CN111018120A - Application of porous ecological filler system in heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater remediation - Google Patents
Application of porous ecological filler system in heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater remediation Download PDFInfo
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Abstract
The invention discloses application of a porous ecological filler system in remediation of heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater. The porous ecological filler system comprises a basic planting layer and a porous ecological mixed soil layer which are paved at the bottom of the artificial wetland treatment system, wherein the porous ecological mixed soil layer is an active porous ecological mixed filler which covers the basic planting layer; the active porous ecological mixed filler is selected from one or more of zeolite, charcoal, compound microbial agent or chlorella; and planting cabbages on the porous ecological mixed soil layer. Aiming at the characteristics of the aquaculture sewage, the invention can durably, effectively and stably reduce the contents of heavy metal and nitrogen and phosphorus in the aquaculture sewage through the synergistic effect of the filler covering layer and the water spinach, and meanwhile, the planted water spinach can be used as silage to return to agricultural production for recycling, so that the effects of changing aquaculture, production and repair are achieved, the operation and management are convenient, the treatment cost is low, and the environmental protection property is good.
Description
Technical Field
The invention belongs to the technical field of livestock and poultry breeding sewage remediation. More particularly, relates to an application of a porous ecological filler system in the remediation of heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater.
Background
The improvement is open, the animal husbandry in China is in a high-speed development period, the proportion of the livestock and poultry breeding industry in China in agricultural production value is increased from 18% to 34% in 1980 in 2003, China is the largest meat and egg producing country in the world at present, and meanwhile, the yields of poultry, pork and eggs are the first world (populus ussuriensis, 2006). With the continuous development of the breeding industry, the breeding industry is moving towards a large-scale and intensive road. But the problems of concentrated excrement and urine and concentrated sewage discharge caused by excessive flushing water amount are caused by large-scale culture, and the environmental pressure around the livestock and poultry field is greatly increased. As shown by the survey in 2002, a large amount of sewage discharged into the environment by a large-scale pig farm is not treated, and the sewage is discharged after anaerobic fermentation in a methane tank, but the content of pollutants in the sewage is far higher than the national environmental protection standard (Jindonxia et al, 2002), but the problem is not solved yet.
Research shows that the biochemical oxygen demand (BOD5) of the wastewater discharged by livestock and poultry farms is as high as 2000-8000 mg/L, the COD is as high as 5000-20000 mg/L, the livestock and poultry wastewater contains a large amount of organic pollutants, suspended matters, N, P and other nutrients, a large amount of pathogenic harmful bacteria, and a certain amount of harmful heavy metal elements (mainly arsenic), and can pollute surface water through surface runoff or underground polluted underground water through soil infiltration; pathogenic microorganisms, parasitic eggs and bred mosquitoes and flies in the livestock and poultry excrement sewage flow with water, so that propagation of certain epidemic diseases can be caused. Trace elements such as high copper, high arsenic and high zinc added in the livestock and poultry feed are accumulated in soil after being discharged out of the body along with excrement and urine, so that the pollution of mineral elements and heavy metals in the soil is caused.
The artificial wetland system is a complete ecological system, forms good internal circulation and has good economic and ecological benefits. However, the artificial wetland has disadvantages such as large occupied area, long hydraulic retention time, large influence of temperature change and plant growth maturity on treatment effect, lack of optimized design specifications and parameters, potential disease transmission media and the like, so further improvement and perfection are needed. Long-term practice projects at home and abroad show that the constructed wetland has higher removal rate of organic matters, but has lower and unstable removal rate of nitrogen and phosphorus, and can better play a role by further improving the existing constructed wetland technology and enhancing the nitrogen and phosphorus removal efficiency. Research shows that the method for increasing the area of the wetland, additionally arranging the pretreatment process, additionally adding aeration, replacing matrix fillers and the like can improve the nitrogen and phosphorus removal efficiency of the artificial wetland, but also brings the defects of increased operation cost and inconvenient process management, and is difficult to implement in rural areas with weak economic foundation.
In the constructed wetland treatment system, the matrix filler is an important nutrient gathering place in the system, and the composition and the quantity of the microbial population adhered to the filler directly influence the purification effect of the system. Different matrices have different abilities to remove contaminants due to their different properties (Xudefu et al, 2007). However, the filler of the current artificial wetland system still depends on natural gravels, sands, soil or gravels, furnace slag and other materials widely, but the materials belong to inert materials and have poor fixing capability on the pollutants in the aquaculture wastewater, so that the artificial wetland system constructed by the inert materials has low efficiency of controlling the pollutants in the aquaculture wastewater.
Reports and related patents for controlling wastewater pollution by using active fillers are gradually appeared in China, such as patents (CN201810437182.7) on a livestock waste nutrient recovery and water quality standard-reaching process method, (CN 201210231294.X) on an artificial wetland sewage treatment method based on modular built-in interstitial fillers, (CN 201710784913.0) a composite artificial wetland system for efficiently treating ammonia nitrogen wastewater, (CN 201210269870.X) on a method for treating rural domestic sewage by using denitrifying phosphorus accumulating bacteria reinforced artificial wetland, and the like, but the patents generally have the following defects: (1) the compact packing of the filler easily causes the complete change of the water body substrate condition, destroys the living environment of benthos, although the effect of covering the initial stage is obvious, the ecological system for repairing the water body is degraded because the benthos is seriously destroyed and difficult to be rebuilt; (2) the filler is single in pollutant release aiming at the controlled wastewater, mainly comprises nitrogen and phosphorus, and cannot effectively control the release of heavy metals; (3) most of the research on the aquatic plants of the artificial wetland focuses on landscape plants (such as canna, reed and the like as wetland plants), and the landscape plants cannot be recycled as the raw materials of the farm, so that the waste of resources is caused; (4) generally aims at the treatment of slightly polluted domestic sewage and the recovery of landscape water bodies, and is rarely directed at the research of moderately and severely polluted culture wastewater. These are clearly significant limitations for the remediation of contaminated aquaculture wastewater where the endogenous release of multiple contaminants needs to be controlled.
