorganism composition capable of performing desulfurization and denitrification treatment on sewage, which simultaneously comprises Thiobacillus, rhodanobacter, arenimonas and Trueera, and preferably comprises the following steps: the amount of microorganisms belonging to the genus Thiobacillus is 40% or more of the amount of viable bacteria.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The data obtained are the average values obtained after at least 3 repetitions, and each repetition is valid.
The first embodiment is as follows: influence of different fillers and S/N of inlet water on denitrification and desulfurization effects
1. The experimental method of this example: the bio-trickling filter was assembled as shown in fig. 1 with a water seal at the gas outlet. The inoculum is derived from return activated sludge of a secondary sedimentation tank of a municipal wastewater treatment plant in a metropolis and biogas slurry in a biogas digester (the two are uniformly mixed according to the volume ratio of 1:1 for use). In the initial stage of domesticating and membrane hanging, polyurethane foam, polyhedral hollow spheres and pall ring fillers are respectively put into an anaerobic container mixed with inoculum (20 percent, V/V) and basic culture medium (80 percent, V/V) for pre-membrane hanging culture, and the constant temperature is 28 ℃. When NO is present in the medium 3 - When 80% of N is removed, the basal medium is replaced with new one. To NO 3 - And (4) the removal rate of-N is stable, the filler subjected to biofilm culturing is irregularly placed into a designed biological trickling filter reactor, 8L of basic culture medium is added to further strengthen biofilm culturing, and the strengthening biofilm culturing period is 15-20 days. Setting the trickling filtration speed to 0.3-0.5L/min and maintainingRoom temperature 28 ℃.
The basic culture medium (g/L) used in the biofilm culturing: na (Na) 2 S 2 O 3 ·5H 2 O 5，KNO 3 4， KH 2 PO 4 2，NaHCO 3 1，MgCl 2 ·6H 2 O 0.5，FeSO 4 ·7H 2 0.01 percent of O and 1mL of trace elements. The pH was adjusted to 7.5 with 1mol/L NaOH solution.
Wherein, the trace elements (g/L): EDTA 0.5, feSO 4 ·7H 2 O0.2 and SL-6100mL of trace elements.
Microelement SL-6 (g/L): znSO 4 ·7H 2 O 0.1，MnCl 2 ·4H 2 O 0.03，H 3 BO 3 0.3，CoCl 2 ·6H 2 O 0.2，CuCl 2 ·2H 2 O 0.01，NiCl 2 ·6H 2 O 0.02，Na 2 MoO 4 ·H 2 O 0.03。
2. A sequencing batch experimental method is adopted, and 3 experimental groups and 1 control group are arranged, and 4 groups of biological trickling filter reactors are arranged. The effect of synchronous desulfurization and denitrification under the conditions of different fillers and different S/N molar ratios of inlet water is researched by taking the S/N molar ratios of the fillers and the inlet water as variables. Considering S 2- Has certain toxic effect on microorganisms, and the experimental selection is low S 2- To a high S concentration 2- The study was performed in 4 stages of concentration. When each S/N molar ratio experiment is completed, emptying the wastewater in 4 groups of trickling filtration towers, pumping the wastewater with the next S/N molar ratio for re-experiment, and monitoring pH, ORP (oxidation reduction potential) and S in the SDD process 2－ 、SO 4 2－ 、NO 3 － -N and NO 2 － -change in N ion concentration. The control filler was removed and sterilized by boiling before the experiment to eliminate interference from biological agents. The specific experimental arrangement is shown in table 1. In Table 1, control of NO 3 - N concentration, as S in the feed water 2- The concentration is variable, the S/N ratio of inlet water is 5/4, 5/3, 5/2 and 5/1, and the corresponding inlet water S 2- The concentrations found were 218, 303, 538 and 1140mg/L, respectively. The inlet water is mixed liquid of a basic culture medium and the biogas slurry, and the initial NO in the biogas slurry is measured 3 - A concentration of N according toAdding the calculated amount to different basal media to adjust different NO in the feed water 3 - Concentration of-N
TABLE 1 comparison table of experimental setup for each group
3. Measuring the change condition of the nitrate by using an ultraviolet spectrophotometry; measuring the nitrite change by using a N- (1-naphthyl) -ethylenediamine photometry method; measuring the change condition of the sulfide by using HACH sulfide1 and sulfide 2 methods; measuring the change condition of the sulfate by using a HACH sulfate 4 method; measuring the pH change by using a model METTLER FE acidity meter; ORP was measured using Liu Heng ORP.