Disclosure of Invention
The invention aims to provide the application of a porous ecological filler system in the remediation of heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater, aiming at the defects of the existing aquaculture wastewater treatment technology and artificial wetland technology. The porous ecological filler system is characterized in that water spinach is planted in a synergistic manner through a porous ecological mixed soil layer, the content of pollutants in the aquaculture wastewater can be remarkably reduced, the heavy metal and/or nitrogen and phosphorus polluted wastewater can be subjected to in-situ remediation for a long time and stably, the water habitat can be rebuilt and restored conveniently, the planted water spinach can be used as silage and returned to agricultural production for recycling, and the effects of variable aquaculture, production and restoration are achieved.
The invention is realized by the following technical scheme:
the porous ecological filler system comprises a basic planting layer and a porous ecological mixed soil layer, wherein the basic planting layer and the porous ecological mixed soil layer are laid at the bottom of an artificial wetland treatment system, and the porous ecological mixed soil layer is an active porous ecological mixed filler covered on the basic planting layer; the active porous ecological mixed filler is selected from one or more of zeolite, charcoal, compound microbial agent or chlorella; and planting cabbages on the porous ecological mixed soil layer.
Through a large amount of exploration and research, the porous ecological filler system which can be applied to the remediation of the heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater is obtained. The porous ecological filler system is used for continuously restoring a polluted water source in situ by constructing an active filler system and cooperatively planting aquatic plants, and the main implementation scheme is as follows: the active porous ecological mixed filler is utilized to form an active filler covering layer on a basic planting layer-water interface, the formed active filler covering layer can effectively reduce the content of heavy metal and nitrogen and phosphorus in the aquaculture wastewater, and the plant water spinach planted on the active porous ecological mixed filler covering layer can synergistically absorb nitrogen and phosphorus nutrient salt and heavy metal in pore water and overlying water.
In some embodiments, the active porous ecological hybrid filler is selected from two or more of zeolite, biochar, complex microbial agents, or chlorella; preferably a mixture of biochar and chlorella, or a mixture of zeolite, biochar, microorganisms and chlorella, or a mixture of biochar and microorganisms, or a mixture of zeolite and microorganisms. According to the invention, by adding zeolite, charcoal, compound microbial agent or chlorella filler, the interaction among plants, matrix and microorganisms is enhanced, the strengthening effect on the wetland is enhanced, and the removal efficiency of heavy metals and nitrogen and phosphorus in sewage is effectively improved.
In some preferred embodiments, the addition amount of the zeolite is 1-15 g/L, preferably 5-10 g/L calculated by mass-volume ratio of the zeolite to the aquaculture wastewater to be repaired; the addition amount of the biochar is 1-15 g/L, preferably 5-10 g/L; the addition amount of the compound microbial agent is 0.05-5 g/L, preferably 0.1-1.5 g/L; the addition amount of the chlorella is 0.1-5 g/L, preferably 0.16-3.5 g/L. The implementation range is obtained by comprehensively considering various factors including the properties of fluidity, dispersibility, viscosity and the like of the porous ecological mixed soil layer, ensuring that the porous ecological mixed soil layer can be well and directly covered on the basic planting layer to form the porous ecological mixed soil layer, and being suitable for the growth of the water spinach, and the synergistic control and removal effects of the porous ecological mixed soil layer and the water spinach on heavy metals and nitrogen and phosphorus pollutants.
In some embodiments, the composite microbial agent is prepared by mixing bacillus subtilis, saccharomycetes, lactic acid bacteria and flocculating bacteria according to the weight ratio of 5-10: 2-10: 1-6: 1-5.
In some preferred embodiments, the total viable bacteria number of the compound microbial agent is more than or equal to 5.0 x 109cfu·g-1Preferably 5.0X 109～5.0×1010cfu·g-1。
In some embodiments, the variety of the water spinach is selected from one or more of green stem leaf water spinach of harbor species, white bone water spinach of Taiwan province, D-95 water spinach of vegetable grower, leaf water spinach of Thailand, white bone water spinach of harbor species, leaf water spinach of Thailand, pure green leaf water spinach of Guangdong, leaf water spinach of green bone, leaf water spinach of Jiangxi, leaf water spinach of North river, leaf water spinach of 999 green bone, leaf water spinach of Jashuai bamboo leaf, leaf water spinach of white stem leaf, water spinach of Thailand, leaf water spinach of Taiwan white bone, leaf water spinach of Taiwan green stem leaf, leaf water spinach of Taiwan white stem leaf, leaf water spinach of Taiwan white stem leaf or oil water spinach.
In other preferred embodiments, the variety of the water spinach is one or more selected from Taiwan white-leaf water spinach, vegetable D-95 water spinach, green-stem-leaf water spinach of harbor species and leaf water spinach of Thailand. Through extensive and intensive research, the invention discovers that the transport coefficients of 4 varieties (Taiwan white-bone water spinach, vegetable D-95 water spinach, green-stem-leaf water spinach and Thailand bamboo-leaf water spinach in harbor) with higher accumulated As content are all larger than 1, namely the As content of the overground part is higher than that of the underground part, wherein the transport coefficient of the water spinach except Thailand bamboo-leaf is 1.08, and the As content of the overground part is slightly higher than that of the underground part. And the biomass of the Taiwan white-leaf water spinach, the vegetable grower D-95 water spinach and the harbor green stem leaf water spinach is higher and is more than 10 g. Therefore, in summary, the swamp cabbage variety with relatively high As accumulation is Taiwan white-leaf swamp cabbage, vegetable D-95 swamp cabbage, green-stem-leaf swamp cabbage of harbor species, and Thailand bamboo leaf swamp cabbage.
In some preferred embodiments, the water spinach is planted according to the planting specification of 15cm × 25cm in plant-row distance.
In some preferred embodiments, the thickness of the basic planting layer is 5-8 cm, preferably 6 cm; the thickness of the porous ecological mixed soil layer is 5-10 cm, and preferably 5-8 cm.
In some preferred embodiments, the porous ecological hybrid soil layer has a porosity of > 30%, preferably 33% to 38%.
In some preferred embodiments, the material of the basic planting layer is one or more of river sand, planting soil or humus.
In some preferred embodiments, the biochar comprises one or more of wheat bran, corn stover charcoal or wheat straw charcoal, preferably wheat bran.
In some preferred embodiments, the biochar has a particle size of 160-200 mesh; the diameter of the zeolite is 0.5-4 cm.
In some preferred embodiments, the zeolite comprises mordenite and/or analcime.
In some preferred embodiments, the chlorella is added as a chlorella solution in logarithmic growth phase.
In some preferred embodiments, chlorella is cultured conventionally to obtain a seed solution, and then the seed solution is cultured in a 1: 10, transferring the mixture into a chlorella acclimation culture medium, and culturing for 12 hours to obtain chlorella liquid. Can be (2-10) x 108The input amount of the CFU is directly added into the chlorella solution in the artificial wetland, or the chlorella solution can be centrifuged, and then the precipitate is weighed and added.
In some embodiments, the method for remedying the heavy metal and/or nitrogen and phosphorus polluted aquaculture wastewater by using the porous ecological filler system comprises the following steps:
adding a basic planting layer material into a mould, mixing and stirring active porous ecological mixed filler and water, pouring the mixture into the mould for forming, controlling the addition of the water to account for 5-10% of the mass of the active porous ecological mixed filler, uniformly coating the surface of the basic planting layer with a layer of the active porous ecological mixed filler to form a porous ecological mixed soil layer, obtaining the modular porous ecological filler, then putting the modular porous ecological filler into an artificial wetland treatment system for breeding wastewater, and planting water spinach on the porous ecological mixed soil layer.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the characteristics of livestock and poultry breeding sewage, the invention utilizes the synergistic strengthening effect of the active porous ecological mixed filler and the water spinach on the wetland, and reduces the contents of heavy metal, organic matters, nitrogen, phosphorus and other pollutants in the water body through the processes of adsorption, ion exchange, plant absorption and transportation, microbial degradation and the like, so that the effluent quality indexes of Total Phosphorus (TP) and ammonia Nitrogen (NH)4 +N) and COD meet the discharge standard of pollutants for livestock and poultry breeding (DB 44/613-2009), and the content indexes of As, Cu and Zn meet the discharge standard of Integrated wastewater (GB 8978-88).
(2) The active filler adopted by the porous ecological filler system is zeolite, biochar, a compound microbial agent, chlorella or a mixture of the zeolite, the biochar, the compound microbial agent and the chlorella, and the active filler can effectively absorb heavy metals and/or nitrogen and phosphorus in the culture wastewater, and can realize one-time coverage and multiple control.
(3) The water spinach planted on the porous ecological mixed soil layer in the porous ecological filler system can effectively cooperate with the porous ecological mixed soil layer to reduce the content of heavy metal and/or nitrogen and phosphorus, is beneficial to restoring and restoring the water body habitat, improves the water body quality, has a good landscape effect, can be recycled as silage to return to agricultural production, and achieves the effects of changing cultivation, production and restoration.
(4) The materials used by the porous ecological filler system are all environment-friendly materials, are cheap and easily available, and the in-situ technology is simple to implement, can obviously reduce the contents of heavy metal and nitrogen and phosphorus in the aquaculture wastewater, and is suitable for general popularization.
Drawings
Fig. 1 is a schematic view of an indoor simulated artificial wetland test site.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are intended to be included in the scope of the present invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Measurement of As, Cu, Zn
(1) Plant sample preparation: weighing 0.2g of plant dry sample, adding 8mL of nitric acid and 2mL of 30% hydrogen peroxide, performing microwave digestion (CEMMars6), determining the content of As in the digestion solution by using a double-channel atomic fluorescence spectrophotometer (AFS-230E, Beijing Korea Hai-Kui optical instruments Co., Ltd.), and determining the content of Cu and Zn in the digestion solution by using an atomic absorption spectrophotometer (ZEEnit700P, Germany Jena).
(2) Water sampling: 5mL of water sample is taken, 5mL of nitric acid is added, microwave digestion (CEM Mars6) is carried out, the content of As in the digestion solution is determined by a double-channel atomic fluorescence spectrophotometer (AFS-230E, Beijing Kochua Hai-Kuai optical instruments Co., Ltd.), and the content of Cu and Zn in the digestion solution is determined by an atomic absorption spectrophotometer (ZEEnit700P, Germany Jena).
Transfer coefficient calculation
Transfer coefficient is the above-ground As content/the underground As content
Determination of water quality
Total phosphorus: ammonium molybdate spectrophotometry (GB 11893-89);
ammonia nitrogen: sodium hypochlorite-salicylic acid spectrophotometry (HJ 534-2009);
CODCr: microwave digestion-Potassium dichromate method, 3mL of water sample was taken in a digestion tank and 1.5mL of a potassium dichromate standard solution (1/6K) was added thereto, in accordance with the method of Dharmadhikari (Dharmadhikari et al, 2005)2CrO70.2500mol/L), 0.06g mercury sulfate, 4.5mL silver sulfate-sulfuric acid solution (5 g silver sulfate is added into 500mL concentrated sulfuric acid), microwave digestion (CEM Mars6) is carried out for 15min, 3 drops of ferroxyl test indicating solution are added, ammonium ferrous sulfate standard solution [ (NH)4)2Fe(SO4)2·6H2O≈0.1mol/L]Titration;
pH: the pH meter (PB-10, Sartorius) directly.
The chlorella strain is purchased from the research institute of aquatic products in Zhujiang of Chinese aquatic science research institute, and is cultured in logarithmic growth phase according to the ratio of 1: 10 to BG11 medium without nitrogen, cultured under light intensity 2700Lx at 28 ℃ for 10 days to logarithmic phase, and centrifuged with 100mL centrifuge tubes at 3000 rpm to collect the pellet.