The method comprises the steps of analyzing the form of bacteria on the surface of sludge in a reactor by using a scanning electron microscope, fixing the form of sludge microorganisms by using FA stationary liquid, performing gradient dehydration by using ethanol solution, performing pretreatment such as drying by using a 2424-SPI type critical point dryer made in America and spraying gold by using an IB-III type sputtering instrument made in Japan, and observing and photographing the microorganisms by using a VEGA TS5136XM scanning electron microscope.
The genomic DNA in the sample was extracted using MO-BIO soil DNA extraction Kit (MO-BIOPowerSoil DNA Isolation Kit Components, american, 12888-50). Both DNA concentration and mass were determined using a NanoDrop1000 spectrophotometer (ThermoFisher, USA). The extracted DNA was diluted to 10. Mu.g/. Mu.L and stored at-80 ℃ until use. The above-described measurement of the index is carried out by the same method as described in this section, unless otherwise specified.
4. And (5) displaying the result.
(1) The pH and ORP changes for each group are shown in FIGS. 2-5. In FIGS. 2 to 9, - [ pH change in T.T. -control group A, - ● -indicates the change in pH of experimental group B, -. Tangle-solidup-indicates the change in pH of the test group C, - ■ -indicates the change in pH of the test group D. -. Means change in ORP value of control group A, -. Smallcircle-indicates the change in ORP value in the experimental group B, - Δ -shows the change in ORP value for test group C, - □ -shows the change in ORP value for test group D. When the S/N molar ratio of the inlet water isAt 5/4 and 5/3, the pH value in the reactor is increased, then decreased and finally stabilized at 7.25-7.5, and the ORP is almost uniformly increased and finally stabilized at about 0 mV. The results obtained from the control group and the experimental group showed a high consistency at this time. And the pH value of the experimental group is changed by less than 0.5 before and after the reaction compared with the initial value, so that the pH regulation and control process in the actual engineering can be reduced, and the operation management program and the engineering investment are reduced. When the S/N molar ratio of the inlet water is increased to 5/2 and 5/1, the influence of the difference of the fillers on the pH value and the ORP is obvious. When the S/N molar ratio of the inlet water is 5/2, the pH values of the experimental group B taking the polyurethane foam as the filler and the experimental group C taking the polyhedral hollow sphere as the filler begin to decrease respectively at about 30 h and 70h, and the pH values of the towers of the control group A and the experimental group D do not begin to decrease until 110 h. And only the ORP change trend in the experiment group B is consistent with the ORP change trend in the low water inflow S/N molar ratio (S/N =5/4, 5/3), and only the time point when the ORP value starts to increase is delayed to be about 40 h. The ORP of test group C increased at a slow rate, with little or no change in ORP value for test group B, D. When the S/N molar ratio of the inlet water is further increased to 5/1, S in the raw water of 400mg/L can be stably removed 2- And (4) concentration. Only when the pH value in the experimental group B starts to decrease at 400h, the pH values of the control group A, the experimental group C and the experimental group D basically do not change after rising and stabilizing at 9.0-9.5. At this time, the ORP change trend in 4 groups of reactors is similar, and finally, the ORP change trend is increased to about 0 mV. From this, it can be seen that when the S/N molar ratio of the feed water is increased to 5/2, the activity of the microbial system in the test group C is significantly reduced compared to that before, and the microbial system in the test group D begins to collapse. When the S/N molar ratio was further increased to 5/1, the microbial system in the experimental group C, D crashed, resulting in no change after the pH was raised. Whereas the non-biological factors in control group a did not directly oxidize sulfides to sulfates and thus the pH stabilized at a fixed range. It should be noted that: when the S/N molar ratio of the inlet water is 5/4 and 5/3, the pH and ORP curves in the control group A not inoculated with the microorganisms and the experimental group B, C, D inoculated with the microorganisms are consistent with the trend of the change, which may be consistent with the residual O in the reactor 2 A small amount of air leakage in the sampling process and a small amount of enrichment of the desulfurization bacteria in the tap water.
(2) S of each group 2- And SO 4 2- Variation of concentration such asAs shown in FIGS. 6 to 9, the desulfurization and denitrification efficiencies are shown in Table 2. Average desulfurization efficiency = C S2- H, wherein C is the initial S 2- Concentration, unit: mg/L; h is the removal of all S 2- Required time, unit: and (4) hours. Average denitrification efficiency = C NO3-/ h, C are initial NO 3 - Concentration, unit: mg/L; h is the removal of all NO 3 -time required, in units: and (4) hours.
TABLE 2 comparison table of desulfurization and denitrification efficiency of each group
The results show that: the lower the S/N molar ratio in the feed water, the lower the S/N molar ratio 2- The higher the removal efficiency. The reason why the sulfide concentration rapidly decreases may be to reduce S 2- Oxidized to elemental S 0 Only a few electrons are needed. When the S/N molar ratio of the influent water was increased to 5/1, the microbial systems in panel C also began to collapse, and S 2- After complete removal of SO 4 2- The concentration still increases slowly. The results show that the water S can be removed slowly by the abiotic action 2- But not the element S 0 Further oxidized to SO 4 2- . When S is still present in the reaction system 2- When present, SO 4 2- The concentration rises only at a very slow rate, if and only if S 2- After complete removal of SO 4 2- The concentration will increase rapidly. This indicates that S is present in the reaction system 2- And S 0 When present, the microorganisms in the system preferentially S 2- Is oxidized to S 0 Wait for S 2- After the removal is complete, S is further removed 0 Is oxidized to SO 4 2- 。
(3) NO of each group 3 - -N and NO 2 - The variation of-N is shown in FIGS. 10 to 13. Control group A NO before and after the Experimental reaction 3 - Only a slight decrease in the concentration of-N, NO 2 - No accumulation of-N concentration occurred. NO in Experimental group B, C and D in low S/N molar ratio feed water conditions (S/N =5/4, 5/3) 3 - N is obviously reduced until the N is completely removed. However, as the S/N molar ratio increases, the effect of the filler on the removal efficiency of N gradually decreases.
Packing factor vs NO as S/N molar ratio of feed water increases 3 - The effect of-N removal rate is obvious, and the bio-trickling filter reactor taking polyurethane foam and polyhedral hollow spheres as fillers has NO effect 3 - The best removal effect of-N is obtained. When the S/N molar ratio of the inlet water is further increased, S in the system 2- If the concentration is too high, the microorganism system in the biological trickling filter reactor filled with the filler with low specific surface area is easy to collapse, so that the denitrification capability is seriously reduced or lost. Moreover, experiments show that NO is generated in the denitrification process 2 - Some accumulation of-N occurs, probably due to NO during denitrification 3 - -N→ NO 2 - -N reacts faster than NO 2 - -N→N 2 . When NO is present 3 - NO when-N is removed to lower concentrations 2 - The N concentration stops accumulating and decreases rapidly.
(4) According to the above results, the polyurethane foam was the optimum filler and the corresponding test group B completely removed S 2- The final relative sulfate content is shown in fig. 14 (measured using a sulfate concentration detector).
(5) And (5) scanning the result by an electron microscope. And after finishing the film forming, taking out each group of fillers, and scanning the microbial film forming condition on the surface of each group of fillers by using an electron microscope. The control group a had a smooth surface and a small amount of biofilm structure was found. The surface of the B, C, D filler in experimental group B had a clear biofilm structure, and the presence of clear yellow sulfur particles was observed in experimental group B. The biofilm structure on the experimental group B filler with polyurethane foam as filler is the most complex and the microorganisms are more tightly bonded to the filler surface. The number of the biological films on the filler of the experimental group C using the polyhedral hollow spheres as the filler is relatively small, and the thickness is slightly thin. The number of the biological films on the filler of the experimental group D taking pall rings as the filler is less, the biological films are sparse, and the thickness is thinner.