Example 1 selection of Water spinach variety
1. Method of producing a composite material
(1) The test is carried out in an ecological farm cement pond (with the length of 1m multiplied by the width of 1m multiplied by the height of 0.65m) of southern China agricultural university, 15 cement ponds are evenly divided into 4 cells (with the area of each cell being 0.5m multiplied by the width of 0.5m) with 60 cells in total, 57 cells (with 3 vacant cells and no plant) are needed for 3 times for all 19 swamp species to be tested, 20 seeds of 19 different swamp species are randomly sowed in each cell, and 4 plants are fixed after the 1 st true leaf of the plant grows out. During the test period, tap water with the same amount is added into the cement pool irregularly (1-2 d). And after planting for 60d (4-6 months in 2015), any one of 4 water spinach in each pool is used for measuring the biomass and arsenic content of 19 water spinach varieties.
(2) The test cement pond soil was from the cultivated layer of the ecological department farm of southern china university of agriculture. Removing broken stone, dead leaves and the like after soil collectionAnd (4) naturally drying sundries, sieving the sundries by a 2mm sieve, and uniformly mixing the sundries for later use. The concentration of As-polluted soil in the cement pool community is set As 50mg As.kg-1(arsenic trioxide is added according to the amount of 30cm of a plough layer), after rice aged As of one season is planted, samples are taken to detect the basic physicochemical properties, and the results are shown in Table 1.
TABLE 1 physicochemical Properties of the soil tested
(3) Treatment of plant samples: separating the overground part and the underground part (root system) of the whole water spinach plant, completely cleaning the water spinach plant by using tap water, distilled water and deionized water in sequence, absorbing the water on the surface of the plant by using absorbent paper, filling the plant into an envelope, numbering the plant, drying the plant in a 60 ℃ oven to constant weight, and weighing the dry weight. Then, the ground upper part and the ground lower part of the water spinach are crushed by a crusher and stored in a sealing bag for analyzing the content of total As.
Transfer coefficient is the aboveground As content/underground As content.
2. Results
(1) Influence of As stress on biomass of water spinach of different varieties
Biomass of table 219 variety of swamp cabbage
Note: all data are mean ± sem (n ═ 3), with different lower case letters in the same column indicating significant differences between species (p < 0.05).
As can be seen from Table 2, the aboveground biomass (dry weight basis) of 19 varieties of water spinach is 1.22-19.43 g, the average value is 9.26g, the variety with the largest biomass is Thailand leaf water spinach, and the variety with the smallest biomass is green-bone leaf water spinach, with a difference of 15.93 times, wherein the biomass difference of the Thailand leaf water spinach from 5 varieties of Thailand leaf water spinach, Taiwan white-bone leaf water spinach, Jiangxi big-leaf water spinach, 999 green-bone leaf water spinach and green-bone leaf water spinach reaches a significant level (p < 0.05); the biomass difference of the Chinese Taiwan green stalk bamboo leaf water convolvulus and the biomass difference of the 999 green bone willow leaf water convolvulus and the green bone willow leaf water convolvulus reaches an obvious level (p is less than 0.05); and no significant difference between the biomass of the remaining varieties (p > 0.05); the biomass range of the underground part is 0.63-4.12 g, the difference is 5.6 times, the average value is 1.79g, and the biomass difference of the underground part among 19 swamp cabbage varieties reaches a significant level (p is less than 0.05).
(2) Differences in As content of different varieties of water spinach
TABLE 3 variety differences of As accumulation in the aerial and underground parts of Water spinach
Note: all data are mean ± sem (n ═ 3), with different lower case letters in the same column indicating significant differences between species (p < 0.05).
As can be seen from Table 3, the difference in As content among the swamp cabbage varieties was large, and the highest As content among the aerial parts was 191.12 mg/kg of green stalk leaf swamp cabbage which is the harbour variety-1The content of As is 0.73 mg/kg for the oil green empty cabbage-1(ii) a The underground part has the highest As content of 229.76 mg/kg of the white bone and willow leaf water spinach of Taiwan-1The variety with the lowest content is green bone willow leaf water spinach with the content of 78.57 mg/kg-1. The transport coefficient difference of 19 swamp cabbage varieties is obvious, the lowest Taiwan white bone willow leaf swamp cabbage is 0.004, and the highest green stem leaf swamp cabbage of the harbor variety is 2.19. Wherein the transport coefficients of 4 varieties of Taiwan white-leaf water spinach, vegetable D-95 water spinach, green-stem-leaf water spinach and Thailand bamboo-leaf water spinach are more than 1.
Example 2 research on purification effect of indoor simulated artificial wetland treatment system on biogas slurry in pig farm
1. Method of producing a composite material
The test is carried out in an environmental ecology laboratory of the college of agriculture of south China university, the test takes a transparent glass jar with the length multiplied by the width multiplied by the height which is 0.5 multiplied by 0.3 multiplied by 0.4 as a container, river sand with the length of 4cm is paved at the bottom layer to fix the root system of the water spinach, and 6 water spinach with the same growth vigor (the plant height of 15cm) are planted in each glass jar. The test was carried out in two stages for a total of 30d (2016, 10-11 months), 15d each. The schematic diagram of the indoor artificial wetland simulation test site is shown in figure 1.
Wherein the compound microbial agent is prepared by mixing bacillus subtilis, saccharomycetes, lactic acid bacteria and flocculating bacteria according to the weight ratio of 7.5: 6: 3: 2.5. The powder is obtained. The total number of viable bacteria is not less than 5.0 multiplied by 109cfu·g-1。
The biogas slurry for test is from a certain pig farm in Guangdong, and is the wastewater discharged after the piggery house flushing wastewater is subjected to slag separation and solid-liquid separation and then is subjected to anaerobic biogas fermentation treatment, and the properties of the wastewater are shown in tables 4 and 5.
TABLE 4 Water quality of biogas slurry (A) in the second and first stages of the experiment
TABLE 5 Water quality of biogas slurry (B) in the second stage of the experiment
(1) The first stage is as follows: according to the weight percentage of water: biogas slurry is 3: 12L of water and 6L of biogas slurry are added according to the proportion of 1, and 8 treatments are carried out in the test. The treatment is shown in Table 6.
Table 6 indoor artificial wet land experimental design treatment group
Each treatment was repeated three times for a total of 24 treatments. The evaporated water in each glass jar was replenished with tap water every 5 days during the test to maintain a constant water sample volume per glass jar. And harvesting the overground part of the water spinach along two sections of the water surface after 15 days of treatment. TP and NH were measured in water on days 1, 3, 5, 7, 10, 15 of the experiment4 +N content, COD content in water determined on days 5, 10 and 15. Measuring Cu and Z in plant sample and water sample after testn and As content.
(2) And a second stage: 12L of biogas slurry (B) is supplemented after the overground part of the water spinach harvested on the 15 th day of the first stage is finished, and the rest treatment is unchanged. The test period was 15 days, during which the evaporating water in each glass jar was replenished with tap water every 5 days to maintain a constant water sample volume per glass jar. TP and NH were measured in water on days 1, 5, 10, and 15 of the experiment4 +The content of N, the COD content in the water was determined on days 1, 7 and 15. And after the test is finished, measuring the contents of Cu, Zn and As in the plant sample and the water sample.
In addition, all data below in this experiment are mean ± sem (n ═ 3), with different lower case letters in the same column indicating significant differences between treatments (p <0.05) and different upper case letters in the same row indicating significant differences at different times (p < 0.05). T1 represents a zeolite; t2 represents biochar; t3 represents zeolite + microorganism; t4 represents zeolite + chlorella; t5 represents biochar + microorganisms; t6 represents biochar + chlorella; t7 represents zeolite + biochar + microorganisms + chlorella.
2. Indoor simulation artificial wetland treatment system removes effect to TP
(1) First stage
TABLE 7 first-stage TP content variation with time (mg/L) of indoor simulated constructed wetland system
As can be seen from table 7, the removal rate of TP treated in the first stage of the indoor simulated artificial wetland treatment system is 71.60% to 92.11%, and the purification capacity is as follows: t6 (biochar + chlorella) > T7 (zeolite + biochar + microorganism + chlorella) > T5 (biochar + microorganism) > T2 (biochar) ═ T3 (zeolite + microorganism) > T4 (zeolite + chlorella) > T1 (zeolite) > CK.
Removal rate by test: t3> T4> T1, T6> T5> T2; the purification effect of the water spinach artificial wetland system enhanced by the combination of the zeolite, the biochar and the compound microbial agent is better than that of the water spinach artificial wetland system by the independent addition of the zeolite and the microbes, and the removal effects of different combinations are inconsistent, but the more the filler is added, the better the purification effect is.
(2) Second stage
TABLE 8 second-stage TP content variation with time (mg/L) of indoor simulated artificial wetland system
As can be seen from table 8, the removal rate of TP treated in each stage of the second stage of the indoor simulated artificial wetland treatment system is between 64.13% and 82.03%, and the purification capacity is as follows: t4 (zeolite + chlorella) > T6 (biochar + chlorella) > T7 (zeolite + biochar + microorganism + chlorella) > T2 (biochar) > T3 (zeolite + microorganism) > CK > T1 (zeolite) > T5 (biochar + microorganism).
In conclusion, the TP removal effect of each treatment in the first stage of the test is better than that in the second stage, the swamp cabbage wetland treatment system has a certain effect on purification of the biogas slurry TP, the adsorption effect of zeolite and biochar is reduced along with the increase of time, and the adsorption limit is certain, but the TP removal effect is kept better by adding the combination of zeolite and chlorella and the combination of biochar and chlorella to the swamp wetland system in the first stage and the second stage.
3. Indoor artificial wetland treatment system simulation NH4 +Effect of removal of-N
(1) First stage
TABLE 9 first-stage NH of indoor simulated artificial wetland system4 +The variation of N content with time (mg/L)
As can be seen from Table 9, NH was treated in each of the first stages4 +The N removal rate is between 88.01 and 99.55 percent, and the purification capacity is: t7 (Zeolite + charcoal + microorganism + Chlorella)>T3 (Zeolite + microorganism)>T5 (charcoal and microorganism)>T6 (charcoal and chlorella)>T4 (Zeolite + Chlorella)>T1 (Zeolite)>T2 (charcoal)>CK。
(2) Second stage
TABLE 10 second-stage NH of indoor simulated artificial wetland system4 +The variation of N content with time (mg/L)
As can be seen from Table 11, the second stage processes NH separately4 +The removal rate of N is between 69.67% and 100.00%, and the purification capacity is as follows: t7 (zeolite + charcoal + microorganism + chlorella) ═ T4 (zeolite + chlorella)>T6 (charcoal and chlorella)>T3 (Zeolite + microorganism)>T5 (charcoal and microorganism)>T2 (charcoal)>T1 (Zeolite)>CK。
In summary, the treatments except T4, T6, and T7 were tested on NH in the second stage4 +The removal effect of-N is better than that of the first stage, and the rest of the treatment is to remove NH in the first stage than in the second stage4 +the-N has better removal effect, and the swamp cabbage constructed wetland has NH4 +the-N has better removal effect, and the zeolite, the biochar, the compound microbial agent and the chlorella are used in a superposition way to remove NH in the first stage and the second stage4 +The best removal is found for-N.
4. COD removing effect of indoor artificial wetland simulating treatment system
(1) First stage
TABLE 11 first-stage COD content variation with time (mg/L) of indoor simulated constructed wetland system
As shown in Table 11, the COD removal rate in each treatment of the first stage is between 80.32% and 84.11%, and the purification capacity is as follows: t7 (zeolite + biochar + microorganism + chlorella) > T5 (biochar + microorganism) > T3 (zeolite + microorganism) ═ T4 (zeolite + chlorella) ═ T6 (biochar + chlorella) > T1 (zeolite) > T2 (biochar) > CK.
(2) Second stage
TABLE 12 second-stage COD content variation with time (mg/L) of indoor simulated constructed wetland system
As can be seen from Table 12, the removal rate of COD in each treatment in the second stage was between 95.10% and 98.77%, and the purification capacity was: t6 (biochar + chlorella) > T5 (biochar + microorganism) > T1 (zeolite) > T4 (zeolite + chlorella) > T7 (zeolite + biochar + microorganism + chlorella) > T3 (zeolite + microorganism) > CK > T2 (biochar).