(6) And (4) analyzing the microbial community structure. After the biofilm culturing experiment is finished, the culture medium in each group of reactors is emptied, the filler is taken out, the DNA of the microorganism contained in the filler is extracted and PCR amplification is carried out, and 16S rRNA sequencing research is carried out. The results show that the absolute dominant genera in each group are Thiobacillus genera, and the relative abundance of the thiobacillus genera is higher than 40%. The next genera with higher relative abundance are Rhodanobacter, arenimonas and Trueera. Bacteria of the genus Thiobacillus were also detected in control group A, which had not been inoculated, probably because a small amount of desulfurization bacteria contained in tap water was enriched. In the experimental group B, C, D for inoculation, thiobacillus, rhodanobacter, arenimonas and Trueera all exist at the same time, which proves that the microorganisms are likely to have the relationship of mutual growth, symbiosis, mutual promotion and the like.
In summary, polyurethane foam was chosen as the filler. With the increase of S/N molar ratio of the inlet water, SO in the product 4 2- The relative content is gradually reduced, and the relative content of the elemental sulfur in the product is gradually increased. When the S/N molar ratio of the inlet water is increased to 5/1, the activity of microorganisms in the system is gradually reduced, and the biological system is endangered to collapse and cannot purify the sulfur-containing wastewater efficiently. Therefore, the preferred scheme is: the S/N molar ratio of the inlet water is between 5/3 and 5/2 (S) 2- Concentrations below 538 mg/L).
Example two: influence of different reaction conditions on denitrification and desulfurization effects
1. Pig manure biogas slurry and pig manure biogas from rural household biogas digesters in Yongan town in double-flow areas of metropolis are used as test samples. Wherein, according to the volume concentration, the marsh gas comprises the following components: 60% of CH 4 10% CO 2 1.5% of O 2 5000ppmv H 2 S, 25.4% nitrogen, and a small amount of the remaining gas.
And preparing nutrient solution by using the treated pig manure biogas slurry. The preparation method of the nutrient solution comprises the following steps: mixing the treated pig manure biogas slurry with activated sludge from an aerobic pool of a sewage plant in a metropolis in a volume ratio of 4/1, adjusting the pH of the mixed solution to 7.0-7.5, carrying out aeration treatment on the mixed solution, and periodically detecting NH in the mixed solution 4+ 、NO 3 - /NO 2 - Ion concentration, and filling with sand and stone with different particle sizes before useThe filtering device carries out filtering treatment. The relevant parameters before and after nutrient solution aeration are shown in table 3.
TABLE 3 comparison table of relevant parameters before and after nutrient solution aeration
2. The present embodiment is provided with three groups: control group a (with polyhedral hollow spheres as filler), experimental group B (with polyurethane foam as filler), and experimental group C (with polyhedral hollow spheres as filler). The experimental group B, C changed a certain amount of aerated nutrient solution each time, and the control group a changed an equal amount of tap water at the same time. Water circulation is carried out through a peristaltic pump, and the flow of circulating liquid is precisely controlled through a glass rotameter. And (4) controlling the gas flow by using a methane booster pump and a glass rotameter. The waste water is discharged from a water outlet at the bottom, and the whole system runs in an environment of 25 +/-2 ℃. In the desulfurization process, the methane enters from the bottom and goes out from the top, and the methane is used for 5m 3 Collecting by a special biogas bag. The content of the desulfurized biogas in the used biogas is 99.9% 2 The S gas cylinder is recycled after being re-distributed.
The experimental method comprises the following steps: in the first embodiment, mainly configured to contain NO 3 - And S 2- The basic culture medium has less influence on the structure of the functional microbial community, while the nutrient solution used in the embodiment has larger influence on the microorganisms, such as NH with higher concentration contained in the biogas slurry 4+ Heavy metal elements such as Al and Fe and indigenous microorganisms containing a large amount of them. In order to enhance the synchronous desulfurization and denitrification effect of the functional microorganisms and improve the anti-interference capability of the system, the embodiment performs the secondary enhanced biofilm formation treatment on the basis of the completed biofilm formation. The essence of the reinforced biofilm formation is that biogas slurry after aeration treatment is taken as nutrient solution to provide NO necessary for the growth of functional microorganisms 3 - /NO 2 - As an electron acceptor, the same asIn the process of using H in the methane 2 S is an electron donor, and a microbial system which is suitable for the biogas slurry after aeration treatment and has the function of synchronous desulfurization and denitrification and takes the biogas slurry as nutrient solution is further formed.