In conclusion, the COD removal effect of each treatment in the second stage is better than that of the first stage, the COD removal effect of each treatment in the first stage is not greatly different, and the later-stage microbial agent, chlorella and charcoal are combined for use to remove COD, so that the obvious advantages are shown.
5. Indoor simulation artificial wetland treatment system has As removal effect
(1) First stage
TABLE 13 first stage As removal Effect on Water (As: μ g/L)
As can be seen from table 13, the removal rate of As in water in each treatment of the first stage of the indoor simulated artificial wetland treatment system test was 74.61% to 83.89%, the highest removal rate was T5, and the lowest removal rate was T1.
(2) Second stage
TABLE 14 Effect of the second stage on As removal from Water (As: μ g/L)
The overlapping application of the microbial agent and the biochar and the overlapping application of the zeolite, the biochar, the microbial agent and the chlorella to the water spinach constructed wetland system show that the water spinach artificial wetland system has a good As removing effect. The removal rate of As in the water by the treatments in the second stage is between 35.38 and 74.09 percent.
In conclusion, the swamp cabbage artificial wetland system has a remarkable effect of removing heavy metal As.
6. Cabbage accumulated heavy metal content in indoor simulation artificial wetland treatment system
TABLE 15 indoor first phase water spinach overground part heavy metal content (mg/kg)
The results show that the accumulation effect of the swamp cabbage on Cu, Zn and As can be reduced by adding the zeolite and the biochar As the adsorbent into the swamp cabbage artificial wetland system, and the reduction of the accumulation effect of the zeolite on Cu is obvious.
TABLE 16 indoor second stage swamp cabbage As content (mg/kg)
As can be seen from Table 16, the accumulated As content in the overground and underground parts of the swamp cabbage of the second stage of the indoor simulated artificial wetland treatment system is As follows: underground part > aboveground part.
In conclusion, zeolite and biochar serving as adsorbents are added into the water spinach artificial wetland system, so that heavy metal Cu of water spinach can be reducedThe accumulated contents of Zn and As and the accumulated Cu content of all the processed water spinach meet the standards of piglet compound feed (Cu is less than or equal to 200mg/kg) in the allowance of Cu in the feed (GB26419-2010) and early-stage compound feed (20 kg-60 kg body weight) (Cu is less than or equal to 150mg/kg) of growing-finishing pigs; the accumulated Zn content of all the treated swamp cabbage accords with the allowance of zinc in feed (NY 929-2005); the accumulated As content of all the processed water spinach meets the feed sanitation standard (GB 13078-2001) (As is less than or equal to 10mg kg)-1). Therefore, the swamp cabbage in the swamp cabbage artificial wetland treatment can be used as silage to return to agricultural production.
Example 3 preparation and application of active porous ecological Filler
1. Raw materials: commercially available zeolite, charcoal, composite microbial agent (prepared by mixing Bacillus subtilis, yeast, lactobacillus and flocculating bacteria), and Chlorella.
2. Raw material treatment: the method comprises the steps of crushing, sieving and cleaning zeolite and biochar, selecting zeolite with the diameter of 0.5-4 cm, sieving the biochar with a 160-mesh sieve, designing the target porosity to be more than 30%, calculating according to the mass-volume ratio of the biochar to be repaired to obtain the culture wastewater, wherein the addition amount of the zeolite is 5g/L, the addition amount of the biochar is 5g/L, the addition amount of the composite microbial agent is 0.1g/L, the addition amount of chlorella is 0.16g/L, and stirring and mixing the zeolite, the biochar, the composite microbial agent, the chlorella and water (the addition amount of control water accounts for 8% of the mass of the active porous ecological mixed filler) to obtain the active porous ecological mixed filler.
3. Preparation: adding river sand into the mold to form a basic planting layer, and controlling the thickness of the basic planting layer to be 6 cm; and (3) directly covering the active porous ecological mixed filler obtained in the step (2) on the basic planting layer, uniformly wrapping the surface of the basic planting layer with a layer of active porous ecological mixed filler to form a porous ecological mixed soil layer, and controlling the thickness of the porous ecological mixed soil layer to be 8cm to obtain the active porous ecological filler.
4. Applications of
The site of this example was performed in an artificial wetland of a pig farm of a company in the Guangzhou Zenghain area. The wastewater discharge amount of the pig raising factory is about 500m per day3Mainly including pigsUrine, partial pig manure and pigsty washing water belong to high-concentration organic wastewater, and the content of suspended matters and ammonia nitrogen is high. The annual average concentration of the main pollutants is: the COD is 11400 mg/L, the total phosphorus is 25mg/L, the ammonia nitrogen is 417mg/L, As is 108 mug/L, Cu is 7mg/L, and Zn is 0.8 mg/L. The method comprises the following specific steps:
and (4) adding the active porous ecological filler prepared in the step (3) into the artificial wetland in a starting operation period. And planting Thailand leaf swamp cabbage on the artificial wet land. In the operation process, the organic wastewater generated by solid-liquid separation of domestic sewage and pig farm waste enters a black film methane tank, a DST microorganism selection pond anaerobic fermentation tank and a DST advanced treatment biochemical tank in sequence after pH value adjustment, and then enters the artificial wetland, and the sewage stays in the artificial wetland for 10 days in a hydraulic power manner. And the water treated by the artificial wetland enters a flocculation sedimentation tank for sedimentation treatment and then enters a drainage tank. Through the interaction among the water spinach, the zeolite, the biochar microorganisms and the chlorella, the contents of pollutants such As heavy metals (mainly As, Cu and Zn), organic matters, nitrogen, phosphorus and the like in the water body are effectively reduced through the processes of adsorption, ion exchange, plant absorption and transfer and the like.
Example 4 preparation and application of active porous ecological Filler
1. Raw materials: commercially available zeolite, charcoal, composite microbial agent (prepared by mixing Bacillus subtilis, yeast, lactobacillus and flocculating bacteria), and Chlorella.