The reinforced re-filming step comprises: (1) a first stage: adjusting the pH value of the system to 6.8-7.2 by using 2mol/L NaOH solution and 2mol/L HCl solution, replacing the electron donor with sodium thiosulfide, wherein the adding mass of the sodium thiosulfide in the system is gradually increased according to 5g/L, 8g/L, 10g/L and 15g/L, the first 3 concentrations are maintained for 2 days, then 15g/L is replaced, 4 days are maintained, the operation is carried out for 6 hours every day, the flow rate of circulating liquid is 25L/h, 2L of aerated nutrient solution is replaced regularly every day, and the liquid level of the nutrient solution is controlled to be 600mm. The first stage film forming time is 10d.
(2) And a second stage: further taking H in the methane on the basis of the first stage of strengthening the film formation 2 S is an electron donor, and the film formation is carried out at the air inlet flow rate of 0.4L/min, 0.8L/min and 1.0L/min respectively. H is set at the flow rate of 0.4L/min 2 And when the S removal rate is stabilized to be more than 95 percent and is stabilized for 3 days, expanding the flow rate to be 0.8L/min, and the like. The total time of the second stage of the reinforced re-filming is about 15 days. No pH control is required in this stage.
3. The control group a, the experimental group B and the experimental group C were set with the air intake load, the electron donor concentration, the empty tower residence time, the hydraulic residence time, the gas-liquid ratio and the liquid level height, respectively, in the manner shown in table 4. In table 4, the flow rate refers to the air flow rate; the empty tower residence time refers to the time that the biogas enters from the bottom of the tank body and then flows out from the top and flows through the whole empty tank body; the superficial gas velocity refers to the velocity of air flowing through the reactor; the circulating flow refers to the spraying speed of the biogas slurry in the actual operation process; the gas-liquid ratio refers to the ratio of the methane to the flow rate to the circulating flow; the intake load refers to the S content in the hydrogen sulfide at the current intake speed.
TABLE 4 comparison table of reaction parameters of each group
4. And (5) displaying the result.
(1) Each stage H 2 S removal rate and NO X The relationship between the-N concentration is shown in FIGS. 15 to 17. FIGS. 15 and 16 show stages H of the experimental group B, C, respectively 2 S removal rate and NO X FIG. 17 is a graph showing the relationship between the concentration of N and the concentration of H in three groups at different stages 2 And S average removal rate. The results show that: the removal rate of the test group B filled with polyurethane foam as a filler was greater than 90% in the monitoring time of 112d, while the removal rate of the test group C filled with polyhedral hollow spheres was greater than 90% only in the monitoring time of 69 d. Experimental group B was stable during each loading phase, with a 2 day transient drop in RE occurring only at the time of the E4 to E5 phase change. This is because the inlet flow rate is increased from 1.5L/min to 2.0L/min, EBRT is from 456s to 342s, and functional microorganisms require a certain adaptation process. The experimental group B has stronger load change resistance and more stable desulfurization efficiency.
With NO 3 - -N based nutrient solutions or NO 2 - The nutrient solution system with the advantage of-N can maintain the good operation of the system, but when two electron acceptor works exist simultaneously, NO is 2 - The N concentration decelerates more rapidly, indicating NO 2 - N is more likely to act as an electron donor in the simultaneous desulfurization and denitrification reactions. When NO is present 3 - -N and NO 2 - The desulfurization effect is influenced when the concentration of-N is less than 50 mg/L. Maintenance of water intake NO 3 - -N or NO 2 - N concentration lower than 140mg/L, to NO 3 - -N and NO 2 - The average removal rate of-N can reach more than 95%. Namely, in the practical engineering, NO in the influent biogas slurry can be controlled 3 - -N and NO 2 - Realization of N concentration on H in biogas 2 S and the removal rate of nitrate nitrogen in biogas slurry is more than 95%.