2. Raw material treatment: the method comprises the steps of crushing, sieving and cleaning zeolite and biochar, selecting zeolite with the diameter of 0.5-4 cm, sieving the biochar with a 200-mesh sieve, designing the target porosity to be more than 30%, calculating the mass volume ratio of the biochar to culture wastewater to be restored, wherein the adding amount of the zeolite is 10g/L, the adding amount of the biochar is 10g/L, the adding amount of a composite microbial agent is 1.5g/L, the adding amount of chlorella is 3.5g/L, and stirring and mixing the zeolite, the biochar, the composite microbial agent, the chlorella and water (controlling the adding amount of water to be 8% of the mass of the active porous ecological mixed filler) to obtain the active porous ecological mixed filler.
3. Preparation: adding planting soil into the mold to form a basic planting layer, and controlling the thickness of the basic planting layer to be 6 cm; and (3) directly covering the active porous ecological mixed filler obtained in the step (2) on the basic planting layer, uniformly wrapping the surface of the basic planting layer with a layer of active porous ecological mixed filler to form a porous ecological mixed soil layer, and controlling the thickness of the porous ecological mixed soil layer to be 5cm to obtain the active porous ecological filler.
4. Applications of
The site of this example was performed in an artificial wetland of a pig farm of a company in the Guangzhou Zenghain area. The wastewater discharge amount of the pig raising factory is about 500m per day3Mainly comprises pig urine, partial pig manure and pigsty washing water, belongs to high-concentration organic wastewater, and has large content of suspended matters and ammonia nitrogen. The annual average concentration of the main pollutants is: the COD is 11400 mg/L, the total phosphorus is 25mg/L, the ammonia nitrogen is 417mg/L, As is 108 mug/L, Cu is 7mg/L, and Zn is 0.8 mg/L. The method comprises the following specific steps:
and (4) adding the active porous ecological filler prepared in the step (3) into the artificial wetland in a starting operation period. And planting Thailand leaf swamp cabbage on the artificial wet land. In the operation process, the organic wastewater generated by solid-liquid separation of domestic sewage and pig farm waste enters a black film methane tank, a DST microorganism selection pond anaerobic fermentation tank and a DST advanced treatment biochemical tank in sequence after pH value adjustment, and then enters the artificial wetland, and the sewage stays in the artificial wetland for 10 days in a hydraulic power manner.
Example 5 preparation and application of active porous ecological Filler
1. Raw materials: commercially available zeolite, charcoal, composite microbial agent (prepared by mixing Bacillus subtilis, yeast, lactobacillus and flocculating bacteria), and Chlorella.
2. Raw material treatment: the method comprises the steps of crushing, sieving and cleaning zeolite and biochar, selecting zeolite with the diameter of 0.5-4 cm, sieving the biochar with a 200-mesh sieve, designing the target porosity to be more than 30%, calculating the mass volume ratio of the biochar to culture wastewater to be restored according to the mass volume ratio of the biochar to be restored, wherein the adding amount of the zeolite is 15g/L, the adding amount of the biochar is 15g/L, the adding amount of the composite microbial agent is 5g/L, the adding amount of chlorella is 5g/L, and stirring and mixing the zeolite, the biochar, the composite microbial agent, the chlorella and water (controlling the adding amount of the water to be 5% of the mass of the active porous ecological mixed filler) to obtain the.
3. Preparation: adding planting soil into the mold to form a basic planting layer, and controlling the thickness of the basic planting layer to be 8 cm; and (3) directly covering the active porous ecological mixed filler obtained in the step (2) on the basic planting layer, uniformly wrapping the surface of the basic planting layer with a layer of active porous ecological mixed filler to form a porous ecological mixed soil layer, and controlling the thickness of the porous ecological mixed soil layer to be 10cm to obtain the active porous ecological filler.
4. Applications of
The site of this example was performed in an artificial wetland of a pig farm of a company in the Guangzhou Zenghain area. The wastewater discharge amount of the pig raising factory is about 500m per day3Mainly comprises pig urine, partial pig manure and pigsty washing water, belongs to high-concentration organic wastewater, and has large content of suspended matters and ammonia nitrogen. The annual average concentration of the main pollutants is: the COD is 11400 mg/L, the total phosphorus is 25mg/L, the ammonia nitrogen is 417mg/L, As is 108 mug/L, Cu is 7mg/L, and Zn is 0.8 mg/L. The method comprises the following specific steps:
and (4) adding the active porous ecological filler prepared in the step (3) into the artificial wetland in a starting operation period. And planting Thailand leaf swamp cabbage on the artificial wet land. In the operation process, the organic wastewater generated by solid-liquid separation of domestic sewage and pig farm waste enters a black film methane tank, a DST microorganism selection pond anaerobic fermentation tank and a DST advanced treatment biochemical tank in sequence after pH value adjustment, and then enters the artificial wetland, and the sewage stays in the artificial wetland for 10 days in a hydraulic power manner.
Example 6 preparation and application of active porous ecological Filler
1. Raw materials: commercially available zeolite, charcoal, composite microbial agent (prepared by mixing Bacillus subtilis, yeast, lactobacillus and flocculating bacteria), and Chlorella.
2. Raw material treatment: the method comprises the steps of crushing, sieving and cleaning zeolite and biochar, selecting zeolite with the diameter of 0.5-4 cm, sieving the biochar with a 200-mesh sieve, designing the target porosity to be more than 30%, calculating the mass volume ratio of the biochar to culture wastewater to be restored according to the mass volume ratio of the biochar, the zeolite with the addition amount of 1g/L, the biochar with the addition amount of 1g/L, the compound microbial agent with the addition amount of 0.1g/L and the chlorella with the addition amount of 0.16g/L, and stirring and mixing the zeolite, the biochar, the compound microbial agent, the chlorella and water (the addition amount of control water accounts for 5% of the mass of the active porous ecological mixed filler) to obtain the active porous ecological mixed.
3. Preparation: adding planting soil into the mold to form a basic planting layer, and controlling the thickness of the basic planting layer to be 5 cm; and (3) directly covering the active porous ecological mixed filler obtained in the step (2) on the basic planting layer, uniformly wrapping the surface of the basic planting layer with a layer of active porous ecological mixed filler to form a porous ecological mixed soil layer, and controlling the thickness of the porous ecological mixed soil layer to be 5cm to obtain the active porous ecological filler.
4. Applications of
The site of this example was performed in an artificial wetland of a pig farm of a company in the Guangzhou Zenghain area. The wastewater discharge amount of the pig raising factory is about 500m per day3Mainly comprises pig urine, partial pig manure and pigsty washing water, belongs to high-concentration organic wastewater, and has large content of suspended matters and ammonia nitrogen. The annual average concentration of the main pollutants is: the COD is 11400 mg/L, the total phosphorus is 25mg/L, the ammonia nitrogen is 417mg/L, As is 108 mug/L, Cu is 7mg/L, and Zn is 0.8 mg/L. The method comprises the following specific steps:
and (4) adding the active porous ecological filler prepared in the step (3) into the artificial wetland in a starting operation period. And planting Thailand leaf swamp cabbage on the artificial wet land. In the operation process, the organic wastewater generated by solid-liquid separation of domestic sewage and pig farm waste enters a black film methane tank, a DST microorganism selection pond anaerobic fermentation tank and a DST advanced treatment biochemical tank in sequence after pH value adjustment, and then enters the artificial wetland, and the sewage stays in the artificial wetland for 10 days in a hydraulic power manner.
Finally, the effluent quality indexes of Total Phosphorus (TP) and ammonia Nitrogen (NH) of the drainage pool of the embodiment 3-6 are measured4 +N) and COD both reach the discharge standard of pollutants for livestock and poultry breeding (DB 44/613-2009), and the content indexes of As, Cu and Zn all reach the discharge standard of Integrated wastewater (GB 8978-88). And isThe removal effect of heavy metal As in examples 3 and 4 is better than that in examples 5 and 6.
In the embodiment of the invention, the treatment time of the sewage in the black film methane tank, the DST microorganism selection pond anaerobic fermentation tank, the DST advanced treatment biochemical tank and the flocculation sedimentation tank can be properly adjusted by technical personnel in the field of aquaculture sewage treatment according to the actual pollution condition.
The applicant declares that the above detailed description is a preferred embodiment described for the convenience of understanding the present invention, but the present invention is not limited to the above embodiment, i.e. it does not mean that the present invention must be implemented by means of the above embodiment. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The application of the porous ecological filler system in the remediation of the heavy metal and/or nitrogen and phosphorus polluted culture wastewater is characterized in that the porous ecological filler system comprises a basic planting layer and a porous ecological mixed soil layer, wherein the basic planting layer and the porous ecological mixed soil layer are laid at the bottom of the artificial wetland treatment system, and the porous ecological mixed soil layer is an active porous ecological mixed filler covered on the basic planting layer; the active porous ecological mixed filler is selected from one or more of zeolite, charcoal, compound microbial agent or chlorella; and planting cabbages on the porous ecological mixed soil layer.
2. The use according to claim 1, wherein the active porous ecological hybrid filler is selected from two or more of zeolite, biochar, a complex microbial agent or chlorella; preferably a mixture of biochar and chlorella, or a mixture of zeolite, biochar, microorganisms and chlorella, or a mixture of biochar and microorganisms, or a mixture of zeolite and microorganisms.
3. The application of the zeolite as claimed in claim 2, wherein the addition amount of the zeolite is 1-15 g/L calculated according to the mass-volume ratio of the zeolite to the aquaculture wastewater to be repaired; the adding amount of the biochar is 1-15 g/L; the addition amount of the compound microbial agent is 0.05-5 g/L; the addition amount of the chlorella is 0.1-5 g/L.
4. The application of claim 3, wherein the compound microbial agent is prepared by mixing bacillus subtilis, saccharomycetes, lactic acid bacteria and flocculating bacteria according to the weight ratio of 5-10: 2-10: 1-6: 1-5.
5. The use according to any one of claims 1 to 4, wherein the variety of the water spinach is selected from one or more of green stem leaf water spinach of harbor species, white bone water spinach of Taiwan China, D-95 water spinach of vegetable grower, Thailand leaf water spinach, Tibet leaf water spinach of Thailand, white bone water spinach of harbor species, middle leaf water spinach of Thailand China, pure green leaf water spinach of Guangdong, green bone leaf water spinach of Qinggu, Dayewater spinach of Jiangxi, big leaf water spinach of Hebei, 999 green bone leaf water spinach of Salix japonica, green leaf water spinach of Jashiba leaves, white stem leaf water spinach of Thailand China, white bone leaf water spinach of Taiwan China, green stem leaf water spinach of Taiwan China, white stem leaf water spinach of Thailand China or oil green water spinach.
6. The application of claim 5, wherein the variety of the water spinach is one or more selected from Taiwan white-leaf water spinach, Caoyang D-95 water spinach, Harbour green-stem-leaf water spinach and Thailand bamboo-leaf water spinach.
7. The use of claim 6, wherein the swamp cabbage is planted at a row spacing of 15cm x 25 cm.
8. The use according to claim 1, wherein the thickness of the basic planting layer is 5-8 cm; the thickness of the porous ecological mixed soil layer is 5-10 cm.
9. The use according to claim 8, wherein the material of the basic planting layer is river sand, planting soil or a mixture of humus; the particle size of the biochar is 160-200 meshes; the diameter of the zeolite is 0.5-4 cm.
10. The application of claim 1, wherein the application method comprises:
adding a basic planting layer material into a mould, mixing and stirring active porous ecological mixed filler and water, pouring the mixture into the mould for forming, controlling the addition of the water to account for 5-10% of the mass of the active porous ecological mixed filler, uniformly coating the surface of the basic planting layer with a layer of the active porous ecological mixed filler to form a porous ecological mixed soil layer, obtaining the modular porous ecological filler, then putting the modular porous ecological filler into an artificial wetland treatment system for breeding wastewater, and planting water spinach on the porous ecological mixed soil layer.
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