When the system is operated to 100 days, the operation is stopped for 25 days at room temperature (10-15 ℃) because of spring festival vacation, but the test group B finishes the recovery restarting process only in 8 days after festival. The experiment shows that: the polyurethane foam is used as the filler, so that better film forming can be completed, and the generation of bubbles can be well inhibited; the multi-surface hollow sphere has poor bubble inhibition capability, even can overflow phenomenon occurs under the condition of 2.0 air inlet load, and finally the problem of bubble can overflow is solved by adding 0.1% (v/v) of organic defoaming agent.
Intake load, gas-liquid ratio, liquid level height and Hydraulic Retention Time (HRT) vs. H 2 The influence of the S-average removal rate is shown in fig. 17. In several stages with consistent air intake load, EBRT and liquid level height and different HRT, the desulfurization efficiency of the experimental group C is gradually increased to 84.5 percent along with the increase of HRT, while the desulfurization efficiency of the experimental group B is stable and is always maintained at about 90 percent. This is probably because the polyurethane foam filler has a greater water holding capacity than the polyhedral hollow spheres and thus exhibits more stable desulfurization efficiency when the liquid level changes and the HRT changes.
(2) Change in methane content. The monitoring result of the methane content in the desulfurization process shows that: the relative content of methane in each stage is almost improved to a certain extent compared with that of inlet gas, and the lifting value of the experimental group B, C is higher than that of the control group A. The reasons for the methane increase may be: the system operates under the micro-aerobic condition, and the biogas slurry contains certain organic matters, so that a certain anaerobic fermentation process can occur; CO in biogas 2 CO in the biogas during operation as an inorganic carbon source for the simultaneous desulfurization and denitrification reaction 2 A certain degradation occurs, thereby increasing CH to a certain extent 4 Relative amounts of (c). The process can not only realize the denitrification process of the biogas slurry wastewater and the desulfurization and purification process of the biogas slurry, but also improve CH in the biogas 4 The relative content of the gas improves the heat value of the methane and enhances the heat efficiency, thereby further enhancing the application advantages of the process.
(3) And (3) performing equation fitting according to the relation between the air inlet load and the elimination capacity, and displaying the result: the difference in desulfurization performance of the experimental group B, C was small under low load conditions, and the difference gradually increased with increasing intake load. The experimental group B using polyurethane foam as the filler has stronger desulfurization performance and stronger load impact resistance.
(4) The change results of pH and ORP in the denitrification process of the synchronous biogas desulfurization biogas slurry show that: in a system for synchronously denitrifying biogas slurry and desulfurizing biogas slurry by taking the biogas slurry as nutrient solution, the pH change of the whole system is stable at 6-8 under the condition of no pH regulation. The ORP value of the experimental group B, C is reduced to between-300 mv and-350 mv along with the increase of the intake load. This shows that properly increasing the air intake load will increase the physiological activity of the microbe with simultaneous desulfurizing and denitrifying functions, thus enhancing the desulfurizing and denitrifying efficiency and increasing the operating cost-effectiveness ratio of the reaction tower.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various changes, modifications, alterations, and substitutions which may be made by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. A bio-trickling filter, which is characterized in that: the filler of the biological trickling filter tower is polyurethane foam.
2. Use of the biotrickling filter of claim 1 for simultaneous denitrification and desulfurization of biogas slurry and/or biogas.
3. Use according to claim 2, characterized in that: in the application, the S/N molar ratio of inlet water is 5/3-5/2.
4. Use according to claim 3, characterized in that: before the synchronous denitrification and desulfurization, firstly, the biogas slurry/biogas to be treated is used for performing biofilm formation treatment on the filler, and then, the filler is used for denitrification and desulfurization, wherein the S/N molar ratio of inlet water is 5/3-5/2 during the biofilm formation treatment.
5. The use according to claim 4, wherein: the film forming treatment comprises the following steps:
(1) Pre-filming: placing the filler into an anaerobic container mixed with biogas slurry to be treated and a basic culture medium, keeping the temperature at 28 ℃, and treating until NO is contained in the culture medium 3 - When the N removal reaches 80%, furtherReplacing with new basic culture medium, and culturing to NO 3 - The N removal rate is stable, and pre-film forming is completed;
(2) Strengthening film hanging: irregularly placing the filler subjected to pre-biofilm formation into the biological trickling filter reactor, adding a basic culture medium to strengthen biofilm formation, wherein the strengthening biofilm formation period is 15-20 days.
6. Use according to claim 5, characterized in that: the basic culture medium comprises: na (Na) 2 S 2 O 3 ·5H 2 O 5g/L，KNO 3 4g/L，KH 2 PO 4 2g/L，NaHCO 3 1g/L，MgCl 2 ·6H 2 O0.5g/L，FeSO 4 ·7H 2 0.01g/L of O and 1mL of trace elements, and adjusting the pH value to 7.5;
the trace elements are: EDTA 0.5g/L, feSO 4 ·7H 2 O is 0.2g/L, and the trace elements SL-6100mL;
the trace elements SL-6 are: znSO 4 ·7H 2 O 0.1g/L，MnCl 2 ·4H 2 O 0.03g/L，H 3 BO 3 0.3g/L，CoCl 2 ·6H 2 O 0.2g/L，CuCl 2 ·2H 2 O 0.01g/L，NiCl 2 ·6H 2 O0.02g/L，Na 2 MoO 4 ·H 2 O 0.03g/L。
7. Use according to any one of claims 5 or 6, characterized in that: after finishing the film forming treatment, performing reinforced film forming treatment again on the filler, and then performing the synchronous denitrification and desulfurization; the reinforced re-filming treatment comprises the following steps:
(1) The first stage is as follows: adjusting the pH value of a system in the biological trickling filtration tower to 6.8-7.2, adding sodium thiosulfide into the system, wherein the adding mass of the sodium thiosulfide is gradually increased according to 5g/L, 8g/L, 10g/L and 15g/L, and the first stage is maintained for 8-12 days;
(2) After the first stage is completed, H is introduced into the system 2 S, the air inlet flow rate is gradually increased by 0.4L/min, 0.8L/min and 1.0L/min, and the second stage is maintained for 12-17 days.
8. According to the claimsThe application of claim 7, wherein: in the first stage, the adding mass of the sodium sulfide is gradually increased according to 5g/L, 8g/L, 10g/L and 15g/L, the first 3 concentrations are maintained for 1 to 3 days, and then 15g/L is replaced for 3 to 5 days; and/or; second stage H 2 The air inlet flow rate of S is gradually increased at 0.4L/min, 0.8L/min and 1.0L/min until H is increased at 0.4L/min 2 When the S removal rate is stabilized at more than 95% for 3 days, the flow rate is increased to 0.8L/min, and so on.
9. A microbial composition for use according to any one of claims 2 to 8, wherein: including the genera Thiobacillus, rhodanobacter, arenimonas and Trueera.
10. The microbial composition of claim 9, wherein: the amount of microorganisms belonging to the genus Thiobacillus is 40% or more of the amount of viable bacteria.
Priority Applications (1)
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| CN101549255A (en) * | 2009-05-05 | 2009-10-07 | 浙江省环境保护科学设计研究院 | Method for treating organic exhaust-gas generated in waste plastic granulation process |
| CN107760626A (en) * | 2017-11-13 | 2018-03-06 | 中国科学院成都生物研究所 | One plant of Bangladesh's pair meningitidis strains and its application |
| CN110270216A (en) * | 2019-07-04 | 2019-09-24 | 上海梅思泰克环境股份有限公司 | It is a kind of using polyurethane material as the biological treatment exhaust device of filler |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101549255A (en) * | 2009-05-05 | 2009-10-07 | 浙江省环境保护科学设计研究院 | Method for treating organic exhaust-gas generated in waste plastic granulation process |
| CN107760626A (en) * | 2017-11-13 | 2018-03-06 | 中国科学院成都生物研究所 | One plant of Bangladesh's pair meningitidis strains and its application |
| CN110270216A (en) * | 2019-07-04 | 2019-09-24 | 上海梅思泰克环境股份有限公司 | It is a kind of using polyurethane material as the biological treatment exhaust device of filler |
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